Abstract
Micro Fibrillated Cellulose (MFC) has gained interest both in academia and industry, but some critical issues must be overcome to exploit the industrial MFC/biocomposites uses. In particular, the first drawback is related to the MFC agglomeration during the primary processing. Encouraging results have been obtained using plasticizers, as dispersing aids, during the extrusion that optimizes the process parameters based on the variation of the melt viscosity. However, even if the plasticizer addition counterbalances the excessive biocomposite stiffness, caused by the addition of the MFC, its eventual migration from the finished product needs to be evaluated to avoid toughness reductions as well as environmental and health issues. In this work, the MFC role in controlling the plasticizer migration was evaluated by analytical modeling based on Fick’s second law. The diffusion coefficient, D, over time was evaluated and correlated with the change in mechanical and thermal properties of cast extruded biocomposites. Mechanical and thermal data, analyzed over a 50-day time span, confirmed the expected benefits. The results obtained proved how the approach adopted in this study can be a valuable industrial manufacturing approach.
Similar content being viewed by others
Data availability
The data supporting this study are available when reasonably requested from the corresponding author.
References
Aliotta L, Cinelli P, Coltelli MB, Lazzeri A (2019) Rigid filler toughening in PLA-Calcium carbonate composites: effect of particle surface treatment and matrix plasticization. Eur Polym J 113:78–88. https://doi.org/10.1016/j.eurpolymj.2018.12.042
Aliotta L, Vannozzi A, Panariello L et al (2020) Sustainable micro and nano additives for controlling the migration of a biobased plasticizer from pla-based flexible films. Polymers 12:1366. https://doi.org/10.3390/polym12061366
Aliotta L, Canesi I, Lazzeri A (2021) Study on the preferential distribution of acetyl tributyl citrate in poly(lactic) acid-poly(butylene adipate-co-terephthalate) blends. Polym Test 98:1–14. https://doi.org/10.1016/j.polymertesting.2021.107163
Aliotta L, Vannozzi A, Cinelli P et al (2022) Wheat bran addition as potential alternative to control the plasticizer migration into PLA/PBSA blends. J Mater Sci 57:14511–14527. https://doi.org/10.1007/s10853-022-07534-9
Araki J, Wada M, Kuga S (2001) Steric stabilization of a cellulose microcrystal suspension by poly(ethylene glycol) grafting. Langmuir 17:21–27. https://doi.org/10.1021/la001070m
Argon AS, Cohen RE (2003) Toughenability of polymers. Polymer 44:6013–6032. https://doi.org/10.1016/S0032-3861(03)00546-9
Arvanitoyannis IS, Bosnea L (2004) Migration of substances from food packaging materials to foods. Crit Rev Food Sci Nutr 44:63–76. https://doi.org/10.1080/10408690490424621
Aversa C, Barletta M, Puopolo M, Vesco S (2020) Cast extrusion of low gas permeability bioplastic sheets in PLA/PBS and PLA/PHB binary blends. Polym Plast Technol Mater 59:231–240. https://doi.org/10.1080/25740881.2019.1625396
Azouz KB, Ramires EC, van den Fonteyne W et al (2012) Simple method for the melt extrusion of a cellulose nanocrystal reinforced hydrophobic polymer. ACS Macro Lett 1:236–240. https://doi.org/10.1021/mz2001737
Botta L, la Mantia FP, Mistretta MC et al (2021) Structure-property relationships in bionanocomposites for pipe extrusion applications. Polymers 13:782. https://doi.org/10.3390/polym13050782
Chanda S, Bajwa DS (2021) A review of current physical techniques for dispersion of cellulose nanomaterials in polymer matrices. Rev Adv Mater Sci 60:325–341. https://doi.org/10.1515/rams-2021-0023
