Pulp Kraft Hemi cellulose Pulp Kraft Ash content Pulp Kraft Lignin,

ISBN : 978-602-17761-4-8 160 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech From the previous research knew that to produce bamboo pulp with a certain lignin content or have a certain Kappa number, it is necessary to use active alkali and sulidity with different concentrations. Furthermore, from the test result knew that to produce pulp with a lignin content of about 5 or have a Kappa number of about 30, it is necessary to use active alkali and sulidity with different concentrations. Cooking of Tali, Temen and Haur bamboo require active alkali and sulidity consecutive ie, 16 and 25, 18 and 25 and 22 and 32. Thus it is known that Tali bamboo requires the lowest chemicals concentration, while Temen bamboo and especially Haur bamboo require chemicals that are relatively higher. This is due to the levels of lignin and extractives of Tali bamboo is the lowest. The use of chemicals is higher on haur bamboo caused by several factors, including ash, extractive and lignin content. From Figure 2. it is known that the cooking conditions as above will produce pulp with Kappa Number and total yield at range between 30.43 - 32.71 and 44.13 - 53.82. Note also that the value of Tali bamboo pulp relatively better than the two other bamboo. All the pulp has iber length between 2 mm - 2.3 mm, diameter of 18.9 μm - 20.8 μm and ines between 5.1 - 6.65, while the lignin content of about 4.21 - 4.89; alpha cellulose 83.86 - 84.82; and hemicellulose between 14.07 - 15.59. Cooking Tali bamboo requires the lowest chemicals, so the it was chosen to be the raw material for reinforcing composites by mixing with a resin. Characteristics of Fiber and Bamboo Pulp {Tali Bamboo G. apus} Fiber and bamboo pulp characteristics after cooking are presented in Figure 3, while the microstructure test results of pulp and bamboo iber by SEM analysis are presented in Figure 4. From Figure 3 known that the levels of lignin, ash and extractive of bamboo pulp from Kraft Process is smaller than bamboo iber, whereas higher levels of cellulose. As has been described above, that it is caused by the cooking process for bamboo iber using lower caustic soda concentration than pulp cooking by Kraft process, so that lignin, ash and extractive in the ibers can not be degradeddissolved entirely. It is known also, that the iber length is about 2 - 4.5 mm, and iber from soda cooking process is longer than pulp, especially than pulp from Kraft cooking process. It may be caused by the concentration of chemicals in Kraft cooking process is higher than the soda cooking process, thus it can partially degrade cellulose ibers. From the test results it is known that the water content of iber and pulp is still below 10, so it is expected does not affect the quality of the composite; because the optimum water content in the manufacture of composites is about 10 - 14 if it is too high, then the lexural rigidity and internal bonding strength of the particle board will decrease [9]. From Figure 4. can be seen that the microstructure of specimen material at a vertical and horizontal position, the material making up the specimen pulp in a vertical position seem their air cavities between the ibers in the pulp, while the bamboo iber specimen at the position appears more compact than pulp. 15 30 45 60 75 90 1 2 3 1. Fiber 2 Pulp Soda

3. Pulp Kraft Hemi cellulose

Alpha cellulose 1 2 3 4 5 1 2 3 1. Fibre 2 Pulp Soda

3. Pulp Kraft Ash content

Extractive 3 6 9 12 15 1 2 3 1. Fiber 2. Pulp Soda

3. Pulp Kraft Lignin,

Moisture content, Fiber length, mm Figure 3. Pulp and Fiber Characteristics of Tali Bamboo after cooking ISBN : 978-602-17761-4-8 161 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Vertical position Horizontal position Vertical position Horizontal position Bamboo pulp Bamboo iber after cooking Figure 4. Micro Structure of Pulp and Fiber Tali Bamboo SEM, 500 X Bamboo Composite Characteristic As described in the method, the manufacture of composites made with variation of pulp or iber fraction of the resin fraction epoxy at certain condition. From the literature it is known to obtain optimal composite manufacturing condition and from preliminary experiments results known that the optimal ratio for pulp or bamboo iber and epoxy matrix is about 1 : 1.5. The characteristic of the resulting composites are presented in Table 2. Table 2. Characteristic of Bamboo Fiber and Pulp Kraft Process Composite Parameter Bamboo Pulp Fiber Thicness, cm 0.95 2.20 Volume, cm 3 7.01 16.18 Volumeweight, m 3 g 0.78 1.46 Speciic gravity, gcm 3 1.27 0.69 From Table 2 it is known that volume and thickness of bamboo iber composites are larger, but lighter than the bamboo pulp composite. On bamboo iber composites, interfacial bonding with the matrix resin is less perfect than composite bamboo pulp, because the content of alpha cellulose is relatively lower Figure 3 , so that the resin portion accumulates and polymerizes on the surface of the iber, causing the composite is much thicker. Therefore, the volume of bamboo iber composite is larger, although the pulp or bamboo ibers and resins used have the same weight component. Volume of bamboo iber composite is greater, then the porosity becomes greater as well. Porosity causes the air trapped in the composite void. The void can be caused by uneven pressure, resin which evaporates, the air trapped in the resin during the mixing, or mixing is not homogeneous. Sample and Composite Microstructures Sample and the microstructures of composite are presented in Figure 5 and 6. From Figure 5, visually known that bamboo iber composite looks denser and darker than the bamboo pulp composite. Besides, from Figure 6, can be seen that there are two components forming composites, i.e. epoxy resin and iber or bamboo pulp which in this case serves as a composite reinforcement. From that igure are visible also the pores or the presence of air cavities voids between the iber or pulp. The voids are the air trapped in the composite. Voids in the composite material can be caused by uneven pressure, resin which evaporates, and the air trapped in the resin at the time of uneven agitationmixing. Through these pores the incoming sound waves vibrate the air molecules in the pores, so that the composite can function as a sound absorber material. Besides that, the bamboo iber composite specimens looks more compact than pulp composite, which will affect to the strength of the composite [34, 35]. ISBN : 978-602-17761-4-8 162 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Figure 5. Composite of Bamboo Fiber left and Bamboo Pulp right Bamboo Fiber Bamboo Pulp Bamboo Fiber Bamboo Pulp Figure 6. Microstructure of Composite SEM, 15 and 350 times magniication Functional Groups Analysis Bamboo iber is a cellulose iber, and its chemical composition contains mostly alpha cellulose [30 in 6]. Cellulose chain is a crystalline structure that is supported by the covalent bonds between the chemical elements. The hydrogen groups on epoxy resin polymer binds to the active group on the cellulose, i.e. -OH group and the CH 2 OH forming hydrogen bonds. The longer the chain of the cellulose molecules, the chemical bond with the polymer resin will be many more, so that the composite will be more solid. In addition, macro porous and micro porous areas will be illed by chemical bonds. The results of functional groups analysis is presented in Figure 7 and 8. Bamboo Fiber Cellulose consists of the elements C, H and O, which forms the molecular formula C 6 H 10 O 5 n . The molecular bond is a very strong hydrogen bonding. The functional group of the cellulose chain is a hydroxyl group -OH, and these groups can interact with one another with a group -O, -N, and -S, forming hydrogen bonds. The hydroxyl group causes the cellulose surface is hydrophilic. Cellulose chain has a -H group at both ends and the tip –C1 have reducing properties. Cellulose chain structure is stabilized by strong hydrogen bonds along the chain. Chemically, cellulose is a polysaccharide compound with a high molecular weight, regular structure which is a linear polymer consisting of repeat units of b- D – glucopyranose. Characteristics of cellulose appear among others, the crystalline and amorphous structures and the formation of micro-ibrils, which eventually became cellulose ibers. The FTIR spectra of bamboo iber is presented in Figure 8.a, while the cellulose absorption wave numbers presented in Table 3. [36]. From FTIR spectra of bamboo iber, it is known that these ibers are cellulose, indicated by the peak at wave number 3417 cm -1 and 2900 cm -1 , which showed a group -OH and -CH. Absorption at wave number 1600 cm -1 is a carbonyl group of the lignin. Bond C = C aromatic symmetrical stretching absorption detected at wave number 1506 cm -1 . The absorption at wave number 1429 cm -1 indicate the presence of asymmetric bending CH- group. Group - CH is also indicated in the absorption wave number 1375 cm -1 . Nonsymmetrical bond in phase ring detected at absorption wave number 1111 cm -1 . In addition, C-O group detected at wave number 1056 cm -1 . ISBN : 978-602-17761-4-8 163 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Table 3. FTIR Spectra of Cellulose Wave numbercm -1 Bond stretching 669 OH out of phase bending 899 Nonsymmetrical out-phase ring 1040 C – O 1070 skeletal vibration C – O 1108 nonsymmetrical in phase ring 1159 Nonsymmetrical bridge C – O – C 1374 CH Bending 1420 CH 2 symmetric Bending Epoxy Resin Epoxy resin ethylene oxide is a thermosetting resin which are widely used as adhesives, coatings, and matrices in polymer composites, because of low viscosity, has good insulation properties of the end product even at high temperatures and resistant to heat and chemicals. There are two main groups, namely glycidyl epoxies and non - glycidyl epoxies resin aliphatic epoxy. The absence of aromatic rings in the epoxy aliphatic cause a decrease in viscosity and resistant to UV rays, making it suitable for outdoor applications. The most common epoxy monomer groups are diglycidyl ether of biphenyl A DGEBA and 3,4 – epoxy cyclohexyl - 3’4’ - epoxy cyclohexane carboxylate ECC [37], as presented in Figure 7. Characterization of epoxy involves more locations oxyren ribbon ring. There are lots of epoxy resin with a different structure, different degrees of polymerization and others. IR spectroscopy can be used to characterize the properties of epoxy and Figure 7.b. shows the FTIR spectra for HDGEBA and DGEBA epoxy. The results of FTIR analysis for the epoxy resin used in this study is shown in Figure 8.b. From this FTIR analysis, it appears that the uptake for the FTIR spectra similar to DGEBA epoxy. Figure 7.a. Epoxy Structure, a DGEBA, b ECC Figure 7.b. FTIR Spectra of HDGEBA and DGEBA Epoxy Bamboo Fiber Composite The reaction between epoxy and hydroxyl groups is the reaction of an acid or base catalysis; but the whole of research in the ield of wood is a base catalysis, i.e. Wood – OH + R – CH –O– CH 2 à Wood –O–CH 2 –CHOH –R [37] ISBN : 978-602-17761-4-8 164 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech a. Bamboo iber b. Epoxy c. Composite x : Wave number cm -1 and y : Transmittance Figure 8. FTIR Spectra of Bamboo Fiber, Epoxy and Composite Figure 8.c is an FTIR analysis of the test results of bamboo iberepoxy composite. By comparing the picture to Figure 10.a. and 10.b. FTIR analysis of bamboo iber and epoxy, it is known that the FTIR spectra of the composite is a combination of the spectra of bamboo iber and epoxy, which is indicated by the peak at the same wave number. Sound Absorption Coeficient Standard human auditory response to the sound of the audio frequency is at range of about 20 - 20,000 Hz. Sound generally consists of many frequencies, namely low, middle, and medium frequency components. Standard frequency that can be chosen as an important representative in the environment acoustic was 125 , 250, 500, 1000, 2000, and 4000 Hz or 128 , 256 , 512 , 1024, 2048, and 4096 Hz. The sound absorber is a material that can absorb sound energy from a sound source [17, 38, 39, 40, 41]. To determine the ability of composite results of this study to absorb sound, then be tested using Impedance Tube at a frequency of 1000 Hz - 6300 Hz [24], as shown in Figure 9. Furthermore, Figure 10. shows sound absorption coeicient of bamboo iber and pulp Kraft Process composites compare to wood and wall. From Figure 9 it is known that the absorption coeficient of bamboo pulp composites tend to rise along with rising frequency, i.e. up to 3150 Hz - 5000 Hz , then decreases; whereas for bamboo iber composites tend to rise along with rising frequency, ie to 2500 Hz, then decreases. It found that the bamboo iber composites provide the largest absorption coeficient in the frequency range between 3150 Hz - 4000 Hz, which is 0.83 to 0.80; while absorption coeficient of bamboo pulp composite in the same frequency range is lower, i.e. 0. 29. From the test results of the sound absorption coeficient obtained an average coeficient of absorption at the standard frequency 1000 Hz - 4000 Hz and high frequency 5000 Hz - 6300 Hz. It is known that composites with bamboo iber reinforcement on standards frequency provide sound absorption coeficient is relatively high with maximum condition α = 0.97 at a frequency of 2500 Hz frequency range based on the ability of the sound system or speakers commonly used is up to 2800 Hz. As well at the high frequency, composite of bamboo iber and pulp provide maximum conditions with α = 0.77 and 0.28 at the frequency of 5000 Hz . Thus the composite have met the minimum standard sound absorption coeficients, i.e. α = 0.25 the reference frequency 5000 Hz based on ISO 11 654: 1997 [17]. Bamboo iber composite is much thicker, so the volume of that composite is larger than bamboo pulp composite Table 2. Therefore, the porosity becomes greater as well. Porosity causes the air trapped in the composite void, and the amount of the void volume indicates that the porosity of bamboo iber composites is greater than bamboo pulp composites, so that the absorption coeficient of the composite is higher. In addition for a porous material, sound absorption capability depends on the volume and thickness, the greater the volume and the thicker the material, the higher the sound absorption ISBN : 978-602-17761-4-8 165 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech coeficients, so that the composite of bamboo iber, in both standard and high - frequency has a suitable sound absorbers more than bamboo pulp composites. From the literature it is known that the sound absorption coeficient of glasswool on sound frequency between 250 Hz and 2000 Hz on average is between 0.4 to 0.8 thickness 15 mm to 100 mm; while the coeficient of sound absorption on wood, tile and wall at the sound frequency between 125 Hz to with 4000 Hz , the average row between 0.06 to 0.15 ; 0.4 to 0.8; and 0.3 to 0.7 [42, 43, 44]. Therefore known that sound absorption coeficient α of bamboo iber composites, with a thickness of about 22 mm is relatively the same as glass wool at 2000 Hz, but when compared to the sound absorption coeficient of the wood and the wall Figure 10, it can be said that the composite has a higher ability to absorb a sound, especially bamboo iber composites.

