Document Type : Research Paper

Authors

1 Ph.D. Student in wood industry and cellulose products, Wood and Paper Science Department, Faculty of Natural Resources, Sari Agricultural Sciences and Natural Resource University Sari, Iran

2 Assist. Prof., Wood and Paper Science Department, Faculty of Natural Resources, Sari Agricultural Sciences and Natural Resource University Sari, Iran

10.22092/ijwpr.2025.368144.1791

Abstract

Background and objectives: The use of polymers with petroleum derivatives in the packaging industry has caused environmental problems due to their non-biodegradability. Development of active and biodegradable packaging is possible by coating biopolymers on packaging materials. In this research, we tried to use biodegradable materials that are easily decomposed after use in the environment. In this regard, the effect of different treatments with Carboxymethyl chitosan (CMCh), purified Guar gum (PGG) and Nanocrystalline cellulose (NCC) on resistance and barrier properties of paper was evaluated.
Methodology: Carboxymethyl chitosan powder and purified Guar gum were dissolved separately in distilled water along with glycerol (40% by weight of biopolymers) as softener. Then the bio composite solutions were heated on a magnetic stirrer for 120 and 90 minutes until the biopolymers were completely dissolved. At the end, they were kept in a static state for 30 minutes to cool down and remove the air bubbles completely. Also, nanocrystal cellulose suspension (3, 6 and 9% based on the weight of biopolymers) was prepared by dissolving in distilled water by ultrasonic device for 3 minutes and then was added to bio composite solution with mixing ratios (30:70, 50:50 and 70:30) and the final suspension was heated on a magnetic stirrer for 120 minutes and it was completely dissolved. Then, in order to cool down and remove the air bubbles completely, it was put in a static state for 30 minutes. At the end, it was centrifuged and let it stand still for 2 minutes to completely remove the air bubbles. Finally, 25 grams of gel was poured into a polystyrene petri dish with a diameter of 10 cm and the petri dishes were placed in an oven at 50 °C for 24 hours. Also, the morphological tests of Carboxymethyl chitosan and bio Nano composite films and the resistance and barrier characteristics of the treatments were studied.
Results: The results of measuring the resistance characteristics of biopolymer films showed that with the increase of Nanocrystal cellulose up to the level of 6%, the tensile strength of the treatments increased significantly, and the highest amount was related to the films CMCh/PGG/NCC (50/50/6%). Also, with the increase of cellulose Nanocrystals up to the level of 9% due to the accumulation of Nanocrystal particles in one area, the tensile strength of bio nano composites decreased. Also, due to the origin of its crystallinity, cellulose Nanocrystals led to the brittleness and reduced flexibility of the treatments to reduce the Elongation at break of bio nano composite films. The solubility of bio composite films has decreased by adding NCC to the biopolymer matrix due to the establishment of hydrogen interactions between the components of this matrix with nanoparticles at different levels, and the lowest water Solubility is related to the films CMCh/PGG/NCC (50/50/6%). The water vapor permeability of the treatments decreased by adding NCC to the CMCh/PGG matrix due to reasons such as the crystalline structure and the hydrophobic nature of cellulose fibers, the reduction of pores and the reduction of the diffusion coefficient of vapor molecules, and the best impermeability was obtained by films CMCh/PGG/NCC (50/50/6%) because of uniform dispersion of nanoparticles.
Conclusion: According to the results, by adding cellulose Nanocrystals to the composite suspension; Tensile strength, resistance to water solubility and impermeability to water vapor of the films increased and only their Elongation at break decreased and the best resistance and barrier properties of bio nano composites produced in the presence of 6% Nanocrystalline cellulose were obtained.

Highlights

Anvar, H. and sheikhloie, H., 2021. Synthesis and Evaluation of Physicochemical and Antimicrobial Properties of Bionanocomposites Based on Carboxymethylchitosan Biopolymer - Montmorillonite Nanoclay in the Presence of TiO₂ Nanoparticles. Journal of food science and technology, 18(112): 283-297. https://doi.org/ 10.52547/fsct.18.112.283

-Ashori, A.R., Shahreki, A. and Ismaeilimoghadam, S., 2019. Effects of cellulose nanocrystal addition on the properties of poly hydroxy butyrate-co-valerate (PHBV) films. Iranian Journal of Wood and Paper Industries, 10(1): 153-164.  20.1001.1.20089066. 1398.10.1.13.0