Clemons C, Sabo R (2021) A review of wet compounding of cellulose nanocomposites. Polymers 13:911. https://doi.org/10.3390/polym13060911
Crank J (1975) The mathematics of diffusion, second. Oxford University Press, England
Drumright RE, Gruber PR, Henton DE (2000) Polylactic acid technology. Adv Mater 12:1841–1846. https://doi.org/10.1002/1521-4095(200012)12:23%3c1841::AID-ADMA1841%3e3.0.CO;2-E
Dufresne A (2017) Cellulose nanomaterial reinforced polymer nanocomposites. Curr Opin Colloid Interface Sci 29:1–8. https://doi.org/10.1016/j.cocis.2017.01.004
Fischer EW, Sterzel HJ, Wegner G (1973) Investigation of the structure of solution grown crystals of lactide copolymers by means of chemical reactions. Kolloid-Zeitschrift Zeitschrift Für Polymere 251:980–990. https://doi.org/10.1007/BF01498927
Gigante V, Coltelli M-B, Vannozzi A et al (2019) Flat die extruded biocompatible poly(lactic acid) (PLA)/poly(butylene succinate) (PBS) based films. Polymers 11:1857. https://doi.org/10.3390/polym11111857
Gigante V, Aliotta L, Coltelli MB et al (2020) Fracture behavior and mechanical, thermal, and rheological properties of biodegradable films extruded by flat die and calender. J Polym Sci 58:3264–3282. https://doi.org/10.1002/pol.20200555
Greco A, Ferrari F (2021) Thermal behavior of PLA plasticized by commercial and cardanol-derived plasticizers and the effect on the mechanical properties. J Therm Anal Calorim 146:131–141. https://doi.org/10.1007/s10973-020-10403-9
Gurunathan T, Mohanty S, Nayak SK (2015) A review of the recent developments in biocomposites based on natural fibres and their application perspectives. Compos A Appl Sci Manuf 77:1–25. https://doi.org/10.1016/j.compositesa.2015.06.007
Hahladakis JN, Velis CA, Weber R et al (2018) An overview of chemical additives present in plastics: migration, release, fate and environmental impact during their use, disposal and recycling. J Hazard Mater 344:179–199. https://doi.org/10.1016/j.jhazmat.2017.10.014
Higa CM, Tek AT, Wojtecki RJ, Braslau R (2018) Nonmigratory internal plasticization of poly(vinyl chloride) via pendant triazoles bearing alkyl or polyether esters. J Polym Sci A Polym Chem 56:2397–2411. https://doi.org/10.1002/pola.29205
Jamal EFA, Hashim MY, Othman MH et al (2018) Optimization of Alkali treatment condition on tensile properties of kenaf reinforced polyester composite using response surface method. Int J Integr Eng 10:40–46. https://doi.org/10.30880/IJIE.2018.10.01.007
Jamarani R, Erythropel H, Nicell J et al (2018) How green is your plasticizer? Polymers 10:834. https://doi.org/10.3390/polym10080834
Johansen MR, Christensen TB, Ramos TM, Syberg K (2022) A review of the plastic value chain from a circular economy perspective. J Environ Manag 302:113975. https://doi.org/10.1016/j.jenvman.2021.113975
Jonoobi M, Harun J, Mathew AP, Oksman K (2010) Mechanical properties of cellulose nanofiber (CNF) reinforced polylactic acid (PLA) prepared by twin screw extrusion. Compos Sci Technol 70:1742–1747. https://doi.org/10.1016/j.compscitech.2010.07.005
Kalia S, Dufresne A, Cherian BM et al (2011) Cellulose-based bio- and nanocomposites: a review. Int J Polym Sci 2011:1–35. https://doi.org/10.1155/2011/837875
Kloser E, Gray DG (2010) Surface grafting of cellulose nanocrystals with poly(ethylene oxide) in aqueous media. Langmuir 26:13450–13456. https://doi.org/10.1021/la101795s
Lamm ME, Li K, Qian J et al (2021) Recent advances in functional materials through cellulose nanofiber templating. Adv Mater 33:2005538. https://doi.org/10.1002/adma.202005538
