Spider Silk Inspired Shape Adaptive and Heat Conductive Thermal Interface Materials

Abstract

Efficient dissipation of waste heat in chips with thermal interface materials (TIM) is essential for high-performance electric devices. The superiorities of thermal conductance, dielectric insulation, and self-healing capability make polymer composites promising candidates for TIM. However, the inherent rigidity limits its shape adaptive contact with chips/sinks. Inspired by the dimension-crossover architecture of semi-crystalline spider silk, we develop an electrically responsive semicrystalline ferroelectric polymer at elevated temperature. The crystalline domains stabilized by weak bonding networks create mechanical anchor points. It enables controllable loading and maintains efficient thermal pathways, depicting remarkable shape adaption (41% elongation) and directional thermal conductance (2.50 W·m⁻¹⋅K⁻¹). The dipole polarization induced localized crystallization, evolving from random coil to twisted to trans conformation in amorphous domains, imitates a controlled inter-chain alignment in spider silk. Additionally, electric stimuli at 500 K activates a self-healing process via reversible chain realignment, which extends the remaining lifetime of electronic devices. This electrically responsive TIM represents a significant advance in the design and optimization of next-generation TIM, and offers a highlight insight into the process–structure–property relationship.

Keywords

conformation evolution / dipole polarization / electric stimuli / ferroelectric polymer / self-healing

References

[1] J. Li, Y. Fu, J. Zhou, et al., “Ultrathin, Soft, Radiative Cooling Interfaces for Advanced Thermal Management in Skin Electronics,” Science Advances 9, no. 14 (2023): eadg1837, https://doi.org/10.1126/sciadv.adg1837.

[2] M. Fattori, S. Cardarelli, J. Fijn, et al., “A Printed Proximity-Sensing Surface Based on Organic Pyroelectric Sensors and Organic Thin-Film Transistor Electronics,” Nature Electronics 5 (2022): 289–299, https://doi.org/10.1038/s41928-022-00762-6.

[3] D. W. Lee, R. Mayberry, D. A. Mackie, et al., “Optimizing Reflowed Solder TIM (sTIMs) Processes for Emerging Heterogeneous Integrated Packages,” in 2022 IEEE 72nd Electronic Components and Technology Conference, (2022), 1228–1237, https://doi.org/10.1109/ECTC51906.2022.00197.

[4] J. Chen, X. Xu, J. Zhou, and B. Li, “Interfacial Thermal Resistance: Past, Present, and Future,” Reviews of Modern Physics 94, no. 2 (2022): 025002, https://doi.org/10.1103/revmodphys.94.025002.

[5] X. Wang, W. Wang, C. Yang, D. Han, H. Fan, and J. Zhang, “Thermal Transport in Organic Semiconductors,” Journal of Applied Physics 130, no. 17 (2021): 170902, https://doi.org/10.1063/5.0062074.

[6] P. Saxena and P. Shukla, “A Comprehensive Review on Fundamental Properties and Applications of Poly (Vinylidene Fluoride) (PVDF),” Advanced Composites and Hybrid Material 4, no. 1 (2021): 8–26, https://doi.org/10.1007/s42114-021-00217-0.

[7] A. Vasilev, T. Lorenz, and C. Breitkopf, “Thermal Conductivities of Crosslinked Polyisoprene and Polybutadiene From Molecular Dynamics Simulations,” Polymers 13, no. 3 (2021): 315, https://doi.org/10.3390/polym13030315.

[8] J. Li, X. Liu, Y. Feng, and J. Yin, “Recent Progress in Polymer/Two-Dimensional Nanosheets Composites With Novel Performances,” Progress in Polymer Science 126 (2022): 101505, https://doi.org/10.1016/j.progpolymsci.2022.101505.

[9] J. Yi, G. Zou, J. Huang, et al., “Water-Responsive Supercontractile Polymer Films for Bioelectronic Interfaces,” Nature 624, no. 7991 (2023): 295–302, https://doi.org/10.1038/s41586-023-06732-y.

