Optimization of 4D Printing Performance of Poly(lactic acid)/Thermoplastic Polyurethane Composites <italic style="font-style: italic">via</italic> Orthogonal Design and the Synergistic Effect of Crosslinking Agent-coupling Agent

Zhen Liu; Bo Wang; Shi-Cheng Wei; Wei Huang; Yu-Jiang Wang; Xin-Yang Wang; Rui-Dong Shi; Zheng-Jie Yang

doi:10.1007/s10118-026-3561-5

Your Location：

Home >

Browse articles >

Optimization of 4D Printing Performance of Poly(lactic acid)/Thermoplastic Polyurethane Composites via Orthogonal Design and the Synergistic Effect of Crosslinking Agent-coupling Agent

RESEARCH ARTICLE | Updated：2026-03-05

- Optimization of 4D Printing Performance of Poly(lactic acid)/Thermoplastic Polyurethane Composites via Orthogonal Design and the Synergistic Effect of Crosslinking Agent-coupling Agent
- Chinese Journal of Polymer Science Vol. 44, Pages: 1-14(2026)
- Affiliations：
  
  a.National Key Laboratory for Remanufacturing, Beijing 100072, China
  b.Department of Naval Architecture Engineering, Naval University of Engineering, Wuhan 430033, China
  c.School of Metallurgy, Northeastern University, Shenyang 110819, China
- Author bio：
  
  wangbobo421@163.com (B.W.)
  scwei33333@163.com (S.C.W.)
- Funds：
- DOI：10.1007/s10118-026-3561-5
  CLC：
- Received：24 October 2025，
  
  Accepted：03 January 2026，
  
  Online First：05 March 2026，
  
  Published：05 April 2026
- Accepted：
Scan QR Code
Liu, Z.; Wang, B.; Wei, S. C.; Huang, W.; Wang, Y. J.; Wang, X. Y.; Shi, R. D.; Yang, Z. J. Optimization of 4D printing performance of poly(lactic acid)/thermoplastic polyurethane composites via orthogonal design and the synergistic effect of crosslinking agent-coupling agent. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3561-5

Zhen Liu, Bo Wang, Shi-Cheng Wei, et al. Optimization of 4D Printing Performance of Poly(lactic acid)/Thermoplastic Polyurethane Composites via Orthogonal Design and the Synergistic Effect of Crosslinking Agent-coupling Agent[J/OL]. Chinese Journal of Polymer Science, 2026, 441-14.
Liu, Z.; Wang, B.; Wei, S. C.; Huang, W.; Wang, Y. J.; Wang, X. Y.; Shi, R. D.; Yang, Z. J. Optimization of 4D printing performance of poly(lactic acid)/thermoplastic polyurethane composites via orthogonal design and the synergistic effect of crosslinking agent-coupling agent. Chinese J. Polym. Sci. https://doi.org/10.1007/s10118-026-3561-5 DOI：

Zhen Liu, Bo Wang, Shi-Cheng Wei, et al. Optimization of 4D Printing Performance of Poly(lactic acid)/Thermoplastic Polyurethane Composites via Orthogonal Design and the Synergistic Effect of Crosslinking Agent-coupling Agent[J/OL]. Chinese Journal of Polymer Science, 2026, 441-14. DOI： 10.1007/s10118-026-3561-5.

摘要

Abstract

This study aimed to systematically regulate the performance of 4D printing composites by investigating the synergistic effects of dicumyl peroxide (DCP) and maleic anhydride-grafted polyethylene (MAH-

-PE) on a poly(lactic acid)/thermoplastic polyurethane (PLA/TPU) matrix. Specifically

using a 70 wt%/30 wt% PLA/TPU matrix and an L

) orthogonal design

composites were evaluated

via

morphology

shape memory

mechanical tests

and multi-criteria analysis. Moderate DCP enhanced crosslinking

improving storage modulus and thermal stability

while excessive DCP caused brittleness. Furthermore

MAH-

-PE effectively improved interfacial compatibility

and its synergy with DCP was dosage-dependent. Consequently

Sample 5 achieved optimal performance

exhibiting uniform fracture morphology

a shape fixation rate of 98.8% with the fastest recovery

and balanced strength-ductility. Multi-criteria analysis identified elongation at break and recovery time as the top contributing factors

with consistent rankings validated by Spearman analysis (

=0.833

0.01). In summary

adjusting DCP and MAH-

-PE contents effectively modulates the crosslinking structure and interfacial properties of PLA/TPU composites

providing a viable strategy for developing high-performance

tunable 4D printing materials.