0,2 0,4

0,6 0,8

1 1000 1250 1600 2000 2500 3150 4000 5000 6300 a lp h a Frequency, Hz Bamboo fiber Bamboo pulp Kraft process

0.2 0.4

0.6 0.8

1000 2000 3000 a lp h a Frequency, Hz Bamboo fiber Bamboo pulp Kraft process Wood Wall Figure 9. Sound Absorption Coeicient α of Bamboo Fiber and Pulp Kraft Process Composites Figure 10.Sound Absorption Coeicient α of Bamboo Fiber and Pulp Kraft Process Composites Compare to Wood and Wall In the future it’s expected that bamboo iber and bamboo pulp are used as a substitute for wood in manufactured wood industry as sound absorber material; because can comply with the applicable standards, i.e. α = 0.25 at the reference frequency 5000 Hz, based on ISO 11 654: 1997 [17]. However, the quality of bamboo iber composite is higher than bamboo pulp composite, because it can reduce noise up to 77 at the reference frequency 5000 Hz and 97 at 2500 Hz. Furthermore, from the subsequent research [45] was known that the bamboo iber composite has high densities, while the physical properties water content, water absorption, changes in the length and thickness, tensile irmness and lexural rigidity can conply with the applicable standards for iberboard High Density Fiber Board T2 45 Type [46]. In addition, as a composite, the value - added products derived from bamboo will increase and can reduce the consumption of wood, which the availability is limited. Moreover, it can reduce the use of synthetic ibers and resin, making it more environmentally friendly. Conclusion Composite of bamboo iber and pulp can be used as sound absorber material, because can compy with the minimum standard sound absorption coeficients {α = 0.25 the reference frequency 5000 Hz}. The quality of bamboo iber composite is higher than bamboo pulp composite, because it can reduce noise up to 77 at the reference frequency 5000 Hz and 97 at 2500 Hz. So this study has been successfully to manufacture composite for sound absorber material from bamboo iber, and obtained the environmentally friendly products, because it can reduce the use of synthetic ibers and resins. Additionally, the physical properties of bamboo iber composite can comply with the applicable standards as iberboard SNI 01 – 4449 - 2006. ISBN : 978-602-17761-4-8 166 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech References 1. Astrom BT. Manufacturing of polymer composites, Chapman Hall, London, Weinheim, New York,1997. 2. Maloney T M. Modern particle board and dry process ibre board manufacturing, Miller Freeman, Inc. San Fransisco,1993. 3. Lukman A. Particle characteristics empty fruit bunch after cold water, hot water, ethanol – benzene immersion, Thesis, Bogor : Fakultas Kehutanan, Institut Pertanian Bogor, 2008. 4. Kollman FFPEW, Kuenzi, Stamm AJ. 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The technical study using bamboo iber as an alternative composite materials on making the vessel wall in terms of bending strength and impact strength, Laporan Kegiatan 2005, Fak. Teknik UNDIP, November. 12. Herliyana EN, Noverita, Lisdar IS. Fungi on yellow bamboo B. vulgaris schard var. vitata and green bamboo B. vulgaris schard var. vulgaris and the resulting degradation rate, Jurnal Teknologi Hasil Hutan 2005, 18 1: 2 -10. 13. Krisdianto GS, A Ismanto, Results of the research of rattan and bamboo, Puslitbang Hasil Hutan, Bogor, 2000. 14. Kusumah SS, B Subiyanto, M Yusram M. Optimization of composite boards manufacturing from waste wood and bamboo, Widyariset 2011, Vol. 14 No. 2, Agustus. 15. Tampobolon E. Repository. USU. ac.id., 2010. 16. Widjaja EA. Identify the types of bamboo in java, Laporan, Pusat Penelitian dan Pengembangan Bilologi, LIPI, Bogor, 2001. 17. Hari S, et.al. Inluence factors of paper type, density and percentage adhesives against bending strength of sound absorption panels composite from waste paper and coconut iber, Performa 2011, Vol. 10, No. 2: p. 89 – 94. 18. Luigi N, Assunta B. Willey encyclopedia of composites, John Willey and Sons, Inc, New York, 1999. 19. Mazumdar SK. Composites manufacturing : Material, product and processing engineering, 2002. 20. Schwartz MM. Composite materials handbook:, 2 nd ed., Mc. Graw – Hill Inc., 1992. 21. Alaya FHM. Potential of bast ibers as an reinforcing ibers in biocomposites for automotive applications, TRAKSI 2013, Vol. 13, No. 2, Desember. 22. Rosato DV, Di Matitia DP. Disigning with plastic and composite : A Handbook, Van Nostrand Reinhold, New York, 1991. 23. Mahieux CA. Environment degradation in industrial composites, Elsevier, London, 2006. 24. ISO 10534-2: Acoustics – Determination of sound absorption coeficient and impedance in impedance tubes – Part 2: Transfer-Function Method 1998, International Standardization Organization. 25. Yeni Aprianis, Syoia Rachayani. Fiber dimensions and evaluation of iber dimension of seven types of wood from Jambi Province, Journal of Forest Product Research 2009, Vol. 27, No. 1, 26. Fatriasari W, Euis H. Fiber morphology analysis and physical - Chemical properties in six type of bamboo as raw materials of pulp and paper, Jurnal Ilmu dan Teknologi Hasil Hutan 2008, 12, 67- 72. ISBN : 978-602-17761-4-8 167 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech 27. Pasaribu RA, AP Tampubolon . Utilization of wood iber technology as raw materials of pulp, Dissemination and Workshop BPHPS Programs to Support Needs of Forest Research Wood Pulp Plant and Network 2007. 28. Syaii W, I Z Siregar. Chemical properties and wood iber dimensions of mangium Acacia mangium willd from three provenance, Jurnal Ilmu dan Teknologi Kayu Tropis 2006, Vol. 4. No. 1. : p. 29-32, Indonesian Wood Research Society. 29. Pettersen R P. The chemical composition of wood – in the chemistry of solid wood, American Chemical Society, 1988. 30. Franck R R. Bast and other plant ibers, The Textile Institute, Woodhead Publishing Ltd., Cambridge, England, 2005. 31. Abrido SH, Leonard SJ, Maulida. Inluence of alkali solution to the bump strength and degradation test of thermoplastic resin and coconut dust composites, Jurnal Teknik Kimia USU 2012, Medan : Fakultas Teknik, USU. 32. Mark JE. Inorganic polymers, Prentice-Hall International, Inc. : New Jersey, 1992. 33. Agustina D. Levels of lignin and lignin constituent monomers type in acacia wood, Thesis, Dep. Hasil Hutan, Fakutas Kehutanan, IPB, Bogor, 2009. 34. Agarwal BD, Broutman LJ. Analysis and performance of ibre composite, Wiley – Inter science, New York, 1990. 35. Christian RK, Mathias K, Poul HK. Flexible mould for frecast concrete element, Proceeding of the International Ass. for Shell and spatial Structure IASS Symposium, Shanghai, China 36. Kondo T. Hydrogen bonds in regioselectively substituted cellulose derivatives, J. of Polymer Science - Part B; Polymer Physics 1994, Volume 32, Issue 7, May 37. González M, Juan CC, Juan B. Applications of FTIR on epoxy resins - identiication, monitoring the curing process in Infrared Spectroscopy - Materials science, engineering and technology, Edited by Theophile Theophanides, ISBN 978-953-51-0537-4, 524 pages, Publisher: InTech, Chapters published, April 25, 2012. 38. Aini Khuriati, Eko K, Muhammad N.Sound absorber design of coconut iber based and sound absorption coeficient measurements, Berkala Fisika 2006, No.1, January, p. 15 – 25. 39. Beranek L L, Ver I L. Noise and vibration control engineering: Principle and application, John Wiley and Sons Inc., New York, 1992. 40. Merve KO, et.al. A Study on the inluence of fabric structure on sound absorption behavior of spacer knitted structures, International Conference – TEXSCI 2010, September 6-8, Liberec, Czech Republic, Istanbul Technical University, Department of Textile Engineering, Istanbul, Turkey. 41. Miasa IM, Sriwijaya R. Study of acoustic properties of materials paper and plastic for noise barriers, Media Teknik 2004, No.1, Year XXVI. 42. Erlina Rusmawati. Absorption coeficient determination by two microphone method on impedance tubes, 2407 100 605, FTI- ITS downloaded October 2015. 43. Mediastika EC. Building acoustics, Erlangga, Jakarta, 2005. 44. Shoshani YZ. Effect of nonwoven backing on the noise absorption capacity of tufted carpets, Textile Research Journal 2011, August, p. 452-456. 45. Theresia Mutia. Composite of pulp and bamboo iber from tali bamboo g. apus for iberboard, Center for Pulp and Paper, Bandung, 2015 46. Anonim. National Indonesian Standard SNI 01 – 4449 - 2006 – Fiber Board. ISBN : 978-602-17761-4-8 168 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech ISBN : 978-602-17761-4-8 169 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech A REVIEW: RECENT RESEARCH IN PAPER PACKAGING FOR FOOD Qanytah a b , Khaswar Syamsu c , Farah Fahma c , Gustan Pari d 1 a Graduate Program of Agroindustrial Technology, Bogor Agricultural University b Indonesian Center for Agricultural Postharvest Research and Development, Bogor c Department of Agro-industrial Technology, Bogor Agricultural University d Forest Products Research and Development Center, Ministry of Environment and Forestry 1 gustanpyahoo.om ABSTRACT Packaging is an important application of paper materials. About 50 of all paper produced is used for packaging. In the recent years, many new food-packaging concepts have been introduce. The recent effort is transformed paper into varies and excellent modern packaging choice in food industry. There are a range of innovations that can enhance performance with regard to consumers’ valued product characteristics and packaging attributes. These include security packaging, smart or intelligent packaging, and active packaging. The main objective of this paper is to provide a review on recent research in paper packaging for food. The material using for paper packaging, method and system for incorporation materials, structure design of paper packaging and its application have discussed and compared. Keywords: intelligent paper, packaging, material, structure design Introduction Packaging is an important application of paper materials. Packaging has many important functions, such as protection, convenience, reusability, production reality, and carrying printed information and graphics. Packaging protected the packaged foods from hazards such as contamination in the distribution environment, facilitating transportation and storing of foods. About 50 of all paper produced is used for packaging Datamonitor, 2008. The largest share of global packaging was accounted by paper and board packaging, with sales of 165 billion in 2003, equating to 39 of the market World Packaging Organisation, 2008. Paper and paperboard also represents the largest proportion by weight of packaging material used. The food and beverage industry is the largest user of packaging generally. Paper has reported to be the most widely used material in packaging applications owing to its characteristics of printability, recyclability, and biodegradability. Currently, paper and paperboard production is increasing every year, packaging paper and paperboard account for more than 50 of total paper and paperboard. Per capita paper consumption has become an international standard measure of a country’s economic development and an important symbol of social civilization. Unfortunately, paper properties such as hygroscopic and porous, its barrier properties against water-vapor, gases and aromas are poor. Paper packaging materials made from cellulose ibers produced from virgin wood, non-wood iber, agricultural residue, recycled iber, or combination of those materials, which usually have the biodegradable and recyclable characteristics. The paper often combined with polymers such as plastics and aluminum or metal foils to form laminates for packaging of speciic products and for their good barriers properties. Unfortunately, this obtained material losses its biodegradation and recyclability characteristics due to the addition of that component. In the recent years, many new food-packaging concepts have been introduced. The recent effort of the cellulose industry to improve its products has transformed paper into varies and excellent modern packaging choice in food industry. However, paper are permeable to gases, moisture, oils and fats. Consequently, these materials often require treatments such as coatings and laminations. These processes may involve speciic materials, plastics and barrier materials, such as aluminum foil, to extend their packaging applications and the shelf life of the products they contain. The development of paper packaging need to be encouraged by improvements in technical performance and inluenced ISBN : 978-602-17761-4-8 170 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech by a number of factors. There are a range of innovations that can enhance performance with regard to consumers’ valued product characteristics and packaging attributes. These include security packaging, smart or intelligent packaging, and active packaging. Security packaging can be achieved by using a paper with a characteristic feature, such as the presence of special ibers, and similar techniques are the subject of continuous development. Intelligent or smart packaging refers to packaging that senses and informs. Development of intelligentsmart packaging is being accelerated by rapid innovation in enabling technologies such as nano-coatings and nano-codes. The main objective of this paper is to provide a review on recent research in paper packaging for food. The material using for paper packaging, method and system for incorporation materials, structure design of paper packaging and its application have discussed and compared. Trend in Food Packaging The packaging sector is an important global industry, representing about 2 of the Gross National Product GNP of the developed countries. Modern food packaging function not only have a passive role in protecting and marketing the product. It has an active role in processing, preservation and in retaining the safety and quality of foods throughout the distribution chain. Indeed, packaging development has changed the preservation methods used for food products. Food packaging developed strongly during recent years, mainly due to increased demands on product safety, shelf-life extension, cost-eficiency, environmental issues, and consumer convenience. Packaging technologies have been evolve. They have great commercial potential to ensure the quality and safety of food with fewer or no additives and preservatives, thus reducing food wastage, food poisoning and allergic reactions. Intelligent packaging can also monitor product quality and trace a product’s history through the critical points in the food supply chain. An intelligent product quality control system thus enables more eficient production, higher product quality and a reduced number of complaints from retailers and consumers. Intelligent packaging will also give the food industry the means to carry out in-house quality control required by food regulators. The food packaging evolution shown in Figure 1. Figure 1. Active food packaging systems, concepts and application matrix Imran et al., 2010. ISBN : 978-602-17761-4-8 171 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech The deinition of active and intelligent packaging according to the