Dielectric polymers are ubiquitous as electrical insulation in electronic devices and electrical systems. Electrical degradation of dielectric polymers tends to initiate catastrophic failure of numerous devices and systems, but its detection and early warning remain challenging. Here we report a general material strategy that signals the electrical degradation of dielectric polymers by autonomously presenting a visually discernible warning in the form of a pronounced colour change. This colour change is induced by the chromogenic response of molecular indicators blended with the polymer, which are chemically activated by the oxygen radicals generated in situ during the electrical degradation of the polymer. We unveil that the structural degradation and electrical properties of the dielectric polymer are quantitatively correlated with the colour difference. Such a chromogenic process is autonomous without the need of human intervention or other external energy, thus offering the convenience to lower or even eliminate the risk of dielectric failure.
This is a preview of subscription content, access via your institution
Access Nature and 54 other Nature Portfolio journals
Get Nature+, our best-value online-access subscription
$29.99 / 30 days
cancel any time
Subscribe to this journal
Receive 12 print issues and online access
$259.00 per year
only $21.58 per issue
Rent or buy this article
Prices vary by article type
Prices may be subject to local taxes which are calculated during checkout
All data are available in the article or its Supplementary Information.
Stark, K. H. & Garton, C. G. Electric strength of irradiated polythene. Nature 176, 1225–1226 (1955).
Yang, Y. et al. Self-healing of electrical damage in polymers using superparamagnetic nanoparticles. Nat. Nanotechnol. 14, 151–155 (2019).
Hackam, R. Outdoor HV composite polymeric insulators. IEEE Trans. Dielectr. Electr. Insul. 6, 557–585 (1999).
Jarvid, M. et al. A new application area for fullerenes: voltage stabilizers for power cable insulation. Adv. Mater. 27, 897–902 (2015).
Loo, J. S. C., Ooi, C. P. & Boey, F. Y. C. Degradation of poly(lactide-co-glycolide) (PLGA) and poly(l-lactide) (PLLA) by electron beam radiation. Biomaterials 26, 1359–1367 (2005).
Uchida, K. & Shimizu, N. The effect of temperature and voltage on polymer chain scission in high-field region. IEEE Trans. Electr. Insul. 26, 271–277 (1991).
Tafazoli, M. A study of on-orbit spacecraft failures. Acta Astronaut. 64, 195–205 (2009).
Paulmier, T., Dirassen, B., Payan, D. & Eesbeek, M. V. Material charging in space environment: experimental test simulation and induced conductive mechanisms. IEEE Trans. Dielectr. Electr. Insul. 16, 682–688 (2009).
Dissado, L. A. Theoretical basis for the statistics of dielectric breakdown. J. Phys. D 23, 1582–1591 (1990).
Reynders, J. P., Jandrell, I. R. & Reynders, S. M. Review of aging and recovery of silicone rubber insulation for outdoor use. IEEE Trans. Dielectr. Electr. Insul. 6, 620–631 (1999).
Zhang, B., Ghassemi, M. & Zhang, Y. Insulation materials and systems for power electronics modules: a review identifying challenges and future research needs. IEEE Trans. Dielectr. Electr. Insul. 28, 290–302 (2021).
Gubanski, S. M. Modern outdoor insulation—concerns and challenges. IEEE Electr. Insul. Mag. 21, 5–11 (2005).
Borghei, M. & Ghassemi, M. Insulation materials and systems for more- and all-electric aircraft: a review identifying challenges and future research needs. IEEE Trans. Transport. Electrific. 7, 1930–1953 (2021).
Levchenko, I., Bazaka, K., Belmonte, T., Keidar, M. & Xu, S. Advanced materials for next-generation spacecraft. Adv. Mater. 30, 1802201 (2018).
Chen, C., Luo, F. & Kang, Y. A review of SiC power module packaging: layout, material system and integration. CPSS Trans. Power Electron. Appl. 2, 170–186 (2017).
Davis, D. A. et al. Force-induced activation of covalent bonds in mechanoresponsive polymeric materials. Nature 459, 68–72 (2009).
Chen, Y. et al. Mechanically induced chemiluminescence from polymers incorporating a 1,2-dioxetane unit in the main chain. Nat. Chem. 4, 559–562 (2012).
Kosuge, T. et al. Multicolor mechanochromism of a polymer/silica composite with dual distinct mechanophores. J. Am. Chem. Soc. 141, 1898–1902 (2019).
Patrick, J. F., Robb, M. J., Sottos, N. R., Moore, J. S. & White, S. R. Polymers with autonomous life-cycle control. Nature 540, 363–370 (2016).
Rifaie-Graham, O., Apebende, E. A., Bast, L. K. & Bruns, N. Self-reporting fiber-reinforced composites that mimic the ability of biological materials to sense and report damage. Adv. Mater. 30, 1705483 (2018).
Li, W. et al. Autonomous indication of mechanical damage in polymeric coatings. Adv. Mater. 28, 2189–2194 (2016).
Di Credico, B., Griffini, G., Levi, M. & Turri, S. Microencapsulation of a UV-responsive photochromic dye by means of novel UV-screening polyurea-based shells for smart coating applications. ACS Appl. Mater. Interfaces 5, 6628–6634 (2013).
