PAPERmaking! Vol.7 No.1 2021 by pita.co.uk

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Volume 7 / Number 1 / 2021

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Volume 7, Number 1, 2021

CONTENTS: FEATURE ARTICLES: 1. Nanocellulose: BNC as reinforcement for Liner Papers. 2. Moulded Pulp: Food Packaging Applications – a Review. 3. Corrugated Packaging: Shock Testing of Corrugated Packages. 4. Recycling of MDF: Evaluation of Fibre from Waste MDF. 5. RO Membrane Fouling: Scaling and Fouling of RO Membranes: Case Study. 6. Process Waters: Application of (super)cavitation to Process Water Recycling. 7. Coating Binders: Natural Rubber Composites for Paper Coating Applications. 8. Biopolymers: Additives for Pulp & Paper Manufacturing: a Comprehensive Review. 9. Certification & Brexit: Machine Certification for UK Manufacturers post-Brexit. 10. Leadership: Increase your Learning Agility: 4 Tips. 11. Change Management: Four Principles of Change Management. 12. Email Etiquette: 10 Top Tips. 13. Remote Working: 10 Top Tips. SUPPLIERS NEWS SECTION: News / Products / Services: Section 1 – PITA Corporate Members: ABB / FMW / VALMET Section 2 – PITA Non-Corporate Members VOITH Section 3 – Other Suppliers Ametech / Andritz / BTG / Exner DATA COMPILATION: Installations: Overview of equipment orders and installations since November 2020 Research Articles: Recent peer-reviewed articles from the technical paper press Technical Abstracts: Recent peer-reviewed articles from the general scientific press The Paper Industry Technical Association (PITA) is an independent organisation which operates for the general benefit of its members – both individual and corporate – dedicated to promoting and improving the technical and scientific knowledge of those working in the UK pulp and paper industry. Formed in 1960, it serves the Industry, both manufacturers and suppliers, by providing a forum for members to meet and network; it organises visits, conferences and training seminars that cover all aspects of papermaking science. It also publishes the prestigious journal Paper Technology International and the PITA Annual Review, both sent free to members, and a range of other technical publications which include conference proceedings and the acclaimed Essential Guide to Aqueous Coating.

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Contents

PAPERmaking! FROM THE PUBLISHERS OF PAPER TECHNOLOGY TE INTERNATIONAL

Volume 7, Number 1, 2021

Application of Bacterial Nano Cellulose as a Reinforcing Material in The Liner Test Paper Daisy A Sriwendari & Edwin K Sijabat. This research is about the application of Bacterial nano cellulose (BNC) as a reinforcing material in the making of liner test paper. BNC was obtained from the fermentation of banana peel extract using Gluconacetobacter xylinum bacteria obtained from the making starter of nata de coco. The reason for using banana peel waste is because it’s available in large number all across Indonesia. BNC is mixed with secondary fiber as a raw material for making liner test paper. From the experimental handsheets results, strength properties and absorption properties were then tested. Variations in the composition of the use of BNC are 0% (blank), 5%, 10%, 15%, 20%, 25%, 30% of the handsheet dry weight. The BNC is also applicated on surface sizing as a substitute for the surface sizing agent. The results of this study indicate that BNC can be used as an alternative raw material on wet end and on surface sizing, because both applications can increase the strength properties of liner test paper, and can reduce the use of chemical additive. The highest increase in strength properties of liner test paper was obtained at the composition of nano cellulose 30% and using surface sizing. Ring crush index is 14.02 Nm / g, concora index is 12.73 Nm / g, bursting index is 3.78 KPa.m² / g, ply bonding is 388.57 J / m². The absorption properties of paper increases but it has a low prosity. The highest cobb size results are obtained at 30% BNC composition, which is 45.30 g / m2 without using surface sizing and 41.83 g / m² using surface sizing. The highest porosity value is obtained at 30% BNC composition, which is 158 s / 100cc using surface sizing. This research is expected to be a reference for further research in the field of BNC, as the alternative raw materials besides wood in paper making. Contact information: Department of Pulp and Paper Processing Technology, ITSB, Jl. Ganesha Boulevard, Lot-A1 CBD Kota Deltamas, Cikarang Pusat, Bekasi, Indonesia Jurnal Bahan Alam Terbarukan, 9(2) (2020) 126 – 134 DOI: https://doi.org/10.15294/jbat.v9i2.26812 Creative Commons Attribution 4.0 International License

The Paper Industry Technical Association (PITA) is an independent organisation which operates for the general benefit of its members – both individual and corporate – dedicated to promoting and improving the technical and scientific knowledge of those working in the UK pulp and paper industry. Formed in 1960, it serves the Industry, both manufacturers and suppliers, by providing a forum for members to meet and network; it organises visits, conferences and training seminars that cover all aspects of papermaking science. It also publishes the prestigious journal Paper Technology International and the PITA Annual Review, both sent free to members, and a range of other technical publications which include conference proceedings and the acclaimed Essential Guide to Aqueous Coating.

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Article 1 – Nanocellulose in Liner

JBAT 9(2) (2020) 126 – 134

Jurnal Bahan Alam Terbarukan

p-ISSN 2303 0623 e-ISSN 2407 2370

Accredited by Directorate General of Strengthening for Research and Development - SK No.: 36b/E/KPT/2016 http://journal.unnes.ac.id/nju/index.php/jbat

Application of Bacterial Nano Cellulose as a Reinforcing Material in The Liner Test Paper Daisy A Sriwendari, Edwin K Sijabat DOI: https://doi.org/10.15294/jbat.v9i2.26812 Department of Pulp and Paper Processing Technology, ITSB, Jl. Ganesha Boulevard, Lot-A1 CBD Kota Deltamas, Cikarang Pusat, Bekasi, Indonesia

Article Info

Abstract

Article history: Received October 2020 Accepted December 2020 Published December 2020 Keywords: Banana peel; Bacterial nano cellulose (BNC); Alternative raw material in paper making; Test liner.

This research is about the application of Bacterial nano cellulose (BNC) as a reinforcing material in the making of liner test paper. BNC was obtained from the fermentation of banana peel extract using Gluconacetobacter xylinum bacteria obtained from the making starter of nata de coco. The reason for using banana peel waste is because it’s available in large number all across Indonesia. BNC is mixed with secondary fiber as a raw material for making liner test paper. From the experimental handsheets results, strength properties and absorption properties were then tested. Variations in the composition of the use of BNC are 0% (blank), 5%, 10%, 15%, 20%, 25%, 30% of the handsheet dry weight. The BNC is also applicated on surface sizing as a substitute for the surface sizing agent. The results of this study indicate that BNC can be used as an alternative raw material on wet end and on surface sizing, because both applications can increase the strength properties of liner test paper, and can reduce the use of chemical additive. The highest increase in strength properties of liner test paper was obtained at the composition of nano cellulose 30% and using surface sizing. Ring crush index is 14.02 Nm / g, concora index is 12.73 Nm / g, bursting index is 3.78 KPa.m² / g, ply bonding is 388.57 J / m². The absorption properties of paper increases but it has a low prosity. The highest cobb size results are obtained at 30% BNC composition, which is 45.30 g / m2 without using surface sizing and 41.83 g / m² using surface sizing. The highest porosity value is obtained at 30% BNC composition, which is 158 s / 100cc using surface sizing. This research is expected to be a reference for further research in the field of BNC, as the alternative raw materials besides wood in paper making.

INTRODUCTION Paper is a product derived from the use of cellulose as a raw material. Paper is widely used from education to packaging industry (Syafii, 2000). The world’s production and consumption of paper and cardboard in 2010 reached 399,795,000 and 395,860,000 tonnes, respectively (FAO, 2010). The demand for corrugated cartons for manufactured product packaging tends to increase consistently in line with the production sector, for example the food industry, electrical equipments, commodity products, cosmetics and medicine (Office of Commercial Attache Embassy of the Republic of Indonesia, 2013). The packaging paper

Corresponding author: E-mail: edwinsijabat@hotmail.com

consensus for the past 10 years has grown by an average of 2.3 percent (Kompas, 2018). As the market develops, there is a high need for packaging paper. The two main ingredients of packaging paper are liner paper as coating and medium paper as its wave component. Liner paper is used to increase the tear resistance in the carton box so that the product inside is protected during the distribution process. Kraft liner is a paper liner made from a composition of at least 75% virgin pulp (NUKP) and combined with recycle waste paper. The virgin pulp high price makes the paper producers switch to test liner paper. The raw material for liner test paper is 100% recycle waste paper, with certain additives © 2018 Semarang State University ISSN 2303-0623 e-ISSN 2407-2370

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added to obtain better quality parameters (Media, 2017) To meet the pulp industry capacity in 2000, 1.2 billion tree trunks were needed with the 166 million tons CO2 unrelated impact (Aswandi, 2001). Increasing green industry awareness provides direction toward substituting raw materials for paper and cardboard from wood to non-wood (Setiawan, 1999). Paper can be made from all pulp containing cellulose. But until now wood cellulose still dominates as the main material used in the paper making process. Wood cellulose used for making paper is still mixed with other ingredients such as lignin and hemicellulose with a content of 16% and 25% of softwood or needle leaf wood (Sjostrom, 1995). Therefore, it is necessary to separate the cellulose from other ingredients. The separation process can be done in three ways, namely mechanical, chemical, and semi-chemical methods (Sjostrom, 1995). According to Syamsu et al. (2012), those three ways have several weaknesses like high energy consumption and can cause high environmental pollution. Environmental pollution rises due to the use of hazardous chemicals for the delignification process (dissolution of lignin) and the pulp bleaching process (on certain paper) using bleaching chemicals that can result in environmental pollution (Indonesia, 1976). Other weaknesses are the wood low productivity, long logging time required, and other environmentalrelated issues. These weaknesses or problems demand an alternative source of cellulose which is expected to replace wood cellulose as the raw material for making paper. One source of alternative cellulose is microbial cellulose (Halib et al., 2012). Microbial cellulose or bacterial cellulose is produced from several types of microorganisms (bacteria) including Acetobacter species, such as A. xylinum, A. aceti, A. cetianum, and A. Pasteuranum. According to Fitriani et al. (2016), bacterial nano cellulose (BNC) is an alternative source of environmentally friendly cellulose obtained from microbial aerobic fermentation of various species of Acetobacter (Erythrina, 2011). According to Syamsu et al. (2012), BNC has several advantages such as pure from chemicals (lignin, hemicellulose), high cellulose content, can be produced in a relatively short time, and the cellulose produced are already in sheet form (Suparto et al., 2012). Cellulose fibers derived from wood must go through a purification process to remove

hemicellulose, lignin, and other extractive substances found in wood. Thus the BNC pulp making process is relatively simple and environmentally friendly. Microbial cellulose that can be harvested after one week of cultivation is more potential than wood cellulose which can only be harvested after 4-6 years (Sijabat et al., 2017). According to Holmes (2004), bacterial cellulose has the same chemical structure as plantderived cellulose and is a straight-chain polysaccharide composed of D-glucose molecules via β-1,4 bonds. The negative charge is caused by the same chemical structure constituting the two materials, namely cellulose, albeit of different sizes. Nano technology is a technology that results from the utilization of molecular properties that are smaller than 100 nanometers (Abdullah, 2009). The BNC has a diameter of about 2-20 nm and a length of 100 - 40,000 nm. The resulting cellulose is stronger, thinner, and lighter compared to cellulose from plants (Stanley et al. 2006). The porosity is also very low with a diameter of 70-80 nm, the degree of crystallinity is quite high at 6080% and the mechanical strength is large and the modulus of elasticity is high (Jonas & Farah, 1998). According to Mahmudah et al. (2014) , making paper by using BNC as an additive material and retention material with the addition of 20% can increase folding resistance up to 500% and as retention material can reduce porosity. BNC that is applied in recycled wood fiber have the strength that can compete with virgin pulp. This research describes the effect of using BNC from banana peel waste as an alternative raw material and as a substitute for using additive materials in the liner test paper making process. Thus it is expected to produce paper of the same quality and productivity yet is more environmentally friendly. According to Sijabat et al. (2017) paper produced with BNC from coconut water performed good physical strength, low porosity value, optimal tensile index was 51.97 at the 30% nanocellulose composition and optimal tear index was 64.64 at the 15% nanocellulose composition. MATERIALS AND METHODS Materials and Equipments The materials used in this study include secondary fiber form Old Corrugated Carton (OCC), BNC, cationic retention aid, cationic starch, and alkyl ketene dimers (AKD) from 127

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Table 1. Raw Material Characteristics. No. 1.

Parameter Fiber Length

Freeness

3. 4. 5. 6.

Initial pH pH washed with NaOH Particle Charge Detector Charge Demand

BNC 26-45 nm 0 ml CSF (Revolution 1000) 3.90 7.49 -157 mV 0.569 μeq/L

(OCC) Short Fiber 1,006 mm 161 ml CSF (Unbeaten) 7.71 -185 mV 0.421 μeq/L

(OCC) Long Fiber 1,209 mm 318 ml CSF (Revolution 1000) 7.87 -173 mV 0.431 μeq/L

Solenis. While the equipments used include beater (PTI), disintegrator (PTI), beaker glass, analytic balance (PTI), vacuum (PTI), filter paper, hot plate (L&W/3-3), dispermat (PTI), handsheet maker (PTI), blotting paper, speed dryer (PTI), turbidity meter (PTI), Canadian Standard freeness (CSF) tester accroding to TAPPI, pH meter, ring crush tester (L&W/5-2), concora tester (Buchel BV/7508-01-0002), cobb tester (Workshop/100CMQ), densometer (PTI), internal bonding test (Huygen/1314).

RESULTS AND DISCUSSION

Methods The 110 gsm hand sheet test liner was made by preparing the ingredients first, the beating nata de banana and secondary fiber process were done separately. Then the freeness, charge, pH, and consistency checks were conducted. The hand sheet blank was made by using 100% old corrugated containers with additional cationic starch, Poly Aluminum Chloride (PAC), AKD and cationic retention, and coating the surface sizing with the surface sizing agent. Whereas the trial hand sheet was made by using variations in the composition of raw materials of old corrugated containers and BNC based on predetermined compositions of 0%, 5%, 10%, 15%, 20%, 25%, and 30% with the addition of cationic starch and AKD only, and coating the surface sizing using BNC as a substitute for the surface sizing agent. Several wet end stock properties (drainage, turbidity, pH) were then tested along with the tests on several paper properties (ring crush index, concora index, bursting index, ply bonding, porosity, and cobb size). Then an analysis was conducted to compare the test results between blank sample and the trial sample.

Freeness Test Results Before being used as raw material for the handsheet, the raw material was beaten by using hollander beater, the OCC long fiber has 318 ml CSF freeness after 1000 rpm beating, the secondary fiber of OCC short fiber has 161 ml CSF freeness unbeaten, and BNC has a 0 ml freeness CSF after 1000 rpm revolution. The BNC must be able to be homogeneously mixed with raw materials or other additive materials before it can be added on the surface sizing. Therefore it must be beaten with a hollander beater at a 7000 rpm revolution. Then the freeness value is checked, which is at 0 ml CSF. According to Sijabat et al. (2017), the absence of water coming out in the BNC freeness test is because the structure of the BNC itself is in the form of gel and very small in size, with a diameter of about 2-20 nm and length of 100 40,000 nm. The non-branched glucose chain makes a long fibrillar structure, because of the high number of free hydroxyl groups that produce extensive intra and intermolecular hydrogen bonds between adjacent chains (Brown, 1985). These fibres are very small and made of nano-sized fibers thus making the braid really strong and tight that even water will struggle to penetrate it. Therefore, in freeness testing, water cannot get out of the CSF tester mesh.

The results from the nata de banana and secondary fiber characteristics test are described in Table 1. Based on table.1, the results from raw materials tests indicate that BNC has the same negative charge as the charge of wood fiber in general. But it has an acidic pH, so it must be washed first with a 1% of natrium hydroxide (NaOH) solution.

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cellulose α content is higher, which is around 70% and the remaining 30% is β cellulose. Whereas in bacterial cellulose, the β cellulose content is higher at 60%. The density of cellulose α is bigger than that of cellulose β, hence the density of bacterial cellulose is smaller than that of wood cellulose (Sugiyama et al., 1991). This bacterial cellulose has a diameter of about 2-20 nm and a length of 100 40,000 nm. The cellulose produced is stronger, thinner, and lighter than the cellulose that comes from plants (Stanley et al., 2006). The porosity is also very low with a diameter of 70-80nm, the degree of crystallinity is quite high, namely 60-80% and has large mechanical strength and high modulus of elasticity (Jonas & Farah, 1998). Therefore it can make the difference in fiber weight between bacterial cellulose and wood cellulose.

Drainage Speed Test Results Figure 1 shows the slowing down of drainage, that is the water takes longer time to get out of the stock. This happens along with the addition of BNC composition into the stock.

Figure 1. Drainage test result. This is because BNC is hydrophilic and the fiber structure is in gel fom and very small, about 220 nm in diameter and 100 - 40,000 nm in length. The non-branched glucose chains make long fibril structures. The high number of free hydroxyl groups produce extensive intra and intermolecular hydrogen bonds between adjacent chains (Brown, 1985). These very small and nano-sized fibers make the braids really strong and tight that even water will struggle to penetrate it. Therefore, the addition of BNC composition into stock must be limited. In this experiment, the maximum BNC composition used was 30% in stock. According to Sijabat et al. (2017), the maximum composition of nanocellulose is 30%, the addition of nanocellulose above 30% can reduce drainage speed and cause problems in the dewatering process. Based on the experimental result, at the trial 6 drainage stock headbox is very slow at 45.16 s/500 ml, because the BNC composition used is at 30%.

Figure 2. Basis weight test result. Ring Crush and Concora Tests Result Figures 3 and 4 show that the ring crush index and concora index are increasing, from the hand sheet blank to the hand sheet trial 6, both in the experiment without surface sizing and in the experiment with surface sizing coating. The increase in the paper ring crush index and concora index values is caused by the increasing BNC composition used from the hand sheet blanko (0% BNC) to the hand sheet trial 6 (30% BNC). According to Wiley (2014), Nanocellulose has a low density (1.6 g.cm-3), and the surface of the -OH group is more reactive than cellulose in general. This is because the high number of free hydroxyl groups produce extensive intra and intermolecular hydrogen bonds between adjacent chains (Brown, 1985). Therefore the nano-sized BNC has a vast surface area, with many highly reactive OH groups that can bind easily and establish very strong fiber bonds. The porosity is also very low at 70-80nm in diameter, the

Basis Weight Test Results Figure 2 shows that the basis weight value is decreasing from the hand sheet blanko to the hand sheet trial 6. The paper basis weight value depends on the paper sheet weight. The paper sheet weight is influenced by the amount and type of pulp given. The decrease in weight base value is caused by the increasing BNC composition used, from the hand sheet blanko to the hand sheet trial 6. In general, cellulose consists of α cellulose and β cellulose. Wood cellulose and bacterial cellulose consist of both cellulose, only with different compositions. In wood cellulose, the 129

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crystallinity degree is quite high at 60-80% and the mechanical strength is high and the elasticity modulus is high (Jonas & Farah, 1998).

Bursting Test and Ply Bonding Results Figures 5 and 6 show that the bursting index and ply bonding values are increasing, from the hand sheet blanko to the hand sheet trial 6, both in the experiment without the surface sizing coating, and in the experiment with surface sizing coating.

Figure 3. The ring crush index result.

Figure 5. Bursting index test result.

Figure 4. The concora test index. Therefore, the ring crush index and concora trial index values obtained are higher, compared to ring crush index and concora index blanko. Thus the use of BNC in trial proved to increase the handsheet strength properties, compared to the use of additives (PAC and cationic retention) in blanko. Surface sizing is the application of adhesive material (size) on the surface of the paper that has been formed. The main objectives of surface sizing are to obtain paper that is resistant to liquid penetration, to increase the paper surface resistance to chemical absorption, and to increase the physical characteristics of the paper such as its resistance from cracking, cracking, pulling, and folding. Thus the resulting ring crush index and concora index with surface sizing coating are better compared to those without surface sizing coating both in blanko using surface sizing agent as well in trial using BNC to replace the surface sizing agent. The increasing ring crush index and concora index are also influenced by coat weight of the sizing. The heavier the coat weight will increase the ring crush index and concora index, and vice versa.

Figure 6. Ply bonding test result. The increase in the paper bursting index and ply index values is caused by the increasing BNC composition used from the hand sheet blanko (0% BNC) to the hand sheet trial 6 (30% BNC). This is because the high number of free hydroxyl groups produce extensive intra and intermolecular hydrogen bonds between adjacent chains (Brown, 1985). Microbial cellulose has several advantages including high degree of crystallinity, has a density between 300 and 900 kg m-3 and is elastic (Krystynowicz & Bielecki, 2001). The use of BNC can also fill the space between fibers. This advantage causes the bursting index and ply bonding values to increase. The highest bursting index and ply bonding value are in the trial handsheet 6, with the BNC composition at 30%. This shows that using BNC can increase internal strength between fiber layers. Thus using BNC in the trial proved to increase the strength properties handsheet, compared to using

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additives (PAC and cationic retention) in the blanko. The values of bursting index and ply bonding with surface sizing coating are better, compared to those without surface sizing coating, both in the blanko which uses surface sizing agent and in the trial which uses BNC to replace the surface sizing agent. The increase in bursting index and ply bonding is also affected by coat weight of the sizing. The heavier the coat weight will increase the ring crush index and concora index, and vice versa.

stock with low consistency. Thus BNC does not bind with AKD, because it is already bound to water. The cobb size result with surface sizing coating decreases compared to that of without surface sizing, both in the blanko, using surface sizing agent and in the trial using BNC to replace surface sizing agent, because the function of adhesive material (sizing) is to make the paper more water resistant, to increase paper strength and its folding power (Fitriani et al., 2016). In the handsheet trial with surface sizing coating, using BNC to replace the surface sizing agent can keep the liquid from penetrating because the starch added also functions as sizing agent that can block access to free OH groups in BNC (Syamsu et al., 2012). Also the BNC composition used on surface sizing is less than in raw materials, namely 5.56% of surface sizing solution. Figure 8 shows that the porosity value is increasing from the hand sheet blanko to the hand sheet trial 6, both in the experiment without the surface sizing coating, and in the experiment with surface sizing coating. The increase in the paper porosity value is caused by the increasing BNC composition used from the hand sheet blanko (0% BNC) to the hand sheet trial 6 (30% BNC).

Cobb Size Test Results Figure 7 shows that the cobb size value is increasing, from the hand sheet blanko to the hand sheet trial 6, both in the experiment without the surface sizing coating, and in the experiment with surface sizing coating. The increase in the paper cobb size value is caused by the increasing BNC composition used from the hand sheet blanko (0% BNC) to the hand sheet trial 6 (30% BNC).

Figure 7. Cobb size test result. According to Windarti & Siahaan (2008), one of the BNC unique characteristics is that its cellulose membrane is very strong and can bind water to more than 100 times of its own weight, thus forming a hydrogel. The ability of cellulose to bind large amounts of water is because the number of OH groups possessed by cellulose, causes cellulose to be hydrophilic. The cellulose ability to bind large amounts of water is due to the numerous -OH groups possessed by cellulose, thus making it to be hydrophilic. As the BNC composition increases in the handsheet trial, it will increase the cobb size value. Because the higher the BNC, the more water can be binded. Whereas using internal sizing (AKD) as penetration barrier in the trial is less effective because the AKD dosing point is carried out on

Figure 8. Porosity test result. According to Mahmudah et al. (2014), paper making can use BNC as an additive and retention material because it’s a large molecule with 4000-6000 in polymerization degree. The nonbranched glucose chain makes a long fibrillar structure, because of the high number of free hydroxyl groups that produce extensive intra and intermolecular hydrogen bonds between adjacent chains (Brown, 1985). These fibres are very small and made of nano-sized fibers thus making the braid really strong and tight that even water will struggle to penetrate it. According to Sijabat et al. (2017), the addition of nanocellulose can reduce porosity 131

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(a)

(b)

(c)

(d)

(e)

(f)

(g) Figure 9. Microscope Test Results on Stock BNC (a) 5% (b) 10% (c) 15% (d) 20% (e) 25% (f) 30% and (g) 35% at 300X Magnification because nanoscellulose, whose size is in nanoscale, will fill the pore gap between wood fibers, so that the pore gap will be getting smaller or even closedup until there is no more gap. In the experiment where the BNC composition used is increasing, there is an increase in the porosity value from the hand sheet blanko (0% BNC) to the hand sheet trial 6 (30% BNC). The porosity result with surface sizing coating increases compared to that of without surface sizing, both in the blanko, using surface sizing agent and in the trial using BNC to replace surface sizing agent, because one of the surface

sizing functions is to smooth the paper surface that the air will struggle to penetrate through the paper sheet. Because according to Syamsu et al. (2012), tapioca functions as a binder between fibers and increases the number of bonds among fibers and reduces the number of pores. Microscope Test Results Microscope testing is conducted at 300X magnification on the stock before the hand sheet was made and the results can be seen in Figure 9. Based on the microscope results on stock blanko (0% BNC) to stock trial 6 (BNC 30%) above, 132

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there is a difference in the structure of each stock variation. The more visible morphology is fiber from pulp secondary fiber (wood fiber) pulp, whereas the BNC morphology is not visible in stock. This is because the BNC size is far smaller than the size of the wood fiber itself. But as the BNC composition used is added, the stock looks denser and clots (flocculation). This is because the non-branched glucose chain makes a long fibrillar structure, because of the high number of free hydroxyl groups that produce extensive intra and intermolecular hydrogen bonds between adjacent chains (Brown, 1985).

ACKNOWLEDGEMENT The authors gratefully acknowledge the research funding granted by Beasiswa Ikatan Dinas Sinarmas (APP) as part of the undergraduate program of the Department of Vocational, Pulp and Paper Processing, Instittut Teknologi dan Sains Bandung (ITSB). REFERENCES Abdullah, Mikrajuddin. 2009. Pengantar Nanosains. Bandung. Penerbit ITB. Aswandi, R., Brahmana. 2001. Pemanfaatan Serat Garut sebagai Bahan Baku Pembuatan Pulp. Skripsi. Jurusan Teknologi Industri Pertanian, IPB, Bogor. Brown, R. M. Jr. 1985. Cellulose microfibril assembly and orientation: Recent developments. Journal of Cell Science. 2:13-32. Erythrina, S. 2011. Kajian Penggunaan Selulosa Mikrobial Sebagai Pensubstitusi Selulosa Kayu dalam Pembuatan Kertas. Skripsi. Departemen Teknologi Industri Pertanian, Fakultas Teknologi Pertanian, Institut Pertanian Bogor. Bogor. FAO. 2010. FAO Year Book Forest Products 20062010. FAO, Roma. Fitriani, Mahidin, Said, S., Busthan, M. 2016. Kajian Penambahan Selulosa Mikrobial Nata de Coco dan Zat Aditif Terhadap Sifat Fisik Kertas Batang Pisang Abaka. Jurnal Hasil Penelitian Industri. 29(2): 5359. Halib, N., Amin, M. C. I. M., Ahmad, I. 2012. Physicochemical properties and characterization of nata de coco from local food industries as a source of cellulose. Sains Malaysiana. 41(2): 205-211. Holmes, D. 2004. Bacterial cellulose. Master Thesis, Department of Chemical and Process Engineering, University of Canterbury, New Zealand. Indonesia. D. K. R. 1976. Vademecum Kehutanan Indonesia. Direktorat Jendral Kehutanan, Departemen Kehutanan Republik Indonesia, Jakarta. Jonas, R., Farah, L. F. 1998. Production and application of microbial cellulose. Polymer Degradation and Stability. Biotechnology. 59: 101–106.

CONCLUSION The conclusions drawn from this study are BNC can be used as the environmentally friendly alternative source of cellulose in making liner test paper because it does not require a delignification process which is generally found in the process of making paper from wood cellulose. There is an increase in strength properties handsheet trial using bacterial nano cellulose without additional PAC and cationic retention compared to the strength properties handsheet blanko with additional PAC and cationic retention. Therefore BNC can be used as a raw material and can reduce the use of chemical additive. BNC can be applied to surface sizing solutions to further improve paper strength properties as the substitute for surface sizing agent. The quality of paper produced by mixing recycle waste paper and BNC as raw material for liner test paper as a whole increases the strength properties of the test liner trial paper. The use of BNC has an impact on decreasing basis weight handsheet, but paper strength properties such as ring crush index, concora index, bursting index, and ply bonding have increased along with the increase in BNC composition in, as well as in the use of BNC in surface sizing solution. The porosity and cobb size values increase with increasing BNC composition in the handsheet. Thus the paper absorption properties is considered not good, because the trial result underwent an increase from the blanko. The BNC composition of 30% (trial 6) achieved the highest value for paper strength properties, both with he composition of BNC 30% (trial 6), is the highest value for paper strength properties, both without surface sizing coating or with surface sizing coating.

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134

PAPERmaking! FROM THE PUBLISHERS OF PAPER TECHNOLOGY TE INTERNATIONAL

Volume 7, Number 1, 2021

Paper and other pulp based eco-friendly moulded materials for food packaging applications: a review Ayan Dey, Priyanka Sengupta, Nilay Kanti Pramanik, Tanweer Alam. Pulp is one of cheap resources with abundant availability. Papers are made using pulp which finds tremendous use in packing the food products. Such materials are also can be recycled and reused to develop moulded articles useful for packaging applications and other food contact items like trays, cup, plate and pouches etc. Last decade has evidenced several advancements in manufacturing technologies and recycle technologies for paper and pulp based moulded articles. However, there are also many constrains and challenges that were faced during manufacturing of products. This review article covers the various papers and pulp based moulded articles that can be used as food contact materials along with their manufacturing and recycling technologies. Moreover, this article also briefs about various characterization techniques used to ensure the quality of paper and pulp based moulded articles. This information is beneficial in making progress in the development of moulded articles using paper and pulp. Contact information: Indian Institute of Packaging, Plot E-2, MIDC Area, Andheri East, Mumbai, India Journal of Postharvest Technology 2020, 08(3): 01-21 www.jpht.in Creative Commons Attribution 4.0 International License

Page 1 of 22

Article 2 – Moulded Pulp

Journal of Postharvest Technology 2020, 08(3): 01-21 www.jpht.in

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PAPERmaking! FROM THE PUBLISHERS OF PAPER TECHNOLOGY TE INTERNATIONAL

Volume 7, Number 1, 2021

Finite Element and Experimental Investigation on the Effect of Repetitive Shock in Corrugated Cardboard Packaging Viet Dung Luong1, Anne-Sophie Bonnin2, Fazilay Abbès1 , Jean-Baptiste Nolot2, Damien Erre2, Boussad Abbès. The primary concern of the current study is estimating the repetitive shock induced damages leading to cumulative fatigue on corrugated cardboard boxes experimentally and numerically. Repetitive shock tests were performed on boxes using a vibration table to construct a Damage Boundary Curve (DBC). To computationally determine this curve, a finite element approach is proposed using an elastoplastic homogenization model for corrugated cardboard. The proposed model was implemented in the finite element software ABAQUS. Thanks to adopted model simplifications, a box can be easily and reliably modelled as a homogenized structure. A calibration method is used to compute a set of effective parameters in homogenized model in order to keep its behavior qualitatively and quantitatively close to the response of a full structural model. For verification, the identified model is used to simulate the box compression test. To replicate the experimental tests, simulations of successive repetitive shock pulses are carried with the proposed model for oligocyclique and limited endurance fatigue. To reduce computational costs, we propose a simple method for unlimited endurance fatigue by extrapolating a trend line after some training cycles. The proposed method shows good agreement with experimental results. Contact information: 1 MATIM, University of Reims Champagne-Ardenne, UFR SEN, Campus Moulin de la Housse, 51100 Reims, France 2 ESIReims, University of Reims Champagne-Ardenne, Esplanade Roland Garros, 51100 Reims, France Journal of Applied and Computational Mechanics 7(2), 2021, 820–830. https://doi.org/10.22055/JACM.2020.35968.2771 Creative Commons Attribution 4.0 International License

Page 1 of 12

Article 3 – Corrugated Packaging

J. Appl. Comput. Mech., 7(2) (2021) 820-830 DOI: 10.22055/JACM.2020.35968.2771

ISSN: 2383-4536 jacm.scu.ac.ir

MATIM, University of Reims Champagne-Ardenne, UFR SEN, Campus Moulin de la Housse, 51100 Reims, France 2 ESIReims, University of Reims Champagne-Ardenne, Esplanade Roland Garros, 51100 Reims, France

Received December 05 2020; Revised December 26 2020; Accepted for publication December 27 2020. Corresponding author: B. Abbès (boussad.abbes@univ-reims.fr) © 2020 Published by Shahid Chamran University of Ahvaz

Abstract. The primary concern of the current study is estimating the repetitive shock induced damages leading to cumulative fatigue on corrugated cardboard boxes experimentally and numerically. Repetitive shock tests were performed on boxes using a vibration table to construct a Damage Boundary Curve (DBC). To computationally determine this curve, a finite element approach is proposed using an elastoplastic homogenization model for corrugated cardboard. The proposed model was implemented in the finite element software ABAQUS. Thanks to adopted model simplifications, a box can be easily and reliably modelled as a homogenized structure. A calibration method is used to compute a set of effective parameters in homogenized model in order to keep its behavior qualitatively and quantitatively close to the response of a full structural model. For verification, the identified model is used to simulate the box compression test. To replicate the experimental tests, simulations of successive repetitive shock pulses are carried with the proposed model for oligocyclique and limited endurance fatigue. To reduce computational costs, we propose a simple method for unlimited endurance fatigue by extrapolating a trend line after some training cycles. The proposed method shows good agreement with experimental results. Keywords: Packaging, Shock test, Fatigue, Finite element simulation, Elastoplastic model.

1. Introduction Corrugated cardboard boxes are designed to protect products from hazards of the distribution, transportation, and storage environment so that the products can be shipped to consumers without damage. When packaged products are shipped, they may encounter many dynamic events such as drops, impacts, compressions, vibrations…etc. during handling and transportation which might cause damage to the product. Shocks are one of the most severe factors that cause damage to products. The intensity of a given shock is characterized by its acceleration level or amplitude, and the duration over which the shock takes place [1]. Another important characterization of a shock pulse is the velocity change, which is represented by the area under the acceleration amplitude versus time curve. The damage boundary curve (DBC) is widely used to determine the shock damage of a product based on its sensitivity to acceleration and velocity change [2]. DBCs were applied to evaluate repetitive‐shock‐induced damage [3-5]. Test procedure to determine DBC usually requires the use of a programmable shock machine, which can vary the amplitude, duration and velocity change parameters of repeated impacts [6-9]. In our study, a test procedure is proposed using a vibration table to generate shocks of various shapes and intensities to construct the DBC of a corrugated cardboard box. Finite element (FE) modelling of corrugated cardboard has been an area of extensive research in static analysis. Biancolini et al. [10-11] developed equivalent material models of corrugated cardboard using a homogenization approach to predict the eigenvalue buckling load, and ultimate compression load from nonlinear static analyses of boxes. Han and Park [12] and Fadiji et al. [13] investigated the effects of vent design on compression strength using FE simulations on ventilated corrugated cardboard boxes. FE modelling of corrugated cardboard packages is fastidious, and the meshing generates heavy models which increases CPU time. In order to deal with this, researchers developed homogenization models that replace 3D structural models with a single-layered shell model. The proposed homogenization methods generally deal only with elastic properties [14-18], while for the description of nonlinear behavior of corrugated cardboard also plasticity must be considered [7, 19]. Rabczuk et al. [20] proposed a homogenization method for sandwich structures based on the equivalence of the continuum stored energy density function and a discrete energy associated to a representative core cell considering material nonlinearities including buckling of the core. They applied this homogenization to different types of cores under dynamic loading and in fluid–structure interaction examples. Recently, Anitescu et al. [21] proposed a method based on artificial neural networks (ANN) and an adaptive collocation strategy that can be applied for such problems. To model the orthotropic plastic behavior of paperboard, the common plasticity models used for are Hill [22], Hoffman [23], Tsai and Wu [24], Xia et al. [25], Mäkelä and Östlund [26], Harrysson and Ristinmaa [27]. Since corrugated cardboard consists of flat paperboard layers (linerboards) distanced by sine-shaped layer (fluting), the determination of effective elastoplastic Published online: December 28 2020

Finite element and experimental investigation on the effect of repetitive shock in corrugated cardboard packaging

821

parameters for shell model that replaces 3D structural corrugated cardboard model is not an easy task. An inverse identification procedure can be used to calibrate effective elastoplastic parameters [7, 19]. The main concern of this study is estimating the effect of repetitive shock on corrugated cardboard boxes. Novelty of this study is the construction of the Damage Boundary Curve (DBC) using a vibration table and a finite element approach with an elastoplastic homogenization model for corrugated cardboard.

2 . Material and Methods In this section, we present the corrugated cardboard and the experimental techniques used in this study. To determine the material parameters, we carried out tensile tests on the papers constituting the corrugated cardboard. Corrugated cardboard boxes were then tested to study their behavior in compression and under repetitive shock leading to cumulative fatigue. 2.1 Corrugated Cardboard For this study, we have used a single wall corrugated cardboard material consisting of a fluted corrugated sheet and two flat linerboards (Fig. (1)). The thickness and grammage (weight per meter square) of each constituent are given in Table (1). The corrugated cardboard was immersed in water to separate the sheets. The peeled off sheets were wrung by pressing them between absorbent papers before their conditioning at 23°C and 50% relative humidity (RH) for two days. 2.2 Tensile Tests Using a cutting table (ZÜND M-1600), we cut ten standard specimens from the constituents of the corrugated cardboard to perform tensile tests in three directions (MD, CD and 45°). To ensure a better grip of the clamps when tightening these specimens, we glued pieces of rigid compact cardboard to both ends. The tensile tests were performed on an MTS Adamel-Lhomargy DY35XL testing machine equipped with 2 kN load cell. The standard test to evaluate a paperboard’s tensile properties was conducted on a 10 mm wide specimen that was clamped with a free span of 100 mm. The specimen was deformed at a constant rate of 10 mm/min while the force is recorded. To minimize the influence of climatic conditions, all tests were performed at 23°C and 50% RH. 2.3 Box Compression Test Corrugated cardboard boxes are often stacked on one another to certain layers to form pallets. The box must have the capacity to bear the load during storage and transport. It is thus important to check the compression strength of the box. The box compression strength is a direct measure of its stacking strength. Figure (2) shows the unfolded box with dimensions LxWxH = 300x200x180 mm3. The box is compressed at a constant rate of 10 mm/min between two rigid platens. The platens are fixed so that they remain parallel on an INSTRON 4204 testing machine equipped with a 5 kN load cell. The compression tests were carried out under standard conditions at 23°C and 50% RH. 2.4 Repetitive Shock Experiments Corrugated cardboard boxes are used to protect their contents from the hazards encountered in handling, transportation, and storage. These packages are at risk of being dropped or damaged during handling and shipping. Shock is one of the more troublesome of these hazards. Shock testing techniques are used to identify the vulnerabilities of engineered products and components. Controlled shock input by shock machines provides a convenient method for evaluating the ability of shipping containers to withstand shocks.

Fig. 1. Geometry and dimensions of flute B corrugated cardboard.

Fig. 2. Unfolded box. Table 1. Thickness and grammage of flute B corrugated cardboard. Thickness (mm)

Grammage (g/m2)

Top linerboard

0.180±0.004

140

Fluting

0.150±0.008

113

Bottom linerboard

0.217±0.004

130

Journal of Applied and Computational Mechanics, Vol. 7, No. 2, (2021), 820-830

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Viet Dung Luong et. al., Vol. 7, No. 2, 2021

Fig. 3. Experimental setup for shock testing on the vibration table.

Fig. 4. Example of a half-sine shock pulse and corresponding response.

Shock tests were performed on the same boxes introduced in previous section using a servo-hydraulic vibration table connected to a real-time vibration controller (SEREME, France) programmed to generate shocks of various shapes and intensities. As in most mechanical shock test procedures, fixturing of the package on the shock test machine may have significant influence on the test results. In this study, the box is fixed on the vibration table by a structure consisting of link bars connected to the table by bolts as shown in Fig. (3). The box is preloaded with a total mass of 8.4 kg. The test procedure for repetitive shock experiment is as follows: the vibration table generates a shock in the vertical direction and the response of the system shown in Fig. (4) is recorded. A box is subjected to repetitive shock with the same intensity until a visible damage is observed on the box. The damaged box is then removed and replaced by a new one to undergo a series of shocks with another level of intensity. The acceleration and velocity change are the two parameters recorded and plotted in the testing procedure. With this procedure, we obtain the Damage Boundary Curve (DBC) which is constructed from the critical acceleration and the critical velocity change when the box is damaged.

3. Material Model To efficiently simulate the mechanical behavior of a corrugated cardboard box, we need to use a homogenization model instead using the full 3D model to reduce the preparation of the model and the computational times. The homogenization consists in representing the corrugated-core sandwich panel by a homogeneous plate. 3.1 Governing equations The dynamic boundary value problem (BVP) in a 3D cartesian frame is written in a strong form as: ߩ‫ݑ‬ሷ ௜ ൌ ߪ௜௝ǡ௝ ൅ ݂௜

(1)

where ‫ݑ‬௜ are the displacement vector components, ߩ is the density value, ߪ௜௝ are the stress tensor components, and ݂௜ are the body force components. The kinematic relations for the strain rates are given as follows: ͳ ௣ ߝሶ௜௝ ൌ ൫‫ݑ‬ሶ ௜ǡ௝ ൅ ‫ݑ‬ሶ௝ǡ௜ ൯ ൌ ߝሶ௜௝௘ ൅ ߝሶ௜௝ ʹ

(2)

௣

where ߝ௜௝ are the strain tensor components, ߝ௜௝௘ and ߝ௜௝ are the components of the elastic and plastic strain tensors. The constitutive equations relating stress rates and elastic strain rates are given by: ௘ ߪሶ௜௝ ൌ ‫ܥ‬௜௝௞௟ ߝሶ௞௟

(3)

where ‫ܥ‬௜௝௞௟ is the matrix of elastic moduli. Considering the decomposition of the strain rate tensor into elastic and plastic components, the Hooke’s law is written in the following form: ௣

ߪሶ௜௝ ൌ ‫ܥ‬௜௝௞௟ ൫ߝሶ௞௟ െ ߝሶ௞௟ ൯

Journal of Applied and Computational Mechanics, Vol. 7, No. 2, (2021), 820-830

(4)

Finite element and experimental investigation on the effect of repetitive shock in corrugated cardboard packaging

823

The boundary conditions set on the ܵ௩ and ܵఙ surfaces, respectively, are: ‫ݑ‬ሶ ௜ ൌ ‫ݒ‬௜ ǡ ‫ܵ ݊݋‬௩ ൜ߪ ݊ ൌ ܶ ǡ ‫ܵ ݊݋‬ఙ ௜௝ ௝ ௜

(5)

where ‫ݒ‬௜ is the loading velocity, ܶ௜ is the traction and ݊௜ is the surface normal. 3.2 Paperboard Elastoplastic Model In this work, the orthotropic elastoplastic material model proposed by Mäkelä and Östlund [26] was used to predict the behavior of the linerboards and the fluting. This model is based on the concept of material equivalent isotropic plasticity (IPE) introduced by Karafillis and Boyce [28]. The IPE-material is a fictitious isotropic material, subjected to a stress state that equals the corresponding stress state in the actual anisotropic material. The yield criterion may be expressed as: ଵȀଶ ͵ ௣ ଵȀ௡ ݂ ൌ ߪ௘௤ െ ߪ௬ ൌ ൬ ‫ۧݏۦ‬ሼ‫ݏ‬ሽ൰ െ ‫ܧ‬଴ ൫ߝ଴ ൅ ߝ௘௤ ൯ ʹ

(6)

௣ where ߪ௬ is the yield stress, ሼ‫ݏ‬ሽ is the deviatoric stress tensor, ߝ௘௤ is the equivalent plastic strain, ‫ܧ‬଴ and ߝ଴ , are two model parameters. However, the definition of the deviatoric stress tensor for the IPE-material differs from J2-flow theory and is expressed as:

‫ݏ‬௫ ʹܽ ‫ݏ‬௬ ͳ ሼ‫ݏ‬ሽ ൌ ൞ ‫ ݏ‬ൢ ൌ ሾ‫ܮ‬ሿሼߪሽ ൌ ൦ܿ െ ܽ െ ܾ ௭ ͵ ܾെܿെܽ ‫ݏ‬௫௬ Ͳ

ܿെܽെܾ ʹܾ ܽെܾെܿ Ͳ

Ͳ ߪ ௫ Ͳ ߪ ൪൝ ௬ ൡ Ͳ ߪ ௫௬ ͵݀

(7)

where ܽ, ܾ, ܿ and ݀ are model parameters. Since this material model is not available in ABAQUS software, it was implemented using the material user subroutine VUMAT [29]. The aim of this material subroutine is to invoke a given increment in total strain and return the corresponding stress state and the internal state variable (the equivalent plastic strain in our case). A backward-Euler approach is adopted in the implementation of the subroutine. The starting point of the calculation of the stress state, corresponding to a given increment in total strain οߝ௜௝ , is the calculation assuming a pure elastic behavior: of the trial stress state ߪ௜௝௧௥ ௡௘௪

ߪ௜௝௧௥

௡௘௪

ൌ ߪ௜௝ ௢௟ௗ ൅ ‫ܥ‬௜௝௞௟ οߝ௞௟

(8)

The value of the loading function ݂ is evaluated by Eq. (6): if ݂ ൏ Ͳ a pure elastic deformation is occurring during the increment and the evaluated stress state is the correct stress state, if ݂ ൐ Ͳ the deformation is partly plastic and the elastic trial stress state must be corrected for plastic deformation such as: ߪ௜௝ ௡௘௪ ൌ ߪ௜௝௧௥

௡௘௪

െ οߣ‫ܥ‬௜௝௞௟

߲݂ ߲ߪ௞௟

(9)

where οߣ is the plastic multiplier increment given by: ߲݂ ‫ ܥ‬οߝ ߲ߪ௜௝ ௜௝௞௟ ௞௟ οߣ ൌ ߲ߪ௬ ߲݂ ߲݂ ‫ܥ‬ ൅ ௣ ߲ߪ௜௝ ௜௝௞௟ ߲ߪ௞௟ ߲ߝ௘௤

(10) ௜௝

3.3 Homogenized Corrugated Cardboard Elastoplastic Model A corrugated-core sandwich plate consists of a fluted corrugated sheet and two flat linerboards, where the fluting shape is defined with a sine function as: ‫ߠۓ‬ሺ‫ݔ‬ሻ ൌ ିଵ ቆ݄݀ሺ‫ݔ‬ሻቇ ۖ ݀‫ݔ‬ ݄௖ ݁ଶ ‫ݔ‬ ‫۔‬ ݄ۖሺ‫ݔ‬ሻ ൌ ൬ െ ൰ ቀʹߨ ቁ ܲ ʹ ʹ ‫ە‬

(11)

where ݄௖ is the distance between the linerboards, ݁ଶ is the flute thickness and ܲ is the fluting period defined in Fig. (5).