    

-Azizi Samir, M.A.S., Alloin, F. and Dufresne, A., 2005. Review of recent research into cellulosic whiskers, their properties and their application in nanocomposite field. Biomacromolecules, 6(2): 612-626. https://doi.org/10.1021/bm0493685

-Chen, L., Du, Y. Tian, Z. and Sun, L., 2005. Effect of the degree of deacetylation and the substitution of carboxymethyl chitosan on its aggregation behavior. Journal of Polymer Science Polymer Physics, 43: 296-305. https://doi.org/10.1002/polb.20212

-Cheng, S., Zhang, Y. Cha, R. Yang, J. and Jiang, X., 2016. Water soluble nanocrystalline cellulose films with highly transparent and oxygen barrier property. Nanoscale, 2: 1-6. https://doi.org/10.1039/c5nr07647a

-Coma, V., Martial-Gros, A. Garreau, S. Copinet, A. Salin, F. and Deschamps, A., 2002. Edible antimicrobial films based on chitosan matrix. Journal of Food Science, 67(3): 1162-1169. https://doi.org/10.1111/j.1365-2621.2002.tb09470.x

-Farag, R.K. and Mohamed, R.R., 2013. Synthesis and Characterization of Carboxymethyl Chitosan Nanogels for Swelling Studies and Antimicrobial Activity.  Molecules, 18(1): 190-203. https://doi.org/10.3390/molecules18010190

-Irimia-Vladu, M., 2014. Green” electronics: biodegradable and biocompatible materials and devices for sustainable future. Chemical Society Reviews, 43(2): 588-610. https://doi.org/10.1039/ c3cs60235d

-Krochta, J.M. and De Mulder-Johnston, C., 1997. Edible and Biodegradable Polymer Films: Challenges and Opportunities. Food Technology Chicago, 51: 61-74.

-Mashak, A., 2014. A Brief Overview on Biodegradable Polymers in Drug Delivery Systems. Polymerization, 4(3): 23-35.

-Missoum, K., Martoïa, F. Belgacem, M.N. and Bras, J., 2013. Effect of chemically modified nanofibrillated cellulose addition on the properties of fiber-based materials. Industrial Crops and Products, 48: 98-105. https://doi.org/10.1016/j.indcrop.2013.04.013

-Muzzarelli, R.A.A., 1988. Carboxymethylated chitins and chitosan’s. Carbohydrate Polymers, 8: 1-21. https://doi.org/10.1016/0144-8617(88)90032-x

-Noushirvani, N., Ghanbarzadeh, B. and Entezami, A.A., 2012. Comparison of Tensile, Permeability and Color Properties of Starch-based Bionanocomposites Containing Two Types of Fillers: Sodium Montmorilonite and Cellulose Nanocrystal. Iranian Journal of Polymer Science and Technology, 24(5): 391-402.

-Oromiahee, A. and Mirlohi, F.S., 2019. Preparation and Evaluation of Physical and Mechanical Properties of Nano Coating of Carboxymethyl Cellulose and Guar Gum and Nanoparticles of Zinc Oxide. Scientific Journal of Packaging science and art, 10(38): 6-17.

-Patale, R.L. and Patravale, V.B., 2011. O, N-carboxymethyl chitosan–zinc complex: A novel chitosan complex with enhanced antimicrobial activity. Carbohydrate Polymers, 85(1): 105-110. https://doi.org/10.1016/j.carbpol.2011.02.001

-Poorna, K.S.V., Singh, A. Rathore, A. and Kumar, A., 2016. Novel cross linked guar gum - g- poly (acrylate) porous superabsorbent hydrogels: Characterization and swelling behavior in different environments. Carbohydrate Polymers, 149: 175-185. https://doi.org/10.1016/j.carbpol.2016.04.077

-Rahmani, S., Mohammadi, Z. Amini, M. Isaei, E. Taheritarigh, S. Rafiee Tehrani, N. and Rafiee Tehrani, M., 2016. Methylated 4-N, N dimethyl aminobenzyl N, O carboxymethyl chitosanas a new chitosan derivative: synthesis, characterization, cytotoxicity, and antibacterial activity. Carbohydrate Polymers, 149: 131-139. https://doi.org/10.1016/ j.carbpol.2016.04.116

-Rezayati-Charani, P., Moradian, M.H. and Saadatnia, M.A., 2018. Sequence analysis using cellulose nanofibers, cationic starch and polyacrylamide in the paper tensile strength. journal of Wood and Forest Science and Technology, 25(3): 73-86.