[10] D. Schneider, N. Gomopoulos, C. Y. Koh, et al., “Nonlinear Control of High-Frequency Phonons in Spider Silk,” Nature Materials 15, no. 10 (2016): 1079–1083, https://doi.org/10.1038/nmat4697.

[11] S. Keten, Z. Xu, B. Ihle, and M. J. Buehler, “Nanoconfinement Controls Stiffness, Strength and Mechanical Toughness of β-Sheet Crystals in Silk,” Nature Materials 9, no. 4 (2010): 359–367, https://doi.org/10.1038/nmat2704.

[12] X. Huang, G. Liu, and X. Wang, “New Secrets of Spider Silk: Exceptionally High Thermal Conductivity and Its Abnormal Change Under Stretching,” Advanced Materials 24, no. 11 (2012): 1482–1486, https://doi.org/10.1002/adma.201104668.

[13] S. Shen, A. Henry, J. Tong, R. Zheng, and G. Chen, “Polyethylene Nanofibres With Very High Thermal Conductivities,” Nature Nanotechnology 5, no. 4 (2010): 251–255, https://doi.org/10.1038/nnano.2010.27.

[14] X. Liu, C. Lin, and Z. Rao, “Thermal Conductivity of Straight-Chain Polytetrafluoroethylene: A Molecular Dynamics Study,” International Journal of Thermal Sciences 159 (2021): 106646, https://doi.org/10.1016/j.ijthermalsci.2020.106646.

[15] M. K. Maurya, J. Wu, M. K. Singh, and D. Mukherji, “Thermal Conductivity of Semicrystalline Polymer Networks: Crystallinity or Cross-Linking?,” ACS Macro Letters 11, no. 7 (2022): 925–929, https://doi.org/10.1021/acsmacrolett.2c00341.

[16] J. He and J. Liu, “Molecular Dynamics Simulation of Thermal Transport in Semicrystalline Polyethylene: Roles of Strain and the Crystalline-Amorphous Interphase Region,” Journal of Applied Physics 130, no. 22 (2021): 225101, https://doi.org/10.1063/5.0067999.

[17] S. Lin, Z. Cai, Y. Wang, L. Zhao, and C. Zhai, “Tailored Morphology and Highly Enhanced Phonon Transport in Polymer Fibers: A Multiscale Computational Framework,” Npj Computational Materials 5, no. 1 (2019): 126, https://doi.org/10.1038/s41524-019-0264-2.

[18] Y. Liu, B. Zhang, W. Xu, et al., “Chirality-Induced Relaxor Properties in Ferroelectric Polymers,” Nature Materials 19, no. 11 (2020): 1169–1174, https://doi.org/10.1038/s41563-020-0724-6.

[19] T. Wongwirat, Z. Zhu, G. Rui, et al., “Origins of Electrostriction in Poly (Vinylidene Fluoride)-Based Ferroelectric Polymers,” Macromolecules 53, no. 24 (2020): 10942–10954, https://doi.org/10.1021/acs.macromol.0c02083.

[20] H. Liu, X. Shi, Y. Yao, et al., “Emergence of High Piezoelectricity From Competing Local Polar Order-Disorder in Relaxor Ferroelectrics,” Nature Communications 14, no. 1 (2023): 1007, https://doi.org/10.1038/s41467-023-36749-w.

[21] Y. Liu, A. Haibibu, W. Xu, Z. Han, and Q. Wang, “Observation of a Negative Thermal Hysteresis in Relaxor Ferroelectric Polymers,” Advanced Functional Materials 30, no. 25 (2020): 2000648, https://doi.org/10.1002/adfm.202000648.

[22] D. Jung, H. J. Shim, Y. Kim, et al., “Highly Conductive and Elastic Nanomembrane for Skin Electronics,” Science 373 (2021): 1022–1026, https://doi.org/10.1126/science.abh4357.

[23] G. Rui, Y. Huang, X. Chen, et al., “Giant Spontaneous Polarization for Enhanced Ferroelectric Properties of Biaxially Oriented Poly (Vinylidene Fluoride) by Mobile Oriented Amorphous Fractions,” Journal of Materials Chemistry C 9, no. 3 (2021): 894–907, https://doi.org/10.1039/d0tc04632a.