Fig. 5. Representation of the periodic unit cell for corrugated cardboard. Journal of Applied and Computational Mechanics, Vol. 7, No. 2, (2021), 820-830

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Viet Dung Luong et. al., Vol. 7, No. 2, 2021

For the elastic homogenization, the classical lamination theory was modified to consider the corrugated sheet. The laminate in plane forces ሼܰሽ, transverse shear forces ሼܶሽ and out of plane moments ሼ‫ܯ‬ሽ can be related to the deformations ሼߝሽ, ሼߛሽ and the curvature ሼߢሽ of the laminate by the following expression: ܰ௫ ‫ܣۍ ۗ ܰ ۓ‬ଵଵ ௬ ‫ܣ‬ଵଶ ۖ ۖ ۖ ܰ௫௬ ۖ ‫Ͳ ێ‬ ۖ ۖ ‫ێ‬ ‫ܯ‬௫ ‫ܤ‬ ൌ ‫ ێ‬ଵଵ ‫ܯ‬ ‫ ۔‬௬ ۘ ‫ܤێ‬ଵଶ ۖ‫ܯ‬௫௬ ۖ ‫Ͳ ێ‬ ۖܶ ۖ ‫Ͳ ێ‬ ۖ ௫ ۖ ‫ܶ ە‬௬ ۙ ‫Ͳ ۏ‬

‫ܣ‬ଵଶ ‫ܣ‬ଶଶ Ͳ ‫ܤ‬ଵଶ ‫ܤ‬ଶଶ Ͳ Ͳ Ͳ

Ͳ Ͳ ‫ܣ‬ଷଷ Ͳ Ͳ ‫ܤ‬ଵଵ Ͳ Ͳ

‫ܤ‬ଵଵ ‫ܤ‬ଵଶ Ͳ ‫ܦ‬ଵଵ ‫ܦ‬ଵଶ Ͳ Ͳ Ͳ

‫ܤ‬ଵଶ ‫ܤ‬ଶଶ Ͳ ‫ܦ‬ଵଶ ‫ܦ‬ଶଶ Ͳ Ͳ Ͳ

Ͳ Ͳ ‫ܤ‬ଷଷ Ͳ Ͳ ‫ܦ‬ଷଷ Ͳ Ͳ

Ͳ Ͳ Ͳ Ͳ Ͳ Ͳ ‫ܨ‬ଵଵ Ͳ

ߝ௫ Ͳ Ͳ ‫ߝ ۓ ې‬௬ ۗ ‫ۖ ߛۖ ۑ‬ Ͳ ‫ ۖ ۑ‬௫௬ ۖ Ͳ ‫ߢ ۑ‬௫ Ͳ ‫ߢ ۔ ۑ‬௬ ۘ Ͳ ‫ߢۖ ۑ‬௫௬ ۖ Ͳ ‫ߛ ۖ ۑ‬௫௭ ۖ ‫ܨ‬ଶଶ ‫ߛ ە ے‬௬௭ ۙ

(12)

with: ݁ଶ ሺଵሻ ሺଶሻ ሺଷሻ ‫ܣۓ‬௜௝ ሺ‫ݔ‬ሻ ൌ ܳ௜௝ ݁ଵ ൅ ܳ௜௝ ൫ߠሺ‫ݔ‬ሻ൯ ߠሺ‫ݔ‬ሻ ൅ ܳ௜௝ ݁ଷ ۖ ݁ଶ ሺଵሻ ሺଶሻ ሺଷሻ ۖ‫ܤ‬௜௝ ሺ‫ݔ‬ሻ ൌ ܳ௜௝ ‫ݖ‬ଵ ݁ଵ ൅ ܳ௜௝ ൫ߠሺ‫ݔ‬ሻ൯‫ݖ‬ଶ ൅ ܳ௜௝ ‫ݖ‬ଷ ݁ଷ ߠሺ‫ݔ‬ሻ ۖ ۖ ݁ଶ ݁ଵଶ ݁ଶଶ ሺଵሻ ሺଶሻ ‫ܦ‬௜௝ ሺ‫ݔ‬ሻ ൌ ܳ௜௝ ቆ‫ݖ‬ଵଶ ݁ଵ ൅ ቇ ൅ ܳ௜௝ ൫ߠሺ‫ݔ‬ሻ൯ ቆ‫ݖ‬ଶଶ ൅ ቇ ͳʹ ߠሺ‫ݔ‬ሻ ͳʹ ଶ ߠሺ‫ݔ‬ሻ ‫۔‬ ଶ ݁ଷ ۖ ሺଷሻ ଶ ۖ ൅ܳ௜௝ ቆ‫ݖ‬ଷ ݁ଷ ൅ ൅ ͳʹቇ ۖ ݁ଶ ሺଷሻ ۖ‫ ܨ‬ሺ‫ݔ‬ሻ ൌ ͷ ൬‫ ܥ‬ሺଵሻ ݁ ൅ ‫ ܥ‬ሺଶሻ ൅ ‫ܥ‬௜௝ ݁ଷ ൰ ௜௝ ൫ߠሺ‫ݔ‬ሻ൯ ‫ ە‬௜௝ ͸ ௜௝ ଵ ߠሺ‫ݔ‬ሻ ሺ௞ሻ

(13)

ሺ௞ሻ

where ܳ௜௝ is the reduced stiffness matrix (Eq. (14)), ‫ܥ‬௜௝ is the transverse shear stiffness matrix (Eq. (15)), and subscripts 1, 2 and 3 denote outer linerboard, inner linerboard and fluting, respectively. ாೣ

ሾܳሿሺ௞ሻ

‫ۍ‬ଵିఔೣ೤ ఔ೤ೣ ൌ ‫ ێ‬ഌ೤ೣಶೣ ‫ ێ‬భషഌೣ೤ഌ೤ೣ ‫Ͳ ۏ‬ ሾ‫ܥ‬ሿሺ௞ሻ ൌ ൤

ഌೣ೤ ಶ೤ భషഌೣ೤ഌ೤ೣ ಶ೤ భషഌೣ೤ഌ೤ೣ

Ͳ Ͳ ሺ௞ሻ ൨ ‫ܩ‬௫௭

‫ܩ‬௬௭ Ͳ

ሺ௞ሻ

Ͳ ‫ې‬ Ͳ ‫ۑ‬ ‫ۑ‬ ‫ܩ‬௫௬ ‫ے‬

(14)

(15)

where ‫ܧ‬௫ , ‫ܧ‬௬ , ߥ௫௬ , ‫ܩ‬௫௬ , ‫ܩ‬௬௭ , ‫ܩ‬௫௭ are the elastic material properties, with ‫ݔ‬ǡ ‫ݕ‬ǡ ‫ ݖ‬the paperboard MD, CD and ZD directions, respectively. The global equivalent stiffness matrix for elastic case is obtained by integrating Eq. (13) over a fluting period ܲ: ௉

‫ ۓ‬౹ ‫ ܣ‬ൌ න ‫ܣ‬௜௝ ሺ‫ݔ‬ሻ݀‫ݔ‬ ۖ ௜௝ ଴ ۖ ௉ ۖ ۖ‫ ܤ‬౹ ൌ න ‫ ܤ‬ሺ‫ݔ‬ሻ݀‫ݔ‬ ௜௝ ۖ ௜௝ ଴ ௉

‫۔‬ ۖ‫ܦ‬௜௝౹ ൌ න ‫ܦ‬௜௝ ሺ‫ݔ‬ሻ݀‫ݔ‬ ۖ ଴ ۖ ௉ ۖ ౹ ۖ‫ܨ‬௜௝ ൌ න ‫ܨ‬௜௝ ሺ‫ݔ‬ሻ݀‫ݔ‬ ‫ە‬ ଴

(16)

Some simplifying assumptions and detailed calculations of the equivalent stiffness terms can be found in [14-17]. The elastic parameters of linerboards and fluting are obtained from standard experimental tensile tests. Then, the homogeneous ௛ stiffnesses of corrugated cardboard are computed using Eq. (16). Finally, the homogenized material stiffness matrix ܳ௜௝ of the corrugated cardboard is obtained from Eq. (17): ௛ ܳ௜௝ ൌ

ͳʹ‫ܦ‬௜௝౹ ‫ݐ‬౹ଷ

(17)

with: ౹ σଷ௡ୀଵ ‫ܦ‬௡௡ ‫ݐ‬౹ ൌ ඨ ଷ ౹ σ௡ୀଵ ‫ܣ‬௡௡

(18)

To find the effective elastoplastic parameters for shell model that replaces 3D structural corrugated cardboard model, an inverse identification procedure is used. We carried out three tensile test simulations on different samples: MD-sample, CD-sample and 45° oriented-sample using a 3D structural model to generate tensile curves, which are then used to identify an equivalent shell. The 3D structural and the 2D homogenized tensile samples are meshed with rectangular reduced integration shells elements (S4R) with a mesh size of 0.5 mm as shown in Fig. (6). The obtained load vs displacement curves are compared to the numerical equivalent shell curves by minimizing the least square error defined in Eq. (19).

Journal of Applied and Computational Mechanics, Vol. 7, No. 2, (2021), 820-830

Finite element and experimental investigation on the effect of repetitive shock in corrugated cardboard packaging

24 mm

825

24 mm 100 mm

100 mm

Fig. 6. Three-dimensional structural and equivalent corrugated cardboard meshes.

Moving plate

Fixed plate

Fig. 7. Boundary conditions for box compression test.

ே

‫ܨ‬௘௥௥ ൌ

ͳ ଶ ෍൫‫ܨ‬౹ ሺሼܲሽǡ ‫ݐ‬௜ ሻ െ ‫ܨ‬ଷ஽ ሺ‫ݐ‬௜ ሻ൯ ܰ

(19)

௜ୀଵ

where ‫ܨ‬௛ and ‫ܨ‬ଷ஽ are the equivalent shell and 3D structural numerical forces at ‫ݐ‬௜ sampling point, respectively, ሼܲሽ ൌ ሼ‫ܧ‬଴ ǡ ߝ଴ ǡ ݊ǡ ܽǡ ܾǡ ܿǡ ݀ሽ is the unknown parameter vector and ܰ is the number of sampling points. The nonlinearity of the objective function and the possibility of non-uniqueness of the solution make the inverse problem a nonconvex optimization problem. Therefore, a robust global optimization method was required. In this study, the Multi-Objective Genetic Algorithm (MOGA-II) [30-31] was used. It uses a smart multisearch elitism for robustness and directional crossover for fast convergence. Its efficiency is ruled by its operators (classical crossover, directional crossover, mutation and selection) and by the use of elitism. In this study, we used the following parameters: population size = 12, Probability of Directional Cross-over = 0.5, Probability of Selection = 0.05, Probability of Mutation = 0.1, and number of generations = 20.

4. Results and Discussion 4.1 Model Calibration We used the method proposed in previous section to evaluate the equivalent elastoplastic parameters of the corrugated cardboard as follows: x Evaluation of the linerboards and the fluting elastic properties from the experimental tensile tests. The obtained properties are given in Table (2). x Simulation of three tensile tests on different samples (MD, CD and 45°) using a 3D structural model to generate tensile curves. x Identification of the equivalent elastoplastic parameters of the corrugated cardboard using inverse analysis procedure by comparing the generated tensile curves with the simulation tensile curves obtained using the homogenized shell. The determined equivalent elastoplastic parameters of the corrugated cardboard are summarized in Table (3). The identified model is finally used to simulate the box compression test presented in section (2.3). The finite element model consists of two rigid plates that transmit loads to the box and which size is the same as experiment (Fig. (7)). For this simulation friction interaction between plates and box was used to model boundary conditions of system. Bottom rigid plate is fixed so it serves as support for box and top plate is moved vertically for a given displacement. Furthermore, the displacements and rotations of top plate is constrained in other directions. The box is meshed using 9603 rectangular reduced integration shell elements (S4R) and 10152 nodes. Table 2. Elastoplastic properties of linerboards and fluting. ‫ܧ‬௫ (MPa)

‫ܧ‬௬ (MPa)

ߥ௫௬

‫ܩ‬௫௬ (MPa)

‫ܧ‬଴ (MPa)

Top linerboard

3008

1505

0.17

834

256

2.03

2.28

1.18

0.0034

ߝ଴

Fluting Bottom linerboard

3072 3034

1454 1502

0.15 0.23

705 737

436 184

1.62 2.06

1 1

2.01 2.21

1.25 2.19

1.13 1.32

0.0010 0.0011

Table 3. Equivalent elastoplastic properties of the corrugated cardboard. ‫ܧ‬௫௛

(MPa)

368.8

‫ܧ‬௬௛ (MPa)

௛ ߥ௫௬

௛ ‫ܩ‬௫௬ (MPa)

‫ܧ‬଴௛ (MPa)

351.8

0.092

166.2

38.5

݊௛

ܽ௛

ܾ௛

ܿ௛

݀௛

2.04

1.65

0.84

1.55

ߝ଴௛ 0.0068

Journal of Applied and Computational Mechanics, Vol. 7, No. 2, (2021), 820-830

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Viet Dung Luong et. al., Vol. 7, No. 2, 2021

Fig. 8. Comparison of numerical and experimental box compression test curves.

Rigid plates

Rigid bolts

Acceleration shock pulse

Fig. 9. Boundary conditions for shock test.

(a)

(b)

Fig. 10. Effect of mesh refinement on variable responses recorded at top rigid plate: (a) acceleration and (b) velocity.

Figure (8) shows the comparison of the experimental and numerical compression curves of the box with a good agreement. The maximum load obtained by the homogenized model is 1716.8 N compared to the experimental value of 1569.1 N giving a relative difference of 9.4%. 4.2 Repetitive Shock Results For the simulation of shock test, the finite element model consists of a box placed between two rigid plates connected by rigid bolts as shown in Fig. (9). Top plate has a mass of 8.4 kg as in experimental test and is free to move only vertically. An acceleration shock pulse is applied to the bottom rigid plate for a short time. Acceleration and velocity change are recorded on the bottom plate during the simulations. For this simulation friction interaction between plates and box was used to model boundary conditions of system. To replicate the experimental fatigue shock tests, simulations of successive shock pulses are carried out until the box is damaged. The box is considered damaged when the equivalent plastic strains exceeds 5%. To gain confidence in the accuracy of our model, we solved the model on progressively finer meshes and compared results. Since we need the accelerations and the velocity variations to plot DBC, we have plotted in Fig. (10) the results obtained for five successive shocks for three mesh refinements (h=8, 4, 2 mm) in the case of acceleration shock pulse of 16g and shock duration of 14.2 ms. The acceleration and velocity responses recorded at top rigid plate show similar trends for the three meshes, but the amplitudes are closer for the meshes h = 4 mm and h = 2 mm. We have also plotted various model energies for the three meshes in Fig. (11). As we perform a dynamic calculation, the internal and kinetic energies change over time (Figs. 11(a) and 11(b)). Figure 11(c) shows also the energy dissipated by plasticity. The energy balance for the three meshes is shown in Fig. 10(d) which should be constant. However, in the numerical model this is only approximately constant, generally with an error of less than 1% which is the case in our simulations. After this sensitivity analysis, we selected the mesh h = 4 mm for relevant computations while keeping a reasonable computational cost. Journal of Applied and Computational Mechanics, Vol. 7, No. 2, (2021), 820-830

Finite element and experimental investigation on the effect of repetitive shock in corrugated cardboard packaging

(a)

(b)

(c)

(d)

827

Fig. 11. Effect of mesh refinement on various model energies: (a) Internal energy, (b) Kinetic energy, (c) Plastic energy dissipation and (d) Energy balance .

Fig. 12. Numerical and experimental damaged box.

Low fatigue cycle, also called “Oligocyclique Fatigue”, is characterized by high stress and low fatigue life. For the limited endurance fatigue, lifetime is intermediate and varies rapidly in function of applied stress. For unlimited endurance fatigue, the lifetime is infinite. In this study, for oligocyclique and limited endurance fatigue, the number of shocks necessary for the box to damage is determined directly from the Abaqus simulations since the number of cycles is low. However, the number of cycles to damage the box can be very high and it is practically not feasible to perform a cycle-by-cycle simulation. To reduce computational costs, we propose a simple method consisting in extrapolating the equivalent plastic strain after some training cycles. This method is based on a trend line, established during finite element analysis for training cycles. This trend is used to extrapolate the remaining cycles. For oligocyclique fatigue, damage of the box is observed after the first shock both experimentally and numerically as shown in Fig. (12). For limited endurance fatigue, damage of the box is observed after several shocks given in Table (4). We can see that our numerical model gives the same order of magnitude as the experimental results. For the unlimited endurance fatigue, we stopped experimental testing after a thousand shocks considering that the box reaches the unlimited endurance zone. We compare in Table (5) shock numbers for box to undergoes damage obtained for experimental tests and with the extrapolation method. Despite the various simplifying assumptions, the proposed model gives satisfactory results. Figure (13) represents the experimental and numerical damage boundary curve of the studied box that define its fragility based on its sensitivity to acceleration and the that occurs during shock. To compare the velocity change experimental and simulation results, Figs. 14(a) and 14(b) display experimental and simulation frequency distribution for grouped data. The distributions are asymmetric and positively skewed, the values tend to cluster toward the lower end of the scale. Hence, in these sets of points, the mean is higher than the median because the latter is dragged in the direction of the tail. Figs. 14(c) and (d) show a good comparison of the approximated Probability Density Function (PDF) and Cumulative Distribution Function (CDF) of experimental and numerical velocity change variables. Journal of Applied and Computational Mechanics, Vol. 7, No. 2, (2021), 820-830

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Viet Dung Luong et. al., Vol. 7, No. 2, 2021

Table 4. Number of shocks for limited endurance fatigue. Acceleration (g)

Shock duration (ms)

Experimental shock number

13.7

Numerical shock number 2

17.0

13.5

16.2

17.2

15.9

13.3

14.2

13.9

14.2

14.4

14.1

7.8

6.65

Fig. 13. Comparison of experimental and numerical shock fatigue results.

(a) Experimental results PDF

(b) Numerical results PDF

(d) CDF

Fig. 14. Statistical comparison of experimental and numerical shock fatigue results. Journal of Applied and Computational Mechanics, Vol. 7, No. 2, (2021), 820-830

Finite element and experimental investigation on the effect of repetitive shock in corrugated cardboard packaging

829

Table 5. Number of shocks for unlimited endurance fatigue. Acceleration (g)

Shock duration (ms)

Experimental shock number

Numerical shock number

49.8

>1000

1740

20.1

>1000

600

25.0

>1000

1273

17.1

>1000

420

59.4

>1000

1505

80.8

>1000

1160

48.7

>1000

140

5. Conclusion In present work, the effect of shock fatigue on corrugated cardboard boxes was estimated by vibration table and finite element methods. The damage boundary curve of the studied box, that define its fragility based on its sensitivity to acceleration and the velocity change that occurs during shock, was constructed using both methods. To efficiently simulate the mechanical behavior of a corrugated cardboard box, we proposed an elastoplastic homogenization model to replace a corrugated-core sandwich panel by a homogeneous plate. The proposed model performs satisfactorily in static and dynamic loading. Experimental characterization can be time-consuming and expensive. We have showed that it is possible to estimate DBC of the package using finite element method with good precision. This technique can easily be applied to other packaging. However, the physical testing is still needed to validate the final design.

Author Contributions V.D. Luong carried out the simulations; A.-S. Bonnin and J.-B. Nolot conducted the experiments and analyzed the experimental results; D. Erre designed the experiments and analyzed the experimental results; F. Abbès and B. Abbès developed the mathematical modeling and examined the theory validation. The manuscript was written through the contribution of all authors. All authors discussed the results, reviewed, and approved the final version of the manuscript.

Conflict of Interest The authors declared no potential conflicts of interest with respect to the research, authorship, and publication of this article.

Funding The authors received no financial support for the research, authorship, and publication of this article.

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[25] Xia, Q.S., Boyce, M.C., Parks, D.M., A constitutive model for the anisotropic elastic-plastic deformation of paper and paper board, International Journal of Solids and Structures, 39(15), 2002, 4053-4071. [26] Mäkelä, P., Östlund, S., Orthotropic elastic-plastic material model for paper materials, International Journal of Solids and Structures, 40(21), 2003, 55995620. [27] Harrysson, A., Ristinmaa, M., Large strain elasto-plastic model of paper and corrugated board, International Journal of Solids and Structures, 45(11-12), 2008, 3334–3352. [28] Karafillis, A.P., Boyce, M.C., A general anisotropic yield criterion using bounds and a transformation weighting tensor, Journal of the Mechanics and Physics of Solids, 41(12), 1993, 1859–1886. [29] Abaqus v. 6.19 documentation, Dassault Systemes Simulia Corporation, 2016. [30] Poloni C., Pediroda, V., GA coupled with computationally expensive simulations: tools to improve efficiency, In Genetic Algorithms and Evolution Strategies in Engineering and Computer Science, John Wiley and Sons, England, 1997. [31] Spicer, D., Cook, J., Poloni C., Sen P., EP20082 Frontier: Industrial MultiObjective Design Optimisation, In Proceedings of the 4th European Computational Fluid Dynamics Conference (ECCOMAS 98), John Wiley and Sons, England, 1998.

ORCID iD Fazilay Abbès https://orcid.org/0000-0003-0036-822X Boussad Abbès https://orcid.org/0000-0003-1192-6549 © 2020 by the authors. Licensee SCU, Ahvaz, Iran. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution-NonCommercial 4.0 International (CC BY-NC 4.0 license) (http://creativecommons.org/licenses/by-nc/4.0/). How to cite this article: Luong V.D., Bonnin A.-S., Abbès F., Nolot J.-B., Erre D., Abbès A. Finite element and experimental investigation on the effect of repetitive shock in corrugated cardboard packaging, J. Appl. Comput. Mech., 7(2), 2021, 820–830. https://doi.org/10.22055/JACM.2020.35968.2771

Journal of Applied and Computational Mechanics, Vol. 7, No. 2, (2021), 820-830

PAPERmaking! FROM THE PUBLISHERS OF PAPER TECHNOLOGY TE INTERNATIONAL

Volume 7, Number 1, 2021

Recycling of Waste MDF by Steam Refining: Evaluation of Fiber and Paper Strength Properties Sebastian Hagel1 · Jesan Joy2 · Gianluca Cicala2 · Bodo Saake1 Currently, most of the collected waste medium-density fiberboards (MDF) is incinerated or landfilled, as economically viable recycling methods are yet to be developed. By steam refining waste medium-density fiberboards (MDF), it is possible to hydrolyze the incorporated resins and isolate a high yield fiber fraction. Further refining of the steam treated fibers might enable the fibers to be utilized in applications such as paper packaging, facilitating a cascading use of the waste material stream. To this end, intimate knowledge of the material is needed. In this study, the steam refined fibers of two waste MDF samples containing differing amounts of softwood and hardwood underwent refining and beating. The resulting fibers were characterized regarding their morphology and paper test sheets were produced to evaluate their strength (compression-, tensile- and tear-strength). Distinct differences in response to refining between the MDF samples were apparent. For the sample with the higher hardwood share an increase in strength properties with increasing steam treatment severities could be observed and it was possible to produce test sheets with comparable compression strength to recycled pulp for industrial corrugated paperboard. For the sample with a higher share of softwood, the steam treatment severity did not show any influence on fiber morphology or paper properties, and the resulting paper strength was low in comparison to the other steam refined waste MDF sample. Contact information: 1 Institute of Wood Science, Chemical Wood Technology, Universität Hamburg, Haidkrugsweg 1, 22885 Barsbüttel, Germany 2 Department of Civil Engineering and Architecture, Università Degli Studi Ci Catania, Viale Andrea Doria 6, 95125 Catania, Italy Waste and Biomass Valorization published online https://doi.org/10.1007/s12649-021-01391-4 Creative Commons Attribution 4.0 International License

Page 1 of 14

Article 4 – Recycling of MDF

Waste and Biomass Valorization https://doi.org/10.1007/s12649-021-01391-4

ORIGINAL PAPER

Recycling of Waste MDF by Steam Reﬁning: Evaluation of Fiber and Paper Strength Properties Sebastian Hagel1 · Jesan Joy2 · Gianluca Cicala2 · Bodo Saake1 Received: 28 October 2020 / Accepted: 10 February 2021 © The Author(s) 2021

Abstract Currently, most of the collected waste medium-density fiberboards (MDF) is incinerated or landfilled, as economically viable recycling methods are yet to be developed. By steam refining waste medium-density fiberboards (MDF), it is possible to hydrolyze the incorporated resins and isolate a high yield fiber fraction. Further refining of the steam treated fibers might enable the fibers to be utilized in applications such as paper packaging, facilitating a cascading use of the waste material stream. To this end, intimate knowledge of the material is needed. In this study, the steam refined fibers of two waste MDF samples containing differing amounts of softwood and hardwood underwent refining and beating. The resulting fibers were characterized regarding their morphology and paper test sheets were produced to evaluate their strength (compression-, tensile- and tear-strength). Distinct differences in response to refining between the MDF samples were apparent. For the sample with the higher hardwood share an increase in strength properties with increasing steam treatment severities could be observed and it was possible to produce test sheets with comparable compression strength to recycled pulp for industrial corrugated paperboard. For the sample with a higher share of softwood, the steam treatment severity did not show any influence on fiber morphology or paper properties, and the resulting paper strength was low in comparison to the other steam refined waste MDF sample. Graphic Abstract

Keywords Waste MDF · Biomass residues · Recycling · Steam treatment · Fibers · Added value products

Statement of Novelty * Bodo Saake Bodo.Saake@uni-hamburg.de Extended author information available on the last page of the article

As there currently is no widely deployed recycling method for waste MDF, the utilization of steam to fractionate waste MDF in the context of a bio reﬁnery, in which all parts of

Vol.:(0123456789)

Waste and Biomass Valorization

the material are processed, might prove a viable recycling concept to fill this void. The fiber fraction represents the major share of the material after the steam treatment, and finding an economic and ecological application for the fibers will be a key element in successful valorization. Because the amount of waste MDF and the demand for fiber based packaging solutions is steadily rising, a deployment of the steamed fibers in packaging applications could be a step in solving both challenges simultaneously. Thus, an investigation into the fiber and resulting paper properties was undertaken to identify problems and evaluate the viability of the concept.

Introduction Medium density fiberboards (MDF) are an engineered wood product made out of lignocellulosic fibers, which are blended with resins and hot-pressed into panel shape [1, 2]. Roughly 80% of the manufactured panels are processed further into furniture or flooring applications [3]. Due to the rising demand, the worldwide production volume of MDF has increased continuously, from roughly 8 million m3 in 1995 to almost 100 million m3 in 2018 [4]. At the same time, shifts in consumer behavior, such as the perception of furniture as a fashion item instead of a durable commodity, have led to increasingly shorter life cycles [5]. Consequently, a rising amount of waste MDF is accumulating. Assuming an average life span of approximately 14 years, a total waste MDF volume of almost 50 million m3 can be calculated just for the year 2016 [6]. In Europe, due a combination of factors such as government subsidies, challenges in sorting of the waste material stream and stability of the waste material supply chain, a major part of the available waste wood is incinerated for energy generation [7]. Following the principles laid out in the Waste Framework Directive of the European Parliament [8], a material recycling should always be given priority over energy recovery or land filling, as by reusing the material before energy recovery, the biomass can be used in a cascade, improving the resource efficiency [9]. Fractionation is a necessary step to enable a material recycling of waste MDF. Using hydrothermal or steam-based treatments it is possible to hydrolyze the urea–formaldehyde (UF) based resins [10–14], which make up the majority of the resins used in MDF production [15]. To compare chemical and structural changes in differing steam-based treatments of lignocellulosic material, the severity factor, which combines the two main process parameters treatment duration and temperature, can be used [16, 17]. In a previous study steam refining was used to fractionate standard waste MDF, the applicability of the severity factor in steaming of waste MDF was confirmed and the influence of differing treatment severities on the chemical composition of the

fractions and the process was evaluated [18]. By steam refining of waste MDF a liquid and a solid fraction is generated. The liquid fraction contains solubilized carbohydrates and lignin as well as a high amount of nitrogen and acids (acetic and formic). The pH of the liquid extract of around 8 is high in comparison to liquid fractions of steam treated native lignocellulosic material, due to a high amount of ammonium hydroxide following the degradation of the urea–formaldehyde resins [12, 13]. As the fiber fraction accounts for the major fraction after the steam refining treatment, the development of an economically viable recycling pathway for the fibers is of prime interest for the advancement of material recycling of waste MDF. The reuse of the separated waste MDF fibers in production of new MDF is the most apparent possible recycling pathway. However, due to a combination of effects such as fiber shortening, changes in the chemical compositions of the fibers and resin residues found on their surface, a deterioration of the mechanical properties in comparison with MDF made from fresh wood can be observed when using hydrothermal or steam-based fractionation processes [19–24]. Recently, Moezzipour et al. [25] have reported that such negative effects on the fibers can be reduced using electrical heating instead of hydrothermal treatments, leading to improved mechanical properties of the newly produced MDF. Other previously investigated potential uses for recovered waste MDF include the production of cellulose nanocrystals [26, 27], wood polymer composites (WPC) [28–30], bio-ethanol [31–33], bio-oil and biogas [34–37], or the substitution of particles in the middle layer of particle boards [38] as well as insulation or oil spill absorbance applications [39]. Another potential recycling path might be the utilization of steam refined waste MDF fibers in paper packaging applications, such as corrugated boards, allowing for extended cascading of the wood fibers. Corrugated board is the packaging material with the highest production volume worldwide [40] and due to the continuing increase in e-commerce, the demand is expected to remain high even in times of uncertain global trade relations [41]. Corrugated board consists of at least one wave-like element called flute and one flat sheet called liner or linerboard [42]. The overall structure of a corrugated board is making use of the engineering beam principle, in which the fluting acts as a supporting structure for the two load-bearing planes. As hardwood fibers are shorter and stiffer than softwood fibers, which makes the papers easy to corrugate but still gives them a rigid structure, the flute is usually made from recycled pulp or from virgin hardwood neutral sulphite semi-chemical pulp. The flat liners are called test liner if manufactured from recycling fibers, or kraft liner if manufactured out of virgin softwood kraft pulps [40]. In Germany, 65% of all packaging material for transportation is made out of corrugated board and

Waste and Biomass Valorization

80% of the produced corrugated board is manufactured with recycling fibers [43]. As a result of limitations in available forest-based materials [44] and growing environmental awareness of the population, the corrugated board industry is utilizing recycling fibers to an increasing degree, which, from an environmental point of view, can be considered a benefit due to reduced emission of CO2 [45]. However, the recycling process causes a deterioration of the mechanical properties of the fibers, which can lead to a strength loss of up to 30% of its original strength [46]. The passage of the fibers through the recycling chain (which includes repeated drying, printing, converting, storing, deinking and re-refining) leads to hornification, a reduction of cell wall porosity, fiber shortening, loss of flexibility, re-adhesion of fibrils onto the fiber surface, micro-indentations and -compressions, loss of degree of polymerization, self-sizing, loss of hemicelluloses on the fibers surface and the accumulation of contaminants, all of which can have a negative impact on the paper strength [46–51]. One potential way of mitigating the effect of the deteriorating quality of the recycled fibers available is the introduction of new fibers into the production process, such as wheat straw pulp [52, 53]. Thus, to converge the afore mentioned challenges of the large quantities of waste MDF to be disposed of, the high demand of fibrous material for the packaging industry, and the deteriorating quality of the recycled pulp, this study aims to assess the viability of utilizing steam refined fibers from post-consumer MDF in recycled paper packaging as filler or reinforcement material. Currently, most MDF in European countries is produced from softwood. As a shift in forest management is leading to a reduction of softwood stands and an increase in hardwood stands in Europe [54], the resulting shortage of softwood and oversupply of hardwood will likely push the MDF manufacturers to increase the amount of hardwood utilized. To take this development into account, a waste MDF sample set containing a high amount of hardwood and one containing a high amount of softwood were used and compared to each other and to recycled fibers used in the industry for manufacturing of corrugated board. The waste MDF samples were treated at six different severity grades, ranging from 2.5 to 4.0. In a previous publication the effect of steam refining on the reactions of chemical components was reported [18]. In the present paper the effect of steaming severity and refining intensity on fiber morphology and strength properties will be evaluated. As the gap between the rotating blades and the inner wall of the steam refining reactor is large (10 to 20 mm) in comparison to typical fiber dimensions (0.6 to 4.4 mm length and 10 to 50 μm diameter [55]), the steam treated waste MDF fibers are present in small fiber bundles [18]. A secondary refining and beating was performed on the steam refined fibers to separate the fiber bundles and improve the fiber properties for papermaking. In refining and beating, flocs and fibers

are deformed in the presence of water by two metallic surfaces moving in relation to each other, causing compressive and shear forces in the pulp. The main positive effects on the fibers are an external and internal fibrillation as well as the formation of fines, leading to an increase of surface area available for fiber to fiber bonding [56–58]. The resulting pulp was characterized using an automated fiber length analyzer and used for test sheet preparation. The tensile-, compression-, and tear-strength, as well as brightness of the test sheets were measured and the relationship between the fiber morphology and paper strength evaluated.

Material and Methods Raw Material and Their Preparation Two chipped, clean waste MDF samples without lamination supplied by École supérieure du bois (Nantes, France) were used in this study. The chipped waste MDF featured a length of roughly 10 to 50 mm, a width of 15 mm and a height of around 10 mm. Batches of 300 g (dry matter) waste MDF chips were steam treated in a 10-l reactor with a diameter of 22 cm and a length of 25 cm (Martin Busch & Sohn GmbH, Germany) at severities ranging from 2.5 to 4. The severity (log R0) of the steam treatments was calculated according to Eq. (1). In the last 30 s of the treatment, the fibers were defibrated within the steam filled reactor by rotation of a built-in four bladed system at a speed of 1455 rpm.

log R0 = log (t × e

(T−100) 14,75

)

(1)

with T: steam temperature in °C, t: steaming duration in min. At the end of the treatment duration, the steam was released through a valve in about 90 s. Subsequently, the fiber fraction was separated from the extract by filtration through a sieve bag and dewatered for 10 min at 2800 rpm in a spin dryer (Thomas Centri 776 SEK, Thomas, Germany). The fiber fraction was passed through a 12Ǝ Sprout-Bauer laboratory refiner (Andritz, Graz, Austria) three times. In the first pass, the gap distance was adjusted to 0.5 mm and the consistency of the pulp was adjusted to 4%. In the following two passes, the gap distances were reduced to 0.2 mm and the consistency decreased continuously due to the addition of rinsing water to a final consistency of around 2%. The fibers were separated from the rinsing water using above mentioned procedure. The complete process is depicted in Fig. 1. In Table 1 the chemical composition of the two waste MDF samples and the fibers after steaming are presented. Detailed information regarding the determination of the chemical composition of the samples, as well as a discussion on the process reactions is given in a previous

Waste and Biomass Valorization Fig. 1 Process ﬂowchart

Table 1 Chemical composition of the waste MDF samples (untreated) and after steaming reﬁning in [%] w/w [18]

Sample

Severity (Log R0)

Glucose (%)

Xylose (%)

Mannose (%)

Lignin (%)

Nitrogen (%)

SR-MDF (A)

Untreated 2.5 2.8 3.1 3.4 3.7 4.0 Untreated 2.5 2.8 3.1 3.4 3.7 4.0

38.3 42.3 42.7 43.0 44.2 45.6 48.2 37.6 46.8 46.7 46.5 48.5 50.4 49.6

12.4 14.0 14.0 13.2 12.6 10.7 8.0 5.7 7.0 6.8 6.5 6.2 5.5 4.4

4.0 4.3 4.3 4.5 4.2 4.7 4.6 7.2 8.6 8.4 8.4 8.7 8.8 8.1

24.4 27.3 26.5 26.6 27.2 30.0 32.9 26.6 31.6 32.1 33.1 32.6 33.7 35.3

4.2 1.2 1.2 0.9 0.9 1.1 1.2 4.4 1.1 1.1 1.1 1.1 1.0 1.1

SR-MDF (B)

publication [18]. In the first sample (SR-MDF A) a higher amount of xylose (12.4%), a lower amount of mannose (4.0%) and a lower amount of lignin (24.4%), than in the second sample (SR-MDF B) with 5.7%, 7.2% and 26.6%, respectively, was determined. The high proportion of xylose with only small amount of mannose is characteristic for hardwood [55]. This indicates that a high amount of hardwood was used in the manufacturing of the first sample. In contrast to that the proportion of mannose and xylose in SR-MDF B shows a slight preference for mannose which is characteristic for softwood, indicating a dominance of softwood fibers in this sample. The nitrogen content of both samples were found to be similar, indicating a similar amount of UF-resin used in production. Due to a high amount of extractable resin at a low severity treatment of 2.5, which can be seen in the changes to the nitrogen content, the fiber yield of the steam treated waste MDF fibers drops and the amount of glucose, xylose, mannose and lignin rises in relation to the raw material. An increasing solubilization of the hemicelluloses following an increase in treatment severity leads to a further increase in fiber yield and consequently, the relative content of lignin and glucose rises. For comparison of the fiber morphology and test paper strength, recycling pulp from two different industrial corrugated paperboard producers was evaluated alongside the SR-MDF samples. The recycled

pulp (RP) samples were taken after sorting, shortly ahead of the headbox.

Pulp and Fiber Characterization All samples were subjected to additional beating in a Jokro mill (FRANK-PTI, Birkenau, Germany) following the procedure described in DIN 54360:2004 [59]. Subsequently, the pulp suspensions were disintegrated according to ISO 52632:2004 [60] for 2 min. Unbeaten samples were disintegrated for 20 min. For representative sampling, the disintegrated pulp was kept in constant movement in a laboratory equalizer until further processing. The beating degree was measured in a Schopper-Riegler freeness tester type SR1 (Karl Schröder KG, Weinheim, Germany) according to ISO 52671:1999 [61]. For fiber morphology characterization, samples of the pulp were analyzed using a kajaaniFiberLab (Metso, Helsinki, Finland). The arithmetic average fiber length L(n) and the length weighted fiber length L(lw) were calculated according to Eqs. 2 and 3, respectively. A high amount of fine material will significantly affect the arithmetic mean, while having a lower influence on the length weighted fiber length. The fiber width was calculated analogous to the arithmetic fiber length L(n), using the width of the fibers. The average fiber Curl(n) was calculated according to Eq. 5. The average kink index Kink(n) was calculated according to Eq. 7.

Waste and Biomass Valorization

∑ (n l ) L(n) = ∑ i i ni

(2)

∑

(ni l2i ) ∑ ni

L(lw) =

(3)

ni = number of fibers in the specified fiber class, li = fiber length in specified class [mm] ) ( Lci − 1 ∗ 100% Curli = (4) Lpi

∑ Curl(n) =

(ni ∗ Curli ) ∑ ni

(5)

Lci = true contour fiber length [mm], Lcp = projected fiber length [mm], Curli = Fiber curl of specified fiber class [%]

Kinki =

(n10−20◦ + 2 ∗ n21−45◦ + 3 ∗ n46−90◦ + 4 ∗ n90+◦ ) Lci ∑

Kink(n) =

(ni ∗ Kinki ) ∑ ni

(6) (7)

nx-y = Numbers of kinks with a kink angle between x° to y°, Kinki = Number of kinks of speciﬁed ﬁber class [1/mm]. Laboratory paper sheets of about 75 g/m2 were produced with a Rapid-Köthen sheet forming machine (FRANK-PTI, Birkenau, Germany) as described by ISO 5269-2:2004 [62] and conditioned for at least 24 h at (23 ± 1) °C and (55 ± 2) % relative humidity before physical testing. The brightness was measured according to TAPPI T525 [63] with an ELREPHO 450X from Datacolor (Rotkreuz, Switzerland). The short

Table 2 Inﬂuence of the treatment severity on the ﬁber morphology of the steam treated waste MDF samples in comparison to morphological characteristics of recycled pulp

Sample

SR-MDF

(A)

SR-MDF

(B)

RP RP

#1 #2

span compressive (SCT) strength was measured according to DIN 54518:2004 [64], the tensile strength according to ISO 1924-2:2009 [65] and the tear strength according to ISO 1974:2012-09 [66]. All instruments used for aforementioned measurements were manufactured by FRANK-PTI Gmbh (Birkenau, Germany). The indices were calculated according to TAPPI T 220 [67].

Results and Discussion Fiber Morphology Key parameters of the fiber morphology of the waste MDF fibers following steam refining treatments of different severity are presented in Table 2 and compared to recycled pulp samples from industrial corrugated paperboard producers. The SR-MDF (B) fibers show widths of 30.1 μm to 31.8 μm and length weighted fiber lengths of 0.87 mm to 1.00 mm in comparison to widths of 24.1 μm to 25.0 μm and length weighted lengths of 0.72 mm to 0.86 mm of the SR-MDF (A) fibers. These differences support the presumption of the different ratios of softwood and hardwood fibers in the corresponding samples, as softwood fibers are usually longer and wider than hardwood fibers [55, 68]. A more severe steam treatment led to a slight reduction in fiber length, while the fiber width and the amount of fines material was mostly unaffected for both SR-MDF sample sets. However, differences in behavior between the SR-MDF sample A and B can be seen in the amount of fiber kink and curl measured. While the amount of fiber curl and kinks were mostly unaffected for the SR-MDF (B) sample, except for a slight increase at the very highest severity degree, a distinct increase in fiber curl and kinks can be observed for

Severity (Log R0)

L(n) (mm)

L(lw) (mm)

Width (μm)

Fines (%)

Fiber Curl (%)

Kink index (1/m)

2.5 2.8 3.1 3.4 3.7 4.0 2.5 2.8 3.1 3.4 3.7 4.0 – –

0.54 0.46 0.47 0.49 0.48 0.46 0.56 0.55 0.56 0.53 0.50 0.50 0.53 0.55

0.86 0.75 0.76 0.78 0.76 0.72 0.96 1.00 0.96 0.95 0.93 0.87 1.09 1.09

25.0 24.7 24.2 25.0 24.8 24.1 30.3 30.1 31.6 30.9 30.8 30.1 22.1 20.7

5.0 8.0 7.1 6.5 6.7 6.9 5.4 6.1 5.3 6.3 7.8 6.7 5.3 5.1

6.2 6.2 6.9 7.4 10.0 11.4 5.2 5.0 4.8 5.0 5.3 5.9 20.1 16.9

356 306 365 434 603 723 296 241 265 256 269 381 1528 1062

Waste and Biomass Valorization

the SR-MDF (A) sample following an increase in treatment severity. In comparison to the recycled pulp samples, the SR-MDF fibers are shorter and wider, show less fiber curling and a lower amount of kinks. Following the refining, all of the SR-MDF samples were beaten for an additional 20, 40 and 60 min to evaluate the influence of the treatment severity on the length and width of the steam refined waste MDF fibers and the resulting test paper strengths over a wide range of beating degrees. In Table 3 the measured fiber lengths and widths are presented. In all samples the fiber width increased and the fiber length decreased with beating time, irrespective of treatment severity. After 60 min of beating, a fiber width increase of roughly 10% can be measured. The width increase can be explained with a flattening of the fibers due to a collapse of the lumen in beating [48]. While the arithmetic average fiber lengths of the SR-MDF (A) and SR-MDF (B) sample do not differ much, considerable differences in the length weighted fiber lengths are visible. This implicates differences in the amount of short fiber fragments and therefore the fiber length distribution between the two samples. In Fig. 2, the length-weighted fiber length distribution for the lowest and

Table 3 Influence of the beating duration on the arithmetic average fiber length L(n), the length weighted fiber length L(lw) and the fiber width of the SR-MDF samples

Treatment severity

Influence of Treatment Severity on the Development of the Beating Degree In Fig. 3 the beating degree of the different samples as a function of the beating time is presented. The beating degree is a measurement of the drainability of a fiber web and an

Beating duration

SR-MDF (A)

SR-MDF (B)

L(n)

L(lw)

Width

L(n)

L(lw)

Width

(Log R0)

(min)

(mm)

(μm)

(mm)

(μm)

2.5

0 20 40 60 0 20 40 60 0 20 40 60 0 20 40 60 0 20 40 60 0 20 40 60

0.54 0.33 0.21 0.18 0.46 0.26 0.21 0.18 0.47 0.27 0.21 0.19 0.49 0.28 0.23 0.21 0.48 0.34 0.28 0.25 0.46 0.34 0.28 0.25

0.86 0.53 0.31 0.26 0.75 0.42 0.31 0.26 0.76 0.43 0.31 0.28 0.78 0.43 0.34 0.30 0.76 0.53 0.42 0.37 0.72 0.52 0.44 0.39

25.0 25.0 26.9 27.8 24.7 25.6 26.8 27.4 24.2 24.9 26.5 27.7 25.0 25.1 26.3 26.9 24.8 25.2 25.8 27.4 24.1 24.6 26.2 25.9

0.56 0.37 0.23 0.18 0.55 0.41 0.23 0.20 0.56 0.31 0.22 0.18 0.53 0.31 0.23 0.20 0.50 0.34 0.25 0.20 0.50 0.29 0.21 0.18

0.96 0.65 0.37 0.28 1.00 0.71 0.36 0.31 0.96 0.51 0.34 0.28 0.95 0.50 0.34 0.29 0.93 0.55 0.39 0.29 0.87 0.47 0.33 0.28

30.3 31.1 33.4 34.4 30.1 32.2 33.8 33.6 31.6 32.5 34.6 34.3 30.9 31.8 33.7 34.6 30.8 31.8 33.1 33.2 30.1 31.7 32.8 33.3

2.8

3.1

3.4

3.7

4.0

highest severity treatments of both samples is presented. A clear shift in fiber length distribution to the lower lengths following an increased beating duration is visible. For the SR-MDF (B) sample, the severity of the steam treatment did not seem to significantly alter the general reduction in fiber length as a function of beating duration. For the SR-MDF (A) fiber samples on the other hand, an increase in treatment severity led to a reduction in the small fiber population after prolonged beating, which is reflected in the increase of the L(lw) at more severe treatments and high beating durations. Without additional beating, the treatment severity had the opposite influence, and the highest length weighted fiber length could be determined at the lower severities. This is reflected in the higher amount of fibers found at a length of 1.5 mm and longer after low severity treatments.

Waste and Biomass Valorization (SR-MDF A; log R0 = 2.5)

(SR-MDF A; log R0 = 4.0)

[%]

Fig. 2 Length-weighted ﬁber length distribution of SR-MDF A (upper row) and SR-MDF B (bottom row) treated at a severity of 2.5 (left column) and 4.0 (right column) in relation to beating duration

2 0

0 0

[%]

0 0

Fiber Length [ mm]

0 minutes additional beating 20 minutes additional beating

40 minutes additional beating 60 minutes additional beating

Beating degree [°SR]

(SR-MDF B; log R0 = 4.0)

(SR-MDF B; log R0 = 2.5)

Fig. 3 Relationship between beating duration and beating degree of a SR-MDF (A) and b SR-MDF (B)

Fiber Length [ mm]

0 0

Beating duration [min]

(a) Log R0 = 2.5

(b)

Log R0 = 2.8

important parameter for comparison of diﬀerent pulps. As expected, for all samples the beating degree increased with the beating duration. The beating degree of SR-MDF A treated at the lowest severity increased from 9 °SR without beating to 41.5 °SR after 60 min of beating, while the beating degree of the same sample treated at the highest severity increased from 17 °SR without additional beating to 71 °SR after 60 min of beating. Therefore, the beating degree resulting from the same beating duration increased with

Beating duration [min]

Log R0 = 3.1

Log R0 = 3.4

Log R0 = 3.7

Log R0 = 4.0

the severity of the steaming treatment, indicating changes in the structural behavior of the fibers following different treatment severities. This effect is less pronounced in sample SR-MDF B, in which the beating degree of all samples was measured to be around 10 °SR without additional beating, and the beating degree after 60 min of beating ranges from 59 °SR at the lowest severity to 64 °SR at the highest severity treatment. In accordance with the findings for the fiber length distribution, the treatment severity did not

Waste and Biomass Valorization

signiﬁcantly inﬂuence the beating degree resulting from the beating duration, except for the samples beaten for 20 min, in which a gap of 17 °SR between the samples treated at the highest and lowest severity was measured.

Paper Strength Properties Hand sheet testing can be used to gain information about the potential contribution of a given pulp to the strength of the final paper product. In Table 4 the paper strength properties of the measured test sheets of SR-MDF (A) and (B) are presented. In general, the paper strength properties of the steam refined waste MDF fibers were improved by intense beating and the highest strength properties could be realized at high beating degrees. However, as the beating degree is a measurement of the drainability of a fiber web, this reduction in dewatering capability leads to a reduction in paper machine speed [40]. In practice, a compromise between the drainability and the paper strength has to be found, and paper strength is usually compared at a similar beating degree.