Actipak project are: 1. Active packaging changes the condition of the packed food to extend shelf life or to improve safety or sensory properties, while maintaining the quality of the packaged food; 2. Intelligent packaging systems monitor the condition of packaged foods to give information about the quality of the packaged food during transport and storage. According to Figure 1, active packaging techniques for preservation and improving quality and safety of foods can be divided into three categories; absorbers i.e. scavengers, releasing systems, and other systems. Absorbing scavenging systems remove undesired compounds such as oxygen, carbon dioxide, ethylene, excessive water, taints and other speciic compounds. Releasing systems actively add or emit compounds to the packaged food or into the head-space of the package such as carbon dioxide, antioxidants, and preservatives. Other systems may have miscellaneous tasks, such as self-heating, self- cooling, and anti microbialpreservation. The system to produce active packaging include: edible ilms, addition of sachet, incorporationdispersion, and coating. Material for Paper Packaging The majority of paper packaging produced and used in many countries today is made from wood iber. The ingredients for papermaking include hardwood andor softwood, wood chips, sawmill residues, water, and chemicals. The rapidly growing demand for paper in the last few years not been fully met by the substitute products introduced lately. The possible solution to this problem is the use of non-wood plants include agricultural waste, which was contain high amounts of cellulose iber, which could be potentially use to produce paper. Some substantial non-wood plant ibers including agricultural ibers such as: a seed ibers cotton, cotton linter; bast ibers lax, hemps, kenaf, jute, rosella; c leaf ibers pineapple, sisal, abaca, banana stalk, switch grass, elephant grass; d agricultural residues rice straw, corn cobs and stalks, oil palm fruit bunch, coconut coir e bamboo; f others bacterial cellulose, algae. Non-wood plant ibers that are currently used or potential to use in the paper industry and its characteristic as shown in Table 1. On the other hand, paper packaging often combined with polymers or metal foils to form laminates for packaging of speciic products. Polymers or metal also become problems with increasing pressure to reduce waste going to landill. In the last decade, environmental issues have become increasingly important, triggering the use of bio-based packaging materials as an alternative to materials produced from nonrenewable resources. Such bio-based packaging materials include naturally occurring proteins, cellulose, starches and other polysaccharides Starch is a kind of important natural polymer with lots of usages and has been widely used in many industry ields such as papermaking. One of newly modiied product from starch is starch polyacrylamide graft copolymer. It application in paper packaging material have been extensively reviewed by Liu et al. 2011. Liu et al 2011 studied the preparation of starch polyacrylamide copolymer and its effects on treating wastewater and paper performance. The increasing of dosage of synthesized St-PAM copolymer resulted the basic weight increased, but decreased the tear strength and the fold endurance. The tensile strength and breaking length increased irstly and then decreased. Regarding these research results, there is no points that explained the future application of the paper packaging produced in this study. The use of natural ibers instead of traditional reinforcement materials provides several advantages. Scientist have been developing a number of novel materials based on cellulose nanoibers including nano composite. The properties of cellulosic ibers inluenced by many factors like internal iber structure, chemical composition, micro-ibril angle and cell dimensions which differ from different parts of a plant as well as from different plants. The mechanical properties of natural ibers also depend on their cellulose type because each type of cellulose has its own crystalline organization, which can determine the mechanical properties. As the properties of natural iber will also inluenced the suitable methods to isolate nanocellulose, a further research was needed. There are some advantage of nanocellulose material such as natural and renewable, biodegradable, reduced carbon footprint, recyclable, reusable, compostable, biocompatible, have high surface area, high ISBN : 978-602-17761-4-8 172 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Table 1. Non-wood plant iber and its characteristic No Non wood plant material Characteristic 1. Sugarcane bagasse Saccharum oficinarum Average iber length is 1.7 mm 0.8-2.8 mm, and width is 0.02 mm 0.01- 0.034 mm. Fibers are thick wall Ilvessalo-Pfafli, 1995. It can used to make printing writing paper, bristol board, tissue paper, glassine, greaseproof paper, duplex and triplex paper. 2. Corn stalks Zea mays Average iber length of 1.5 mm 0.5-2.9 mm and width of 0.018 mm 0.014- 0.024 mm. Typical ibers are narrow, thick wall and have blunt or pointed ends [4] Ilvessalo Pfafli, 1995. 3. Cotton stalks Goossypium Average iber length of 0.6-0.8 mm and an average iber diameter of 0.02-0.03 mm Ilvessalo Pfafli, 1995. 4. Rice straw Oryza sativa It has high silica content. Average iber length is 1.4 mm and width is 0.009 mm Ilvessalo-Pfafli, 1995. It can used to make printing and writing paper, glassine and greaseproof paper, duplex and triplex paper, corrugating medium, straw board and “B” grade wrapping paper. 5. Wheat straw Triticum aestivum Average length of 1.4 mm 0.4-3.2 mm and width of 0.015 mm 0.08-0.034 mm. Typically, ibers are narrow, thick-wall and have a blunt or pointed ends Ilvessalo-Pfafli, 1995. It can be used to make printing and writing paper, glassine and greaseproof paper, duplex and triplex paper, corrugating medium, strawboard and “B” grade wrapping paper 6. Bamboo Dendrocalamus strictus It grows from sea level to the snow line, fastest growing plants available for pulp. Fiber length varies from species to species. In some species it also varies from bottom to top and, in some cases, it varies with intermodal length. Average iber length is 2.7-4.0 mm and diameter is 0.015 mm Ilvessalo-Pfafli, 1995. It can used to make printing and writing paper, bristol board, duplex and triplex paper, linerboard, wrapping and bag paper, multiwall sack and newsprint substitute. 7. Abaca Manila hemp Musa textilis Under normal conditions, the irst harvest completed from 18-24 months after planting. Subsequent harvests completed at 3-4 month intervals. Average iber length of 6.0 mm and it has an average iber diameter of 0.024 mm. It can used to make specialty papers like superine, lightweight, bond, ledger, currency and security paper, tea bags, ilters, linerboards, wrapping and paper bag. 8. Cotton linters The iber length of milling runs is approximately 3-7 mm; irst cuts are 5-7 mm and second cuts are 3-5 mm. The average iber diameter is 0.03 mm. It can used to make high-grade bond ledger book and writing paper. 9. Sago pith iber The iber length 2,03 - 2,37 mm 10. Water-hyacinth Cellulose content about 65.41 Joedodibroto, 1983. ISBN : 978-602-17761-4-8 173 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech strength and modulus, light weight, dimensional stability, thermal stability, high optical transparency, high thermal conductivity, and low oxygen permeability. Regarding its suitable character as pulp and paper production, some study conduct to investigate its application on pulp and paper. Mihranyan et al. 2012 produce nanocellulose from Cladophora alga mixing with Tween-80 coating to produce paper composite. It results showed that mechanical properties of Polimer PolypyrrolePPy– Nanocellulose paper was improved, and nanocellulose iber coating with PPy increased bigger pore and resulted composite with open surface area, and lighter paper. Composite electroactivity character depends on its total porosity. Kajanto and Kosonen 2012 research on paper production using 2 types of nanocellulose type AS or KS with dosage level of nanocellulose 0, 1 resulting the increasing of paper mechanical properties, even in low dosssage. The 2 types of nanocellulose give the same result. Taipale et al. 2010 study on addition of 6 nanosellulose in paper where the pulp raw material have long iber and bleach. It showed that paper Scott Bond + 55 increased and tensile index increased up to + 15 Nmg. The consumer demands for safe, high quality and extended shelf life foods, driving for innovation in food packaging. As result of this requirement, there were the development idea of new concept that some active interactions between the package and the product may have positive effects. Antimicrobial packaging AM technology is an innovative concept to extend the lag phase andor reduce the growth rate of the microorganisms. The development of antimicrobial ilms that Quintero et al. 2012 study was the active antimicrobial substances in directly incorporated in the packaging material. Antimicrobial substances incorporated into packaging materials can control contamination by reducing the growth rate and maximum growth population andor extending the lag phase of the target microorganism or by inactivating microorganisms by contact. According to Quintero et al. 2012, the preparation method of the ilms produced a huge effect on the antimicrobial and other properties of the ilms. Optical properties changed depending on the organoclay and the antimicrobial compound used. The mechanical properties of the nanocomposites improved when Cloisite 30B used. Thermal degradation temperature and transition temperature decreased in ilms containing organoclay and antimicrobial compounds because of a plasticizer effect. The antimicrobial showed strong inhibitor effects against S.cerevisiae, L.innocua and E.coli, obtaining a reduction in the antimicrobial activity of at least 2.0 log CFUmL. Methods and System for Incorporation Material Paper is often associated with other materials, such as plastic material and aluminum, for their good barrier properties that can be advantageously combine with paper stiffness. Paper could coated with some polymer such as ethyl vinyl alcohol EVOH or polyoleins, but the addition of synthetic polymer layer caused the paper packaging loses its biodegradation and recyclability characteristics. Naturally, renewable biopolymers have been the focus of much research in recent years because of their potential use as edible and biodegradable ilms and barrier coating for food packaging. Such biodegradable coatings have the potential to replace current synthetic paper coatings. Agriculturally derived alternatives to synthetic paper coatings provide an opportunity to strengthen the agricultural economy and reduce importation of petroleum and its derivatives. Active packaging has become one of the major areas of research in food packaging. Antimicrobial packaging is of great importance because it could be a potential alternatives solution to extend the shelf life and assure the innocuousness and preservation of food products. Some research of different types of component and biopolymers investigated as paper coating material presented in Table 2. Natural coating have been the focus of much research in recent years due to their potential use as edible and biodegradable ilms and coating for food packaging. Tabel 2 showed that natural component can be used as barrier coating on paper packaging materials, such as Activated Carbon, Polystyrene Silver, Wheat Gluten, Active parafin formulation with essential oil, and Chitosan. The different coating material have different character and different purposes. Activated Carbon is used as ethylene absorbers for produce packaging. Ethylene absorbers can be ISBN : 978-602-17761-4-8 174 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Table 2. Different types of component and biopolymers as paper coating material No Coating Paper Material Results Refference 1. Activated Carbon AC using g l u c o m a n n a n GC as binder Rice Straw • Increase in the AC content implies a decrease in thickness, increase the smoothness and grammage • Increase in the AC content decrease tensile index, burst index, folding endurance, and tear index • The potential application of AC-rice straw papers would be as a separate bag or wrapper or as a laminate inside carton to extend the shelf life of agricultural products that are sensitive to ethylene banana, mango, tomato, and apple S o t h o r n v i t and Sampoom puang 2012 2. Polystyrene PS n a n o c o m p o s i t e extracted from rice straw then dissolved by toluene solvent. The solution then added by silver nano particle. Waste paper from newsprint paper • Paper dipping in PS solution and silver nanoparticles improve tensile strength. When silver nanoparticles irst added to the pulp during making paper sheet before coating by PS, tensile strength decreased. • Silver nanoparticles would be the promising applicants as new antimicrobial Nassar and Y o u s s e f 2012 3. Wheat Gluten WG Paper made from bleached pulp with 2 kinds of treatment: • Surface coated with calcium carbonate and starch TP • U n t r e a t e d paper UTP • UTP displayed a higher level of protein penetration than TP • The coating of paper by WG solution resulted in a signiicant reduction in oil wettability • Coating paper with WG reduced in water vapor permeability • WG coating led to signiicant gas permeability Guillaume et al 2010 4. Active parafin formulation con- taining essential oil from: cinna- mon leaf oil, bark cinnamon oil, oregano, and clove Kraft Paper • Active paper manufactured with essential oil has activity against A. alternate, where solid parafin coating incorporate with active agent have better activity than parafin emulsion. • Active parafin-based paper packaging is very useful approach to extend the cherry tomato shelf life. Lafuente et al 2010 5. Chitosan Kraft Paper Coated chitosan on paper matrix have a good fat barrier that could be a potential process to develop paper-based packaging material to pet food application. Pichavant et al 2005 6. Microfibrillated Cellulose MFC with different amount of NaClO Base paper • Tensile index and burst index increased irstly and then decreased with the increase of NaClO amount. • The folding endurance of coated paper and air permeability was increased by increasing the NaClO. Li et al 2014 ISBN : 978-602-17761-4-8 175 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech particularly useful in produce warehouses where ethylene gas, a natural plant growth regulator, can rapidly accumulate. During storage, high concentrations of ethylene can lead to accelerating respiration rate and subsequent senescence. Use of ethylene absorbers can signiicantly extend shelf life, thereby reducing waste in the supply chain and deriving economic beneit for suppliers and retailers. These absorbers can be embedded into paper bags or corrugated iberboard transit packaging used for produce storage and transport. They can also be incorporated as sachets into retail packs of produce to extend produce shelf life for the beneit of the