Small‐angle X‐ray scattering study of modified porous suspension–poly(vinyl chloride) particles

Small‐angle X‐ray scattering (SAXS) was applied to investigate the microstructure of unmodified and modified porous commercial suspension‐type poly(vinyl chloride) (PVC) particles. The modified PVC particles were prepared by an in situ stabilizer‐free polymerization/crosslinking of particles absorbed with a monomer/crosslinker/peroxide solution. The modifying polymers include styrene with or without divinyl benzene (DVB) as a crosslinker and methyl methacrylate (MMA) with or without ethylene glycol dimethacrylate (EGDMA) as a crosslinker. The SAXS method was used to highlight the effect of polystyrene (PS) on the microstructure of PVC particles and to evaluate the characteristic lengths, both in the PVC/PS and the PVC/XPS (PS crosslinked with 0 and 5% DVB, respectively) systems. A model is suggested, where during the synthesis modification process, swelling of PVC by styrene and styrene polymerization occur simultaneously. PVC swelling by styrene causes destruction of the PVC subprimary particles, whereas styrene polymerization leads to phase separation resulting from incompatibility of the polymers. It was further suggested that because of PVC swelling by styrene, structure of the subprimary particles is lost. Therefore the characteristic lengths of PVC/PS and PVC/XPS, as calculated from the SAXS measurements, were attributed to the size of the phase‐separated PS and XPS inclusions, respectively. The SAXS method also shows that PMMA and XPMMA do not influence the PVC microstructure. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 95: 1024–1031, 2005     

Harnessing the Melting Peculiarities of Ultra‐High Molecular Weight Polyethylene Fibers for the Processing of Compacted Fiber Composites

Summary: Compacted fiber composites offer unique properties due to their lack of an extraneous matrix. The conditions of processing ultra‐high molecular weight polyethylene (UHMWPE) fibers were simulated in a heated pressure cell. In situ X‐ray diffraction measurements were used to follow the relevant transitions and the changes in the degree of crystallinity during melting and crystallization. The results strongly support the suggestion that the hexagonal crystal phase, in which the chain conformation is extremely mobile on the segmental level, constitutes the physical basis of compaction technologies for processing UHMWPE fibers into a single‐polymer composite. This report suggests that using a pseudo‐phase diagram outlining the occurrence of different phases during slow heating and the degree of crystallinity can provide valuable insight into the technological parameters relevant for optimal processing conditions.

Degree of crystallinity as a function of pressure and temperature in a region relevant to compaction processes.     

A Random Nonstationary Pulse Train Model

A simple and mathematically tractable model of a nonstationary process is developed.The process is the sum of waves where the parameters of the waves are random. Explicit expressions for the mean and autocorrelation function at each position as a function of time are obtained.In the case of infinite time, the model evolves into a stationary process. The time-frequency distribution at each position is also obtained. An explicit example is given where the initial waves are Gaussian. The case where there is dispersion in the propagation is also discussed.     

Fatigue testing of PVC pipe fittings

The fatigue resistance of 6 inch Schedule 40 PVC solvent-bonded pipe fittings was investigated. It has often been assumed that the performance of PVC fittings is comparable to that of the corresponding pipe. The results of this study indicate that the fatigue performance of PVC fittings is much lower than that of the pipe. Several fittings were exposed to a repetitive surge cycle of 90 to 180 psig at a rate of 0.111 hertz. Failures of several tees occurred between 13,000 and 16,000 cycles, much sooner than the predicted lifetime of pipe under these conditions.     

Toughenability of Nylon-6 with CaCO3 filler particles: new findings and general principles

The mechanical behavior of Nylon-6 blends modified by two types of CaCO₃ particles of 0.7 and 3.5 μm diameter with particle volume fractions ranging from 0.05 to 0.28 was studied between −30 and 60°C in slow tension, and at 20°C in bending impact. Additional experiments were also carried out at 20°C to determine the plane stress fracture toughness of the blends in Single-Edge-Cracked-Plate configurations; all fracture behavior was followed extensively by SEM fractography.

Experiments demonstrated that the particles are attached to the matrix only through a differential thermal–contraction–pressure and particle separation preceded plastic response in all instances. As a consequence of the above ease in debonding, the yield strengths of the blends drop systematically with increasing particle concentration.

In slow tension all blends showed a well defined plastic stretching response following necking, but the stable post-necking stretch was severely limited by an overabundance of large particle clusters which acted as super-critical flaws to initiate premature termination of stretching. The present findings show that in these blends with their high plastic resistances, critical flaw sizes that trigger brittle response are in the range of 8–12 μm, well under the sizes of many of the particle clusters encountered in the blends.

In contrast with the attractively tough response of the rubber modified Nylon-6 blends of Murato lu et al. [Polymer 36 (1995) 921; Polymer 36 (1995) 4771] all present blends showed only disappointing brittle behavior under Izod impact conditions. This was traced to the development of substantial levels of triaxial tensile stresses arising from only partial separation of rigid particles from the matrix in the early phases of impact response.

Based on the new findings a number of general principles on toughenability with both compliant and rigid particle modification are presented and supported by simple micro mechanical models.     