Li X, Xiao Y, Wang B et al (2012) Effects of poly(1,2-propylene glycol adipate) and nano-CaCO3 on DOP migration and mechanical properties of flexible PVC. J Appl Polym Sci 124:1737–1743. https://doi.org/10.1002/app.35183
Li D, Jiang Y, Lv S et al (2018) Preparation of plasticized poly (lactic acid) and its influence on the properties of composite materials. PLoS ONE 13:e0193520. https://doi.org/10.1371/journal.pone.0193520
Li Z, Reimer C, Wang T et al (2020) Thermal and mechanical properties of the biocomposites of Miscanthus biocarbon and poly(3-hydroxybutyrate-co-3-hydroxyvalerate) (PHBV). Polymers 12:1300. https://doi.org/10.3390/polym12061300
Li K, Mcgrady D, Zhao X et al (2021) Surface-modified and oven-dried microfibrillated cellulose reinforced biocomposites: Cellulose network enabled high performance. Carbohydr Polym 256:117525. https://doi.org/10.1016/j.carbpol.2020.117525
Lundsgaard R (2010) Migration of plasticisers from PVC and other polymers. PHD Thesis-Technical University of Denmark
Ma Y, Liao S, Li Q et al (2020) Physical and chemical modifications of poly(vinyl chloride) materials to prevent plasticizer migration-Still on the run. React Funct Polym 147:104458. https://doi.org/10.1016/j.reactfunctpolym.2019.104458
Marais A, Kochumalayil JJ, Nilsson C et al (2012) Toward an alternative compatibilizer for PLA/cellulose composites: grafting of xyloglucan with PLA. Carbohydr Polym 89:1038–1043. https://doi.org/10.1016/j.carbpol.2012.03.051
Marra A, Silvestre C, Duraccio D, Cimmino S (2016) Polylactic acid/zinc oxide biocomposite films for food packaging application. Int J Biol Macromol 88:254–262. https://doi.org/10.1016/j.ijbiomac.2016.03.039
Mekonnen T, Mussone P, Khalil H, Bressler D (2013) Progress in bio-based plastics and plasticizing modifications. J Mater Chem A Mater 1:13379. https://doi.org/10.1039/c3ta12555f
Mercer A, Castle L, Comyn J, Gilbert J (1990) Evaluation of a predictive mathematical model of di-(2-ethylhexyl) adipate plasticizer migration from PVC film into foods. Food Addit Contam 7:497–507. https://doi.org/10.1080/02652039009373911
Mistretta MC, Botta L, Arrigo R et al (2021) Bionanocomposite blown films: insights on the rheological and mechanical behavior. Polymers 13(7):1167. https://doi.org/10.3390/polym13071167
Molinari G, Gigante V, Fiori S et al (2021) Dispersion of micro fibrillated cellulose (MFC) in poly(lactic acid) (PLA) from lab-scale to semi-industrial processing using biobased plasticizers as dispersing aids. Chemistry 3:896–915. https://doi.org/10.3390/chemistry3030066
Müller K, Fürtauer S, Schmid M, Zollfrank C (2022) Cellulose blends from gel extrusion and compounding with polylactic acid. J Appl Polym Sci 139:1–15. https://doi.org/10.1002/app.52794
Pole SS, Isayev AI (2021) Correlations in rheological behavior between large amplitude oscillatory shear and steady shear flow of silica-filled star-shaped styrene-butadiene rubber compounds: experiment and simulation. J Appl Polym Sci 138:1–28. https://doi.org/10.1002/app.50660
Qian S, Sheng K (2017) PLA toughened by bamboo cellulose nanowhiskers: role of silane compatibilization on the PLA bionanocomposite properties. Compos Sci Technol 148:59–69. https://doi.org/10.1016/j.compscitech.2017.05.020
Qian S, Zhang H, Yao W, Sheng K (2018) Effects of bamboo cellulose nanowhisker content on the morphology, crystallization, mechanical, and thermal properties of PLA matrix biocomposites. Compos B Eng 133:203–209. https://doi.org/10.1016/j.compositesb.2017.09.040
Rana AK, Frollini E, Thakur VK (2021) Cellulose nanocrystals: pretreatments, preparation strategies, and surface functionalization. Int J Biol Macromol 182:1554–1581. https://doi.org/10.1016/j.ijbiomac.2021.05.119
