The dynamic control of thermal transport properties in solids must contend with the fact that phonons are inherently broadband. Thus, efforts to create reversible thermal conductivity switches have resulted in only modest on/off ratios, since only a relatively narrow portion of the phononic spectrum is impacted. Here, we report on the ability to modulate the thermal conductivity of topologically networked materials by nearly a factor of four following hydration, through manipulation of the displacement amplitude of atomic vibrations. By varying the network topology, or crosslinked structure, of squid ring teeth-based bio-polymers through tandem-repetition of DNA sequences, we show that this thermal switching ratio can be directly programmed. This on/off ratio in thermal conductivity switching is over a factor of three larger than the current state-of-the-art thermal switch, offering the possibility of engineering thermally conductive biological materials with dynamic responsivity to heat.
Subscribe to Journal
Get full journal access for 1 year
only $15.58 per issue
All prices are NET prices.
VAT will be added later in the checkout.
Rent or Buy article
Get time limited or full article access on ReadCube.
All prices are NET prices.
Wehmeyer, G., Yabuki, T., Monachon, C., Wu, J. & Dames, C. Thermal diodes, regulators, and switches: physical mechanisms and potential applications. Appl. Phys. Rev. 4, 041304 (2017).
Gou, X., Ping, H., Ou, Q., Xiao, H. & Qing, S. A novel thermoelectric generation system with thermal switch. Energy Procedia 61, 1713–1717 (2014).
Zhang, X. & Zhao, L.-D. Thermoelectric materials: energy conversion between heat and electricity. J. Materiomics 1, 92–105 (2015).
DiPirro, M. J. & Shirron, P. J. Heat switches for ADRs. Cryogenics 62, 172–176 (2014).
Jia, Y. & Ju, Y. S. A solid-state refrigerator based on the electrocaloric effect. Appl. Phys. Lett. 100, 242901 (2012).
Shin, J. et al. Thermally functional liquid crystal networks by magnetic field driven molecular orientation. ACS Macro Lett. 5, 955–960 (2016).
Cho, J. et al. Electrochemically tunable thermal conductivity of lithium cobalt oxide. Nat. Commun. 5, 4035 (2014).
Ihlefeld, J. F. et al. Room-temperature voltage tunable phonon thermal conductivity via reconfigurable interfaces in ferroelectric thin films. Nano Lett. 15, 1791–1795 (2015).
Zhang, T. & Luo, T. High-contrast, reversible thermal conductivity regulation utilizing the phase transition of polyethylene nanofibers. ACS Nano 7, 7592 (2013).
Shen, S., Henry, A., Tong, J., Zheng, R. & Chen, G. Polyethylene nanofibres with very high thermal conductivities. Nat. Nanotech. 5, 251–255 (2010).
Singh, V. et al. High thermal conductivity of chain-oriented amorphous polythiophene. Nat. Nanotech. 9, 384–390 (2014).
Kim, G.-H. et al. High thermal conductivity in amorphous polymer blends by engineered interchain interactions. Nat. Mater. 14, 295–300 (2015).
Wang, X., Ho, V., Segalman, R. A. & Cahill, D. G. Thermal conductivity of high-modulus polymer fibers. Macromolecules 46, 4937–4943 (2013).
Phan, L. et al. Reconfigurable infrared camouflage coatings from a cephalopod protein. Adv. Mater. 25, 5621–5625 (2013).
Sariola, V. et al. Segmented molecular design of self-healing proteinaceous materials. Sci. Rep. 5, 13482 (2015).
Vural, M. et al. Programmable molecular composites of tandem proteins with graphene oxide for efficient bimorph actuators. Carbon 118, 404–412 (2017).
Demirel, M. C., Cetinkaya, M., Pena-Francesch, A. & Jung, H. Recent advances in nanoscale bioinspired materials. Macromol. Biosci. 15, 300–311 (2015).
Pena-Francesch, A. et al. Materials fabrication from native and recombinant thermoplastic squid proteins. Adv. Funct. Mater. 24, 7401–7409 (2014).
Jung, H. et al. Molecular tandem repeat strategy for elucidating mechanical properties of high-strength proteins. Proc. Natl Acad. Sci. USA 113, 6478–6483 (2016).
George, M. C., Rodriguez, M. A., Kent, M. S., Brennecka, G. L. & Hopkins, P. E. Thermal conductivity of self-assembling symmetric block copolymer thin films of polystyrene-block-poly(methyl methacrylate). J. Heat Transfer 138, 024505 (2016).
Losego, M. D., Moh, L., Arpin, K. A., Cahill, D. G. & Braun, P. V. Interfacial thermal conductance in spun-cast polymer films and polymer brushes. Appl. Phys. Lett. 97, 011908 (2010).
Foley, B. M. et al. Protein thermal conductivity measured in the solid state reveals anharmonic interactions of vibrations in a fractal structure. J. Phys. Chem. Lett. 5, 1077–1082 (2014).
Ghossoub, M. G., Lee, J.-H., Baris, O. T., Cahill, D. G. & Sinha, S. Percolation of thermal conductivity in amorphous fluorocarbons. Phys. Rev. B 82, 195441 (2010).
Einstein, A. Elementary observations on thermal molecular motion in solids. Annalen der Physik 35, 679–694 (1911).
