Polystyrene blend with poly , surface

The materials analyzed were blends of polystyrene (PS) and poly(vinyl methyl ether) (PVME) in various ratios. The two components are miscible in all proportions at ambient temperature. The photooxidation mechanisms of the homo-polymers PS and PVME have been studied previously [4,7,8]. PVME has been shown to be much more sensitive to oxidation than PS and the rate of photooxidation of PVME was found to be approximately 10 times higher than that of PS. The photoproducts formed were identified by spectroscopy combined with chemical and physical treatments. The rate of oxidation of each component in the blend has been compared with the oxidation rate of the homopolymers studied separately. Because photooxidative aging induces modifications of the surface aspect of the material, the spectroscopic analysis of the photochemical behavior of the blend has been completed by an analysis of the surface of the samples by atomic force microscopy (AFM). A tentative correlation between the evolution of the roughness measured by AFM and the chemical changes occurring in the PVME-PS samples throughout irradiation is presented. 

The membrane surfaces have also been grafted or coated with polyacrylamide, poly(acrylic acid) [70, 71], poly(vinyl alcohol) and cellulose derivatives [72]. Another possibility for improving the membrane properties is the use of polymer blends. Blends of PVDF/PVP [73, 74], PVDF/poly(ethylene glycol) (PEG) [75], PVDF/sulfonated polystyrene [76], PVDF/poly(vinyl acetate) [77] and PVDF/ poly(methyl methacrylate) [78] have been used in the preparation of micropor-ous membranes. 

Hyperbranched and comb polymers have also been used as surface active additive. Ariura et al. synthesized by combination of anionic and cationic polymerization a monodispersed hyperbranched polystyrene [73]. The authors proved by combination of DSIMS and neutron reflectivity the preferential surface enrichment of the branched protonated macromolecules when blended with its deuterated linear polystyrene counterparts with the same molar mass. Other systems involving the segregation of the branched macromolecules in binary blends were demonstrated such as in polyamide [74] or poly (methylmethacrylate) [75]. 

The use of more complex systems such as ternary blends allows the functionalization of the surfaces with varies chemical functionalities. For instance a PS matrix was mixed with two block copolymers, a hydrophobic (PS-b-P5FS) and an amphiphilic polystyrene-b-poly[poly(ethylene glycol) methyl ether methacrylate] (PS-6-P(PEGMA)) copolymer [96], The chemical distribution of the resultant surface pattern implies an enrichment of the holes in the amphiphilic copolymer with an external surface mainly functionalized in the fluorinated copolymer with low surface energy (Scheme lO.lg). Other ternary blends combining incompatible copolymers and homopolymers have been reported leading to more complex topographies and chemical distributions [148],... 

Surface-directed spinodal decomposition was first observed in an isotopic polymer blend (Jones et al. 1991) thin films of a mixture of poly(ethylene-propylene) and its deuterated analogue were annealed below the upper critical solution temperature and the depth profiles measured using forward recoil spectrometry, to reveal oscillatory profiles similar to those sketched in figure 5.30. Similar results have now been obtained for a number of other polymer blends, including polystyrene with partially brominated polyst)u-ene (Bruder and Brenn 1992), polystyrene with poly(a-methyl styrene) (Geoghegan et al. 1995) and polystyrene with tetramethylbisphenol-A polycarbonate (Kim et al. 1994), suggesting that the phenomenon is rather general. 

Poly(dimethylsiloxane) (PDMS) is a well-known hydrophobic polymer with higher repellency for water than PS crosslinked siUcone elastomers (WCA = 112° for a smooth film) are commonly used for fabricating microfluidic devices. But forming solid fibers comprised solely of linear PDMS is not possible, due to its low glass transition temperature. Instead of using linear homopolymer PDMS, Ma et al. [21] electrospun fibers of poly(styrene-b-dimethylsiloxane) block copolymers blended with 23.4 wt% homopolymer polystyrene (PS-PDMS/PS) from a solution in a mixed solvent of THF and DMF. The resultant fiber mat, with fiber diameters in the range of 150-400 nm, exhibited a WCA of 163° and a hysteresis of 15°. An illustration of water droplets beaded up on such a mat is provided in Fig. 3. A PS mat of similar fiber diameter and porosity exhibited a WCA of only 138°. The difference was attributed to the lower surface tension of the PDMS component, combined with its spontaneous segregation to the fiber surface. X-ray photoelec-... 

Thin films of blended deuterated polystyrene (dPS) and poly(vinyl methyl ether) (PVME) were imaged as a fimction of the dPS PVME ratio. Near the critical composition of 35% dPS, an imdulating, spinodal-like structure was observed, whereas for compositions away from the critical mixture ratio, regular mounds or holes (< dPS < < crit and < dPS > (pent, respectively) were present. These variations were assigned to surface tension effects (120). Blends of PBD, SBR, isobutylene-brominated p-methylstyrene, PP, PE, natural rubber, and isoprene-styrene-isoprene block rubbers were imaged (Fig. 18). Stiff, styrenic phases and rubbery core-shell phases were evident as the authors utilized force-modulated afm to determine detailed microstructure of blends, including those with fillers such as carbon-black and silica (121). 

The characterization of surface structure for miscible blends is a more formidable task, requiring techniques that are sensitive to the composition of the blend within several nanometers of the surface. X-ray photoelectron spectroscopy (xps) provided the first direct and quantitative evaluation of surface composition and surface composition gradients for miscible polymer blends of poly(vinyl methyl ether) (PVME) and polystyrene (PS) (22,23). Since that time, the situation has changed dramatically with the advance of theory and the application of exciting new experimental techniques to this problem. In addition to xps and pendant drop tensiometry (22,23), forward recoil spectroscopy (28), neutron (29) and x-ray reflectivity (30), secondary ion mass spectroscopy (either dynamic or time-of-flight-static) (31,32), and attenuated total reflectance Fourier transform infrared spectroscopy (33-35), have been applied successfully to study surface segregation. The advent of these new tools has enabled a multitechnique experimental approach toward careful examination of the validity of current surface segregation theories (36-39). 

For example, blends and semi-IPN of polypyrrole and EPDM rubber, prepared by calendering, absorb 85% of microwave radiation in the 10-13 GHz range [167]. Surface deposition of polypyrrole onto poly-(vinylchloride) produced composites with microwave absorption properties in the 0.1-20 GHz frequency range [168]. The same authors also studied the shielding characteristics of blends of polyaniline and poly(3-octylthiophene) with polystyrene and with the copolymer of ethylene and vinyl acetate. For defense purposes, however, a larger frequency range should be covered, but this only encourages continuation of the research. 

Figure 26.13 Surface segregation of cyclic poly(oxyethylene) (1.5kg/mol) from its blend with polystyrene by annealing in a high-humidity environment. Images of water drops are shown with then-contact angles above the as-spun-cast film (left) and after annealing (right).

Figure 22 offers another example of the interfacial gradient, specifically showing that the volume fraction of chemically end-grafted polystyrene chains varies as a function of distance from a surface for its blends with different matrix polymers. Polybutadiene (PBD) and poly(methyhnethacrylate) (PMMA) are immiscible with polystyrene (PS) in the bulk PS is chemically identical with the grafted chains, while poly(vinyl methylether) (PVME) and a blend of polyCphenylene oxide) and PS (PPO/PS) are miscible with polystyrene in the bulk. The chemically grafted material concentrates at the surface and does not extend any further than 350 A into the bulk. 

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