-Sessini, V., Navarro-Baena, I. Arrieta, M.P. Dominici, F. Lopez, D. Torre, L. Kenny, J.M. Dubois, P. Raquez, J.M. and Peponi, L., 2018. Effect of the addition of polyester-grafted-cellulose nanocrystals on the shape memory properties of biodegradable PLA/PCL nanocomposites. Polymer Degradation and Stability, 152: 126-138. https://doi.org/10.1016/j. polymdegradstab.2018.04.012

-Sodeifi, B., Nazarnezhad, N. and Sharifi, S.H., 2019. Investigation of resistance and optical properties of the papers treated with cellulose nanocrystals and zinc oxide nanoparticles. Iranian Journal of Wood and Paper Industries, 10(3): 407-415.  20.1001.1. 20089066.1398.10.3.8.9

-Sodeifi, B., Sharifi, S.H. and Nazarnezhad, N., 2023. Production and the investigation of cellulose nanocrystals properties obtained from cotton linter and their use as a reinforcing agent in polycaprolactone nanocomposite films. Iranian Journal of Wood and Paper Science Research, 38(3): 225-236. https://doi.org/10.22092/ijwpr.2023.360 955.1741

-Sodeifi, B., Sharifi, S.H. and Zabih zadeh, S.M., 2024. Investigating the resistance and optical properties of papers coated with Bio nanocomposite carboxymethyl chitosan/guar gum/nanocrystalline cellulose. Iranian Journal of Wood and Paper Industries, 15(2): 137-151.  10.22034/ijwp.2024. 2022214.1647

-Sorrentino, A., Gorrasi, G. and Vittoria, V., 2007. Potential perspectives of bio-nanocomposites for food packaging applications. Trends in Food Science and Technology, 18: 84-95. https://doi.org/10.1016/ j.tifs.2006.09.004

-Suriyatem, R., Auras, R.A. and Rachtanapun, P., 2018. Improvement of mechanical properties and thermal stability of biodegradable rice starch-based films blended with carboxymethyl chitosan. Industrial Crops and Products, 122: 37-48. https://doi.org/ 10.1016/j.indcrop.2018.05.047

-Tatari, A.A. and Shekarian, A., 2014. The Importance of Cellulose Derivatives in the Production of Biodegradable Films for Food Packaging. Journal of Applied Science and Technology, 5(19): 22-31.

-Thanakkasaranee, S., Jantanasakulwong, K. Phimolsiripol, Y. Leksawasdi, N. Seesuriyachan, P. Chaiyaso, T. Jantrawut, P. Ruksiriwanich, W. Rose Sommano, S. Punyodom, W. Reungsang, A. Ngo, T.M.P. Thipchai, P. Tongdeesoontorn, W. and Rachtanapun, P., 2021. High Substitution Synthesis of Carboxymethyl Chitosan for Properties Improvement of Carboxymethyl Chitosan Films Depending on Particle Sizes. Molecules, 26(19): 1-16. https://doi.org/10.3390/molecules26196013

-Vaezi, Kh. and Asadpour, Gh., 2022. Effects of HCl Hydrolyzed Cellulose Nanocrystals from Waste Papers on the Hydroxypropyl Methylcellulose/ Cationic Starch Biofilms. Waste and Biomass Valorization, 13(4): 2035-2051. https://doi.org/ 10.1007/s12649-021-01651-3

-Xu, Q., Gao, Y. Qin, M. Wu, K. Fu, Y. and Zhao, J., 2013. Nanocrystalline cellulose from aspen kraft pulp and its application in deinked pulp. International Journal of Biological Macromolecules, 60: 241-247. https://doi.org/10.1016/j.ijbiomac.2013.05.038

 

 

 

 

 

