A Highly Ductile Composite of 3D-Printed Poly(Lactic Acid) With InSe Particles and Flakes as a Filler

Abstract

The biodegradable polymer poly(lactic acid) (PLA) is brittle. PLA-based composites reinforced by indium selenide (InSe) particles or flakes are prepared; each is found to have outstanding plasticity. InSe nanosheets are prepared by sonication of solid InSe in N-methyl pyrrolidone, followed by washing/dispersion in ethanol, and subsequent drying. These InSe nanosheets, or in separate studies InSe particles, are mixed with PLA to make composite materials. The PLA composite materials are 3D-printed into “dogbone” samples that are tensile-loaded. The optimum dogbone specimen is 1.5 times stronger and 5.5 times tougher than neat PLA specimens prepared in the same way. To the best of our knowledge, this concurrent improvement in tensile strength and toughness has not been achieved before in PLA with any filler type. Finite element analysis, together with experimental analysis of (i) fracture surfaces, (ii) the PLA crystal structure, and (iii) the internal structure by micro-CT scanning, suggests that the exceptional mechanical performance is due to the intrinsic properties of InSe and, particularly, the emergence of crack shielding and crack deflection at the interfaces of PLA and InSe flakes. These findings indicate that PLA–InSe composites may offer opportunities to broaden the applications of PLA composites, including as load-bearing materials.

Keywords

3D printing / InSe / PLA composites / strength / toughness

References

[1] L. T. Lim, R. Auras, and M. Rubino, “Processing Technologies for Poly(Lactic Acid),” Progress in Polymer Science 33, no. 8 (2008): 820–852.

[2] F.-L. Jin, R.-R. Hu, and S.-J. Park, “Improvement of Thermal Behaviors of Biodegradable Poly(Lactic Acid) Polymer: A Review,” Composites, Part B: Engineering 164 (2019): 287–296.

[3] S. Liu, S. Qin, M. He, D. Zhou, Q. Qin, and H. Wang, “Current Applications of Poly(Lactic Acid) Composites in Tissue Engineering and Drug Delivery,” Composites, Part B: Engineering 199 (2020): 108238.

[4] A. P. Mathew, K. Oksman, and M. Sain, “Mechanical Properties of Biodegradable Composites From Poly Lactic Acid (PLA) and Microcrystalline Cellulose (MCC),” Journal of Applied Polymer Science 97, no. 5 (2005): 2014–2025.

[5] W. He, L. Ye, P. Coates, F. Caton-Rose, and X. Zhao, “Reactive Processing of Poly(Lactic Acid)/Poly(Ethylene Octene) Blend Film With Tailored Interfacial Intermolecular Entanglement and Toughening Mechanism,” Journal of Materials Science & Technology 98 (2022): 186–196.

[6] S. Su, M. Duhme, and R. Kopitzky, “Uncompatibilized PBAT/PLA Blends: Manufacturability, Miscibility and Properties,” Materials 13, no. 21 (2020): 4897.

[7] J. Chai, G. Wang, A. Zhang, et al., “Ultra-Ductile and Strong In-Situ Fibrillated PLA/PTFE Nanocomposites With Outstanding Heat Resistance Derived by CO₂ Treatment,” Composites, Part A: Applied Science and Manufacturing 155 (2022): 106849.

[8] R. O. Ritchie, “The Conflicts Between Strength and Toughness,” Nature Materials 10, no. 11 (2011): 817–822.

[9] X.-Z. Tong, F. Song, M.-Q. Li, X.-L. Wang, I.-J. Chin, and Y.-Z. Wang, “Fabrication of Graphene/Polylactide Nanocomposites With Improved Properties,” Composites Science and Technology 88 (2013): 33–38.

[10] P. Liu, Z. Jin, G. Katsukis, et al., “Layered and Scrolled Nanocomposites With Aligned Semi-Infinite Graphene Inclusions at the Platelet Limit,” Science 353, no. 6297 (2016): 364–367.

