The effect of molecular weight on the solvent-induced self-assembly of mixed poly(methyl methacrylate) (PMMA)/polystyrene (PS) brushes on silicon wafers was studied. For a series of mixed brushes with a fixed PMMA M(n) and systematically changed PS M(n), a transition in water advancing contact angle (theta(a)) from 74 degrees, the value for a flat PMMA surface, to 91 degrees, the value for a flat PS film, was observed with increasing PS M(n) after treatment with CHCl(3). Atomic force microscopy studies showed smooth surfaces for all samples. While no significant changes in surface morphologies were observed after treatment with cyclohexane, a selective solvent for PS, contact angle and XPS studies indicated that the mixed brushes with a PS M(n) slightly smaller than that of PMMA underwent self-reorganization, exhibiting a different theta(a). Intriguing surface morphologies composed of relatively ordered nanoscale domains were found from mixed brushes with PS M(n) slightly smaller than or similar to that of PMMA after treatment with acetic acid, a selective solvent for PMMA. The nanodomains are speculated to be of a micellar structure, with PS chains forming a core shielded by PMMA chains.
We have studied the scaling of controlled nonlinear buckling processes in materials with dimensions in the molecular range (i.e., approximately 1 nm) through experimental and theoretical studies of buckling in individual single-wall carbon nanotubes on substrates of poly(dimethylsiloxane). The results show not only the ability to create and manipulate patterns of buckling at these molecular scales, but also, that analytical continuum mechanics theory can explain, quantitatively, all measurable aspects of this system. Inverse calculation applied to measurements of diameter-dependent buckling wavelengths yields accurate values of the Young's moduli of individual SWNTs. As an example of the value of this system beyond its use in this type of molecular scale metrology, we implement parallel arrays of buckled SWNTs as a class of mechanically stretchable conductor.
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