Degradation of a mechanically recycled polylactide/halloysite nanocomposite in an ethanolic food simulant

Freddys R. Beltrán, Marina P. Arrieta, Yaiza Hortal, Gerald Gaspar, Mª Ulagares de la Orden, Joaquín Martínez Urreaga


This work aims to study the effect of immersion in a ethanolic food simulant in mechanically recycled poly(lactic acid) (PLAR) and its nanocomposites reinforced with halloysite nanotubes (HNT). PLAR was obtained by subjecting PLA to an accelerated ageing process, which includes photochemical, thermal and hydrothermal ageing steps, followed by a final demanding washing step. PLAR was further reinforced with 4 %wt. HNT to improve the properties of the PLAR films. The materials were melt compounded by melt extrusion and processed into films by compression molding. The resulting films were exposed to food simulant D1 (50 %vol. ethanol solution) for 10 days at 40 °C. The intrinsic viscosity, crystallization behavior, thermal stability as well as the mechanical performance were analyzed before and after the contact with the food simulant. The swelling, plasticizing and hydrolyzing effect of the food simulant led to an important decrease of the intrinsic viscosity of all the samples, along with a significant increase of the crystallinity. Thermal stability was negatively affected by the decrease of the molecular weight, while the high crystallinity values resulted in materials with higher Vickers hardness values after the immersion in the food simulant.


poly(lactic acid); halloysite; nanocomposites; mechanical recycling; food simulant

Full Text:



Agüero, A., Morcillo, D.M., Quiles-Carrillo, L., Balart, R., Boronat, T., Lascano, D., & Fenollar, O. (2019). Study of the influence of the reprocessing cycles on the final properties of polylactide pieces obtained by injection molding. Polymers, 11(12), 1908.

Arrieta, M.P., Castro-López, M., Rayón, E., Barral-Losada, L., López-Vilariño, J.M., López, J., & González-Rodríguez, M.V. (2014). Plasticized poly(lactic acid)-Poly(hydroxybutyrate) (PLA-PHB) blends incorporated with catechin intended for active food-packaging applications. Journal of Agricultural and Food Chemistry, 62(41), 10170-10180.

Arrieta, P.M., Samper, D.M., Aldas, M., & López, J. (2017). On the use of PLA-PHB blends for sustainable food packaging applications. Materials, 10(9), 1008.

Badia, J.D., Santonja-Blasco, L., Martínez-Felipe, A., & Ribes-Greus, A. (2012). Hygrothermal ageing of reprocessed polylactide. Polymer Degradation and Stability, 97(10), 1881-1890.

Beltrán, F.R., de la Orden, M.U., Lorenzo, V., Pérez, E., Cerrada, M.L., & Martínez Urreaga, J. (2016). Water-induced structural changes in poly(lactic acid) and PLLA-clay nanocomposites. Polymer, 107, 211-222.

Beltrán, F.R., Lorenzo, V., Acosta, J., de la Orden, M.U., & Martínez Urreaga, J. (2018a). Effect of simulated mechanical recycling processes on the structure and properties of poly(lactic acid). Journal of Environmental Management, 216, 25-31.

Beltrán, F.R., de la Orden, M.U., & Martínez Urreaga, J. (2018b). Amino-modified halloysite nanotubes to reduce polymer degradation and improve the performance of mechanically recycled poly(lactic acid). Journal of Polymers and the Environment, 26, 4046-4055.

Beltrán, F.R., Climent-Pascual, E., de la Orden, M.U., & Martínez Urreaga, J. (2020). Effect of solid-state polymerization on the structure and properties of mechanically recycled poly(lactic acid). Polymer Degradation and Stability, 171, 109045.

Castro-Aguirre, E., Iñiguez-Franco, F., Samsudin, H., Fang, X., & Auras, R. (2016). Poly(lactic acid)-Mass production, processing, industrial applications, and end of life. Advanced Drug Delivery Reviews, 107, 333-366.

Cosate de Andrade, M.F., Souza, P.M.S., Cavalett, O., & Morales, A.R. (2016). Life cycle assessment of poly(lactic acid) (PLA): Comparison between chemical recycling, mechanical recycling and composting. Journal of Polymers and the Environment, 24(4), 372-384.

European Bioplastics. (2020). Bioplastics market data 2019.

European Comission. (2018). A european strategy for plastics in a circular economy. Available at

European Comission. (2019). Directive (EU) 2019/904 of the European Parliament and of the Council of 5 June 2019 on the reduction of the impact of certain plastic products on the environment.

Farah, S., Anderson, D.G., & Langer, R. (2016). Physical and mechanical properties of PLA, and their functions in widespread applications - A comprehensive review. Advanced Drug Delivery Reviews, 107, 367-392.