One of the major functions of a packaging material is the protection of its content during transportation. For this, the ability to endure compressive forces is especially important, as it is a measure of its stacking strength [69]. The stacking strength of a corrugated board box is greatly influenced by the edgewise compression strength (ECT) and the flexural stiffness [70]. As there is a direct relationship between the ECT of a corrugated board and the compression strength of the individual parts [71, 72], the compression strength of the liner and flute, measured either by the Ring-CrushTest (RCT) or by the Short-Compression-Test (SCT), can be used to assess the suitability of a given paper substrate for corrugated boards. In this study the SCT was used to determine the compression strength, as the SCT is reported to show a better correlation to ECT than the RCT [73, 74]. In a field study, Adamopoulos et al. [75] have evaluated 16 different recycled liners and 7 different corrugating recycledmediums and have found an average Compression Index (CI) in machine direction of 28.8 and 30.8 N m g−1 and an average CI in cross direction of 15.3 and 17.3 N m g−1,

Table 4 Paper strength properties of SR-MDF (A) and SR-MDF (B) Treatment severity

SR-MDF (A)

SR-MDF (B)

Beating degree CompressionIndex

Tensile-Index Tear-Index Beating degree CompressionIndex

(Log R0)

(°SR)

(Nm/g)

(mN*m2/g) (°SR)

(Nm/g)

(mN*m2/g)

2.5

9.0 16.5 32.0 41.5 11.0 29.5 41.0 51.5 11.5 32.0 44.5 54.5 14.5 33.5 62.5 66.5 16.0 47.5 62.5 66.5 17.0 48.5 63.5 71.0

– 10.6 11.3 14.0 – 11.2 13.2 14.7 – 12.3 15.5 17.8 9.7 17.3 20.4 22.4 11.2 20.6 25.1 27.7 9.9 19.4 24.2 26.1

1.2 5.6 5.3 6.8 3.7 7.4 10.1 12.7 4.2 9.1 11.6 13.0 4.5 11.8 18.0 22.2 8.8 22.8 29.2 32.8 7.6 21.3 26.3 31.8

0.6 0.6 0.7 0.7 0.9 0.8 0.8 0.8 0.9 0.8 0.8 0.8 1.0 1.0 1.1 1.3 1.4 1.9 1.7 1.8 1.3 1.7 1.8 1.7

– – – 17.5 – – 11.8 15.6 – – 12.3 15.2 – 11.7 14.3 16.1 – 15.0 16.9 16.0 – 11.3 13.1 15.9

2.5 6.4 6.0 11.3 2.6 7.3 7.6 10.4 2.2 3.7 6.4 10.2 2.7 6.5 10.0 11.4 1.2 7.1 9.5 10.9 1.6 6.2 9.9 11.3

0.7 0.8 0.7 1.0 0.7 0.8 0.8 0.8 0.9 0.8 0.8 0.8 0.8 0.9 0.8 0.9 0.7 0.9 0.9 0.8 0.7 0.8 1.0 0.9

2.8

3.1

3.4

3.7

4.0

Values marked as “–” were too low to be measurable

11.0 25.0 46.5 59.0 10.5 24.5 50.5 63.0 10.0 35.0 48.0 59.0 9.5 36.0 50.0 60.0 9.0 39.0 51.0 62.5 9.0 42.0 56.0 64.0

Tensile-Index Tear-Index

Waste and Biomass Valorization

respectively. The CI measured from the two recycled pulps gathered from industrial manufacturers of corrugated board production for comparison presented in Table 5 is found to be similar, ranging from 12.4 to 27.4 N m g−1. The CI of the SR-MDF (A) samples measured in this study range from roughly 10 N m g−1 at low beating degrees up to 27 N m g−1 at high beating degrees in combination with a high severity treatment, showing similar compression strength to recycled pulp currently found in industrial use. At a beating degree of roughly 35 °SR for example, a CI of 17.3 N m g−1 was determined for the SR-MDF (A) sample treated with a severity of 3.4, falling between the CI of recycled pulp #1 with 12.4 N m g−1 and recycled pulp #2 with 21.2 N m g−1. The tensile and tear strength achievable with the SR-MDF samples are low in comparison to the paper strengths of the two recycled pulps. The steaming of the wood in the TMP process of the MDF production is done at temperatures ranging from 160 to 180 °C for a duration of 3 to 6 min [1]. This steaming leads to a softening of the lignin as the glass transition point is exceeded and an ensuing coating of the fiber surface with lignin, which hinders the defibrillation in the subsequent refining [55]. However, steam treatment of higher severities are reported to lead to softening of the fibers and an increased flexibility [76, 77], which can be advantageous in the subsequent refining steps. Distinct differences in the influence of the steam treatment severity on the achievable paper strengths between the two steam treated waste MDF samples were observable. For the SRMDF (A) sample, a higher treatment severity had a positive effect on the paper strength, leading to higher paper strength at the same beating degree in most cases. The SR-MDF (B) sample saw no influence of treatment severity on the resulting paper strength, reflecting the unchanged fiber morphology described in Sect. 3.1. While at a low severity of 2.5 the achievable paper strength of the two SR-MDF samples does not differ greatly, a substantial higher paper strength could be achieved using the SR-MDF (A) sample treated at high severities. As the two sample sets underwent the exact same treatment and evaluation processes, the differences in response to the steam treatment must be caused by differences in the two MDF sample sets.

Table 5 Paper strength properties of recycled pulp gathered from two diﬀerent industrial corrugated paperboard producers

Recycled pulp #1

Recycled pulp #2

The different behavior of the two samples might be explainable with a differing amount of softwood and hardwood fibers in the sample. Due to the carbohydrate compositions (Table 1), the fiber dimensions (Table 2), and the high amount of acetic acid found in the liquid phase after steaming of sample SR-MDF (A) [18], a higher content of hardwood in sample SR-MDF (A) was concluded. However, generally a high amount of softwood fibers in the pulp correlates positive with the compression and tensile strength of the produced paper due to the higher fiber length [58, 75], and thus higher paper strengths could be expected for sample SR-MDF (B). One possible explanation for the low influence of the steaming treatment on the fiber and paper properties of SR-MDF (B) could be a less intense autohydrolysis of the main components in the steam treatment due to the lower amount of acetyl groups in softwood. The reduced autohydrolysis might lead to a lower flexibility of the fibers of SR-MDF (B) in comparison to SR-MDF (A). Another difference between softwoods and hardwoods is the reaction of lignin constituents under steam treatment. Guaiacyl lignin, which makes up the majority of the lignin found in softwood, is prone to condensation reactions [78, 79], and a high degree of lignin repolymerization might decrease the flexibility of the fibers. The potential effect of lignin repolymerization, might be overcome by the addition of condensation inhibitors such as 2-naphtol, which might be advantageous. Another aspect to look into is the addition of mineral acids in the steaming of waste MDF samples with a high share of softwood to compensate for the lower amount of acetyl-groups. The effect of raw material composition and process conditions of the MDF production on the subsequent recycling deserves further attention.

Optical Properties The severity of the steaming treatment shows a direct influence on the coloration of the fibrous material and the produced test sheets as presented in Fig. 4. At higher severities, a distinctively darker shade of brown can be observed with the eye than at lower severities, while no differences between SR-MDF (A) and SR-MDF (B) were discernible.

Beating duration (min)

Beating degree (°SR)

Compression-Index (Nm/g)

Tensile-Index (Nm/g)

Tear-Index (mN*m2/g)

0 2 4 0 2 8 10

37.0 53.5 61.5 18.0 37.5 54.5 61.5

12.4 17.0 18.3 12.8 21.2 25.2 27.4

19.6 28.5 30.6 14.1 34.2 46.5 50.9

5.8 5.2 4.5 5.5 8.1 6.2 5.7

Waste and Biomass Valorization Fig. 4 Testsheets made out of SR-MDF (A) without additional beating steam treated at severities of 2.5, 2.8, 3.1, 3.4, 3.7 and 4.0 (from left to right)

SR-MDF (B). The explanation might be differences in the share of hardwood and softwood in the waste MDF samples concluded from the chemical composition. While it was possible to produce fibers with comparable compression strength to recycled pulp from the sample SR-MDF (A), the paper strengths achievable from sample SR-MDF (B) were lacking. From these findings it can be concluded that the composition of the waste MDF raw material does not only influence the chemical interactions during the steaming process [18], but also the papermaking quality of the resulting pulp. Consequentially, intimate knowledge of the waste MDF composition is needed for process optimization and will likely play a key role in successful valorization. Additionally, the surface of MDF is often laminated using thermoplastic polymers which tend to melt in high moisture and high temperature environment such as the steam treatment presented in this study. Thus, efficient sorting will be of substantial importance. Although the tensile and tear strength of the test sheets produced from the MDF (A) samples were not as high as the ones produced from the recycled pulp utilized in industry, a comparable compressive strength was determined. This is the one of the most important properties for application in corrugated board packaging. Using the information provided in this study as a basis, optimization of the processes might further improve the attainable paper strengths. Besides the attainable paper strengths, the final price of the steam treated

Besides the shade of brown, the severity of the steam treatment also influenced the brightness of the test sheets, with higher severity treatments leading to a lower brightness value, as presented in Fig. 5. A slight increase in measured brightness following more intense beating can be observed for both MDF samples, irrespective of treatment severity. The brightness values for SR-MDF (B) and for SR-MDF (A) do not differ considerable, ranging from around 10% for high severity treatments up to around 27% for low severity treatments. The darkening and the loss of brightness of steam treated fibers has been reported before [76, 77] and can be attributed to the creation of chromophoric groups in the lignin following condensation and oxidation reactions [80]. However, the low brightness and dark brown hue of the waste MDF fibers should not be detrimental to the application in packaging material if used in the central layers of linerboard or in the flute, as their optical properties play a subordinated role.

Conclusion

25 Brightness [%]

Fig. 5 Inﬂuence of treatment severity and beating duration on the brightness of test sheets made from SR-MDF (A) (a) and SR-MDF (B) (b)

Brightness [%]

Distinct differences in response to the refining treatment between the two steam treated waste MDF samples were found. An increase in treatment severity had a positive effect on the paper making quality of the SR-MDF (A) fibers, while no such influence could be found for the fibers of

5 0

Beating degree [°SR]

Log R0 = 2.8

Beating degree [°SR]

(a) Log R0 = 2.5

(b) Log R0 = 3.1

Log R0 = 3.4

Log R0 = 3.7

Log R0 = 4.0

Waste and Biomass Valorization

waste MDF fibers in comparison to recycling pulp will be of great importance for a potential utilization, as the fiber material used for the flute of paperboard packaging is a bulk product and often considered filler material. Given favorable environmental policy and legislative changes, steam treated waste MDF fibers might find application in corrugating medium or the test liner middle ply as outlined in this study, enabling an extension of the waste material cascade. Acknowledgements A special thank you goes to Mark Irle from Ècole supérieure du bois (Nantes, France) for supplying the MDF material. Author Contributions All authors have read and agree to the published version of the manuscript. Conceptualization, SH and BS; methodology, SH; formal analysis, SH and JJ; experimental investigation, SH and JJ; writing—original draft preparation, SH; writing—review and editing, SH, JJ, GC and BS; visualization, SH; supervision, BS; project administration and funding acquisition, BS. Funding Open Access funding enabled and organized by Projekt DEAL. This research was performed in the project “FLEXIBI” funded in the program FACCE SURPLUS 2 by the PTJ, BMBF based on a decision of the German Parliament, grant number 031B0610. Data Availability Experimental material is not available from the authors.

Compliance with Ethical Standards Conflict of interest The authors declare no conﬂict of interest. Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article’s Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article’s Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/.

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Authors and Affiliations Sebastian Hagel1 · Jesan Joy2 · Gianluca Cicala2 · Bodo Saake1 1

Institute of Wood Science, Chemical Wood Technology, Universität Hamburg, Haidkrugsweg 1, 22885 Barsbüttel, Germany

Department of Civil Engineering and Architecture, Università Degli Studi Ci Catania, Viale Andrea Doria 6, 95125 Catania, Italy

PAPERmaking! FROM THE PUBLISHERS OF PAPER TECHNOLOGY TE INTERNATIONAL

Volume 7, Number 1, 2021

Benchmarking of scaling and fouling of reverse osmosis membranes in a power generation plant of paper and board mill: an industrial case of a paper and board mill study S. Z. J. Zaidi1,2 · A. Shafeeq1 · M. Sajjad1,3 · S. Hassan4 · M. S. Aslam5 · T. Saeed6 · F. C. Walsh2 The present study reports the characterization of reverse osmosis (RO) technology at water treatment plant Cogen-2 in paper and Board mills, Pakistan. RO is a commonly used process to obtain de-mineralized water for high-pressure boiler operation in thermal power plants. Scaling and fouling in three-stage RO plants is a major challenge in chemical industry due to the use of raw brackish water in the power plant of paper and board mills. In our study, the feed water quality of RO was changed from soft water to raw water to make it economical. The cleaning frequency was increased three times than normal, which was unsafe for operation and it was required to control scaling and fouling to achieve the desired result. Differential pressures behavior of all stages for 2-month data was observed without acid treatment, and the results of Langelier Saturation Index (LSI) control parameters (temperature, pH, total dissolved solids, calcium hardness, and alkalinity) clearly showed the abnormality. To optimize scaling and fouling of RO, the LSI factor was controlled in total reject water for the next 2 months by acid treatment in feed water. Duration of chemical cleaning and membranes’ life has been extended by fouling and scaling control. Understanding the effect of operational parameters in RO membranes is essential in water process engineering due to its broad applications in drinking water, sanitation, seawater, desalination process, wastewater treatment, and boiler feed water operation. The product flow increased from 18.3 to 19.9 m3/h, and this was due to a decrease in the rejection flow from 8.2 to 6.7 m3/h. The total reject stream pressure also increased from 8.1 to 9 bar. A lower value of LSI of 1.6 is obtained in the reject water stream after the acid treatment. Contact information: 1 Institute of Chemical Engineering and Technology, University of the Punjab, Lahore, Pakistan 2 Electrochemical Engineering Laboratory, Energy Technology Research Group, Faculty of Engineering and Environment, Engineering Sciences, University of Southampton, Highfield, Southampton SO17 1BJ, UK 3 Paper & Board Mills Ltd, Multan Road, Kasur, Pakistan 4 Mechanical Engineering, Faculty of Engineering and Environment, Engineering Sciences, University of Southampton, Highfield, Southampton SO17 1BJ, UK 5 Institute of Biochemistry and Biotechnology, University of the Punjab, Lahore, Pakistan 6 Department of Chemistry, Government Jinnah Degree College for Women, Lahore, Pakistan International Journal of Environmental Science and Technology https://doi.org/10.1007/s13762-020-03015-1 Creative Commons Attribution 4.0 International License

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Article 5 – RO Membrane Fouling

International Journal of Environmental Science and Technology https://doi.org/10.1007/s13762-020-03015-1

ORIGINAL PAPER

Abstract The present study reports the characterization of reverse osmosis (RO) technology at water treatment plant Cogen-2 in paper and Board mills, Pakistan. RO is a commonly used process to obtain de-mineralized water for high-pressure boiler operation in thermal power plants. Scaling and fouling in three-stage RO plants is a major challenge in chemical industry due to the use of raw brackish water in the power plant of paper and board mills. In our study, the feed water quality of RO was changed from soft water to raw water to make it economical. The cleaning frequency was increased three times than normal, which was unsafe for operation and it was required to control scaling and fouling to achieve the desired result. Differential pressures behavior of all stages for 2-month data was observed without acid treatment, and the results of Langelier Saturation Index (LSI) control parameters (temperature, pH, total dissolved solids, calcium hardness, and alkalinity) clearly showed the abnormality. To optimize scaling and fouling of RO, the LSI factor was controlled in total reject water for the next 2 months by acid treatment in feed water. Duration of chemical cleaning and membranes’ life has been extended by fouling and scaling control. Understanding the effect of operational parameters in RO membranes is essential in water process engineering due to its broad applications in drinking water, sanitation, seawater, desalination process, wastewater treatment, and boiler feed water operation. The product flow increased from 18.3 to 19.9 m3/h, and this was due to a decrease in the rejection flow from 8.2 to 6.7 m3/h. The total reject stream pressure also increased from 8.1 to 9 bar. A lower value of LSI of 1.6 is obtained in the reject water stream after the acid treatment. Keywords Acid treatment · LSI · Membrane · Reverse osmosis · Fouling

Editorial responsibility: Samareh Mirkia. * S. Z. J. Zaidi zohaib.icet@pu.edu.pk 1

Institute of Chemical Engineering and Technology, University of the Punjab, Lahore, Pakistan

Electrochemical Engineering Laboratory, Energy Technology Research Group, Faculty of Engineering and Environment, Engineering Sciences, University of Southampton, Highﬁeld, Southampton SO17 1BJ, UK

Paper & Board Mills Ltd, Multan Road, Kasur, Pakistan

Mechanical Engineering, Faculty of Engineering and Environment, Engineering Sciences, University of Southampton, Highﬁeld, Southampton SO17 1BJ, UK

Institute of Biochemistry and Biotechnology, University of the Punjab, Lahore, Pakistan

Department of Chemistry, Government Jinnah Degree College for Women, Lahore, Pakistan

Introduction Raw water cannot be used directly in high-pressure boilers in steam turbine operation due to the total hardness and presence of higher concentrations of total dissolved solids and other salts and chlorides. These solids and salts can strongly corrode and scale in boiler tubes and must be removed prior to feed in the boilers (Ansari and Pandit 2020). In addition, scaling creates a barrier to heat transfer which results in higher fuel consumption and maintenance cost which are required to overcome all these issues (Das et al. 2018). To overcome these issues permanently, the feed water quality must be improved. There are a lot of methods for the treatment of raw water in order to maintain water quality and to obtain the desired results of diﬀerent parameters (pH, total dissolved solids (TDS), hardness, alkalinity, chlorides, silica, and iron) of boiler feed water. For example, there are electrochemical approaches (Zaidi et al. 2018, 2019),

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International Journal of Environmental Science and Technology

forward osmosis (Al Hawli et al. 2019), photocatalysis (Tran et al. 2020), nanofiltration (Shahriari and Hosseini 2020), capacitive deionization (Qin et al. 2019), and reverse osmosis. In reverse osmosis (RO) plant, water passes through a semi-permeable membrane from a higher concentration of salts to lower the concentration by applying force through the use of a high-pressure pump (Qasim et al. 2019). Product water is collected in the middle stream, and rejected water which has high salt concentration is collected in another stream. RO consumes relatively low energy as compared to other approaches (Park et al. 2020). Scaling and fouling in RO depend on the feed quality of water (Čuda et al. 2006). Collection of deposition of particles on the surface of membranes is called membrane fouling. Fouling causes a decline in flux flow of RO and results in membrane damage requiring replacement due to permanent adsorption over the membrane surface. Significant types of fouling are organic, inorganic, and biological. There are different techniques which are used to control fouling on the membrane surface, including pretreatment, water softening, coagulation, and flushing. Usage of soft water for the RO plant enhances plant recovery and resolves the problem of scaling and fouling. To control fouling, residual chlorine removal and disinfection are frequently used. Oxygen removal from feed water can also reduce fouling in RO. The proper dosage rate of antiscalant and biocides help to control fouling and scaling. Till now, the mechanism of scaling and fouling has not been correlated with operating conditions like temperature, flow velocity, pH, and total dissolved solids (TDS) (Al-Ahmad and Aleem 1993). Precipitation of hard minerals such as deposition of CaSO4, CaCO3, and silica on the surface of membranes is known as scale formation. Several types of membranes have been developed to slow down the scaling such as spiral wound membranes offer slower scale formation than cross flow membranes (Lee and Lee 2005). In another development, Pramanik et al. (Pramanik et al. 2017) used polyaspartic acid and its derivative as an anti-scaling agent in lab-scale RO followed by examination of the used membrane using a scanning electron microscope (SEM) and x-ray diffraction XRD for determining the type of fouling. Tong et al. (2020) studied the characteristic of fouling (e.g., biofouling, inorganic, organic) in a two-stage industrial RO system for reclamation of wastewater. Yin et al. (2019) focused on the silica scaling and studied its relationship with membrane surface chemistry to enhance surface flux in a RO plant. In this paper, the membrane distillation process was examined, and fouling techniques were used for the distillation process in a real industrial setting. Fouling mechanism was discussed by the usage of brackish water. Moreover, a three-stage filtration RO plant was used in which the trend of fouling and scaling was different from two-stage or singlestage RO plants operated at the same feed water quality.

Recovery and water quality of plants were changed in correlation with stages and as well scale formation tendency (Bonné et al. 2000; Hoek et al. 2000). The eﬀectivity of acid treatment in this work was benchmarked using Langelier Saturation Index (LSI) value which is widely used in an industrial setting for examining scale formation mostly calcium carbonate.

Material and methods Experiments were carried out on a three-stage RO plant (Fig. 1) installed at water treatment plant Cogen-2 in paper and Board mills (PBM) Limited, Pakistan. Water testing was performed in a PBM water lab, Pakistan. The RO plant which was chosen for experimentation has a capacity of 20 tonnes/h product flow and 6.6 tonnes/h flow discharge in the reject water stream. This RO plant has raw water, high-pressure pump, and pre-filtration including multimedia filter and cartridge filter of 5 and 1 microns, respectively. Feed, product, and reject flow meter was installed to measure the flow rate. Scaling and fouling have been controlled by reducing feed velocity. Another treatment suggested was the usage of caustic regime instead of lime for brackish water. The concentration of feed water was changed by changing the softening process. In this way, permeate flow remained constant over a long period (Amiri and Samiei 2007). Sulfuric acid (98%) and antiscalants were added at 0.28 and 3 ppm, respectively, to the RO feed to moderate the Langelier Saturation Index (LSI) value in the concentrate stream to < 2, and the plant was safely operated up to recovery of 85% without any BaSO4 scale formation. Daily consumption of sulfuric acid and antiscalant was 10 and 2 kg per day. Sulfuric acid is preferred over HCl due to environmental impact and less cost consumption. An organophosphate biopolymer antiscalant, HDC-ASI-ECO1, which is a biodegradable antiscalant, was provided by Hatenboer-water Rotterdam, Netherlands. Pressure gauges were installed on all stages, as shown in Fig. 1. LSI factor was used to calculate the tendency of scaling. This equilibrium model is derived from the theoretical concept of saturation, and it provides an indicator of the degree of saturation of water in CaCO3. The LSI was calculated using the equation provided by Antony et al. (2011). The product was collected in the middle stream and stored in a 400-tonnes capacity RO tank, while reject water was collected in the concentrated stream. Membranes were installed in the RO plant with the specifications provided in Table 1. Each stage had an individual sample point, as shown in Fig. 1. Water samples were collected from the feed of first, second, third stage, and total reject of RO. The temperature was calculated with a simple thermometer while for pH and TDS testing,

International Journal of Environmental Science and Technology Fig. 1 Experimental setup of three-stage RO Plant. The raw water is pumped through ﬁlters and doses of biocide, antiscalant, and sulfuric acid are added before it is introduced in the RO tank

Table 1 Speciﬁcation and characterization of RO plant

Results and discussion

Product

BW30–400

Benchmarking of RO plant without acid treatment

Part number Active area ft2 (m2) Feed spacer thickness (mil) Permeate ﬂow rate gpd (m3/d) Stabilized salt rejection (%) Minimum salt rejection (%) Membrane type

98,650 400 (37) 28 10,500 (40) 99.50% 99% Polyamide thinﬁlm composite 113 F( 45 C) 600 psig ( 41 bar) 15 psig (1 bar) 2–11 1–13 19 m3/hr 5 < 0.1 ppm

Max operating temperature Max operating pressure Max pressure drop pH range, continuous operation pH range, short-term cleaning Max feed ﬂow Max feed silt density index Free chlorine tolerance

the meter of HANNA (model # HI 83,141, HI 8734) was used. LSI factors (calcium hardness and alkalinity) were calculated by the titration method in the lab.

Effect of pressure of RO plant at different stages with time Figure 2 shows an increase of pressures at all the stages of RO plant rapidly with the passage of time as compared to expected pressures. The RO plant was operated at 75% recovery, and the trend of increase in pressures was found to be very rapid, which was caused by fouling and scaling of membrane abruptly. This, in turn, resulted in an increase in cleaning frequency. Repeated cleaning of RO membranes increased to TDS which caused a decline in salt rejection. The first-stage pressure of RO increased from 8.8 to 10.6 bar having a pressure drop of 1.8 bar and increased linearly. Similarly, the second- and third-stage pressures were also increased. Figure 2 describes the increase of pressure due to cake formation on the membrane surface and in the first stage almost 20% increase in pressure was observed while in second, third stage, and total reject increase of pressures was found to be 23%, 30%, and 44% of initial values, respectively, over 2 months. In the second and third stages, the increase in pressures was relatively higher as compared to the first stage. Feed water had a high concentration of salts

International Journal of Environmental Science and Technology

in the second and third stages. Fouling and scaling phenomenon occurred more rapidly in these stages. Effect of LSI factor against time Figure 3 shows clearly LSI values of all stages of RO without acid plotting against time. In normal operation, when LSI factor was calculated, it resulted in high LSI values of all stages, particularly total reject where its LSI Value went up to 2.5. Due to the high LSI factor, RO membranes caused scaling and fouling rapidly and resulted in a rapid increase of RO pressures. Rapidly increased pressures and product ﬂow drop needed chemical cleaning of RO membranes. Thus, RO membranes were cleaned repeatedly in order to normalize the pressure and product ﬂow (Hoek et al. 2000).

Fig. 2 Eﬀect of pressure curve of all stages against time for RO plant. The pressure increase is signiﬁcant at each pressure stage. The salt concentration is higher at high pressure stage

Benchmarking of RO plant after acid treatment Sulfuric acid started to dose in the feed line of RO. Table 2 clearly shows that after acid treatment product flow started to recover instead of dropped while pressures increment was normal during 2 months in Table 3. Therefore, scaling and fouling have been optimized as per regular operation. From Table 2, we can see that due to the acid treatment that has been applied to the raw water; the reject flow is constantly being reduced from 8.2 to 6.7 m3/h, while the product flow is increased from 18.4 to 19.9 m3/h. The pressure at each stage is also increased, as we can see from Table 3. The increase in pressure is due to the flow increase in the product flow. Tables 2 and 3 show that the acid treatment has improved the efficiency of the whole operation. Effect of pressure of RO plant with time Pressures of all stages with the passage of time did not increase abruptly as increased without acid addition, as shown in Fig. 4. Acid treatment is effective in such a way that pressure increment of first stage was 7.5% which was

Fig. 3 LSI factor on RO membrane with time before acid treatment. High LSI values are observed for every stage, including the total reject. LSI factor on RO membrane with time

Table 2 Eﬀect of ﬂow rates during 2 months with acid treatment

Date

1-Nov-19 10-Nov-19 20-Nov-19 30-Nov-19 9-Dec-19 19-Dec-19 29-Dec-19

26.6 Feed ﬂow (m3/h) 18.4 Product (m3/h) Reject ﬂow (m3/h) 8.2

26.6 18.6 8

26.6 18.9 7.7

26.6 19.2 7.4

26.6 19.5 7.1

26.6 19.7 6.9

26.6 19.9 6.7

Table 3 Eﬀect of pressures of all stages during 2 months with acid treatment Date First-stage pressure Second-stage pressure Third-stage pressure Total reject pressure

Bar Bar Bar Bar

1-Nov-19

10-Nov-19

20-Nov-19

30-Nov-19

9-Dec-19

19-Dec-19

29-Dec-19

10.6 9.6 9.1 8.1

10.7 9.7 9.2 8.2

10.9 9.9 9.4 8.4

11 10 9.5 8.5

11.1 10.1 9.6 8.6

11.3 10.3 9.9 8.9

11.4 10.4 10 9

International Journal of Environmental Science and Technology

scaling and fouling in RO membranes. Hence, pressures of all stages did not increase rapidly (ASTM D3739-19 2019). Free mineral acidity and pH at cation exchanger

Fig. 4 Eﬀect of optimized pressure curve of all stages against time for RO plant after acid treatment. The pressure increases at each stage, but it is not a huge change from the pressure which is observed without the acid treatment

reduced three times. Pressure increment in the second stage, third stage, and total reject was 8.3%, 9.8% and 11.1% respectively. Cleaning frequency and operational cost were reduced while maintaining the quality of permeate (Redondo and Lomax 2001).

Effect on LSI factor after acid treatment Figure 5 shows the controlled LSI value by H2SO4 addition in the feed line to reduce pH from 7.6 to 7.2. Lowering the pH resulted in a lower value of LSI (1.6) in total reject. This controlled LSI factor resulted in minimizing the formation of

Fig. 5 LSI factor at RO membrane after acid addition with time. The scaling and fouling in RO membrane is reduced due to the acid treatment

Free mineral acidity (FMA) can be measured by the anions of strong acids, namely sulfuric, nitric, and hydrochloric acid, which is free to react at the outlet of the cation exchanger (Ramzan et al. 2012). In Fig. 6, a stable FMA value around 52 was observed due to the injection of sulfuric acid during acid treatment in the feed line. All the anions of strong acid were filtered at the primary anion exchanger, which was shown the value of FMA reduced to 0 at the primary anion exchanger outlet. This shows that the ion exchangers are relatively stable over time and there was no leakage at the primary anion exchanger. The pH at the cation exchanger was significantly decreased from about 7.7 to 2.9 due to acid injection, which is shown in Fig. 7. These pH values are still within the operational range of the RO plant, which is 2–11 for continuous operation, as given in Table 1. Effect of permeate water flow rate with time Figure 8 shows clearly that product flow decreased with the passage of time due to fouling and scaling on RO membranes and resulted in a decrease of permeate flux as well as recovery rate. It clearly indicates that flux declined on the surface of the RO membrane was due to crystal formation and these crystals caused fouling and scaling by which hindrance to feed water, and it caused decease in permeate water. Flux decline mechanism involved in the crystalline layer formation on the porous surface of membranes (Brusilovsky et al. 1992).

Fig. 6 Free mineral acidity (FMA) versus time. Both cation exchanger outlet and primary anion exchanger outlet values remain extremely stable over a long period of time

International Journal of Environmental Science and Technology

Effect of feed TDS with permeate TDS against time Feed water quality directly aﬀected the product. Higher TDS in feed resulted in higher TDS in the product, as shown in Fig. 9. For this reason, a high concentration of salts in feed was rejected by membranes and collected in the concentrate stream. These salts increased load on the membrane surface, and hence membrane permeates water quality automatically increased correspondingly (Sridhar 2002). The normalized concentration of salt in reject water against time

Fig. 7 The graph of pH at the cation exchanger versus time. The pH outlet is extremely stable, while the inlet pH shows a slight increase over a long period of time

The concentration of sodium, potassium, chloride, and sulfate ions was measured at the reject water tank, as shown in Fig. 10. It was found that breakthrough of several ions such as sodium, potassium, and sulfate can be observed, and the normalized concentrations were increased by 6.12%, 6.06%, and 2.52% from 900 to 2400 h for sulfate, potassium, and sodium ions, respectively. On the other hand, no chloride ion leakage was found. The salt leakage may lead to calcium carbonate scaling formation due to the following reactions.

CaCl2 (aq) + Na2 CO3 (aq) → Ca2 CO3 (s) + NaCl(aq)

(1)

CaCl2 (aq) + K2 CO3 (aq) → Ca2 CO3 (s) + KCl(aq)

(2)

CaCl2, Na2CO3, and K2CO3 are soluble in water while Ca2CO3 is not soluble, creating precipitate or scaling (Jimoh et al. 2018). Due to no leakage in chloride ion, those breakthrough values still met the operational condition in which the recommended LSI is below 1.8 by the industrial standard

Fig. 8 Effect of flow rate at the inlet and outlet of the RO membrane with time. The outlet flow decrease over time is significant. The outlet flow increase causes an increase in reject flow in RO membrane

Effect of reject water flow rate with time It is obvious from Fig. 8 that with the passage of time, highly concentrated water was not allowed to pass through the membrane pores, and it was directed into the reject stream. Therefore, fouling and scaling occurred and ultimately reject flow increased (Radu et al. 2012). The RO membrane was unable to handle the increased flow of highly concentrated water, this resulted in the increase of the Rejected water, which also caused more scaling. This resulted in a vicious circle, which is due to constant increasing scaling, the RO membrane becomes less and less effective, which causes more scaling and so on.

Fig. 9 Eﬀect of TDS at the inlet and outlet of the RO membrane with time. The product and Feed TDS are almost the same. This is due to the feed TDS having an impact on the product TDS

International Journal of Environmental Science and Technology

Fig. 10 Normalized concentration of salt in reject water versus time. The concentration of only Chloride remains the same and the concentration of every chemical increases over time in the rejected water

(Kucera 2015). The LSI value was found to be below 1.5 at the third stage in Fig. 3, meaning some scale formation occurred but still was at acceptable levels. Washing of membrane was minimized; hence, the quality of membrane for salt rejection can be preserved. This study was focused on RO plant utilization, and different parameters related to the efficiency and operational analysis of parameters inlet and outlet of total dissolved solids, flow rates, LSI factor and thus the same meaningful results were concluded. As shown in results that designed RO three-stage plant in which first stage feed was rejected as a feed to second stage, and second stage was rejected to the feed of third stage. It was concluded that feed of the third stage of RO contained higher TDS, hardness in terms of CaCO3, and total alkalinity. In the third stage, membrane load seemed to be higher than the other two stages. Due to the presence of higher salt concentration, the membrane fouling and scaling were seen. It was concluded that the rapid increase in pressure of all stages is due to membrane fouling and scaling in the RO plant. Hence, the LSI value depends on various factors (temperature, pH, TDS, calcium hardness, and total alkalinity) which can be controlled by changing these parameters. In this research, pH value was adjusted by the addition of H2SO4 to control LSI and to avoid rapid fouling and scaling on the surface of membranes. It was obvious that under acidic condition, CaCO3 was dissolved and reduction in alkalinity minimized the effect of pressure; fouling and scaling were controlled, which resulted in normalization of cleaning frequency. Keeping in view the results; pressures, flow rate, and LSI value changed after acid treatment in all stages of the RO plant. Three-stage RO unit with high LSI

value in total reject water stream more than 2.5, resulted in fouling and scaling in membrane and pressures of all stages got higher subsequently. In order to control the LSI value, sulfuric acid had been dosed in the feed line and maintained pH up to 7.2 or 7.3. Ultimately, the LSI value was obtained < 1.5. Hence, by controlling of LSI value, fouling and scaling of RO-Membranes were optimized. Therefore, instead of a change of pH of feed water, alternate options are available that we can change temperature, calcium hardness, and total dissolved solids of feed water in order to reduce fouling and scaling in the RO membrane. Water consumption is increasing day by day as the availability of clean water is shortened. The RO is the heart of the desalination process. Therefore, it is necessary to enhance the life of RO plants. Further research is required in this ﬁeld due to its severity. In two-stage RO, fouling and scaling trends are to a smaller extent as compared to three-stage plant due to less concentrations of salts in the reject stream. Thus, the LSI value will be < 1.5 in the total reject of twostage RO and ultimately fouling and scaling will be controlled. Hence, it is an alternate solution of optimization of fouling and scaling on RO membranes to change its design.

Conclusion In the current paper, the reverse osmosis (RO) technology is used to improve the water treatment processing of a paper manufacturing plant. The same process can be applied to improve water processing in every industry where water is used. To study the improvements in the treatment of raw water, a before and after method was used to see how the RO and the chemical used have improved the processing of the raw water. There is a significant improvement in both the processing and efficiency of the raw water. The process increased the amount of the treated water which is obtained at the output and decreased the rejected outflow which is waste. The improved water flow caused increase in scaling at the RO membrane which decreased the overall efficiency of the process. The addition of acid improves the efficiency of the water treatment process while also maintaining the quality of the water obtained in the product flow. Acknowledgments The authors wish to thank all who assisted in conducting this work.

Compliance with ethical standards Conflict of interest The authors declare no conﬂict of interest. Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source,

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Volume 7, Number 1, 2021

Application of (super)cavitation for the recycling of process waters in paper producing industry Janez Kosel (a), Matej Šuštaršič (b), Martin Petkovšek (c), Mojca Zupanc (c), Mija Sežun (b), Matevž Dular (c)

In paper production industry, microbial contaminations of process waters are common and can cause damage to paper products and equipment as well as the occurrence of pathogens in the end products. Chlorine omission has led to the usage of costly reagents and products of lower mechanical quality. In this study, we have tested a rotation generator equipped with two sets of rotor and stator assemblies to generate developed cavitation (unsteady cloud shedding with pressure pulsations) or supercavitation (a steady cavity in chocked cavitation conditions) for the destruction of a persistent bacteria Bacillus subtilis. Our results showed that only supercavitation was effective and was further employed for the treatment of waters isolated from an enclosed water recycle system in a paper producing plant. The water quality was monitored and assessed according to the chemical (COD, redox potential and dissolved oxygen), physical (settleable solids, insolubles and colour intensity) and biological methods (yeasts, aerobic and anaerobic bacteria, bacterial spores and moulds). After one hour of treatment, a strong 4 logs reduction was achieved for the anaerobic sulphate reducing bacteria and for the yeasts; a 3 logs reduction for the aerobic bacteria; and a 1.3 logs reduction for the heat resistant bacterial spores. A 22% reduction in COD and an increase in the redox potential (37%) were observed. Sediments were reduced by 50% and the insoluble particles by 67%. For bacterial destruction in real industrial process waters, the rotation generator of supercavitation spent 4 times less electrical energy in comparison to the previously published cavitation treatments inside the Venturi constriction design. Contact information: a Institute for the Protection of Cultural Heritage of Slovenia, Slovenia b Pulp and Paper Institute of Ljubljana, Slovenia c Faculty of Mechanical Engineering, University of Ljubljana, Slovenia Ultrasonics - Sonochemistry 64 (2020) 105002 https://doi.org/10.1016/j.ultsonch.2020.105002 Creative Commons Attribution 4.0 International License

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Article 6 – Ultrasonication of Process Waters

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Ultrasonics - Sonochemistry journal homepage: www.elsevier.com/locate/ultson

Application of (super)cavitation for the recycling of process waters in paper producing industry ⁎

Janez Kosela, , Matej Šuštaršičb, Martin Petkovšekc, Mojca Zupancc, Mija Sežunb, Matevž Dularc a

Institute for the Protection of Cultural Heritage of Slovenia, Slovenia Pulp and Paper Institute of Ljubljana, Slovenia c Faculty of Mechanical Engineering, University of Ljubljana, Slovenia b

A R T I C L E I N FO

A B S T R A C T

Keywords: Rotational cavitation generator Hydrodynamic cavitation Paper mill industry Bacillus subtilis Anaerobic sulphate reducing bacteria COD Redox potential

In paper production industry, microbial contaminations of process waters are common and can cause damage to paper products and equipment as well as the occurrence of pathogens in the end products. Chlorine omission has led to the usage of costly reagents and products of lower mechanical quality. In this study, we have tested a rotation generator equipped with two sets of rotor and stator assemblies to generate developed cavitation (unsteady cloud shedding with pressure pulsations) or supercavitation (a steady cavity in chocked cavitation conditions) for the destruction of a persistent bacteria Bacillus subtilis. Our results showed that only supercavitation was eﬀective and was further employed for the treatment of waters isolated from an enclosed water recycle system in a paper producing plant. The water quality was monitored and assessed according to the chemical (COD, redox potential and dissolved oxygen), physical (settleable solids, insolubles and colour intensity) and biological methods (yeasts, aerobic and anaerobic bacteria, bacterial spores and moulds). After one hour of treatment, a strong 4 logs reduction was achieved for the anaerobic sulphate reducing bacteria and for the yeasts; a 3 logs reduction for the aerobic bacteria; and a 1.3 logs reduction for the heat resistant bacterial spores. A 22% reduction in COD and an increase in the redox potential (37%) were observed. Sediments were reduced by 50% and the insoluble particles by 67%. For bacterial destruction in real industrial process waters, the rotation generator of supercavitation spent 4 times less electrical energy in comparison to the previously published cavitation treatments inside the Venturi constriction design.

1. Introduction Water is essential for the paper producing process, because it permits the ﬁbres to be transported from the apparatus which de-ﬁbres the wood-pulp down to the manufacturing wire of the sheet of paper [1]. However, the continuously recycled process water (white water) contains organic substrates (starch), has favourable temperatures and a neutral pH, which is all in all an optimal environment for microbial growth [2]. Additionally, the development of bacteria gives rise to the accumulation of slime, which causes holes and spots or even breakage of the continuous paper sheet leading to expensive delays [3]. For disinfection purposes, chlorine is most commonly applied, however chlorination has several shortcomings among them the formation of carcinogenic organochlorines and the need for careful control of chlorine dosing [4,5]. Consequently, the Directorate-General for the Environment [6] issued guidelines for the elimination of all chemical molecules containing chlorine atoms in any form to produce cellulose

⁎

bleached without chlorine- and chlorine derivatives (TCF or Totally Chlorine Free) and to label these products as ecologically friendly (Ecolabel flower; www.ecolabel.eu). However, the pulp that fulfils these standards has lower mechanical properties, requires larger quantities of wood and uses costly reagents, such as ozone. Therefore, alternative methods are being developed that are safe, easy to perform, inexpensive, less labour intensive but effective, and hydrodynamic cavitation is one of such options [7]. Cavitation is a physical phenomenon caused by the formation of vapour bubbles in an initially homogeneous liquid due to the decrease of local pressure at an approximately constant temperature [8]. It is composed of various physical (pressure pulses, shear forces, high local temperatures) and chemical side effects (decomposition of H2O mainly to %OH and other radicals). Ultrasonic cavitation has been proven to be efficient for the intensification of oxidation reactions (H2O2 and %OH) [9,10] and for the destruction of bacteria [11–13]. It provides significantly higher rates for the Weissler reaction (oxidation of iodide to

Corresponding author at: Poljanska 40, SI-1000 Ljubljana, Slovenia. E-mail address: janez.kosel@zvkds.si (J. Kosel).

https://doi.org/10.1016/j.ultsonch.2020.105002 Received 26 August 2019; Received in revised form 3 February 2020; Accepted 3 February 2020 $YDLODEOH RQOLQH )HEUXDU\ (OVHYLHU % 9 $OO ULJKWV UHVHUYHG

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iodine by the cavitation produced H2O2) in comparison to the hydrodynamic cavitation [14]. In specific energy terms, hydrodynamic cavitation has a maximum efficiency of about 5 × 10−11 mol of tri-iodide/ joule of energy compared with the maximum of almost 8 × 10−11 mol of tri-iodide/joule for ultrasonic cavitation [15]. Consequently, ultrasonic cavitation has been successfully applied in various industrial applications [16-19]. These include the synthesis of nanomaterials [16], the generation of highly viscoelastic micelles [20] and the disinfection of wastewater [17]. However, hydrodynamic cavitation can treat larger volumes for a similar energy input and can be easily adopted for large scale continuous flow-through industrial applications with significantly lower equipment costs [21]. Therefore, even though hydrodynamic cavitation produces a lesser amount of reactive oxygen species it is still more efficient considering the relative energy input and the scale of operation [22]. Hydrodynamic cavitation forms due to relative velocity increase between the liquid and the submerged body. Cavitation bubbles form, when the local velocity increases and causes static pressure to drop below the critical vaporization pressure. Most common hydrodynamic cavitation can be seen on hydraulic turbine machinery on rotor’s blades passing through the liquid [23,24] or behind the constrictions, where liquid is forced to pass through [25]. Several types of hydrodynamic cavitation can form; specifically, for the present setup, we could observe developed unsteady cavitation and supercavitation. Developed unsteady cavitation is formed when cavitation clouds start to shed thus creating pressure pulsations, vibration, erosion, high local temperatures and noise, and can be used for the destruction of bacteria [26,27]. When system pressure is decreased or when flow velocity is increased a small cavity will grow and a large single steady vapour filled supercavity will develop [8], for which larger disturbances in pressure and temperature are uncommon (noise, vibration and erosion are absent). Therefore, it can be expected that supercavitation does not cause any significant physical damage to microbial cells. Nonetheless, Šarc et al. [28] observed that supercavitation generated inside the Venturi constriction was effective for the disinfection of the pathogenic bacteria Legionella pneumophila in tap water, while developed unsteady cavitation removed only 28% of the viable count. They proposed that the disinfection mechanism could be attributed to the rapid pressure change between the entrance and exit of the supercavitation cavity. Similarly, Gottlieb et al [29] proposed that a mixture of effects such as instant pressure decrease –pressure shock at the entrance point of the supercavity (transition from the liquid/vapour phase) and instant pressure increase (at the closure of supercavity) play a role in the rupture of bacterial wall. Our aim was to assess the applicability of the rotation generator of hydrodynamic cavitation (RGHC) [30] for the treatment of process waters from a paper producing plant. For this purpose, the starting cavitation experiments were performed on tap water spiked with a Gram-positive bacteria Bacillus subtilis. This sporogenic, biofilm forming bacteria was selected because it has a thicker peptidoglycan cell wall (in comparison to Gram-negative bacteria which have a much thinner peptidoglycan layer) and is thus more resistant to mechanical stresses [31], is persistent in paper industry as it can hydrolyse fibre-bound galactoglucomannans from soft-wood pulp to produce simple sugars [32], can spoil surface sizing materials of paper making [33], and can survive high temperature treatments in paper mills [34]. To examine the effect of both developed unsteady cavitation and supercavitation, two sets of specifically designed rotors and stators were produced for the RGHC machine and were tested on spiked tap water preparations. Finally, to verify our RGHC device, we sampled real process waters from an enclosed recycling system of a paper producing plant and after cavitation treatments the survivability of the major classes of microorganisms and the chemical and physical changes of samples were assessed.

Fig. 1. Rotor-stator design for developed cavitation (left) and supercavitation (right).

2. Methods 2.1. Hydrodynamic cavitation set-up In this study, the effects of cavitation on different microorganisms problematic for paper mill industry were investigated using a rotational generator of hydrodynamic cavitation (RGHC) which was first described by Petkovšek et al. [30]. The RGHC is based on the centrifugal pump design which has a modified rotor and a stator added in its housing (Fig. 1). The RGHC is powered by an electric motor of 500 W that propels the modified rotor. Maximum rotational frequency of the electric motor is 10,000 revolutions per minute (rpm). The stator’s position is opposite to the rotor (both 50 mm in diameter; r = 25 mm) and the housed unit of rotor and stator forms the so-called cavitation treatment chamber. The RGHC preserves its flow-through pumping function, which makes its installation into the water pipe system simple with no additional pumping required. In our experimental setup, the RGHC was placed in a closed loop experimental water system which is presented in Fig. 2. The experimental setup is made of piping which connects a 2 L reservoir, a heat exchanger, pressure and flow meters and the RGHC device. The piping and connections are made of standard household water system materials [35]. Two different rotor and stator designs were used in order to generate developed cavitation and supercavitation (Fig. 1). The rotor and stator pair used for developed cavitation have a specially designed surface geometry with 12 radial teeth, 3 mm deep and 4 mm wide. The area of each tooth of this serrated rotor disc has been designed in a way that its surface is angled at 8°, giving it a sharp leading edge. When aligned, the space between the angled surface of the individual rotor’s tooth and the completely flat surface of the individual stator’s tooth resembles the Venturi nozzle geometry (Fig. 3A). In the case of supercavitation set-up, an additional flow regulation valve was installed at the inlet of the RGHC (Fig. 2B) to manipulate the pressure inside the treatment chamber. By closing the valve, the flow rate through the RGHC gets severely reduced. The surface geometry of the rotor used for supercavitation consists of two symmetrical teeth (hence its name the two teeth rotor), which resembles the symmetrical Venturi design, first described by Zupanc et al. [36] (Fig. 3C). The divergence angle of the teeth’s cross section is 10° and the secondary divergence angle is 30° (Fig. 3B). The surface of the added stator is completely flat and has no teeth with the aim not to induce any additional pressure fluctuations (this allows for the development of a large steady supercavity behind each rotor’s tooth). When using the rotor–stator configuration for supercavitation the electric motor is able to achieve the maximum rotary frequency (10,000 rpms), while in the case of rotor–stator configuration with grooves for developed cavitation, the rotary frequency is reduced to 9000 rpms due to motor’s power limitations. For both the serrated rotor and the two teeth rotor, the gaps between the rotor and the stator were set to be 1 mm (gap length; l). When in motion, the rotor’s teeth force the liquid to move in a radial direction - causing centrifugal forces, which result in a pumping function of the RGHC. The high frequency of rotation also causes the movement of

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Fig. 2. Experimental setup scheme for the developed cavitation (A) and supercavitation (B).

Hygrosens DRTRAL-10 V-R16B pressure probe (uncertainty of ± 0.2%). The ﬂow rate was measured using the Buerkert SE32 ﬂow meter (uncertainty of ± 1%). Sample temperature was monitored by a resistance temperature sensor Pt100 (uncertainty of ± 0.2 K), installed directly into the reservoir. In the experimental setup the installed heat exchanger was cooled by an external fan with ambient air, preventing any heating of the treated sample above 30 °C. The stator was made of transparent acrylic glass due to visualization and functioned as a cover. High-speed visualization was performed using Photron SA-Z, which enables recording with 20,000 frames per seconds at full resolution (1024 × 1024 pixels) and can go up to 2.100,000 fps at reduced resolution. For the present case visualization was performed with 75,000 fps at resolution of 512 × 465 pixels. The illumination was performed with high intensity LED, focused into the observed area from the same

liquid in the tangential direction. The narrow gap between the rotor and the stator and sharp edges cause high shear stress and consequently intense pressure pulsations resulting in cavitation formation (Fig. 3). In the case of the two teeth rotor there is enough space between the teeth so that a large and stable cavitation cavity forms behind each tooth, which resembles a supercavitation cavity (Fig. 3B). Each entire ﬂow of the 2 L sample through the treatment chamber is deﬁned as one cavitation pass. Both rotors were made of stainless steel and both stators were made of a transparent acrylic glass and these also functioned as a cover. Both materials used are inert and don’t allow for any chemical reactions between the sample liquid and the machine. Measurements of the local system pressure (PL), were conducted upstream of the treatment chamber (on the suction side) using the

Fig. 3. Scheme of the treatment chamber of the rotation generator. The rotor and stator pairs used for developed cavitation and supercavitation are presented under A and B, respectively. Both rotors are rotating in a counter clockwise fashion where water is entering in the axial direction through the stator before exiting in the radial direction. Under C the geometry of a Venturi constriction is presented. Angles are indicated by α (8°), β (10°) and γ (30°).