[24] X. Xu, J. Chen, J. Zhou, and B. Li, “Thermal Conductivity of Polymers and Their Nanocomposites,” Advanced Materials 30, no. 17 (2018): 1705544, https://doi.org/10.1002/adma.201705544.

[25] K. Kronenberger and F. Vollrath, “Spiders Spinning Electrically Charged Nano-Fibres,” Biology Letters 11, no. 1 (2015): 20140813, https://doi.org/10.1098/rsbl.2014.0813.

[26] X. Meng, T. Pandey, J. Jeong, et al., “Thermal Conductivity Enhancement in MoS₂ Under Extreme Strain,” Physical Review Letters 122, no. 15 (2019): 155901, https://doi.org/10.1103/physrevlett.122.155901.

[27] A. J. Lovinger, “Annealing of Poly (Vinylidene Fluoride) and Formation of a Fifth Phase,” Macromolecules 15, no. 1 (1982): 40–44, https://doi.org/10.1021/ma00229a008.

[28] W. M. Prest and D. J. Luca, “The Formation of the γ Phase From the α and β Polymorphs of Polyvinylidene Fluoride,” Journal of Applied Physics 49, no. 10 (1978): 5042–5047, https://doi.org/10.1063/1.324439.

[29] B.-E. E. Mohajir and N. Heymans, “Changes in Structural and Mechanical Behaviour of PVDF With Processing and Thermomechanical Treatments. 1. Change in Structure,” Polymer 42, no. 13 (2001): 5661–5667, https://doi.org/10.1016/s0032-3861(01)00064-7.

[30] J. B. Lando, H. G. Olf, and A. Peterlin, “Nuclear Magnetic Resonance and X-Ray Determination of the Structure of Poly (Vinylidene Fluoride),” Journal of Polymer Science - Part A-1: Polymer Chemistry 4 (2003): 941–951, https://doi.org/10.1002/pol.1966.150040420.

[31] S. Deng, J. Yuan, Y. Lin, et al., “Electric-Field-Induced Modulation of Thermal Conductivity in Poly (Vinylidene Fluoride),” Nano Energy 82 (2021): 105749, https://doi.org/10.1016/j.nanoen.2021.105749.

[32] H. Yoon, B. S. Jung, and H. Lee, “Correlation Between Electrical Conductivity, Thermal Conductivity, and ESR Intensity of Polyaniline,” Synthetic Metals 41, no. 1–2 (1991): 699–702, https://doi.org/10.1016/0379-6779(91)91162-4.

[33] S. Plimpton, “Fast Parallel Algorithms for Short-Range Molecular Dynamics,” Journal of Computational Physics 117 (1995): 1–19, https://doi.org/10.1006/jcph.1995.1039.

[34] H. Meng, X. Yu, H. Feng, Z. Xue, and N. Yang, “Superior Thermal Conductivity of Poly (Ethylene Oxide) for Solid-State Electrolytes: A Molecular Dynamics Study,” International Journal of Heat and Mass Transfer 137 (2019): 1241–1246, https://doi.org/10.1016/j.ijheatmasstransfer.2019.04.021.

[35] H. Qin, Y. Feng, K. Liu, J. Mi, L. Zhang, and M. Tian, “From Molecular-Scale Cavities to Nanoscale Dielectric Breakdown in Polydimethylsiloxane Induced by Local Electric Field,” Macromolecules 55, no. 5 (2022): 1690–1699, https://doi.org/10.1021/acs.macromol.1c02641.

[36] Y. Cui, Z. Qin, H. Wu, M. Li, and Y. Hu, “Flexible Thermal Interface Based on Self-Assembled Boron Arsenide for High-Performance Thermal Management,” Nature Communications 12, no. 1 (2021): 1284, https://doi.org/10.1038/s41467-021-21531-7.

[37] B. Zhang, Y. Liang, W. Liu, and Z. Liu, “Effects of the Filler Property, Electron–Phonon Coupling on Thermal Conductivity, and Strain Rate on the Mechanical Property of Polyethylene Nanocomposites,” Journal of Physical Chemistry C 124, no. 47 (2020): 26001–26011, https://doi.org/10.1021/acs.jpcc.0c07489.