Fortunati, E., Peltzer, M., Armentano, I., Torre, L., Jiménez, A., & Kenny, J.M. (2012). Effects of modified cellulose nanocrystals on the barrier and migration properties of PLA nano-biocomposites. Carbohydrate Polymers, 90(2), 948-956.

Haider, T., Völker, C., Kramm, J., Landfester, K., & Wurm, F.R. (2018). Plastics of the future? the impact of biodegradable polymers on the environment and on society. Angewandte Chemie International Edition, 58(1), 50-62.

Iñiguez-Franco, F., Auras, R., Burgess, G., Holmes, D., Fang, X., Rubino, M., & Soto-Valdez, H. (2016). Concurrent solvent induced crystallization and hydrolytic degradation of PLA by water-ethanol solutions. Polymer, 99, 315-323.

Iñiguez-Franco, F., Auras, R., Rubino, M., Dolan, K., Soto-Valdez, H., & Selke, S. (2017). Effect of nanoparticles on the hydrolytic degradation of PLA-nanocomposites by water-ethanol solutions. Polymer Degradation and Stability, 146, 287-297.

Kale, G., Auras, R., & Singh, S.P. (2007). Comparison of the degradability of poly(lactide) packages in composting and ambient exposure conditions. Packaging Technology and Science, 20(1), 49-70.

Liu, M., Guo, B., Zou, Q., Du, M., & Jia, D. (2008). Interactions between halloysite nanotubes and 2,5-bis(2-benzoxazolyl) thiophene and their effects on reinforcement of polypropylene/halloysite nanocomposites. Nanotechnology, 19(20), 205709.

Maga, D., Hiebel, M., & Thonemann, N. (2019). Life cycle assessment of recycling options for polylactic acid. Resources, Conservation and Recycling, 149, 86-96

Meaurio, E., López-Rodríguez, N., & Sarasua, J.R. (2006). Infrared spectrum of poly(l-lactide): Application to crystallinity studies. Macromolecules, 39(26), 9291-9301.

Niaounakis, M. (2019). Recycling of biopolymers - the patent perspective. European Polymer Journal, 114, 464-475

Perego, G., Cella, G. D., & Bastioli, C. (1996). Effect of molecular weight and crystallinity on poly(lactic acid) mechanical properties. Journal of Applied Polymer Science, 59(1), 37-43.;2-N

Raquez, J., Habibi, Y., Murariu, M., & Dubois, P. (2013). Polylactide (PLA)-based nanocomposites. Progress in Polymer Science, 38(10-11), 1504-1542.

Risyon, N.P., Othman, S.H., Basha, R.K., & Talib, R.A. (2020). Characterization of polylactic acid/halloysite nanotubes bionanocomposite films for food packaging. Food Packaging and Shelf Life, 23, 100450 fpsl.2019.100450

Rojas-Lema, S., Quiles-Carrillo, L., Garcia-Garcia, D., Melendez-Rodriguez, B., Balart, R., & Torres-Giner, S. (2020). Tailoring the properties of thermo-compressed polylactide films for food packaging applications by individual and combined additions of lactic acid oligomer and halloysite nanotubes. Molecules, 25(8), 1976. molecules25081976

Rossi, V., Cleeve-Edwards, N., Lundquist, L., Schenker, U., Dubois, C., Humbert, S., & Jolliet, O. (2015). Life cycle assessment of end-of-life options for two biodegradable packaging materials: Sound application of the European waste hierarchy. Journal of Cleaner Production, 86, 132-145.

Samper, M.D., Arrieta, M.P., Ferrándiz, S., & López, J. (2014). Influence of biodegradable materials in the recycled polystyrene. Journal of Applied Polymer Science, 131(23), 41161.

Samper, M.D., Bertomeu, D., Arrieta, M.P., Ferri, J.M., & López-Martínez, J. (2018). Interference of biodegradable plastics in the polypropylene recycling process. Materials, 11(10), 1886.

Tuna, B., & Ozkoc, G. (2017). Effects of diisocyanate and polymeric epoxidized chain extenders on the properties of recycled poly(lactic acid). Journal of Polymers and the Environment, 25, 983-993.

Villegas, C., Arrieta, M.P., Rojas, A., Torres, A., Faba, S., Toledo, M.J., ..., & Valenzuela, X. (2019). PLA/organoclay bionanocomposites impregnated with thymol and cinnamaldehyde by supercritical impregnation for active and sustainable food packaging. Composites Part B: Engineering, 176, 107336.

Abstract Views

Metrics Loading ...

Metrics powered by PLOS ALM


  • There are currently no refbacks.

This journal is licensed under a  Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International

Universitat Politècnica de València

e-ISSN: 2695-8821