Spatial and temporal sequence of events in cell adhesion: from molecular recognition to focal adhesion assembly

A new concept that attributes a pivotal role to the pericellular coat in the regulation of the early stages of cell adhesion is presented. Quick, adaptable, and transient adhesion through multiple cooperative weak interactions provides the cell with an additional level of modulation in the decision-making process that precedes the commitment to adhesion at a particular site. Hyaluronan emerges as a modulator of cell adhesion in certain cells, mediating binding or repulsion through its polyelectrolyte character, in addition to its chirality and molecular-recognition properties. The biophysical properties of hyaluronan as well as its ultrastructural organization are analyzed in relation to this proposed function.     

Specimen edge effects on bending fatigue of carburized steel

The effects of specimen geometry on the fatigue behavior of SAE 4320 steel carburized at 927 °C were evaluated with two sets of cantilever bend specimens, one set machined with square edges and one set machined with round edges. The specimens with square edges exhibited a 13% lower fatigue limit. In comparison to the rounded samples, the lower fatigue limit in the square-edged samples was attributed to the presence of a higher volume fraction of retained austenite in the sample corners and a lower surface residual compressive stress. As a result of the differences in residual stress, preferential crack initiation sites existed in the square-edged samples at a location approximately 200 to 900 ώm from the square edge. The implications of this study on laboratory analyses of the bending fatigue performance of carburized gear steels are discussed.     

Blends of imidized acrylic polymers with SAN copolymers and with PVC

A series of imidized acrylic polymers of varying structural composition generated by reaction of methylamine with poly(methyl methacrylate) were blended with a range of styrene/acrylonitrile or SAN copolymers (0–33% AN) and with poly(vinyl chloride). On the basis of glass transition behavior determined by differential scanning calorimetry, some but not all imidized acrylic structures were found to be miscible with PVC and with SAN copolymers within a limited window of AN levels. Acid functionality in the imidized acrylics appears to hinder their miscibility with SAN rather significantly and with PVC to a lesser extent. Miscible SAN blends showed lower critical solution temperature behavior whereas miscible blends with PVC did not up to the highest attainable temperatures. The composition factors that influence the phase behavior are described and interpreted in terms of possible mechanisms.     

The crystallization and transition behavior of poly(vinylidene fluoride)/copoly(chlorotriofluorethylene-vinylidene fluoride) blends

Thermal analysis of solution precipitated blends of two crystallizable polymers, poly(vinylidene fluoride) (PVDF) and copoly(chlorotrifluorethylene-vinylidene fluoride) (copoly(CTFE-VDF)), has been carried out to study the transition temperatures, crystallinity, and crystallization rates. PVDF crystallizes over the whole blend composition either during precipitation from solution or upon cooling from the melt. The high degree of crystallinity attained, higher than in PVDF by itself, suggests the occurrence of partial PVDF-copolymer cocrystallization. The melt crystallization temperature, decreasing with cooling rate, is lower in PVDF-rich blends than for lean blends. However, the heat of crystallization increases with cooling rate, suggesting that the crystal composition depends on crystallization rate. No significant melting temperature depression due to blending was observed. However, the blends glass transition (T_g) changes linearly with composition, but less than expected by any mixing rule applicable to compatible systems. Annealing of the blends above T_g results in an additional crystalline phase consisting mainly of the copolymer. The amount of these crystals increases with PVDF content, due to partial cocrystallization and kinetic effects. The addition of the copolymer to PVDF results in a volume-filling spherulitic structure consisting of spherulites which decrease in size with increasing copolymer content.     

Cholelithiasis in hamsters: Effects of cholic acid and calcium on gallstone formation

Dietary cholic acid (0.1%) and/or calcium (2.6% as calcium carbonate) were added to a semipurified diet containing cholesterol and ethynyl estradiol to determine whether the incidence of pigment and/or cholesterol gallstones would be changed. Male golden Syrian hamsters were fed the experimental diets for 96 days (Group 1, control; Group 3, cholic acid plus calcium) or only an average of 60 days (Group 2, 0.1% cholic acid). Animals in Group 2 became ill (weight loss, low food intake, diarrhea) possibly due to cholic acid (or deoxycholic acid) toxicity. Cholesterol gallstones and crystals were absent in all experimental groups. The incidence of pigment gallstones was: control, Group 1, 12/16; 0.1% cholic acid, Group 2, 3/13; and 0.1% cholic acid plus calcium, Group 3, 11/22. Cholic acid with or without calcium produced an elevation of both liver and plasma cholesterol: Group 2, 80.1 mg/g and 501 mg/dl; Group 3, 103.7 mg/g and 475 mg/dl vs Group 1, 65 mg/g and 209 mg/dl, respectively. The lithogenic indices of the bile were lower in Groups 2 and 3 compared to Group 1, controls, 0.45 and 0.58 vs 1.16, respectively. The extent of the portal tract pathology could not be correlated with the presence or absence of pigment gallstones or with the levels of lithocholic acid in the hamster bile. In summary, when semipurified diets were supplemented with ethynyl estradiol and cholic acid, with and without calcium supplementation, no cholesterol gallstones formed and the incidence of pigment gallstones was not altered.