Raquez JM, Habibi Y, Murariu M, Dubois P (2013) Polylactide (PLA)-based nanocomposites. Prog Polym Sci 38:1504–1542. https://doi.org/10.1016/j.progpolymsci.2013.05.014
Reddy NN, Mohan YM, Varaprasad K et al (2010) Surface treatment of plasticized poly(vinyl chloride) to prevent plasticizer migration. J Appl Polym Sci 115:1589–1597. https://doi.org/10.1002/app.31157
Righetti MC, Aliotta L, Mallegni N et al (2019) Constrained amorphous interphase and mechanical properties of poly(3-hydroxybutyrate-co-3-hydroxyvalerate). Front Chem 7:1–16. https://doi.org/10.3389/fchem.2019.00790
Ruiz MB, Pérez-Camargo RA, López Jv et al (2021) Accelerating the crystallization kinetics of linear polylactides by adding cyclic poly (-lactide): nucleation, plasticization and topological effects. Int J Biol Macromol 186:255–267. https://doi.org/10.1016/j.ijbiomac.2021.07.028
Scaffaro R, Maio A, Gulino EF et al (2020) The effects of nanoclay on the mechanical properties, Carvacrol release and degradation of a PLA/PBAT blend. Materials 13:983. https://doi.org/10.3390/ma13040983
Sergi C, Sbardella F, Lilli M et al (2020) Hybrid cellulose-basalt polypropylene composites with enhanced compatibility: the role of coupling agent. Molecules 25:4384. https://doi.org/10.3390/molecules25194384
Shazleen SS, Yasim-Anuar TAT, Ibrahim NA et al (2021) Functionality of cellulose nanofiber as bio-based nucleating agent and nano-reinforcement material to enhance crystallization and mechanical properties of polylactic acid nanocomposite. Polymers 13:1–19. https://doi.org/10.3390/polym13030389
Sheldon RA, Norton M (2020) Green chemistry and the plastic pollution challenge: towards a circular economy. Green Chem 22:6310–6322. https://doi.org/10.1039/D0GC02630A
Sheng K, Zhang S, Qian S, Fontanillo Lopez CA (2019) High-toughness PLA/Bamboo cellulose nanowhiskers bionanocomposite strengthened with silylated ultrafine bamboo-char. Compos B Eng 165:174–182. https://doi.org/10.1016/j.compositesb.2018.11.139
Sudharsan Reddy K, Prabhakar MN, Kumara Babu P et al (2012) Miscibility studies of hydroxypropyl cellulose/poly(ethylene glycol) in dilute solutions and solid state. Int J Carbohydr Chem 2012:1–9. https://doi.org/10.1155/2012/906389
Suryanegara L, Nakagaito AN, Yano H (2009) The effect of crystallization of PLA on the thermal and mechanical properties of microfibrillated cellulose-reinforced PLA composites. Compos Sci Technol 69:1187–1192. https://doi.org/10.1016/j.compscitech.2009.02.022
Suzuki K, Okumura H, Kitagawa K et al (2013) Development of continuous process enabling nanofibrillation of pulp and melt compounding. Cellulose 20:201–210. https://doi.org/10.1007/s10570-012-9843-9
Tian J, Cao Z, Qian S et al (2022) Improving tensile strength and impact toughness of plasticized poly(lactic acid) biocomposites by incorporating nanofibrillated cellulose. Nanotechnol Rev 11:2469–2482. https://doi.org/10.1515/ntrev-2022-0142
Vergnaud JM (1995) General Survey on the mass transfers taking place between a polymerand a liquid. J Polym Eng 15:57–78. https://doi.org/10.1515/POLYENG.1995.15.1-2.57
Wang Q, Ji C, Sun J et al (2020) Structure and properties of polylactic acid biocomposite films reinforced with cellulose nanofibrils. Molecules 25:3306. https://doi.org/10.3390/molecules25143306
Wei X-F, Linde E, Hedenqvist MS (2019) Plasticiser loss from plastic or rubber products through diffusion and evaporation. Npj Mater Degrad 3:18. https://doi.org/10.1038/s41529-019-0080-7
