Polymer, Vol.46, No.7, 2331-2337, 2005
Surface fluctuations of polymer brushes probed by diffuse X-ray scattering
The diffuse scattering from the surfaces of melt and glassy polymer brushes has been studied systematically for the first time using polystyrene (PS) and poly(n-butylacrylate) (PnBA) brushes synthesized by free radical polymerization. The data show unambiguously that the diffuse scattering behavior varies systematically with brush thickness for both types of brushes. We attribute a cross-over in scattering with q(x) the in-plane scattering vector, to the presence of surface thermal fluctuations and their suppression for longer wavelengths, a phenomenon already reported for films of untethered chains. Long wavelength fluctuations are suppressed more strongly on the surface of a PS brush than on the surface of a film of untethered ('free') PS chains of comparable thickness, so that even in films of thickness, d, such that d/R-g> 5 clear evidence of the suppression of fluctuations can still be seen in the experimentally available range of q(x), Fluctuations are suppressed for q(x) less than a lower wavevector cut-off, q(Lc) which changes with film thickness, though much more weakly than for films of free chains. For values of d/R-g < 4, where R-g is the unperturbed radius of gyration of a comparable free chain, q(Lc) drops as d increases. For d/R-g> 4 q(Lc) begins to increase with brush thickness, in qualitative agreement with theory, indicative of a transition to a true 'brush' state in which stretching of the chains makes longer wavelength fluctuations at the surface unfavorable. Measurements with PnBA brushes having T-g substantially below room temperature confirm the trends mentioned above. Further, they give evidence that the value of q(Lc) is temperature insensitive above T-g. (c) 2005 Elsevier Ltd. All rights reserved.