[11] P.-P. Xu, S. Yang, X.-R. Gao, et al., “Constructing Robust Chain Entanglement Network, Well-Defined Nanosize. Crystals and Highly Aligned Graphene Oxide Nanosheets: Towards Strong, Ductile and High Barrier Poly(Lactic Acid) Nanocomposite Films for Green Packaging,” Composites, Part B: Engineering 222 (2021): 109048.

[12] Y. Qian, C. Li, Y. Qi, and J. Zhong, “3D Printing of Graphene Oxide Composites With Well Controlled Alignment,” Carbon 171 (2021): 777–784.

[13] L. Peng, Y. Han, M. Wang, et al., “Multifunctional Macroassembled Graphene Nanofilms With High Crystallinity,” Advanced Materials 33, no. 49 (2021): 2104195.

[14] T. Liang and B. Wang, “Interlayer Covalently Enhanced Graphene Materials: Construction, Properties, and Applications,” Acta Physico Chimica Sinica 38, no. 1 (2022): 2011059.

[15] S. H. Park, S. G. Lee, and S. H. Kim, “Isothermal Crystallization Behavior and Mechanical Properties of Polylactide/Carbon Nanotube Nanocomposites,” Composites, Part A: Applied Science and Manufacturing 46 (2013): 11–18.

[16] P. G. Seligra, F. Nuevo, M. Lamanna, and L. Famá, “Covalent Grafting of Carbon Nanotubes to PLA in Order to Improve Compatibility,” Composites, Part B: Engineering 46 (2013): 61–68.

[17] R. Kotsilkova, I. Petrova-Doycheva, D. Menseidov, E. Ivanov, A. Paddubskaya, and P. Kuzhir, “Exploring Thermal Annealing and Graphene-Carbon Nanotube Additives to Enhance Crystallinity, Thermal, Electrical and Tensile Properties of Aged Poly(Lactic) Acid-Based Filament for 3D Printing,” Composites Science and Technology 181 (2019): 107712.

[18] Y. Wang, Y. Mei, Q. Wang, et al., “Improved Fracture Toughness and Ductility of PLA Composites by Incorporating a Small Amount of Surface-Modified Helical Carbon Nanotubes,” Composites, Part B: Engineering 162 (2019): 54–61.

[19] J. Li, H. Li, L. Xu, et al., “Biomimetic Nanoporous Aerogels From Branched Aramid Nanofibers Combining High Heat Insulation and Compressive Strength,” SmartMat 2, no. 1 (2021): 76–87.

[20] M. Kim, J. H. Jeong, J.-Y. Lee, et al., “Electrically Conducting and Mechanically Strong Graphene–Polylactic Acid Composites for 3D Printing,” ACS Applied Materials & Interfaces 11, no. 12 (2019): 11841–11848.

[21] C. Lee, X. Wei, J. W. Kysar, and J. Hone, “Measurement of the Elastic Properties and Intrinsic Strength of Monolayer Graphene,” Science 321, no. 5887 (2008): 385–388.

[22] Q. Zhao, P. Chen, D. Zheng, T. Wang, A. Castellanos-Gomez, and R. Frisenda, “Multifunctional Indium Selenide Devices Based on Van Der Waals Contacts: High-Quality Schottky Diodes and Optoelectronic Memories,” Nano Energy 108 (2023): 108238.

[23] Z. Ali, M. Mirza, C. Cao, et al., “Wide Range Photodetector Based on Catalyst Free Grown Indium Selenide Microwires,” ACS Applied Materials & Interfaces 6, no. 12 (2014): 9550–9556.

[24] D. Xu, J. Li, Y. Xiong, et al., “Fast and Direct Identification of SARS-CoV-2 Variants via 2D InSe Field-Effect Transistors,” InfoMat 5, no. 2 (2023): e12398.

[25] D. H. Mosca, N. Mattoso, C. M. Lepienski, et al., “Mechanical Properties of Layered InSe and Gase Single Crystals,” Journal of Applied Physics 91, no. 1 (2002): 140–144.

[26] Y. Li, C. Yu, Y. Gan, et al., “Elastic Properties and Intrinsic Strength of Two-Dimensional InSe Flakes,” Nanotechnology 30, no. 33 (2019): 335703.