Cahill, D. G., Watson, S. K. & Pohl, R. O. Lower limit to the thermal conductivity of disordered crystals. Phys. Rev. B 46, 6131–6140 (1992).
Rashidi, V., Coyle, E. J., Sebeck, K., Kieffer, J. & Pipe, K. P. Thermal conductance in cross-linked polymers: effects of non-bonding interactions. J. Phys. Chem. B 121, 4600–4609 (2017).
Pena-Francesch, A. et al. Pressure sensitive adhesion of an elastomeric protein complex extracted from squid ring teeth. Adv. Funct. Mater. 24, 6227–6233 (2014).
Flory, P. J. Principles of Polymer Chemistry (Cornell Univ. Press, Ithaca, NY, 1953).
Treloar, L. R. G. The Physics of Rubber Elasticity (Oxford Univ. Press, New York, NY, 1975).
Atilgan, A. R. et al. Anisotropy of fluctuation dynamics of proteins with an elastic network model. Biophys. J. 80, 505–515 (2001).
Pena-Francesch, A. et al. Mechanical properties of tandem-repeat proteins are governed by network defects. ACS Biomater. Sci. Eng. 4, 884–891 (2018).
Sakai, V. G. & Arbe, A. Quasielastic neutron scattering in soft matter. Curr. Opin. Colloid Interface Sci. 14, 381–390 (2009).
Zaccai, G. How soft is a protein? A protein dynamics force constant measured by neutron scattering. Science 288, 1604–1607 (2000).
Gabel, F. et al. Protein dynamics studied by neutron scattering. Q. Rev. Biophys. 35, 327–367 (2002).
Gordon, M. & Taylor, J. S. Ideal copolymers and the second-order transitions of synthetic rubbers. i. Non-crystalline copolymers. J. Appl. Chem. 2, 493–500 (1952).
Volino, F. & Dianoux, A. J. Neutron incoherent scattering law for diffusion in a potential of spherical symmetry: general formalism and application to diffusion inside a sphere. Mol. Phys. 41, 271–279 (1980).
Allen, P. B. & Feldman, J. L. Thermal conductivity of disordered harmonic solids. Phys. Rev. B 48, 581–588 (1993).
Larkin, J. M. & McGaughey, A. J. H. Thermal conductivity accumulation in amorphous silica and amorphous silicon. Phys. Rev. B 89, 144303 (2014).
Shenogin, S., Bodapati, A., Keblinski, P. & McGaughey, A. J. H. Predicting the thermal conductivity of inorganic and polymeric glasses: the role of anharmonicity. J. Appl. Phys. 105, 034906 (2009).
Allen, P. B., Feldman, J. L., Fabian, J. & Wooten, F. Diffusons, locons and propagons: character of atomic vibrations in amorphous Si. Philos. Mag. B 79, 1715–1731 (1999).
Feldman, J. L., Kluge, M. D., Allen, P. B. & Wooten, F. Thermal conductivity and localization in glasses: numerical study of a model of amorphous silicon. Phys. Rev. B 48, 12589 (1993).
Feldman, J. L., Allen, P. B. & Bickham, S. R. Numerical study of low-frequency vibrations in amorphous silicon. Phys. Rev. B 59, 3551 (1999).
Meyer, A., Dimeo, R. M., Gehring, P. M. & Neumann, D. A. The high-flux backscattering spectrometer at the NIST Center for Neutron Research. Rev. Sci. Instrum. 74, 2759–2777 (2003).
Copley, J. R. D. & Cook, J. C. The Disk Chopper Spectrometer at NIST: a new instrument for quasielastic neutron scattering studies. Chem. Phys. 292, 477–485 (2003).
J.A.T. and P.E.H. acknowledge support from the Office of Naval Research (grant no. N00014-15-12769). M.C.D., B.D.A., A.P.-F. and H.J. were supported by the Army Research Office (grant no. W911NF-16-1-0019) and the Materials Research Institute of Pennsylvania State University. Access to the HFBS was provided by the Center for High Resolution Neutron Scattering, a partnership between the National Science Foundation and NIST under agreement no. DMR-1508249. Certain commercial material suppliers are identified in this paper to foster understanding. Such identification does not imply recommendation or endorsement by the NIST, nor does it imply that the materials or equipment identified are necessarily the best available for the purpose.
The Penn State Research Foundation and the University of Virginia Patent Foundation have applied for a US provisional patent, application no. 62/711,010, filed 27 July 2018, related to the structural protein-based thermal switch produced in this work.
Publisher’s note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
About this article
Cite this article
Tomko, J.A., Pena-Francesch, A., Jung, H. et al. Tunable thermal transport and reversible thermal conductivity switching in topologically networked bio-inspired materials. Nature Nanotech 13, 959–964 (2018). https://doi.org/10.1038/s41565-018-0227-7
Anomalously Suppressed Thermal Conduction by Electron‐Phonon Coupling in Charge‐Density‐Wave Tantalum Disulfide
Advanced Science (2020)
Angewandte Chemie International Edition (2020)
Physical Review Materials (2020)
Thermal diffusivity modulation driven by the interfacial elastic dynamics between cellulose nanofibers
Nanoscale Advances (2020)
Current Opinion in Biotechnology (2020)