[38] J. M. Kim, R. Locker, and G. C. Rutledge, “Plastic Deformation of Semicrystalline Polyethylene Under Extension, Compression, and Shear Using Molecular Dynamics Simulation,” Macromolecules 47, no. 7 (2014): 2515–2528, https://doi.org/10.1021/ma402297a.

[39] H. Ma and J. C. Suhling, “A Review of Mechanical Properties of Lead-Free Solders for Electronic Packaging,” Journal of Materials Science 44, no. 5 (2009): 1141–1158, https://doi.org/10.1007/s10853-008-3125-9.

[40] S. Xu, X.-L. Shi, M. Dargusch, C. Di, J. Zou, and Z.-G. Chen, “Conducting Polymer-Based Flexible Thermoelectric Materials and Devices: From Mechanisms to Applications,” Progress in Materials Science 121 (2021): 100840, https://doi.org/10.1016/j.pmatsci.2021.100840.

[41] W. Wu, G. Ye, G. Zhang, and X. Yang, “Composite Phase Change Material With Room-Temperature-Flexibility for Battery Thermal Management,” Chemical Engineering Journal 428 (2022): 131116, https://doi.org/10.1016/j.cej.2021.131116.

[42] X. Yang, X. Zhong, J. Zhang, and J. Gu, “Improvement of Thermal Conductivities and Simulation Model for Glass Fabrics Reinforced Epoxy Laminated Composites via Introducing Hetero-Structured BNN-30@BNNS Fillers,” Journal of Materials Science & Technology 68 (2021): 209–215, https://doi.org/10.1016/j.jmst.2021.01.018.

[43] Y. Lin, Q. Kang, Y. Liu, et al., “Flexible, Highly Thermally Conductive and Electrically Insulating Phase Change Materials for Advanced Thermal Management of 5G Base Stations and Thermoelectric Generators,” Nano-Micro Letters 15, no. 1 (2023): 31, https://doi.org/10.1007/s40820-022-01003-3.

[44] J. Hennig, “Anisotropy and Structure in Uniaxially Stretched Amorphous High Polymers,” Journal of Polymer Science Part C: Polymer Symposia 16, no. 5 (2014): 2751–2761, https://doi.org/10.1002/polc.5070160528.

[45] Z. Y. Jiang, J. Y. Li, Z. G. Qu, L. Wang, and J. Y. Miao, “Theoretical Analysis on Thermal Grease Dry-Out Degradation in Space Environment,” International Journal of Thermal Sciences 179 (2022): 107694, https://doi.org/10.1016/j.ijthermalsci.2022.107694.

[46] H. P. Zhang, J. Niemczura, G. Dennis, K. Ravi-Chandar, and M. Marder, “Toughening Effect of Strain-Induced Crystallites in Natural Rubber,” Physical Review Letters 102, no. 24 (2009): 245503, https://doi.org/10.1103/physrevlett.102.245503.

[47] Z. Luo and J. Jiang, “Molecular Dynamics and Dissipative Particle Dynamics Simulations for the Miscibility of Poly(Ethylene oxide)/poly(vinyl Chloride) Blends,” Polymer 51, no. 1 (2010): 291–299, https://doi.org/10.1016/j.polymer.2009.11.024.

[48] L. Tao, J. He, T. Arbaugh, J. R. McCutcheon, and Y. Li, “Machine Learning Prediction on the Fractional Free Volume of Polymer Membranes,” Journal of Membrane Science 665 (2023): 121131, https://doi.org/10.1016/j.memsci.2022.121131.

[49] T. Lu and F. Chen, “Multiwfn: A Multifunctional Wavefunction Analyzer,” Journal of Computational Chemistry 33, no. 5 (2011): 580–592, https://doi.org/10.1002/jcc.22885.

[50] F. Cai, G. You, K. Luo, H. Zhang, X. Zhao, and S. Wu, “Click Chemistry Modified Graphene Oxide/Styrene-Butadiene Rubber Composites and Molecular Simulation Study,” Composites Science and Technology 190 (2020): 108061, https://doi.org/10.1016/j.compscitech.2020.108061.

