Abstract
The motivation of this study was the need to decrease the permeability without compromising the others properties of nanocellulose-starch films. For this, we produced films with untreated cassava starch and hydroxypropylated cassava starch in combination with nanocellulose submitted to four fibrillation levels and compared with the films made with the same starches and cellulose. The films were submitted to physical, morphological, mechanical and thermal tests. All films are low permeability to air regardless of starch type and level of nanocellulose fibrillation. Films produced using nanocellulose with a higher degree of fibrillation absorbed more water, had the higher contact angles for glycerol and lower contact angles for water. The apparent density was not affected by starch type and level of nanocellulose fibrillation, with an average density of 0.98 g m−3. Films produced using more fibrillated nanocellulose had smaller crystallinity. The best mechanical properties were obtained with films made with untreated cassava starch. The greatest increase in the mechanical properties of cassava starch films was 146% for the burst index using nanocellulose N300, and 244% for the tensile index using nanocellulose N540. Thermal stability increased with increasing crystallinity.
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References
Anglès MN, Dufresne A (2000) Plasticized starch/tunicin whiskers nanocomposites. 1. Structural analysis. Macromolecules 33:8344–8353. https://doi.org/10.1021/ma0008701
Aulin C, Gällstedt M, Lindström T (2010) Oxygen and oil barrier properties of microfibrillated cellulose films and coatings. Cellulose 17:559–574. https://doi.org/10.1007/s10570-009-9393-y
Beelam K, Vijay S, Lalit S (2012) Various techniques for the modificartion of starch and the applications of its derivatives. Int Res J Pharm 3(5):25–31
Beitzen-Heineke EF, Balta-Ozkan N, Reefke H (2017) The prospects of zero-packaging grocery stores to improve the social and environmental impacts of the food supply chain. J Clean Prod 140:1528–1541. https://doi.org/10.1016/J.JCLEPRO.2016.09.227
Bhatnagar A, Sain M (2005) Processing of cellulose nanofiber-reinforced composites. J Reinf Plast Compos 24:1259–1268. https://doi.org/10.1177/0731684405049864
Carey FA (2003) Organic chemistry, 5th edn. McGraw-Hill, New York
Charoenkul N, Uttapap D, Pathipanawat W, Takeda Y (2011) Physicochemical characteristics of starches and flours from cassava varieties having different cooked root textures. LWT - Food Sci Technol 44:1774–1781. https://doi.org/10.1016/J.LWT.2011.03.009
Chaudhry Q, Castle L (2011) Food applications of nanotechnologies: an overview of opportunities and challenges for developing countries. Trends Food Sci Tech 22:595–603. https://doi.org/10.1016/J.TIFS.2011.01.001
Chen Q, Liu Y, Chen G (2019) A comparative study on the starch-based biocomposite films reinforced by nanocellulose prepared from different nonwood fibers. Cellulose 26:2425–2435. https://doi.org/10.1007/s10570-019-02254-x
de Souza CO, Silva LT, Silva JR et al (2011) Mango and acerola pulps as antioxidant additives in cassava starch bio-based film. J Agric Food Chem 59:2248–2254. https://doi.org/10.1021/jf1040405
de Souza CO, Silva LT, Druzian JI (2012) Estudo comparativo da caracterização de filmes biodegradáveis de amido de mandioca contendo polpas de manga e de acerola. Quím Nov 35:262–267. https://doi.org/10.1590/S0100-40422012000200006
Delgado-Aguilar M, González I, Pèlach MA, De La Fuente E, Negro C, Mutjé P (2015) Improvement of deinked old newspaper/old magazine pulp suspensions by means of nanofibrillated cellulose addition. Cellulose 22:789–802. https://doi.org/10.1007/s10570-014-0473-2
Dole P, Joly C, Espuche E et al (2004) Gas transport properties of starch based films. Carbohydr Polym 58:335–343. https://doi.org/10.1016/j.carbpol.2004.08.002
Dufresne A, Vignon MR (1998) Improvement of starch film performances using cellulose microfibrils. Macromolecules 31:2693–2696. https://doi.org/10.1021/ma971532b