retailer. Packaging containing anti-microbial coatings and treatments are increasingly being used to extend the shelf life of a wide range of perishable food. The preservative effect of the agent results in signiicant reductions in food spoilage and infections caused by microbial growth. According to those studies, we understand that antimicrobial component has speciic activity against speciic microbial. There are increasing concerns globally about non-biodegradable plastics, or plastics-based packaging pollution. Some research also have been extensively reviewed regarding the properties, technology, functionalities, and potential uses of biopolymer ilms and coatings which done by Kester and Fennema 1986, Anker 1996, Guilbert et al. 1997, Krochta 2002, and Khwaldia et al. 2004. Paper Packaging Application and Design Companies continually seek to deliver a better user experience to differentiate their brands and enhance consumer appeal, minimize costs and enhance supply chain performance, and improve the environmental credentials of their products and services. A main challenge for industry is to optimize design of the packaging system. This involves striving to create packaging that balanced in terms of providing product protection and preservation, is cost-effective, creates maximum consumer appeal and at the same time takes into account environmental responsibility Nampak, 2010. Considering the contrast between the need of standardization and the request of diversiication, today materials and technologies represent an opportunity for new structural and functional solution, they have the power of suggestion for packaging designers. The work done followed this evolution of design: products are becoming dynamic, smart, interactive, and emotional. The project focused on the functionality of packaging and future steps will be addressed to the communication and emotional aspects of the developed packaging. Companies design and purchase packaging made by different materials that ensure given performance and that made using the most varied techniques, according to the type of contents to be preserved, protected and transported. It has considered that packaging has its present form by way of continuously following the evolutionary paths of the materials and packaging technologies. The materials have evolved considerably, modifying the possibility of use and broadening their own range of applications to new segments, inventing new solutions, stealing secrets from other sectors and thus transferring them from one material to another in a continuous shift of technological progress. Many package style and structural designs are possible and often speciic. Structure design of paper packaging plays an important role in designing packaging. The biodegradable and recyclable characteristics of paper material make paper packaging have very broad prospects of development. Structure design of package containers based on the fundamental functions such as protection, convenience, and reusability and production reality. In modem package design, the structure has become a bond between new materials and new technologies; it is an important part to make packages as close as possible to perfect. This paper review the research of Xiao and Huang 2010 on structure design of paper packaging. In structuring design for papers packaging there are some consideration such as the cost of paper packaging material, the eficiency paper needs, the paper and packaging utilization. Xiao and Huang 2010 described the principle in designing package such as: a functional principles, b adaptation principles, c humanity principles, d ecological principles, e simple principles, f aesthetic principles, and g innovation principles. In this research, of Xiao and Huang 2010 analyzed the example of inkstone packaging using the computation methods on stacking capacity, the material using for paper production, and the molding process. The invention and development of new instruments and new technologies on the subsystem will ISBN : 978-602-17761-4-8 176 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech resulting a variety of advanced equipment and instruments used in design and production of packaging structure. The automation present challenges in paper packaging and its subsequent reconiguration to meet the variety of packs. Dai and Caldwell 2010 studied the principle of multi station-based operation, reconiguration and the corresponding technologies for paper and paperboard packaging and developed robotic tooling and its mechanisms. Through motion analysis, the reconiguration of paper and board packaging will understood. Then, the robotic inger designed as reconigurable tools for folding and tucking the paper material. Using robotic tooling for reconiguration in paper-and-board packaging the package design for both fast food and confectionary market ware produced. Dai and Caldwell 2010 stated that the technology on conigurability and adaptability of inger-type tooling mechanisms can be used to meet the demand of variety and innovation in food handling and packaging and leads to free or rapid changeover in the technology. Convenience features, which enhance pack usability, particularly with regard to ergonomics and open ability, represent another important trend. With the ageing population in many advanced economies, packaging designs that facilitate quick identiication of product, provide good legibility, offer ease of opening and use will gain favor with discriminating older consumers. Pack usability is also important to many of today’s younger consumers who may have higher expectations regarding convenience. Consumers are less tolerant of brands that do not fully consider their needs and, increasingly, will switch to brands that do. Ease of opening of food packaging is a high priority for many consumers, particularly the elderly, the visually impaired and those with disabling conditions such as arthritis, who often have dificulty opening cans, bottles and plastic packs. Paper and paperboard-based packaging with ease-of-tear open or pull-open features may offer convenient solutions. For example, paper-based composite cans and retortable paperboard-based cartons with their easy pack opening features present an alternative option to the metal can. An example of a disruptive innovation offering ease of opening and reseal ability of packages for dried product is the Zipbox® w ww.zipbox.net from the US. This is a liner less paperboard carton combined with a heat seal attached lexible ilm header containing a Double Zip zipper proile. Zipbox ® claims other beneits for consumers include product freshness and improved ease of pouring. Smart or intelligent packaging can serve to monitor quality and prevent product wastage, thereby saving resources. Conventional ‘use by’ and ‘best before’ date labelling are relatively crude measures, which often result in products being thrown away unnecessarily. It is expected that labels incorporating devices – such as combined temperature and time indicators TTIs, freshness indicators, chillness and produce ripeness indicators – for use with paper and paperboard packaging, will become a widespread feature within the retail marketplace. These labels are sensitive to changes in the internal condition of the pack. It will effect a visible color change to alert or inform the consumer or user. This technique also be employed to indicate package tampering. For example, tamper proof labels are available for hermetically sealed gas lushed or vacuum packs which, if exposed to the atmosphere, either though accident or malicious intent, can effect an oxidative color change of the label. Paper-based active packaging containing anti-microbial coatings and treatments are increasingly being used to extend the shelf life of a wide range of perishable food, including baby food, fresh produce, cheese, snacks and cold meats. For example, odorless and taste neutral anti- microbial agents can be released onto the exposed surfaces of food where microbial contamination is most likely to occur. The preservative effect of the agent results in signiicant reductions in food spoilage and infections caused by microbial growth. Recent development is paper coated with silver nanoparticles killer paper which, reportedly, could provide an alternative to common food preservation methods such as radiation, heat treatment and low temperature storage. There are also packages where a paperboard-based complete side wall is heat sealed during injection molding to a plastic framework of minimal weight. A similar package has been developed where the sidewall with a glued side seam is attached to the rim such that it is easily removed from the plastic frame for separate recycling after the container has been used. There is a wide range of tamper evident packaging features available for paper and paperboard packaging, ranging from simple traditional paper security seals to holographic labels and other more sophisticated designs and technologies. Security packaging is an on- going development area and there are several possible methods to achieve anti- ISBN : 978-602-17761-4-8 177 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech counterfeit and tamper evidence. This can be achieved by using a paper or paperboard with a characteristic feature, such as the presence of special ibers, and similar techniques are the subject of continuous development. Other methods are achieved by using special printing techniques, such as using inks that are only readable under speciic lighting or using colors that change under speciic conditions, for example UV light identiiable QR codes and printed security marks, together with forensic and track- and-trace systems. Conclusion Natural component used as barrier coating on paper packaging materials, such as Activated Carbon, PolystyreneSilver, Wheat Gluten, Active parafin formulation with essential oil, and Chitosan. The different coating materials have different character and different purposes. In structuring design for papers packaging there are some consideration such as the cost of paper packaging material, the eficiency paper needs, the paper and packaging utilization. The automation present challenges in paper packaging and its subsequent reconiguration to meet the variety of packs. Refferences 1. Anker M. 1996. Edible and biodegradable ilms and coatings for food packaging: a literature review. Goteborg, Sweden: SIC. 2. Barlow CY and Morgan DC. 2013. Polymer ilm packaging for food: An environmental assessment. Resources, Conservation and Recycling 78 2013 74-80. 3. Dai JS and Caldwell DG. 2010. Origami-based robotic paper-and-board packaging for food industry. Trends in Food Science Technology 21 2010 153-157. 4. Datamonitor. 2008. ‘Global Paper and Paperboard – Industry Proile’, June 2008. Available from: http:www.datamonitor.com. [Accessed Februari 2016]. 5. Guillaume C, Pinte J, Gontard N, and Gastaldi E. 2010. Wheat gluten-coated papers for bio-based food packaging: Structure, surface and transfer properties. Food Research International 43 2010 1395-1401. 6. Guilbert S, Cuq B, Gontard N. 1997. Recent innovations in edible andor biodegradable packaging materials. Food Additives Contam 14:741–51. 7. Imran M, Revol-Junelles AM, Martyn A, Tehrany EA, Jacquot M, Linder M, and Desobry SE. 2010. Active Food Packaging Evolution: Transformation from Micro- to Nanotechnology. Journal of Food Science and Nutrition, 50:9, 799-821. 8. Kajanto I and Kosonen M. 2012. The Potential Use Of Micro- And Nanoibrillated Cellulose As A Reinforcing Element In Paper. Journal of Science Technology for Forest Products and Processes: VOL.2, NO.6, 2012 9. Kester JJ, Fennema OR. 1986. Edible ilms and coatings: a review. Food Technol. 4012:47– 59 10. Khwaldia K, Perez C, Banon S, Desobry S, Hardy J. 2004. Milk proteins for edible ilms and coatings. Crit Rev Food Sci Nutr 44:239–51. 11. Khwaldia K, Tehrany EA, and Desobry S. 2010. Biopolymer coating on paper packaging materials. Comprehensive reviews in food science and food safety vol. 9, 2010, 82-91. 12. Krochta JM. 2002. Proteins as raw materials for ilms andcoatings:deinitions,current status, and opportunities. In: Gennadios A, editor. Protein-based ilms and coatings. Boca Raton, Fla.; London; New York; Washington, D.C.: CRC Press. p 1–32. 13. Lafuente AR, Nerin C, and Battle R. 2010. Active parafin-based paper packaging for extending the shelf life of cherry tomatoes. J.Agric.Food Chem. 2010, 58, 6780-6786. 14. Li L, Yunzhi C, Zhengjian Z. 2014. Preparation of the microibrillated cellulose and its application in the food packaging paper. Applied Mechanics and Materials Vol 469 2014 pp 87-90. 15. Liu QX, Xu WC, and Li JL. 2011. Preparation of starch polyacrylamide graft copolymer and its application in paper packaging material. Material Science Forum Vols. 663-665 2011 pp 1268-1272. 16. Mihranyan A, Esmaeili M, Razaq A, Alexeichik D, Lindstrom T. 2012. Inluence of the nanocellulose raw material characteristics on the electrochemical and mechanical properties of conductive paper ISBN : 978-602-17761-4-8 178 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech electrodes. J Mater Sci 2012 47:4463–4472 DOI 10.1007s10853-012-6305-6. 17. Nampak. 2010. ‘Sustainable Packaging, Annual Report 2010’, p. 46, sustainability report. Available from: http:www.nampak.comDynamicDataAnnualReportCurrent Sustainability20report.pdf [Accessed October 2012]. 18. Nassar MA and Youssef AM. 2012. Mechanical and antibacterial properties of recycled carton paper coated by PSAg nanocomposites for packaging. Carbohydrate Polymers 89 2012 269-274. 19. Pichavant FH, Sebe G, Pardon P, and Coma V. 2005. Fat resistance properties of chitosan-based paper packaging for food applications. Carbohydrate Polymers 61 2005 259-265. 20. Quintero RI, Rodriguez F, Bruna J, Guarda A, and Galotto MJ. 2012. Cellulose acetate butyrate nanocomposites with antimicrobial properties for food packaging. Packaging Technology and Science 2012. 21. Sothornvit R and Sampoompuang C. 2012. Rice straw paper incorporated with activated carbon as an ethylene scavenger in a paper-making process. International Journal of Food Science and Technology 2012, 47, 511-517. 22. Taipale T, Osterberg M, Nykanen A, Ruokolainen J, and Laine J. “Effect of Microibrillated Cellulose and Fines on the Drainage of Kraft Pulp Suspension and Paper Strength,” Cellulose 175:1005- 1020 2010. 23. World Packaging Organisation. 2008. Market Statistics and Future Trends in Global Packaging, p. 11. Available from: h ttp:www.worldpackaging.orgpublications documentsmarket- statistics.pdf. [Accessed Februari 2016]. 