Production of TPU-reinforced 3D printing PLA filaments: Structural, Phase Transition and Crystallinity Properties

Öz

Polylactic acid (PLA) has emerged as a vital biodegradable polymer due to its significant potential to reduce environmental pollution and dependence on fossil-based plastics and PLA with improved properties were required in material science. Thus, the main purpose of this study was to examine the influence of both polyethylene-based colorant and termoplastic polyurethane (TPU) addition on the crucial features of PLA filaments. The neat and reinforced filaments were fabricated by extrusion method with five channels. The structural characterization, thermal behavior and crystallinity properties of the produced filaments were investigated meticulously by comparing the commercial PLA (eSUN). The obtained findings showed that the percentage of the additive substantially affected the main characteristic behavior of PLA filaments, thus, the optimum production level of the additives was tried to determine for the filament samples. ATR-FTIR analysis depicted that all the filament showed characteristic absorption bands and the structural character of the filaments did not affected by the additives. Moreover, TPU and PLA exhibited good compatibility thanks to probable secondary bonds formed. Furthermore, DS analyses revealed that ,at high TPU contents, no glass transition (Tg) could be observed due to the decrease in chain mobility, and Fetaplast filaments showed lower Tg values than the commercial one (eSUN). Moreover, cold crystallization temperature (Tcc) value of eSUN PLA filament shifted relatively higher temperature with the addition of TPU since the addition of TPU probbaly augment the rigidity of PLA. Additionally, melting point (Tm) of eSUN was found as 167 °C with sharp peak, while all other filaments depicted Tm at about 151 °C with little shifts by showing broader peaks. This melting temperature decrement was attributed to disruption of TPU and PE-based color (Albosa Masterbatch) fillers to crystalline regions of PLA by hindering their ability to align. Accordingly, the results showed that all Fetaplast filaments possessed relatively lower degree of crystallinity compared to eSUN.

Anahtar Kelimeler

• Polylactic acid (PLA)
• TPU
• structural characterization
• DSC
• phase transition
• degree of crystallinity.

Kaynakça

1. Getahun M.J., Kassie B.B., Alemu T.S. (2024). Recent advances in biopolymer synthesis, properties, & commercial applications: A review. Process Biochemistry, 145 261-287.
2. Fredi G., Dorigato A. (2024). Compatibilization of biopolymer blends: A review. Advanced Industrial and Engineering Polymer Research, 7(4) 373-404.
3. Joseph T.M., Kallingal A., Suresh A.M., Mahapatra D.K., Hasanin M.S., Haponiuk J., Thomas S. (2023). 3D printing of polylactic acid: recent advances and opportunities. International Journal of Advanced Manufacturing Technology. 125(3-4) 1015-1035.
4. Thompson R.C., Moore C.J., vom Saal F.S., Swan S.H. (2009). Plastics, the environment and human health: current consensus and future trends. Philosophical Transaction of the Royal Society B, 364(1526) 2153-2166.
5. Khouri N.G., Bahú J.O., Blanco-Llamero C., Severino P.,. Concha V.O.C, Souto E.B. (2024). Polylactic acid (PLA): Properties, synthesis, and biomedical applications - A review of the literature. Journal of Molecular Structure, 1309.
6. Taib N.A.A.B.,. Rahman M.R, Huda D., Kuok K.K., Hamdan S., Bin Bakri M.K., Bin Julaihi M.R.M., Khan A. (2023). A review on poly lactic acid (PLA) as a biodegradable polymer. Polymer Bulletin, 80(2) 1179-1213.
7. Swetha T.A., Bora A., Mohanrasu K., Balaji P., Raja R., Ponnuchamy K., Muthusamy G., Arun A. (2023). A comprehensive review on polylactic acid (PLA)-Synthesis, processing and application in food packaging. International Journal of Biological Macromolecules, 234.
8. Chomachayi M.D., Jalali-arani A., Beltrán F.R., de la Orden M.U., Urreaga J.M. (2020). Biodegradable nanocomposites developed from PLA/PCL blends and silk fibroin nanoparticles: study on the microstructure, thermal behavior, crystallinity and performance. Journal of Polymer Environment, 28(4) 1252-1264.

