Mesomorphism, molecular structure and dynamics of polydiethylsiloxane

The correlation between the phase behaviour of polydiethylsiloxane (PDES) and conformational and motional changes at the various disordering transitions has been investigated by nuclear magnetic resonance (n.m.r.), dielectric relaxation and shear experiments. Diffusive rotation of the chain segments around the long axis of the molecules is indicated by 29Si n.m.r. below the isotropization transition. The remarkably fluid character is explained in part by the coexistence of anisotropic and isotropic motional states of the -OSiEt2- segments, which indicate microscopic domain formation. The molecular motion in the α2- and β2-phases is restricted but still fast with respect to the 29Si n.m.r. timescale. Transmission electron micrographs show, besides chain-folded lamellae, also extended-chain lamellae. These differences in the morphologies can explain why the interconversion of α2-PDES into the thermodynamically more stable β2-polymorph is slow, in spite of the pronounced mobility of the polymer segments. Long-range reorganization processes have to be considered to allow the morphological changes observed by electron microscopy

Crystalline and disordered state of poly(dihexylsilylene) copolymers

A systematic comparison of random copolymers, derived from poly(dihexylsilylene) (PDHS) by incorporation of monomeric units with shorter unbranched alkyl side chains, has been carried out based on calorimetry, variable temperature UV spectroscopy, and 29Si MAS (magic angle spinning) solid state NMR investigations. Also, hexylmethylsilylene units and branched monomers have been copolymerized. Up to 10% comonomer with shorter linear side chains (i. e., pentyl to propyl) could be incorporated into PDHS without impeding the all-trans order of the crystalline phase. In this case, the UV absorption maximum of the crystalline low-temperature phase was affected only slightly according to the length and fraction of the comonomer side chains. A less ordered crystal structure (λmax = 345-355 nm) was observed when the content of comonomers with shorter side chains was about 20%. Yet, all these materials form conformationally disordered mesophases. A clear disordering transition and corresponding thermochromism was not observed any more when 50% of propyl side chains were incorporated. The order of the crystalline and the mesophase is also strongly perturbed if only a small fraction (4%) of the side chains are branched at C2

Spinodal phase separation in semi-interpenetrating polymer networks - polystyrene-cross-polymethacrylate

Morphology control in semi-interpenetrating polymer networks has been achieved by means of a two-step process, separating morphology formation and polymerization/crosslinking. Phase textures formed during spinodal liquid/liquid demixing of a solution of atactic polystyrene in methacrylate monomers were arrested by thermoreversible gelation of the polymer-rich phase as this phase passed its glass transition temperature. The phase separated structure was permanently stabilized by low-temperature crosslinking ultraviolet (UV) polymerization of the methacrylate monomer, and studied by transmission electron microscopy. Thus, it was directly observed how the initial demixing process depended on the initial viscosity of the polymer solution and the mode of quenching. Arrest of the earliest stage of spinodal demixing resulted in separated domains of 0.05-0.08 m thickness, which were separated by a distance of the spinodal wavelength . A cocontinuous network only developed in a relatively late stage of demixing

Synthesis of poly(vinyl ether)s with perfluoroalkyl pendant groups

2-Perfluoro(alkyl)ethyl vinyl ethers, F(CF2)nCH2CH2OCHCH2, (n = 6 or 8), were synthesized and polymerized by means of cationic initiators (HI/ZnI2 and CF3SO3H/(CH3)2S). The perfluorohexyl-substituted poly(vinyl ether) is completely amorphous. The polymer with perfluorooctyl segments shows side chain crystallization with a disordering transition. For the corresponding perfluorooctyl monomer a liquid-crystalline phase was observed before melting. Copolymerization experiments of the flurocarbon-segmented monomers with a vinyl ether containing a cyanobiphenyl group in the side chain did not give homogeneous copolymers. This is attributed to the slower rate of polymerization of the fluorinated vinyl ethers as compared with the liquid-crystalline comonomer

Influence of the bulk and surface morphology on adhesion of polystyrene-inter-poly-cross-2-ethylhexyl-methacrylate films and particles

The adhesion behavior of semi-interpenetrating polymer networks (semi-IPNs) of linear polystyrene (PS) in crosslinked poly-2-ethylhexylmethacrylate (EHMA) was studied by variation of the bulk and surface morphology, i.e., domain size, continuity, and concentration in the domains. Semi-IPNs were prepared by liquid-liquid demixing upon cooling of a homogeneous solution of PS in methacrylate monomer, followed by gelation of the PS-rich phase and UV polymerization of the methacrylate resin. Welding of films allowed the preparation of larger objects provided that (1) the samples were phase separated to a high degree and contained domains with a high PS concentration (>90%) and (2) polystyrene was present at the interface. For semi-IPN films, a linear dependence of the adhesion strength on the (crack healing time)1/4 was obtained. Based on these considerations, a process was developed to obtain melt-processable semi-IPN particles, by quenching droplets of the polymer solution into a cold liquid. These particles obtained a PS-rich skin layer and showed good adhesion after blending with a thermoplast

Contact Angle Hysteresis on Superhydrophobic Stripes

We study experimentally and discuss quantitatively the contact angle hysteresis on striped superhydrophobic surfaces as a function of a solid fraction, $\phi_S$. It is shown that the receding regime is determined by a longitudinal sliding motion the deformed contact line. Despite an anisotropy of the texture the receding contact angle remains isotropic, i.e. is practically the same in the longitudinal and transverse directions. The cosine of the receding angle grows nonlinearly with $\phi_S$, in contrast to predictions of the Cassie equation. To interpret this we develop a simple theoretical model, which shows that the value of the receding angle depends both on weak defects at smooth solid areas and on the elastic energy of strong defects at the borders of stripes, which scales as $\phi_S^2 \ln \phi_S$. The advancing contact angle was found to be anisotropic, except as in a dilute regime, and its value is determined by the rolling motion of the drop. The cosine of the longitudinal advancing angle depends linearly on $\phi_S$, but a satisfactory fit to the data can only be provided if we generalize the Cassie equation to account for weak defects. The cosine of the transverse advancing angle is much smaller and is maximized at $\phi_S\simeq 0.5$. An explanation of its value can be obtained if we invoke an additional energy due to strong defects in this direction, which is shown to be proportional to $\phi_S^2$. Finally, the contact angle hysteresis is found to be quite large and generally anisotropic, but it becomes isotropic when $\phi_S\leq 0.2$.Comment: 17 pages, 8 figure