Han, T., Liu, L., Wang, D., Yang, J. & Tang, B. Z. Mechanochromic fluorescent polymers enabled by AIE processes. Macromol. Rapid Commun. 42, 2000311 (2021).
Dissado, L. A. Understanding electrical trees in solids: from experiment to theory. IEEE Trans. Dielectr. Electr. Insul. 9, 483–497 (2002).
Venkatesulu, B. & Thomas, M. J. Corona aging studies on silicone rubber nanocomposites. IEEE Trans. Dielectr. Electr. Insul. 17, 625–634 (2010).
Boersma, A., Cangialosi, D. & Picken, S. J. Mobility and solubility of antioxidants and oxygen in glassy polymers. III. Influence of deformation and orientation on oxygen permeability. Polymer 44, 2463–2471 (2003).
Shimizu, N. & Laurent, C. Electrical tree initiation. IEEE Trans. Dielectr. Electr. Insul. 5, 651–659 (1998).
Hollahan, J. R. & Carlson, G. L. Hydroxylation of polymethylsiloxane surfaces by oxidizing plasmas. J. Appl. Polym. Sci. 14, 2499–2508 (1970).
Malatesta, V., Millini, R. & Montanari, L. Key intermediate product of oxidative degradation of photochromic spirooxazines. X-ray crystal structure and electron spin resonance analysis of its 7,7,8,8-tetracyanoquinodimethane ion-radical salt. J. Am. Chem. Soc. 117, 6258–6264 (1995).
Uznanski, P., Amiens, C., Donnadieu, B., Coppel, Y. & Chaudret, B. Oxidation of photochromic spirooxazines by coinage metal cations. Part I. Reaction with AgNO3: formation and characterisation of silver particles. New J. Chem. 25, 1486–1494 (2001).
Malatesta, V. et al. Reductive degradation of photochromic spiro-oxazines. Reaction of the merocyanine forms with free radicals. J. Org. Chem. 60, 5446–5448 (1995).
Kim, D.-H. et al. Stretchable and foldable silicon integrated circuits. Science 320, 507–511 (2008).
Pelrine, R., Kornbluh, R., Pei, Q. & Joseph, J. High-speed electrically actuated elastomers with strain greater than 100%. Science 287, 836–839 (2000).
Kumagai, S. & Yoshimura, N. Polydimethylsiloxane and alumina trihydrate system subjected to dry-band discharges or high temperature part I: chemical structure. IEEE Trans. Dielectr. Electr. Insul. 11, 691–700 (2004).
Korcek, S., Chenier, J. H. B., Howard, J. A. & Ingold, K. U. Absolute rate constants for hydrocarbon autoxidation. XXI. Activation energies for propagation and the correlation of propagation rate constants with carbon–hydrogen bond strengths. 100 Years CSC Pages CJC 01, 2285–2297 (2011).
Sharma, G., Wu, W. & Dalal, E. N. The CIEDE2000 color-difference formula: implementation notes, supplementary test data, and mathematical observations. Color Res. Appl. 30, 21–30 (2005).
Luo, M. R., Cui, G. & Rigg, B. The development of the CIE 2000 colour-difference formula: CIEDE2000. Color Res. Appl. 26, 340–350 (2001).
Lichtenberg, G. C. De nova methodo naturam ac motum fluidi electrici investigandi (Joann Christian Dieterich, 1778).
Dissado, L. A., Dodd, S. J., Champion, J. V., Williams, P. I. & Alison, J. M. Propagation of electrical tree structures in solid polymeric insulation. IEEE Trans. Dielectr. Electr. Insul. 4, 259–279 (1997).
This work was supported by the National Key R&D Program of China grants 2018YFE0200100 (J. He, Q.L. and J. Hu) and the National Natural Science Foundation of China grants 51921005 (J. He and Q.L.). We thank G. Tian for her help with the UPLC-HRMS analysis and the isolation of activated indicators. We thank M. Zhou for her help with analysing the chemical structure of indolinooxazole (1′) by using NMR spectroscopy. We thank R. Hu for her help with the microscopic observation and elemental analysis of electro-degraded polymers by using SEM. We also thank Y. Xia, H. Yang and T. Tan for fruitful discussions.
The authors declare no competing interests.
Peer review information
Nature Materials thanks Gregory Sotzing, Daniel Q. Tan and the other, anonymous, reviewer(s) for their contribution to the peer review of this work.
Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.
Supplementary Notes 1–8, Figs. 1–50, Schemes 1–7 and Tables 1–8.
ACN solution of spirooxazine (1) (left) and ACN solution of BPO (right) were preheated to 80 °C. After BPO/ACN was added to 1/ACN, the mixed solution immediately changed from light blue to yellow, indicating that the chromogenic reaction was instantaneously completed.
About this article
Cite this article
Huang, X., Zhang, S., Zhang, P. et al. Autonomous indication of electrical degradation in polymers. Nat. Mater. (2023). https://doi.org/10.1038/s41563-023-01725-8