关键词

Keywords

references

[Rahmatabadi, D.; Yousefi, M.A.; Shamsolhodaei, S.; Baniassadi, M.; Abrinia, K.; Bodaghi, M.; Baghani, M. 4D printing of polyethylene glycol-grafted carbon nanotube-reinforced polyvinyl chloride–polycaprolactone composites for enhanced shape recovery and thermomechanical performance. Adv. Intell. Syst . 2025 , 7 , 2500113..

Lai, J.; Xiong, T.; Chen, S.; Zhou, Z.; Liu, J.; Yang, B.; Tuan, R.S.; Li, Z.A. Facile single-nanocomposite 4D bioprinting of dynamic hydrogel constructs with thickness-controlled gradient. Adv. Sci. 2025 , 12 , e09449..

Huang, W.; Chen, W.; Singh, V.; Zhang, J.; Wang, Y.; Alabdullatif, M.; Bele, E.; Lye, G.J.; Hailes, H.C.; Tiwari, M.K. Modulation-enabled healable and stretchable shape-memory polymer composites for digital light processing 4D printing. Addit. Manuf. 2025 , 101 , 104699..

Yousefi, M.A.; Rahmatabadi, D.; Baniassadi, M.; Bodaghi, M.; Baghani, M. 4D printing of multifunctional and biodegradable PLA-PBAT-Fe 3 O 4 nanocomposites with supreme mechanical and shape memory properties. Macromol. Rapid Commun. 2025 , 46 , 2400661..

[Mirasadi, K.; Yousefi, M.A.; Jin, L.; Rahmatabadi, D.; Baniassadi, M.; Liao, W.; Bodaghi, M.; Baghani, M. 4D printing of magnetically responsive shape memory polymers: Toward sustainable solutions in soft robotics, wearables, and biomedical devices. Adv. Sci . 2025 , 12 , e13091..

Khan, N.; Mohamed S.; Hasan, N. Shape memory polymers: From materials to emerging biomedical applications. Eur. Polym. J. 2026 , 243 , 114460..

Wan, X.; Xiao, Z.; Tian, Y.; Chen, M.; Liu, F.; Wang, D.; Liu, Y.; Bartolo, P.J.D.S.; Yan, C.; Shi, Y.; Zhao, R.R.; Qi, H.J.; Zhou, K. Recent advances in 4D printing of advanced materials and structures for functional applications. Adv. Mater. 2024 , 36 , 2312263..

[Rahmatabadi, D.; Ghasemi, I.; Baniassadi, M.; Abrinia, K.; Baghani, M. 4D printing of PLA-TPU blends: Effect of PLA concentration, loading mode, and programming temperature on the shape memory effect. J. Mater. Sci . 2023 , 58 , 7227–7243..

Rahmatabadi, D.; Soltanmohammadi, K.; Pahlavani, M.; Aberoumand, M.; Soleyman, E.; Ghasemi, I.; Baniassadi, M.; Abrinia, K.; Bodaghi, M.; Baghani, M. Shape memory performance assessment of FDM 3D printed PLA-TPU composites by box-behnken response surface methodology. Int. J. Adv. Manuf. Technol. 2023 , 127 , 935−950..

[Zhai, H.; Li, X.; Yu, S.; Wang, J.; Zhou, L.; Xiong, X.; Li, J.; Chang, Y.; Liu, T.; Yu, X.; Li, B. 4D printing of nd-fe-B composites with both shape memory and permanent magnet excitation deformation. Compos. Part A: Appl. Sci. Manuf . 2024 , 187 , 108443..

[Doostmohammadi, H.; Baniassadi, M.; Bodaghi, M.; Baghani, M. 4D printing of magneto-thermo-responsive PLA/PMMA/Fe 3 O 4 nanocomposites with superior shape memory and remote actuation. Macromol. Mater. Eng . 2024 , 309 , 2400090..

Faghihi-Rezaei, V.; Khonakdar, H.A.; Goodarzi, V.; Darbemamieh, G.; Otadi, M. Hydroxyapatite/TPU/PLA nanocomposites: Morphological, dynamic-mechanical, and thermal study. Green Process. Synth. 2022 , 11 , 996−1012..

Nejatpour, M.; Fallah, A.; Koc, B. Shape memory PLA/TPU blend using high-speed thermo-kinetic mixing. ACS Omega 2025 , 10 , 193−206..