24. Xiao Y and Huang Y. 2010. Comparison of integrated and split design in structure design of paper package. DOI 978-1-4244-7974-01026.00 2010 IEEE. ISBN : 978-602-17761-4-8 179 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech STUDY OF KINETICS AND THERMODYNAMICS ADSORPTION Cu 2+ ION BY SYNTHETIC ZEOLITE FROM COAL FLY ASH Ahmad Zakaria 1 , Wittri Djasmasari, Henny Rochaeni, Yustinus Purwamargapratala a 2 a AKA Bogor, Bogor 16154, Indonesia a PSTBM-BATAN, Tangerang Selatan, 15314, Indonesia 1 ahmad-zakariakemenperin.go.id 2 pratala_yustinusyahoo.com ABSTRACT The aim of this research was to deine the order of kinetics model and thermodynamic parameters such as free energy, entropy and enthalpy of adsorption process of metal ion Cu2+ by synthetic zeolite from coal ly ash and the effect of the presence of coexisting ion against of the eficiency of Cu 2+ adsorption. Experiment using synthetic zeolite as adsorbent and it was carried out at pH adsorbat, contact time and adsorbent concentration optimum that were obtained in the previous study. Kinetics experiment was performed at various contact time 5, 15, 30, 45, 60, 75 and 90 minutes while the thermodinamyc parameters studies was done at temperature 27, 32, 37 and 42 o C. The inluence of coexisting ion Mn 2+ and Pb 2+ to the adsorption process was examined here. The kinetics data were evaluated using a pseudo irst-order and a pseudo second-order Lagergren equation. The results revealed that the kinetic data correlated well with the pseudo second-order kinetics model. Thermodynamic studies indicated that the adsorption process was spontaneous and accompanied by an increase in entropy and decrease in Gibbs energy. The coexisting ions PbII or MnII decreased the adsorption capacity of synthetic zeolite in the Cu 2+ adsorption, but increased the total adsorption capacity. Keywords : Kinetics model, Synthetic zeolite, Coal ly ash, Coexisting Ions, Gibbs energy Introduction Industrial development in various countries also led to increased industrial pollution signiicantly, Hence the growing problem of industrial waste . This resulted in the treatment of industrial waste treatment into global topics. Heavy metals such as copper are examples of contaminants that have the potential to destroy the system of human physiology and other biological systems when passing tolerance level. Metals such as copper are produced by industrial metal plating, alloy, steel, dyes, electrical wiring, insecticides, pipelines, and paint Sarkar et al., 2010. Therefore the government through Kep-51 MENLH101995 establishing efluent standards for industrial class 1 copper metal content of less than 2 mgL and for the plating industry under 0.6 mgL. The presence of Cu ions in industrial waste is usually accompanied by other heavy metal ions. In the plating industry wastes, heavy metal ions Cu is the ifth largest concentration after metals Fe, and Cr, Sn, and Zn, followed by the metal ions with smaller concentrations, namely Ni, Mn, Pb, Cd, and Ag Venkatiswaran et al., 2007. Some treatment methods for treating heavy metal ions in industrial efluents have been reported in the literature Sarkar et al., 2010, Gupta Bhattacharayya 2008, Fan et al., 2008. Among these methods are neutralization, precipitation, ion exchange, biosorption and adsorption. For low metal ion concentration, the adsorption process is the recommended method for taking the metal ion. The process of adsorption involves intermolecular attractive forces, ion exchange, and chemical bonding. Synthetic zeolite derived from coal ly ash is one of the materials that can be used to adsorb heavy metal ions and has the ability to adsorb heavy metal ions is greater than the ly ash Zakaria et al., 2012. Reaction of synthetic zeolite is similar to the condition of the earth’s crust. The synthesis is done by making the reactants into a gel and then placed in autoclave at temperature range 70 o C-150 o C. Sutarno, 2009. Synthetic zeolite were used for the study came from the coal ly ash of power plant ISBN : 978-602-17761-4-8 180 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Suralaya Zakaria et al., 2011. The aim of this research was to deine the order of kinetics model and thermodynamic parameters such as free energy, entropy and enthalpy of adsorption process of metal ion Cu 2+ by synthetic zeolite from coal ly ash and the effect of the presence of coexisting ion agains of the eficiency of Cu 2+ adsorption. Materials and Methods Materials and Equipment The materials needed consist of test materials and chemicals. Test materials used are synthetic zeolite from coal ly ash, while chemicals used consisting of NaOH, HCl, H 2 SO 4 , CuSO 4 , MnCl 2 ,, PbNO 3 2 , all quality materials from Merck. The tools used in this experiment are: Atomic Absorption Spectrophotometer, Water bath with temperature control, Oven, shaker, sieve size of 40 mesh, pH meter, balance of 0.1 mg accuracy, whatman ilter paper 42, pipette, 50 mL volumetric pipette, funnel, lask 50 mL and 100 mL glass and other tools. Determination of Reaction Kinetics This experiment was performed after optimization experiments has done. The results obtained experimental optimization of adsorbate pH 4 and adsorbent concentration at 50 mg 100 mL The stages of this experiment has been carried out by Zakaria et al, 2012. The experiments were performed by varying the reaction time as the independent variable and the other two as variables remain. A number of 50 mL of adsorbate solution with a concentration of 80 mgL pH optimum is added to the synthetic zeolite optimum weight in 100 mL erlenmeyer glass. Erlenmeyer glass then agitated with a shaker at 150 rpm for a 5, 15, 30, 45, 60, 75, and 90 minutes. Each variation of a certain time, the sample was iltered and the iltrate was measured using the AAS to determine the concentration of Cu II in solution. From these experiments it is known that reaction order information matches the adsorption system by looking at the value of the correlation coeficient on each order of reaction. Determination of Thermodynamic Parameters Thermodynamic parameters are determined by varying the temperature of the experiment, ie 27, 32, 37 and 42 o C and the other variables are constant. This experiment was done by a number of 50 mL of adsorbate solution pH optimum with a concentration of 80 mgL added into 100 mL erlenmeyer glass already containing synthetic zeolite optimum weights and then agitated for the optimum time. After the sample iltered, and then the iltrate was measured using the AAS to determine the concentration of Cu II in solution. Adsorption Experiment for Binary Metal Systems This experiment performed binary adsorption system, in example by adding a number of metal ions Mn or Pb adsorbate in the solution of Cu II. So it is known relationships adsorption capacity of Cu II with the presence of Mn or Pb metal ions in a solution of the system as well as comparison of the strength of the interaction of Mn 2+ and Pb 2+ on the adsorbent. Experiments done by making a solution of adsorbate containing 80 mgL Cu II, the combined concentration of 80 mgL Cu II with 25 mgL Pb II, and the combined concentration of 80 mgL Cu II with 25 mgL Mn II. Then the erlenmeyer shaken during the optimum time, then the sample was iltered and the iltrate was measured using the AAS. ISBN : 978-602-17761-4-8 181 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Calculation The amount of heavy metal adsorbed by adsorben ly ash was calculated using the following equation : ................................ 1 Co is the initial concentration mgL -1 , Ce is the inal concentration in the solution phase equilibrium mgL -1 , Qe is adsorption capacity or the concentration of adsorbate on the adsorbent at equilibrium mgg -1 , m is adsorbent mass and V is volume of adsorbate. Result and Discussion Effect of Contact Time Adsorption kinetics describes the solute retrieval speed by the adsorbent during the adsorption reaction time. This parameter is important because it determines the eficiency of the adsorption process. Effect of contact time on the adsorption capacity can be seen in Figure 1,. In the Figure 1, it can be seen the increasing adsorption capacity of the adsorbent aligned with the contact time and in the 75th minute equilibrium has occurred. The time needed for equilibrium depends once the adsorbate and the adsorbent used and the interaction of both. Gupta and Bhattacharyya 2008 have reported the equilibrium time of 180 minutes for adsorbates of Pb II and Ni II with kaolin adsorbent and montmorilonite. Figure 1. Effect of contact time on the adsorption capacity of Cu 2+ Increased speed of adsorption occurs at the beginning of the contact time, but after almost all sides actively interact with metal ions, the adsorption rate decreases. So there is no signiicant increase in the adsorption capacity as the active adsorbent was saturated, so the adsorption rate is only dependent on the migration of metal ions in the liquid phase to the surface of the complex adsorbent - adsorbate Yu et al., 2000. ISBN : 978-602-17761-4-8 182 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Figure 2. Relationship adsorption capacity versus contact time for 1 st order kinetics T he irst order kinetics equation models and second-order false done by plotting t against log qe-qt versus t and tqt as Lagergren equation Figure 2, so that the known value of the adsorption rate constant k, the optimum adsorption capacity prediction qe and coeficient ditermination. In this experiment used adsorbate concentration of Cu 2+ 80 mg.L -1 . Figure 3. Relationship adsorption capacity versus contact time for 2nd order kinetics. C oeficient ditermination for the pseudo irst-order analysis is smaller than the second-order false. Predictive value of adsorption capacity compared to the experimental value of the optimum adsorption capacity have error reaches -70.5 Table 1. So that the pseudo irst-order kinetics equation is less suitable to be applied as a model for the adsorption kinetics of synthetic zeolite adsorbent. Therefore, continued evaluation using pseudo-second-order equation. Data results of the coficient ditermination R 2 0.99 igure 3 and Table 1, while the validity test error obtained adsorption capacity of synthetic zeolite is 1.91. This suggests that the kinetic parameters of adsorbent satisfy pseudo second-order equation because it has a high degree of accuracy in predicting the optimum adsorption capacity experiments. Table 1 Comparison of irst-order rate constant and the pseudo second-order and predictions and experimental qe values Adsorbent C mg L -1 qe mgg experiment Pseudo second-order kinetics parameters K 1 minutes -1 qe cal error R 2 K 2 gmg mnts qe cal error R 2 Synthetic zeolite from coal ly ash 80 44.2 0.062 13.04 -70.5 0.9369 0.0130 45.04 1.91 0.9998 ISBN : 978-602-17761-4-8 183 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Effect of Temperature Adsorption of copper ions increases with increasing temperature of 300-315 K experiment Figure 4. The increase in the adsorption capacity due to the higher temperatures that occur from activation of the active surface of the adsorbent, increased metal ion kinetic energy, and the formation of smaller metal ions due to the reduction of the effects of hydration, so that it may penetrate the deeper layers of pores Fan et al., 2008 Figure 4. Effect of temperature on the adsorption capacity qe of Cu 2 + by synthetic zeolite at pH 4 Energy enthalpy H synthetic zeolite adsorption-adsorbate concentration of 80 mgL -1 was 62 KJ mol -1 Table 2 are endothermic. Some studies have been reported of them by Fan et al. 2008 for the adsorbent and adsorbate Penicillium simplicissium Cd II, Zn II and Pb II, as well as Barnidele et al. 2010 with the Bulgarian zeolite and adsorbate Cu II. In Table 2, the change in entropy of adsorption energies are all positive values. From these data it can be concluded that an increase in the degree of irregularity in the adsorbent-adsorbate system, so the metal ions adsorbed on the adsorbent are more disordered Kubilay et al., 2007. This phenomenon in the adsorption system is very beneicial because it can increase the stability of the adsorbent-adsorbate complex. Table 2 Thermodynamic parameters of adsorption of Cu 2 + by coal ly ash Adsorbent A d s o r b a t Cu 2+ mg L -1 Temperature o C Thermodynamic parameters G Kj mol -1 H Kj mol -1 S J mol -1 Synthetic zeolite 80 27 32 37 42 -2.200 -3.270 -4.340 -5.410 62 214 Value of the Gibbs free energy of adsorption systems is negative in all experimental temperature conditions see Table 2. This proves the formation of spontaneous adsorption system. The calculation of the free energy at temperature of 27, 32, 37 and 42, the value of which tends to be negative, indicates that the spontaneous adsorption process at higher temperatures. The increase in temperature causes the adsorption process easier due to increased metal ion kinetic energy making it easier for the metal ion adsorbed on the pore deeper layers. ISBN : 978-602-17761-4-8 184 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Figure 5. Plot Van’t Hoff adsorption of Cu 2 + 80 mg L -1 by synthetic zeolite from coal ly ash. Values of thermodynamic parameters of adsorption of Cu 2 + by coal ly ash adsorbent, obtained from the calculation of the slope and intercept of linear equations and Van’t Hoff plot Figure 5. Effect of Co Ions Heavy metal ions Mn and Pb is a metal ion that is often found in industrial efluents with metals Cu. The presence of these ions commonly found in industrial waste plating, iron, and steel. Therefore, please note the effect of co metal ions on the adsorption capacity of Cu II. In this experiment, adsorbate Cu II is made from salt sulfate and applied to a binary system consisting of two types of ions in solution adsorbate, ie metal ions Cu 2 + with Mn 2 + and Cu 2 + and Pb 2 + . Eficiency and adsorption capacity of Cu 2 + ions was inluenced by Mn 2 + and Pb 2 + . The presence of these ions in a solution of copper adsorbate can decrease the eficiency and capacity of the copper adsorption. Table 3. This is due to the competition between the metal ions of Cu, Mn and Pb in getting the site active adsorbent to adsorbent-adsorbate complexes formed. Table 3 Effect of co ions on the adsorption eficiency of Cu 2 + by zeolite synthetic adsorbent Adsorbent Initial concentration mg L -1 Adsorption capacity mg g -1 Adsorption eficiency Cu Pb Mn Cu Pb Mn Total Cu Pb Mn Zeolite synthetic 80 80 80 25 25 25.78 25.40 25.16 - 8.300 - - - 3.081 25.78 33.70 28.24 96.97 95.64 94.56 - 100 - - - 38.06 The presence of Pb or Mn ions with copper ions can simultaneously reduce the adsorption capacity of Cu II by synthetic zeolite adsorbent, but can improve overall adsorption capacity, so the beneit of heavy metal ion adsorption process. This phenomenon is due to a shift in the equilibrium towards the formation of adsorbent-adsorbate complex with increasing concentration of the adsorbate Gufta Bhattacharayya 2008. The mechanism of adsorption of metal ions was also due to the precipitation of metal hydroxides on the surface of the adsorbent Hui et al., 2005. As supporting data, the value of Ksp Mn OH 2 , Pb OH 2 and Cu OH 2 in a row is 4 x 10 -14 , 3 x 10 -16 , and 2 x 10 -19 . So Pb 2 + is faster settles over Mn ions II, thus the Pb ions adsorbed on the adsorbent surface is greater and causes increasing the eficiency of adsorption Zakaria et al., 2014. ISBN : 978-602-17761-4-8 185 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Conclusion Adsorption kinetics is determined as the pseudo second-order . Adsorption reactions tend to be spontaneous and endothermic. The presence of Mn or Pb ions decreases the eficiency of adsorption of Cu 2 + but increase the total capacity of adsorption. Acknowledgement The authors would like to thanks The Director Polytechnic of AKA Bogor. References 1. Fan T, Liu Y, Feng B, Zeng G, Yang C, Zhou M, Zhou H, Tan Z, Wang X. 2008. Biosorption of cadmiumII, zincII, and leadII by penicillium simplicissium: Isoteherm, kinetics and thermodynamics. Journal of Hazardous Materials 160: 655-661 Gupta SS, Bhattacharayya GK. 2008. Immobilization of PbII, CdII, NiII ions on kaolinite and montmorillonite surfaces from aqueos medium. Journal of Enviromental Management 87: 46-58. 