In numerous applications in microfluidics, cell growth, soft lithography, and molecular imprinting, the surface of poly (dimethylsiloxane) (PDMS) is modified from a hydrophobic methyl-terminated surface to a hydrophilic hydroxylterminated
surface. In this study, we investigated molecular structural and orientational changes at the PDMS-air interface in response to three commonly used surface modification processes: exposure to long-wavelength ultraviolet light (UV), exposure to short-wavelength UV that generates ozone ( UVO), and exposure to oxygen plasma (OP). The surfaces of two PDMS compositions (10: 1 and 4: 1 of base polymer / curing agent) were probed during modification, using monolayer-sensitive IR + visible sum frequency generation (SFG ) vibrational spectroscopy, with two different polarization combinations. During PDMS surface modification, the peak intensities of CH3 side groups and CH2 cross-link groups decreased, while peak intensities of Si-OH groups increased. There was no significant change in
the average orientation of the CH3 groups on the PDMS surface during modification. The concentration of CH3 groups on the surface decreased exponentially with time, for all three UV, UVO, and OP modification processes, with first order kinetics and time constants of approximately 160, 66, and 0.3 min, respectively. At steady state, residual CH3 groups were detected at the PDMS surface for UV and UVO treatments; however, there were negligible CH3 groups detected after OP modification.
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