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in these two real water samples differed from the standard colony counting technique. Firstly, 5-fold serial dilutions were prepared and 1 mL of each dilution was poured into a screw-cap tube (20 × 150 mm) containing 10 mL of freshly autoclaved, still molten (at 50 °C in a water bath), iron-sulphite agar medium (Merk™, 10 g/L of pancreatic digest of casein, 1 g/L of Na2SO3, 0.1 g/L of iron powder and 2% agar). During anaerobic incubation, the tubes were almost completely filled with media and were tightly sealed with screw caps. Additionally, the iron inside the media combined with any dissolved oxygen and thus provided an anaerobic environment. The strongest serial dilution that still proved positive (black colouration) after a 7 days long incubation at 37 °C was determined as the concentration of sulphate reducing bacteria and was presented in Log10 CFU mL−1 according to its logarithmic order of dilution. All values reported in this paper are the mean of at least two independent biological treatments and three replicates for each treatment. The average values and standard deviations are given. To evaluate the impact of cavitation on the overall growth reduction, a specific decay rate constant (μ) was calculated as follows:

direction, but with a slight angle to the camera. The camera was focused perpendicularly to the rotor’s teeth in axial direction of the rotor. The motor’s power and energy consumption were monitored with a Power Analyzer Norma 4000. 2.2. Microbiological measurements 2.2.1. Working suspension preparation B. subtilis ATCC® 6633™ acquired from the Veterinary Faculty at the University of Ljubljana was cultured at 37 °C on standard count agar plates (SCA, Merck™; 3,0 g/L of meat extract, 5,0 g/L of peptone from casein, 5 g/L of sodium chloride, and 12 g/L of agar). For the hydrodynamic cavitation experiments colonies from fresh culture plates (24 h old) were harvested, suspended and diluted in sterile Ringer solution (Merck™) until a concentration of around 5 Log10 CFU mL−1 (high initial bacterial titer) or 2 Log10 CFU mL−1 (low initial bacterial titer) was achieved. Bacterial concentration was determined by optical density measurements at 650 nm (OD650). The prepared suspension was then stored on ice in a Styrofoam box and just before the cavitation run, the bacterial culture was further diluted 100 and 10,000 times to a ﬁnal working concentration of around 1.0 × 105 CFU mL−1 (high initial titer) and of around 1.0 × 102 CFU mL−1 (low initial titer). The sample volume for the rotation generator was 2 L.

μ=

lnXf − lnX0 t f − t0

(1)

Specific decay rate (1/h) is the slope of the microbial growth curve and is negative when cells start dying [38]. X0 is colony count per millilitre at the beginning of treatment; Xf is colony count per millilitre at the end of treatment; t0 is time at the beginning of treatment and tf is time at the end of treatment. To ensure that the hydrodynamic device was free of microorganisms, before and after each hydrodynamic cavitation experiment, the device was cleaned using a washing protocol. This consisted of one rinse with tap water (running the hydrodynamic cavitation device filled with tap water for 5 min), two 15 min long rinses with 0.5% organic peroxide (peracetic acid, Persan® S15, Belinka Perkemija, d.o.o., Slovenia), and finally six successive device volume rinses with tap water (each lasting 5 min). The rinsed water was disposed after an overnight exposure to active chlorine. To determine the effectiveness of washing between cavitation experiments, the tap water from the last rinse was sampled and quantified by colony counts. Additionally, before each cavitation run, the effect of possible bacterial attachment on the interior surfaces of the cavitation reactor was tested. For this purpose, samples were taken immediately before (sampled directly form the flask containing the prepared bacterial suspension) and after filling the reactors with tap water containing around 5 Log10 CFU mL−1 or 2 Log10 CFU mL−1 of bacteria B. subtilis, and colony counts were compared. If compared values were similar (before and after filling), no significant bacterial attachment was present.

2.2.2. Sampling and quantification Apart from the experiments with the B. subtilis working suspension, 5 L samples were also taken from real technological process waters isolated from a board paper mill plant. These samples were collected from the individual pool (recycled water or RW) or from the central pool (central recycled water or CRW) of an enclosed water recycle system and were analysed for the presence of anaerobic sulphate reducing bacteria, aerobic bacteria, bacterial spores as well as for yeasts and moulds (Fig. 4). The original pH value of RW and CRW samples was 7.6. All samples were kept refrigerated (4 °C) until analysis. Before each experiment, 2 L of sample were introduced into the feeding reservoir and then cavitated for a predetermined time (30 and 60 min for both developed cavitation and supercavitation). The samples for analysis were taken prior, during and after the experiments, and for each sample 40 mL of suspension were released from the device through the sampling valve and poured back into the cavitation device through the entry valve. This ensured that the trapped dead volume inside the sampling pipe (that was not cycled through the cavitation device) was not analysed. Then the next 10 mL were released for the same sampling pipe and were stored in 50 mL tubes on ice in a Styrofoam box. The impact of hydrodynamic cavitation on the destruction of bacteria B. subtilis was monitored by colony counts. For this, samples of 1 mL were plated on the SCA agar medium using the 10-fold successive dilution method in saline solution. Colonies were counted after a 48 h long incubation period at 37 °C and results were expressed in Log10 CFU mL−1. For the selective isolation and quantification of yeasts from RW and CRW samples, 1 mL was plated on the Sabouraud Dextrose Agar plates (SDA, Merck™, 10 g/L of peptone, 40 g/L of dextrose, 2.0% agar) and colonies were counted after a 7 days long aerobic incubation at 28 °C. For the quantification of aerobic bacteria from RW and CRW samples, 1 mL was plated on SCA Petri plates and colonies were counted after 48 h at 37 °C. The bacterial spore count was performed in the same manner as for the aerobic bacteria with the exception of additional thermal pre-treatment of samples (80 °C for 20 min) before plating on solid SCA plates. The thermal shock destroys the vegetative portion of cells and only spores survive. Mould colony counts for the RW and CRW samples were performed by adding 1 mL of sample into a screw-cap tube (20 × 150 mm) containing 30 mL of freshly autoclaved, still molten (at 50 °C in a water bath) SDA agar medium. The content was vortexed, poured into a Petri plate and incubated at 25 °C for 5 days [37]. Quantification of the anaerobic sulphate reducing bacteria

2.3. Physicochemical analysis Organic matter (chemical oxygen demand, COD), was measured using COD kits (Hach Lange LCK 314 for samples with a COD value between 15 mgO2/L − 150 mgO2/L and LCK 714 for samples with a COD value between 100 mgO2/L − 600 mgO2/L) and a spectrophotometer DR3900 Hach Lange. pH value, redox potential and dissolved oxygen level were determined during sampling on site, using a Multi 340i analyser (WTW, Germany). Redox potential values (Pt electrode) measured in the field with an Ag/AgCl reference electrode were normalized to 25 °C and referenced to the standard hydrogen electrode (Eh). Settleable solids were analysed according to the Deutsches Institut fur Normung DIN 38409–2 [39], in which settleable substances were shaken and timed sedimentation was determined in a measuring container. Insolubles were determined according to SIST ISO 11,923 [40], for which Sartorius Glass-Microfibre Discs GMF3 filter paper was used for filtration. After drying the filter at 105 °C, the weight of the residual mass on the filter was measured. Colour intensity measurements were carried out in terms of the spectral absorption

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Fig. 4. The schematic presentation of the production section in the board paper mill plant Vipap Videm Krško from which 5 L samples were taken. The ﬁrst sample was collected from the individual pool (RW1 = RW) and the second sample from the central pool (CRW) of an enclosed water recycle system. The places of sampling on the scheme are presented in bold and are underlined.

observed (Fig. 5 B). In order to generate supercavitation the RGHC was equipped with the two-teeth rotor (rrotor of 0.025 m) which was spun at around 10,000 rpm with a tangential speed of fluid reaching 26.0 m/s. Because of the chocked cavitation conditions (generated using an added valve installed at the inlet of the RGHC) the entire set-up presented in Fig. 2 B had a flow rate of only 0.2 L/min. Filming with the high speed camera revealed the formation of a large and stable vapour cavity which filled most of the volume behind every tip of both teeth (Fig. 5D). In detail, two specific features of cavitation were formed on the presented supercavitation rotor. Cavitation cavity at the outer parts of the rotor resembled a unified supercavity. The second feature comprised of cavitation shedding that was caused because fluid velocity was dropping towards the centre of the rotor. For the purposes of clarity, we will be using the term supercavitation to describe the simultaneous formation of the unified supercavity and the shedding part of cavitation.

coefficient (SAC) using absorbance measurements at three wavelengths (436 nm, 525 nm and 620 nm) by UV–visible absorption with a Varian Cary 50 UV–Vis spectrophotometer (1 cm cell width, Agilent) after the samples were filtered using a 0.45 μm filter in accordance with the ISO 7887 [41]. In this way, SAC values were calculated according to the below equation:

SAC (m−1) =

100 × Abs (λ ) d

(2)

where Abs(λ) is the absorbance at a given wavelength (λ), and d represents the measuring cell width (mm). 3. Results 3.1. Hydrodynamic cavitation development To visualise the cavitation development inside the treatment chamber a series of image sequences were recorded using a high-speed camera Photron SA-Z (Fig. 5). The sequences follow a series of five 0.4 ms long intervals. The rotor was rotating in a counter clockwise fashion. In order to generate developed unsteady cavitation, the RGHC was equipped with the serrated rotor (and stator; rrotor of 0.025 m) which was spun at 9,000 rpm with a tangential speed of fluid reaching 23.6 m/s. The entire set-up presented in Fig. 2 A had a flow rate of 1.8 L/min (Table 1). According to our high-speed camera measurements performed in this study, a strong form of developed cavitation was visible behind every gap between the tips of the teeth of the opposing rotor and stator. Violent shedding and bubble collapsing were

3.2. Validation of cleaning and bacterial attachment The washing protocol employed for the RGHC device successfully removed all B. subtilis presence between different cavitation experiments. Additionally, we found that colony counts of B. subtilis samples that were taken immediately before and after the filling of the RGHC device (with the B. subtilis suspension) differed only slightly (a maximum difference of 0.15 log10 CFU mL−1). 3.3. Hydrodynamic cavitation for the destruction of B. Subtilis The effect of hydrodynamic cavitation generated inside the RGHC

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Fig. 5. Hydrodynamic characteristic of the rotation generator equipped with the serrated rotor (A) (for developed cavitation) and the two teeth rotor (C) (for supercavitation). Developed cavitation can be observed under column B and supercavitation under column D.

60 min, which relates to 6 supercavitation passes. After 6 supercavitation passes, the COD for the RW and CRW samples was reduced by 22%, and by 10%, respectively (Fig. 7). However, the redox potential was increased by cavitation. Speciﬁcally, the increase in the redox potential was much stronger for the CRW samples (77%) than for the RW samples (37%) reaching 160 mV and 107 mV, respectively. Supercavitation treatment increased the content of dissolved oxygen from 5.3 mgO2/L to 7.3 mgO2/L for the RW samples and from 4.6 mgO2/L to 7.4 mgO2/L for the CRW samples. After supercavitation the level of sediments was reduced by 50% and by 95% for the RW and CRW samples, respectively (Fig. 8). Similar results were obtained for the insoluble materials of the RW and CRW samples for which a 67% and a 48% reduction was achieved. Contrary to this, the SAC values increased for both sample types. The SAC436, SAC525, and the SAC620 values (m−1) increased by 96%, 93% and by 97% for the RW samples and by 43%, 28% and by 63% for the CRW samples, respectively. Supercavitation treatment strongly reduced the viable count of all the major classes of microorganisms which were found to be present in the RW and CRW samples. During the cavitation treatment the viable count of aerobic bacteria in the RW sample was reduced from 5.9 Log10 CFU mL−1 to 3.2 Log10 CFU mL−1. Therefore, a staggering 2.7 logs reduction was achieved after 6 supercavitation passes (a 99.81% destruction). However, for the CRW samples the reduction of the aerobic bacterial count was smaller (1.2 logs reduction). A 4.2 logs (a 99.99% destruction) and 2.8 logs (a 99.84% destruction) strong reduction of the anaerobic sulphate reducing bacteria was observed for the RW and the CRW samples, respectively. Viable yeast count reduction was also strong, again reaching 4 logs (a 99.99% destruction) and 2.5 logs (a 99.72% destruction) for the RW and CRW samples, respectively. Viability of bacterial spores was reduced from 2.6 Log10 CFU mL−1 to 1.3 Log10 CFU mL−1 for the RW samples and from 2.8 Log10 CFU mL−1

on the destruction of bacteria B. subtilis is presented in Fig. 6. In these experiments, the samples were exposed to cavitation for 60 min, which relates to 54 cavitation passes for developed cavitation and to 6 cavitation passes for supercavitation (as described in Šarc et al. [42]). When the RGHC device was equipped with the serrated rotor for the formation of multiple zones of developed cavitation, the viable count of the high initial bacterial titer (5.0 Log10 CFU mL−1) remained relatively unaffected for the first 27 passes through the treatment zone. After that, the viable count decreased slowly until the end of the experiment when the count was reduced down to 4.6 Log10 CFU mL−1. In all, a slight reduction of 0.4 logs was achieved after 54 cavitation passes. However, when the RGHC was equipped with the two-teeth rotor for the generation of supercavitation, the viable count of the high initial bacterial titer (5.4 Log10 CFU mL−1) rapidly declined and after 6 supercavitation passes the count was reduced down to only 3.1 Log10 CFU mL−1. In all, a staggering 2.3 logs reduction (a 99.50% destruction) was achieved. Similar trends were observed for low initial bacterial titers. When RGHC was spun with the serrated rotor, the low initial titer (2.6 Log10 CFU mL−1) was slowly reduced to 2.3 Log10 CFU mL−1 after 54 cavitation passes. The total reduction of viable count was almost the same as that observed for the high initial titers. However, when supercavitation was generated (two-teeth rotor), the low initial titer count (2.8 Log10 CFU mL−1) was again strongly reduced and after 6 supercavitation passes only 1.6 log10 CFU mL−1 remained viable. 3.4. Supercavitation for the recycling of real process waters The effects of supercavitation (RGHC equipped with the two-teeth rotor), on the destruction of the major classes of microorganisms which were found to be present in the RW and CRW samples and on the chemical and physical characteristics of these samples are presented in Figs. 7–9. The RW or CRW samples were exposed to cavitation for Table 1 Operational characteristics of the rotation generator. RGHC operation

Rotor type

Flow rate (L/min)

Revolutions of rotor (rpm)

PL (kPa)

Developed unsteady cavitation Supercavitation

Serrated rotor Two-teeth rotor

1.8 0.2

9,000 10,000

117.2 93.3

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Fig. 6. The Inﬂuence of developed cavitation (serrated rotor; circles) or supercavitation (two-teeth rotor; squares) generated inside the RGHC device on the destruction of high (ﬁlled symbols) or low (empty symbols) spiked titers of the bacteria Bacillus subtilis.

to 1.0 Log10 CFU mL−1 for the CRW samples. Finally, although present at lower concentrations, moulds were reduced by 0.6 Log10 CFU mL−1 and by 0.3 Log10 CFU mL−1 for the RW and CRW samples, respectively.

costs only relate to electric energy consumption of each individual run and do not include any potential cooling costs, and capital or maintenance costs are also excluded (plant production, amortization and operation). The EEO value for the removal of the bacteria Escherichia coli (with a starting concentration of 1 x104 CFU mL−1) from wastewater using the Venturi device was 268.6 kWh/m3/order [43]. For a similar starting bacterial titer (~1 × 105 CFU mL−1) of B. subtilis, the RGHC spent 347.5 kWh/m3/order and 67.2 kWh/m3/order for the developed cavitation and for the supercavitation, respectively. When the RW sample was treated using supercavitation, the RGHC spent 56.2, 36.4, 39.0, 117.4 and 253.5 kWh/m3/order for the aerobic bacteria, anaerobic sulphate reducing bacteria, yeasts, bacterial spores and for moulds, respectively.

3.5. Economic evaluation Operational eﬀectiveness of the RGHC equipped with the serrated (for developed unsteady cavitation) or the two-teeth rotor (for supercavitation) was compared with the eﬀectiveness of the Venturi device, which was assembled by Arrojo et al. [43] and which could generate a developed form of cavitation. For both devices, electric energy per order (EEO; kWh/m3/order) was calculated [44], which is the amount of electric energy required to bring a decrease in viable colony counts (CFU/mL) by one order of magnitude. Its equation is presented below:

EEO =

P × tf X

V × Log10 ( X0 ) f

4. Discussion

(3)

In this work, we studied 2 diﬀerent types of hydrodynamic cavitation, developed unsteady cavitation (using a serrated rotor and stator) and supercavitaiton (using a two-teeth rotor), that were generated inside the RGHC device. The high-speed camera revealed that behind every gap between the tips of the teeth of the opposing serrated rotor and stator a developed unsteady form of cavitation was accompanied by

where P is the power input of the system [kW], V is the volume of treated water [m3] in time t [h], and X0 and Xf are the starting and ending viable colony counts of bacteria per one millilitre (CFU/mL). Higher EEO values correspond to lower removal eﬃciencies. Table 2 shows the average EEO values and approximate costs (€/m3) for each experimental run. Nevertheless, we have to keep in mind that these

Fig. 7. The eﬀect of the RGHC supercavitation treatment (two-teeth rotor) on the chemical parameters of samples isolated from real process waters.

8OWUDVRQLFV 6RQRFKHPLVWU\

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Fig. 8. The eﬀect of the RGHC supercavitation treatment (two-teeth rotor) on the physical parameters of samples isolated from real process waters.

achieved. A strong reduction of 3 logs was also observed for the aerobic bacteria (μ of −6.26). Interestingly, even bacterial spores which are highly resistant to mechanical and physical stresses were reduced by 1.3 logs (μ of −2.9). The destruction of these groups of microorganisms is particularly important for the paper producing industry especially when an enclosed water recycle system is employed [2,34,46]. Supercavitation treatment decreased COD and increased the dissolved oxygen content and redox potential (up to 77%) in the RW samples. Decrease in COD indicates that supercavitation significantly contributed to the degradation of organic contaminants. This could be due to the formation of %OH radicals which act as oxidants for organic molecules [47]. As described in chapter 3.1, supercavitation, which is formed on the presented rotor, also consists of the shedding part where due to individual bubble collapses radical formation is possible. To determine if the COD removal is caused by radicals a scavenger such as methanol could be added to the sample. At similar pH values (pH of 7) to that of the RW samples (pH of 7.6), the %OH radicals exhibit a strong redox potential of + 2.31 V as measured by the normal hydrogen electrode [48]. Therefore, the formation of %OH radicals and the increase in dissolved oxygen level consequently elevated the redox potential of water [49]. When water jets in hydrodynamic cavitation systems travel through air, they draw substantial quantities of air and the high pressures which are generated during cavitation can dissolve the air into the water [50]. Supercavitation reduced the sediments and the insoluble materials and generally intensified all the SAC colour values in the RW samples. Because bacteria represent a significant part of the sediment, the destruction of cells by supercavitation could cause a reduction in insoluble sediments. Furthermore, Poyato et al. [51] showed that cavitation can break insoluble particles into smaller sized fragments which are termed

bubble cloud shedding and collapse. Moreover, when the two-teeth rotor was spun, almost the entire section behind every tip of both teeth was engulfed within a vapour cavity (Fig. 5D). These two types of hydrodynamic cavitation generated inside the RGHC device were further tested for their antimicrobial potential against the high titers of bacteria B. subtilis. Unsteady developed cavitation generated inside the RGHC had a weak impact on the viability of B. subtilis and only slowly reduced its viable count (μ of −0.83). However, when supercavitation was applied, the viable count of B. subtilis was reduced by 2.3 logs (μ of −5.22). Therefore, for the same treatment times (1 h), the destruction of bacteria B. subtilis was 5.8 times more eﬃcient for the supercavitation in comparison to the unsteady developed cavitation (0.4 logs reduction). Similar trends were repeated for the low initial bacterial titers. Even though for supercavitation larger disturbances in pressure are uncommon [8] it has already been successfully applied for the destruction of the troublesome bacteria L. pneumophila [28]. The main mechanism by which supercavitation disrupts bacterial cells is currently unknown, however it might be the result of multiple simultaneous eﬀects such as instant pressure decrease at the entrance of supercavity (transition from liquid to vapour phase) [29] and the generation of very high shear forces (shear rate of 2.6.104 s−1; which is circumferential velocity/1 mm gap height between rotor and stator). In fact, according to literature, high shear stress can cause extensive cell damage ending with cell hemolysis [45]. Supercavitation treatment was found to reduce the viability of all the major classes of microorganisms present in the RW samples which were isolated from a paper producing plant. This was especially evident for the anaerobic sulphate reducing bacteria (μ of −9.70) and for the yeasts (μ of −9.00) for which a strong reduction of around 4 logs was

8OWUDVRQLFV 6RQRFKHPLVWU\

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Fig. 9. The eﬀect of the RGHC supercavitation treatment (two-teeth rotor) on the destruction of the major classes of microorganisms which were present in real process waters.

The economic analysis showed that for a similar initial bacterial titer, our RGHC, which generated supercavitation, spent 4 times less electrical energy for the reduction of bacteria B. subtilis (67.2 kWh/m3/ order) in comparison to the Venturi device which was used for the reduction of E. coli (268.6 kWh/m3/order) and was assembled by Arrojo et al. [43]. Moreover, it has to be mentioned that in our experiments the highly resistant Gram-positive B. subtilis was used (wall thickness of 30 nm [55]; may bear a turgor pressure of 2.6 MPa [56]) whereas in the experiments performed by Arrojo et al. [43] the more susceptible Gram negative E. coli was adopted (wall thickness of 2–4 nm [57,58]; may bear a turgor pressure of 29 kPa [59]). Furthermore, the eﬃciency of the RGHC was especially high for the anaerobic sulphate reducing bacteria and for yeasts isolated form the RW samples (3.6 €/m3 − 3.9 €/m3). This device possesses a number of advantages over previous designs. For example, the RGHC can generate greater shear forces (during supercavitation shear rate was 2.6.104 s−1; and Rotational Reynolds number was 1.1.106 [60]) which are caused by the rotation of the rotor and the liquid that is located between the rotor and the stator.

as total suspended solids (TSS), and these are small enough not to settle down and will indefinitely remain suspended in the solution which isn’t subjected to any form of motion. Colour pollutants in water samples are problematic because they limit the amount of light entering into the water consequently having an inhibiting effect on photosynthesizing organisms and phytoremediation [52]. The increase in colour by supercavitation is, however, not alarming, because it did not exceed the concentration limits of emission into water determined by the European Norm EN ISO 7887, which are 7 m−1 for 436 nm (yellow), 5 m−1 for 525 nm (red), and 3 m−1 for 620 nm (blue) [53]. In accordance with our results, Lorimer et al. [54] observed that ultrasonic cavitation reduces the colour removal capability of the electrolytic treatment by disintegrating solid particles present in the samples. The disintegration of larger insoluble particles into many smaller sized particles can contribute to the intensification of colour values. Lastly, in comparison to the RW samples, supercavitation had a significantly smaller impact on the destruction of microorganisms and on the reduction of COD in the CRW samples. One clear difference between these two types of samples was that only the CRW samples were intensely foaming during cavitation. Due to the foaming the cavitation could not result in one stable supercavity, instead large number of smaller cavitation bubbles were formed, which might have reduced the chance of bacteria entering into the area of low pressure. Additionally, the higher amount of smaller bubbles could lead to the cushioning effect which decreases the intensity of bubble collapses and amount of formed radicals and results in lower COD removal.

5. Conclusions This study evaluates the eﬃciency of a lab-scale rotation generator of hydrodynamic cavitation for the treatment of a process water isolated from an enclosed water recycle system of a paper producing plant. Two set-ups capable of generating diﬀerent type of cavitation, namely developed cavitation and supercavitation, were tested. Our results

8OWUDVRQLFV 6RQRFKHPLVWU\

1.8.103A 4.8.104 1.4.103 1.7.103 5 1.0.101 2.0.101 5

268.6A 347.5 67.2 56.2 36.4 39.0 117.4 253.5

26.9A 34.7 6.7 5.6 3.6 3.9 11.7 25.4

showed that supercavitation was more efficient for the destruction of B. subtilis, Gram positive bacteria problematic in paper mill production plants. The results were evaluated in terms of chemical, physical and microbiological characterisation. Using the supercavitation set-up we were able to destroy 2.3 logs of B. subtilis, 4.2 logs of anaerobic sulphate reducing bacteria, 4 logs of yeast, 3 logs of aerobic bacteria and 1.3 logs of bacterial spores. In terms of chemical characterisation of samples, we achieved 22% COD reduction, a 77% increase in redox potential and a 27% increase in dissolved oxygen levels. Evaluation of physical characterisation of treated samples showed that sediment portion was reduced by 50% and the insoluble portion by 67%. When the achieved results are compared to different cavitation set-ups, it can be deduced that rotation cavitation generator of supercavitation is economically more feasible than for example a Venturi device. Based on the achieved results we plan to investigate the efficiency of the rotation generator of hydrodynamic cavitation on a pilot scale integrated into the enclosed water recycle system of a paper plant. Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper. Acknowledgments The authors would like to thank the Slovenia’s Smart Specialisation Strategy for funding the Research, development and innovation project (RDI) Cel.Cycle: »Potential of biomass for development of advanced materials and bio-based products« (contract number: OP20.00365), which is cofinanced by the Ministry of Education, Science and Sport of the Republic of Slovenia and the European Union as part of the European Regional Development Fund 2016 – 2020; and the Slovenian Research Agency for funding the core research No. P2-0401. We thank the paper company Vipap Videm Krško for their cooperation and support. Mathematical and grammatical help was provided by Professors Franc Kosel and Bernarda Kosel. References

Results obtained from Arrojo et al. [43].

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5A 0.250 0.305 0.310 0.310 0.310 0.310 0.310 2A 1 1 1 1 1 1 1 Developed unsteady cavitation Developed unsteady cavitation Supercavitation Venturi #3 RGHC Serrated rotor RGHC Two teeth rotor

Escherichia coli Bacillus subtilis Bacillus subtilis Aerobic bacteria (RW) Anaerobic sulphate reducing bacteria (RW) Yeasts (RW) Bacterial spores (RW) Moulds (RW)

0.05A 0.002 0.002 0.002 0.002 0.002 0.002 0.002

1.104A 1.1.105 2.6.105 8.9.105 7.8.104 8.2.104 3.9.102 2.0.101

−0.85A −0.83 −5.22 −6.26 −9.70 −9.01 −2.9 −1.4

Cost (€/m3) EEO (kWh/m3/order) μ (tf - t0) (1/h) Xf (CFU/mL) X0 (CFU/mL) V (m3) TMP (kW) tf (h) Bacterial species Cavitation development Device

Table 2 Electrical eﬃciency of the rotation generator equipped with the serrated (for developed unsteady cavitation) or the two-teeth rotor (for supercavitation) in comparison to the Venturi device assembled by Arrojo et al. [43].

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PAPERmaking! FROM THE PUBLISHERS OF PAPER TECHNOLOGY TE INTERNATIONAL

Volume 7, Number 1, 2021

Natural Rubber Composites for Paper Coating Applications Pieter Samyn 1, Frank Driessen 2 and Dirk Stanssens 2,

Natural rubbers are characterized by extremely high molecular weight that might be beneficial in the formation of a protective barrier layer on paper substrates, providing good cohesive properties but limited adhesion to the substrate. In parallel, the low glass transition temperature of natural rubber might give the opportunity for good sealability, in contrast with severe problems of tack. Therefore, natural rubbers can be good candidates to serve as an alternative ecological binder in paper coatings for water and grease barrier resistance. In order to tune the surface properties of the paper coating, the effect of different fillers in natural rubber coatings are evaluated on rheological, thermo–mechanical and surface properties. The fillers are selected according to common practice for the paper industry, including talc, kaolinite clay and a type of organic nanoparticle, which are all added in the range of 5 to 20 wt.-%. Depending on the selected natural rubber, the dispersibility range (i.e., dispersive and distributive mixing) of the fillers in the latex phase highly varies and filler/matrix interactions are the strongest for nanoparticle fillers. An optimum selection of viscosity range allows us to obtain homogeneous mixtures without the need of surface modification of the additives. After bar-coating natural rubber latex composites on paper substrates, the drying properties of the composite coatings are followed by spectroscopy, illustrating the influences of selected additives on the vulcanization process. In particular, the latter most efficiently improves in the presence of nanoparticle fillers and highly increases the coating hydrophobicity in parallel, reducing the adhesive tack surface properties, as predicted from calculated work of adhesion. Contact information: 1 Institute for Materials Research (IMO-IMOMEC), Applied and Analytical Chemistry, University of Hasselt, 3500 Hasselt, Belgium; Pieter.Samyn@uhasselt.be 2 Topchim N.V. (a Solenis International LCC Company), 2160 Wommelgem, Belgium; FDriessen@solenis.com Materials Proceedings Conference: 2nd Coatings and Interfaces Web Conference DOI: http://dx.doi.org/10.3390/CIWC2020-06832 Creative Commons Attribution 4.0 International License

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Article 7 – Natural Rubber Coating Binders

Proceedings

Natural Rubber Composites for Paper Coating Applications † Pieter Samyn 1, Frank Driessen 2 and Dirk Stanssens 2,* Institute for Materials Research (IMO-IMOMEC), Applied and Analytical Chemistry, University of Hasselt, 3500 Hasselt, Belgium; Pieter.Samyn@uhasselt.be 2 Topchim N.V. (a Solenis International LCC Company), 2160 Wommelgem, Belgium; FDriessen@solenis.com * Correspondence: DStanssens@solenis.com; Tel.: +32-11-26-84-95 † Presented at the 2nd Coatings and Interfaces Web Conference, 15–31 May 2020; Available online: https://ciwc2020.sciforum.net/. 1

Published: 13 May 2020

Abstract: Natural rubbers are characterized by extremely high molecular weight that might be beneficial in the formation of a protective barrier layer on paper substrates, providing good cohesive properties but limited adhesion to the substrate. In parallel, the low glass transition temperature of natural rubber might give the opportunity for good sealability, in contrast with severe problems of tack. Therefore, natural rubbers can be good candidates to serve as an alternative ecological binder in paper coatings for water and grease barrier resistance. In order to tune the surface properties of the paper coating, the effect of different fillers in natural rubber coatings are evaluated on rheological, thermo–mechanical and surface properties. The fillers are selected according to common practice for the paper industry, including talc, kaolinite clay and a type of organic nanoparticle, which are all added in the range of 5 to 20 wt.-%. Depending on the selected natural rubber, the dispersibility range (i.e., dispersive and distributive mixing) of the fillers in the latex phase highly varies and filler/matrix interactions are the strongest for nanoparticle fillers. An optimum selection of viscosity range allows us to obtain homogeneous mixtures without the need of surface modification of the additives. After bar-coating natural rubber latex composites on paper substrates, the drying properties of the composite coatings are followed by spectroscopy, illustrating the influences of selected additives on the vulcanization process. In particular, the latter most efficiently improves in the presence of nanoparticle fillers and highly increases the coating hydrophobicity in parallel, reducing the adhesive tack surface properties, as predicted from calculated work of adhesion. Keywords: paper; biopolymer; fillers; rheology; contact angle; adhesion

1. Introduction The demand for bio-based solutions in paper coating technology is urgent to replace oil-based polymers building protective coatings with high hydrophobicity. However, many biomaterials, such as cellulose, starch, carbohydrates, proteins, and glycerol, have hydrophilic properties and provide a solution for oil-barrier properties, but the range of hydrophobic biopolymers is more restricted. As an alternative, natural rubbers have intrinsic hydrophobic properties and are naturally dispersed in an aqueous latex phase, providing molecular structures with extremely high molecular weight. However, the material is often difficult to process into coating layers and its stability relies on the natural stabilization of the polyisoprene particles in the latex phase. On the other hand, the low glass transition temperatures of natural rubbers are favorable for the formation of film properties with rubbery characteristics at room temperature. The natural rubbers were applied as film former in Mater. Proc. 2020, 2, 29; doi:10.3390/CIWC2020-06832

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pharmaceutical coatings [1]: while providing excellent physical properties, such as high elasticity, high tensile strength and ease of film-forming, the films are soft and sticky [2]. The use of natural rubber as paper coatings is less developed, although the application on paperboard provides low water affinity and low absorption rates of the coated surfaces [3]. Although it has good potential to replace unrecyclable wax coating material on packaging papers, the blocking (sticking) tendency needs to be decreased with the content increase fillers—e.g., adding modified lignin can efficiently reduce the sticking problem of the coating [3]. In combination with cellulose fabrics, the natural rubber coatings were applied in a calendaring machine with good adhesion to the substrate, which is presumably due to the good mechanical and chemical compatibility of natural rubber and lignocellulose fibers [4]. In order to tune the composition and properties of the natural rubber coatings, additives are required to provide the requested surface properties, although compatibility with rheological properties and the molecular profile of the natural rubber should be investigated. In this work, typical coating fillers used in paper technology, including kaolinite, talc and organic styrene–maleimide nanoparticles, are used in combination with a natural rubber latex binder in order to investigate the effects on the processing and surface properties of the coating. 2. Materials and Methods 2.1. Materials Vytex Natural Rubber Latex (Vystar, Worcester, MA, USA) was used as a commercially available “ultra-low protein” natural rubber latex with an intrinsic solid content of 60% (w/w) and pH = 10.4. Three different types of fillers were used, including kaolinite (KAO) powder with particle diameter < 2 ΐm and aspect ratio 20:1 (Imerys, Paris, France), talc powder, and styrene–maleimide (SMI) nanoparticles that were in-house synthesized according to a previous protocol [5]. The latex was used in non-diluted conditions for mixing with different filler types in concentrations of 5, 10, 20% (wt./wt.), using a three-blade propeller mixer under constant medium shear for about 1 h. The mixed latex suspensions were applied as a paper coating on a laboratory scale K303 Multicoater (RK Print Coat Instruments Ltd., Litlington, Royston, Hertfordshire, UK), using a black metering bar number 4 (close wound wire diameter 0.51 mm) resulting in a wet film thickness of about 40 ΐm. The coatings were dried for 2 min in a hot-air oven and further dried for one week under environmental lab conditions (23 °C; 50% RH). A reference paper grade was used for deposition of the films, including bleached Kraft pulp and internal sizing (350 ΐm thickness). In parallel, free standing rubber films of the same composition were cast on a PTFE foil for following adhesion measurements (the free films were more flexible and used as counterpart for an adhesive loop test). 2.2. Characterization Rheological measurements on mixed latex suspensions were performed on Ares G2 equipment (TA Instruments) with a cylindrical bob-cup geometry operating at a gap distance of 2.10 mm. A suspension volume of 20.1 mL was added into the cup and first kept at rest for about 30 min before testing to relieve internal stresses. A continuous rotational shear test was performed under controlled shear rate between 0 and 1000 sƺ1 at a controlled temperature of 25 °C, while applying three subsequent sequences of ramp up (15 min)–rest at 1000 sƺ1 (5 min)–ramp down (15 min)–rest at 0 cmƺ1 (5 min)–ramp up (15 min), monitoring viscosity changes by eventual effects of hysteresis and/or internal history. The differential scanning calorimetry (DSC) measurements were done on a Q200 equipment (TA Instruments) on a sample mass of 8.5 mg in a heating range from ƺ90 to 180 °C at 20 °C/min under continuous nitrogen flow. The results for Tg (glass transition temperature) and Ǌcp (heat capacity) are taken from the second heating step and averaged from two samples. Attenuated total reflection Fourier transform infrared spectroscopy (ATR-FTIR) was done on separate natural rubber films (no paper coating) in order to focus on the effect of the fillers on the coating structure, without interfering spectral bands of the base paper. The measurements were done

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on a Vertex 70 station (Bruker, Karlsruhe, Germany) with a diamond crystal (PIKE), collecting the spectra in a spectral range of 600–4000 cmƺ1 with a resolution of 4 cmƺ1. A DTGS detector was installed to summarize 32 scans for 1 spectrum. The scanning electron microscopy (SEM) was done on a Tabletop TM3000 microscope (Hitachi, Krefeld, Germany) under an acceleration voltage of 15 kV and backscattered secondary electron compositional mode. The magnification of 4000× was operated under a working distance of 8400 ΐm. The other paper surface properties were determined by static contact angle measurements of deionized water and diiodomethane, applying a sessile drop method with drop volume of 2 ΐmL (water) and 0.8 ΐl (CH2I2), respectively. The adhesive properties of the coated paper surfaces were evaluated by an adhesive loop test on rubber films in contact with the coated paper of the same rubber composition, using a universal tensile tester (Schimadzu, Kyoto, Japan). A representative geometry of a film loop with width of 1 cm and length of 5 cm was clamped in between the upper dies and brought to a distance of 1 cm above the coated paper substrate that was horizontally fixed in the lower dies. The tack is characterized as the maximum force upon withdrawal of the rubber film from the coated paper surface, where experimental values of adhesive force are comparable due to the constant geometries. 3. Results 3.1. Rheological Properties The rheological properties of the coating suspensions are presented as the variation of shear viscosity as a function of shear rates over three subsequent cycles, as given in Figure 1. The curves are recorded for suspensions with different fillers relative to the native natural rubber latex with solid content 60% (note: the viscosity scale of the materials is different for most detailed representations of the values). All filler types increased the viscosity of the original rubber latex to a different extent; however, all of them showed a shear-thinning effect with decreasing viscosity as a function of shear rate. The shear thinning behavior is enhanced in the presence of the fillers in most cases. The highest viscosities are observed for kaolinite fillers with an almost linear decrease in viscosity with shear rate at the highest concentrations, while the hysteresis of the kaolinite fillers is relatively low. This indicates the presence of strong mixing interactions between the kaolinite fillers and strong interactions with the natural rubber latex. The viscosity increase for SMI nanoparticles is significant with a more pronounced shear thinning effect, as the orientation of the nanoparticles under shear may additionally influence the structure of the suspension. The viscosity effects of nanoparticles are different from the microsize kaolinite, as an increase in nanoparticle concentration involves a decrease in viscosity. Therefore, it can be concluded from a viscosity-reducing effect of the nanoparticles that shear-induced mechanisms are influencing the nanoparticle mobility in the suspension and eventually lead to the orientation effects. The effects of reorganization of nanofillers in the rubber latex is also indicated by the relatively high hysteresis observed between the first and second ramp-up sequences for all concentrations, which was not observed for kaolinite fillers. Indeed, the nanoscale particles may have stronger influence on the latex flow properties compared to microscale particles. The latter are minimized in the case of talcum fillers, where very little alterations in viscosity and shear thinning effects are observed compared to the native rubber latex. However, the hysteresis effects for talc are also more pronounced than for kaolinite as it may be expected that the talc has a platelet structure that can be affected more by orientation effects under flow, while the kaolinite particles have a rather symmetrical shape. As it is observed that the viscosity for intermediate talc concentrations of 10 wt.-% decreases and the viscosity for the high talc concentrations of 20 wt.-% increases, the possible benefits of the orientation of the platelet structures are optimized at intermediate concentrations and hindered at the highest concentrations, where the highest concentrations might eventually lead to platelet–platelet interactions rather than platelet–latex interactions. The chemical interactions between the fillers and the natural rubber latex were not further studied at this stage, but besides particle shape, they can be attributed to specific surface interactions owing to the functional groups at the surface of the fillers, size distribution of the fillers and/or variations in zeta potential. While the present aim is to provide a view on the influence of the rheological

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properties on the coating formation, the latter interactions are the subject of more fundamental study in future.

Figure 1. Rheological properties of natural rubber suspensions with different fillers at different concentrations, relative to the unfilled natural rubber suspension (purple curve), (a) Kaolinite, (b) SMI nanoparticles, (c) Talc.

3.2. Microstructural Properties The effects of fillers on the microstructure of the natural rubber latex are evidenced by results of DSC analysis, as summarized in Figure 2. The pure natural rubber is characterized by a low glass transition temperature of Tg = ƺ64.53 °C and no further thermal transitions were noticed over the temperature range up to 180 °C as no specific vulcanization agents were added. The change in heat capacity Ǌcp = 0.4940 J/(g°C) over the glass transition is a measure for the change in the molecular mobility in the amorphous phase during the glass transition and may indicate variations in molecular structure induced—e.g., by chain interactions or cross-linking reactions in the amorphous phase.

Figure 2. DSC results of natural rubbers with a detail on the glass transition in the presence of different types and concentrations of fillers, listing glass transition temperature Tg and heat capacity change Ǌcp (compositions in wt.-%).

The slight but consistent variations in Tg and Ǌcp were noticed in the presence of fillers to different extents, depending on the filler type and concentration. A detail of the glass transition step during heating indeed shows either a shift in the temperature Tg and/or a reduction in the value Ǌcp in the presence of fillers. The natural rubber composites with fillers show a reduction in Ǌcp, relative to the pure natural rubber, which progressively decreases further as a function of higher filler concentrations: the reduction is the highest for the SMI nanoparticles (to a final value of Ǌcp = 0.3996

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J/(g°C)), the lowest for the talc fillers (to a final value of Ǌcp = 0.4510 J/(g°C), and intermediate for the kaolinite fillers (to a final value of Ǌcp = 0.4142 J/(g°C). This would indicate that the fillers assist in creating cross-links between the molecular chains of the natural rubber, preventing molecular mobility during the glass transition. The nanoparticles are indeed most efficient in creating crosslinks, likely due to the surface chemistry of the nanoparticles with residual free amic acid groups and imidized moieties, as detailed before [5], in combination with the nanoscale surface area effect. The effects of fillers on the structure of natural rubbers are further illustrated from the ATR-FTIR spectra shown in Figure 3. The spectra both confirm the presence of the fillers in different concentrations in parallel with some changes in the natural latex molecular structure. The FTIR spectra of natural rubbers are characterized by the presence of characteristic bands for cis-1,4polyisoprene, including 2960 cmƺ1 (CH3 symmetric stretching), 2913, 2852 cmƺ1 (CH2 asymmetric and symmetric stretching), 1655 (-C=C-), 1445 cmƺ1 (CH3 and CH2 bending), 1376 cmƺ1 (CH3 bending), and 842 cmƺ1 (=CH wagging). Apart from that, the spectra of different fillers are characterized by separate absorption bands characteristic for SMI nanoparticles: 1713 cmƺ1 (C=O, imide), 701 cmƺ1 (aromatic, styrene); kaolinite: 500 to 700 cmƺ1 (Si-O), 900 cmƺ1 (OH deformation), 1000 cmƺ1 (Si-O stretching) 3600 cmƺ1 (OH stretching, Al-OH stretching); talc: 672 cmƺ1 (Si-O-Si symmetric stretching), 1017 cmƺ1 (SiO-Si asymmetric stretching), and sharp band at 3670 cmƺ1 (OH).

Figure 3. FTIR spectra of natural rubber composites with different concentrations of fillers, (a) SMI nanoparticles, (b) Kaolinite, (c) Talc (same color legends for overview spectra and details on the right).

The related spectral bands of the fillers are independent of the natural rubber matrix and progressively increase at the higher filler concentrations. A single interaction between the SMI nanoparticles and the matrix can be seen at the shoulder peak around 1360 cmƺ1: the band is present in pure natural rubbers and gradually intensifies with the higher SMI concentrations, while the band

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did not appear in single SMI nanoparticles. The latter might indicate physical interactions between the SMI nanoparticles and the CH3 side groups of the natural rubber polymer chain. In addition, an intensified broad peak over the 3200–3500 cm–1 region is most pronounced for the SMI nanoparticle fillers and less present for the kaolinite and talc fillers. This absorption band might be related to the presence of hydroxyl groups that appear to be generated through interactions between the natural rubber with the SMI nanoparticles. On the other hand, no direct changes in the -C=C- double bonds were observed due to chemical cross-linking reactions for either of the fillers. In conclusion, it can be confirmed that strongest physical interactions between the natural rubber matrix and SMI nanoparticles are observed. 3.3. Paper Coating Properties The morphology of paper surfaces with natural rubber composite coatings are illustrated in Figure 4, representing top views of the different coating compositions. The pure natural rubber coating was fully flat and covered the paper surface as a smooth polymer film. The aspect of kaolinite fillers is observed as a homogeneous and smooth distribution over the coating surface with progressively more dense coverage at the higher concentrations, while they bring good coating density and likely some topographical roughness effects. The SMI nanoparticles are homogeneously distributed within the coating, causing the creation of small micrometer-scale domains. The talc particles are much rougher and are densely present at the surface in an inhomogeneous distribution over the surface. Due to the platelet morphology of talc particles, they are randomly oriented at the surface either perpendicularly sticking out or embedded parallel to the surface.

Figure 4. SEM evaluation of natural rubber coatings on paper with different filler types and concentrations (magnification ×4000 for all images).

The results of surface properties, including wetting and adhesive properties, are summarized in bar charts of Figure 5. The static contact angle values of water and diiodomethane in Figure 5a show slight and consistent variations among the different coating types and filler concentrations, relative to the pure natural rubber coating. The contact angles remained stable on the coatings for about 15 seconds, except for the pure natural rubber, as the homogeneity and coverage of the coating was not perfect and fully continuous for the pure natural rubber coating. The exposure of paper fibers at the

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surface created voids for the flow of the water through the coating, while the presence of fillers improved the coating coverage and density, providing better bulkiness compared to the pure natural rubber. The original rubber coating had a water contact angle of 95°, being in the hydrophobic range. The presence of kaolinite gradually increases the coating hydrophobicity, likely due to the hydrophobic properties of the fillers in combination with the creation of some additional surface roughness, seen in the microscopic images. The talc particles are hydrophilic, and their properties consequently prevail while exposed at the surface, resulting in a gradual decrease in hydrophobicity with the higher talc concentrations. The hydrophobic properties of SMI nanoparticles are beneficially exploited while added in different concentrations, rising up to a maximum water contact angle of 110°. While the water contact angle indicates the polar interactions, the diiodomethane is an apolar liquid and often shows opposite trends to the water contact angles.

Figure 5. Surface properties of natural rubber coatings on paper substrates, (a) static contact angles for water (blue bars) and diiodomethane (orange bars), (b) calculated work of adhesion Wa, (c) experimental adhesion force from loop test.

The adhesion between coated surfaces of natural rubber composites has been studied in the frame of the tendency for self-adhesion of natural rubber materials. The work of adhesion, Wa = ·L (1 + cos Ό) with ·L = liquid tension, and taking into account the contact between similar rubber coating materials, can theoretically be calculated from the water and diiodomethane contact angles. The

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calculated values are represented in Figure 5b, where it can be noticed that the predicted adhesion varies for the different coating types. The theoretical adhesion is highest for the pure natural rubber and is lower in the presence of filler materials: with increasing filler concentrations, the adhesion gradually decreases in the presence of kaolinite fillers and SMI nanoparticles, while the adhesion increases in the presence of talc particles. This can indeed be related to the hydrophobic effect of the kaolinite and SMI nanoparticles and the hydrophilic effect of the talc particles. The results of experimental adhesion measurements from a loop test with contact between similar rubber composite materials is represented in Figure 5c, and confirm the trends from theoretical calculations. From that, it is mainly revealed that the tendency for adhesion of rubber composite coatings can be predicted from water contact angle measurements and is steered by the hydrophobicity of the coated surface. 4. Conclusions Different macro- and nanoscale fillers can be homogeneously mixed with a natural rubber latex and applied as a paper coating. The use of hydrophobic nanoparticles shows the most interactions with the latex through interactions with the molecular side chains of the poly-isoprene, while the nanoparticles also provide the highest hydrophobicity and reduced tendency for self-adhesion (tack). Author Contributions: Experimental design, D.S., P.S. and F.D.; sample preparation, F.D.; experimental characterization P.S.; data processing, P.S. and F.D.; manuscript writing, P.S., F.D. and D.S. All authors have read and agreed to the published version of the manuscript. Funding: This research was funded by VLAIO HBC 2017.0310_BioBAR. Conflicts of Interest: The authors declare no conflict of interest.

References 1. 2. 3. 4. 5.

Panrat, K.; Boonme, P.; Taweepreda, W.; Pichayakorn, W. Formulations of natural rubber latex as film former for pharmaceutical coating. Proc. Chem. 2012, 4, 322–327. Jianprasert, A.; Monvisade, P.; Yamaguchi, M. Combinatino of tung oil and natural rubber latex in PVA as water based coatings for paperboard application. MATEC Web Conf. 2015, 30, 03010. Wang, H.; Easteal, A.; Edmonds, N. Prevulcanized natural rubber latex/modified lignin dispersion for water vapour barrier coatings on paperboard packaging. Adv. Mater. Res. 2008, 47–50, 93–96. Das, D.; Datta, M.; Chavan, R.B.; Datta, S.K. Coating of jute with natural rubber. J. App. Polym. Sci. 2005, 98, 484–489. Samyn, P.; Deconinck, M.; Schoukens, G.; Stanssens, D.; Vonck, L.; Van den Abbeele, H. Synthesis and characterization of imidized poly(styrene-maleic anhydride) organic nanoparticles in stable aqueous dispersion. Polym. Adv. Technol. 2012, 23, 311–325. © 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).