2. Gupta SS, Bhattacharayya GK. 2008. Immobilization of PbII, CdII, NiII ions on kaolinite and montmorillonite surfaces from aqueos medium. Journal of Enviromental Management 87: 46-58. 3. Hui KS, Chao CYH, Kot SC. 2005. Removal of mixed heavy metal ions in wastewater by zeolite 4A and residual products from recycled coal ly ash. Journal of Hazardous Materials B 127: 89-101. 4. Kubilay RS, Gurkan A, Savran T, Sahan. 2007. Removal of CuII, ZnII and CoII ions from aqueous solution by adsorption onto natural bentonite. Adsorption. 13:41-51. 5. Mazari Magazine. 2009. Abu terbang batubara sebagai adsorben. terhubung berkala. http: mazarimagazine.com200906 abu-terbang batubara-sebagai adsorben. 15 Februari 2009. 6. [MenLH] Menteri Negara dan Lingkungan Hidup. 1995. Keputusan Menteri Negara dan Lingkungan Hidup No.Kep-51Menlh101995 tentang Baku Mutu Limbah Cair Kegiatan Industri. 7. Sarkar B, Xi Y, Megharaj M, Krishnamurti GSR, Rajarathnam D, Naidu R. 2010. Remediation of hexavalent chromium through adsorption by bentonite based Arquad 2HT-75 organoclays. Journal of Hazardous Materials. 183: 87-97. 8. Sutarno. 2009. Sintesis, karakterisasi, dan aplikasi MCM-41. Di dalam: Aryanto Y, editor. Material canggih; Rekayasa material berbasis sumber daya alam silika-alumina. Kelompok Minat Kimia Material Universitas Gajah Mada. 2009. hlm 83-116. 9. Ventkatiswaran P, Vellaichanny S, Palanivelu K. 2007. Speciation of heavy metals in electroplating industry sludge and wastewater residue using inductively coupled plasma. International Journal Environ Sci. Tech. 44: 497-504. 10. Yu B, Zhang Y, Shukla A, Shukla SS, Dorris KL. 2000. The removal of heavy metal from aqueous solution by sawdust adsorption-removal of copper. Journal of Hazardous Materials B 80: 33-42. 11. Zakaria, Ahmad , Eti Roheti, Irmanida Batu Bara, Sutisna dan Yustinus Purwamargapratala. 2012. Adsorpsi CuII Menggu-nakan Zeolit Sintetis dari Abu Terbang Batu Bara. Prosiding Pertemuan Ilmiah IPTEK BAHAN 2012. PT BIN-BATAN. 12. Zakaria, Ahmad , Eti Roheti, Irmanida Batu Bara, Sutisna dan Yustinus Purwamargapratala. 2011. Karakterisasi Zeolit Sintetis dari Abu terbang Batu Bara dengan Difraksi Sinar –X. Prosiding Seminar Nasional Hamburan Neutron dan sinar X ke-8 . PT BIN-BATAN 13. Zakaria, Ahmad , Eti Roheti, Irmanida Batu Bara, Sutisna dan Wittri Djasmasari. 2014. Study of Kinetics and Thermodynamics as well as The Effect of the Presence of Co Ions in Inluencing adsorption Cu 2+ ion by coal ly ash adsorbent. Proceeding ASEAN COSAT 2014. LIPI Press ISBN : 978-602-17761-4-8 186 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech ISBN : 978-602-17761-4-8 187 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech SYNTHESIS Li 4 Ti 5 O 12 -Sn ANODE MATERIALS AS LITHIUM BATTERY WITH ULTRASONOMETRY Yustinus Purwamargapratala a 1 , Jadigia Ginting a 2 , Mardianto b 3 a PSTBM-BATAN, Tangerang Selatan, 15314, Indonesia b University of Lampung, Lampung, Indonesia 1 pratala_yustinusyahoo.com 2 jadigia.gintingyahoo.com 3 mardianto.isikagmail.com ABSTRACT Synthesis of Li 4 Ti 5 O 12 -Sn Anode Materials As Lithium Battery With Ultrasonometry. The research of synthesis Li 4 Ti 5 O 12 has been realisized using ultrasonic method that was aimed to know the inluence of the addition Sn to the conductivity and the materials structure of lithium titanate. Synthetic materials used were LiOH and TiO 2, while as additives used Sn with percentages of 0, 5, 10, 15 and 20. Lithium hydroxide, titanium dioxide, and Sn were mixed into the media aquabidest and stirred for two hours at a rate of 300 rpm. Then reacted with ultrasonic for two hours, iltered and washed with distilled water and then rinsed with acetone. Drying was carried out over night at room temperature, compacted with hydraulic press at a pressure of 4000 psi and pellets formed were sintered in the furnace at 800 °C for two hours. Characterization was performed using LCR meter to measure the conductivity of the material, X-ray diffraction XRD to determine the crystal structure, optical microscopy to determine the morphology of materials with SEM-EDS and to know the composition of the material. XRD characterization results showed that between ive samples Li 4 Ti 5 O 12 formed , the highest intensity at the angle 2 q : 35,6 o . Li 4 Ti 5 O 12 have solid particles with the conductivity optimum 6.57658 x 10 -6 Scm with Sn addition of 5 . Keywords: Li 4 Ti 5 O 12 , anode, lithium batteries, ultrasonic Introduction Battery is a device that can convert the chemical energy as an active material with its electrical energy known by the electrochemical process in oxidation and reduction changement. The battery consists of three parts, namely the anode, cathode and electrolyte. The anode is deined as the electrode where the oxidation tacking place negative electrode and the cathode is the reduction positive electrode processing. Battery anodes used in lithium batteries are generally composed by graphite. The advantages of graphite which has high capacity and also has real limitations not useful for high discharge rates force to litiation form dendritic anode coating and susceptible to the occurrence of a short circuit in the battery and cause an explosive in terms of the safety. Therefore were formation other materials that have a high enough voltage difference against LiLi and ensuring the formation of the phenomenon litiasion on the electrode surface [1]. One that has been useful is the LTO material developmet with is lithium titanate ceramic material. Li 4 Ti 5 O 12 are ceramic lithium-titanium oxide, better known as lithium titanate having spinel structure in a face-centered cubic in space groups . The main properties of the ceramic material is the ability of the structure not material that change the shape during a Li + ion insertion. Kingo Ariyoshi et al [2], reported in their observation that very precision using synchroton XRD to measure the change in the crystal lattice that are very small, at the 0002 A and 0006 A discharge lattice shrinkage in subsequent discharge process. Lithium titanate is one of the most promizing anode material for lithium batteries despite having a lower speciication capacity of graphite 175 mAhg -1 meanwhile graphite has a capacity of 372 mAhg -1 [3]. Lithium titanate Li 4 Ti 5 O 12 , called LTO in battery industry is a good anode material for applications ISBN : 978-602-17761-4-8 188 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech that have battery power capability and long life cycle. LTO superiority lies in its power density and chemical stability, but the battery LTO-based batteries have a higher voltage: 2.5 V compare to LiCoO 2 [4] and 1.9 V compare to LFP [5]. Lower operating voltage brings signiicant advantages in terms of security. These batteries can also be recharged quickly. Data show that the battery can be safely charged at higher rate of 10 o C, and can be charged in less than 10 minutes. LTO-based batteries also have operating temperature range wider and replenishment eficiencies exceeding 98. Energy density is lower compared to other lithium ion batteries, but still higher than the lead-acid accu and NiCd batteries [6]. In various studies, some addition to simply synthesized with only LiOH and TiO either, many researchers are adding additives into lithium titananat. Various additives were added: chromium Cr [7], silicon Si [8], magnesium Mg [9], graphene [10], aluminum Al [11], and carbon C [12]. This research will be focused the synthesis Li 4 Ti 5 O 12 with variations addition of tin Sn as an additive to ind its effect to increase the conductivity and its material structures. This research is the development of Li 4 Ti 5 O 12 research that has been done before[13]. Use of Sn and ultrasonometri process is expected to produce composite particles LTO-Sn with a homogeneous and increase the conductivity LTO. It is necessary to optimalise of the concentration of Sn added in to composite formation LTO-Sn. Materials and Methods Tools and Materials The tools used in the study is a spatula, micro balance, measuring cups, glass beaker, magnetic stirrer hotplate, ultrasonic, vacuum ilter, compacting, furnace, X-ray diffraction XRD, impedance capasitance resistance LCR meter, optical microscopy and scanning microscope electron - energy dispersive spectrometer SEM-EDS. While the materials used are aquabidest, lithium hydroxide, titanium dioxide, SnO and acetone. Experimental Methods Lithium hydroxide was mixed with 60 mL aquabidest and stirred for 30 minutes with a magnetic stirrer was then added titanium dioxide, stirred for 15 minutes and then added SnO, stirring was continued for 15 minutes. Addition of SnO varied to obtain various samples with Sn concentrations: 0, 5, 10, 15 and 20 that. Samples formed suspension was treated by ultrasonic for 2 hours at a frequency of 50 Hz and then iltered using a vacuum ilter and washed with acetone, powdering results were dried for 15 hours at room temperature. The powder samples was compacted with 4000 psi for 1 minute to form pellets. The ifth sample in the form of pellets sintered in a furnace at a temperature of 800 °C for two hours. Characterization is done by XRD X-ray diffractometer to determine the phase of the sample, the conductivity was measured with LCR meter and the morphological observation with an optical microscope and SEM- EDS Scanning Electron Microscope Energy Dispersive Spectroscopy. Results and Discussion The results of the sample characterization using X-ray diffraction, is shown in Fig. 1. a-e, and analyzed by standard material Li 4 Ti 5 O 12 for diffraction patterns of PCPDFWIN 79-0911. The results of the analysis by X-ray diffraction showed that the samples after ultrasonometri LiOH and TiO 2 and continued with heat process can produce Li 4 Ti 5 O 12 . Ultrasonometry intended to produce a homogeneous particle distribution with a small grain size. It was very helpful in optimizing the calcination process. Fig. 1 shows that the addition of 5 Sn causes diffraction peaks appear at 2 q = 17,36 o which is a characteristic Sn peak. This means that the LTO-Sn composite formation can be done on the addition of 5 Sn. The addition of Sn exceed 10 can result a new phase at 2 q : 18,37 o ; 35,60 o ; 43,27 o ; 62,85 o ; ISBN : 978-602-17761-4-8 189 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech 82,33 o and indicated as SnO. This shows that there is an excess of SnO which can no longer useful interact with Li 4 Ti 5 O 12 . Fig 1. X-ray diffraction pattern of the sample with additives Li 4 Ti 5 O 12 -Sn: a.0 Sn, b.5 Sn, c.10 Sn, d.15 Sn, and e.20 Sn. Observations using optical microscopy showed the morphology of the distribution Sn in the sample. Sn particles in the sample with concentration of 5 Sn seemed to spread more homogeneous than samples with higher concentrations of Sn. This shows that the use of Sn to 5 effective as an additive. This is conirmed by the measurement results of EDS energy dispersive spectrometer in the range of 0-20 keV and counting rate of 2449 cps, as shown in Fig. 2, it appears the Sn peak. Fig. 2. Results of EDS measurements of samples with Sn addition of 5 SEM observation and the results shown in Fig. 3. Distribution Sn Li 4 Ti 5 O 12 sample will affect the value of the ionic conductivity of the sample. More smoothed distribution of Sn on a material, the conductivity increases. This is because the ions will low evenly throughout the surface of the material so that the conductivity of the material become better. Inversely unclear distribution of Sn in the material, then the value of the conductivity of the material will be decreases. This is because the ions will only low through dots or lines formed in some parts of the sample and not entire of the sample traversed by the ions. ISBN : 978-602-17761-4-8 190 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech a b c d e Fig 3. Observation of morphology of samples SEMa 0 Sn b 5 Sn; c 10 Sn; d 15 Sn; e Sn 20 LCR meter measurement results the sample Li 4 Ti 5 O 12 -Sn of Sn 0, 5, 10, 15 and 20 obtained conductivity values as shown in Table 1. Table 1. Values Li 4 Ti 5 O 12 conductivity by percentage Sn No Sn conductivity Sm F range Hz 1. 2.6121 x 10 -5 4000 – 8000 2. 5 6.57658 x 10 -6 2000 – 6000 3. 10 3.31894 x 10 -5 2000 – 6000 4. 15 3.03389 x 10 -6 100 – 500 5. 20 8.41395 x 10 -7 500 - 900 Conductivity value of Li 4 Ti 5 O 12 luctuation or changes indeterminate on each additional Sn. Optimum conductivity value is Li 4 Ti 5 O 12 happened with the addition of Sn by 5 while the value of the lowest conductivity of Li 4 Ti 5 O 12 , is addition of 20 Sn. Value Li 4 Ti 5 O 12 inluenced by the distribution of Sn in the sample. More equitable distribution of Sn in the sample will give higher conductivity value will be higher. Nor vice versa, the uneven distribution of Sn in the sample, then making conductivity become lower as well. This can be observed that looking the distribution of Sn using optical microscopy showed the distribution of samples Li 4 Ti 5 O 12 -Sn good on the addition of 5 Sn. Conclusion We are successfully performed the synthesis and the characterization of Li 4 Ti 5 O 12 -Sn using LiOH, TiO 2 and Sn as additive with ultrasonometry techniques and sintering at a temperature of 800 o C for two hours. XRD characterization results showed that from the ive samples, formation of Li 4 Ti 5 O 12 phase takes place with the highest intensity at 35,60 o . Li 4 Ti 5 O 12 formed are solid particles with optimum conductivity value is 6.57658x10 -6 S.cm -1 with 5 Sn addition. ISBN : 978-602-17761-4-8 191 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Acknowledgement The author would like to thank all those who have helped in this research, in particular to the Head of Advanced Materials Science And Technology. References 1. Subhan, Achmad dan Bambang Prihandoko. “Pembuatan Komposit Anoda Li 4 Ti 5 O 12 dan Soda Lime Silica.” Jurnal Ilmu Pengetahuan Dan Teknologi Telaah Volume 29. Pusat Penelitian Fisika LIPI: Serpong, Tangerang Selatan. 2011. 2. Kingo Ariyoshi, Ryoji Yamato, Tsutomu Ohzuku. “Zero-strain Insertion Mechanism of Li[Li 13 Ti 53 O 4 ] for Advanced Lithium-Ion Shuttlecock Batteries”, Electrochimica Acta 51 2005 1125-1129. 2005. 3. Jin, Yun-Ho, et. al. “Facile Synthesis Of Nano Li 4 Ti 5 O 12 For High Rate Li-Ion Battery Anodes.” A Springer Open Journal Of Nanoscale Research Letters. 2012. 4. Tian, B.B., H. F. Xiang., L. Zhang, Z. Li., H. H. Wang. “Niobium Doped Lithium Titanate As a High Rate Anode Material For Li-Ion Batteries”. Electrochim. Acta 55. 5453-5458. 2010. 5. Yang, S. B., X. L. Feng, K. Mullen. “Graphene-Base Titanium Nanosheets With High Surface Area For Fast Lithium Storage.” Sandwich Like. Adv. Mater 13. 