Determination of the Molecular Structure of Interphases Between Epoxy/4,4′-Diaminodiphenylsulfone Adhesives and Silver Substrates Using SERS and XPS

Abstract

Abstract The molecular structure of interphases formed by curing an epoxy/4,4′-diaminodiphenylsulfone (DADPS) adhesive against rough silver substrates was determined using surface-enhanced Raman scattering (SERS) and x-ray photoelectron spectroscopy (XPS). SERS spectra obtained from the adhesive deposited onto silver island films were very similar to SERS spectra obtained from the DADPS curing agent spun onto silver island films, indicating that DADPS in the adhesive system segregated to the interphase and was preferentially adsorbed onto the silver substrate. Differences in the relative intensity of several bands in the normal Raman and SERS spectra of DADPS were observed. For example, the band near 1603 cm−1 was stronger in SERS spectra of DADPS than in normal Raman spectra. The band near 1150 cm−1 was weaker in SERS spectra of DADPS than in normal Raman spectra. These results implied that DADPS was adsorbed through one of the NH groups with an end-on conformation. Consistent results were also obtained from XPS spectra. C(ls) spectra of the adhesive and silver fracture surfaces of specimens prepared by curing the adhesive against silver substrates were more similar to the C(ls) spectra of DADPS than to those of the bulk adhesive. These results confirmed the preferential adsorption of DADPS onto the silver substrate from the adhesive system. The similarity of the C(ls) spectra obtained from adhesive and silver fracture surfaces indicated that a thin DADPS-rich interphase was formed between the bulk adhesive and the silver substrate and that the locus of failure was partially within this layer. However, less nitrogen and sulfur were detected on the silver fracture surface than on the adhesive fracture surface. A large amount of silver was observed on the substrate fracture surface and a trace was found on the adhesive fracture surface. These results indicated that failure of the adhesive joints was within the interphase but near the silver substrate. No evidence of chemisorption of DADPS onto the substrate was observed.