An Ying, Hu Pei, Li Kaitao, Kang Yu, Hu Gang, Tian Rui, Lu Chao, Duan Xue
State Key Laboratory of Chemical Resource Engineering, Beijing University of Chemical Technology, Beijing 100029, China.
Quzhou Institute for Innovation in Resource Chemical Engineering, Quzhou 324000, China.
ACS Cent Sci. 2025 Apr 23;11(5):694-703. doi: 10.1021/acscentsci.5c00067. eCollection 2025 May 28.
Polymer coatings are currently being employed for preservation of metal artifacts. However, there is insufficient awareness that inevitable aging of polymer coatings is bound to damage metal artifacts due to the lack of a direct and sensitive methodology to study the aging behaviors of polymers coated on the artifacts. Herein, we have developed an in situ and three-dimensional strategy to visualize the early stage aging behaviors of polymers coated on metal artifacts by lighting carboxyl groups generated from polymer aging. It is disclosed that polymer aging occurred simultaneously at the surface and the interface with metal artifacts, generating carboxyl groups and hydroxyl radicals to induce the corrosion and oxidation of metallic artifacts. In turn, the generated metallic ions could further aggravate the aging of polymer coatings, manifested as the larger volume of the aged sites at the interface with metal artifacts in comparison with that at the surface of polymer coatings. Such a circular reaction is validated using real metal artifact samples. These findings raised a timely alarm for the conservation ability and potential threat of polymer coatings on metal artifacts. It is anticipated that the proposed strategy could provide solid supports for the implementation of advanced conservation strategies for metal artifacts.
聚合物涂层目前正被用于金属文物的保护。然而，由于缺乏一种直接且灵敏的方法来研究涂覆在文物上的聚合物的老化行为，人们对聚合物涂层不可避免的老化必然会损坏金属文物这一点认识不足。在此，我们开发了一种原位三维策略，通过照亮聚合物老化产生的羧基来可视化涂覆在金属文物上的聚合物的早期老化行为。结果表明，聚合物老化在与金属文物的表面和界面处同时发生，产生羧基和羟基自由基，从而引发金属文物的腐蚀和氧化。反过来，生成的金属离子会进一步加剧聚合物涂层的老化，表现为与聚合物涂层表面相比，与金属文物界面处老化部位的体积更大。使用真实的金属文物样本验证了这种循环反应。这些发现及时为聚合物涂层对金属文物的保护能力和潜在威胁敲响了警钟。预计所提出的策略可为实施先进的金属文物保护策略提供有力支持。
