1992 рік

X-ray diffraction profiles of highly oriented poly (p-phenylene vinylene) (PPV) samples have been acquired at temperatures ranging from 20 to 700 K. The resulting equatorial data have been analysed using a linked-atom-least-square structure factor refinement algorithm that allows for a more complete characterization of the polymer structure and of its temperature-dependent evolution. The resulting analysis identifies strong librational motions of the phenyl rings, a finding in agreement with recent n.m.r, studies. In additon, thin films of PPV are found to possess measurable equatorial anisotropy with [200-1 and [ 110-1 lattice planes preferentially oriented parallel to the film surface.

Детальніше...  

The dielectric permittivity, e', and loss, s", during the crosslinking or curing of diglycidyl ether of bisphenol-A with diamino diphenyl methane and various amounts of an elastomer, amine-terminated butadiene acrylonitrile (ATBN), have been measured from their sol to gel to glass-formation regions. As the elastomer-containing thermoset cures, both e' and e" initially decrease and then increase with time. e' finally decreases to a value near 3, but e" goes through a sharp minimum followed by a peak and ultimately decreases to about 10- 3. The initial increase in both e' and e" has been interpreted as an onset of liquid-liquid phase separation, which becomes nearly complete before the monotonic decrease in e' begins as a result of network formation in the curing thermoset. The time for the onset of phase separation is relatively insensitive to the amount of elastomer in the thermoset, and indicates the time of cure at which the network structure reaches a molecular weight when the elastomer becomes immiscible in it. Both the conductivity and permittivity increase with the increase in the elastomer content, with the consequence that the onset of gelation, which is marked by an approach of conductivity to near zero, is masked by the dipolar relaxation process. Corresponding analysis in the electrical modulus formalism confirms these observations and shows further that the conductivity follows a Maxwell relaxation. The e" of the cured thermoset plotted against temperature shows broad peaks and shoulders to these peaks. These are a combination of the sub-Tg relaxations in both the elastomer and the thermoset's network structure and the a-relaxation of the elastomer which appears at 240 K at 1 kHz. The permittivity and dielectric loss of the cured thermoset increase with an increase in the weight fraction of ATBN.

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Dynamic mechanical spectroscopy and transmission electron microscopy were utilized to investigate the properties of composites resulting from the formation of a cross-linked inorganic network via the polymerization of tetraethoxysilane (TEOS) in situ in a poly(methyl methacrylate) (PMMA) binder. The results show that the morphology and physical properties obtained are governed by sample preparation and by the catalyst used to polymerize the TEOS ; major differences are obtained when the polymerization of TEOS is performed in different pH regimes. The morphologies which develop are consistent with the known differences in gel structures obtained during the polymerization of TEOS in acidic or basic media. When TEOS is reacted under acidic conditions at elevated temperatures, small (< 100/k) SiO 2 domains which are well dispersed in the PMMA matrix result, producing a composite material with a high plateau modulus above the Tg of PMMA which extends to at least 250°C. The time-temperaturetransformation concept, proposed by Gillham for thermosetting organic polymers, is employed to explain some of these results.

Детальніше...  

The morphology of binary mixtures of low-molar-mass linear polyethylene (L2.5: M w = 2500, Mw/M . = 1.15) and higher-molar-mass branched polyethylenes, with 0.5 mol% of butyl branches (BB0.5) or 1.5 mol% of ethyl branches (BE1.5), has been studied by differential scanning calorimetry, polarized light microscopy and transmission electron microscopy. A progressive change from curved to straight lamellae and a strong decrease in average amorphous thickness is observed with increasing content of the linear polymer. Data obtained by model calculations of the average amorphous thickness assuming complete co-crystallization of the linear and branched polymers show good correspondence with the experimental data obtained for blends of L2.5 and BE 1.5 except for the blend consisting of 80% of L2.5 but a pronounced deviation for blends of L2.5 and BB0.5. For the majority of the blends of L2.5 and BEI.5 there is a good agreement between calorimetric crystallinity and crystallinity determined by transmission electron microscopy, which indicates co-crystallization of the components. There is, however, significant deviation between the two crystallinity values for all blends of L2.5 and BB0.5, and for the blend of L2.5 and BEI.5 with 80% of L2.5, which can be explained by partial segregation of L2.5.