Liu, Z.; Wang, B.; Wei, S.; Huang, W.; Wang, Y.; Liang, Y.; Wang, X.; Yang, Z. Mechanistic study on rheological, thermal, and shape memory properties of polyester-type and polyether-type PLA/TPU composites for 4D printing. Polym. Adv. Technol. 2025 , 36 , e70346..

[Liu, H.; Wang, F.; Wu, W.; Dong, X.; Sang, L. 4D printing of mechanically robust PLA/TPU/Fe 3 O 4 magneto-responsive shape memory polymers for smart structures. Compos. Part B: Eng . 2023 , 248 , 110382..

Ren, Z.; Ding, K.; Zhou, X.; Ji, T.; Sun, H.; Chi, X.; Wei, Y.; Xu, M. Fluorescent polylactic acid composite incorporating lignin-based carbon quantum dots for sustainable 4D printing applications. Int. J. Biol. Macromol. 2024 , 277 , 134207..

Zu, R.; Chen, W.; Huang, Y.; Chen, Y.; Du, C.; Fan, Q.; Li, H.; Liu, H. Tailor-made 3D printing TPU/PLA composites for damping and energy absorption. Mater. Des. 2025 , 252 , 113752..

Die, J.; Ma, J.; Li, H.; Zhang, Y.; Li, F.; Cao, Y.; Hao, W.; Tu, J.; Zhang, K.; Yu, R. Effects of maleic anhydride-grafted polyethylene on the properties of artificial marble waste powder/linear low-density polyethylene composites with ultra-high filling content. Materials 2023 , 16 , 4036..

Mo, X.; Wei, F.; Tan, D.; Pang, J.; Lan, C. The compatibilization of PLA-g-TPU graft copolymer on polylactide/thermoplastic polyurethane blends. J. Polym. Res. 2020 , 27 , 33..

Jiang, X.; Zhang, Z.; Cheng, J.; Ai, Y.; Zhang, Z.; Wang, S.; Xu, S.; Gao, H.; Dong, Y. Development of electric/near-infrared light-driven shape memory rGO/EVA composite films for deployable structures. Pigment. Resin. Technol. 2024 , 45 , 9−22..

[Guo, W. 3D-printed PLA/PEG bone scaffold: Body-adaptive thermally responsive shape memory and enhanced biological performance. J. Surf. Interfaces . 2025 , 113 , 105712..

Xia, Y.; He, Y.; Zhang, F.; Liu, Y.; Leng, J. A review of shape memory polymers and composites: Mechanisms, materials, and applications. Adv. Mater. 2021 , 33 , 2000713..

Dong, K.; Panahi-Sarmad, M.; Cui, Z.; Huang, X.; Xiao, X. Electro-induced shape memory effect of 4D printed auxetic composite using PLA/TPU/CNT filament embedded synergistically with continuous carbon fiber: A theoretical & experimental analysis. Compos. Part B: Eng. 2021 , 220 , 108994..

Kostopoulos, G.; Stamoulis, K.; Lappas, V.; Georgantzinos, S.K. Shape morphing of 4D-printed polylactic acid structures under thermal stimuli: An experimental and finite element analysis. Aerospace 2024 , 11 , 134..

Shin, E.; Jung, Y.; Park, C.; Lee, S. Eco-friendly TPU/PLA blends for application as shape-memory 3D printing filaments. J. Polym. Environ. 2023 , 31 , 3182−3196..

Sorimpuk, N. P.; Choong, W. H.; Chua, B. L. Thermoforming characteristics of PLA/TPU multi-material specimens fabricated with fused deposition modelling under different temperatures. Polymers 2024 , 14 , 4304..

Xiao, H.; Zhou, M.; Sun, F.; Song, X.; Huang, A. Ternary synergistic toughening of biodegradable polylactic acid foams by elastomer, rolling and supercritical fluid foaming for enhanced anisotropy. J. Polym. Environ. 2025 , 33 , 885−898..

Liu, Q.; Ruan, Y.; Ling, Z.; Du, J.; Qiu, J. Photo-thermal dual responsive shape memory MOF derived carbon/EVA composites with radar wave stealth. Carbon 2025 , 234 , 119976..

Wang, Q. High toughness and programmable strength in ion gels via hydrogen bond-induced microphase separation. Chem. Eng. J. 2025 , 505 , 159608..

Khatir, O.; Bouiadjra, B.A.B.; Yerou, A.; Bellali, M.A.; Mechab, B.; Salem, M.; Elmeguenni, M. Analysis of the mechanical properties of 3D-printed polylactic acid/thermoplastic polyurethane multi-materials. J. Mater. Eng. Perform. 2025 , 34 , 289−301..