3575-3579. 2011. 6. Priyono, Slamet dan Bambang Prihandoko. “Studi Awal Substitusi TiO 2 Lokal Pada Sintesis Li 4 Ti 5 O 12 Dengan Metode Metalurgi Serbuk.” Prosiding Simposium Nasional Inovasi dan Pembelajaran Sains 2015 SNIPS 2015 Bandung. 2015. 7. Li, Song-Ying, et. al. “Electrochemical Properties Of Citric Acid-Assisted Combustion Synthesis Of Li 4 Ti 5 O 12 Adopting Cr By The Solid-State Reaction Process.” Ionics, DOI 10.1007s11581-014- 1329-3. 2014 8. Chen, Chunhui, Richa Agrawal dan Chunlei Wang. “High Performance Li 4 Ti 5 O 12 Si Composite Anodes For Li-Ion Batteries.” Journal Of Nanomaterials. Department of Mechanical and Materials Engineering, Florida International University, Miami. 2015 9. Shenouda, Atef Y. dan K. R. Murali. “Electrochemical Properties Of Doped Lithium Titanate Compounds And Their Performance in Lithium Rechargeable Batteries.” Journal Of Powder Source 176. 332-339. 2007. 10. Shi, Ying, Wen, Lei dan Hui-Ming Cheng. “Nanosized Li 4 Ti 5 O 12 Graphene Hybrid Material With Low Polarization For High Rate Lithium Ion Batteries.” Journal Of Powder Source 196. 8610-8617. 2011. 11. Lin, Jeng-Yu, et. al. “Sol-Gel Synthesis Of Alumunium Doped Lithium Titanate Anode Material For Lithium Ion Batteries.” Journal Of Electrochemica Acta 87. 126-132. 2013. 12. Li, Baohua, et. al. “Synthesis And Characterization of Long Life Li 4 Ti 5 O 12 C Composite Using Amorphous TiO 2 Nanoparticles.” International Journal Electrochemical Science Vol. 6. 3210-3223. 2011. 13. Purwamargapratala Yustinus dan Jadigia Ginting. “Li 4 Ti 5 O 12 Synthesis As a Battery Anode Materials With Solid State Reaction Method”. Proceeding of 2 nd Nuclear Energy Technology Seminar, Denpasar. 2015. ISBN : 978-602-17761-4-8 192 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech ISBN : 978-602-17761-4-8 193 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech MODIFIED OPERATION OF A LABORATORY REFINER FOR OBTAINING DRIED THERMOMECHANICAL PULP FROM NON- WOOD FIBERS Lilik Tri Mulyantara a b 1 , Roni Maryana b , Vu Thang Do b , Atanu Kumar Das bc , Hiroshi Ohi b2 , Keiichi Nakamata d a Center of Agricultural Engineering Research and Development, Ministry of Agriculture in Indonesia, b University of Tsukuba, 1-1-1 Tennodai, Tsukuba Ibaraki 305-8572, Japan, c Current afiliation: PT. Indah Kiat Pulp Paper Tbk. Perawang Mill, Indonesia d Hokuetsu Kishu Paper Co., Ltd., 3-2-2 Hongoku-cho Nihonbashi, Chuo-ku Tokyo 103-0021, Japan 1 lilik_tmyahoo.com 2 oi.hiroshi.gmu.tsukuba.ac.jp ABSTRACT A process for the production of thermomechanical pulp TMP from non-wood ibrous materials has not been industrialized. On the other hand, there is a requirement for the production of dried TMP from non-wood ibers for the preparation of medium density iberboard MDF board as an alternative to wood and as a possible method of treatment of agricultural wastes. Dried ibers are required to produce high quality MDF board. Sugarcane Saccharum oficinarum bagasse SB and empty fruit bunch EFB of oil palm Elaeis guineensis are non-wood ibrous materials that are easily available in Indonesia, and have the potential to be developed as ibers for use in materials of MDF board. This research is aimed at modifying the operation of a laboratory pressurized TMP reiner to obtain dried ibers from non-wood iber sources for fabricating MDF materials under suitable conditions. An approximate solid content of 80 of oil palm EFB dried ibers were obtained by this modiied method. These ibers then could be fully dried to obtain a solid content of 90. On observing the results from iber fractionation and the length of these dried ibers, it was found that the oil palm EFB dried ibers were comparable to mixed light hardwoods ibers produced in an industrial MDF board process. Keywords: Thermomechanical pulp, oil palm empty fruit bunch, medium density iberboard, iber fractionation, iber length Introduction The pulp yield of approximately 90 obtained in the mechanical reining process is one of the advantages of using empty fruit bunch EFB of oil palm Elaeis guineensis as a raw material in the pulp and paper industry 1 . In the reining process of thermomechanical pulp TMP, individual ibers are separated by mechanical forces and then substantially developed to meet their papermaking properties 2 . Usually, higher temperatures can have a better softening effect on ibers, leading to easier initial iber separation and ibrillation 3 , which leads to better single iber properties 4 . The ideal reining process removes the middle lamella and outer layers from the single iber cell wall to produce ibers and ines with good bonding potential 3 . It is possible to preserve the iber length with softening by increasing the temperature 5 . Reining pressure had a signiicant effect on the mechanical properties of medium density iberboard MDF board. 6, 7 The increment of steam pressure in reining signiicantly improved the mechanical properties of MDF board fabricated from oil palm trunk 8 . In Japan, one of the reining equipment used for TMP is a laboratory pressurized reiner model: BRP45-300SS manufactured by Kumagai Riki Kogyo Co., LTD. Nerima, Tokyo, and it mainly comprises three parts: machine, processing, and outlet. The machine of TMP reiner includes a main electric motor that has a maximum disk rotation of 3000 rpm. The processing part consists of a pressurized hopper material input and heater, a screw conveyor material feeder, a gearbox for the speed reduction ratio, a disk-clearance plate gap adjustment, a belt-pulley for transmission, and a single disk reiner consisting of a rotor and stator of 300 mm diameter with a certain pattern Disk pattern J in this study. The outlet part includes a pulp container blow tank Fig. 1 1, 9, 10 . ISBN : 978-602-17761-4-8 194 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech In this study, the TMP reiner was equipped with a steam boiler model: SU-200 supplied by MIURA Co., LTD. Matsuyama, Ehime that provides a maximum steam pressure of 0.98 MPa. Additionally, the pulp blow tank can be connected to a conical bottom joint, an on-off blow valve, a blowing pipe, and a pulp blow box to fabricate dried ibers for use in the manufacturing of MDF board. The pulp blow box had a length of 72 cm, width of 60 cm, and height of 58 cm with four 60 mesh 250 µm opening stainless steel wire sides. A process that produces TMP from non-wood ibrous materials such as sugarcane Saccharum oficinarum bagasse SB and EFB of oil palm has not been industrialized. On the other hand, there is a requirement for the manufacture of dried TMP from these non-wood ibers for the preparation of MDF board, which can be an alternative to wood, and a possible method of treatment of agricultural wastes. Dried ibers are required to produce high quality MDF board. SB and oil palm EFB are non-wood ibrous materials that are easily available in Indonesia, and have the potential to be developed as ibers for use in MDF board. This research was aimed at modifying the operation of a laboratory pressurized TMP reiner to obtain dried ibers from SB and oil palm EFB for fabricating MDF materials under suitable conditions. Experimental Material Preparation In this study, SB and oil palm EFB were obtained from PT. Madukismo in Yogyakarta, Indonesia and PT. Perkebunan Nusantara VIII in Bogor, West Java, Indonesia, respectively. SB was manually washed twice and dried in direct sunlight. The moisture level after drying was approximately 8–10. The dried SB was cut into 0.5–2.0 cm size pieces using a shredding machine, while the oil palm EFB was cut into 0.5–4.0 cm size pieces by a laboratory disk mill. A chemical 6 g of NaOH: 2 dosage based on materials was added to water and the solution was then mixed with the oil palm EFB. The advantages of using the chemical for oil palm EFB has been explained in a previous study 11 Operating Procedure of TMP Reiner The TMP reiner was kept under pressurized conditions, where the pressure of the steam was adjusted to 0.7 MPa at 165 o C. The disk clearance was set at 0.10 mm, which was recommended in a Fig. 1 Technical drawing of a TMP reiner ISBN : 978-602-17761-4-8 195 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech previous study 1 where the oil palm EFB was reined at 0.10-0.20 mm clearance, and the obtained ibers were characterized by fractionation. After retaining for 20 min in the pressurized hopper, a screw feeder was started and at the same time, the pulp blow valve with a conical bottom joint was immediately opened. Reining, which included the inishing of all materials was completed in 3 min, the screw feeder was then stopped, and the blow valve was closed. The disk temperature was recorded at 1 min intervals. Final Drying of Obtained Pulp Finally, the obtained pulp was dried by blowing a warm air into the pulp blow box from its bottom wire side for 180 min for oil palm EFB and 360 min for SB using a commercial warm-air drier Mitsubishi Electric AD-X80. The low rate and temperature of the drier were approximately 20 Lmin and 60– 65°C, respectively. After separating the pulp into two parts in the pulp blow box, the solid content of pulp was determined. The drying duration was conirmed as the solid content of the pulp in one part had reached 90–92. Evaluation of Pulp Properties The properties of the ibers can be classiied by the fractionation methods using dried ibers and wet ibers 12 . In this study, iber fractionation was done according to the condition of the dried ibers. Three screens with 850, 355, and 180 µm opening 20, 45, and 80 mesh, respectively were used for this method. Ten grams oven-dried weight of reined ibers was charged into the upper screen 850 µm opening with 30 stainless steel balls 12.5 mm diameter to disperse the ibers and to send them smoothly to the subsequent screens during shaking for 2 min. The four fractions were named as “on 850 µm opening”, ‘355–850 µm opening”, “180–355 µm opening”, and “pass 180 µm opening”. The reined ibers of SB and oil palm EFB were compared to the reined ibers of MLH obtained from the industrial process of Hokushin Co., Ltd. Additionally, the three fractions except the longest fraction “on 850 µm opening” dispersed in water, and the iber length and width of each fraction was determined by a Lorentzen–Wettre iber tester CODE 912. Results and Discussion Solid Content of Obtained Pulp The SB and oil palm EFB ibers obtained in the pulp blow box were divided into two parts depending on the difference between average solid contents, and named as irst grade higher solid contents and second grade lower solid contents. The separation should occur as follows: After the pulp blow valve was opened and the pressurized steam blew the reined ibers through the pulp blow pipe to the blow box, the locks of reined ibers hit the stainless steel wall of the pulp blow box, which was on the opposite side of the pulp blow pipe. Then, the locks of ibers that separated from the steam turned toward to the wall at the other side of the pulp blow box to become individually separated ibers, which resulted in suficiently dried ibers. The irst and second grade oil palm EFB ibers had a solid content of 81.4–86.8 and 46.6–53.4, respectively Table 1 . The irst and second grade SB ibers had a solid content of 55.6 and 50.2, respectively. These ibers can be used for MDF board preparation after obtaining a solid content of more than 90. Table 1 Solid content and weight ratios of the irst and second grade ibers No. Materials Liquid to EFB ratio Lkg Solid content Weight 1 st grade 2 nd grade 1 st grade 2 nd grade 1 EFB 0.1 86.8 53.4 70 30 2 EFB 4.0 81.4 49.9 60 40 3 EFB-2 NaOH 4.0 81.9 46.6 73 27 4 SB 0.1 55.6 50.2 67 32 ISBN : 978-602-17761-4-8 196 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Characterization of Fiber Fractionation The results of the fractionation of the dried ibers showed that the ratios of the “355–850 µm opening” fractions for oil palm EFB and SB reined ibers were almost the same as that of MLH ibers Fig. 2. The ratio of the coarse “on 850 µm opening” fraction for oil palm EFB ibers without water was slightly higher than those of other oil palm EFB and SB conditions. The reason for this observation could be that impregnation with water softens the lignin prior to reining 13, 14 . The result of iber fractionation shows that oil palm EFB ibers impregnated with water prior to reining had the lowest ratio of the coarse fraction. Fig. 2 Fractionation of dried ibers Next, the iber length of each classiied fraction was determined by a Lorentzen–Wettre iber tester. Table 2 shows that the iber length of the “355–850 µm opening” fraction for oil palm EFB ibers impregnated with water was longer than those of the oil palm EFB ibers without water and oil palm EFB ibers with alkaline solution 2 NaOH. Additionally, the iber lengths of these fractions of all oil palm EFB ibers were shorter than that of MLH reined ibers. Table 2 Comparison of mean iber length and width of EFB laboratory reined ibers and mill MLH ibers No. Materials Opening 355–850 µm Opening 180–355 µm Opening 180 µm pass Length µm Width µm Length µm Width µm Length µm Width µm 1 EFB-without water 767 31.9 493 28.9 425 29.2 2 EFB-with water 893 30.5 537 26.9 368 26.6 3 EFB-2 NaOH 826 31.5 694 29.5 462 28.2 4 SB-without water 1055 39.0 591 38.8 473 37.0 5 MLH mill ibers 1134 28.6 788 28.5 596 30.8 a Determined using a Lorentzen-Wettre iber tester CODE 912. Conclusions This research is aimed at modifying the operation of a laboratory pressurized TMP reiner to obtain dried ibers from non-wood materials such as SB and oil palm EFB for fabricating MDF materials under suitable conditions. A solid content of approximately 80 of oil palm EFB dried ibers and approximately 55 of SB dried ibers were obtained by this modiied method for the production of MDF materials. These ibers could be fully dried to a solid content of 90–92 for fabricating MDF materials. ฀According to the results from iber fractionation and the measurement of the iber length of ISBN : 978-602-17761-4-8 197 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech these dried ibers, the SB and oil palm EFB dried ibers were comparable to the mixed light hardwoods ibers produced in an industrial MDF board process. Acknowledgements The authors are grateful for the assistance offered by Dr. Hideaki Takahashi, Hokushin Co., Ltd. References 1. Harsono, Mulyantara LT, Rizaluddin AT, Nakagawa-izumi A, Ohi H, Nakamata K 2015 Properties of ibers prepared from oil palm empty fruit bunch for use as corrugating medium and iberboard. Jpn TAPPI J 69: 1349–1359̶̶̶̶ 2. Gorski D, Hill J, Engstrand P, Johansson L 2010 Review: Reduction of energy consumption in TMP reining through mechanical pre-treatment of wood chips. Nord Pulp Paper Res J 25 2:156– 161 3. Li B, Li H, Zha Q, Bandekar R, Alsaggaf A, Ni Y 2011 Review: Effects of wood quality and reining process on TMP pulp and paper quality. Bioresources 6:3569–3584 4. Muhic D 2010 Improved energy eficiency in double disc chip reining, Thesis, Mid Sweden University, SE-851 70 Sundsvall, Sweden 5. Kure KA, Sabourin MJ, Dahlqvist G, Helle T 1999 Adjusting reining by changing reiner plate design and rotational speed-effect on structural ibre properties. J Pulp Pap Sci 26:J346–352 