Xiao H, Lu W, Yeh J (2009) Effect of plasticizer on the crystallization behavior of poly(lactic acid). J Appl Polym Sci 113:112–121. https://doi.org/10.1002/app.29955
Xu H, Yang X, Xie L, Hakkarainen M (2016) Conformational footprint in hydrolysis-induced nanofibrillation and crystallization of poly(lactic acid). Biomacromolecules 17:985–995. https://doi.org/10.1021/acs.biomac.5b01636
Xu H, Zhou J, Odelius K et al (2021a) Nanostructured phase morphology of a biobased copolymer for tough and UV-resistant polylactide. ACS Appl Polym Mater 3:1973–1982. https://doi.org/10.1021/acsapm.1c00057
Xu L, Zhao J, Qian S et al (2021b) Green-plasticized poly(lactic acid)/nanofibrillated cellulose biocomposites with high strength, good toughness and excellent heat resistance. Compos Sci Technol 203:108613. https://doi.org/10.1016/j.compscitech.2020.108613
Yetiş F, Liu X, Sampson WW, Gong RH (2020) Acetylation of lignin containing microfibrillated cellulose and its reinforcing effect for polylactic acid. Eur Polym J 134:109803. https://doi.org/10.1016/j.eurpolymj.2020.109803
Zhang S, Liang Y, Qian X et al (2020) Pyrolysis kinetics and mechanical properties of poly(lactic acid)/bamboo particle biocomposites: effect of particle size distribution. Nanotechnol Rev 9:524–533. https://doi.org/10.1515/NTREV-2020-0037/MACHINEREADABLECITATION/RIS
Zhang Y, Li J, Su G (2022) Comprehensively screening of citric acid ester (CAE) plasticizers in Chinese foodstuffs, and the food-based assessment of human exposure risk of CAEs. Sci Total Environ 817:152933. https://doi.org/10.1016/j.scitotenv.2022.152933
Zheng T, Pilla S (2020) Melt processing of cellulose nanocrystal-filled composites: toward reinforcement and foam nucleation. Ind Eng Chem Res 59:8511–8531. https://doi.org/10.1021/acs.iecr.0c00170
Zhou L, Ke K, Yang M-B, Yang W (2021) Recent progress on chemical modification of cellulose for high mechanical-performance poly(lactic acid)/cellulose composite: a review. Compos Commun 23:100548. https://doi.org/10.1016/j.coco.2020.100548
Acknowledgments
Not applicable
Funding
Not applicable.
Author information
Authors and Affiliations
Contributions
LA: Conceptualization, Methodology, Formal Analysis, Data curation, Visualization, Writing original draft. VG: Conceptualization, Methodology, Formal Analysis, Data curation, Visualization, Writing original draft. GM: Investigation, Data Curation, Writing—Review & Editing. RD’A: Investigation, Data Curation, Writing—Review & Editing. LB: Methodology. Validation, Investigation, Writing—Review & Editing. FPLaM: Resources, Supervision, Writing—Review & Editing. AL: Resources, Supervision, Writing—Review & Editing.
Corresponding author
Ethics declarations
Conflict of interests
The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
Ethical approval
Not applicable.
Consent for publication
All authors have seen and approved the manuscript.
Additional information
Publisher's Note
Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Rights and permissions
Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted manuscript version of this article is solely governed by the terms of such publishing agreement and applicable law.
About this article
Cite this article
Aliotta, L., Gigante, V., Molinari, G. et al. Effect of biobased plasticizers, used as dispersing aids, on mechanical, rheological and thermal properties of micro fibrillated cellulose (MFC)/poly (lactic acid) (PLA) biocomposites over the time: how MFC controls the plasticizer migration?. Cellulose 30, 2237–2252 (2023). https://doi.org/10.1007/s10570-022-05010-w
Received:
Accepted:
Published:
Issue Date:
DOI: https://doi.org/10.1007/s10570-022-05010-w