PAPERmaking! FROM THE PUBLISHERS OF PAPER TECHNOLOGY TE INTERNATIONAL

Volume 7, Number 1, 2021

Utilization of bio-polymeric additives for a sustainable production strategy in pulp and paper manufacturing: A comprehensive review Soumya Basu, Shuank Malik, Gyanesh Joshi, P.K. Gupta, Vikas Rana

Renewable and bio-based materials have gained great interest on an industrial scale owing to environmental issues. Paper industries also are constantly exploring bio-resources for intrinsic chemico-physical property enhancement of paper and paper products. These bio-resources will potentially increase their cyclability besides making paper compatible beyond traditional uses. Mechanical beating or use of chemical additives or the combination of these methods are widely used to improve critical paper characteristics such as strength, surface smoothness, density, brightness, filler retention, water and grease resistivity etc. These chemical additives as mill effluents are hazardous and have detrimental effect on environment. So, to move ahead of traditional practices, the present review discusses about the production and utility of abundantly available renewable bio-polymers and their products such as starch, cellulose, plant-based proteins, microbial biopolymers, animal-based biopolymers, and natural gums etc. They represent ample prospect in terms of research and development on their functionality and industrial applications. Contact information: Cellulose & Paper Discipline, Forest Products Division, Forest Research Institute, Dehradun-248006, Uttarakhand, India Carbohydrate Polymer Technologies and Applications 2 (2021) 100050 DOI: https://doi.org/10.1016/j.carpta.2021.100050 Creative Commons Attribution 4.0 International License

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Article 8 – Biopolymers

Carbohydrate Polymer Technologies and Applications 2 (2021) 100050

Contents lists available at ScienceDirect

Carbohydrate Polymer Technologies and Applications journal homepage: www.elsevier.com/locate/carpta

Utilization of bio-polymeric additives for a sustainable production strategy in pulp and paper manufacturing: A comprehensive review Soumya Basu, Shuank Malik, Gyanesh Joshi, P.K. Gupta, Vikas Rana∗ Cellulose & Paper Discipline, Forest Products Division, Forest Research Institute, Dehradun-248006, Uttarakhand, India

a r t i c l e

i n f o

Keywords: Cellulose and derivatives Hemicelluloses Starch and derivatives Bio-polymeric additive Pulp and paper manufacturing Paper industries

a b s t r a c t Renewable and bio-based materials have gained great interest on an industrial scale owing to environmental issues. Paper industries also are constantly exploring bio-resources for intrinsic chemico-physical property enhancement of paper and paper products. These bio-resources will potentially increase their cyclability besides making paper compatible beyond traditional uses. Mechanical beating or use of chemical additives or the combination of these methods are widely used to improve critical paper characteristics such as strength, surface smoothness, density, brightness, filler retention, water and grease resistivity etc. These chemical additives as mill effluents are hazardous and have detrimental effect on environment. So, to move ahead of traditional practices, the present review discusses about the production and utility of abundantly available renewable bio-polymers and their products such as starch, cellulose, plant-based proteins, microbial biopolymers, animal-based biopolymers, and natural gums etc. They represent ample prospect in terms of research and development on their functionality and industrial applications.

1. Introduction The key to sustainable chemical processes on an industrial scale requires the development of eco-friendly products from renewable resources (Beard, Ledward & Sergeeva, 2017). In an era of plastic menace followed by a ban of plastic based handy materials in many countries (European commission, 2011; Jambeck et al., 2015; Rochman et al., 2013), paper serves to be an excellent alternative medium that can be extensively used in various applications ranging from printing/writing, packaging, household products, micro-fluidic devices and so on. Paper is lightweight, biodegradable, mechanically stable and a recyclable commodity (Rastogi & Samyn, 2015). Researchers are involved in the development of various kind of products by zero chemical use and discharge for the maintenace of enviornment sustainability (Gupta, Joshi, Rana, Rawat & Sharma, 2020). It can be produced from woody or nonwoody biomass or recycled fibres through chemical and/or mechanical pulping. The chemical pulping processes solubilise lignin fraction from the cellulose matrix, followed by the conversion of the later into paper sheets (Shen, Fatehi & Ni, 2014). Lignin solubilization is a desirable process in paper manufacturing but loss of hemicelluloses due to peeling action of alkali and their leaching with black liquor is an unwanted phenomenon which directly impacts on pulp yield and responsible for poor strength properties in final paper sheet due to low content of hemicelluloses (Bi et al., 2021; Gulsoy & Eroglu, 2011; Malik, Rana, Joshi,

∗

Gupta & Sharma, 2020). To overcome this loss of hemicelluloses, additive pulping has been established as a tool to target high pulp yield with enhanced recovery of hemicelluloses. The commonly used pulping additives are sodium borohydride (NaBH4 ), hydrogen sulphide (H2 S) gas, polysulphide (PS) and anthraquinone (AQ) (Ban & Lucia, 2003; Gulsoy & Eroglu, 2011; Hart & Rudie, 2014; Istek & Gonteki, 2009; Olm & Tormund, 2000). Applications of one or more of these yield increasing agents are capable to stabilize the reducing ends in hemicellulosic structure, and leads to check in peeling reactions. Amongst these additives, AQ has been explored extensively due to its low cost, high efficiency towards increased pulp production and environmental protection. Further, its application for different types of lignocellulosic raw materials, categorized it separately from other pulping additives. Recently AQ has been successfully explored for pulping of different type of raw materials such as agricultural waste or residues (Ferrer, Vargas, Jameel & Rojas, 2015; Hedjazi, Kordsachia, Latibari & Tschirner, 2009; Omer, Khider, Elzaki, Mohieldin & Shomeina, 2019; Potůček, Gurung & Hájková, 2014), woods (Erisir, Gumuskaya, Kirci & Misir, 2015; Francis, Bolton, Abdoulmoumine, Lavrykova & Bose, 2008; Venica, Chen & Gratzl, 2008) and bamboos (DENiZ, Okan, Serdar & Şahin, 2017; Jahan, Sarkar & Rahman, 2015; Kamthai, 2007; Nurul, Suhaimi & Rushdan, 2015) etc. Although paper sheets from virgin (raw) biomass is superior in terms of physical properties as compared to recycled fibres, the later has

Corresponding author. E-mail addresses: ranav@icfre.org, vikasranaji@gmail.com (V. Rana).

https://doi.org/10.1016/j.carpta.2021.100050 Received 19 July 2020; Received in revised form 19 February 2021; Accepted 19 February 2021 2666-8939/© 2021 The Author(s). Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/)

S. Basu, S. Malik, G. Joshi et al.

Carbohydrate Polymer Technologies and Applications 2 (2021) 100050

Table 1 Common bio-additives used for diﬀerent grade for papers. Bio-additive

Type of Pulp/ Paper

Reference

Cationic cellulose

Carboxymethyl cellulose

- Bleached softwood kraft pulp - Recycled cardboard boxes pulp

Strand et al., 2017; Tarrés et al., 2018

Cellulose nanoﬁbers

Tarrés et al., 2018; Delgado Aguilar et al., 2015; Espinosa et al., 2015; Jin, Tang, Liu, Wang & Ye, 2021

Cationic starch

- Bleached softwood pulp with pine/spruce ratio 70:30 - Bleached softwood kraft pulp - Bleached bagasse soda pulp

Ulbrich et al., 2012; Strand et al., 2017; Hamzeh, Ashori, Khorasani, Abdulkhani & Abyaz, 2013

Hemicelluloses

- Sulphate kraft pulp - Eucalyptus kraft pulp

Lima et al., 2003

Chitosan

- Bleached bagasse soda pulp - Old corrugated containers (OCC) recycled pulp

Hamzeh et al., 2013; Bhardwaj et al., 2016

Carrageenan

- Bleached pinewood kraft pulp

Liu et al., 2017

Proteins (soy, cottonseed)

- OCC, Neutral sulphite semichemical pulp (NSSC), Virgin kraft pulp - Whatman paper, speciality paper

Salam et al., 2015; Cheng et al., 2017

Guar gum

- Tissue Paper

Dasgupta, 1999

Bleached chemithermo-mechanical pulp (BCTMP) Recycled pulp Unbleached wheat straw soda pulp Unbleached bagasse soda pulp

Recycled cardboard boxes pulp Bleached kraft hardwood pulp (BKHP) Semichemical wheat straw pulp Food packaging paper

been in focus owing to environmental intendancy measures. The loss in strength properties by recycling of fibre is ascribed to its repetitive drying phase, which results in irreversible hornification of the fibres. Since, the hornified fibres fail to achieve their actual configuration comparable to its virgin state, the inter-fibre bonding (interaction of functional bonding groups like carboxyl, hydroxyl and carbonyl) is largely affected (Fernandes Diniz, Gil & Castro, 2004; Hubbe, Venditti & Rojas, 2007; Minor & Atalla, 1992; Nazhad & Sodtivarakul, 2004). A number of chemicals are used in the manufacturing of paper sheets and paper-based products to abridge these gaps in recycled fibres and also enhance the performances of virgin fibres. These chemical additives are employed to engineer conventional paper properties like strength, printability, opacity and brightness. Besides these features, additives can confer special attributes to paper based cellulosic fibres such as gas barrier, magnetic properties, superhydrophobicity, flame retardancy, electrical conductivity, photocatalytic activity etc. (Arbatan, Zhang, Fang & Shen, 2012; Lahtinen, Nättine & Vartiainen, 2009; Shen, Song, Qian & Ni, 2011). However, paper mill effluents comprise of these chemical additives and happen to be detrimental to living forms since they can disturb the overall systemic behaviour in species. Moreover, such effluents often result in oxygen depletion of water bodies and the aquatic organisms are posed with alarming threats of anoxia (Bijan & Mohseni, 2004; Kim Oanh et al., 1999; Lacorte et al., 2003; Thacker, Nitnaware, Das & Devotta, 2007). Hence, more sustainable additives can be selected on the basis of relevant criteria including low toxicity, compatibility with the host material, retention capability and expense. The application of bio-polymers has been a successful method to minimize the risk of environmental abasement and enhance the strength properties of cellulosic fibre networks in paper production (Fatehi, Qian, Kititerakun, Rirksomboon & Xiao, 2009). Natural polymers like starch (cationic, anionic, oxidized starch etc.) (Johansson, Lundström, Norgren & Wågberg, 2009; Lindström, Fellers, Ankerfors & Nordmark, 2016; Shen et al., 2014), gums (Lee, Lee & Youn, 2005; Lima, Oliveira & Buckeridge, 2003), car-

Gao et al., 2016; Rana et al., 2021

rageenan (Liu, Li & Xie, 2017), soy protein (Salam, Lucia & Jameel, 2015), crop grain based gluten (Andersson, 2008; Guazzotti, Marti, Piergiovanni & Limbo, 2014), molasses (Fahmy, 2014), cellulose derivatives (Fatehi et al., 2009; Lindström et al., 2016; Shen et al., 2014), chitosans (Balan, Guezennec, Nicu, Ciolacu & Bobu, 2015), alginates (Andersson, 2008) etc. serve as additives in paper production to address diverse functions starting from strength addition to coating, sizing agents to retention aids (Andersson, 2008; Ren, Peng, Peng & Sun, 2011; Zakrajšek & Golob, 2009). Table 1 represents the application of some common bio additives for their use in diffeent type of pulp and paper manufacturing. Nature of charge on the biopolymers or their derivatives further influence the interactive behaviour with negatively charged paper furnish. Anionic biopolymers do not readily interact in bonding as the paper furnish is itself anionic in nature. Anionic biopolymer requires an additional cationic unit such as alum which act as an intermediate for their ability to enhance fibre bonding. In case of anionic biopolymer, the concentration of alum and pH (4.2–4.7) of the system plays a vital role in retention and adsorption of the biopolymer. The use of cationic and anionic biopolymer together provides flexibility in use of anionic biopolymers as the need of alum is eliminated in this case. The anionic biopolymer should be added first followed by the cationic biopolymer in the system for avoiding the system shear. Photographic grade paper is one such example of combination of anionic and cationic polymer (Gao, Li, Shi & Cha, 2016; Read, 1983). The surface charge density of a biopolymer could reverse after cationic or anionic modification. The surface charge density of cationic modified cellulose increases in comparison to unmodified cellulose fibres. However, it was much greater in case of cationic starch. The addition of cationic modified biopolymer could decrease the zeta potential because of existing positive charge. On the other hand, the zeta potential of pulp suspension increases on addition of anionic modified biopolymer (Gao et al., 2016; Read, 1983).

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Our research team have been dedicatedly working in the ﬁeld of carbohydrate chemistry as well as functional modiﬁcation of cellulose to promote sustainable and environment friendly measures in pulp and paper technology (Gupta et al., 2020; Joshi et al., 2019, 2015; Joshi, Naithani, Varshney, Bisht & Rana, 2017; Rana, Das, Gogoi & Kumar, 2014; Rana, Malik, Joshi, Rajput, & Gupta, 2021). The purpose of the present review is to bring together and explicitly discuss the production, functional-chemistry and applications of bio-based polymers as substitutes of harmful chemical additives and depleting fossil based chemicals (Shen et al., 2014) used in pulp and paper industries. This review mainly covers the topic for the duration of last two and half decades i.e., studies carried out from 1995 to 2020.

tion parameters with varying raw material, due to their difference in fibre morphology and chemical makeup (Gao et al., 2016). Although many processes have been reported regarding the production of cationic cellulose, alkalization-cationization dual step conversion has been the most effective one (Moral, Aguado, Ballesteros & Tijero, 2015). Alpha cellulose extracted from a cellulosic biomass can be etherified with 2‑hydroxy-3-trimethyl ammonium propyl group by the reagent 2,3-epoxypropyltrimethyl ammonium chloride (EPTAC). Since this chemical is toxic and highly unstable, alternatively 3‑chloro-2hydroxypropyltrimethyl ammonium chloride (CHPTAC) can be used. The cationization process is preceded by an essential alkali mediated charging procedure of the hydroxyl groups of cellulose (Fig. 1) (Khalil, Beliakova & Aly, 2001; Liu, Ni, Fatehi & Saeed, 2011; Rana et al., 2021; Su et al., 2016). The degree of substitution of quaternary ammonium group on the cationic cellulose can be confirmed by determination of nitrogen content before and after modification (Moral et al., 2015). Since the cationic modification of cellulose makes its surface positively charged, the same when used as an additive while paper making results in high filler retention, surface homogeneity, improved drainage property, improved absorption of anionic fines and strength enhancement (Halab-Kessira& Ricard, 1999; Montplaisir, Chabot & Daneault, 2006; Sain & Boucher, 2002; W. Xie, Feng & Qian, 2008). Gao et al. (2016) have specifically emphasized on the production and utilization of cationized cellulose fibrils (CCF). CCF additive has comparable influence of paper strength enhancement (2–3% tensile index improved) as done by popular cationic starch (CS) additive. Tensile index is the maximum force per unit width developed in a paper specimen before rupture under prescribed conditions divided by grammage (gsm) of paper. The authors also found that CCF confers slightly improved (∼12%) tear strength in paper than CS at low (2–4%) concentrations. Hence cationic cellulose can be considered as a promising alternative of conventional synthetic cationic poly-electrolytes used for paper strength enhancement.

2. Cellulose and derivatives Cellulose is the most abundant polysaccharide available in nature as a primary structural constituent of plant cell wall composed of 𝛽(1–4) linked d-glucose units (Fig. 1). Apart from plants, cellulose is also found in bacteria from various genera like Aerobacter, Agrobacterium, Gluconacetobacter, Acetobacter, Azotobacter, Achromobacter, Escherichia, Sarcina, Salmonella and Rhizobium. Since cellulose is mechanically strong, renewable and biodegradable, it has been in focus for diverse small to large scale applications (Rangaswamy, Vanitha & Hungund, 2015). Cellulose is the backbone of pulp and paper products. To further broaden its application domain, the multiple hydroxyl groups of the cellulose can be modified with chemical agents. Typically, cellulose derivatives are resultants of esterification and/or etherification of hydroxyl groups of cellulose. Apart from these, nano-cellulose has gained attention as an application tool in material science innovations as well as biomedical applications in recent times (Gao et al., 2016; Lahtinen et al., 2014; Shaghaleh, Xu & Wang, 2018). The chemical and physical properties of cellulose derivatives depend upon the type of substituting group, the degree of substitution (DS), the uniformity of substitution and the length of the cellulose molecules. In practice, it is very difficult to completely replace all the hydroxyl groups present in cellulose by other functional groups due to steric factors. The steric crowding may inhibit complete reaction. Accessibility, another factor may restrict the complete replacement of hydroxyl groups. Since the reactions are conducted under heterogeneous reaction environment, not all the hydroxyl groups may be accessible to the reaction, principally those in the crystalline regions. In overall, not all the accessible hydroxyl groups are equally reactive. The three hydroxyl groups of glucose units differ in their reactivity and the relative rates are not necessarily the same for other reagents. Most of the commercial cellulose derivatives are the products of only partial reaction, i.e. they contain a definite proportion of unsubstituted hydroxyl groups. The physical and chemical properties of cellulose derivatives are strongly affected by the DS and the degree of polymerization (DP). Properties that are mostly influenced by fluctuating the DS are the solubility, swelling and plasticity. Derivatives of low DS are more sensitive to water. Derivatives having high DS with nonpolar substituents, the water solubility is decreased, the sorption of water is decreased, and the solubility in organic solvents is increased. On the other hand, the plasticity is increased by the substitution of nonpolar groups. If the mechanical properties are important in the final end product, a balance must be struck between a low DP, which will confer ease of fabrication, and the somewhat higher DP crucially required for adequate mechanical properties (Mcginnis & Shafizadeh, 1979). Some common derivatives of cellulose and their route of synthesis are presented in Fig. 1 (Abdel-Halim, 2014; De Carvalho Oliveira et al., 2010; Joshi et al., 2015, 2019; Rana et al., 2021).

2.2. Carboxymethyl cellulose (CMC) There has been rigorous research and commercial applications when it comes to carboxymethyl cellulose. It is a versatile cellulosic product that can be synthesized from plant based biomass and/or recycled fibres and finds its use beyond traditional paper science (Fatehi, Kititerakun, Ni & Xiao, 2010; Joshi et al., 2015). CMC is an anionic polymer with high surface charge (negative) that has been identified as a potential strength enhancer in papermaking. Its absorption onto fibres enhances under acidic conditions (Jokinen, Niinimäki & Ämmälä, 2006; Watanabe, Gondo & Kitao, 2004). The synthesis of carboxymethyl cellulose (Fig. 1) proceeds in the same manner as that of cationic cellulose i.e. alkali mediated activation of hydroxyl group followed by etherification (carboxymethylation) [Williamson’s ether synthesis followed by carboxymethylation in SN 2 mechanism]. The commonly used carboxymethylating agent is sodium monocloroacetate under optimized conditions of temperature, time and chemical concentration depending upon raw material type (Joshi et al., 2015; Tijsen, Kolk, Stamhuis & Beenackers, 2001; Varshney & Naithani, 2011; Varshney et al., 2006). In a general context, carboxymethyl cellulose improves the hydrophobicity of paper based (cellulosic) products, enhances surface strength, improves oil resistance, decreases porosity (increased air resistance) and thickens coating materials (rheology modifications) etc. (Dulany, Batten, Peck & Farley, 2011; Holik, 2006; Shen & Qian, 2012; Tang, Zhou, Zhang & Zhu, 2013). Delving deeper into the properties of CMC, the work of Taggart, Schuster and Schellhamer (1991) offers a clear picture of CMC when used alongside conventional starch derivatives. CMC (with DS∼ 1.4 M/AGU) in an aqueous solution (0.1–5%) has been specifically utilized as a retention aid and strength enhancer alongwith cationic starch onto a paper furnish. Interestingly, the adsorption of starch increases by ∼60% when added in combination to CMC and by ∼30% when CMC is added after

2.1. Cationic cellulose Standardized procedures have been devised for the production of cationic cellulose; however, the same requires unique optimiza3

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Fig. 1. Preparation routes for diﬀerent cellulosic products used in paper making .

starch (starch:CMC=10:1). However, separate addition (starch followed by CMC) was found to be most effective in enhancing the Mullen index by ∼35%, tensile index by ∼23% and filler retention by ∼50%. The work establishes the properties of CMC as strength additive and retention aid by utilizing different commercial starch and CMC varieties as well as different pulp types e.g. virgin chemical pulp, mixed pulp, recycled pulp etc. with consistent results.

kali cellulose formation (by treating with sodium hydroxide under controlled physico-chemical conditions) followed by a reaction with gaseous ethylene oxide. This reaction results in a series of etheriﬁcation of the hydroxyl groups by converting the same into hydroxyethyl groups. This makes the overall molecule water soluble. Hydroxyethylation can also be done in a single step by a treatment of cellulose with high ethylene oxide concentration (200% w/w of cellulose) in presence of higher alkali charge (>20%) at a considerably high temperature (100 °C) and often under high pressure. Hydroxyethyl cellulose has superlative capabilities as thickening, binding, emulsifying, and dispersing agent. It has superior water retention capabilities hence producing solutions of varying viscosities. For these properties, it has been utilized in paper industry as a surface sizing and pigment coating agent. Hydroxyethyl cellulose (at a concentration 0.5–2%) has also been found to have

2.3. Hydroxyethyl cellulose Hydroxyethyl cellulose is another attractive cellulose derivative which is water soluble and non-ionic. It is prepared from bleached/deligniﬁed cellulosic substrate by a two step process (Fig. 1). Industrial production of hydroxyethyl cellulose comprises of active al4

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enhanced the dry tear strength of paper by 14% in bleached wood pulp (Abdel-Halim, 2014; Bülichen, Kainz & Plank, 2012; Miura, Nishizawa, Nishimura & Sekigawa, 1972; Tang et al., 2013).

tensile index of paper made from Eucalyptus bleached pulp. The tensile index of the handmade paper from same pulp has been enhanced by ∼11% with the action of NCC. The application of NCC ranges from pulp and paper industries to pharmaceuticals and from food to cosmetics (Bai, Holbery & Li, 2009; De Jesus Silva, De Almeida, De Oliveira, Da Silva & De Mendonça Neto, 2013; Ditzel et al., 2017; Liu, Chen, Yue, Chen & Wu, 2011; Peng, Dhar, Liu & Tam, 2011).

2.4. Nanocellulose The latest and the most acclaimed area of applied cellulosic science is the production and application of nanocellulose (Hubbe, 2019; Raghav, Sharma & Kennedy, 2021). There are primarily two types of nanocellulose:

2.5. Other cellulose derivatives Methyl cellulose is another important water-soluble cellulose derivative produced by alkaline activation of cellulose under heat treatment followed by a reaction with methyl sulphate or methyl chloride (Fig. 1). It works as adhesives, thickeners, binders, emulsiﬁers and stabilizers. Methyl cellulose is widely used as sizing agents in paper industries (Karrasch, Jäger, Saake, Potthast & Rosenau, 2009; Lavanya, Kulkarni, Dixit, Raavi & Krishna, 2011). Another derivative, hydroxypropyl cellulose, is produced commercially by alkali activation followed by reaction with propylene oxide at high temperature (120–160 °C) (Miura et al., 1972) (Fig. 1). Hydroxypropyl cellulose and hydroxypropyl methyl cellulose (HPMC) are used as surface coating and barrier additives. HPMC as coating additive controls water absorption capacity, ﬂexibility and mechanical properties of paper (Khwaldia, 2013; Klass, 2011; Sothornvit, 2009).

(a) Nano-Fibrillated Cellulose (NFC) (b) Nano-Crystalline Cellulose (NCC) NFC or microfibrillated cellulose differs from NCC or cellulose nanocrystals in the process of manufacturing; the former is produced from mechanical shearing whereas the latter is manufactured purely by chemical hydrolysis (Arbatan et al., 2012; Aulin, Lindström & Strom, 2013; Lavoine, Desloges, Dufresne & Bras, 2012; Martins et al., 2012; Mertaniemi, Laukkanen, Teirfolk, Ikkala & Ras, 2012; Pajari, Rautkoski & Moilanen, 2012; Syverud & Stenius, 2009). The disintegration process for obtaining NFC from cellulosic raw material differs with nature of raw material. Enzymatic and chemical pre-treatment methods of cellulosic mass or delignified pulp prior to mechanical homogenization have also been reported. This process predominantly yields homogeneous fibrils of width ranging between 3 and 20 nm. Since, the composition of fibres is conserved; the fibrils have anionic surface charge. This negative charge is conferred by carboxyl groups of hemicellulosic origin (Ahola, Österberg & Laine, 2008). This surface to charge ratio is the most important property of NFC that imparts mechanical strength (both wet and dry) to paper sheets (Ahola et al., 2008; Nakagaito, Iwamoto & Yano, 2005; Pääkkö et al., 2008; Saito, Nishiyama, Putaux, Vignon & Isogai, 2006). The adsorption and activity of cationic poly-electrolytes (in very low concentrations) have improved in a bi-layer system by the addition of nano-fibrillated cellulose due to increment of bonding sites provided by NFC. The wet and dry tensile strength has increased upto ∼40% by the addition of NFC. The same also indicates that NFC has the potency to replace various chemical strength additives or minimize their concentration used in paper manufacturing (Ahola et al., 2008). Sehaqui et al. (2013) have experimentally established that NFC increases the tensile index and tensile energy absorption (TEA) in unbeaten softwood pulp and the results are comparable to the same achieved by mechanical beating of identical pulp. TEA is the work done when a paper specimen is stressed to rupture in tension under prescribed conditions as measured by the integral of the tensile strength over the range of tensile strain from zero to maximum strain. It is expressed as energy per unit area (test span × width) of paper specimen. The strength indices are found to increase by 20–30% as compared to control due to improved inter-fibre stress transfer offered by NFC. This gives a significant perspective that amalgamates improvement of paper properties alongwith the reduction of energy during the production of high density paper sheets (Sehaqui, 2013; Sehaqui et al., 2012). The other form of well acclaimed nanocellulose is NCC. It can be produced on a good scale from microcrystalline cellulose obtained from acid hydrolysis of delignified lignocellulosic biomasses. Nanoscale miniaturization is commonly done by sulphate hydrolysis and high-pressure homogenization followed by differential centrifugation. NCC is generally needle shaped with dimensions around 60 × 10 nm. The acidic production of NCC imparts negative charges on its surface (Ditzel, Prestes, Carvalho, Demiate & Pinheiro, 2017). Hence it functions as an excellent binder in paper production besides conferring the same with barrier, magnetic and electronic properties. Another unique feature of NCC is the capability to form chiral nematic (parallel orientated crystal) phase beyond a critical threshold. Anionic nano-crystalline cellulose has shown synergistic effect with cationic starch (charge ratio 1:1) to increase the

3. Hemicelluloses Hemicellulose unlike cellulose is a complex branched polymer comprising pentosans and hexosans found in plant cell walls. Based on origin hemicellulose may be broadly classified in to hardwood hemicellulose (Glucuronoxylans and glucomannan), softwood hemicelluloses (galactoglucomannan, and arabinoglucuronoxylan) and storage hemicellulose (Galactomannans). Glucouranoxylan is composed of 𝛽-d-(1→4) xylose units backbone with acetyl substitution at C-2 or C-3 of the xylose and side chains of 4-O-methylglucuronic acid units whereas glucomannans mainly composed of (1→4) linked 𝛽-d-glucopyranose and 𝛽d-mannopyranose units. Galactoglucomannans consist mainly 𝛽-(1→4) backbone of d-glucose and d-mannose with side chains of galactose moieties. 𝛽-(1→4) linked d- xylopyranose units with (1→2) linked branches of d-glucopyranosyluronic acid is the main feature of arabinoglucuronoxylan with 𝛼-(1→3) linked side chains of l-arabinofuranose (Rowell, Pettersen, Han, Rowell & Tshabalala, 2005). The interaction varies with the degree of galactosylation of the linear xyloglucan backbone (Buckeridge, Dietrich & de Lima, 2000; De Lima & Buckeridge, 2001; Vincken, De Keizer, Beldman & Voragen, 1995). Galactomannans are chief storage hemicelluloses in leguminous seeds having linear 𝛽-(1–4) linked mannose with single galactosyl branch units (Buckeridge, Pessoa dos Santos & Tiné, 2000). Hemicellulose enhances fibrillation in pulp fibres as well as plasticity and surface area thereby conferring increased fibre-fibre bonding and subsequently higher tensile strength in paper sheets. Ascribed to its hydrophilic properties, hemicelluloses increase the swelling of fibres, hence resulting in increased fibre flexibility and bonding conformations (Anjos, Santos & Simoes, 2004). So, hemicelluloses can act as binders while imparting improved tensile and burst indices. However, hemicellulose as additive has been proven to be more effective than in-situ hemicelluloses in terms of strength promotion due to the fact that greater part of in-situ hemicelluloses lie deeper into the cell wall and cannot participate in fibre bonding. Hemicellulose content reduces refining energy of pulp, although higher hemicellulose (∼20%) content has been shown to be detrimental to pulp strength (tear vs. tensile) as compared to lower hemicellulose content when the refining energy is increased (2–5 N/m) (Mobarak & Fahmy, 1973). It has also been found that hemicellulose as wet end additives provide better strength to pulp fibres when added after refining due to enhanced hydrogen bonding between cellulose and hemicellulose (Anjos et al., 2004; Mobarak & Fahmy, 1973). 5

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Lima et al. (2003) have emphatically portrayed the property enhancement of paper-sheets made from Eucalyptus pulp by the action of hemicellulose from different legumes. The article experimentally demonstrated that after addition of hemicellulose, tear and burst indices significantly improved upto a maximum of 30% and 20% respectively. Furthermore, retention of fines enhanced by 3% [Increase in Apparent Specific Weight (ASW in kg/m3 )], tensile index by 11%, TEA by 19% and specific elastic modulus by 3% as compared to control (without added hemicellulose) samples. An interesting fact has been established by Mobarak and Fahmy (1973) in their research on hemicellulose additives. They have shown that the retention of added hemicellulose which was previously extracted from hardwood has lowered (by ∼4%) in hardwood pulp itself with respect to the retention of hemicellulose obtained from straw. Besides, straw pulp has 5% enhanced capacity to retain hemicelluloses than hardwood. Owing to this fact, sheet prepared from straw pulp was more compact than that of hardwood pulp after hemicellulose addition.

sulfonium, phosphonium etc. forms. However, alkaline charging followed by a reaction with 3‑chloro-2-hydroxypropyltrimethylammonium chloride (CHPTAC) is the most common method for producing cationic starch (Fig. 2). Gelatinized (gelatinization of starch increases the reaction rate) starch in presence of alkali and CHPTAC forms quaternary ammonium cationic starch ether at temperatures around 40 °C with a starch concentration of 25–35% (w/v) (Ghasemian, Ghaffari & Ashori, 2012). Sodium sulphate is often used to maintain the integrity of the unswollen starch granule during the entire reaction period. A reaction efficiency of around 85% and degree of substitution around 0.5 is considered legible for the application of the modified product. Interestingly, amylose and amylopectin have different adsorption potential in pulp fibres and amylose is more potent in getting adsorbed. Although cationic starch shows low Langmuir type isotherms (rate of adsorption as a function of applied pressure), its affinity to fibre-fibre bonding is comparatively higher than other modified starch forms. The adsorption of cationic starch onto fibres depends upon the electrolyte concentration in the system (Ulbrich, Radosta, Kießler & Vorwerg, 2012). The properties conferred by cationic starch can be grouped in four main sections: (i) Enhancement of mechanical strength, (ii) Retention aids to fines and fillers, (iii) Improved drainage, and (iv) Generating low toxic paper-mill effluent. The reactive cationic groups provides strong adsorption interface between fibres, fines and fillers through electrostatic attraction (Carr & Bagby, 1981; Ghasemian et al., 2012; Lee et al., 2002; Pettersson, Höglund & Wågberg, 2007; Solarek, 1986; Ulbrich et al., 2012; Xie, Yu, Liu & Chen, 2006; Yang, Qiu, Qian & Shen, 2013; Zakrajšek, 2008; Zakrajšek & Golob, 2009). Ghasemian et al. (2012) have repored that cationic starch can significantly increase the tear, tensile and burst indices of virgin and mixed pulps. A maximum tensile index of 29.2 Nm/g, tear index of 18.7 mKm2 /g and burst index of 2.74 kPam2 /g was observed in handsheets made from mixed pulps with cationic starch additive. The strength properties have increased by 2–3 folds as compared to untreated pulp. Ulbrich et al. (2012) have statistically established the correlation between cationic starch adsorption onto cellulose fibres and its effect on strength enhancement.

4. Starch and derivatives 4.1. Starch Starch is the widely used additive in paper industry showing diverse array of functional attributes owing to its chemical compatibility, abundance and inexpensiveness. Commercial starches are extracted from grain crops, tubers and legume plants. It is a biopolymer formed by the amalgamation of polymeric glucans viz. amylose and amylopectin linked by glycosidic bonds. Amylose is a linear chain of repetitive glucose units linked by 𝛼−1,4-glucosidic bond, whereas amylopectin is a highly branched macromolecule, which consists of short chains of (1→4)-linked 𝛼-d-glucose with (1→6)-𝛼-linked branches. The crystallinity of starch depends upon the relative content as well the structural orientation of amylose and amylopectin. The high viscosity (because of extensive hydrogen bonding of amylopectin) of native or unmodified starch limits its overall accessibility when used as additives in paper making. This drawback is counteracted by plasticization (using solvents like glycerol, sorbitol etc.) or depolymerisation and/or modification (chemical or enzymatic) or blending with other compounds or combination of ionic starch forms (Tomasik & Zaranyika, 1995). Chemical modification is the most frequently used method of commercial starch derivation into functional products like cationic starch, oxidized starch, hydroxyethyl starch etc. For chemical modification, the substitutable hydroxyl groups of starch are to be taken into account. Hydroxyl group at C6 in starch is primary alcohol whereas C2 & C3 are secondary ones; in the presence of glucose ring portion –CHOH–CHOH- instead of C2 & C3 carbons, starch is a triol, whereas glycosidic bonds at this juncture makes it a hemiacetal. The three hydroxyl groups in glucose subunit make starch susceptible to a number of possible modifications. The basic chemical modification of starch is usually done via oxidation, esterification and etherification. Unmodified starch as an additive has been proved to have conferred mechanical strength (to some extent), surface smoothness and optical property to paper (Bajpai, 1999; Hermansson & Svegmark, 1996; Jane, 1995; Larotonda, Matsui, Sobral & Laurindo, 2005; Matsui et al., 2004; Perry & Donald, 2000; Santayanon & Wootthikanokkhan, 2003; Tomasik & Zaranyika, 1995; Vásconez, Flores, Campos, Alvarado & Gerschenson, 2009). Preparation route and structure of some important starch derivatives are presented in Fig. 2 (Colussi et al., 2015; Fu, Zhang, Ren & BeMiller, 2019; Nasir, Abdulmalek & Zainuddin, 2020; Yi, Zhang & Ju, 2014).

4.3. Oxidized starch Oxidative modification of starch is another popular modification procedure employed to make highly viscous native starch to be industrially compatible. The primary and secondary alcohol groups are oxidized under controlled set of conditions to substitute hydroxyl groups with reactive aldehyde and/or carboxyl groups. The modification agents are chosen on the basis of origin and final utilization of the product. Commercially produced oxidized starch are modified at 25–30 °C with low oxidant concentrations (<3%) in controlled batch processes (in presence of oxygen and/or transition metal ion catalysts). Although the most common oxidant used is sodium hypochlorite (Fig. 2), other chemicals such as permanganates, hydrogen peroxide, periodates, persulphates, dichromates etc. were also practiced in recent past (Jonhed, 2006). The carbonyl or carboxylic groups present in anionic (oxidized) starch prevents retrogradation of starch and hence generates a stable modified product that can exert its function under high temperature (cooking) systems besides lowering gelatinizing temperature of starch itself (Vanier, El Halal, Dias & da Rosa Zavareze, 2017). Ascribed to this property, oxidized starch is popularly used as a coating material in paper industry since it prevents clustering of pigments in coating formulations (Jonhed, 2006; Lee et al., 2002; Lewicka, Siemion & Kurcok, 2015; Shen et al., 2014; Vanier et al., 2017; Xie et al., 2006).

4.2. Cationic starch 4.4. Other starch-derived additives Cationic starch is the most popular starch derivative in paper industry imparting useful properties to various kinds of pulp for quality enhancement. It is commercially produced in amino, ammonium,

Acetylated starch is another popular starch derivative of commercial value in paper and food industries. It is produced commercially by alkali 6

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Fig. 2. Diﬀerent starch products as paper additives.

activation followed by acetylation with reagents like acetic acid or acetic anhydride or ketene or vinyl acetate or a combination of all (Fig. 2). Acetylation of starch prevents its retrogradation, reduces enthalpy or ∆H (which depicts the alteration of amylopectin helices) and subsequently reduces crystallinity (improves reactivity). These properties invoke acetylated starch to be an excellent surface sizing agent in paper industry (Ayucitra, 2012; Bello-Pérez, Agama-Acevedo, Zamudio-Flores, Mendez-Montealvo & Rodriguez-Ambriz, 2010; Chen, Kaur & Singh, 2017; Halal et al., 2015; Khalil, Hashem & Hebeish, 1995; Rutenberg & Solarek, 1984). Hydroxypropyl starch, another starch derivative used

for paper coating and surface engineering, is commercially produced in presence of alkali and propylene oxide. Hydroxypropylation again reduces gelatinization temperature, increases swelling power, solubility and improved freeze-thaw stability of starch (Jonhed, 2006; Kaur, Singh & Singh, 2004; Rastogi & Samyn, 2015). 5. Chitosan Chitosan is a deacetylated derivative of chitin (Fig. 3), which happens to be the second most abundant polymer after cellulose in na7

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Fig. 3. Structure of chitosan and its cyanoethyl derivative.

ture found in the exoskeletons of crustaceans, molluscs, insects and also fungi. The main commercial sources of chitin are shrimp and crab shells. Chitosan can be obtained by enzymatic deacetylation of chitin or treatment of the later with NaOH at high temperature. The chemical backbone of chitin unlike cellulose consists of linear chains of complex glycan 𝛽-(1–4)−2-acetamido-2-deoxy-d-glucopyranose, from which chitosan has been derived to possess amine instead of acetamide group. Chitosan unlike its parent molecule has greater solubility due to this substitution (Cissé, Montet, Tapia, Loiseau & Ducamp-Collin, 2012; Puvvada, Vankayalapati & Sukhavasi, 2012; Rinaudo, 2006). Commercially used chitosans are low (50–150 kDa) and medium (700–1000 kDa) molecular weight varieties. Chitosan has been successfully explored to have influenced mechanical, hydrophilic, retention and barrier properties when used at low concentrations (1–2%) (Fernandes et al., 2010). When used in surface engineering, ‘low molecular weight-low concentration’ (LMW-LC) chitosan has been found to reduce water adsorption by ∼20% (increase water barrier properties) in paper than ‘medium molecular weight-higher concentrations’ (MMWHC). This fact can be positively correlated with identical studies resulting in reduction of Cobb-60 Index (water absorption capacity) by 80– 90% and reduction in water vapour transmission rate (WVTR). The same has also been found to lower the hardness and roughness by ∼50% (with and without fillers) of papers, hence proving to be an excellent surface sizing agent. LMW-LC enhances the dry strength of paper (dry strength is inversely proportional to the concentration of LMW chitosan) which is established by a considerable increase in tensile index (reported to be ∼10%) and burst index (reported to be ∼10%) (Habibie, Hamzah, Anggaravidya & Kalembang, 2016). Electron-micrographs and other chemical analytics in earlier studies have confirmed the equilibrium stoichiometry between LMW-LC chitosan and cellulose present in paper. This property may be due the fact that LMW-LC presents with greater area (homogeneity) and hence scope for inter fibre bond formation than MMW-HC. When it comes to wet end addition, chitosan (concentration ∼1–3%) has also been reported to improve the burst strength by 20–30%, breaking length by 20–30% and wax pick number (or surface strength index) by ∼2 units in paper boards from reclaimed pulp (Bhardwaj, Bhardwaj & Negi, 2016). Wax pick number is the average highest numerical designation of the wax that does not disturb the surface of the paper. It is also called the Critical Wax Strength Number and it corresponds to the surface strength of paper. Generally, a pick occurs when the surface of the paper specimen blisters, breaks, or lifts and/or coating substance adheres to the surface of the wax. Chitosan, chitosan derivatives like cyanoethyl chitosan (Fig. 3) and other biopolymers (e.g. carboxymethyl cellulose etc.) have also been found to have synergistic effects on paper strength properties (Bhardwaj et al., 2016; Nada, El-Sakhawy, Kamel, Eid & Adel, 2006). The dielectric properties and thermal stabilities also improve in paper by the addition of chitosan derivatives. Chitosan in solution form (in acetic acid) has been found to

confer antimicrobial properties against both gram positive and gramnegative bacteria in paper. Evidently, the diverse array of functional attributes makes chitosan a promising bio-polymeric additive for paper industry (Bhardwaj et al., 2016; Fatehi et al., 2010; Fernandes et al., 2010; Habibie et al., 2016; Miranda et al., 2013; Nada et al., 2006; Nassar, El-Sakhawy, Madkour, El-ziaty & Mohamed, 2014; Rastogi & Samyn, 2015; Vainio & Paulapuro, 2005; Zakaria et al., 2015). 5. Proteins 5.1. Soy-based Soy flour is an abundantly available bio-product of soybean oil industry that has been reported to be comprised of 51% protein, containing 18 polar and non-polar amino acids. The polar amino acids take part in inter-fibre bonding through chemical cross-links thereby conferring enhanced mechanical, thermal and hydrophilic properties. Crosslinked soy protein has been proved to have increased the mechanical strength of bio-degradable polymers and paper (Chabba, Matthews & Netravali, 2005; Dastidar & Netravali, 2013; Kellor, 1974). Chemically cross-linked [by using diethylenetriaminepentaacetic acid (DTPA) and sodium hypophosphite] and conjugated soy protein (with chitosan) have been explored for strength enhancing effects on virgin as well as recycled (hornified) pulp fibres. The same has been found to have increased tensile index of different types of pulp. In a detailed study of soy flour (Salam et al., 2015), the authors established the capability of soy flour glycoprotein as a mechanical property enhancer. In the mentioned study, when added at a concentration of 1.5% on reclaimed pulp, soy flour glycoprotein has increased the tensile and burst indices of handsheets by ∼5%. Soy flour protein also under similar conditions enhanced the tensile and burst indices by ∼5%. Soy flour protein conjugated with chitosan increased the tensile and burst indices by ∼20% whereas soy flour glycoprotein enhanced the same by ∼10% and 20% respectively. Soy flour protein (as well as glycoprotein) conjugated with DTPA and chitosan increased the tensile and burst indices by ∼50%. Soy flower glycoprotein-DTPA-chitosan conjugate (1%) improved the tensile index of reclaimed and kraft pulp handsheets by 52.6% and 57.8% respectively; burst index by 39.2% and 42.5% respectively and compression index by 39.9% and 48.6% respectively. The superlative rise in mechanical properties are conferred by intense inter-fibre bond formation (H-bond and esterification) by -OH, -COOH and -NH2 functional groups in glycoprotein conjugates. In addition to the soy protein, cotton seed protein was also used as a wet and dry strength additive in paper (Cheng, Villalpando, Easson & Dowd, 2017). 5.2. Cottonseed protein The global production of cottonseed accounts to 39–44 million metric tons (MMT) per annum during the year 2014–17 which imply 8.3 8

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to 9.4 MMT availability of cotton seed protein (Balandrán-Quintana, Mendoza-Wilson, Montfort, & Huerta-Ocampo, 2019). Globulins are the predominant cottonseed proteins followed by albumins and gliadins. Utilization of cotton seed protein as a wet and dry strength additive in paper was studied by Cheng et al., 2017. The authors reported that on addition of 11% cottonseed solution to paper, the dry and wet strength increased by 33 and 16% respectively. Moreover, the combined use of cottonseed protein and an acid (acetic, adipic, aspartic, and citric acids) to promote adhesion resulted in even greater dry paper strength as compared to wet strength of paper. Since very limited work has been done on the use of cotton seed protein as strength additive during paper manufacturing, there is a scope for research and development.

glutens can be classiﬁed as gliadins (alcohol soluble) and glutenins (alcohol insoluble). Commercially available glutens (purity 80–90%) can be used in coating formulations for improved oxygen as well as chemical contaminant (grease) barriers in paperboards and packaging materials (Guazzotti et al., 2014). Wheat gluten, corn gluten and calcium caseinate have been combined to generate coating formulations and their relative adsorption rates were determined with chemical analytics. Wheat gluten has superior adsorption potential followed by corn gluten and caseinate; however, the relative amount varies with raw material of the paperboards (Andersson, 2008; Gastaldi, Chalier, Guillemin & Gontard, 2007; Guazzotti et al., 2014). 6. Gums

5.3. Casein based 6.1. Alginates Caseins are special classes of phosphorylated proteins (𝛼 S1 -, 𝛼 S2 -, 𝛽- and 𝜅-caseins) with high surface activity present in milk in an aggregated form. 𝛼- and 𝛽-Caseins although has the tendency to precipitate in low ionic solutions, 𝜅-casein oppose the precipitation, forming stable colloidal suspensions. Caseinates (sodium, calcium) are generated by precipitating casein micelles through lowering the pH of milk to 4.6. The property of caseinates to generate stable colloids and selfassembly makes it a promising agent imparting superior bonding capabilities as well as electrostatic attractions. Caseinates have been found to form stable ﬁlms in aqueous medium due to inter-chain cohesion. They have also been shown to improve mechanical properties when used as coating additives in cellulose-based packaging materials (Khaoula Khwaldia, Basta, Aloui & El-Saied, 2014). Strength, moisture barrier, oil barrier and ductile properties of paperboards have improved by coating with sodium caseinate. Combinations of sodium caseinate (10–13%) with carnauba wax (0.8%), mica (1.2%) and glycerol (0.6%) have generated superior coating formulations conferring water vapour barrier and mechanical strength to coated papers. Conjugate of caseinate with chitosan imparts thermal stability as an additive when applied to paper and paper products (Horne, 2002, 2008; Huppertz, 2013; Khwaldia, 2010; Khwaldia et al., 2014, 2006).

Alginates are natural polysaccharides found extensively in brown seaweeds (Family Phaeophyceae) typically from the genera Laminaria and Macrocystis as well as bacterial genera Pseudomonas and Azotobacter. Having a chemical backbone of 𝛽-d-mannuronate and its epimer 𝛼-l-guluronate linked by 1–4 glycosidic bonds (Fig. 4a) (Szekalska, Puciłowska, Szymańska, Ciosek & Winnicka, 2016), alginate may constitute around 40% dry weight of the organism, representing a striking analogy with cellulose in terrestrial plants (Draget, Smidsrød & Skjåk-Bræk, 2005). Bacterial alginate is synthesized by a 12-gene (alggenes) operon family under tight regulation but their polymerization as well as translocation is poorly understood (Draget et al., 2005; Remminghorst & Rehm, 2006a, 2006b; Remminghorst, Hay & Rehm, 2009). Alginates are used as thickening, stabilizing, adhesive and filmforming agents (Shen et al., 2014). Alginates are produced on a commercial scale in the form of fine fibres as sodium and/or calcium ionic forms. Sodium alginate (SA) by virtue of its film-forming ability has been proven to have enhanced bonding homogeneity with paper fibres and can be successfully utilized in combination with other additives/complexes resulting improved dry as well as wet strength (Rhim, Lee & Hong, 2006). SA has been used in eco-friendly paper additive formulations by Song, Yao and Jin (2012). From the study it was observed that, SA enhanced the adsorption of poly-electrolytes on papersheets (from bleached pine kraft pulp) and subsequently enhanced the tensile index by a maximum of ∼40–45%. Algin has also been combined with natural gums (guar, tamarind kernel polysaccharide) and used in pigment coating as well as surface sizing agents Yin & Lewis (1981). However, hydrophilic properties of alginate limits its application since it decreases water resistivity of paperboard (Hay, Rehman, Moradali, Wang & Rehm, 2013; Rhim et al., 2006; Rinaudo, 2014; Song et al., 2012; Yin & Lewis, 1981).

5.4. Whey proteins Whey proteins comprise of 18–20% of total milk proteins primarily constituted by 𝛼-lactalbumin and 𝛽-lactoglobulin. Other smaller fractions like serum albumin, immunoglobulins, lactoferrin, lactolin etc. are also present in whey protein. The diversity of amino acid composition gives whey protein high levels of structural complexities. Whey protein is heat labile and its thermal denaturation is dependant upon the pH of the medium (denaturation is inversely proportional to pH). Heat dependant co-aggregation is another astounding property of whey protein. Heat denaturation exposes the sulphahydril groups in lactoglobulins and makes it susceptible to form disulphide bonds with other proteins in the vicinity. Whey protein isolate/cellulose-based ﬁlms, produced by the action of glycerol in aqueous medium with glutaraldehyde and cellulose xanthate was combined with bee wax to form a bilayer coating system onto paperboards by heating compression (Han, Salmieri, Le Tien & Lacroix, 2010). The coating improves water barrier capacities by diminishing WVTR by 77–78%. Whey protein concentrates (80% w/w, plasticized with glycerol, sorbitol or polyethylene glycol) have also been proved to impart superior grease resistance capability hence facilitating long term storage of paperboards (Andersson, 2008; Han et al., 2010; Jovanovi, Bara & Ma, 2005; Lin & Krochta, 2003).