6. Xing C, Deng J, Zhang SY, Riedl B, Cloutier A 2006 Properties of MDF from black spruce tops as affected by thermomechanical reining conditions. Holz Roh Werkst 64:507–512 7. Aisyah HA, Paridah MT, Sahri MH, Astimar AA, Anwar UMK 2012 Inluence of thermomechanical pulping production parameters on properties of medium density iberboard made from kenaf bast. J Appl Sci 12:575-580 8. Ibrahim Z, Aziz AA, Ramli, R, Mokhtar A, Lee SJ 2013 Effect of reining parameters on medium density iberboard MDF properties from oil palm trunk Elaeis guineensis, Open J of Compos Mater 3:127–131 9. Han G, Umemura K, Zhang M, Honda T, Kawai S 2001 Development of high-performance UF- bonded reed and wheat straw medium-density iberboard. J Wood Sci 47:350–355 10. Kamijo Y, Sugino M, Miyanishi T 2015 Fiber morphologies and sheet properties of hardwood thermomechanical pulp. Jpn TAPPI J 69:1125–1133 11. Mulyantara LT, Harsono H, Maryana R, Ohi H 2016 Properties of thermomechanical pulps from sugarcane bagasse and oil palm empty fruit bunch as non-wood materials. Proceedings of 83rd Pulp Pap. Res. Conf. Jpn TAPPI, 22–23 June, Tokyo, pp 119–122 12. Benthien JT, Bahnisch C, Heldner S, Ohlmeyer M 2014 Effect of iber size distribution on medium- density iberboard properties caused by varied steaming time and temperature of deibrillation process, Wood Fiber Sci 46 2:1–11 13. Back EL, Salmen L 1982 Glass transition of woods component hold implications for molding and pulping processes. TAPPI 657:107–110 14. Illikainen M 2008 Mechanism of thermomechanical pulp reining, Thesis, Faculty of Technology, Dept. of Process and Environmental Engineering, University of Oulu, Finland ISBN : 978-602-17761-4-8 198 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech ISBN : 978-602-17761-4-8 199 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech BRIGHTNESS STABILITY OF DISSOLVING PULPS: EFFECT OF THE BLEACHING SEQUENCE Jordan Perrin 1 , Dominique Lachenal, Christine Chirat Grenoble INP-Pagora, 461 Rue de la papeterie, 38402 St Martin d’Hères, France 1 jordan.perringrenoble –inp.org ABSTRACT The factors governing the brightness reversion of dissolving pulps under heat exposure have been investigated. Carbonyl groups CO were intentionally introduced on fully bleached pulp by oxidation. They were clearly responsible for a loss of brightness stability. These groups were partly eliminated by an alkaline extraction stage E, which improved brightness stability. However, an alkaline peroxide stage P was more eficient than E to decrease brightness reversion, but without any additional CO loss. Moreover, an unbleached dissolving pulp was bleached in the laboratory with ECF and TCF ozone based sequences to the same brightness. The CO content was about the same in both cases and at a very low level. The ECF bleached pulp showed substantial lower brightness stability than the TCF pulp. These results suggest that the chemistry of chromophores present in the unbleached pulp also govern brightness stability. In situ detection of phenolic chromophores in bleached dissolving pulp was performed by EPR spectroscopy and UV Raman. Their content depended on the bleaching sequence, which may be related to brightness reversion differences. Keywords: brightness reversion; dissolving pulp; carbonyl groups; UV Raman spectroscopy; EPR spectroscopy; ECF and TCF bleaching Introduction The mechanism of brightness reversion of bleached chemical pulps under heat exposure is still not fully understood. Several factors were claimed to play a key role in brightness reversion. Among them, hexenuronic acid groups HexA [1,2], carbonyl groups [3,4] or residual lignin [5] are the more often cited. However these factors could not explain the origin of some contradictory conclusions on the respective brightness stability of ECF and TCF bleached pulps [6]. It was shown that peroxide treatment is more effective than chlorine dioxide stage to improve the brightness stability of a bleached pulp [7]. The purpose of this study was to try to understand better the ageing of dissolving pulps by combining the analysis of their oxidized functional groups CO and carboxyl COOH groups, EPR spectroscopy and UV Raman spectroscopy measurements, and their behaviour upon heat exposure. Experimental A bleached commercial eucalyptus dissolving pulp 4.5 hemicellulose, DP 690 and its unbleached counterpart kappa number 2.7 were used in this study. The bleached pulp was oxidized by sodium hypochlorite 0.5 and 2 on pulp under acidic conditions pH 4.7 to generate oxidized groups mostly CO [3]. These steps are referenced as H 0.5 and H 2 . E 1 NaOH, 10 consistency, 80°C for 1h and P as E with 0.8 H 2 O 2 added stages were performed on the oxidized pulp. The unbleached pulp was bleached according to DEopDP ECF and ZEoZEoZP TCF sequences. Ozone stages Z were run at high consistency around 38 and pH 2.5. Alkaline extraction stage was reinforced with 2 bars of oxygen Eo. DEopDP was performed at 10 consistency. First chlorine dioxide D stage was carried out at 60°C for 60 min and the second at 75°C for 80 min. Eop and P were run at 80°C for 70 and 60 min respectively. The chemical charges were chosen to reach 89+ inal brightness. Pulp brightness was measured according to the ISO 2470 standard. Ageing of pulp was carried out in an oven for 24h at 105°C. Brightness reversion is expressed by the post color number PCN. Pulp viscosity was measured according to ISO 5351 and the values converted into DPv [8]. After oxidation ISBN : 978-602-17761-4-8 200 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech DPv was also measured after borohydride reduction to prevent cellulose depolymerization during the viscosity measurement reduced DPv. Carbonyl and carboxyl content were determined by CCOA and FDAM measuring uronic groups methods respectively [9,10]. EPR spectroscopy was performed on a Bruker EMX Plus spectrometer equipped with a ER-4102ST Bruker cavity at 9.4GHz at ambient temperature on inely ground pulp. UV Raman was performed on handsheets with Renishaw 1000 UV Raman spectrometer, connected to a Leica DMLM microscope and an Innova 90C FreD frequency- doubled Ar+ ion laser. The excitation wavelength of the laser was 244 nm; power output, 10 mW; and measuring transmittance, 25. The spectra were normalized to cellulose peak at 1094 cm−1. Results and Discussion Impact of Oxidation on Yellowing The oxidation of the commercial bleached eucalyptus dissolving pulp by sodium hypochlorite creates carbonyl and to a lesser extent carboxyl groups on the pulp carbohydrates Table 1. Figure 1 represents the carbonyl content against the molecular mass. Both formation of carbonyl groups and cellulose depolymerization are observed. Post color number PCN values indicate that pulp oxidation causes a decrease in brightness stability. Table 1 Effect of hypochlorite oxidation on stability CO and COOH contents and brightness stability of bleached dissolving pulp Euca TCF H 0.5 H 2 Brightness ISO 89.0 91.2 92.1 PCN 0.18 0.50 1.34 DPv 690 560 230 Reduced DPv nd 620 300 CO µmolg 5.1 16.2 67.6 COOH µmolg 13.6 13.0 22.4 The oxidized pulps were treated with E and P stages. Figure 1 and Table 2 reveal that carbonyl groups are substantially decreased during the alkaline extraction. Conversely uronic carboxyl groups content is not reduced. As expected, a parallel decrease of the PCN and CO content is observed. It is interesting to notice that the PCN is decreased further in P compared to E, whereas the CO and COOH content does not differ signiicantly. Therefore, the beneicial effect of H 2 O 2 on brightness stability would be also due to other factors than carbohydrate CO and COOH content. This effect would be related to the chemistry of H 2 O 2 with some pulp chromophores [11]. This chemistry would be likely the one responsible for the brightness improvement observed during P bleaching. Table 2 Effect of E and P stages on the characteristics of oxidized bleached dissolving pulp 2 hypochlorite H 2 E treated P treated Brightness ISO 92.1 90.9 93.2 PCN 1.34 0.87 0.75 DPv 230 190 170 CO µmolg 67.6 44.4 45.9 COOH µmolg 22.4 25.1 27.9 ISBN : 978-602-17761-4-8 201 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Fig. 1. Effect of E and P stages on Mw and CO distribution of oxidized bleached dissolving pulp 2 hypochlorite Inluence of The Bleaching Sequence on The Brightness Stability of Bleached Dissolving Pulp The unbleached dissolving pulp was bleached in the laboratory with both DEopDP ECF and ZEoZEoZP TCF sequences. Table 3 gives the main properties of these pulps, before and after the inal P stage. Final brightness is the same whether the pulp is bleached with chlorine dioxide- or ozone-based sequences. The cellulose is slightly more depolymerized after the TCF sequence, indicating that the pulp carbohydrates have been slightly more oxidized. However DP is quite acceptable for viscose applications. Unexpectedly, the ECF pulp has lower brightness stability than the TCF pulp. The difference is especially high before the last P stage. The inal peroxide stage reduces the gap, but the TCF pulp remains superior. If carbonyls are considered in parallel, it is shown that here the pulp with the higher content in CO has the better brightness stability, which again indicates that the CO content is not the only factor acting on brightness stability. Table 3 Effect of ECF and TCF bleaching on the characteristics of dissolving pulp before and after the last P stage ZEoZEoZ ZEoZEoZP DEopD DEopDP Brightness ISO 88.5 89.8 88.8 89.6 PCN 0.46 0.3 0.71 0.38 DPv 660 620 770 740 CO µmolg nd 6.5 nd 4.2 nd: not determined Study of The Formation of Phenolic Structures by Alkaline Treatment of Oxidized Cellulose EPR spectroscopy is a very sensitive method to observe organic radicals. Lignin samples generally exhibits an intense band which corresponds to stabilized semiquinone radicals [12]. This band is found also in unbleached pulp and is still visible in fully bleached pulps [13]. These radicals must belong to extended conjugated phenolic structures. Whether or not these structures, when present in kraft pulps, originate from wood lignin is uncertain since the cooking of fully bleached pulp under kraft conditions leads to a more intense EPR signal for the cooked carbohydrates, suggesting that the carbohydrates themselves may form such phenolic structures [13]. After an alkaline extraction applied on an oxidized pulp H 2, see above we observed that the brightness was decreased. During the alkaline extraction, some carbonyl groups disappeared. If β-elimination is the most considered reaction to explain the carbonyl removal, it cannot be responsible for the yellowing of the cellulose. EPR spectroscopy was used for detection of radicals in pulps. Figure 2 shows that an oxidized fully bleached pulp H has a low intensity signal, which might be due to residual phenolic structures. After ISBN : 978-602-17761-4-8 202 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech the alkaline extraction HE, the intensity of the signal is strongly increased, meaning that some stable radicals similar to those observed in lignin are formed. Fig. 2. EPR spectrum of hypochlorite oxidized pulp H before and after alkaline extraction E Fig. 3. Raman spectrum of hypochlorite oxidized pulp H before and after alkaline extraction E UV Raman spectra of these pulp were recorded Figure 3.The curves are normalized taking the 100 cm -1 band cellulose as internal standard The phenol and the conjugated double bonds quinones bands are observed at ~1600 cm -1 and ~1650 cm -1 respectively. Differences between signals are easier to visualize by drawing the difference spectra Δ after – before E between 1400 and 1800 cm -1 . Figure 4. The increase of the peaks at 1605 and 1645cm -1 during the alkaline extraction HE-H conirms the parallel formation of both phenols and quinones in alkaline conditions. These lignin-like structures are formed by degradation of oxidized cellulose. However, during a peroxide stage, neither phenolic structures nor quinones stay in the pulp since the difference in raman spectra is close to zero. This explains the better brightness after P. The formation of phenolic structures and quinones from oxidized cellulose under alkaline conditions is in accordance with previous work by Vikkula and al. [14] who proposed a cyclisation mechanism leading to both phenols and quinones from carboxymethyl cellulose. Fig. 4. Difference in Raman spectrum of hypochlorite oxidized pulp H before and after alkaline extraction E ISBN : 978-602-17761-4-8 203 Proceedings of 2 nd REPTech Crowne Plaza Hotel, Bandung, November 15-17, 2016 © 2016 Published by Center for Pulp and Paper through 2 nd REPTech Study of the occurrence of phenolic and quinone structures in ECF and TCF bleached dissolving pulp The two DEopDP ECF and ZEoZEoZP TCF bleached dissolving pulps were analysed by UV Raman spectroscopy Figure 5 . It is shown that the ECF bleached pulp contains more phenolic structures and quinones than the TCF bleached pulp. The origin of these structures may be either residual lignin or modiied carbohydrates cooked carbohydrates and E treated oxidized carbohydrates are prone to form phenolic structures and quinones as discussed previously. The relative ineficiency of chlorine dioxide to get rid of quinones has already been observed [6]. Moreover quinones are formed when lignin reacts with chlorine dioxide [6]. The presence of quinones in greater quantity in the ECF pulp would be one reason for its lower brightness stability. Fig. 5. UV Raman spectrum of ZEoZEoZP and DEopDP bleached pulps Conclusions 1. Carbonyl groups introduced in fully bleached dissolving pulp by oxidation increase their brightness reversion upon heat exposure. E stage performed after oxidation dramatically decreases the CO content and improves the brightness stability. 2. The addition of hydrogen peroxide in E P stage does not improve the carbonyl removal further. However, it has a positive impact on brightness and brightness stability. 3. Ozone-based TCF sequences give a pulp with better brightness stability than conventional ECF. 4. Brightness reversion would be impacted not only by the oxidation state of the carbohydrates but also by the chemical structure of some residual chromophores, which, according to UV Raman spectroscopy would be more quinonic after ECF bleaching. 5. Some lignin-like structures phenols and quinones are formed from oxidized cellulose during alkaline extraction. At the same time the CO content of cellulose is reduced. These two effects would have an opposite inluence on brightness stability, which may complicate the picture. Adding H 2 O 2 has a positive effect on brightness stability likely because it destroys quinones. Acknowledgements The authors would like to thank Pr Antje Potthast for welcoming one of us at BOKU University to run the CCOA and FDAM experiments, and COST FP1205 for funding this stay, and Pr Tapani Vuorinen for UV Raman analysis. References 1. T. Liitiä and T. Tamminen, in 3rd Int. Conf. Eucalyptus Pulp ICEP, Belo Horizonte, Brazil 2007. 2. V. L. Silva, A. G. Lino, R. A. Ribeiro, J. L. Colodette, A. Forsström, and E. Wackerberg, BioResources

6, 4801 2011. 3. M. Lewin, Macromol. Symp. 118, 715 1997.