Keywords

Main Subjects

Anvar, H. and sheikhloie, H., 2021. Synthesis and Evaluation of Physicochemical and Antimicrobial Properties of Bionanocomposites Based on Carboxymethylchitosan Biopolymer - Montmorillonite Nanoclay in the Presence of TiO₂ Nanoparticles. Journal of food science and technology, 18(112): 283-297. https://doi.org/ 10.52547/fsct.18.112.283
-Ashori, A.R., Shahreki, A. and Ismaeilimoghadam, S., 2019. Effects of cellulose nanocrystal addition on the properties of poly hydroxy butyrate-co-valerate (PHBV) films. Iranian Journal of Wood and Paper Industries, 10(1): 153-164.  20.1001.1.20089066. 1398.10.1.13.0
    
-Azizi Samir, M.A.S., Alloin, F. and Dufresne, A., 2005. Review of recent research into cellulosic whiskers, their properties and their application in nanocomposite field. Biomacromolecules, 6(2): 612-626. https://doi.org/10.1021/bm0493685
-Chen, L., Du, Y. Tian, Z. and Sun, L., 2005. Effect of the degree of deacetylation and the substitution of carboxymethyl chitosan on its aggregation behavior. Journal of Polymer Science Polymer Physics, 43: 296-305. https://doi.org/10.1002/polb.20212
-Cheng, S., Zhang, Y. Cha, R. Yang, J. and Jiang, X., 2016. Water soluble nanocrystalline cellulose films with highly transparent and oxygen barrier property. Nanoscale, 2: 1-6. https://doi.org/10.1039/c5nr07647a
-Coma, V., Martial-Gros, A. Garreau, S. Copinet, A. Salin, F. and Deschamps, A., 2002. Edible antimicrobial films based on chitosan matrix. Journal of Food Science, 67(3): 1162-1169. https://doi.org/10.1111/j.1365-2621.2002.tb09470.x
-Farag, R.K. and Mohamed, R.R., 2013. Synthesis and Characterization of Carboxymethyl Chitosan Nanogels for Swelling Studies and Antimicrobial Activity.  Molecules, 18(1): 190-203. https://doi.org/10.3390/molecules18010190
-Irimia-Vladu, M., 2014. Green” electronics: biodegradable and biocompatible materials and devices for sustainable future. Chemical Society Reviews, 43(2): 588-610. https://doi.org/10.1039/ c3cs60235d
-Krochta, J.M. and De Mulder-Johnston, C., 1997. Edible and Biodegradable Polymer Films: Challenges and Opportunities. Food Technology Chicago, 51: 61-74.
-Mashak, A., 2014. A Brief Overview on Biodegradable Polymers in Drug Delivery Systems. Polymerization, 4(3): 23-35.
-Missoum, K., Martoïa, F. Belgacem, M.N. and Bras, J., 2013. Effect of chemically modified nanofibrillated cellulose addition on the properties of fiber-based materials. Industrial Crops and Products, 48: 98-105. https://doi.org/10.1016/j.indcrop.2013.04.013
-Muzzarelli, R.A.A., 1988. Carboxymethylated chitins and chitosan’s. Carbohydrate Polymers, 8: 1-21. https://doi.org/10.1016/0144-8617(88)90032-x
-Noushirvani, N., Ghanbarzadeh, B. and Entezami, A.A., 2012. Comparison of Tensile, Permeability and Color Properties of Starch-based Bionanocomposites Containing Two Types of Fillers: Sodium Montmorilonite and Cellulose Nanocrystal. Iranian Journal of Polymer Science and Technology, 24(5): 391-402.
-Oromiahee, A. and Mirlohi, F.S., 2019. Preparation and Evaluation of Physical and Mechanical Properties of Nano Coating of Carboxymethyl Cellulose and Guar Gum and Nanoparticles of Zinc Oxide. Scientific Journal of Packaging science and art, 10(38): 6-17.
-Patale, R.L. and Patravale, V.B., 2011. O, N-carboxymethyl chitosan–zinc complex: A novel chitosan complex with enhanced antimicrobial activity. Carbohydrate Polymers, 85(1): 105-110. https://doi.org/10.1016/j.carbpol.2011.02.001
-Poorna, K.S.V., Singh, A. Rathore, A. and Kumar, A., 2016. Novel cross linked guar gum - g- poly (acrylate) porous superabsorbent hydrogels: Characterization and swelling behavior in different environments. Carbohydrate Polymers, 149: 175-185. https://doi.org/10.1016/j.carbpol.2016.04.077