Dufresne A, Dupeyre D, Vignon MR (2000) Cellulose microfibrils from potato tuber cells: processing and characterization of starch-cellulose microfibril composites. J Appl Polym Sci 76:2080–2092. https://doi.org/10.1002/(SICI)1097-4628(20000628)76:14%3c2080:AID-APP12%3e3.0.CO;2-U
Egharevba HO (2020) Chemical properties of starch and its application in the food industry. In: Emeje M (ed) Chemical properties of starch. IntecOpen, London
Forssell P, Lahtinen R, Lahelin M, Myllärinen P (2002) Oxygen permeability of amylose and amylopectin films. Carbohydr Polym 47:125–129. https://doi.org/10.1016/S0144-8617(01)00175-8
French AD (2014) Idealized powder diffraction patterns for cellulose polymorphs. Cellulose 21:885–896. https://doi.org/10.1007/s10570-013-0030-4
French AD, Santiago Cintrón M (2013) Cellulose polymorphy, crystallite size, and the Segal Crystallinity Index. Cellulose 20:583–588. https://doi.org/10.1007/s10570-012-9833-y
García NL, Ribba L, Dufresne A, Aranguren MI, Goyanes S (2010) Physico-mechanical properties of biodegradable starch nanocomposites. Macromol Mater Eng 294:169–177
González I, Boufi S, Pèlach MA et al (2012) Nanofibrillated cellulose as paper additive in eucalyptus pulps. BioResources 7:5167–5180
Gunaratne A, Hoover R (2002) Effect of heat–moisture treatment on the structure and physicochemical properties of tuber and root starches. Carbohydr Polym 49:425–437. https://doi.org/10.1016/S0144-8617(01)00354-X
Guo W, Tao J, Yang C et al (2012) Introduction of environmentally degradable parameters to evaluate the biodegradability of biodegradable polymers. PLoS ONE 7:e38341. https://doi.org/10.1371/journal.pone.0038341
Habibi Y, Lucia LA, Rojas OJ (2010) Cellulose nanocrystals: chemistry, self-assembly, and applications. Chem Rev 110:3479–3500. https://doi.org/10.1021/cr900339w
Hansen NML, Blomfeldt TOJ, Hedenqvist MS, Plackett DV (2012) Properties of plasticized composite films prepared from nanofibrillated cellulose and birch wood xylan. Cellulose 19:2015–2031. https://doi.org/10.1007/s10570-012-9764-7
He M, Yang G, Cho B-U, Lee YK, Won JM (2017) Effects of addition method and fibrillation degree of cellulose nanofibrils on furnish drainability and paper properties. Cellulose 24:5657–5669. https://doi.org/10.1007/s10570-017-1495-3
Hubbe MA, Ferrer A, Tyagi P, Yin Y, Salas C, Pal L, Rojas OJ (2017) Nanocellulose in thin films coatings and plies for packaging applications: a review. BioResources 12(1):2143–2233
ISO—International Organization for Standardization (2017) ISO/TS 20477:2017 Nanotechnologies—standard terms and their definition for cellulose nanomaterial. Geneva
Iwamoto S, Nakagaito AN, Yano H (2007) Nano-fibrillation of pulp fibers for the processing of transparent nanocomposites. Appl Phys A 89:461–466. https://doi.org/10.1007/s00339-007-4175-6
Julkapli NM, Bagheri S (2016) Developments in nano-additives for paper industry. J Wood Sci 62:117–130
Kaushik A, Kaur R (2016) Thermoplastic starch nanocomposites reinforced with cellulose nanocrystals: effect of plasticizer on properties. Compos Interfaces 23:1–17
Kumar A, Singh SP, Singh AK (2014) Preparation and characterization of cellulose nanofibers from bleached pulp using a mechanical treatment method. Tappi J 13:25–31
Lengowski EC, de Muniz GIB, Nisgoski S, Magalhães WLE (2013) Cellulose acquirement evaluation methods with different degrees of crystallinity. Sci For 41:185–194
Lengowski EC, de Muñiz GIB, de Andrade AS et al (2018) Morphological, physical and thermal characterization of microfibrillated cellulose. Rev Árv. https://doi.org/10.1590/1806-90882018000100013
Lengowski EC, Bonfatti Júnior EA, Kumode MMN et al (2019) Nanocellulose in the paper making. In: Inamuddin, Thomas S, Kumar Mishra R, Asiri A (eds) Sustainable polymer composites and nanocomposites. Springer International Publishing, Cham, pp 1027–1066
Li F, Biagioni P, Bollani M, Maccagnan A, Piergiovanni L (2013) Multi-functional coating of cellulose nanocrystals for flexible packaging applications. Cellulose 20(5):2491–2504. https://doi.org/10.1007/s10570-013-0015-3
Mali S, Grossmann MVE, García Ma et al (2004) Barrier, mechanical and optical properties of plasticized yam starch films. Carbohydr Polym 56:129–135. https://doi.org/10.1016/J.CARBPOL.2004.01.004
