{"title":"Enhancing Self-Healing and Mechanical Robustness through Aluminum Acetylacetonate-Driven Metal–Ligand Coordination for Skin-Inspired Sensing","authors":"Yi-An Chen, Rou-Han Lai, Wan-Chi Lin, Hung-Yi Huang, Szu-Jou Chen, Chun-Ming Yeh, Hsiang-Ling Huang, Mohamed M. Elsenety, Chi-Chang Hu, Chi-Hua Yu* and Ho-Hsiu Chou*, ","doi":"10.1021/acsapm.4c00545","DOIUrl":null,"url":null,"abstract":"<p >In the field of advanced materials science, the application of aluminum ions as dynamic metal salt cross-linkers in self-healing polymers has been less prevalent compared to transition or rare earth metal ions, attributable to the relatively modest self-healing and mechanical properties of aluminum ions. Our study introduces an alternative strategy by combining aluminum ions with acetylacetonates (acac<sup>–</sup>) as counteranions and integrating a pyridine-capped polyurethane-urea polymer backbone (PTD) and phosphorus-rich small molecules (3N2AP) to develop a composition, Al<sub>ac</sub>-3N2AP-PTD. This formulation exhibits phosphorus-based flame retardancy, improved self-healing capabilities, and enhanced mechanical properties. It demonstrates superior performance compared to existing aluminum-based systems and is competitive with traditional transition metal ion-based systems. To elucidate the underlying mechanisms of these enhancements, molecular dynamics (MD) simulations were conducted to examine the coordination dynamics and the effects of counteranions within the polymer network. The simulation results indicated longer coordination bond lengths in the system incorporating acac<sup>–</sup>, supporting its efficacy and clarifying the mechanisms contributing to the increased self-healing capabilities and mechanical robustness. In our development of a stretchable, self-healing, and conductive composite, we fabricated PPy-Al<sub>ac-0.25</sub>-3N2AP-PTD via an electrochemical deposition process. This material acts as an electronic skin (e-skin) strain sensor, exhibiting strain sensitivity while preserving its inherent mechanical and self-healing properties, thus differentiating it from traditional doping methods. The use of acac<sup>–</sup> as dynamic counteranions in metal-coordinated polymers represents an advancement in material performance, offering substantial potential for the development of electronic materials.</p>","PeriodicalId":7,"journal":{"name":"ACS Applied Polymer Materials","volume":null,"pages":null},"PeriodicalIF":4.4000,"publicationDate":"2024-06-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/epdf/10.1021/acsapm.4c00545","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"ACS Applied Polymer Materials","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acsapm.4c00545","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"MATERIALS SCIENCE, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
In the field of advanced materials science, the application of aluminum ions as dynamic metal salt cross-linkers in self-healing polymers has been less prevalent compared to transition or rare earth metal ions, attributable to the relatively modest self-healing and mechanical properties of aluminum ions. Our study introduces an alternative strategy by combining aluminum ions with acetylacetonates (acac–) as counteranions and integrating a pyridine-capped polyurethane-urea polymer backbone (PTD) and phosphorus-rich small molecules (3N2AP) to develop a composition, Alac-3N2AP-PTD. This formulation exhibits phosphorus-based flame retardancy, improved self-healing capabilities, and enhanced mechanical properties. It demonstrates superior performance compared to existing aluminum-based systems and is competitive with traditional transition metal ion-based systems. To elucidate the underlying mechanisms of these enhancements, molecular dynamics (MD) simulations were conducted to examine the coordination dynamics and the effects of counteranions within the polymer network. The simulation results indicated longer coordination bond lengths in the system incorporating acac–, supporting its efficacy and clarifying the mechanisms contributing to the increased self-healing capabilities and mechanical robustness. In our development of a stretchable, self-healing, and conductive composite, we fabricated PPy-Alac-0.25-3N2AP-PTD via an electrochemical deposition process. This material acts as an electronic skin (e-skin) strain sensor, exhibiting strain sensitivity while preserving its inherent mechanical and self-healing properties, thus differentiating it from traditional doping methods. The use of acac– as dynamic counteranions in metal-coordinated polymers represents an advancement in material performance, offering substantial potential for the development of electronic materials.
期刊介绍:
ACS Applied Polymer Materials is an interdisciplinary journal publishing original research covering all aspects of engineering, chemistry, physics, and biology relevant to applications of polymers.
The journal is devoted to reports of new and original experimental and theoretical research of an applied nature that integrates fundamental knowledge in the areas of materials, engineering, physics, bioscience, polymer science and chemistry into important polymer applications. The journal is specifically interested in work that addresses relationships among structure, processing, morphology, chemistry, properties, and function as well as work that provide insights into mechanisms critical to the performance of the polymer for applications.