Understanding molecular structures of silanes at buried polymer interfaces using sum frequency generation vibrational spectroscopy and relating interfacial structures to polymer adhesion

• Published in: Journal of colloid and interface science Vol. 331; no. 2; pp. 408 - 416
• Main Authors: Vázquez, Anne V., Shephard, Nick E., Steinecker, Cheryl L., Ahn, Dongchan, Spanninga, Sarah, Chen, Zhan
• Format: Journal Article
• Language: English
• Published: United States Elsevier Inc 15.03.2009
• Subjects: Interfacial structure; PDMS; PET; Polymer adhesion; Silane coupling agents; Sum frequency generation; Sum frequency generation; Interfacial structure; Polymer adhesion; Silane coupling agents; PET; PDMS
• ISSN: 0021-9797; 1095-7103
• DOI: 10.1016/j.jcis.2008.11.065

The use of silane adhesion promoters to improve adhesion of elastomeric materials to polymers has become increasingly common in many industrial applications. However, little is understood about the molecular-level mechanisms of how adhesion promoters enhance adhesion. Here, sum frequency generation (SFG) vibrational spectroscopy was used to probe the buried interface between poly(ethylene terephthalate) (PET) and (3-glycidoxypropyl)trimethoxysilane ( γ-GPS), and the interface between PET and a mixture of γ-GPS and a methylvinylsiloxanol (MVS), a known adhesion-promoting mixture. Furthermore, the interfaces between PET and uncured silicone with incorporated silane or silane mixture and the interfaces between PET and cured silicone with incorporated silane or silane mixture were studied. The γ-GPS methoxy groups were found to order at the polymer interface and the presence of MVS increased the interfacial segregation and/or order of γ-GPS. For comparison, two other silanes, N-octadecyltrimethoxysilane (OTMS) and (tridecafluoro-1,1,2,2-tetrahydroctyl)trimethoxysilane (TDFTMS), as well as their mixtures with MVS were also studied at the various interfaces, and were found to exhibit different interfacial behaviors than γ-GPS and the known silane adhesion-promoting mixture of γ-GPS and MVS. Further, X-ray photoelectron spectroscopy (XPS) was used to investigate the exposed PET surfaces resulting from peeling the PET/cured silicone elastomer with TDFTMS and with the TDFTMS/MVS mixture interfaces, and it was shown that the fluorinated silane does segregate to the polymer interface. When correlated to adhesion testing results, it is inferred that segregation and ordering of the silane methoxy groups at the polymer/silane and polymer/silicone elastomer interfaces is crucial for adhesion promotion in this system. SFG spectra have been successfully collected from the buried PET/cured PDMS (with silane or silane mixture) interface. Only γ-GPS molecules are ordered at this buried interface. No SFG signal was detected from two other types of silane molecules.