Minelli M, Baschetti MG, Doghieri F et al (2010) Investigation of mass transport properties of microfibrillated cellulose (MFC) films. J Membrane Sci 358:67–75. https://doi.org/10.1016/J.MEMSCI.2010.04.030
Missio AL, Mattos BD, de Ferreira DF et al (2018) Nanocellulose-tannin films: from trees to sustainable active packaging. J Clean Prod 184:143–151. https://doi.org/10.1016/J.JCLEPRO.2018.02.205
Mohanty A, Drzal LT, Manjusri M (2003) Nano-reinforcement of bio-based polymers-the hope and reality. Polym Mater Sci Eng 88:60–61
Myllärinen P, Partanen R, Seppälä J, Forssell P (2002) Effect of glycerol on behaviour of amylose and amylopectin films. Carbohydr Polym 50:355–361. https://doi.org/10.1016/S0144-8617(02)00042-5
Oleyaei SA, Zahedi Y, Ghanbarzadeh B, Moayedi AA (2016) Modification of physicochemical and thermal properties of starch films by incorporation of TiO2 nanoparticles. Int J Biol Macromol 86:256–264. https://doi.org/10.1016/j.ijbiomac.2016.04.078
Oliveira VRL, Xavier TDN, Araújo NO, Almeida JGL, Aroucha EMM, Santos FKG, Leite RHL, Silva KNO (2017) Evaluation of biopolimeric films of cassava starch with incorporation of clay modified by ionic exchange and its application as a coating in a fruit. Mater Res 20:758–766
Ottesen V, Syverud K, Gregersen ØW (2016) Mixing of cellulose nanofibrils and individual furnish components: effects on paper properties and structure. Nord Pulp Paper Res J 31:441–447. https://doi.org/10.3183/npprj-2016-31-03-p441-447
Pelissari FM, Ferreira DC, Louzada LB et al (2019) Starch-based edible films and coatings: an eco-friendly alternative for food packaging. Starches Food Appl. https://doi.org/10.1016/B978-0-12-809440-2.00010-1
Plackett D, Anturi H, Hedenqvist M et al (2010) Physical properties and morphology of films prepared from microfibrillated cellulose and microfibrillated cellulose in combination with amylopectin. J Appl Polym Sci. https://doi.org/10.1002/app.32254
Podsiadlo P, Choi S-Y, Shim B et al (2005) Molecularly engineered nanocomposites: layer-by-layer assembly of cellulose nanocrystals. Biomacromol 6(6):2914–2918. https://doi.org/10.1021/BM050333U
Porta R, Sabbah M (2017) Plastic pollution and the challenge of bioplastics. J Appl Biotechnol Bioeng 2:111. https://doi.org/10.15406/jabb.2017.02.00033
Rojas J, Bedoya M, Ciro Y (2015) Current trends in the production of cellulose nanoparticles and nanocomposites for biomedical applications. In: Poletto M, Ornaghi HL Jr (eds) Cellulose—fundamental aspects and current trends. InTech, Rijeka, pp 193–228
Sacui IA, Nieuwendaal RC, Burnett DJ, Stranick SJ, Jorfi M, Weder C, Foster EJ, Olsson RT, Gilman JW (2014) Comparison of the properties of cellulose nanocrystals and cellulose nanofibrils isolated from bacteria, tunicate, and wood processed using acid, enzymatic, mechanical, and oxidative methods. ACS Appl Mater Interfaces 6:6127–6138
Savadekar NR, Mhaske ST (2012) Synthesis of nano cellulose fibers and effect on thermoplastics starch based films. Carbohydr Polym 89:146–151. https://doi.org/10.1016/J.CARBPOL.2012.02.063
Segal L, Creely JJ, Martin AE, Conrad CM (1959) An empirical method for estimating the degree of crystallinity of native cellulose using the X-ray diffractometer. Text Res J 29:786–794. https://doi.org/10.1177/004051755902901003
Sehaqui H, Allais M, Zhou Q, Berglund LA (2011) Wood cellulose biocomposites with fibrous structures at micro- and nanoscale. Compos Sci Technol 71(3):382–387. https://doi.org/10.1016/j.compscitech.2010.12.007
Silva JBA, Pereira FV, Druzian JI (2012) Cassava starch-based films plasticized with sucrose and inverted sugar and reinforced with cellulose nanocrystals. J Food Sci 77:N14–N19. https://doi.org/10.1111/j.1750-3841.2012.02710.x
Singh R, Arora S, Lal K (1996) Thermal and spectral studies on cellulose modified with various cresyldichlorothiophosphates. Thermochim Acta 289:9–21. https://doi.org/10.1016/S0040-6031(96)03057-2
Sorrentino A, Gorrasi G, Vittoria V (2007) Potential perspectives of bio-nanocomposites for food packaging applications. Trends Food Sci Technol 18:84–95. https://doi.org/10.1016/J.TIFS.2006.09.004