[51] J. Liu and R. Yang, “Tuning the Thermal Conductivity of Polymers With Mechanical Strains,” Physical Review B 81, no. 17 (2010): 174122, https://doi.org/10.1103/physrevb.81.174122.

[52] C. M. Hartquist, S. Lin, J. H. Zhang, S. Wang, M. Rubinstein, and X. Zhao, “An Elastomer With Ultrahigh Strain-Induced Crystallization,” Science Advances 9, no. 50 (2023): eadj0411, https://doi.org/10.1126/sciadv.adj0411.

[53] B. Zhang, Y. Liang, B. Liu, W. Liu, and Z. Liu, “Enhancing the Thermo-Mechanical Property of Polymer by Weaving and Mixing High Length–Diameter Ratio Filler,” Polymers 12, no. 6 (2020): 1255, https://doi.org/10.3390/polym12061255.

[54] S. Hu, J. Chen, N. Yang, and B. Li, “Thermal Transport in Graphene With Defect and Doping: Phonon Modes Analysis,” Carbon 116 (2017): 139–144, https://doi.org/10.1016/j.carbon.2017.01.089.

[55] J. Shiomi and S. Maruyama, “Non-Fourier Heat Conduction in a Single-Walled Carbon Nanotube: Classical Molecular Dynamics Simulations,” Physical Review B 73, no. 20 (2006): 205420, https://doi.org/10.1103/physrevb.73.205420.

[56] T. Liang, M. Zhou, P. Zhang, P. Yuan, and D. Yang, “Multilayer in-Plane Graphene/Hexagonal Boron Nitride Heterostructures: Insights Into the Interfacial Thermal Transport Properties,” International Journal of Heat and Mass Transfer 151 (2020): 119395, https://doi.org/10.1016/j.ijheatmasstransfer.2020.119395.

[57] X. Yu, R. Li, T. Shiga, et al., “Hybrid Thermal Transport Characteristics of Doped Organic Semiconductor Poly (3,4-ethylenedioxythiophene):Tosylate,” Journal of Physical Chemistry C 123, no. 43 (2019): 26735–26741, https://doi.org/10.1021/acs.jpcc.9b09105.

[58] B. Zhang, X. Zhou, Z. Zhang, S. Rui, J. Wang, and W. Zhang, “Temperature-Dependent Heat Transfer Deterioration in Ordered Graphene/Ceramic Composites,” Journal of the American Ceramic Society 108, no. 3 (2024): e20253, https://doi.org/10.1111/jace.20253.

[59] G. C. Loh, E. H. T. Teo, and B. K. Tay, “Phonon Localization Around Vacancies in Graphene Nanoribbons,” Diamond and Related Materials 23 (2012): 88–92, https://doi.org/10.1016/j.diamond.2012.01.006.

[60] Y. Liu, L. Qiu, J. Liu, and Y. Feng, “Excellent Heat Transfer Enhancement of CNT-Metal Interface by Loading Carbyne and Metal Nanowire Into CNT,” International Journal of Heat and Mass Transfer 209 (2023): 1241–1246, https://doi.org/10.1016/j.ijheatmasstransfer.2022.122533.

[61] L. Yang, N. Yang, and B. Li, “Extreme Low Thermal Conductivity in Nanoscale 3D Si Phononic Crystal With Spherical Pores,” Nano Letters 14, no. 4 (2014): 1734–1738, https://doi.org/10.1021/nl403750s.

[62] Z. Li, S. Xiong, C. Sievers, et al., “Influence of Thermostatting on Nonequilibrium Molecular Dynamics Simulations of Heat Conduction in Solids,” Journal of Chemical Physics 151, no. 23 (2019): 234105, https://doi.org/10.1063/1.5132543.

[63] J. Lee, V. Varshney, A. K. Roy, J. B. Ferguson, and B. L. Farmer, “Thermal Rectification in Three-Dimensional Asymmetric Nanostructure,” Nano Letters 12, no. 7 (2012): 3491–3496, https://doi.org/10.1021/nl301006y.

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