1999 рік

This work was concerned with how the crystallization temperature of a thermotropic liquid crystalline polymer (TLCP) was lowered when blended with a second TLCP, with both TLCPs believed to be composed of various ratios of terephthalic acid, 4-hydroxybenzoic acid (HBA), hydroquinone, and hydroquinone derivatives. Specifically, HX6000, with a melting temperature of 332°C, was melt blended with HX8000, with a melting temperature of 272°C. Measuring the complex viscosities of the melt blends as they were cooled showed that a linear relationship between composition and solidification temperature existed. Studying the blends using differential scanning calorimetry (DSC) demonstrated that the crystallization temperature was lowered by addition of HX8000, as well as by using faster cooling rates. Dynamic mechanical analysis revealed that the storage and loss moduli decreased with the addition of HX8000 and the moduli declined sharply at lower temperatures relative to neat HX6000. Additional testing was performed to help understand this behavior, with the results suggesting that the TLCPs reacted with one another when the test samples were injection molded.

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Static and dynamic light scattering from p-conjugated poly(4BCMU) in toluene solutions were measured at 353 K (yellow phase) and 323 K (red phase) to evaluate the hydrodynamic radius Rh and the fractal dimension D. It was suggested that poly(4BCMU) may exist not as an isolated worm-like chain but as a weakly interacted cluster-like domain in the yellow phase. The domain was considered to be elaborated by inter-molecular hydrogen bondings formed newly through a thermal break of intra-molecular hydrogen bondings between side chains along a main chain. On the other hand, the increases in Rh and D have revealed that poly(4BCMU) chains aggregated gradually in the red phase, after taking a single extended rod-like conformation. The subsequent aggregation seemed to be promoted not only by lowering a solvent quality but also by increasing the effective concentration, accompanied by the conformational transition.

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The development of a novel method for the processing of nascent UHMWPE leading to high ductility and strength extrudates is described. The addition of a surface wetting agent, in this case 10 wt% mineral oil, followed by compaction and extrusion below the melting point leads to the formation of a self-blend of melted and recrystallized UHMWPE and unmelted UHMWPE powders. The presence of the self-blend, indicated by the d.s.c. results, enhances the cohesion between powder particles which leads to an extrudate with more uniform mechanical properties, as demonstrated in Part 2 of this two-part paper. This partial melting during compaction and extrusion is aided by the mineral oil, which also helps to enhance the ductility of the extrudates. The d.s.c. results also provide evidence for chain alignment. The mineral oil acts as a processing aid by allowing the blend to be processed at temperatures at least 10°C higher than are usual for the pure nascent powder. It also acts as a heat transfer agent and solvent for the UHMWPE.

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Amorphous films of poly(ethylene 2,6-naphthalate) (PEN) were drawn isothermally at 145°C up to the desired draw ratios mainly to study structure formation during uniaxial drawing by differential scanning calorimetry and to characterise the shrinkage behaviour of the drawn films with or without heat treatment. During drawing, a rigid phase structure is induced and the amount of induced rigid phase structure is linearly related to the square root of the extra first strain invariant. The stress–strain curves are characterised by a necking behaviour and the end of the yielding or necking is reached when the amount of induced rigid phase is attaining 50%. The stretching behaviour of PEN is characterised more by the strain induced rigid phase formation (SIRP) than by the stress or strain induced crystallisation. The shrinkage behaviour is characterised by two regimes. A first one for draw ratios below the necking behaviour where the films shrink back to their original length for temperatures between 100 and 140°C with a mid-value of 120°C, corresponding to the glass transition temperature of the amorphous phase. The second regime, for draw ratios above the necking behaviour is characterised by a shrinkage behaviour for temperatures between 120 and 160°C, with a mid-value of 140°C, corresponding to the transition temperature of the induced rigid phase structure. In this regime, the films never shrink back below the draw ratio after necking and a linear relation between the initial draw ratio and the final draw ratio after shrinkage is obtained. A heat treatment of the oriented films with fixed ends stabilises the induced structures and the shrinkage of these heat-set films is zero for temperatures up to the heat-setting temperature.

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Blends of nylon 6 and polyethylene were investigated over a range of compositions. The polyethylenes used were grafted with maleic anhydride and, thus, have the potential to react with the amine end groups of nylon 6 during melt processing. This study focuses on the effects of the concentration, viscosity and functionality of the maleated polyethylenes (PE-g-MA) on the rheological, morphological, and mechanical properties of nylon 6/PE-g-MA blends. The impact properties of these blends are strongly influenced by the amount and type of maleated polyethylene used. A low viscosity maleated polyethylene was shown to be ineffective in toughening nylon 6; this was because of the propensity of polyethylene to become continuous even when nylon 6 was the majority component. Two higher viscosity maleated polyethylenes were able to produce blends with high impact strength and excellent low temperature toughness over a range of compositions. It was demonstrated that polyethylene materials containing a very low degree of anhydride functionality can generate blends with excellent impact properties. A brief portion of this study focused on ternary blends of nylon 6, maleated polyethylene and nonmaleated polyethylene; in general, the impact properties of these blends improved as the nylon 6 molecular weight increased and as the ratio of maleated polyethylene to nonmaleated polyethylene increased.