6.2. Guar gum Guar gum is a versatile and popular plant-based gum (exudate) obtained from Guar plant (Cluster bean or Cyamopsis tetragonolobus; Family: Leguminosae). The natural gum contains around 87% polysaccharide composed primarily of poly-d-galactose and d-mannose unitsusually in the ratio of 1:2 (polygalactomannans). The linear 𝛽-dmannopyranosyl chain has side branches of 𝛼-d-galactopyranosyl units (Fig. 4b) (Mudgil, Barak & Khatkar, 2014). Guar gum has the astounding property of maintaining a solution of constant viscosity for a prolonged period either in unmodiﬁed form or modiﬁed forms (oxidized, carboxymethylated, hydroxyalkylated etc.). Guar gum although like other galactomannan gums serve as thickeners in textile and paper industries; it has applications in various other industries on a commercial scale. Dasgupta (1999) emphatically established the strength enhancing effects of cationic and anionic guar gum by using wide range of commercially available gum forms. The study demonstrates that anionic guar gum (by reacting guar gum with caustic soda followed by monochloroacetate, propylene oxide etc. generating carboxymethyl, hydroxypropyl

5.5. Glutens Glutens are abundant storage proteins typically found in wheat and corn. The diverse protein constituents of gluten make it highly viscous and elastic. Additionally, the low hydrophilicity of gluten is attributed by its higher non-polar amino acid composition. In a broader sense, 9

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a concentration of 0.5–1.0%) have maximally enhanced the tensile index of paper between ∼10–35%. Higher molecular weight guar gum addition corresponds to considerable increase in paper strength. Usually the guar additives are added in a low pulp consistency and neutral pH (Chudzikowski, 1971; Dasgupta, 1999). A novel blend of guar with, algin and tamarind kernel polysaccharide finds its effective use in paper coating and surface sizing (Yin & Lewis, 1981). Ionic and nonionic guar gum has successfully increased the strength and retention of fillers in tissue paper manufacturing Wang (2013). Moreover, guar gum combined with precipitated calcium carbonate and organic titanium enhances fibre cross-linking and higher retention of fillers (by ∼2–8%) in paperboards (Chudzikowski, 1971; Dasgupta, 1999; Lee et al., 2005; Wang, 2013; Xie, Song, Liu & Qian, 2016; Yin & Lewis, 1981). 6.3. Carrageenan Carrageenan is a commercially important natural, abundantly available, sulphated polysaccharide (gum) extracted from red algae Gelidium elegans that has promising application in paper science and nanotechnology besides traditional uses in cosmetics, medicine and food thickening (Cadirci et al., 2016; Chen, Lee, Juan & Phang, 2016; Lin, Liang & Chang, 2016; Seo, Lee, Lee & You, 2010). Carrageenan is a polymer with alternate units of galactose and 3.6-anhydrogalactose linked by 𝛽-(1–4) and 𝛼 (1–3) glycosidic bond with 15–40% sulphated monosaccharide units, hence defining its anionic nature (Necas & Bartosikova, 2013). Commercial carrageenans are mainly constituted by three types namely 𝜅-, 𝜄-, and 𝜆-carrageenan. 𝜅-Carrageenan has one sulfate ester, while 𝜄-and 𝜆carrageenan contain two and three sulfates per repeating dimer, respectively. Fig. 4(c)−4(e) shows the structural behaviour of three types of carrageenans (Rhein-Knudsen, Ale & Meyer, 2015). Carrageenan due to its sulphate groups participate in extensive hydrogen bonding with cellulose fibers in paper by abridging the inter-fibre gaps (Liu et al., 2017). As reported earlier, by virtue of this bonding property, carrageenan as an additive confers superior strength in paper, thereby increasing tensile index by ∼25% and burst index by ∼15% when compared to sheets without carrageenan (Huq et al., 2012; Liu et al., 2017; Przybysz, Dubowik, Kucner, Przybysz & Buzała, 2016; Xie et al., 2016). 6.4. Xanthan gum Xanthan gum is produced by gram-negative yellow pigmented bacteria Xanthomonas campestris. The gum has the property to produce stable aggregates (pseudoplasticity) in aqueous medium owing to the capability of forming extensive hydrogen bonding. Hence it generates highly viscous aqueous solution even at low concentrations. Xanthan backbone comprises of pentasaccharide repetitive units having (1–4)-𝛽-dglucopyranose unit along with tri-sachharide lateral branches attached at every C-3 carbon of the alternate sugar residue of the main chain. The lateral chains consist of 𝛽-d-mannopyranose residue linked to (1– 4) 𝛽-d-glucuronic acid which is linked with (1–2) 𝛼-d-mannopyranose residue. Apart from these, pyruvate acetal groups are present at the end of d-mannopyranose (C6-OH position) unit (Patel, Maji, Moorthy & &Maiti, 2020). Fig. 4(f) represents the complex structure of xanthan gum (Patel et al., 2020). The chemical complexity of xanthan provides its capability of bonding and rheological modifications. Industrially used xanthan gum has 37% glucose, 43.4% mannose, 19.5% glucuronic acid, 4.5% acetate and 4.4% pyruvate (Lachke, 2004). Xanthan gum used alone and in combination with other gums and polyelectrolytes as wetend additive increases the tensile strength of paper (Mukherjee et al., 2014). Taggart, Schuster and Schellhamer (1992) showed that xanthan has promising capabilities as both retention aid and strength enhancer when used with starch on kraft-softwood mixed pulp. In the study, retention of starch was reported to increase by 60–70% by separately adding xanthan. The same also increased the tensile index by ∼10% and burst index by ∼35%. Besides these, xanthan has been effectively used as a

Fig. 4. Structures of common gums used as additive in paper making (a) Sodium alginate; (b) guar galactomannan; (c) 𝜅-carrageenan; (d) 𝜆-carrageenan; (e) 𝜄carrageenan; (f) xanthan.

derivatives) and cationic guar (derivatized with glycidyltrimethylammonium chloride) in synergism or alone enhances the tensile index of paper without compromising with the softness, when added to a bleached pulp furnish. Cationic guar alone (at a concentration of 1.0%) has been reported to increase tensile strength by ∼15%; whereas anionic guar (at a concentration of 1.0%) enhances the tensile index by ∼17% (Dasgupta, 1999). The blends of cationic and anionic guar (at

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ﬂocculant, paper coating agent and a rheology modiﬁer for high size press in paper manufacturing (Castro & Cheng, 2014; Lachke, 2004; Mukherjee et al., 2014; Taggart et al., 1992).

and paper industries when compared with synthetic chemical additives. With the constantly increasing price of petro-chemicals and fossil fuel based chemicals, it is important to understand the economic and environmental need to switch from chemical to renewable bio-based polymers. Most of these bio-materials are abundant and cheap (e.g. cellulose and starch based products). Furthermore, these bio-polymers can be obtained/ recycled from natural and household wastes. Recent research (Díez-Pascual, 2019) highlighted these aspects while discussing the production, impact and economical signiﬁcance of bio-based polymers in the manufacture of bio-composites. It was mentioned that although the cost of production of bio-polymers is a matter of concern, the same can be compensated from the functional diversity, properties and eco-friendliness. The approximate average price range of various commercially available biopolymers has been reviewed from the latest price lists of reputed manufactures and listed in Table 3 to provide a perspective on the commercial viability of bio-based polymers. However, a comparative economic blue-print comprising the utilization of synthetic and bio-based polymers has not yet been devised. Hence, there is an ample scope of research and analysis in order to design sustainable industrial practices in future.

7. Other bio-based polymeric additives of importance Molasses extracted from sugarcane have recently been explored as a potential additive in paper industry (Fahmy, 2014). It comprises of around 32–44% sucrose, besides trace amount glucose and fructose. Molasses also contains 3–5% gums (and starch). Sucrose interactions with cellulose ﬁbrils happen to enhance breaking length and water uptake of paper. Molasses at a concentration of 15–20% (w/w) has been reported to increase the dry breaking length (by −10%), wet breaking length (by ∼6%) and water retention value (by ∼30%) in paperboards (Allan et al., 2005; Allan, Stoyanov, Ueda & Yahiaoui, 2001; Fahmy, 2014, 2006). Tamarind kernel powder or tamarind kernel polysaccharide (TKP) is another commercially available xyloglucan obtained by husking and milling seed kernels of Tamarindus indica Linn. TKP blended with algin and guar has been used a size press solution, pigment coating formulation, ink hold-out agent and water retention additive in paper manufacturing (Yin & Lewis, 1981). This novel blend imparts properties as thickener, emulsiﬁer, stabilizer, lubricator, binder and chemical stabilizers. Crude TKP has successfully substituted the conventional wet end additives like starch and galactomannans in paper-making. TKP xyloglucan when used with NFC has been found to enhance the tensile strength and TEA of unbeaten softwood pulp by ∼20–30% (Goyal, Kumar & Sharma, 2008; Sehaqui, 2013; Yin & Lewis, 1981).

10. Future strategy The consistently high consumption of paper and paper based products eventually increases the demand of chemical additives in order to meet the needs of the industry. As discussed in this review, additives perform a wide array of functions starting from surface engineering (surface strength, barrier properties, sizing, coating, enhancing the shelf-life, recyclability etc.) to mechanical strength enhancement (tear, tensile etc.) and from retention aid (for fines, filler, other additives etc.) to paper rheology modifications. Hence, additives form an inseparable domainin pulp and paper manufacturing. The production, availability, chemistry and specific utility of chemical additives are well known to paper technologists and are extensively utilized in paper manufacturing (Bajpai, 2015; Hubbe, Nanko & McNeal, 2009; Pelton & Hong, 2002). However, it is important to understand the consequences of using these harmful chemicals on an environmental perspective. Hundreds of hazardous chemicals and their derivatives are generated during the papermaking process and are released as mill effluents (Ali & Sreekrishnan, 2001). Although effluent recycling and treatments are devised to minimize such risks, the same measures are unable to completely mitigate the potential long term hazards of these harmful chemicals (Bajpai, 2017; Cesaro, Belgiorno, Siciliano & Guida, 2019). Hence, to cut-down the hazards of chemical additives, the present review discusses the significance of polymers derived from nature that are potential functional substitutes of chemical additives in paper industries. Besides being eco-friendly and biologically benign, the striking feature of bio-polymeric additives is their versatility i.e., one biopolymer can be used to impart diverse functions even at very low concentrations. In other words, a single bio-polymer additive carries the potential to substitute a group of chemical additives used in paper production (Table 2). Secondly, the chemical make-up of bio-polymers shows compatibility with cellulose fibrils and synergism with other bio-polymers; hence can be used in innumerable combinations as per requirement. Finally, bio-polymers can be obtained from abundant, and renewable resources. However, modified bio-polymers, are often criticized on a commercial perspective considered their higher production cost. Having considered such limitations, wide array of bio-polymers are available that can be concurrently produced in paper industries (e.g., modified cellulose, modified starch, modified gums etc.), hence transforming a paper mill into an integrated one for additional revenue and employment opportunities (Hamaguchi, 2013). Table 4 summarises the sources and application of potential bio-polymeric additives that can be used in paper industries.

8. Environmental perspective The pulp and paper industry has been designated as one of the most notoriously polluting industries on a global scale. The intense manufacturing processes not only generate hazardous chemicals, gases and toxic water in leaps and bounds but also produces huge amount of sludge comprised of fibres (Bajpai, 2017; Hashim & Sen Gupta, 1998; Veluchamy & Kalamdhad, 2017). Adsorbable organic halides (AOX), heavy metals, sulphide gases, phenolics, suspended particles, acids and various other detrimental compounds are produced and released in the environment. These compounds not only pollute the habitat and disrupt the food chain, but also affect the systemic and genetic make-up of microscopic to large organisms adversely (Antoni Ginebreda et. al., 2006; Lacorte et al., 2003). A unique utility of biopolymers was devised by researchers that focuses on the recycling of fibres from effluents. In their study, commonly used bio-polymeric additives like guar gum, xanthan gum and locust bean gum were employed to recover cellulosic fibres from paper-mill effluent. Guar gum proved to be the most promising bio-polymeric flocculent as compared to chemical flocculent (alum) with a capability of removing turbidity of paper-mill effluent by ∼95% (Mukherjee et al., 2014). Recently, Dixit, Gupta, Liu and Shukla (2019) have brilliantly highlighted the environmental health aspect of pulp and paper mill pollutants in detail. The study also describes state of art techniques in waste recycling and the scope of eco-friendly measures. In this context, the commonly used chemical additives and the potential environmental threats from them can be overviewed. Table 2 represents some of the functional chemical additives used widely in paper industry, the potential hazards from these chemicals and corresponding bio-polymeric additives that have the potential to execute similar functions. 9. Economy and prospects The commercialization of biopolymers on a global scale is still at its naive stage. Moreover, there is no authentic scientific report that discusses the economy related to the application of bio-polymers in pulp

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Table 2 Common chemical additives in paper industries and their ill-eﬀects. Function in Paper Industry

Common chemical additives in paper industries (Antoni Ginebreda et. al., 2006)

Retention aids

Polyaluminium chloride (PAC) Bentonite Polyacrylamide (PAM)

Polyethylenimine (PEI)

Polyvinylamine (PVA)

Sizing agents

Alkyl ketene dimer (AKD)

Styrene derivatives

Rosin

Strength additive

Urea formaldehyde (UF)

Melamine formaldehyde (MF)

Poly-amideamine epichlorohydrin (PAE) Coating agents

Titanium dioxide

Styrene-butadiene

Polyvinyl compounds Diaminostilbenedisulphonic acid derivatives

Harmful eﬀect(s) of the chemicals

Bio-polymers imparting similar functions

Decreases pH of water bodies; lethal to aquatic zooplanktons (Jančula, Mikula & Maršálek, 2011) Cytotoxic and neurotoxic effect in animals (Nones, Riella, Trentin & Nones, 2015) Carcinogenic; mutagenic, teratogenic, epidermiological effects, metabolic distress to aquatic organisms, neurotoxic etc. (King & Noss, 1989) Detrimental to microbial population in the environment (bacteria and fungi), eco-toxic (Mortimer, Kasemets, Heinlaan, Kurvet & Kahru, 2008) Detrimental to microbial population in the environment (Westman, Ek, Enarsson & Wågberg, 2009) Toxic to ﬁshes and microbial population (Demirel, Güdül, Temiz, Kustas & Aydin, 2018; Hermens, 1990) Detrimental to microbial population, hepatotoxic effects, carcinogenic effects (Loprieno et al., 1976; Vodicka et al., 2006) Risk of systemic toxicity and genotoxic effect in grazing animals (Stegelmeier, Gardner, James, Panter & Molyneux, 1996) Risks of respiratory diseases, allergies, systemic disorders, neurotoxic effects (L’Abbé & Hoey, 1984; Norman & Newhouse, 1986; Songur, Ozen & Sarsilmaz, 2010) Detrimental to phytoplanktons, risks of male infertility, systemic effects, neurotoxic effects (Hall & Mirenda, 1991; Khalil, Awad & Ali, 2017; Songur et al., 2010) Causes male infertility; mutagenic; carcinogenic (Eder & Weinfurtner, 1994; Velí’scar, Davídek, Davídek & Hamburg, 1991) Systemic toxicity in ﬁshes and small mammals (Chen, Dong, Zhao & Tang, 2009; Federici, Shaw & Handy, 2007; Wang et al., 2007) Carcinogenic effects, mutagenic effects, risks of respiratory disorders (Anttinen-Klemetti, Vaaranrinta, Mutanen & Peltonen, 2006; Ward et al., 1996) Immunogenic effects, hepatotoxic effects in small mammals (DeMerlis& Schoneker, 2003) Non-degradable, deposits in waste water (Wong-Wah-Chung, Mailhot & Bolte, 2001)

Cationic starch, molasses, guar gum, xanthan gum

Table 3 Approximate costs of commercially available biopolymers. Type

Quantity (g)

Approximate Price (in INR)#

Microcrystalline cellulose (powder) Cellulose acetate Hydroxyethyl cellulose (quaternized) Hydroxypropyl cellulose Hydroxypropyl-methyl cellulose Sodium carboxymethyl cellulose Alginate-sodium salt Chitosan Starch∗∗ Hydroxyethyl starch 𝜅- Carrageenan 𝜆- Carrageenan Wheat gluten Tamarind kernel powder Carboxymethyl tamarind kernel powder Whey protein powder Casein-protein powder

250 500 50 250 100 1000 500 250 250 500 100 25 500 1000 1000 1000 1000

2000–3000 8000–10,000 7000–9000 19,000–22,000 8000–11,000 10,000–12,000 5000–7000 20,000–25,000 2000–14,000 12,000–13,000 12,000–13,000 48,000–50,000 1000–3000 40–50 60–80 800–2000 600–2000

# ∗∗

Price is based on high to highest purity;. Price range is based on diﬀerent sources of starch.

Starch, oxidized starch, cellulose derivatives, cationic cellulose, alginate, casein, whey proteins, chitosan, tamarind kernel polysaccharide, hemicellulose, polyhydroxyalkanoates

Cellulose derivatives, cationic starch, hemicellulose, chitosan, alginate, guar gum, tamarind kernel polysachharide, carrageenan, xanthan, poly‑hydroxy-alkanoates

Cellulose derivatives, cationic starch, hemicellulose, chitosan, alginate, guar gum, tamarind kernel polysachharide, carrageenan, xanthan, poly‑hydroxy-alkanoates, glutens

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Table 4 Overview of sources, types and applications of bio-based polymers in paper making. Source

Classes of Bio-polymers

Crop grains (wheat, rice, maize etc.) Tubers (cassava, potato)

Starch

Plant biomass (woody and non-woody) Fibre wastes Bacteria (various genera)

Cellulose

Plant biomass (woody & non-woody) Leguminous seeds

Hemi-celluloses

Crustaceans Molluscs Insects Fungi Brown seaweed (family Phaeo-phyceae) Bacteria Milk (casein, whey) Soy Wheat & Corn (gluten)

Chitosan

Derived from natural carbohydrates by fermentation using Lactobacillus sp. Tamarindus indica Linn. Bacteria (Pseudomonas sp., Alcaligenes spetc.) Sugar cane (Saccharum oﬃcinarum) Sea weed (Gelidium elegans) Guar plant (Cyamopsis tetragonolobus) Bacteria (X. campestris)

Alginate

Types and derivatives Unmodiﬁed starch Oxidized starch Hydroxyethyl starch Acetyl starch Cationic starch

Carboxymethyl cellulose Hydroxyethyl cellulose Methyl cellulose Hydroxypropyl cellulose Hydroxypropyl methyl cellulose - Nanocellulose - Cationic cellulose

–

References

Sizing, pigment coating, dry strength additive, wet strength additive, retention aid

(Andersson, 2008; Ghasemian et al., 2012; Hermansson & Svegmark, 1996; Holik, 2006; Kochkar, Morawietz & Hölderich, 2001; Lindström et al., 2016; Ray, Ghosh, Gupta & Rajrana, 2011; Ulbrich et al., 2012; Vanier et al., 2017; Zakrajšek & Golob, 2009) (Abdel-Halim, 2014; Ahola et al., 2008; Hamada, Beckvermit & Bousﬁeld, 2010; Holik, 2006; Joshi et al., 2015; Karrasch et al., 2009; Khwaldia, 2013; Khwaldia, Arab-Tehrany & Desobry, 2010; Klass, 2011; Moral et al., 2015; Pajari et al., 2012; Salam et al., 2015; Shen et al., 2014; Sothornvit, 2009;, Lavanya et al., 2011) (Anjos et al., 2004; Denis U. Lima et al., 2003; Mobarak & Fahmy, 1973; Shen et al., 2014) (Fernandes et al., 2010; Nada et al., 2006; Nicu, Bobu & Desbrieres, 2011; Zakaria et al., 2015) (Song et al., 2012; Yin & Lewis,1981)

Dry strength additive, wet strength additive, coating, sizing

Tear & tensile strength, sizing and surface strength

- Unmodiﬁed chitosan - Cyanoethyl chitosan - Carboxymethyl chitosan –

Protein-based polymers

Functions

Strength, sizing, barrier, thermal stability, antimicrobial properties Dry and wet strength; sizing and coating

Casein based Whey protein Soy based Glutens

Dry strength additive, sizing and coating (barrier properties)

(Andersson, 2008; Guillaume, Pinte, Gontard & Gastaldi, 2010; Khwaldia et al., 2006; Salam et al., 2015)

Poly-lactic acid (PLA)

–

Mechanical strength, Coating

(Jamshidian, Tehrany, Imran, Jacquot & Desobry, 2010)

Tamarind kernel powder (TKP)

–

Polyhydroxy-alkanoates (PHA)

–

Molasses

–

Water retention, sizing, binders, coating Tensile strength, barrier properties; Sizing and coating Dry and wet strength additive, Retention aid Dry strength additive, soating, rheology modiﬁer, retention aid

(Goyal et al., 2008; Yin & Lewis,1981) (Arrieta et al., 2014; Kuusipalo, 2000a, 2000b) (Fahmy, 2014)

Gums

- Carrageenan - Guar gum (cationic and anionic) - Xanthan gum

11. Conclusion

(Dasgupta, 1999; Liu et al., 2017;Lachke, 2004; Taggart et al., 1992)

3 Decrease toxicity/reduce harmful eﬀects from chemical processes and mill-eﬄuents

Available literatures suggest that the specific properties imparted by bio-polymeric additives differ adversely with varying raw material type and reaction conditions. Hence, intensive research and development is necessary to utilize bio-polymeric resources with well defined reaction parameters specific to individual raw materials. This in turn will help in formulating sustainable industrial protocols. To conclude, it can be said that the scope of biopolymers in paper industry is well attributed from the three functional domains that a potential paper additive must address such as:

From the present review, it can be understood that biopolymers have the potential to administer all aforesaid aspects. In this context it can also be mentioned that our research group is relentlessly working on potential bio-polymeric blend formulations to generate economically viable additives for quality paper manufacturing. Credit author statement Soumya Basu: Literature survey, writing and editing. Shuank Malik: Literature survey, writing and editing. Gyanesh Joshi: Inspection and validation of referred literature. P. K. Gupta: Writing and suggestions for content. Vikas Rana: Conceptualization, writing and editing.

1 Minimize chemical and energy charge of industrial paper manufacturing (hence, the production cost) 2 Enhance the quality of the ﬁnal product. 13

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Carbohydrate Polymer Technologies and Applications 2 (2021) 100050

Declaration of Competing Interest

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PAPERmaking! FROM THE PUBLISHERS OF PAPER TECHNOLOGY TE INTERNATIONAL

Volume 7, Number 1, 2021

(1) Are you ready for the changes to EU Authorised Representatives? & (2) One vital thing UK manufacturers of machinery and safety component must do to prepare for Brexit Two articles from long-standing PITA member Derek Coulson, concerning the vital subject of certification of machinery in this post-Brexit world. For more information about either item, or the subject in general, go to www.holdtechfiles.eu or email derek@holdtechfiles.eu Contact details: Derek Coulson Hold Tech Files Ltd Dun Iseal House Newtown Gaulsmills Ferrybank Waterford Ireland X91 F638 www.holdtechfiles.eu derek@holdtechfiles.eu About Hold Tech Files Ltd: Hold Tech Files Ltd is a company based in the Republic of Ireland that holds Technical Documentation within the EU on behalf of manufacturing companies based outside the EU. For companies that sell to the UK as well, files can be held in the UK by Hold Tech Files’ UK-based subsidiary. www.holdtechfiles.eu

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Article 9 – Certification & Brexit

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FROM THE PUBLISHERS OF PA APER TECHNOLOGY

Volume 7, Number 1, 2021

(1) Are you ready for the changes to EU Authorised Representatives? If you supply CE marked products, including machinery, into the EU you need to be ready for the new Regulation 2019/1020 on market surveillance and compliance of products. This Regulation comes into force on 16th July 2021 and aims to strengthen the requirements for market surveillance by Member States; however, there are also important implications for manufacturers and suppliers. Regulation 2019/1020 introduces requirements relating to an ‘economic operator’ and certain goods are prohibited from being placed on the market unless there is an economic operator established in the EU. The economic operator is responsible for ensuring the conformity documentation is available, co-operating with market surveillance authorities and informing authorities if there are reasons to believe that a product presents a risk. The new requirements relating to an economic operator will impact many businesses based outside the EU, including UK businesses. An economic operator can be any of these: • the manufacturer of the goods, • the importer (where the manufacturer is not established in the EU), • an authorised representative, or • a fulfilment service provider when none of the above are established in the EU. Article 3 of the Regulation provides definitions for these four terms. A ‘manufacturer’ is any natural or legal person who manufactures a product or has a product designed or manufactured, and markets that product under its name or trademark. An ‘importer’ is any natural or legal person established within the Union who places a product from a third country on the Union market. An ‘authorised representative’ is any natural or legal person established within the Union who has received a written mandate from a manufacturer to act on its behalf in relation to specified tasks with regard to the manufacturer's obligations under the relevant Union harmonisation legislation or under the requirements of this Regulation. A ‘fulfilment service provider’ is any natural or legal person offering, in the course of commercial activity, at least two of the following services: warehousing, packaging, addressing and dispatching, without having ownership of the products involved, excluding postal services as defined in point 1 of Article 2 of Directive 97/67/EC of the European Parliament and of the Council, parcel delivery services as defined in point 2 of Article 2 of Regulation (EU) 2018/644 of the European Parliament and of the Council, and any other postal services or freight transport services. Currently machinery manufacturers based outside the EU must have a person to ‘compile’ the Technical File who must be identified on the Declaration of Conformity. This person’s only responsibility is for providing a Technical File on reasoned request from authorities such as trading standards or health and safety authorities. However, from 16th July 2021 the new Regulation requires an Authorised Representative with a mandate to co-operate with the authorities if there is no other economic operator. The requirements apply to products affected by Directives listed in Annex I of Regulation 2019/1020 including 2006/42/EC (Machinery Directive), 2014/30/EU (EMC Directive), 2014/35/EU (Low Voltage Directive) and 2014/68/EU (Pressure Equipment Directive). To bolster market surveillance, a Union Product Compliance Network is being established from January 1st 2021. This will ‘serve as a platform for structured coordination and cooperation between enforcement authorities of the Member States and the Commission, and to streamline the practices of market surveillance within the Union, thereby making market surveillance more effective’. This new Union Product Compliance Network makes it all the more important that manufacturers meet the requirements relating to economic operators and Authorised Representatives. Hold Tech Files Ltd. can act as the person to compile Technical Files for the Machinery Directive, and can act as the Authorised Representative for any of the Directives listed in Annex I of Regulation 2019/1020. Page 2 of 3

Article 9 – Certification & Brexit

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FROM THE PUBLISHERS OF PA APER TECHNOLOGY

Volume 7, Number 1, 2021

(2) One vital thing UK manufacturers of machinery and safety component must do to prepare for Brexit There is no escaping the fact that the UK’s relationship with the European Union has been different since 1st January 2021. UK machine builders exporting to the European Economic Area (EEA) must continue to CE mark their machines to the Machinery Directive as they do now, but there is one vital change for which they must be ready: a person in the EEA has to be named on the Declaration of Conformity (DoC) as authorised to compile the Technical File. If the DoC still names somebody in the UK, then there is a risk that exported machines will be stopped at customs. And the same is true for UK-based manufacturers of partly completed machinery and safety components that fall within the scope of the Machinery Directive. Larger companies that already have a subsidiary in the EU can simply change the DoC to show the name and address of a person in the EEA authorised to compile the Technical File, rather than someone in the UK. However, smaller companies without an EEA subsidiary will probably not want to set one up in the last few weeks before the transition period ends on 31st December. Fortunately, there is a simple, expedient and cost-effective way to comply with the requirement to name a person in the EEA on the DoC – or, of course, the Declaration of Incorporation (DoI) for partly completed machinery. Hold Tech Files Ltd is established in Eire and can be named on a DoC or DoI as the person authorised to compile the Technical File. Note that the official ‘Guide to application of the Machinery Directive 2006/42/EC’ makes it clear that ‘The person authorised to compile the technical file is a natural or legal person’ – in other words, the ‘person’ named can, in fact, be a company. Hold Tech Files Ltd has created a web-based service for manufacturers of machines, partly completed machines and safety components covered by the Machinery Directive. After signing a mandate and paying a fee (all fees are published on the website and there are no ‘hidden extras’), the relevant file can be uploaded and it is then backed up onto a separate server. Payment of a one-off fee entitles the manufacturer to name Hold Tech Files on the DoC or DoI for a period of ten years.

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Article 9 – Certification & Brexit

PAPERmaking! FROM THE PUBLISHERS OF PAPER TECHNOLOGY TE INTERNATIONAL

Volume 7, Number 1, 2021

How to Increase Your Learning Agility: 4 Tips In times of change, leaders need to be more agile than ever. Adapting to new business strategies, working across cultures, dealing with virtual teams, and taking on new assignments all demand that leaders be flexible and agile. The willingness and ability to continue learning throughout your career is more important now than ever, as the workplace has been upended, business models are changing, and technology and industries shift. What do you do when you don’t know what to do? To be a high-performer and increase your long-term potential, you need a way to deal with the unknown — and fast. We all need to learn to adapt and thrive in ambiguous or new situations, and as noted in Learning Agility: Unlock the Lessons of Experience, when you don’t know what to do, learning agility is the key. The ability to learn from experience is also a critical predictor of success as a leader, according to decades of our research. (Learn more about how to gauge if you’re an agile learner likely to have a long career.) Learning agility is about knowing how to learn — knowing what to do when you don’t know what to do. It’s about learning from experience and applying it in new ways, adapting to new circumstances and opportunities. It’s never too soon (or too late) to increase your learning agility. So, if you want to increase your performance — and your long-term potential — you can boost your learning agility in several ways. https://www.ccl.org/

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Article 10 – Leadership

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FROM THE PUBLISHERS OF PA APER TECHNOLOGY

Volume 7, Number 1, 2021

How to Build Learning Agility With improved learning agility, you’re able to make the most out of your experiences. As you build the habits that help you figure things out as you go, you’ll improve how you navigate new and difficult situations and increase your contribution to your organization. To excel at learning from experience and to succeed in changing times, follow our 4 tips for learning agility: 1. Be a Seeker. Seek out new and diverse experiences. Memorable experiences impact the way in which you lead and manage, so seek out more and different experiences. Immerse yourself in situations that broaden your skills and perspective. Explore new pathways. x

Embrace the challenge of the unfamiliar; don’t just go through the motions. If you react to the new learning opportunity by staying close to your comfort zone, you minimize struggle and discomfort — and you also miss out on the corresponding rebound in growth and performance. The end result is that you’re pretty much the way you were before, and the full power of the new experience is lost. Take on a new challenge that scares you. Find something that is meaningful, but not so important that failure will have serious personal consequences. Most importantly, tell others what you’re doing, and ask for their help and support. Taking on new challenges allows you to develop new skills and perspectives that may become an important part of your repertoire in the future. Don’t get stuck on first solutions. We often choose the first solution to come to mind, rather than taking time to consider whether it’s truly the optimal course over the long term. By trying out new approaches, you can uncover ways of doing things that could save time and energy and surface new learning that may otherwise haven’t been considered. Look beyond the obvious or the easy. Bring in other points of view. Find another way to understand the problem. Approach it from a different angle. If you’re typically data-driven, seek out stories or go get some hands-on, action-driven insight. For each problem you face, challenge yourself to come up with new solutions, even if seemingly tried and trusted ones exist. Make it a habit to push for new ideas — the less traditional, the better. When faced with a challenge, ask yourself 2 questions: What’s holding me back from trying something new and different? If these constraints weren’t in place, how would I approach this situation differently?

2. Hone Your Sense-Making. In today’s high-stakes, complex, ambiguous, and fast-moving situations, you don’t have the luxury of time. You need to dive in and start making things happen. This means you need to take an active approach to making sense of the new challenges you face. Be curious and willing to experiment. Ask “Why?” “How? and “Why not?” x x x

Really actively listen to understand what others are saying, and trust that you’ll have a response when they’ve finished talking. When you find yourself feeling stressed, pause. Don’t just say or do the first thing that comes to your head — when facing leadership stress, take a moment to consider what’s really required. Find another way to understand a problem. Utilize multiple techniques, engage different senses, and tap into your emotions to wrest understanding, insight, and meaning from the experience. Elevated sense-making is an essential skill to develop for high-potential leaders.

3. Internalize Experiences and Lessons Learned. This process is needed to solidify insights and lessons learned for recall and application later. If you don’t process the learning, you may miss important clues to next steps. Lean on others for this if you need to. Learning-agile people recognize that others are essential to their learning and performance. They build ties and relationships that increase their access to people who can provide new experiences and opportunities to learn; they can collaborate across boundaries. x

Ask for feedback and be open to criticism. Find someone who you trust to give you open and honest feedback. Show that you’re open to the process by only asking clarifying questions. Take time to think about what happened and what you’re learning. View feedback as a gift that someone’s giving you. You may not like it, and it may be uncomfortable, but there’s value in it nonetheless. Regardless of the other party’s motivations for giving you feedback, there’s always the opportunity to learn something about yourself. Don’t defend. Resist the temptation to explain your actions or make excuses. When you enter a mode of self-preservation and try to defend what is, you close yourself off to what could be. To Page 2 of 3

Article 10 – Leadership

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FROM THE PUBLISHERS OF PA APER TECHNOLOGY

Volume 7, Number 1, 2021

practice non-defensiveness, always try to thank the other person. Consider the feedback carefully so you can see patterns (and changes) over time. Reflect, both alone and with others. Learning occurs when you take the time to reflect, to shift your thinking beyond merely what happened to ask why things happened the way they did. Reflection helps to surface the intuitive and lock it in for future reference. So step back from the busyness and figure out what you’re learning from a project, from an interaction, from a new experience. Talk about what’s currently working well and what isn’t — or debrief what’s already happened. Conduct afteraction reviews where you, and relevant others, reflect by asking questions: What happened? Why did it happen that way? What should we stop/start/continue doing in order to ensure success in the future? What changes in knowledge, skill level, attitudes, behavior, or values resulted from the experience?

4. Adapt and Apply. Through your experiences, you’ve learned things. Over time, you get better at applying those learnings to navigate new and challenging situations. x

Learn to rely on your intuition. Concentrate on principles and rules of thumb. People who rate high on learning agility tell us they operate largely on feel and flexibility. When faced with something new, look for similarities between the situation and things you’ve done in the past. Draw on these similarities to frame the new challenges. Don’t overthink. Under pressure, you probably feel the urge to get things done quickly. Ironically, consciously searching your mind for ideas and solutions closes us off to both the wisdom of others and our own experience. Inspiration often comes from the unconscious; being open to this can spark new ideas and strengthen performance. Be a flexible leader and don’t shy away from experimentation as you venture into new territory.

Our research has found that learning-agile superstars engage in these 4 behaviors at a significantly higher level of skill and commitment than everyone else — and get great results over and over again. (That’s why it’s often said that great leaders are great learners.) Ultimately, your ability to continuously learn and adapt will determine the extent to which you thrive in today’s turbulent times — and succeed in the future. If you follow our tips to improve your learning agility, you’ll make the most of your experiences. By seeking, sense-making, internalizing, and applying, you’ll do more, learn more, and have a more satisfying career.

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Article 10 – Leadership

PAPERmaking! FROM THE PUBLISHERS OF PAPER TECHNOLOGY TE INTERNATIONAL

Volume 7, Number 1, 2021

The Four Principles of Change Management: How to Support Change in Your Organization No organization can afford to stand still. There are always new challenges to meet, and better ways of doing things. However, every change you need to make should be planned and implemented with care, otherwise it could end up doing more harm than good! That's where change management comes in. It's a structured approach that ensures changes are implemented thoroughly and smoothly – and have the desired impact. In this article, we explain how you can enact positive and productive change in your organization using four core principles of successful change management. https://www.mindtools.com/pages/article/newPPM_87.htm

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Article 11 – Change Management

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FROM THE PUBLISHERS OF PA APER TECHNOLOGY

Volume 7, Number 1, 2021

What Is Change Management? Change management draws on theories from many disciplines, including psychology, behavioral science, engineering, and systems thinking. And there are many different models to choose from. For example, Lewin's Change Management Model splits the change process into three key stages known as "unfreezechange-refreeze," while Kotter's 8-Step Change Model provides a more comprehensive guide through change. A central idea of all change management theories is that no change ever happens in isolation. In one way or another, change impacts the whole organization and all of the people in it. But with good change management, you can encourage everyone to adapt to and embrace your new way of working. The Four Principles of Change Management Successful change management relies on four core principles: x Understand Change. x Plan Change. x Implement Change. x Communicate Change. Let's explore each of these in turn, along with some tools and techniques that you can use to put them into practice: Principle 1: Understand Change To successfully promote the benefits of the change, you need to understand them yourself. So, think about: x Why you need to change. What are your key objectives? x What will the benefits of the change be to the organization? x How will it impact people positively? x How will it affect the way that people work? x What will people need to do to successfully achieve the change? It can also be helpful to think about what the negative outcomes of not making the change would be. Beckhard and Harris' Change Equation shows that, for change to work, there has to be sufficient dissatisfaction with the old way of doing things. But people also need to feel confident that the new approach will be better – and that there's a clear route to get there. Principle 2: Plan Change Effective change doesn't just happen by chance, and any plan you make has to be right for your organization. The way that change projects are managed can vary from organization to organization. Some have very rigid change methodologies, while others are more open and flexible in their approach. However, in general, you'll need to consider the following: x Sponsorship. How will you secure, engage and use high-level support and sponsorship of the change? x Involvement. Who is best positioned to help you to design and implement the change? For example, will you need external expertise? Or can you use internal resources? x Buy-in. Change is most effective when you are able to win support from people across the business. How do you plan to achieve this? x Impact. Finally, think about what success should look like. How will you predict and assess the impact of the change that you need to make? What goals do you need to achieve? Principle 3: Implement Change So how exactly are you going to make change happen? As we've seen, there are many different strategies that you can choose to put your change into practice. Kotter's 8-Step Change Model, for example, explains how to inject a sense of urgency into your actions, so that you build momentum and encourage everyone to get behind your changes. Meanwhile, the Change Curve reminds you to be mindful of people's feelings while putting your plan into action. It shows the stages that we all tend to go through during organizational change – from shock and denial, to the point where we're fully invested in the new approach.

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Article 11 – Change Management

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FROM THE PUBLISHERS OF PA APER TECHNOLOGY

Volume 7, Number 1, 2021

Whatever tools you choose, the following steps can help you to implement change in a positive way: x Ensure that everyone involved in the changes understands what needs to happen – and what it means for them. x Agree success criteria for your changes, and make sure that they're regularly measured and reported on. x Map and identify all of the key stakeholders that will be involved in the change and define their level of involvement. x Identify any training needs that must be addressed in order to implement the change. x Appoint "change agents," who'll help to put the new practices into place – and who can act as role models for the new approach. x Find ways to change people's habits, so that the new practices become the norm. x Make sure that everyone is supported throughout the change process. Principle 4: Communicate Change Communication can be a make-or-break component of change management. The change that you want to implement has to be clear and relevant, so people understand what you want them to do and why they need to do it. But you also have to set the right tone, so that you get the emotional reaction you're hoping for. It's a good idea to link the changes that you're planning to your organization's mission or vision statements. Not only will this help people to see how the change positively impacts the "bigger picture," it will also provide them with an inspiring, shared vision of the future. Also be sure to practice good stakeholder management. This will ensure that you give the right people the right message, at the right time, to get the support that you need for your project. The ADKAR Change Management Model is a particularly useful tool that you can use to help communicate your change. It outlines five things you should address in your communications: x Awareness (of the need for change). x Desire (to participate in and support it). x Knowledge (of how to change). x Ability (to change). x Reinforcement (to sustain the change in the long term). What Can Prevent Change? Even the best-laid plans can suffer setbacks, so be ready for problems when they arise. Some people may be pessimistic about your plans, so you'll need to acknowledge, understand and address any resistance to change You may even come up against cultural barriers to change. If your organizational culture doesn't embrace change – or even pushes against it – you'll have to find ways to reward flexibility, create role models for change, and repeat your key messages until the mood starts to improve. Which Leadership Style Is Best for Change Management? There's no "one-size-fits-all" approach to change management – so there's no perfect way to lead it. But, in general, it's important to stay authentic and to lead in a way that's right for you. You can also flex and adapt your approach to suit the particular challenges that your organization faces – and the behaviors that you're trying to change. Successful change leaders tend to show the following characteristics: x The ability to build coalitions and inspire trust. x Strong communication skills at every stage. x Emotional intelligence to pick up on resistance to change and acknowledge the personal difficulties that people have with it. x The ability to think strategically and link the change to the "bigger picture."

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Article 11 – Change Management

PAPERmaking! FROM THE PUBLISHERS OF PAPER TECHNOLOGY TE INTERNATIONAL

Volume 7, Number 1, 2021

10 top tips for email etiquette With a predicted 306.4 billion emails sent and received each day in 2020, it’s vital for employees to get email communication right. Here’s ten email etiquette tips for HR and People teams to share with employees: 1. Include a clear subject matter Short and snappy summary will likely be more effective than a full sentence. If it’s for review, put that at the beginning of the subject line to make it more eye-catching. 2. Always use an appropriate greeting If you’re writing to a close colleague, an informal ‘Hi’ will likely be sufficient, but if you’re writing to someone you don’t know so well, then always add a formal salutation and an introduction. 3. Only use shorthand if you know your recipients If you’re writing to your own team about a project that you’ve been discussing, then you can write short emails with a list of bullet points. 4. Be wary of using humour or colloquialism across cultures Be aware of funny sayings or colloquialisms. Instead, keep your emails to the point and as clear as possible. 5. Consider the purpose of your email Always state if your email needs an action and by when. You could even bold this or italicise a due date or the action needed so it’s clear. 6. Think before you use an emoji If you’re sending them to people you know well, and you know will understand them, then that’s fine. If not, then consider if they’re really needed. 7. Don’t hit reply all or CC everyone By replying to people who don’t need to be copied, it’ll only clog up their inbox – and potentially yours if they reply to something you don’t need them to. 8. Reply in a timely fashion Always reply within 24 hours, even if it’s to acknowledge an email and explain that you will revert with an appropriate response within a defined timescale. 9. Think about where your email could end up Never use inappropriate language in a work email. The reality is that your email will remain on the server long after you have deleted it. 10. Always spell check Take the time to re-read your emails, make sure they make sense and have the right tone before you send them. https://www.sage.com/en-gb/blog/hr-guide-email-etiquette/ The Paper Industry Technical Association (PITA) is an independent organisation which operates for https://www.sage.com/en-gb/blog/hr-guide-email-etiquette/

the general benefit of its members – both individual and corporate – dedicated to promoting and improving the technical and scientific knowledge of those working in the UK pulp and paper industry. Formed in 1960, it serves the Industry, both manufacturers and suppliers, by providing a forum for members to meet and network; it organises visits, conferences and training seminars that cover all aspects of papermaking science. It also publishes the prestigious journal Paper Technology International and the PITA Annual Review, both sent free to members, and a range of other technical publications which include conference proceedings and the acclaimed Essential Guide to Aqueous Coating.

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Article 12 – Email Etiquette

PAPERmaking! FROM THE PUBLISHERS OF PAPER TECHNOLOGY TE INTERNATIONAL

Volume 7, Number 1, 2021

10 top tips for working remotely One major result of COVID has been the increase in remote working. For those used to working in offices, or with teams of others, this can be a difficult transition. The attached sheet gives 10 top tips from The Chartered Institute of Personnel and Development.

https://www.cipd.co.uk/knowledge/fundamentals/relations/flexible-working/remote-working-top-tips#73289

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Article 13 – Remote Working Tips

TEN TOP TIPS: Managing remote teams

AGREE WAYS OF WORKING Make sure every team member is clear about how you will work together remotely, how you keep each other updated, and how frequently.

SHOW THE BIG PICTURE BUT BE PREPARED TO FLEX Remind your team about the big picture and how their work fits into it. If some members can’t carry out all their usual functions, consider skills they can lend to others to meet team goals.

SET EXPECTATIONS AND TRUST YOUR TEAM Be clear about mutual expectations and trust your team to get on without micromanaging. Focus on results rather than activity.

MAKE SURE YOUR TEAM HAVE THE SUPPORT AND EQUIPMENT THEY NEED This includes any coaching they might need to use online systems and work remotely. Keep your calendar visible and maintain a virtual open door.

This is essential for keeping connected as a team, to check in on each other’s well-being and keep workflow on track. It needn’t be long, but regularity is key.

This maintains a sense of structure and continuity for all.

SHARE INFORMATION AND ENCOURAGE YOUR TEAM TO DO THE SAME Opportunities to pick up information in passing are more limited when working remotely. Share appropriate updates or learnings from other meetings and projects and invite your team to do the same.

TAILOR YOUR FEEDBACK AND COMMUNICATIONS People can be more sensitive if they’re feeling isolated or anxious, so take this into account when talking or writing. Communicate regularly, not just when things go wrong, whether it is information, praise or criticism.

HAVE A DAILY VIRTUAL HUDDLE

KEEP THE RHYTHM OF REGULAR 1-2-1 AND TEAM MEETINGS

LISTEN CLOSELY AND READ BETWEEN THE LINES Not being in the same room means you don't have extra information from body language or tone to get the sense of what people are thinking or feeling. Home in on what’s not being said and ask questions to clarify.

FOSTER RELATIONSHIPS AND WELL-BEING Make time for social conversations. This increases rapport and eases communication between people who may not meet often. It also reduces feelings of isolation.

For more information and resources visit cipd.co.uk/coronavirus

PAPERmaking! FROM THE PUBLISHERS OF PAPER TECHNOLOGY TE INTERNATIONAL

Volume 7, Number 1, 2021

Products & Services & News PITA CORPORATE SUPPLIER MEMBERS Page 2 Page 4 Page 6 Page 7 Page 8 Page 9 Page 10 Page 11 Page 12

ABB ABB ABB ABB FMW Valmet Valmet Valmet Valmet

Online Porosity Sensor Felt Moisture and Permeability Meters ABB Ability™ Sheet Break Performance Paper Quality Performance (Digital Service) FMW Appoints new UK Representative Fiberline Analyzer Maintenance Operations Agreement Blade Consistency Measurement Paper-Lab with S-Test Module

PITA NON-CORPORATE SUPPLIER MEMBERS Page 13 Page 14 Page 15

Voith Voith Voith

OnPerformance.Lab Digital Optimisation System ProTect NG Felt Measurement System IntensePress PU Press Roll Covers

OTHER SUPPLIERS Page 16 Ametek Page 17 Andritz Page 18 BTG Page 19 BTG Page 20 Exner

Surface inspection system (Sensor) TwinFlo Prime LC Refining MACSashTM Paper Quality Optimizer Single Point Morphology (SPM-5550) Turbidity Sensor (Sensor)

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Products & Services

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Volume 7, Number 1, 2021

ABB PARTNERS WITH ACA SYSTEMS TO OFFER NEW ONLINE POROSITY SENSOR FOR PAPER MILLS ABB has entered into a partnership with ACA Systems, the leading supplier of porosity sensors, to offer paper mill customers a proven technology that stabilizes the process to enable excellent roll quality when measuring online porosity. The single point ACA Permi sensor uses a continuous air flow method that is 50 to 100 times faster than other systems available on the market to reduce air permeance variations, enabling better product quality, optimized energy usage and reduced raw material costs. The multiple advanced calibration features improve the accuracy of the measurements while also enabling faster grade changes, improving overall runnability. This accuracy means that the level of fines can be better controlled while monitoring the direct effect of refining, retention, broke addition and vacuum levels. When stabilized air permeability is at the desired level, the roll is considered highest quality. In contrast to laboratory measurements that take 5 to 10 points from the produced roll, ACA Permi measures more than 10,000 points in real time and makes a sophisticated, statistical analysis on the quality of the roll. Under the partnership, ABB will supply the user-friendly ACA Permi to customers as the porosity option within its own portfolio. It is designed to be used in paper mills with requirements for online porosity measurement as a standalone solution or as part of the quality control systems (QCS) package. It serves ABB’s L&W installed base by providing a replacement for the soon-to-be obsolete Porolog while augmenting the current QCS offering with the industry-leading porosity measurement that is easily integrated into the QCS for data, display and control. When combined with QCS, it can leverage the ABB Ability™ Quality Management System with its System 800xA backbone. It also has potential to be installed and used with ABB’s remote support. “Our customers have reported faster grade change times of between 15 percent and 50 percent when controlling the roll quality with ACA Permi. This is a major benefit for operators focused on minimizing production loss and maximizing return on investment, ” said Vesa Kukkamo, CEO of ACA Systems. The sensor offers a wide measurement range that usually requires one single calibration, so there is typically no need to change parameters or physical parts for various grades. Plus, the automatic cleaning cycle and smart construction make for easy maintenance and installation. The measurement signal is also compatible with all mill-wide systems and cloud services. “ACA was strategically chosen for its leadership position, attained through extensive expertise in this space, and abilities to provide continuous measurement and strong service capability. The ACA Permi delivers more accurate, faster measurement results and therefore a higher quality output, which we know is crucial for our customers,” said Ad de Brouwer, Product Manager at ABB. ACA Permi’s unique measurement head design, tailored with special coatings for challenging applications such as decor paper, provides excellent contact with the web and eliminates the leakage of air, dust and other disturbances. Both vacuum and air blow methods are available, resulting in a very high correlation between the ACA Permi and any lab standard. Page 2 of 20

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Volume 7, Number 1, 2021

The sensor suits a wide range of paper grades, including sack paper, MG-kraft paper, cigarette paper, security paper, decor paper, photo base paper, thermal paper, carbonless paper, saturating paper and base paper before coating.