-Rahmani, S., Mohammadi, Z. Amini, M. Isaei, E. Taheritarigh, S. Rafiee Tehrani, N. and Rafiee Tehrani, M., 2016. Methylated 4-N, N dimethyl aminobenzyl N, O carboxymethyl chitosanas a new chitosan derivative: synthesis, characterization, cytotoxicity, and antibacterial activity. Carbohydrate Polymers, 149: 131-139. https://doi.org/10.1016/ j.carbpol.2016.04.116
-Rezayati-Charani, P., Moradian, M.H. and Saadatnia, M.A., 2018. Sequence analysis using cellulose nanofibers, cationic starch and polyacrylamide in the paper tensile strength. journal of Wood and Forest Science and Technology, 25(3): 73-86.
-Sessini, V., Navarro-Baena, I. Arrieta, M.P. Dominici, F. Lopez, D. Torre, L. Kenny, J.M. Dubois, P. Raquez, J.M. and Peponi, L., 2018. Effect of the addition of polyester-grafted-cellulose nanocrystals on the shape memory properties of biodegradable PLA/PCL nanocomposites. Polymer Degradation and Stability, 152: 126-138. https://doi.org/10.1016/j. polymdegradstab.2018.04.012
-Sodeifi, B., Nazarnezhad, N. and Sharifi, S.H., 2019. Investigation of resistance and optical properties of the papers treated with cellulose nanocrystals and zinc oxide nanoparticles. Iranian Journal of Wood and Paper Industries, 10(3): 407-415.  20.1001.1. 20089066.1398.10.3.8.9
-Sodeifi, B., Sharifi, S.H. and Nazarnezhad, N., 2023. Production and the investigation of cellulose nanocrystals properties obtained from cotton linter and their use as a reinforcing agent in polycaprolactone nanocomposite films. Iranian Journal of Wood and Paper Science Research, 38(3): 225-236. https://doi.org/10.22092/ijwpr.2023.360 955.1741
-Sodeifi, B., Sharifi, S.H. and Zabih zadeh, S.M., 2024. Investigating the resistance and optical properties of papers coated with Bio nanocomposite carboxymethyl chitosan/guar gum/nanocrystalline cellulose. Iranian Journal of Wood and Paper Industries, 15(2): 137-151.  10.22034/ijwp.2024. 2022214.1647
-Sorrentino, A., Gorrasi, G. and Vittoria, V., 2007. Potential perspectives of bio-nanocomposites for food packaging applications. Trends in Food Science and Technology, 18: 84-95. https://doi.org/10.1016/ j.tifs.2006.09.004
-Suriyatem, R., Auras, R.A. and Rachtanapun, P., 2018. Improvement of mechanical properties and thermal stability of biodegradable rice starch-based films blended with carboxymethyl chitosan. Industrial Crops and Products, 122: 37-48. https://doi.org/ 10.1016/j.indcrop.2018.05.047
-Tatari, A.A. and Shekarian, A., 2014. The Importance of Cellulose Derivatives in the Production of Biodegradable Films for Food Packaging. Journal of Applied Science and Technology, 5(19): 22-31.
-Thanakkasaranee, S., Jantanasakulwong, K. Phimolsiripol, Y. Leksawasdi, N. Seesuriyachan, P. Chaiyaso, T. Jantrawut, P. Ruksiriwanich, W. Rose Sommano, S. Punyodom, W. Reungsang, A. Ngo, T.M.P. Thipchai, P. Tongdeesoontorn, W. and Rachtanapun, P., 2021. High Substitution Synthesis of Carboxymethyl Chitosan for Properties Improvement of Carboxymethyl Chitosan Films Depending on Particle Sizes. Molecules, 26(19): 1-16. https://doi.org/10.3390/molecules26196013
-Vaezi, Kh. and Asadpour, Gh., 2022. Effects of HCl Hydrolyzed Cellulose Nanocrystals from Waste Papers on the Hydroxypropyl Methylcellulose/ Cationic Starch Biofilms. Waste and Biomass Valorization, 13(4): 2035-2051. https://doi.org/ 10.1007/s12649-021-01651-3
-Xu, Q., Gao, Y. Qin, M. Wu, K. Fu, Y. and Zhao, J., 2013. Nanocrystalline cellulose from aspen kraft pulp and its application in deinked pulp. International Journal of Biological Macromolecules, 60: 241-247. https://doi.org/10.1016/j.ijbiomac.2013.05.038