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Non-isothermal crystallization of poly(vinylidene fluoride) during cooling at various rates was investigated by differential scanning calorimetry (d.s.c.). The data were analysed with the new model of non-isothermal crystallization developed by Ziabicki. The application of this model to experimental data allows separate determination of the rate of steady-state crystallization and the effect of time-dependent mechanisms. It was shown that the measured crystallization rate is higher than the rate of the steady-state process. It is probable that the accelerating factor is the athermal mechanism predicted by Ziabicki’s model. The analysis presented of non-isothermal crystallization data gives the possibility of determining the steady-state crystallization rates over the whole temperature range of the crystallization process. The previous method of determination of crystallization rate from isothermal measurements applied to polymers with high crystallization rate, like poly(vinylidene fluoride) or polyethylene, can provide data only for a narrow temperature range lying at the end of the upper branch of the crystallization curve.

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The effects of various reaction parameters on the styrene miniemulsion polymerizations stabilized by nonylphenol polyethoxylate with an average of 40 ethylene oxide units per molecule (NP-40) and dodecyl methacrylate (DMA) at 80°C were investigated. These parameters include the concentrations of DMA ([DMA]), NP-40 ([NP-40]), sodium persulfate ([SPS]), and 2,2 0 -azobisisobutyronitrile ([AIBN]). A water-insoluble dye was also incorporated into the reaction system to gain a better understanding of the related particle nucleation mechanisms. The polymerization rate decreases with increasing [DMA], whereas it increases with increasing [NP-40], [SPS] and [AIBN]. Several competitive events (e.g. coalescence among the monomer droplets, nucleation in the monomer droplets and micelles, formation of particle nuclei in water, and particle growth) occur simultaneously in the course of polymerization. This is due to the fact that the steric stabilization effect provided by NP-40 is greatly reduced at 80°C and the CMC of the miniemulsion is far below the NP-40 concentrations used in this work. Mixed modes of particle nucleation are operative in this reaction system, but monomer droplet nucleation becomes more important by increasing [DMA] or decreasing [NP-40], [SPS] and [AIBN].

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We have performed a series of morphology and CO2-probe diffusion analyses to ascertain the existence and composition dependence of voids in graphite/poly(vinylidene fluoride) composites both above and below the graphite percolation threshold, as determined from electrical conductivity measurements. Sorption data indicate that, with increasing graphite loading: (i) the diffusivity of CO2 in the composite material decreases; and (ii) the volume fraction of voids in the material increases. Differential scanning calorimetry reveals that polymer crystals nucleate heterogeneously on graphite particles and that samples containing graphite have higher degrees of crystallinity than the neat polymer. Crystallinity effects appear to dominate barrier properties at low graphite loadings, while porosity effects dominate at high graphite loadings. Our results strongly suggest that, although voids in these composites are probably associated with relatively poor adhesion along graphite/polymer interfaces, the voids are also discrete (i.e. they do not form a continuous network, even if the graphite particles do).

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PET/0.6 PHB melt, where PET is poly(ethylene terephthalate), PHB is p-hydroxybenzoic acid and 0.6 is the mole fraction of the second (liquid crystal, LC) component in the copolymer, was subjected to constant magnetic fields at several temperatures in the range 240–315°C, cooled to 25°C, and then studied by x-ray diffractometry, electron diffractometry, scanning electron microscopy (SEM), dilatometry (TMA) and thermogravimetry (TGA). Given the anisotropy of the magnetic susceptibility, significant orientation effects are found. The extent of orientation was evaluated as a function of the magnetic field strength, time of the field imposition and temperature; cyclic fields were also applied. Large changes in the extent of material orientation are connected to the phase transitions determined before [9]. The LC-rich islands [4] cause channeling of flexible sequences between the LC sequences, as predicted from an extension [20] of the statistical–mechanical theory of Flory [21]. In the phase region of coexistence of the smectic E, smectic B and isotropic phases there is a growth of the size of the islands—a consequence of increased mobility. However, in the next higher temperature region, where the smectic E phase is no longer present, one observes gradual dissolution of the islands along with the temperature increase. These conclusions are derived from both x-ray diffractometry and SEM. The phase transition temperatures from TMA agree with those found by other techniques. Linear expansivity is negative along the orientation direction, but it becomes ⬇ 0 after heating to 150°C. Electron diffractometry shows that the islands are elongated. TGA results show that the thermal degradation of the material in air plays a role only above 360°C. In general, the properties seem to depend on the extent of orientation but not on the nature of the field such as shear or magnetic.

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The relative viscosities of aqueous solutions of a polyethylene glycol sample and a polyvinyl alcohol sample were measured in a viscometer, the capillary wall surface of which was coated with paraffin. The results were compared with the data obtained from the original non-coated viscometer. Slippage occurs in the former case due to the hydrophobic nature of paraffin, while in the latter case, conventional viscous flow operates since both the solvent water and solution either wet and/or are adsorbed on to the glass capillary surface of the viscometer. The experimental data were analyzed with the aid of the recently proposed theory of the effect of solute adsorption on relative viscosity measurements. The formula, accounting for the effect of solute adsorption of polymer solutions down to the extremely dilute concentration region, are also applicable to non-wetting polymer solutions in which solute adsorption is eliminated. The results obtained were compared and analyzed using the idea of extrapolation length of slip flow proposed by de Gennes PG. CR Acad Sci Paris 1979;288B:219. The extrapolation length could be evaluated unambiguously from the relative or reduced viscosity data for polymer solutions down to the extremely dilute concentration region.

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