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Volume 7, Number 1, 2021

ABB UNVEILS NEW FEATURES WITH UPGRADES TO FELT MOISTURE AND PERMEABILITY METERS FOR PAPER MILLS ABB has upgraded its industry-leading L&W Felt Moisture and Felt Permeability Meters with new software, unlocking new features that improve their value for paper mill customers as a key process measurement solution to optimize press section performance. Having helped identify the effectiveness of felt conditioning for decades, these instruments provide paper mills, and felt and chemical suppliers, with industry-standard results for felt moisture and permeability measurement. Now, in addition to their handheld use, both felt meters have functionality for online scanner usage that will enable mills to maximize their scanner investment while also extending the lifecycle of their felts. Included in the upgrade of L&W Felt Moisture and Permeability Meters is the addition of ABB’s new easy-to-use PressView 3D software application that streamlines device setup and enables more detailed review and analysis on a PC. With a dedicated function for online scanner usage, operators also gain access to unique zone-related 3D mapping and Graphical Fast Fourier Transformation ( FFT) analysis. These features help visualize problems that appear at certain frequencies – linking them to machine problem areas – and provide the exact coordinates on the felt safely without additional effort. The updates create a simplified user experience with keyless operation for scanner and extension handle usage. A new high-definition storage feature allows safer and more accurate data viewing and retrieval for quick and reliable measurements with a minimum of settings. These are the only process measurement instruments available that provide an accurate automatic felt line detection without any sensitivity adjustments necessary from the user. The new features make more frequent measurement easier and more informative – even with handheld use – to not only create a more efficient felt conditioning program, but also for mills themselves to further optimize press felts to maximize machine runnability and overall profitability. “With more stringent safety requirements and the increased development in online scanners for felt measurement, these new features help papermakers to maximize their investment in online scanners and make more frequent measurements ,” said Ad de Brouwer, Product Manager for process measurements, ABB Pulp and Paper. “ The upgrades demonstrate our commitment to continuous product development that helps customers reduce energy and raw material usage, enhance felt life and performance and achieve maximum speed and runnability for their paper machines.” Existing L&W Felt Moisture and Felt Permeability customers can perform a software upgrade to receive the enhanced feature set, while new customers receive the more advanced features at no additional cost. Obtaining complete data on felt moisture content is critical to keep up with the demands on press felts and increase its lifecycle. Accurate and frequent measurement of felt status using the meters enables customers to take immediate corrective actions to overcome unnecessary high energy costs in the dryer section. It reduces unscheduled shutdowns, increases maximum felt lifetime with optimum de-watering performance, maximizes machine speed, optimizes cleaning using high pressure showers, improves paper quality and reduces paper breaks. Page 4 of 20

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Volume 7, Number 1, 2021

For further information on Felt Moisture Meter, please visit: https://new.abb.com/pulppaper/abb-in-pulp-and-paper/products/lorentzen-wettre-products/process-optimizationinstruments/l-w-felt-moisture-meter For Further information on Felt Permeability Meter, please visit: https://new.abb.com/pulppaper/abb-in-pulp-and-paper/products/lorentzen-wettre-products/process-optimizationinstruments/l-w-felt-permeability-meter

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Volume 7, Number 1, 2021

ABB’S NEW DIGITAL SHEET BREAK ANALYSIS HELPS MAXIMIZE OPERATIONAL PERFORMANCE TO IMPROVE PRODUCTION AND PROFITABILITY IN PAPER MILLS ABB has released Sheet Break Performance, an ABB Ability™ Performance Service that automatically curates, calculates and contextualizes key data points into an intuitive user interface to reduce the time to identify the root cause of sheet breaks for swift corrective action, while also determining optimal operational parameters to help prevent unplanned downtime. The digital service quickly pinpoints the underlying issues and recurring trends that prohibit optimum performance in paper mills and specifically addresses pain points such as frequent sheet breaks, long recovery times and increases in paper rejects. The diagnosis and root cause identification of each sheet break event is traditionally performed manually by operators who often need to access the information from different sources, such as process control systems, drives and quality management systems. This requires the breakdown of data from multiple systems and interactions between process variables, which is time consuming. ABB’s digital offering, which is built on a powerful combination of a proprietary analytics engine, advanced algorithms and online monitoring , provides a root cause analysis within one minute after the break. With the ability to monitor the real time variations in the operating parameters as well as the interactions between the various sections of the paper machine, operators are alerted to abnormalities and detrimental changes in the system that could lead to sheet breaks. This serves as an early warning system allowing the operators to take corrective actions and prevent unplanned downtime. This switch from manual to digital analysis can prove to be a useful stepping stone in a mill’s transformation and can also help to make a mill more sustainable by lowering energy usage, raw material and water footprint while improving fiber recovery. Plus, it reduces safety concerns with operators less frequently having to enter the dryer to extract broken paper. “Unlike similar offerings, ABB’s deep process and domain expertise - coupled with an integrated data fusion technique that curates and contextualizes data from multiple sources provides a holistic view across multiple systems and processes for both customer and ABB experts to better identify root causes of sheet breaks and prevent downtime,” says Ramesh Satini, Global Product Manager, Pulp & Paper Control Systems, ABB. “This overcomes the issue of mills having limited time or resource to manage manual break analysis, which cannot account for correlation among hundreds of process parameters and their impact on each other. ABB guides operations and fast-tracks improvement initiatives with recommended grade-specific parameters and predictive alerts to maximize operational effectiveness. ” Delivered via the ABB Ability™ Collaborative Operations service delivery model, it is fully integrated with ABB Ability™ Analytics framework, with on-premise or cloud deployment options. Page 6 of 20

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Volume 7, Number 1, 2021

ABB LAUNCHES PAPER QUALITY PERFORMANCE AND BECOMES FIRST TO OFFER ONLINE, TIME-BASED VARIABILITY ANALYSIS Paper Quality Performance, a new digital service that identifies, tracks and analyzes current and changing trends in paper variability, has been released by ABB. It will enable optimization of quality properties measured by Quality Control Systems (QCS) during all operational conditions. By reducing the variability, papermakers will be able to keep process parameters closer to targets, resulting in lower raw material and energy requirements while still meeting specifications. ABB Paper Quality Performance is the only solution on the market to offer continuous, time-based variability analysis in addition to online reelbased variability analysis and control utilization monitoring. This helps maintain QCS-measured quality targets more consistently and proactively than any other solution and empowers customers with data that is curated, calculated and analyzed in a way previously not possible. Until now, operators typically only had access to quality reports output by QCS systems, commonly known as reel-based variability, which show the overall average variability in a reel of paper. This solution helps mills to optimize online-measured paper properties through fast, precise controls made possible by in-depth diagnostics, comprehensive performance monitoring of key paper quality related KPIs, expert-based recommendations, proactive improvement actions and predictive notifications. “Our new solution will be particularly beneficial to mills that may not have the resource, ability or expertise for such detailed variability analysis. Customers will benefit from access to our paper variability experts who can support implementation actions, either remotely or onsite, including control optimization and detailed process analytics,” said John Schroeder, Global Product Manager, Pulp & Paper, ABB. “By reducing the amount of off-spec paper and production rejects, and improving sheet break and start-up recovery times, it enables superior runnability which can have a positive impact on a mill’s overall profitability.” The new ABB Ability™ Performance Service for paper mills, delivered via Collaborative Operations service delivery model, provides unparalleled accuracy and enables both proactive and predictive action to be taken for improved runnability. It leverages ABB’s automation and domain know-how to develop an intuitive dashboard with informative alerts, alarms and suspend actions, enabling operators to identify recommendations faster. ABB Paper Quality Performance is part of a comprehensive and integrated solution set, backed by end-to-end quality control expertise, enabling optimization opportunities on a larger scale. Its modular ability enables a low barrier entry and easy, cost-effective expansion for other digital solutions, proving the ideal stepping stone in a mill’s transformation.

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Volume 7, Number 1, 2021

FMW FÖRDERANLAGEN GMBH HAS NEW REPRESENTATION IN THE UK FMW Förderanlagen GmbH (FMW) are pleased to announce that we are now represented in the U.K. by Papermachine Consultancy Services Ltd (PCS). FMW is the Austrian engineering company specialized in handling systems for the pulp, paper, energy, chipboard and recycling industry. We provide the full spectrum of products and services from consulting, design, project execution to after-sales services. FMW have been supplying equipment into the U.K. market for many years already, so we know that you will appreciate the advantages of having a locally based support team. Mike Mason and his PCS team are available 24/7 to handle your queries and spares requirements. For more information on how we can “engineer YOUR progress” please contact: Mike Mason 07884 556542 pm-consults@outlook.com

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Volume 7, Number 1, 2021

THE NEW VALMET FIBERLINE ANALYZER FULFILLS ALL MAJOR PROCESS CONTROL NEEDS IN THE PULP MILL Valmet introduces the new Valmet Fiberline Analyzer to enable pulp makers to improve total pulp quality management, boost process stability and gain major savings in chemical costs from the digester blow line right up to final pulp storage. The Valmet Fiberline Analyzer includes the major advances in measuring technology gained through four generations of Valmet Kappa Analyzers. It measures pulp lignin content and brightness in addition to enhanced fiber and shive property measurements using the latest highdefinition imaging techniques. Measurement data from automatically extracted pulp samples, in addition to inline sensor information can be combined with real-time production targets to provide setpoints for chemical controls from the digester to final bleaching stages. “This is the most robust analyzer solution we have ever developed for the pulp mills and it provides a very good basis for advanced process control,” says Kari Lampela, Business Manager, Automation business line, Valmet. Application specific measurements and controls Built-in controls can provide external setpoints to the chemical dosage controllers using easily understood function blocks to perform filtering and calculations. For softwood pulps, the basic controller uses a Kappa factor control modified with predictive feedback taking Kappa/brightness, shive content and COD (Chemical Oxygen Demand) into account. Valmet Fiberline Analyzer can also separately measure lignin and hexenuronic acid (HexA) to provide significantly improved control of the complex chemistry of cooking and delignification, especially with hardwood pulps. These measurement and control capabilities, coupled with the analyzer’s unique ability to accurately measure final brightness, close the loop for true fiberline process optimization and quality control. User-friendliness and remote support The analyzer requires minimal maintenance and features chemical based self-cleaning for trouble free operation. With the built-in touch screen display, all analyzer operating parameters, operating sequences and diagnostics together with operating instruction are all instantly available. Remote configuration and operation as well as Valmet Industrial Internet (VII) capabilities provide the possibilities of remote specialist support and assistance from Valmet around the world. For further information, please contact: Kari Lampela, Business Manager, Automation, Valmet, tel. +358503423951 Matias Ruuskanen, Product Manager, Automation, Valmet, tel. +358469201695 Read more: www.valmet.com/fiberline-analyzer

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g PAPERmaking! FROM THE PUBLISHERS OF PAP PER TECHNOLOGY INTERNATIONAL

Volume 7, Number 1, 2021

VALMET INTRODUCES MAINTENANCE OPERATIONS AGREEMENT As part of “Valmet’s way to serve” concept for the best customer experience at all the touchpoints of the lifecycle, Valmet is introducing Maintenance Operations Agreement. Valmet offers the service agreement for development and outsourcing of mill and plant maintenance operations for energy, pulp, paper, board and tissue customers. “We want to ensure the maximal reliability and optimized performance of our customers’ production processes. Together with customers, we set up a maintenance operation dream team with modern maintenance processes and a mindset committed to safe and more sustainable maintenance operations to meet the customer’s targets on site,” says Timo Harjunpää, Director, Maintenance Operations and Development, Services at Valmet. Targets achieved through collaboration Valmet continuously develops its way to manage maintenance, maintenance procedures and new maintenance solutions to meet customer’s needs. Reliable maintenance operations will make the site run at its best throughout the lifecycle, allowing energy, pulp, paper, board or tissue customers to focus on their core business. “In brownfield cases, we can help customers to reduce maintenance costs by approximately 10 to 20 percent and increase efficiency by 5 to 10 percent. With a new investment, we help to secure a world class start-up curve and accelerate the return on the investment. We will establish a maintenance management model and organization already before the start,” Harjunpää says. Continuous success through Valmet’s service agreements Valmet’s service agreements help customers achieve the optimal outcome throughout the lifecycle of the equipment and processes. The agreement is tailored to customer needs, whether it is about easy access to Valmet experts, high-quality products and services, costeffectiveness, maintenance or the continuous development of performance to achieve mutually agreed targets. Valmet’s typical service agreements range from corporate-level frame agreements to milllevel partnership agreements. Valmet’s services offering, including Industrial Internet solutions, forms the building blocks for customized agreements. For further information, please contact: Timo Harjunpää, Director, Maintenance Operations and Development, Services, Valmet, tel. +358 40 824 4253

Page 10 of 20

Products & Services

g PAPERmaking! FROM THE PUBLISHERS OF PAP PER TECHNOLOGY INTERNATIONAL

Volume 7, Number 1, 2021

VALMET LAUNCHES A NEW BLADE CONSISTENCY MEASUREMENT FOR PULP AND PAPER PRODUCERS Valmet launches a redesigned Valmet Blade Consistency Measurement (Valmet SP) for pulp and paper producers. With the latest technology, new user interface, and patented internal detection principle, the transmitter continues to offer reliable, accurate, and cost-efficient consistency measurement for all applications. “Valmet Blade Consistency has been a standard consistency measurement in the market for decades. We want to continue the good performance and reliability of the previous generations with improved technology and user experience. By utilizing all the good features of the old transmitter, we developed a more reliable and easier-to-use device. All the development decisions were made with reliability, accuracy, and long lifetime in mind,” says Bengt Johansson, Product Manager, Measurement products, Automation business line, Valmet. Cost-efficient consistency measurement Valmet Blade Consistency Measurement is an economic option with easy installation and low maintenance needs. With modular design and low lifetime costs, it offers reliable consistency measurements without moving parts or need for preventive maintenance. The new patented detection principle utilizing contactless technology ensures reliability also in the future. With shear force measurement technology and a large blade and process couplings portfolio, it is possible to measure fiber consistency ranging from 0,7 to 16 percent in all types of installations in the entire pulp process. New user interface for enhanced operation Commissioning, calibration, and operation have been enhanced with a new Valmet Link user interface, a flexible platform with secure remote connection possibilities. With graphical display and clear menu structure, set-up and operation are fast and easy. Intuitive user interface and bigger display enable easier calibration and give a better overview of calibration data. The user interface is prepared for different communication protocols and can be updated for future functionalities. The industrial standard in consistency measurement Valmet’s measurement technology was first patented in 1954, and since then Valmet Blade Consistency Measurement has been a market leader in the industry. Over the years, it has become a standard shear force measurement for fiber consistency in many mills and it is the most sold consistency measurement globally. Still utilizing the same measurement principle, the 4th generation sensor continues to offer accurate and reliable fiber consistency measurement for all applications. Read more: Valmet Blade Consistency Measurement

Page 11 of 20

Products & Services

g PAPERmaking! FROM THE PUBLISHERS OF PAP PER TECHNOLOGY INTERNATIONAL

Volume 7, Number 1, 2021

VALMET UPDATES PAPER-LAB WITH NEW S-TEST MODULE Valmet enhances the offering of Valmet Paper Lab, an automated paper testing laboratory, for linerboard applications. In recent years, a large share of the Valmet Paper Lab deliveries has already been for linerboard applications. With a new S-Test module, Valmet Paper Lab offers a complete laboratory package for linerboard producers.| “The new S-Test module offers even more benefits by saving operators’ time, materials and providing real-time valuable quality information. In typical linerboard measurements, such as tensile strength, basis weight, short span compression (SCT), burst, caliper, surface properties, and porosity, Valmet Paper Lab has become a cornerstone of the laboratory automation,” says Bogdan Pavlovic, Business Manager, Board and Paper Analyzers, Automation business line, Valmet. Faster and easier classification with S-Test Compared to the time-consuming and user-dependent standard manual laboratory procedure known as Concora Medium Test (CMT), the S-Test offers a fast and easy method for estimating the strength classification of containerboard medium fluting. There is no need to corrugate or tape the test pieces, which makes the strength classification fast and easy, and provides significant savings in time and materials. The S-Test has been standardized by German Institute for Standardization and confirmed by The Cepi Container Board, a European industry association of producers of corrugated case materials.

Page 12 of 20

Products & Services

g PAPERmaking! FROM THE PUBLISHERS OF PAP PER TECHNOLOGY INTERNATIONAL

Volume 7, Number 1, 2021

VOITH LAUNCHES THE ONPERFORMANCE.LAB - A REMOTE SERVICE CENTER FOR THE DIGITAL OPTIMIZATION OF PAPER PRODUCTION With the OnPerformance.Lab, Voith is now offering paper manufacturers the opportunity to identify and exploit improvement potential for their production through an in-depth analysis of process data. The Remote Service Center at the Heidenheim site became operational at an interactive online event attended by customers and Voith experts. “The remote digital services provided by the OnPerformance.Lab enable customers to significantly improve the performance and availability of their production lines,” explained Dr. Jürgen Abraham, President Products & Services and Digital Business Officer at Voith Paper. “Within the scope of a service agreement, we leverage AI-assisted analysis and evaluation methods and the expertise of our engineers to help customers optimize their processes and reduce the use of resources in the paper manufacturing process.” The optimization is based on process and machine data that are transferred via a VPN or cloud connection to the OnPerformance.Lab, where they are analyzed with the help of data mining methods and artificial intelligence. The continuous monitoring at the process level registers deviations immediately and allows fast and accurate corrections to be made. In addition, the industry-specific expertise of Voith's specialists facilitates the evaluation of the data and the development of individual, specific and implementable recommendations to stabilize and increase machine efficiency. All OnPerformance.Lab services are designed to increase the performance and availability of the customer’s machines and reduce the use of resources in the paper manufacturing process. To guarantee a comprehensive improvement in all process steps, Voith experts proactively develop optimization proposals for discussion with the customer. The OnPerformance.Lab services are available for the entire production line from stock preparation to winder and can be scaled as necessary. In their service agreement, customers can specify a range of important KPIs such as fiber consumption, basis weight, paper moisture and grade change times, and can add others at any time. With the OnPerformance.Lab, Voith is supporting the digital transformation of the paper industry. The efficiency improvements achieved through the Remote Service Center help manufacturers to enhance their competitiveness and at the same time make their production processes more sustainable. (Voith Paper GmbH & Co KG)

Page 13 of 20

Products & Services

g PAPERmaking! FROM THE PUBLISHERS OF PAP PER TECHNOLOGY INTERNATIONAL

Volume 7, Number 1, 2021

NEW PROTECT NG PRESS FELT MEASUREMENT SYSTEM FROM VOITH When measuring press felts manually, there is often a risk of jamming, tripping and slipping. At some positions, the employee is additionally exposed to enormous heat and the constant danger of a felt break also represents a significant, permanent safety risk. Yet, the measurement of felts is an important component in the papermaking process. The automated measurement with Voith´s ProTect NG (Next Generation) therefore offers an excellent alternative to determine the important felt data without risk. The ProTect system consists of an autonomous carriage and one or more fixed rails (traverses). The user waits on the runway during the measurement and thus no longer remains in the hazardous area. A carriage can be used in different paper machines. It does not matter how wide the machines are, and whether the carriage has to run to the left or to the right. The new generation of the ProTect NG carriage also offers programmable measuring cycles, self-diagnosis and remote service access. Furthermore, the carriage speed can be reduced to the point where 3D mapping travel is possible. The traverses can be installed in almost any position, even those that are difficult to access. No water, electricity or compressed air connection is required at the actual measuring points, as the ProTect NG carriage is a "self-supplier". Only the charging station needs a 110/220V power connection and in the best case a water connection to fill the tank. Optimized diagnostic options with the new ProTect NG The new ProTect NG continues the global success of ProTect and offers several new benefits for customers. "With the experience of much more than 200 installed positions, ProTect has become the standard for semi-automatic press felt measurements. ProTect NG is the consistent further development of the original ProTect system with improvements in all areas. In addition to weight reduction and optimized serviceability, functionality has been improved above all," explains Torben Beckmann, Global Product Manager at Voith Paper. "Besides the ability to program individual macros for more customized measurements, ProTect NG has a number of pre-programmed procedures, including detailed edge analysis, automatic CD and MD measurements and variable speed measurements. ProTect NG offers the service expert the flexibility for individual measurements, while making standard measurements as easy as possible," says Beckmann. ProTect NG provides an optimized diagnostic option, which can be combined with all available measuring instruments. The integrated display shows the most important carriage parameters as well as the pre-installed measuring run programs. The intuitive operability provides even inexperienced operators with quick access to the various analysis options. ProTect NG also convinces with its further reduced weight, which is achieved by using carbon and 3D-printed parts. The lower weight is important for more comfortable handling combined with increased safety for the staff. 3D diagnosis of the press felts in CMD In combination with suitable felt measuring devices, the very low speed of the ProTect NG enables three-dimensional scanning of felt surface temperatures, moisture and water permeability profiles of the press felts. Depending on the machine width, a 3D scan can take several minutes, during which time the service technician now no longer needs to be in the dangerous area. Voith offers a tensiometer specially developed for felt tension measurements that saves the values on a USB stick during the measurement. After the measurement, the measured values are read out in the PC.

Page 14 of 20

Products & Services

g PAPERmaking! FROM THE PUBLISHERS OF PAP PER TECHNOLOGY INTERNATIONAL

Volume 7, Number 1, 2021

VOITH LAUNCHES NEW PU ROLL COVER FOR PRESS ROLLS Problems are often encountered with conventional rolls when processing pulp. The rolls cause high specific pressures as well as a short nip. To prevent this, Voith is now offering a new polyurethane (PU) roll cover that has been developed for press rolls: the IntensePress. This has been specifically designed for use in the demanding applications of pulp machines and twin-wire presses. The decisive advantage of IntensePress is its high chemical resistance. Furthermore, it is characterized by a high level of temperature resistance. Both features increase the running time of the roll, simplify work processes, and thus increase the machine’s productivity. The high chemical and temperature resistance are made possible by a new type of polyurethane. To provide customers with the best possible output when using IntensePress, Voith is investing in individually tailored advice. The roll cover’s PU surface is modified according to individual requirements, for example, to achieve a greater open surface and thus increased dewatering performance and a higher dry content. IntensePress can also ensure a wider nip and, in doing so, minimize the specific pressure. Voith determines what the optimal nip load will look like for each customer, taking into account the individual operating conditions. IntensePress can be used on all current machines on the market. The Chinese pulp and paper manufacturer Asia Symbol Rizhao has already used the roll cover for a test run. “Unlike conventional PU covers, IntensePress has demonstrated a reliable performance level in the critical chemical environment of pulp machines,” reports Guangcai Xiao, Pulp Line Director at Asia Symbol Rizhao. She adds: “The project is very successful, as it is generating considerable energy savings for us.” But that is not all: IntensePress has also increased the productivity of the machine, and the service life of the forming fabric has been increased from one month to two, resulting in less downtime and reduced costs. IntensePress has also been used successfully in Sweden, where the roll cover was tested in the Södra Cell Mösterås pulp mill and scored particularly well in terms of abrasion and temperature resistance. With IntensePress, the machines can now reportedly be left to run uninterrupted between annual mill shutdowns. Previously, this was impossible on account of the high wear to the wire drive roll. As IntensePress can handle the high temperature in this position, interim shutdowns are no longer necessary. In addition, IntensePress maintains its strength and thus prevents polygonization of the roll. The test run reportedly showed that the service life of the roll could be increased from between eight and 10 months up to 12 to 18 months. Voith not only offers the new type of polyurethane for press rolls but also for suction press rolls. The PU cover IntenseFlow, for example, has the same properties as IntensePress but differs in its surface geometry, which has been adapted to suction press rolls. IntensePress is available in the following four versions: smooth, blind-drilled, grooved, and blind-drilled and grooved. In addition to the suction holes, IntenseFlow is available with the following surface finishes: blind-drilled, grooved, and blind-drilled and grooved.

Page 15 of 20

Products & Services

g PAPERmaking! FROM THE PUBLISHERS OF PAP PER TECHNOLOGY INTERNATIONAL

Volume 7, Number 1, 2021

COLOR CAMERA INSPECTION SYSTEMS ADDRESS CHALLENGING CLASSIFICATION ISSUES IN PULP APPLICATIONS AMETEK Surface Vision, a leading provider of online surface inspection solutions, is helping address the challenges in detecting pulp contamination with its advanced automated color inspection technology. Surface inspection systems are integral to the pulp-making process by providing a full inspection of the pulp, an essential raw material in the production of paper. The production process presents a unique set of challenges as pulp is not a homogeneous product due to the presence of different fibers and particles of varying colors. Additionally, the dirt content of pulp is an important quality factor in determining its suitability for fine paper production. The Technical Association of the Pulp and Paper Industry defines dirt as “any foreign material in a pulp sheet which, when examined by reflected light, has a marked contrasting color and an equivalent black area of 0.04 mm2 or greater.” AMETEK Surface Vision provides the pulp and paper industry with automated inspection systems, using multiple line scan cameras installed across the inspected material, supporting the pulp-making process by providing a complete and thorough inspection. The SmartView® system provides a highly-effective and accurate automated inspection system optimized for pulp inspection, utilizing a combined transmission-reflection view. Volker Köelmel, Surface Vision’s Global Manager of Plastic, Nonwovens & Paper ,said: “Our technology in surface inspection systems successfully supports the pulp-manufacturing process by providing tools specifically designed for pulp inspection, including defect area statistics, dirt count, and parts per million. By delivering the best aspects of light and reflection through SmartView, the inspection image looks smoother, images of the defects from the inspected surface are precise, and defects located inside the pulp are sufficiently visible.” About AMETEK Surface Vision AMETEK Surface Vision is a world leader in automated online surface inspection solutions with a broad product portfolio optimized for web and surface inspection and monitoring and process surveillance applications. Its product portfolio includes two distinct product lines: SmartView® systems and SmartAdvisor® systems. Each product line uniquely enables customers to inspect the surfaces of materials processed in a continuous fashion across the metals, paper, plastics, nonwovens, and glass industries.

Page 16 of 20

Products & Services

g PAPERmaking! FROM THE PUBLISHERS OF PAP PER TECHNOLOGY INTERNATIONAL

Volume 7, Number 1, 2021

ANDRITZ LAUNCHES TWINFLO PRIME – A DEVELOPMENT IN LC REFINING ANDRITZ has launched the latest innovation in low-consistency refining – the TwinFlo Prime refiner, combining concentrated performance in a very compact design. The TwinFlo Prime builds on the success of more than 2,000 LC refining plants from ANDRITZ operating all over the world. The newly developed LC refiner combines the wellproven basic principles of the current ANDRITZ TwinFlo refiner with the higher energy input possible, reduced maintenance needs, and increased refiner plate lifetime. The ANDRITZ TwinFlo Prime features the following innovations: •

Fixed connection between rotor and shaft. Both components move together in axial direction. There are no impediments to axial movement in the process area because this movement is transferred to the coupling via the bearing unit.

•

Hydrodynamic, water-lubricated plain bearing. This bearing technology makes the extremely compact design of the new LC refiner possible and enables the rotor and shaft to float freely in axial direction. This leads to a 30% reduction in refiner length and a gain of up to 25% in energy input – with the resulting higher performance – compared to the current TwinFlo refiner.

•

Reduced wear on refiner plates. Optimum pulp flow to each refining zone eliminates uneven wear on refiner plates and provides longer plate lifetime as well as reduced maintenance costs.

•

Advanced operating conditions. The new LC refiner is environmentally friendly, operating without oil, and features a special damping device to ensure excellent refining results as well as safe operation.

•

Versatile in application. The TwinFlo Prime is suited to all LC refining applications regardless of the raw materials and process set-up used.

Markus Pichler, Vice President of the Mechanical Pulping, Paper, Fiber and Recycling Division at ANDRITZ: “The challenges and demands of our customers have always been at the forefront of our research and development work. That’s why we are especially proud to present our new LC refiner, which offers extensive solutions to meet these demands. I am convinced that the new TwinFlo Prime is the right way to achieve our customers’ high performance goals.”

Page 17 of 20

Products & Services

g PAPERmaking! FROM THE PUBLISHERS OF PAP PER TECHNOLOGY INTERNATIONAL

Volume 7, Number 1, 2021

BTG INTRODUCES MACSASHTM TO OPTIMIZE PAPER QUALITY MACSashTM is an innovative solution that combines model predictive control, innovative measurements and support services. The integrated solution stabilizes ash levels in the wet end of the papermaking process resulting in reduced filler variability in the final sheet. The solution can be implemented in packaging as well as printing and writing applications. Additional demonstrated benefits of MACSash TM include increased machine speeds, reduced chemical costs, as well as a reduction of web breaks and quality variability - generating further economic benefit for the mill. MACSashTM has recently been implemented at Brigl & Bergmeister at Niklasdorf. The benefits delivered by the solution has resulted in a return on the investments in eight (8) months. ”Thanks to MACSash, we have transformed our operations, stabilizing our ash content and getting a better quality of our paper for the full satisfaction of our customers. We are thankful to the BTG specialists with whom we had outstanding collaboration with during the entire project.” says Ing. DI (FH) Michael Leisenberger, Head of Production. In the specific case of the Brigl & Bergmeister project, MACSash TM was primarily implemented remotely during the COVID-19 pandemic. This flexibility enables producers to initiate an attractive payback project in these challenging times.

Page 18 of 20

Products & Services

g PAPERmaking! FROM THE PUBLISHERS OF PAP PER TECHNOLOGY INTERNATIONAL

Volume 7, Number 1, 2021

BTG INTRODUCES THE SPM FOR FIBER MORPHOLOGY SOLUTIONS The BTG Single Point Morphology (SPM-5550) is the newest addition to the BTG portfolio, providing valuable information to better understand fibers. It is an online Morphology analyser, measuring several fiber properties including length, surface, kink and shives content. The SPM-5550 is mounted directly to the fiber processing pipe and contains all unit operations of the traditional multi-point Morphology analyser, the result being a much faster measurement frequency to support 4.0 solutions. It is the key building block of many solutions in the areas of pulping, graphic paper, packaging and tissue. Solutions incorporating the SPM have been demonstrated to impact key performance indicators such as fiber costs, energy costs, chemical costs and product quality.

Page 19 of 20

Products & Services

g PAPERmaking! FROM THE PUBLISHERS OF PAP PER TECHNOLOGY INTERNATIONAL

Volume 7, Number 1, 2021

OPTIMISED TURBIDITY SENSOR As a result of the optimisations carried out and extensive series of tests, the tried and tested EXspect 271 turbidity sensor can now be approved for an extended pressure range. The NIR backscatter sensor EXspect 271 from EXNER is not only characterised by its economic use, but also by its compact and at the same time robust design. It is mainly used in the food and beverage industry as well as in many other applications where it is necessary to determine turbidity in medium and high measuring ranges. Cleaning and sterilization using CIP and SIP processes are of course possible. Another advantage of the sensor is the spherical design of the measuring optics. This minimizes the adhesion of air bubbles and the formation of deposits. The compact sensor EXspect 271 has not only successfully completed extensive test series, but has also established itself in practical use. Thanks to the optimisations that have now been carried out, it is possible to use the sensor not only in applications with a process pressure of up to 20 bar (290 psi), but also in vacuum applications.

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Products & Services

PAPERmaking! FROM THE PUBLISHERS OF PAPER TECHNOLOGY Volume 7, Number 1, 2021

Installations The following pages contain a summary of the various installations and orders from around the world of papermaking, wood panel and saw mills, and bio-power generation, received between the start of November 2020 and beginning of May 2021.

Page 1 of 9

Installations

g PAPERmaking!

FROM THE PUBLISHERS OF PAP PER TECHNOLOGY

Volume 7, Number 1, 2021

COMPANY, SITE Anon Austria Anon China Anon Fabriano area Italy Anon Slovenia Anon USA

SUPPLIER Jagenberg Paper Systems Runtech Systems

ORDER DESCRIPTION modernisation of winder

URL link

vacuum systems for five machines rebuild of drive and automation system

link

Jagenberg Paper Systems Siempelkamp

rebuild of Gobel Optislit winder

link

composites press system (wood panel)

link

Ahlstrom-Munksjö Billingsfors Sweden Ahlstrom-Munksjö Sweden Aktül Kagit Aktül Kagit Üretim Pazarlama A.S., Pamukova, Sakarya Province Turkey Amarande SAS Lussac les Châteaux France

Valmet

IQ Steam Profiler and associated cross-direction moisture control

link

Tresu

custom-designed coating line

link

Valmet

new 5.6m tissue production line

link

Andritz

link

Arauco Bio Bío Region Chile

Valmet

Arauco Licancel Cellulose Plant Chile Arkhangelsk Pulp and Paper Mill, Jsc Novodvinsk Russia Asaleo Care New Zealand Bedford Paper De Pere Wisconsin BillerudKorsnäs Frövi Mill Sweden Cartiere di Trevi Italy Cascades Ashland Mill Virginia USA

ABB

an elliptical cylinder pre-needler to process shoddy and natural fibres for the production of heavy felts (nonwovens) extensive Industrial Internet services for Mill Line 3, making it the world’s most autonomous pulp mill Modernisation DCS and the Ethernet network

Valmet

IQ QCS and moisturiser system for BM1

link

Runtech Systems

vacuum system

link

PCMC

Tissue converting line

link

Andritz

HERB recovery boiler and a high-density concentrator solution for the black liquor line fast-unloading pope winder

link

stock preparation solution for conversion project (newsprint to recycled CCM)

link

Sael

De Iuliis Kadant

Page 2 of 9

Installations

link

g PAPERmaking!

FROM THE PUBLISHERS OF PA APER TECHNOLOGY

Volume 7, Number 1, 2021

COMPANY, SITE Cascades Bear Island Mill Virginia USA Drewsen Spezialpapiere Lachendorf Germany DS Smith Contoire-Hamel France Emami Paper Mills Balasore Mill Odisha India Europap Tezol Kağit Mersin Turkey Fargesbois France Finnish Fibreboards Heinola Finland FINSA Nelas Portugal Fjernvarme Fyn Produktion A/S Odense (island of Funen) Denmark Greenpaper Mexico GS Paperboard & Packaging Group Malaysia Guangxi Chongzuo Lelin Forestry Development Co. Ltd. Chongzuo Guangxi Province China Guararapes Paineis, S/A Caçador plant Santa Catarina state Brazil Guararapes Paineis, S/A Caçador plant Santa Catarina state Brazil

SUPPLIER Valmet

ORDER DESCRIPTION paper grade conversion rebuild (to produce testliner) with automation and services

BW Papersystems

small volume sheeter

link

Valmet

IQ Moisturise system (PM1)

link

Valmet

metering size press with starch preparation

link

Toscotec

tissue machine

link

Jartek

sorting line for green lumber

link

Argos Solutions

digital vision grading system

link

Dieffenbacher

four glue-saving systems for two production lines

link

Andritz

Biomass boiler plant 180MWth (Energy Company)

link

Bellmer

rebuild of press section and predryer system (PM3) digitisation solutions for production planning

link

Andritz

World’s largest chip washing system and pressurised refining system to MDF line (wood panel)

link

Siempelkamp

MDF plant (wood panel)

link

Valmet

defibrator EVO system for MDF plant (wood panel)

link

Tietoevry

Page 3 of 9

Installations

URL link

link

g PAPERmaking!

FROM THE PUBLISHERS OF PAP PER TECHNOLOGY

Volume 7, Number 1, 2021

COMPANY, SITE Hansol Paper Janghang Mill & Cheonan Mill & Shintanjin Mill All in South Korea

SUPPLIER Valmet

Hengan International Group Shandong Mill and Hunan Mill China Homanit Group Pagirai Lithuania Iggesund Paperboard Iggesund Mill Sweden Iggesund Paperboard Iggesund Mill Sweden INPEL Santo Antônio de Pádua Rio de Janeiro Brazil ITC Bhadrachalam unit Telangana India JSC Management Company of the Holding Belorusskie oboi Belarus Kingdecor Zhejiang Co., Ltd. China Kuhmo Oy Finland LD Celulose S.A. Indianópolis Brazil LD Celulose S.A. Triângulo Mineiro region Brazil Lee & Man Paper (Dongguan, Guangdong Province, and Jiujiang, Jiangxi Province China Liansheng Pulp & Paper (Zhangzhou) Zhangzhou Fujian province China

Toscotec

URL link

link

Dieffenbacher

THDF manufacturing plant (wood panel)

link

ABB

drives and control system for KM2

link

Tasowheel

refurbishing 2 more headbox slice control systemsfor headboxes 1 and 4 on KM1 Modernise TM2 – replacement of Fourdrinier with crescent former

link

Andritz

evaporation plant for kraft black liquor

link

Andritz

folding boxboard production line

link

A.Celli

Paper rewinder

link

Jartek

packaging plant (saw mill)

link

Andritz

maintenance contract

link

Babcock & Wilcox

cooling towers for a pulp mill

link

Andritz

two semi-chemical fibrelines

link

A.Celli

four tissue and two paper rewinder

link

Hergen

Page 4 of 9

ORDER DESCRIPTION analyzers and Industrial Internet solutions: two Valmet Fiber Furnish Analyzers to JM; one to CM; and a Valmet Brightness Measurement to SM TAD tissue machine to each site

Installations

link

g PAPERmaking!

FROM THE PUBLISHERS OF PA APER TECHNOLOGY

Volume 7, Number 1, 2021

COMPANY, SITE Liansheng Pulp & Paper (Zhangzhou) Zhangzhou Fujian province China Lotus Teknik A.Ş. Turkey Macedonian Paper Mill Thessaloniki Greece Mashaan Huawang New Material Technology Co., Ltd Hangzhou Plant China Medite Smartply Waterford Ireland MEPCO Saudi Arabia Metsä Board (Kemi, Kyro, Simpele, Tako and Äänekoski Mills) all in Finland Metsä Board Kemi Bioproduct Mill Finland

SUPPLIER Valmet

Metsä Fibre Kemi Bioproduct Mill Finland

Afry

Metsä Fibre Kemi Bioproduct Mill Finland Metsä Fibre Kemi Bioproduct Mill Finland Metsä Fibre Kemi Bioproduct Mill Finland

Andritz Ircon-Solaronics

A.Celli

ORDER DESCRIPTION folding boxboard making line (BM1), a fine paper making line (PM3) and a bleached chemi thermo mechanical pulp (BCTMP) production line Wetlace carded pulp line (nonwovens) project to replace electrical infrared drier with gas infrared system décor paper winder

URL link

link link

link

Buettner

high performance dryer with energy plant (wood panel)

link

Toscotec

tissue machine

link

ABB

L&W Autoline automated paper testing solution at each mill

link

Valmet

link

Aquaflow

full production process from wood handling to baling, as well as automation system and Industrial Internet solutions project management services for the whole mill, detail engineering services for all engineering disciplines for Balance of Plant (BOP) and the digitalisation services of the mill with BIM (Building Information Modelling) and PIM (Process Information Modelling) of the project including establishment of SSOT (Single-Source-of-Truth) concept towards digital twin. AFRY will also provide project management, engineering and site services for the chlorine dioxide plant wastewater treatment plant

Andritz

two log-yard cranes

link

Caverion

electrical and ICT systems

link

Page 5 of 9

Installations

link

g PAPERmaking!

FROM THE PUBLISHERS OF PAP PER TECHNOLOGY

Volume 7, Number 1, 2021

COMPANY, SITE Metsä Fibre Kemi Bioproduct Mill Finland Metsä Fibre Kemi Bioproduct Mill Finland

SUPPLIER Linde

ORDER DESCRIPTION on-site oxygen supply

Raumaster

link

Metsä Fibre Kemi Bioproduct Mill Finland Metsä Fibre Kemi Bioproduct Mill Finland Metsä Fibre Rauma Mill Finland Metsä Group worldwide Metsä Tissue Mänttä Mill Finland Minet S.A, Ramnicu Valcéa Romania Modern Karton Turkey Modern Karton Ergene Turkey

Sulzer Pumps

wood chip and bark handling area machinery as well as conveyor systems for gasifier and recovery boiler and main part of lime, caustic sludge and causticizing conveyors pumps and mixers

VR Transpoint

logistics partner

link

Caverion

electrical and ICT systems (saw mill)

link

Zalaris

link

Valmet

Multi-Country Payroll technology and outsourcing services rebuild tissue machine (PM10)

Andritz

Spunlace line (nonwovens)

link

Projet

link

Mondi Frantschach Mill Germany Nile Wood S.A.E. Sadat City Egypt

Jagenberg Paper Systems

high pressure showers for the forming section modernisation of OCC line (PM3), new stock preparation line for pulp and recovered paper, and upgrade and extension of existing DIP line rider roll rebuild (PM6)

link

Nine Dragons China various mills Nine Dragons China various mills Norske Skog Skogn Mill Norway

Andritz

complete MDF plant, including a chip washing and pressurized refining system (in cooperation with Dieffenbacher) (wood panel) white liquor plant, three ash recrystallization systems, and six recausticizing plants six fibrelines, two recovery boilers and two lime kilns Manufacturing Execution System (MES) for pulp and paper

link

Voith

Andritz

Valmet

ABB

Page 6 of 9

Installations

URL link

link

g PAPERmaking!

FROM THE PUBLISHERS OF PA APER TECHNOLOGY

Volume 7, Number 1, 2021

COMPANY, SITE North Pacific Paper Company Longview Washington USA Oji Fibre Solutions Penrose Mill Auckland New Zealand Oji Papéis Especiais Piracicaba Mill São Paulo Brazil Oji Papéis Especiais Piracicaba Mill São Paulo Brazil Papresa Rentería Spain Pfleiderer Baruth Brandenburg Germany Pfleiderer Group Gütersloh Germany Progroup Eisenhüttendstadt Germany

SUPPLIER Andritz

ORDER DESCRIPTION upgrade of OCC line with new drum pulper, cleaning and reject handling equipment

ABB

winder safety system

link

Valmet

Two QCS with six scanners for paper machine and coater machine

link

Voith

modernisation of MP2 and Coater PC3

link

Voith

OCC stock preparation system (700tpd)

link

Dieffenbacher

retrofit of steam preheater to MDF line (wood panel)

link

Argos Solutions

link

Pureko Sp. z o.o. Myszków Poland Renewcell Ortviken Sundsvall Sweden Republic Paperboard Company LLC Lawton Oklahoma USA Rizhao Huatai Paper Rizhao City China SCA Ortviken Pulp Mill Sweden SCA Ortviken Pulp Mill Sweden

Andritz

three inspection systems for melamine-laminated and coated board deliver the world’s first artificial intelligence (AI) based Valmet IQ Web Inspection System (WIS) to PM2 a needlepunch line (nonwovens)

Valmet

textile recycling plant equipment

link

Voith

curtain coater for gypsum linerboard line

link

PMP Group

headbox for sack kraft machine (PM3)

link

Afry

piping engineering assignment for CTMP project

link

Valmet

new flash drying and baling line and a rebuild of the existing integrated CTMP line

link

Valmet

Page 7 of 9

Installations

URL link

link

g PAPERmaking!

FROM THE PUBLISHERS OF PAP PER TECHNOLOGY

Volume 7, Number 1, 2021

COMPANY, SITE Segezha Group (a subsidiary of Sistema PJSFC) Sokol Vologda Region Russia Shanying International Holdings Co., Ltd. Anhui Mill China Shanying International Zhaoqing Mill China Shanying International Zhaoqing Mill China Shanying International Zhaoqing Mill China Shanying Paper Guangdong China Simka Kagit Sanayi VE Ticaret AS Kayseri Turkey Södra Cell Mönsterås Pulp Mill Sweden Södra Cell Värö Mill Sweden Smurfit Kappa Ania Italy Starwood Orman Urunleri Sanayi A.S. İnegöl Turkey Starwood Orman Urunleri Sanayi A.S. İnegöl Turkey Starwood Orman Urunleri Sanayi A.S. İnegöl Turkey Stora Enso Forshaga Mill Sweden Stora Enso Forshaga Mill Sweden

SUPPLIER Bellmer

ORDER DESCRIPTION new paper machine for unbleached greaseproof paper

Valmet

extension the unique roll service and condition monitoring agreement

link

Kadant

two OCC systems for PM53 and PM54

link

Runtech Systems

vacuum systems for linerboard machines PM52 and PM53

link

Valmet

Containerboard making line with extensive automation and services (PM53) three hot dispersion systems (PM52)

link

Voith

OnQuality QCS scanners and sensors to PM1

link

Valmet

a new evaporation line 3 to replace the oldest evaporation line 1 pulper rebuild

link

Runtech Systems

vacuum system rebuild to PM2 and PM3

link

Andritz

second MDF fibre production line (wood panel)

link

Buettner

fibre dryer for MDF/HDF line (wood panel)

link

Siempelkamp

thin MDF/HDF line (wood panel)

link

UMV Coating Systems

offline coater for application of dispersion barrier coatings

link

Ircon-Solaronics

drying system for UMV coating system

link

Cellwood

Page 8 of 9

Installations

URL link

link

g PAPERmaking!

FROM THE PUBLISHERS OF PA APER TECHNOLOGY

Volume 7, Number 1, 2021

COMPANY, SITE Stora Enso Forshaga Mill Sweden Stora Enso Oulu Mill Finland Stora Enso Skoghall Mill Värmland Sweden Stora Enso Skutskär Mill Sweden Strathcona Napanee Mill Canada Tampereen Sähkölaitos Oy Tampere Finland UPM Changshu China UPM Paso de los Toros Uruguay Uvadrev-Holding Uva Russia Veolia Energie ČR, a.s. Prerov Czech Republic Versowood's Vierumäki Finland Zellstoff Pöls AG Austria Zhejiang Jingxing Paper Co., Ltd. China

SUPPLIER Valmet

ORDER DESCRIPTION Web Inspection System to coating and laminating plant

Procemex

web monitoring and web inspection systems (BM7 conversion) convert feed system in pulp cooking plant

link

BTG

sensors for pulp mill

link

Projet

tail and deckle cutter

link

Valmet

Automation systems (bio-energy plant)

link

Valmet

Valmet Fiber Furnish Analyzer (Valmet MAP Q) for PM3

link

Andritz

maintenance contract (for new 2.1Mtpy pulp mill)

link

Siempelkamp

particleboard line

link

Valmet

multifuel boiler plant 40MWth

link

Jartek

modernization of a dry sorting plant (saw mill) doctor winder

link

Zhumadianshi Baiyun Paper Co. Suiping County Zhumadian City China

Mineral Technologies

IQ Steam Profiler and DNA Machine Monitoring systems with condition monitoring analysis and diagnosis services (for PM12 & PM16) build a PCC plant

Valmet

Jagenberg Paper Systems Valmet

Page 9 of 9

Installations

URL link

link

PAPERmaking! FROM THE PUBLISHERS OF PAPER TECHNOLOGY TE INTERNATIONAL

Volume 7, Number 1, 2021

Research Articles Most journals and magazines devoted to the paper industry contain a mixture of news, features and some technical articles. Very few contain research items, and even fewer of these are peer-reviewed. This listing contains the most recent articles from four of the remaining specialist English language journals that publish original peer-reviewed research: x x x x

IPPITA JOURNAL JOURNAL OF KOREA TAPPI (English abstract only) NORDIC PULP & PAPER RESEARCH JOURNAL TAPPI JOURNAL

Notes: 1. In 2019 APPITA JOURNAL separated from the APPITA MAGAZINE, and the last edition to date was Oct-Dec 2019. 2. IPPTA JOURNAL has reappeared as a biannual rather than quarterly journal, and alongside traditional research articles now includes more general items. 3. The excellent J-FOR+ (successor to the JOURNAL OF PULP & PAPER SCIENCE) from Canada ceased publication in late 2018 (Vol.7, No.6). 4. JOURNAL OF KOREA TAPPI is an excellent open-access research journal – abstracts are in English but articles in Korean. 5. TAPPI JOURNAL went open-access in 2020. 6. JAPAN TAPPI JOURNAL is another excellent journal, but the full papers are only reproduced in Japanese with a short abstract in English, and access is restricted.