9. Wang X.Y., Huang L.J., Li Y.S., Wang Y.N., Lu X.Y., Wei Z.H., Mo Q., Zhang S.Y., Sheng Y., Huang C.X., Zhao H., Liu Y. (2024). Research progress in polylactic acid processing for 3D printing. Journal of Manufacturing Processes, 112 161-178.
10. Ngo T.D., Kashani A., Imbalzano G., Nguyen K.T.Q., Hui D. (2018). Additive manufacturing (3D printing): A review of materials, methods, applications and challenges. Composites Part B-Engineering, 143 172-196.
11. Atakok G., Kam M., Koc H.B. (2022). Tensile, three-point bending and impact strength of 3D printed parts using PLA and recycled PLA filaments: A statistical investigation. Journal of Material Research and Technology, 18 1542-1554.
12. Nofar M., Salehiyan R., Ray S.S. (2019). Rheology of poly (lactic acid)-based systems. Polymer Review, 59(3) 465-509.
13. Bala A., Arfelis S., Oliver-Ortega H., Méndez J.A. (2022). Life cycle assessment of PE and PP multi film compared with PLA and PLA reinforced with nanoclays film. Journal of Cleaner Production, 380
14. Thurber C.M., Xu Y.W., Myers J.C., Lodge T.P., Macosko C.W. (2015). Accelerating reactive compatibilization of PE/PLA blends by an interfacially localized catalyst. ACS Macro Letter Journal, 4(1) 30-33.
15. Arunkumar N., Sathishkumar N., Sanmugapriya S.S., Selvam R. (2021). Study on PLA and PA thermoplastic polymers reinforced with carbon additives by 3D printing process. Mater Today:Proceedings, 46 8871-8879.
16. Rahmatabadi D., Ghasemi I., Baniassadi M., Abrinia K., Baghani M. (2022). 3D printing of PLA-TPU with different component ratios: Fracture toughness, mechanical properties, and morphology. Journal of Material Research and Technology, 21 3970-3981.
17. Nofar M., Mohammadi M., Carreau P.J. (2020) Effect of TPU hard segment content on the rheological and mechanical properties of PLA/TPU blends. Journal of Applied Polymer Science, 137(45).
18. Fang H., Zhang L.J., Chen A.L., Wu F.J. (2022) Improvement of mechanical property for PLA/TPU blend by adding PLA-TPU copolymers prepared via in situ ring-opening polymerization. Polymers-Basel,14(8).
19. Lee H.W., Insyani R., Prasetyo D., Prajitno H., Sitompul J. (2015). Molecular weight and structural properties of biodegradable PLA synthesized with different catalysts by direct melt polycondensation. Journal of Engineering and Technological Science, 47(4) 364-373.
20. Soykan U. (2020). Role of percent grafting and chain length of fully fluorinated pendant units in the grafted acrylic compound on crucial characteristic properties of high density polyethylene. Journal of Fluorine Chemistry, 236.
21. Çetin S., Sen B.Ö., Soykan U., Firat E.E., Yildirim G. (2016). Experimental and theoretical approaches for structural and mechanical properties of novel side chain LCP-PP graft coproducts. Turkish Journal of Chemistry, 40(3) 467-483.
22. Soykan U. (2022). Development of turkey feather fiber-filled thermoplastic polyurethane composites: Thermal, mechanical, water-uptake, and morphological characterizations, Journal of Composite Materials, 56(2) 339-355.
23. Zhu X.S., Li X.J., Mi H.Y., Jing X., Dong B.B., He P., Liu C.T., Shen C.Y. (2022). Graphene oxide/thermoplastic polyurethane wrinkled foams with enhanced compression performance fabricated by dynamic supercritical CO foaming. Journal pf Applied Polymer Science, 139(27).
24. Lazaridou M., Klonos P.A., Barmpa E.D., Kyritsis A., Bikiaris D.N. (2023). Thermal transitions and molecular mobility in polymeric blends based on polylactide (PLA) and poly(3,3-ethylene dithiodipropionate) (PEDPA). Polymer, 277.
25. Shin E.J., Jung Y.S., Park C.H., Lee S.H. (2023). Eco-friendly TPU/PLA blends for application as shape-memory 3D printing filaments, Journal of Polymer Environment, 31(7) 3182-3196.
26. Azadi F.,. Jafari S.H, Khonakdar H.A., Arjmand M., Wagenknecht U., Altstädt V. (2021). Influence of graphene oxide on thermally induced shape memory behavior of PLA/TPU blends: correlation with morphology, creep behavior, crystallinity, and dynamic mechanical properties. Macromolecular Materials and Engineering, 306(2).
27. Ladakhan S.H., Sreesha R.B., Adinarayanappa S.M. (2024). 4D printing of polylactic acid (PLA)/PLA-thermoplastic polyurethane (TPU)-based metastructure: examining the mechanical, thermal, and shape memory properties, Smart Materials and Structures, 33(10).
28. Monfared A.R., Omranpour H., Tuccitto A.V., Zaoui A., Rahman S.S., Kheradmandkeysomi M., Jalali A., Park C.B. (2024). Sustainable PLA bio-nanocomposites: integration of TPU nanofibrils and CNC for enhanced crystallization, toughness, stiffness, transparency, and oxygen barrier properties. ACS Sustainable Chemistry and Engineering Journal, 12(34) 13017-13029.
29. Greco A., Ferrari F. (2021). Thermal behavior of PLA plasticized by commercial and cardanol-derived plasticizers and the effect on the mechanical properties. Journal of Thermal Analysis and Calorimetry, 146(1) 131-141.
30. Beauson J., Schillani G., van der Schueren L., Goutianos S. (2022). The effect of processing conditions and polymer crystallinity on the mechanical properties of unidirectional self-reinforced PLA composites. Composite Part A-Applied Science and Manufacturing, 152.
31. Hamidi M.N., Abdullah J., Mahmud A.S., Hassan M.H., Zainoddin A.Y. (2025). Influence of thermoplastic polyurethane (TPU) and printing parameters on the thermal and mechanical performance of polylactic acid (PLA) / thermoplastic polyurethane (TPU) polymer, Polymer Testing, 143.