[27] Q. Zheng, C. Liang, J. Jiang, and S. Li, “Elastic Properties and Deformation Mechanisms in the Van Der Waals Single-Crystalline Indium Selenide,” Physica Status Solidi (RRL)—Rapid Research Letters 16, no. 3 (2022): 2100418.

[28] T.-R. Wei, M. Jin, Y. Wang, et al., “Exceptional Plasticity in the Bulk Single-Crystalline Van Der Waals Semiconductor Inse,” Science 369, no. 6503 (2020): 542–545.

[29] N. Curreli, M. Serri, D. Spirito, et al., “Liquid Phase Exfoliated Indium Selenide Based Highly Sensitive Photodetectors,” Advanced Functional Materials 30, no. 13 (2020): 1908427.

[30] E. Petroni, E. Lago, S. Bellani, et al., “Liquid-Phase Exfoliated Indium–Selenide Flakes and Their Application in Hydrogen Evolution Reaction,” Small 14, no. 26 (2018): 1800749.

[31] L. S. D Bortoli, R. Farias, D. Z. Mezalira, L. M. Schabbach, and M. C. Fredel, “Functionalized Carbon Nanotubes for 3D-Printed Pla-Nanocomposites: Effects on Thermal and Mechanical Properties,” Materials Today Communications 31 (2022): 103402.

[32] L. Yang, S. Li, X. Zhou, et al., “Effects of Carbon Nanotube on the Thermal, Mechanical, and Electrical Properties of PLA/CNT Printed Parts in the FDM Process,” Synthetic Metals 253 (2019): 122–130.

[33] C. Sriprachuabwong, S. Duangsripat, K. Sajjaanantakul, A. Wisitsoraat, and A. Tuantranont, “Electrolytically Exfoliated Graphene–Polylactide-Based Bioplastic With High Elastic Performance,” Journal of Applied Polymer Science 132, no. 6 (2015): 41439.

[34] S. Xu, J. F. Tahon, I. De-Waele, G. Stoclet, and V. Gaucher, “Brittle-to-Ductile Transition of PLA Induced by Macromolecular Orientation,” eXPRESS Polymer Letters 14, no. 11 (2020): 1034–1047.

[35] M. Razavi and S.-Q. Wang, “Why Is Crystalline Poly(Lactic Acid) Brittle at Room Temperature?,” Macromolecules 52, no. 14 (2019): 5429–5441.

[36] M. R. Mohamed Zin, A. Mahendrasingam, C. Konkel, and T. Narayanan, “Effect of D-Isomer Content on Strain-Induced Crystallization Behaviour of Poly(Lactic Acid) Polymer Under High Speed Uniaxial Drawing,” Polymer 216 (2021): 123422.

[37] W. Wang, K. Sadeghipour, and G. Baran, “Finite Element Analysis of the Effect of an Interphase on Toughening of a Particle-Reinforced Polymer Composite,” Composites, Part A: Applied Science and Manufacturing 39, no. 6 (2008): 956–964.

[38] J. G. Williams, “Particle Toughening of Polymers by Plastic Void Growth,” Composites Science and Technology 70, no. 6 (2010): 885–891.

[39] J. Gao, B. A. Patterson, Y. Kashcooli, D. O’Brien, and G. R. Palmese, “Synergistic Fracture Toughness Enhancement of Epoxy-Amine Matrices via Combination of Network Topology Modification and Silica Nanoparticle Reinforcement,” Composites, Part B: Engineering 238 (2022): 109857.

[40] S. Liu, J. Liu, Z. Xu, et al., “Artificial Bicontinuous Laminate Synergistically Reinforces and Toughens Dilute Graphene Composites,” ACS Nano 12, no. 11 (2018): 11236–11243.

[41] A. Bisht, S. S. Samant, S. Jaiswal, K. Dasgupta, and D. Lahiri, “Quantifying Nanodiamonds Assisted Exfoliation of Graphene and Its Effect on Toughening Behaviour of Composite Structure,” Composites, Part A: Applied Science and Manufacturing 132 (2020): 105840.

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