Dow Performance Silicones, Auburn, Michigan 48611, United States.
Core R&D, The Dow Chemical Company, Midland, Michigan 48674, United States.
Langmuir. 2022 Mar 1;38(8):2590-2600. doi: 10.1021/acs.langmuir.1c03218. Epub 2022 Feb 15.
Covalent bonding is one of the most robust forms of intramolecular interaction between adhesives and substrates. In contrast to most noncovalent interactions, covalent bonds can significantly enhance both the interfacial strength and durability. To utilize the advantages of covalent bonding, specific chemical reactions are designed to occur at interfaces. However, interfacial reactions are difficult to probe in situ, particularly at the buried interfaces found in well-bonded adhesive joints. In this work, sum frequency generational (SFG) vibrational spectroscopy was used to directly examine and analyze the interfacial chemical reactions and related molecular changes at buried nylon/silicone elastomer interfaces. For self-priming elastomeric silicone adhesives, silane coupling agents have been extensively used as adhesion promoters. Here with SFG, the interfacial chemical reactions between nylon and two alkoxysilane adhesion promoters with varied functionalities (maleic anhydride (MAH) and epoxy) formulated into the silicone were observed and investigated. Evidence of reactions between the organofunctional group of each silane and reactive groups on the polyamide was found at the buried interface between the cured silicone elastomer and nylon. The adhesion strength at the nylon/cured silicone interfaces was substantially enhanced with both silane additives. SFG results elucidated the mechanisms of organo-silane adhesion promotion for silicone at the molecular level. The ability to probe and analyze detailed interfacial reactions at buried nylon/silicone interfaces demonstrated that SFG is a powerful analytical technique to aid the design and optimization of materials with desired interfacial properties.
共价键是胶粘剂和基质之间最稳定的分子内相互作用形式之一。与大多数非共价相互作用相比,共价键可以显著提高界面强度和耐久性。为了利用共价键的优势,设计了特定的化学反应来发生在界面上。然而,界面反应很难进行原位探测,特别是在粘结良好的胶粘剂接头中发现的埋入界面。在这项工作中,和频产生(SFG)振动光谱被用来直接检查和分析埋入尼龙/硅橡胶界面的界面化学反应和相关的分子变化。对于自固化弹性硅橡胶胶粘剂,硅烷偶联剂已广泛用作附着力促进剂。在这里,利用 SFG,观察和研究了两种烷氧基硅烷附着力促进剂(马来酸酐(MAH)和环氧)与硅酮的界面化学反应,这些附着力促进剂具有不同的官能团。在固化硅橡胶和尼龙之间的埋入界面处发现了每个硅烷的有机官能团与聚酰胺的反应性基团之间的反应证据。两种硅烷添加剂都显著提高了尼龙/固化硅橡胶界面的附着力。SFG 结果阐明了硅烷在分子水平上促进硅酮附着力的机制。在埋入尼龙/硅橡胶界面探测和分析详细界面反应的能力表明,SFG 是一种强大的分析技术,可以帮助设计和优化具有所需界面性能的材料。