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Research Articles

g PAPERmaking! FROM THE PUBLISHERS OF PAP PER TECHNOLOGY INTERNATIONAL

Volume 7, Number 1, 2021

IPPTA JOURNAL, Vol.32(2), 2020 1. Advancement in cloning technology of Eucalyptus to increase productivity for pulp and paper industry 2. Advances in ZLD Technologies 3. Best Practices in the Field of Manufacturing – SPB unit Erode 4. Best Practices in the Process Optimization of Paper Machines 5. Bleaching of Agro Raw Material Pulps by Chlorine free Bleaching Sequence: The “Brand Green Bleaching” Concept for Indian Agro Pulp and Paper Industry 6. Competitive strategies for operational excellence in optimization of enzymatic conversion of native starch cooking for size press application 7. Employer Branding: Employees and HRM Brand ambassadors 8. Energy Management and Effluent Treatment by Using Anaerobic and Aerobic Process - Case Study at Emami Paper Mills Limited – Balasore 9. Everything About “Brand Equity” 10. I am ok & you are ok to neither you nor me ok 11. Image Rebuilding For Indian Paper Industry 12. Implementation and enhancement of data management system using ERP Automation in a Pulp and Paper industry 13. Implementation of innovative process control techniques to minimize variations, improve quality and increase production in paper industry 14. Intelligent roll applications and case studies for better nip profiles and runnability 15. Naini Group - A Step towards Industry 4.0 16. Paper a ‘Threnody’? 17. Rethink Sales Channel as a Strategic Tool for Business Performance 18. Study of Characteristics of Ground Coal Fly Ash for Potential Use as Filler in High Opacity Specialty Papers 19. The Electric Power Saving through highly Developed Technology & the successful Case Study at SPP (Stock Preparation Plant) JOURNAL OF KOREA TAPPI, Vol.52(6), December 2020 1. Advanced Technology and Prospect of the Ink-jet Printing (I): Ink Characteristics and Ink-jet Paper 2. A Study on the Reaction of a 1064 nm Wavelength Fiber Laser to the Aluminium Metalizing Layer through the Surface of the Silver PET Label 3. Changes in the Hydrophobization Efficiency of Paper by Humidification Pretreatment during Gas Grafting Treatment Using Palmitoyl Chloride 4. Exploration of Alternative Woody Biomass for Manufacturing Biopellets 5. Study on the Multilayer Barrier Coating Using Cellulose Nanofibrils and Internal Sizing Agent 6. Effects of Cellulose Nanofibril on Emulsion Droplet Size and Stability 7. A Study on Efficiency of Different Kinds of Moisture Content Measurement Equipments for Enhancing Reliability of Quality of Recovered Paper Bales 8. Scientific Approach to Confirm the Excellence of Seokgayeoraehaengjeoksong as Korean Cultural Heritage 9. Effects of PAE-PVA and PAE-MP Dual Polymer Systems on Strength Properties of Paper 10. Comparison of Pulping Characteristics of Barrier Coated Papers by Image Evaluation 11. Effects of Recycling Paper Container for Beverages on Process Water Quality 12. Preparation of Cellulose Nanocrystal-based Poly (m-aminobenzene sulfonate) Copolymer for Heavy Metal Cr (VI) Adsorption

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Research Articles

g PAPERmaking! FROM THE PUBLISHERS OF PAP PER TECHNOLOGY INTERNATIONAL

Volume 7, Number 1, 2021

13. Effects of Pulp Type and Stock Concentration on Foamability and Bubble Size of Fiber Foam 14. Strength Improvement of the Coloring Paper for Fruit Bag by Using Non-woody Bamboo Kraft Pulp 15. Basic Study on Manufacturing Ink-jet Paper for High Speed Coating (I): Composition of Binder and Properties of Ink-jet Paper 16. Production of Cellulose Beads with TEAH-Urea Solvent and Dropping Technique: Effect of Inner Diameter of Syringe Needle 17. Impact on Rheology Modifier as Cellulose Nanofibril, Carbomers by Salts JOURNAL OF KOREA TAPPI, Vol.53(1), February 2021 1. Fracture Toughness, Measurement, and Applications Related to Paper Break 2. Changes in Physical Properties of Korean Paper according to the Amount and Temperature of Hibiscus manihot Root Mucilage 3. Characteristics of Organosolv Lignin Precipitated via pH Control 4. Changes in the Compositions of Organosolv Micronized Residues by Repeated Dissolution in NaOH/Urea 5. Dissolution and Regeneration of Residual Lignin-Controlled Micronized-Residues by Washing Methods 6. Fabrication of Superabsorbent Biogel from Carboxymethyl Cellulose 7. Chemical Surface Modification and Addition of Additive for Manufacturing CNF Powder with Good Dispersibility 8. Development of Biodegradable Cigarette Filter Material from Microfibers (Part 1): Preparation of the Filter Raw Materials and their characteristics 9. Properties of MFCs and MFC Films from Radiata Pine Pulps 10. Production of Cellulose Beads with Tetraethylammonium Hydroxide-Urea Solvent and Dropping Technique : Effects of Concentration of Cellulose Solution 11. Advanced Technology and Prospect of the Ink-Jet Printing (II): Coating Compositions and Coating Color Rheology NORDIC PULP & PAPER RESEARCH JOURNAL, Vol.35(4), December 2020 1. Review: Evolution of biobased and nanotechnology packaging – a review 2. Chemical pulping: Evaluation of sodium salt scaling in black liquor evaporators using existing process data 3. Chemical pulping: Assessing the value of a diversified by-product portfolio to allow for increased production flexibility in pulp mills 4. Bleaching: Effect of introducing ozone in elemental chlorine free bleaching of pulp on generation of chlorophenolic compounds 5. Bleaching: Chlorine dioxide bleaching of nineteen non-wood plant pulps 6. Bleaching: A solid-phase extraction method that eliminates matrix effects of complex pulp mill effluents for the analysis of lipophilic wood extractives 7. Mechanical pulping: Development of fibre properties in mill scale high- and low consistency refining of thermomechanical pulp (Part 1) 8. Mechanical pulping: Measurement and interpretation of spatially registered barforces in LC refining 9. Paper technology: Production of a fine fraction using micro-perforated screens 10. Paper technology: The effect of Plantago psyllium seed husk flour on the properties of cellulose sheet 11. Paper technology: Comprehensive evaluation of the industrial processing effects on the fiber properties of the pulps from wood residues

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Research Articles

g PAPERmaking! FROM THE PUBLISHERS OF PAP PER TECHNOLOGY INTERNATIONAL

Volume 7, Number 1, 2021

12. Paper chemistry: Application of CS-CHO-g-PMMA emulsion in paper reinforcement and protection 13. Paper chemistry: Effects of metal ions and wood pitch on retention and physical properties of TMP 14. Coating: Effect of the glass-transition temperature of latexes on drying-stress development of latex films and inkjet coating layers 15. Nanotechnology: Study of LCNF and CNF from pine and eucalyptus pulps 16. Miscellaneous: The component composition of planted pine wood cultivated in the boreal zone NORDIC PULP & PAPER RESEARCH JOURNAL, Vol.36(1), March 2021 1. Chemical pulping: Sodium salt scaling in black liquor evaporators and the effects of the addition of tall oil brine 2. Bleaching: Characterization of fibers after xylanase and modified laccaseglutamate system biobleaching of old newsprint pulp 3. Mechanical pulping: Low-consistency refining of CTMP targeting high strength and bulk: effect of filling pattern and trial scale 4. Paper technology: Model and optimal operational windows for hydrodynamic fiber fractionation 5. Paper physics: Full-field hygro-expansion characterization of single softwood and hardwood pulp fibers 6. Paper chemistry: Selective addition of C-PVAm to improve dry strength of TMP mixed tissue paper 7. Paper chemistry: A transparent polyurethane based on nanosilica in reinforcing papers 8. Packaging: Laboratory measurement method for the mechanical interaction between a tactile sensor and a cartonboard package – presentation and evaluation 9. Environmental impact: Concentrated sulfuric acid production from noncondensable gases and its effect on alkali and sulfur balances in pulp mills 10. Recycling: Characterization of recycled waste papers treated with starch/organophosphorus-silane biocomposite flame retardant 11. Nanotechnology: Effects of lignin content and acid concentration on the preparation of lignin containing nanofibers from alkaline hydrogen peroxide mechanical pulp 12. Nanotechnology: Rice straw paper sheets reinforced with bleached or unbleached nanofibers 13. Chemical technology/modifications: Preparation and characterization of cellulose bromo-isobutyl ester based on filter paper 14. Chemical technology/modifications: Preparation and thermostability of hydrophobic modified nanocrystalline cellulose 15. Chemical technology/modifications: Hardwood kraft pulp fibre oxidation using acidic hydrogen peroxide TAPPI JOURNAL, November 2020 1. Guest Editorial: Coating research addresses new product demands in response to global pandemic 2. Pigmented aqueous barrier coatings 3. Multifunctional barrier coating systems created by multilayer curtain coating 4. Numerical analysis of slot die coating of nanocellulosic materials

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Research Articles

g PAPERmaking! FROM THE PUBLISHERS OF PAP PER TECHNOLOGY INTERNATIONAL

Volume 7, Number 1, 2021

5. 6.

The use of hollow sphere pigments as strength additives in paper and paperboard coatings—Part 1: The predictive nature of packing models on coating properties The use of hollow sphere pigments as strength additives in paper and paperboard coatings—Part 2: Optimization in paperboard formulations for opacity and strength

TAPPI JOURNAL, January 2021 1. Editorial: Agility and adaptation in a dynamic business world 2. Application of foamed additives to the surface of wet handsheets 3. Spraying starch on the Fourdrinier— An option between wet end starch and the size press 4. Understanding wet tear strength at varying moisture content in handsheets 5. The effect of contact time between CPAM and colloidal silica on the flocculation behavior in the approach flow 6. Co-ground mineral/microfibrillated cellulose composite materials: Recycled fibers, engineered minerals, and new product forms 7. The effect of microfibrillated cellulose on the wet-web strength of paper TAPPI JOURNAL, February 2021 1. Editorial: Change, reality, and vision in the pulp and paper industry 2. Key material properties in crease cracking of kraft paper 3. An evaluation of household tissue softness 4. A case study review of wood ash land application programs in North America 5. Modeling and parameter optimization of the papermaking processes by using regression tree model and full factorial design 6. Continuous tannin extraction by use of screw reactor TAPPI JOURNAL, March 2021 1. Editorial: PFAS—Intersections with the pulp and paper industry 2. Incorporation of post-consumer pizza boxes in the recovered fiber stream: Impacts of grease on finished product quality 3. Boiler retrofit improves efficiency and increases biomass firing rates 4. Extension of a steady-state chlorine dioxide brightening model for Z-ECF bleaching of softwood kraft pulps 5. Development of converging-diverging multi-jet nozzles for molten smelt shattering in kraft recovery boilers 6. Black liquor evaporator upgrades— life cycle cost analysis

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Research Articles

PAPERmaking! FROM THE PUBLISHERS OF PAPER TECHNOLOGY Volume 7, Number 1 2021

Technical Abstracts The general peer-reviewed scientific and engineering press consists of several thousand journals, conference proceedings and books published annually. In among the multitude of articles, presentations and chapters is a small but select number of items that relate to papermaking, environmental and waste processing, packaging, moulded pulp and wood panel manufacture. The abstracts contained in this report show the most recently published items likely to prove of interest to our readership, arranged as follows:

Page 2

Biorefinery Coating

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Environment

Page 5

Moulded Pulp

Page 6

Nano-Science

Page 7

Novel Products Packaging Technology

Page 8

Starch Testing

Page 9

Tissue

Page 10

Waste Treatment

Page 12

Wood Panel

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Technical Abstracts

g PAPERmaking!

FROM THE PUBLISHERS OF PA APER TECHNOLOGY

Volume 7, Number 1, 2021

BIOREFINERY “Review of waste biorefinery development towards a circular economy: From the perspective of a life cycle assessment”, Yang Liu, Yizheng Lyu, Jinping Tian, Jialing Zhao, Ning Ye, Yongming Zhang & Lujun Chen, Renewable and Sustainable Energy Reviews, 139, April 2021, 110716. Nowadays, reducing the environmental impact of biorefinery is a common concern of scholars. Life cycle assessment (LCA) is a widely used method to evaluate the environmental impact of biorefinery. Considering the lack of a latest review on the progress and existing problems related to biorefinery based on LCA studies, this paper carried out a systematic review of the evaluation of environmental impact of biorefinery based on LCA, and proposed the development strategies for waste biorefineries by targeting literature on LCA methods. After finding out the imperfections existing in the current researches, the paper then constructed a comprehensive and systematic biorefinery framework with a standard LCA employed as a reference template for following researches. 92 peer-reviewed articles published in Web of Science, Springer and Scopus from 2015 to 2019 with LCA and biorefinery as the keywords were considered. The key findings are as follows: (1) Agricultural waste and industrial residues are the top two feedstocks widely employed, accounting for 32.61% and 29.35% respectively; (2) the primary data is scarce. The foreground data of LCA is 56.52% from the researches of other scholars; (3) the LCA methods are not standardized. 30.26% and 18.42% have unclear system boundaries and functional units; and (4) there is a lack of estimating the influences of various uncontrollable external factors in the biorefinery process. Furthermore, the review highlighted and discussed the defects of biorefineries, a robust LCA template that can be used for evaluating the environmental impact of biorefinery was constructed, taking algae biorefinery as an example. “Integrated Forest Biorefinery: A Proposed Pulp Mill of 2040”, Wilke, Caroline, Lestelius, Magnus & Germgård, Ulf, Digitala Vetenskapliga Arkivet, OPEN ACCESS. Negative environmental impact from greenhouse gas emissions and a dwindling oil supply have resulted in an interest in biorefineries based on renewable resources. The objective of a biorefinery is to upgrade the biomass to more valuable products such as biofuels, electricity, materials, and chemicals. Wood biomass is a suitable raw material for a biorefinery since it is abundant, renewable and can be harvested all year round. In the kraft pulping process, only half of the wood biomass is converted into pulp while the remaining part is turned into energy. A conventional kraft pulp mill could be transformed into an integrated forest biorefinery, and thus produce for example biofuels and chemicals in addition to the traditional pulp and paper products, by implementing several new processes that could utilize the byproducts. Utilization of the byproducts for other purposes than energy would obviously affect the energy balance but also the important sodium/sulfur balance. The processes that are discussed in this report have the potential to be included in a BAT pulp mill built in 2040. The processes are black liquor gasification, on-site production of sulfuric acid, production of tall oil diesel, and lignin and hemicellulose extraction. The possibility to produce a cleaner green liquor through a new membrane filter is also discussed. COATING “Regenerative Superhydrophobic Paper Coatings by In Situ Formation of Waxy Nanostructures”, Cynthia Cordt, Andreas Geissler & Markus Biesalski, Advanced Materials Interfaces, 8(2), 2001265. This scientific−technical approach describes a unique selfǦstructuring coating material made of wax and polysaccharide derivatives, which results in extremely waterǦrepellent properties if applied to solid surfaces. When Page 2 of 13

Technical Abstracts

g PAPERmaking!

FROM THE PUBLISHERS OF PA APER TECHNOLOGY

Volume 7, Number 1, 2021

cooling the coating down from the molten state, the material forms a nanostructured superhydrophobic surface within seconds. This possibility of a fast thermally induced regeneration of nanoscale surface textures creates the potential to restore superhydrophobic coating properties even after mechanical damage caused, among others, by longǦterm use and complex processing and machining steps. Therefore, this coating material has great potential for engineering applications such as superhydrophobic wettability of paper surfaces. Depending on a particular application, there are different requirements for the interaction of paper with water. The highest possible water resistance, which is achieved by superhydrophobic properties, is a quality feature for a majority of paper products, such as packaging materials or novel construction materials, since the ingress of moisture is a major cause of paper damage. “Surface coating of chitosan of different degree of acetylation on non-surface sized writing and printing grade paper”, Nishi Kant, Bhardwaja Yuvraj & Singh Negib, Carbohydrate Polymers, online, 117674. Chitosan is a renewable biopolymer which can be applied on the surface of writing and printing (W&P) grade paper to enhance its different properties. A variety of chitosan is available based on degree of acetylation (DA), molecular weight, viscosity, etc. DA has a profound effect on the performance of chitosan in many applications. Present study compared the performance of different DA chitosan for surface application of W&P grade paper. Chitosan samples of 23%, 16% and 6% DA were studied for their impact on various physical and surface properties of W&P grade paper. Surface coating of chitosan was done at 1.6 ± 0.2 g/m2 (lower dose) and 2.3 ± 0.3 g/m2 (higher dose) on W&P grade paper. Some properties including air permeance, TEA, showed considerable effect of DA in which high DA chitosan outperformed the low DA. Broadly, chitosan with different DA had varied impact on individual properties of paper. “Developing bagasse towards superhydrophobic coatings”, Chengrong Qin, Wei Wang, Wei Li, Song Zhang & Zerong Li, Cellulose, 28, 3617–3630, (2021). Superhydrophobic surfaces have attracted great attention due to their interesting properties. The ever-increasing environmental concern accelerated the development of bio-based superhydrophobic coating materials. As a high-yield agricultural waste, bagasse is cheap, ready available, renewable and biodegradable. It would be an ideal raw material for the preparation of bio-based superhydrophobic coatings to further improve its application value. Although the hydrophobization of bagasse have been reported, the according works mainly focus on the reaction mechanism and/or their oil-absorption properties. As far as we know, the design of bagasse-based superhydrophobic coatings has been uncovered. Herein, mechanically pretreated bagasse was esterified with stearoyl chloride. Spray-coating the suspension of as-synthesized bagasse esters onto various substrates (glass slide, aluminum flake and filter paper), superhydrophobic surfaces were generated. SEM images in combination with the high-resolution C1s XPS deconvolution spectra implied that nano-structured bagasse esters were deposited on the synthesized micro-scaled esters, which was necessary for their superhydrophobicity. The as-prepared superhydrophobic surfaces exhibited good anti-fouling, oil absorption performance and high time/temperature/pH stability. This research would provide a novel perspective for the design of other bio-based superhydrophobic coatings. “The Influence of Drying Conditions of Clay-Based Polymer Coatings on Coated Paper Properties”, Petronela Nechita, Coatings, 11(1), 12, OPEN ACCESS. Coatings based on pigment and polymer binders are applied on paper surfaces to improve their surface, optical, and printing properties. Besides the coating composition, the structure and properties of the coated papers are influenced by the coating layer consolidation upon Page 3 of 13

Technical Abstracts

g PAPERmaking!

FROM THE PUBLISHERS OF PA APER TECHNOLOGY

Volume 7, Number 1, 2021

drying. In this study, the influence of drying conditions on the structure and properties of coating layers based on natural pigments (clay) and polymer binders (butadiene acrylonitrile latex) has been analyzed. Using a laboratory rod Mayer device, the coatings were applied as thin layer (about 15–16 g/m2) on the paper surface and samples of coated paper were dried at 20 and 105 °C temperatures. The optical, structural, and water absorption properties of the coating layer were evaluated by the measurement of gloss, opacity, void fraction, light scattering, and contact angle. The obtained results highlighted that both the drying temperature and latex content in the coating color have a synergic effect on the coated paper quality ENVIRONMENT “Metagenomic analysis for profiling of microbial communities and tolerance in metal-polluted pulp and paper industry wastewater”, Pooja Sharma, Sonam Tripathi & Ram Chandra, Bioresource Technology, 324, March 2021, 124681. This work aimed to study the profiling and efficiency of microbial communities and their abundance in the pulp and paper industry wastewater, which contained toxic metals, high biological oxygen demands, chemical oxygen demand, and ions contents. Sequence alignment of the 16S rRNA V3-V4 variable region zone with the Illumina MiSeq framework revealed 25356 operating taxonomical units (OTUs) derived from the wastewater sample. The major phyla identified in wastewater were Proteobacteria, Bacteroidetes, Firmicutes, Chloroflexi, Actinobacteria, Spirochetes, Patesibacteria, Acidobacteria, and others including unknown microbes. The study showed the function of microbial communities essential for the oxidation and detoxifying of complex contaminants and design of effective remediation techniques for the re-use of polluted wastewater. Findings demonstrated that the ability of different classes of microbes to adapt and survive in metal-polluted wastewater irrespective of their relative distribution, as well as further attention can be provided to its use in the bioremediation process. “Efficiency of pulp and paper industry in the production of pulp and bioelectricity in Brazil”, Andres Susaeta & Fabricia Gladys Rossato, Forest Policy and Economics, 128, July 2021, 102484. We examine the efficiency of Brazilian pulp and paper companies in the production of pulp and bioelectricity using an output-oriented data envelopment analysis. We assume that pulpwood volume, energy consumption, installed capacity and number of workers are the inputs to generate pulp and bioelectricity. We conduct this analysis by first determining the traditional efficiency scores, and secondly calculating a composite index of efficiency to rank the performance of pulp and paper companies. We also conduct a post-efficiency analysis to gauge the impacts of externalities and other related variables on the efficiency in pulp and bioelectricity production. Our results suggest that pulp and paper companies are efficient in pulp and bioelectric production, reaching an average efficiency and composite index of efficiency of 0.9776 and 0.8291, respectively. The post-efficiency analysis suggests that pulp and paper companies could minimally decrease their adjusted efficiencies by increasing the total forest area, power capacity, and outsourced employment. On the other hand, the adjusted efficiency in the production of pulp and bioelectricity might not be statistically impacted by higher socioeconomic levels. “Unlocking the potential of pulp and paper industry to achieve carbon-negative emissions via calcium looping retrofit”, Mónica P.S. Santos, Vasilije Manovic & Dawid P.Hanak, Journal of Cleaner Production, 280, Part 1, 20 January 2021, 124431. Pulp and paper is considered to be the fourth most energy-intensive industry (EII) worldwide. However, as most of the CO2 emissions are of biomass origin, this sector has Page 4 of 13

Technical Abstracts

g PAPERmaking!

FROM THE PUBLISHERS OF PA APER TECHNOLOGY

Volume 7, Number 1, 2021

the potential to become a carbon-negative industry. This study proposes a new concept for conversion of the pulp and paper industry to carbon negative that relies on the inherent CO2 capture capability of the Kraft process. The techno-economic performance of the proposed carbon-negative system, based on calcium looping (CaL) retrofitted to a pulp and paper plant, was evaluated. The effect of CaL design specifications and cost assumptions on the thermodynamic and economic performance were evaluated. Under the initial design assumptions, the reference pulp and paper plant was shown to turn from electricity importer to electricity exporter with the cost of CO2 avoided equal to 39.0 €/tCO2. The parametric study showed that an increase in the fresh limestone make-up rate resulted in a linear increase of the specific primary energy consumption for CO2 avoided (SPECCA) and a reduction in the amount of electricity exported to the electric grid. This translates into an increase in the price of pulp and newsprint, and the cost of CO2 avoided. This study has also demonstrated that the pulp and paper industry has high potential to become carbon negative. It has been shown that carbon capture and storage would become economically viable in this industry if the negative CO2 emissions are recognised and a negative CO2 emissions credit of at least 41.8 €/tCO2 is implemented. “A Review on the Life Cycle Assessment of Cellulose: From Properties to the Potential of Making It a Low Carbon Material”, Firoozeh Foroughi, Erfan Rezvani Ghomi, Fatemeh Morshedi Dehaghi, Ramadan Borayek & Seeram Ramakrishna, Materials 2021, 14(4), 714. The huge plastic production and plastic pollution are considered important global issues due to environmental aspects. One practical and efficient way to address them is to replace fossil-based plastics with natural-based materials, such as cellulose. The applications of different cellulose products have recently received increasing attention because of their desirable properties, such as biodegradability and sustainability. In this regard, the current study initially reviews cellulose products’ properties in three categories, including biopolymers based on the cellulose-derived monomer, cellulose fibers and their derivatives, and nanocellulose. The available life cycle assessments (LCA) for cellulose were comprehensively reviewed and classified at all the stages, including extraction of cellulose in various forms, manufacturing, usage, and disposal. Finally, due to the development of low-carbon materials in recent years and the importance of greenhouse gases (GHG) emissions, the proposed solutions to make cellulose a low carbon material were made. The optimization of the cellulose production process, such as the recovery of excessive solvents and using by-products as inputs for other processes, seem to be the most important step toward making it a low carbon material. MOULDED PULP “Potential Use of Oil Palm Fronds for Papermaking and Application as Molded Pulp Trays for Fresh Product under Simulated Cold Chain Logistics”, Lerpong Jarupan, Ratanapat Hunsa-Udom & Nattinee Bumbudsanpharoke, Journal of Natural Fibers, March 2021. Waste paper from newsprint, a key feedstock for molded pulp trays, is globally deficient due to digital shifts. Hence, the alternative fiber source needs to be explored. The potential use of fiber from oil palm fronds for protective packaging under humid conditions was studied. Fibers were isolated from petioles by sulfate pulping with 30.72% yield. The high α-cellulose content (38%) showed valuable for papermaking. Runkle’s ratio (0.63), rigidity coefficient (38.46), and slenderness value (100) suggested that the paper would have excellent mechanical properties. Under cold chain logistics, packaging must withstand high humidity and low temperature (90%RH, 12°C). Addition of 1.4% cationic starch and 0.5% AKD significantly enhanced water absorption resistance from 59 to 23250 sec and improved the burst (6.68%) and tensile index (26.47%). The Page 5 of 13

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FROM THE PUBLISHERS OF PA APER TECHNOLOGY

Volume 7, Number 1, 2021

molded pulp trays fabricated from 70% sized frond fibers and 30% OCC fiber provided 7.71% higher compressive strength than neat OCC tray. All physical properties indicated that the as-prepared trays have potential use for protective material. A simulation with green apple demonstrated that the trays were impractical for use with soft-skinned fruit as the dense and rough surface of the packaging. Further study to evaluate cushioning performance for harder skin fruit is, therefore, necessary. “The impact of molded pulp product process on the mechanical properties of molded Bleached Chemi-Thermo-Mechanical Pulp”, Claire Dislaire, Yves Grohens, Bastien Seantier & Marion Muzy, Functional Composite Materials, 2, Article 7 (2021). This study was carried out using bleached softwood Chemi-Thermo-Mechanical Pulp to evaluate the influence of Molded Pulp Products’ manufacturing process parameters on the finished products’ mechanical and hygroscopic properties. A Taguchi table was done to make 8 tests with specific process parameters such as moulds temperature, pulping time, drying time, and pressing time. The results of these tests were used to obtain an optimized manufacturing process with improved mechanical properties and a lower water uptake after sorption analysis and water immersion. The optimized process parameters allowed us to improve the Young’ Modulus after 30h immersion of 58% and a water uptake reduction of 78% with the first 8 tests done. NANO-SCIENCE “Reinforcement Potential of Modified Nanofibrillated Cellulose in Recycled Paper Production”, Ayhan Tozluoglu, Hakan Fidan, Ahmet Tutuş, Recai Arslan, Selva Sertkaya, Bayram Poyraz, Sibel Dikmen Küçük, Tamer Sözbir, Bekir Yemşen & Mehmet Onurhan Gücüş, BioResources, 16(1), (2021), OPEN ACCESS. The influence of nanofibrillated cellulose (NFC) was investigated as a reinforcing agent to improve strength properties of papersheets fabricated from recycled pulp fibers of mixtures of old newspapers, old magazines, and old corrugated cardboards. To determine the effects of the NFC on the mechanical and physical properties of the recycled pulp papers, cellulose nanofibrils (NFC) were isolated from wheat straw, pretreated chemically and enzymatically (NFC-OX), and then added to the bulk suspensions of papermaking pulp slurries at various percentages. The electrokinetic and drainage properties of the pulps and the mechanical and physical properties of the papersheets were analyzed and compared. As expected, the addition of NFC/NFC-OX significantly increased the strength properties of papers. Papers containing 4% of NFC-OX (periodate pretreated) presented higher increases in tensile index (43%) and burst index (59.3%) than other papers. However, a high addition of NFC/NFC-OX increased the water retention, which is undesirable for papermaking. Hence, with optimum selection of NFC/NFC-OX and process conditions, higher mechanical properties could be acquired without increasing drainage rate. Compared to the other pretreated NFC/NFC-OX types, sodium-periodate-oxidized NFC-OX samples significantly increased the mechanical properties of the papers fabricated from the recycled pulps. “Chapter 10: Applications of Nanocellulose in the Paper Industry”, Hye Jung Youn & Hak Lae Lee, in Nanocellulose: Synthesis, Structure, Properties and Applications, 323-357 (2021). Nanocellulose, due to its sustainability, biodegradability, and high performance such as high tensile stiffness and low thermal expansion coefficient, can potentially replace the fossil fuel-based materials for different applications. Among them, paper and the board industry is the most promising field because of the massive product tonnage of paper. It can be used both as a dry and wet-end in the paper industry such as papermaking, paper coating, packaging, and for the production of hygienic and absorbent Page 6 of 13

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Volume 7, Number 1, 2021

products. In this chapter, the first part of the chapter discusses the recent progress in the applications of nanocellulose as a dry- and wet-strength agent. The second part describes the use of nanocellulose in coating and barrier packaging. It needs to provide prospects of nanocellulose by reducing its production cost and post-processing, and explore novel application for paper-based products. NOVEL PRODUCTS “Functional paper-based materials for diagnostics”, Laura M. Hillscher, Valentina J. Liebich, Olga Avrutina, Markus Biesalski & Harald Kolmar, ChemTexts, 7, Article 14 (2021). Functional papers are the subject of extensive research efforts and have already become an irreplaceable part of our modern society. Among other issues, they enable fast and inexpensive detection of a plethora of analytes and simplify laboratory work, for example in medical tests. This article focuses on the molecular and structural fundamentals of paper and the possibilities of functionalization, commercially available assays and their production, as well as on current and future challenges in research in this field. PACKAGING TECHNOLOGY “Fiber characterization of old corrugated container bleached pulp with laccase and glycine pretreatment”, Guozheng Chen, Junjing Dong, Jinquan Wan, Yongwen Ma & Yan Wang, Biomass Conversion and Biorefinery, (2021). In response to deal with the increasingly serious environmental problems and shortage of fiber raw materials, biological enzyme pretreatment is an effective way to replace a large number of chemical additives to improve the properties of waste paper fibers. Fiber characterization of old corrugated container bleached pulp with laccase and glycine (Lac/Gly) pretreatment was investigated by means of Fourier transform infrared spectroscopy (FTIR), headspace gas chromatography (HSGC), fiber quality measurements (FQA), X-ray diffraction method (XRD), and atomic force microscope (AFM). Results showed that, compared with the control pulp, the whiteness and brightness of the Lac/Gly-treated pulp increased by 16.17% and 7.41%, respectively. And the FTIR showed that Lac/Gly pretreatment promotes the effective removal of lignin by hydrogen peroxide (H2O2) bleaching. The content of carboxyl groups in pulp increased remarkably by 21.92%. The paper physical analysis showed that the paper strength properties have improved remarkably. The fiber quality analyses indicated that the fiber length, coarseness, and curl index changed a little. The XRD analysis showed that the crystallinity decreased by 5.83% due to Lac/Gly treatment. The AFM analysis showed that through Lac/Gly treatment, the lignin and extracts over the fiber surface are decreased significantly. “Biopolymers and Biocomposites from Agro-Waste for Packaging Applications: 2 Antimicrobial coated food packaging paper from agricultural biomass”, Khadija El Bourakadi, Fatima-Zahra Semlali, Aouragh Hassani, Abou El Kacem Qaiss & Rachid Bouhfid, Biopolymers and Biocomposites from Agro-Waste for Packaging Applications, Woodhead Publishing Series in Composites Science and Engineering, 2021, 35-63. Recently, the research and development of novel antimicrobial food packaging paper have been accrued a considerable attention due to their ultimate advantages namely contain food in a cost-effective way that satisfies industry requirements and consumer desires, maintains food safety, and minimizes environmental impact also to increase the shelf life of foodstuff. These unique food packaging papers can be prepared through different materials such as synthetic polymers, nature or bio-polymers owing to their numerous properties. Therefore, in order to enhance the biological properties particularly the antimicrobial activity against the most pathogenic bacteria and Page 7 of 13

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biodegradability of the packaging material, the polymeric matrix can be reinforced with different fillers mainly biofiber, clay and agriculture biomass. Herein, this chapter book reviews the different classes of food packaging paper and their roles, manufacturing, applications and also the effects of antimicrobial agents on the final properties of packaging papers. The major aim of this review was to highlight the effect of several antibacterial agents on final mechanical and biological properties of biomass-based composites and nanocomposites materials. This chapter is divided into three parts, the first one is dedicated to the classifications and roles of food packaging systems, the second part is devoted to the manufacturing of packaging paper based on agriculture biomass, the third part concern the applications of these materials and the side effect of the antibacterial agents on their properties. From the results obtained in this research work, we can conclude that the agricultural biomass can be used to manufacture food packaging by several techniques mostly pulp manufacturing processes. Also, the mechanical and antibacterial properties of these materials can enhanced by the addition of divers antibacterial agents. STARCH “Improving the adhesion-to-fibers and film properties of corn starch by starch sulfoitaconation for a better application in warp sizing”, Wei Li, Zhengqiao Zhang, Lanjuan Wu, Zhifeng Zhu & Zhenzhen Xu, Polymer Testing, 98, June 2021, 107194. The purpose of this work was to develop a new starch-based sizing agent [sulfoitaconylated starch (SIS)] with high adhesion and film properties, through starch sulfoitaconation containing itaconation of acid-hydrolyzed starch (AHS) with itaconic anhydride and subsequent sulfonation with NaHSO3 in aqueous medium. The granular SIS was characterized by Fourier transform infrared (FTIR) spectroscopy and scanning electron microscopy (SEM) techniques. The adhesion of SIS to cotton fibers was evaluated by a standard method (FZ/T 15001–2008). And its film properties were also investigated in terms of tensile strength, breaking elongation, moisture regain, bending endurance and degree of crystallinity, etc. The experimental results showed that the SIS samples had higher adhesion to cotton fibers and lower film brittleness than AHS as a control. Increasing the level of starch sulfo-itaconation could gradually enhance bonding strength to cotton fibers, and increase breaking elongation and bending endurance of SIS film, indicating that increasing the number of sulfo-itaconate substituents could play a significantly positive role in overcoming the shortcomings (insufficient adhesion and brittle film) of starch. Considering the previous results, the granular SIS with a modification level range of 0.034–0.041 showed potential for the use as a new starch-based sizing agent in paper-making and textile industry. TESTING “Estimation of the Compressive Strength of Corrugated Cardboard Boxes with Various Perforations”, Tomasz Garbowski & Tomasz Gajewski, Energies 2021, 14(4), 1095. This paper presents a modified analytical formula for estimating the static top-tobottom compressive strength of corrugated board packaging with different perforations. The analytical framework is based here on Heimerl’s assumption with an extension from a single panel to a full box, enhanced with a numerically calculated critical load. In the proposed method, the torsional and shear stiffness of corrugated cardboard, as well as the panel depth-to-width ratio is implemented in the finite element model used for buckling analysis. The new approach is compared with the successful though the simplified McKee formula and is also verified with the experimental results of various packaging designs made of corrugated cardboard. The obtained results indicate that for boxes containing specific perforations, simplified methods give much larger estimation error than the Page 8 of 13

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Volume 7, Number 1, 2021

analytical–numerical approach proposed in the article. To the best knowledge of the authors, the influence of the perforations has never been considered before in the analytical or analytical–numerical approach for estimation of the compressive strength of boxes made of corrugated paperboard. The novelty of this paper is to adopt the method presented to include perforation influence on the box compressive strength estimation “Vibration levels of stacked parcel packages in laboratory test environment. Overtested or under-tested?”, Zsófia Németh, Bence Molnár, Csaba Pánczél & Péter Böröcz, OPEN ACCESS, DOI: https://doi.org/10.14513/actatechjaur.00603. Courier express parcel (CEP) shipments become one of the most important delivery methods in the Business-to-Consumer sales model. This paper observed and analyzed the vertical vibration levels that occur in stacked and unsecured parcels during express delivery versus the simulation in the laboratory. At the end, a detailed comparison is reported between the field and laboratory vibration levels (based on standard PSD test profile) in the frequency range of 1 – 200 Hz. For the measurement a three-layer stacked unit was used building from corrugated box samples. The result shows and analyzes the vibration levels in the stacked layers in comparison to the ISTA (International Safe Transport Association) vibration protocol where only a single parcel is required to be tested without any stacking configuration. TISSUE “Energy system optimization model for tissue papermaking process”, Yang Zhang, Mengna Hong, Jigeng Li, Jingzheng Ren & Yi Man, Computers & Chemical Engineering, 146, March 2021, 107220. The drying process accounts for the largest proportion of energy consumption in paper mills. Energy system optimization has a great significance for reducing the energy consumption of the paper drying process. The drying process is a complex system that consists of several subsystems, such as cylinder and air hood systems. Previous optimization models for energy systems usually focused on these subsystems. A global optimization methodology for the entire drying process is lacking, and no existing models can be applied in practice. In this work, an energy system optimization model for the tissue paper drying process is proposed based on a process simulation model. The modeling process integrates the various subsystems and fully considers the coupling of the paper drying process, which greatly enhances the industrial application value of the model. Industrial operating data are used to test the simulation model, and the results show that the simulation error of each key variable is within 5%, which meets the real-world production requirements and lays the foundation for an energy efficiency analysis of each subsystem. Applying the optimization model to a tissue paper mill, the results show that it can reduce drying costs by 8.71%. “Optimizing the brightness and mechanical strength of tissue paper made of deinked pulp using isolated soy protein and chitosan by using response surface methodology”, Seyed Sajad Sazmand, Yahya Hamzeh, Sahab Hedjazi & Hamid Reza Rudi, Journal of Forest and Wood Product, 73(4), 491-502. The lower mechanical properties of paper made from recycled fiber is due to their inherent properties of the used fibers. In order to improve strengths, various polymers such as cationic polymer are used, while today the global trend is the utilization of natural and renewable materials. In this study, two biopolymers including chitosan (Ch), isolated soy protein (ISP) along with glutaraldehyde (GA) were used to optimize the mechanical properties of the tissue paper made from the de-inked fibers. For this purpose, at the first chitosan solution with loading level of 0% to 2%, then glutaraldehyde with loading level of 2% to 6%, and finally isolated soy protein with 1% to 3% levels were added to the pulp suspension. The properties of Page 9 of 13

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handsheets were measured by standard test methods and the results were modeled using Design Expert.10 software and response surface method (RSM). The results and obtained models showed that addition of these additives did not make a significant difference on brightness of the hand sheet paper compared with the control sample. However, the addition of these additives increased the dry and wet tensile and tear strengths, which in the optimal addition level the increasing levels for mentioned properties were 145%, 35% and 70%, respectively, compared with the control sample. The increasing rate of tensile and tear resistance were higher than increasing rate obtained by conventional dry strength agents, such as cationic starch. “Machine Learning-Based Energy System Model for Tissue Paper Machines”, Huanhuan Zhang, Jigeng Li & Mengna Hong, Processes 2021, 9(4), 655, OPEN ACCESS, DOI https://doi.org/10.3390/pr9040655. With the global energy crisis and environmental pollution intensifying, tissue papermaking enterprises urgently need to save energy. The energy consumption model is essential for the energy saving of tissue paper machines. The energy consumption of tissue paper machine is very complicated, and the workload and difficulty of using the mechanism model to establish the energy consumption model of tissue paper machine are very large. Therefore, this article aims to build an empirical energy consumption model for tissue paper machines. The energy consumption of this model includes electricity consumption and steam consumption. Since the process parameters have a great influence on the energy consumption of the tissue paper machines, this study uses three methods: linear regression, artificial neural network and extreme gradient boosting tree to establish the relationship between process parameters and power consumption, and process parameters and steam consumption. Then, the best power consumption model and the best steam consumption model are selected from the models established by linear regression, artificial neural network and the extreme gradient boosting tree. Further, they are combined into the energy consumption model of the tissue paper machine. Finally, the models established by the three methods are evaluated. The experimental results show that using the empirical model for tissue paper machine energy consumption modeling is feasible. The result also indicates that the power consumption model and steam consumption model established by the extreme gradient boosting tree are better than the models established by linear regression and artificial neural network. The experimental results show that the power consumption model and steam consumption model established by the extreme gradient boosting tree are better than the models established by linear regression and artificial neural network. The mean absolute percentage error of the electricity consumption model and the steam consumption model built by the extreme gradient boosting tree is approximately 2.72 and 1.87, respectively. The root mean square errors of these two models are about 4.74 and 0.03, respectively. The result also indicates that using the empirical model for tissue paper machine energy consumption modeling is feasible, and the extreme gradient boosting tree is an efficient method for modeling energy consumption of tissue paper machines WASTE TREATMENT “Pulp and paper mill wastes: utilizations and prospects for high value-added biomaterials”, Adane Haile, Gemeda Gebino Gelebo, Tamrat Tesfaye, Wassie Mengie, Million Ayele Mebrate, Amare Abuhay & Derseh Yilie Limeneh, Bioresources and Bioprocessing, 8, Article 35 (2021). A wide variety of biomass is available all around the world. Most of the biomass exists as a by-product from manufacturing industries. Pulp and paper mills contribute to a higher amount of these biomasses mostly discarded in the landfills creating an environmental burden. Biomasses from other sources have been used to produce different kinds and grades of biomaterials Page 10 of 13

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such as those used in industrial and medical applications. The present review aims to investigate the availability of biomass from pulp and paper mills and show sustainable routes for the production of high value-added biomaterials. The study reveals that using conventional and integrated biorefinery technology the ample variety and quantity of waste generated from pulp and paper mills can be converted into wealth. As per the findings of the current review, it is shown that high-performance carbon fiber and bioplastic can be manufactured from black liquor of pulping waste; the cellulosic waste from sawdust and sludge can be utilized for the synthesis of CNC and regenerated fibers such as viscose rayon and acetate; the mineral-based pulping wastes and fly ash can be used for manufacturing of different kinds of biocomposites. The different biomaterials obtained from the pulp and paper mill biomass can be used for versatile applications including conventional, high performance, and smart materials. Through customization and optimization of the conversion techniques and product manufacturing schemes, a variety of engineering materials can be obtained from pulp and paper mill wastes realizing the current global waste to wealth developmental approach. “Design and development of eco-friendly cutlery out of paper waste through molding next generation waste management”, Richa Pandey, Rahul Singh, Phuleshwar Baitha & Roshan Topno, Materials Today: Proceedings, online 3 March 2021. The waste of paper or the paper dump is a serious problem and its occurrence is widespread in various institutions. Wastepaper can be recycled to produce some important and usable products that are ecological and biodegradable. For example, it is used to extract new paper from the old by chemical decomposition. Other products such as paper plates, paper cups, paper spoons, tiles, toys, crafts, etc. can be formed from the slurry. This project also initiates a mould that makes cups and plates from the wastepaper management circuit. With learning institutions being the main consumers, most paper are usually eliminated after its use. The waste remains undeveloped and unused, although is a valuable resource. Studying the design of a manual, economical and efficient paper recycling machine, it can be surmised that the design uses the integration of the knowledge gained about the recycling technology that exists manually from the paper recycling machines used to form a cheap but effective paper recycling system. The advantages of the machine are not only of recycled paper, but also the advantages of the interaction of the manual drive system, which will also reduce the high cost. As the design is not 100% effective, the transmission, belt and chain transmission correspond to the estimated 90% efficiency using the 90% for the design. The power consumption for the design is 450 W and since an average user can produce 100 W constant, it takes 5 people to drive the machine. “High loaded moving bed biofilm reactors treating pulp & paper industry wastewater: Effect of hydraulic retention time, filling degree and nutrients availability on performance, biomass fractions and nutrients utilization”, Maurício C. Matheus, Maria Ekenberg, João P.Bassin, Márcia W.C. Dezotti & Maria Piculell, Journal of Environmental Chemical Engineering, 9(1), February 2021, 104944. For treating pulp and paper (P&P) industry wastewaters, the high-loaded/nutrient-limited moving bed biofilm reactor (MBBR) is frequently followed by an activated sludge, in the Biofilm-Activated Sludge (BAS) configuration. Evidences show that the MBBR performance relies on a complex surface-volume relation, affecting the biosolids dynamics. That subject was addressed in parallel lab-scale MBBRs, with carrier filling degrees of 15% and 45%, fed with P&P wastewater. The removal of chemical oxygen demand (COD) and utilization of nutrients were evaluated for varying hydraulic retention times (HRT, 1.6– 4.9 h), and availabilities of nitrogen and phosphorous. Nutrients excess and 4.9 h HRT led Page 11 of 13

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to soluble COD removal close to 50% (totality of the biodegradable portion) in both reactors, but only 32% was achieved at 1.6 h HRT and 45% filling degree. Restrained wastewater-biosolids contact time rather than overload justified that, as the maximum capacity (Kincannon–Stover model, 30.6 kg sCOD/(m3 d)) was substantially higher than the apparent removal rates (≤ 14.1 kg sCOD/(m3 d)). The performance at 4.9 h HRT was matched at 3.2 h HRT with threefold filling ratio, which compensated the lower contact time. Higher HRT was also responsible for i) improving nutrients usage (up to 1.72 times higher sCOD/P and 1.47 sCOD/N); ii) superior suspended solids content, corresponding up to 30% of total biomass at 4.9 h, against 8.6% at 1.6 h; and iii) up to 2.45 times greater planktonic maximum specific activity. Nutrients restriction boosted the sCOD/nutrient consumption ratio up to 2.65 times for the limited nutrient and 1.70 for the abundant one, with minimal sCOD:N:P (100:0.70:0.14) at limited N and 4.9 h HRT. “Overview of Wastewater Characteristics of Cardboard Industry”, S. Harif, M.A. Aboulhassan & L. Bammou, Scientific Study & Research Chemistry & Chemical Engineering, Biotechnology, Food Industry, 22(1), 001-011, (2021). The purpose of this study is to characterize wastewater from the corrugated cardboard industry and to highlight the nature and sources of pollution. Wastewaters from the corrugator and printing processes as well as homogenization tank, which collects all effluents from industrial processes, were analysed using standard methods. The results indicate that these effluents had a significant pollution load. The wastewater from the homogenization tank had high concentration of COD (24243 ± 2374.6 mg∙L-1), BOD5 (413.33 ±17.14 mg∙L-1) and total solids (36.84 ± 10.62 g∙L-1). In addition, the biodegradability indices were less than 0.4, indicating that the effluents from the cardboard industry are not readily biodegradable. The printing process is the main source of liquid pollution in the cardboard industry facilities. The pollution load resulting from this process was much greater than that of the corrugator process wastewater. In accordance with current standards, these industrial effluents require treatment before discharge or re-use. WOOD PANEL “Development of surrogate predictive models for the nonlinear elasto-plastic response of medium density fibreboard-based sandwich structures”, Yong Jie Wong, K.B. Mustapha, Yoshihisa Shimizu, Akinori Kamiya & Senthil Kumar Arumugasamy, International Journal of Lightweight Materials and Manufacture, 4(3), September 2021, 302-314. Medium-density fibreboard (MDF) belongs to a class of engineered wood products facilitating efficient use of wood wastes. For this class of materials, the development of predictive models is crucial for the simulation of their responses under mechanical loads. In this study, samples of sandwich structures based on MDF as the skins and a mushroom-based foam as the core are fabricated and tested under edgewise compression tests. Results from the tests support the idea that increasing the thickness of the skins strengthens the response of the sandwich structure against buckling failure, but also revealed that thicker skins are susceptible to complex failure modes. Towards data-driven constitutive modelling of the nonlinear elastic-plastic response of this bio-based structure, predictive models premised on feedforward backpropagation neural network (FFNN), cascade-forward backpropagation neural network (CFNN), and generalized regression neural network (GRNN) were developed. Performance of the models was assessed via error criteria that include the coefficient of determination (R2), root mean squared error (RMSE) and mean absolute error (MAE). Results from the models indicate that CFNN with 15 hidden neurons under the LevenbergMarquardt backpropagation training algorithm outperformed FFNN and GRNN models, with R2 = 1.0, RMSE = 0.0030 and MEA = 0.0019. Page 12 of 13

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“Natural based polyurethane matrix composites reinforced with bamboo fiber waste for use as oriented strand board”, Mariana Dias Machado Lopes, Magno de Souza Pádua, Juliana Peixoto Rufino Gazem de Carvalho, Noan Tonini Simonassi, Felipe Perissé Duarte Lopez, Henry A. Colorado & Carlos Maurício Fontes Vieira, Journal of Materials Research and Technology, 12, May–June 2021, 2317-2324. Composites that use natural fibers as reinforcement have generated great interest in the industrial and scientific community due to the need for materials that present environmental responsibility and are economically viable. This work aimed to develop and establish a comparative analysis of the mechanical properties and physical characteristics between a castor oil based polyurethane resin composites reinforced with fibrous bamboo residue and a commercial Oriented Strand Board (OSB), in which where determined the technical issues of using these composites as OSB panels. Bamboo fibers used were obtained as a residue from a barbecue sticks industry. Composites were made with 20 and 40% volume fraction of continuous and aligned bamboo fiber. The density, moisture absorption, and mechanical strength of the composites were tested and compared with the commercial OSB. The composites not only presented mechanical performance superior to the commercial OSB, surpassing 1000 J/m, 85 MPa and 4.4 GPa for impact resistance, flexural strength, and flexural elastic modulus, respectively, but also fulfilled the standard requirements, while the commercial OSB, failed in most of the observed standards criteria. In addition, the developed materials contribute to a sustainable environment by using both bamboo waste and castor oil based polyurethane resin in a composite material. “Effects of shear deformation and orthotropy on the buckling behaviour of oriented strand boards”, Stanley Emeka Iwuoha & Werner Seim, Wood Material Science & Engineering, online March 2021. The literature is replete with studies conducted on wood-based boards. However, studies involving the influence of orthotropy and shear deformation on the one-dimensional buckling behaviour of oriented strand boards are lacking. This study is a step-by-step approach towards investigating and discussing the influence of orthotropy and shear deformation on the bending and one-dimensional buckling behaviour of oriented strand boards using specimens which are 12, 18, and 25 mm in thickness, measuring 400 and 780 mm in length for the bending analyses and 400, 425, 450, 475, and 500 mm for the buckling analyses. FE-models were developed which considered the boards as orthotropic and were able to determine their load-displacement behaviour considering the effects of geometric non-linearities. Results of the analyses showed that orthotropy have significant effects on the bending while shear deformation influences both the bending and buckling behaviour of oriented strand boards. In bending, the effects are generally higher in the main strength than in the secondary strength direction. In buckling, it is a reduction in the buckling loads in a range of between 4% and 26%, compared to what would have been obtained using the Euler equation. An alternative Equation with a better ability to predict the one-dimensional buckling load of wood-based boards was presented and discussed.

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