Jerusalem, R. D. L.; Maricanov, M.; Katzenberg, F.; Tiller, J. C. Cross-linked shape memory polymer blends with tunable heating rate sensitivity. ACS Appl. Polym. Mater. 2025 , 7 , 932−937..

Zeng, C.; Liu, L.; Zhao, W.; Xin, X.; Liu, Y.; Leng, J. Advances in shape-memory polymers and composites for biomedical device applications. Adv. Eng. Mater. 2025 , 298 , 2402145..

Sanaka, R.; Sahu, S. K.; Sreekanth, P. S. R.; Giri, J.; Mohammad, F.; Al-Lohedan, H. A.; Saharudin, M. S.; Ma, Q. Heat-responsive PLA/PU/MXene shape memory polymer blend nanocomposite: mechanical, thermal, and shape memory properties. Polymers 2025 , 17 , 338..

Cheung, T.C.; Choi, S.Y.; Jiang, S. Manipulation of printing direction and temperature on the mechanical properties and shape reco very of thermoplastic polyurethane 4D-printed polymer-textile composites. J. Appl. Polym. Sci. 2025 , 142 , 53289..

Zhou, Y.; Yang, L.; Zou, Q.; Xu, S.; Ma, M.; Ye, C. A comparative applied study on optimizing printing parameters for six fused deposition modeling materials. J. Mater. Eng. Perform. 2023 , 32 , 5249−5260..

Kayacan, M.Y. Mechanical investigation of compositing by resin filling in lattice structures manufactured with fused deposition modelling. J. Reinf. Plast. Compos. 2024 , 43 , 961−979..

Kohnechi P.; Fasihi M.; Eshaghi H. Rheology, mechanical properties and peel adhesion of hot-melt adhesive based on thermoplastic polyurethane/nanosilica. Int. J. Adhes. Adhes. 2023 , 125 , 9..

Wang J.; Mu T.; Xia Y. Temperature-responsive 4D printing with shape memory polymers: Advancing simulation with a viscoelastic constitutive model. Appl. Mater. Today 2025 , 33 , 102604..

Tang Z.; Guo Q.; Guo L. High-performance shape memory cyanate ester with two-way shape memory effect and reconfigurability. Eur. Polym. J. 2025 , 181 , 113735..

Valim, F.; Oliveira, G.; Vasconcelos, G.; De Paiva, L.; Santillo, C.; Lavorgna, M.; Andrade, R. Unraveling the impact of phase separation induced by thermal annealing on shape memory effect of polyester-based thermoplastic polyurethane. J. Appl. Polym. Sci. 2022 , 139 , 51723..

Views

Downloads

CSCD

Alert me when the article has been cited

Submit

Tools

Publicity Resources

A Strategy to Tailor Mechanical Properties of Thermoplastic Polyurethane through Altering the Terminal Diisocyanate Structure of Hard Segment

4D Printing Micelle-enhanced Shape Memory Polymer for Minimally Invasive Implant

Simultaneous Improvement of Strength and Toughness of Poly(lactic acid) via Multiple Dynamic Pressure

Related Author

Ze-Hao Wang

Chen-Ding Wang

Xiao-Li Zhao

Xiao-Niu Yang

Fu-Kang Liu

Zhe Lu

Jing-Jing Cui

Yun-Long Guo

Related Institution

Key Laboratory of High-Performance Synthetic Rubber and its Composite Materials & Key Laboratory of Polymer Science and Technology, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences

School of Applied Chemistry and Engineering, University of Science and Technology of China

State Key Laboratory of Polymer Physics and Chemistry & Key Laboratory of Polymer Science and Technology, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences

State Key Laboratory of Flexible Electronics (LOFE) & Institute of Flexible Electronics (IFE), Northwestern Polytechnical University

National Engineering Research Center of Novel Equipment for Polymer Processing, Key Laboratory of Polymer Processing Engineering, Ministry of Education, Guangdong Provincial Key Laboratory of Technique and Equipment for Macromolecular Advanced Manufacturing, School of Mechanical and Automotive Engineering, South China University of Technology

⁰

Optimization of 4D Printing Performance of Poly(lactic acid)/Thermoplastic Polyurethane Composites via Orthogonal Design and the Synergistic Effect of Crosslinking Agent-coupling Agent

DOI：10.1007/s10118-026-3561-5

摘要

Abstract

关键词

Keywords

references