Spence KL, Venditti RA, Rojas OJ, Habibi Y, Pawlak JJ (2010) The effect of chemical composition on microfibrillar cellulose films from wood pulps: water interactions and physical properties for packaging applications. Cellulose 17:835–848. https://doi.org/10.1007/s10570-010-9424-8
Stelte W, Sanadi AR (2009) Preparation and characterization of cellulose nanofibers from two commercial hardwood and softwood pulps. Ind Eng Chem Res 48:11211–11219. https://doi.org/10.1021/ie9011672
Sudharsan K, Chandra Mohan C, Azhagu Saravana Babu P et al (2016) Production and characterization of cellulose reinforced starch (CRT) films. Int J Biol Macromol 83:385–395. https://doi.org/10.1016/j.ijbiomac.2015.11.037
Syverud K, Stenius P (2009) Strength and barrier properties of MFC films. Cellulose 16:75–85. https://doi.org/10.1007/s10570-008-9244-2
Taiz L, Zeiger E, Møller IM, Murphy A (2015) Plant physiology and development. Sinauer Associates, Cary
TAPPI—Technical Association of Pulp and Paper Industry (2013a) TAPPI T 402 sp-13: standard conditioning and testing atmospheres for paper, board, pulp handsheets, and related products. Atlanta
TAPPI—Technical Association of Pulp and Paper Industry (2013b) TAPPI T 441 om-13: water absorptiveness of sized (non-bibulous) paper, paperboard, and corrugated fiberboard (cobb test). Atlanta
TAPPI—Technical Association of Pulp and Paper Industry (2013c) TAPPI T 494 om-13:tensile properties of paper and paperboard (using constant rate of elongation apparatus). Atlanta
TAPPI—Technical Association of Pulp and Paper Industry (2015) TAPPI/ANSI T 403 om-15: bursting strength of paper. Atlanta
TAPPI—Technical Association of Pulp and Paper Industry (2016a) TAPPI T 460 om-16: air resistance of paper (gurley method). Atlanta
TAPPI—Technical Association of Pulp and Paper Industry (2016b) TAPPI T 220 sp-16: physical testing of pulp handsheets. Atlanta
van Soest JJG, Vliegenthart JFG (1997) Crystallinity in starch plastics: consequences for material properties. Trends Biotechnol 15:208–213. https://doi.org/10.1016/S0167-7799(97)01021-4
Viana LC, Potulski DC, de Muniz GIB, de Andrade AS, da Silva EL (2018) Nanofibrillated cellulose as an additive for recycled paper. Cerne 24:140–148. https://doi.org/10.1590/01047760201824022518
Vivian MA, SilvaJúnior FG, Fardim P, Segura TES (2017) Evaluation of yield and lignin extraction from Eucalyptus grandis × Eucalyptus urophylla wood chips with the hydrotropic compound sodium xylenesulphonate (SXS). BioResources 12:6723–6735. https://doi.org/10.15376/biores.12.3.6723-6735
Wilhelm H-M, Sierakowski M-R, Souza GP, Wypych F (2003) Starch films reinforced with mineral clay. Carbohydr Polym 52:101–110. https://doi.org/10.1016/S0144-8617(02)00239-4
Wilpiszewska K (2019) Hydrophilic films based on starch and carboxymethyl starch. Pol J Chem Technol 2:26–30
Wu Q, Henriksson M, Liu X, Berglund LA (2007) A high strength nanocomposite based on microcrystalline cellulose and polyurethane. Biomacromol 8:3687–3692. https://doi.org/10.1021/bm701061t
Xu X, Liu F, Jiang L, Zhu JY, Haagenson D, Wiesenborn DP (2013) Cellulose nanocrystals vs. cellulose nanofibrils: a comparative study on their microstructures and effects as polymer reinforcing agents. ACS Appl Mater Interfaces 5:2999–3009
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The authors are thankful to the NANOCELIA (CYTED) network, the Federal University of Paraná and the University of Waterloo for the structure and support. This study was financed in part by Brazil’s Office to Improve University Personnel (CAPES), Finance Code 001, and by the National Council for Scientific and Technological Development (CNPq).
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Lengowski, E.C., Bonfatti Júnior, E.A., Simon, L. et al. Different degree of fibrillation: strategy to reduce permeability in nanocellulose-starch films. Cellulose 27, 10855–10872 (2020). https://doi.org/10.1007/s10570-020-03232-4
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DOI: https://doi.org/10.1007/s10570-020-03232-4