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Mechanical and structural properties of extruded strands of blends of a liquid-crystalline copolyester (LCP), containing p-hydroxybenzoic acid and 2,6-hydroxynaphthoic acid, with poly(ethylene terephthalate) (PET) were investigated using tensile testing, X-ray diffraction measurements and scanning electron microscopic observation. The extruded strands of the blends consist of a crystalline and oriented LCP phase and an amorphous and unoriented PET phase. The tensile modulus increases almost linearly with increasing LCP content for the strands of the blends of more than 10% LCP content. The LCP component hardly contributes to the improvement of the mechanical tensile properties for the strands of the blends of less than 5% LCP content. The LCP phase tends to form fibrous structures, which orient almost parallel to the direction of extrusion in the blend strands. The fibrils of the LCP component become longer and thinner with increasing extension draw ratio of the blend strands. A relationship between the mechanical tensile properties and the morphology of the LCP phase in the blend strands was discussed.

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The formation of molecular composites by the in situ polymerization of tetraethoxysilane in various organic polymers has been studied. The results show that highly homogeneous, transparent composites can be formed for polymers such as poly (methyl methacrylate), poly (vinyl acetate), poly (vinyl pyrrolidone), and poly(N,N-dimethylacrylamide). These composites have improved mechanical properties and increased solvent resistance. Strong interactions between the SiO2 networks and these polymers were observed, and the data suggest hydrogen bonding between residual hydroxyls on the SiO2 and carbonyl groups on the polymer chains as the major source of these interactions.

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Small angle neutron scattering measurements of deuterated poly(methyl methacrylate) (d-PMMA) and poly(epichlorohydrin) (PECH) blends were used to elucidate differential scanning calorimetry (d.s.c.) measurements previously obtained on similar blends. Debye-Bueche type scattering from the d-PMMA/PECH blends indicated the presence of two phases with correlation lengths of several hundred /~ngstr6m. These lengths show a rough compositional correlation with the overall breadth of the glass transition temperature (Tg) events found by d.s.c. The original hypothesis that the broad Tg events were indicative of large scale concentration fluctuations in the blend appears to be incorrect; the broad T s events are more likely due to separate phases with differing Tgs within the polymer mixture. This interpretation is consistent with a more detailed d.s.c, investigation presented here

Детальніше...  

Thermal behaviour and miscibility of poly(3-hydroxybutyrate) (P(3HB))/poly(vinyl alcohol) (PVA) blend films prepared by casting have been analysed by d.s.c., n.m.r, and density measurements. Blends containing glycerine were also analysed by d.s.c. Melting temperature (Tin) of the P(3HB) crystalline phases decreased as PVA content increased, whereas T m of the PVA phase remained almost unchanged. The crystallinity of P(3HB) in the blends also decreased with increase of PVA content. These results indicated that the thermal behaviour of the P(3HB) phase was influenced by the existence of PVA. Glycerine had no effect on the thermal properties of the blend, except for depression of Tm of the PVA phase. Miscibility in the amorphous phase of the blend has been analysed by density measurement. If P(3HB) is completely immiscible with PVA, the crystallinity of PVA can be estimated from the crystallinity of P(3HB) and the density of the sample. However, the crystallinities of the PVA phase estimated for some blend samples were greater than unity. This behaviour can be accounted for when these blends are partially miscible in the amorphous phase. In order to investigate the miscibility in detail, we have determined the 1H spin-lattice relaxation times in the laboratory frame (T1) and in the rotating frame (Tip). Both Ta and Tap values for the P(3HB) and PVA phases tend to approach those of blend partners with increase of PVA content. That is to say, the increase of PVA content in a blend enhances the miscibility.

Детальніше...  

A novel class of macromonomer, in which the macromolecular part is a hyperbranched dendritic polyether prepared by the 'convergent-growth' approach, is synthesized and characterized. Free-radical copolymerization with styrene at various feed ratios gives a series of unique copolymers

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The application of solid state n.m.r, techniques to the characterization of ethene-propene copolymers is described. This study illustrates how the mechanical properties of a copolymer can be related to the polymer chemistry by the use of selective n.m.r, experiments. In particular, evidence for a rigid copolymer phase was sought to help identify the nature of the copolymer-polypropene matrix interface. No evidence for a rigid copolymer phase was in fact found, suggesting amorphous polypropene forms the interface. On the other hand there was clear evidence for crystallizable runs ofethene with a domain size in excess of 30 A or so.

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