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Title: ATR-FTIR spectroscopy and Raman microscopy studies of organosilane diffusion and hydrolysis in PVC films
Author: Eaton, Peter Jonathan
ISNI:       0000 0001 1701 6015
Awarding Body: Sheffield Hallam University
Current Institution: Sheffield Hallam University
Date of Award: 1998
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Organosilanes are widely used to bond organic materials such as polymers to inorganic materials in polymer composites. However, the mechanism of adhesion is poorly understood. One postulated mechanism is the interdiffusion of the silane and polymer, along with condensation of the silane to form an interpenetrating polymer network (IPN). The techniques of attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR) and Raman confocal microscopy have been used to study the diffusion, hydrolysis and condensation of three organosilanes in silicon / PVC / silane laminates. These processes are thought to contribute to the formation of the IPN, and hence to be vital for adhesion. The organosilanes studied were [3-(amino)propyl]trimethoxysilane, also known as A1110, [3-(phenylamino)propyl]trimethoxysilane, known as Y9669, and [3-(mercapto)propyl]triethoxysilane, known as A1891.ATR-FTIR was shown to be an excellent technique for studying the kinetics of silane diffusion through PVC films. It was shown that at room temperature, no diffusion through unplasticised PVC films occurred. At 70 °C, however, diffusion occurred readily for Y9669 and A1891. In plasticised PVC films, diffusion was observed for all three silanes at room temperature. It was shown that the diffusion occurred more quickly with higher plasticiser concentrations, and hence lower glass transition temperatures. The kinetics of diffusion was found to fit a dual mode sorption model. Hydrolysis of the silanes was also followed by infrared spectroscopy, and the kinetics of hydrolysis and condensation were shown to be highly dependent upon silane type, the concentration of water, and the presence of an acid catalyst. The hydrolysis of the silanes was found to slow their diffusion through both plasticised and unplasticised PVC films. It was shown that the presence of water in the films caused the hydrolysis of the silanes in situ. Raman depth profiles were measured of the films before, during and after diffusion. The spatial resolution was shown to be adversely affected by refraction at the air / PVC interface. It was shown that it is possible to deconvolve the confocal response of the microscope from the depth profiles, resulting in greater spatial resolution. Hydrolysis of the silanes was followed in solution by Raman spectroscopy, and it was found that each of the three silanes showed different rates of hydrolysis and condensation. It was shown that it was also possible to follow the kinetics of diffusion by Raman microscopy, and the results agreed well with those shown by ATR-FTIR spectroscopy.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Attenuated total reflectance; Fourier transform