Important aspects of adhesion occur at interfaces, including structures that may be different from those in the bulk materials. However, probing the orientation of molecules in functional adhesives poses a significant challenge because adhesive molecules are always located at a buried interface. The limited penetration depth of surface-specific analysis prohibits the study of buried interfaces using those techniques. The large quantity of bulk molecules relative to the adhesive molecules interacting at the interface results in the bulk signal swamping out adhesive signal in bulk analysis techniques. An interface-specific technique is required to study functional adhesives. One such technique that has shown promise in recent years is Vibrational sum frequency generation (VSFG) spectroscopy. This technique is useful for studying interactions that occur at surfaces and interfaces because it selectively probes regions of broken inversion symmetry. Despite the ability of VSFG to isolate signal from a buried interface, a non-resonant signal that is produced simultaneously with the resonant signal corrupts the vibrational data of interest and greatly impedes reliable analysis of VSFG spectra. Over the last several years, researchers have experimentally removed non-resonant signal by delaying the upconverting pulse with respect to the initial excitation. Obtaining reliable results from VSFG data depends upon complete removal of non-resonant signal. However, complete removal of non-resonant signal presents a challenge because it can be present in spectra even when the indicators of non-resonant signal are absent. By taking advantage of polarization selection rules for VSFG and the differing symmetry of an azimuthally isotropic film and an azimuthally non-isotropic substrate, spectra containing non-resonant signal can be easily identified. These and other advances in VSFG methodology have enabled the study of surface and interfacial systems of interest. In a study of the effects of plasma treatment on polystyrene thin films, plasma exposure was found to affect not only the free surface but also portions of the sub-surface polymer, challenging previous assumptions that plasma effects are constrained to the free surfaces of materials. The next step is to use VSFG to study functional adhesives under known amounts of applied stress. An apparatus is in place to simultaneously collect VSFG spectra during mechanical testing of a functional adhesive, and in preliminary studies, an increase in VSFG non-resonant signal has been observed when a pulling force is applied to the adhesive bond.



College and Department

Physical and Mathematical Sciences; Chemistry and Biochemistry



Date Submitted


Document Type





adhesion, plasma treatment, surface spectroscopy, sum-frequency generation spectroscopy, nonlinear spectroscopy, polymers, strength testing, spin-coating, signal processing