Morphology development in polymer blends

The major morphological changes during polymer blending occur during the initial softening stage. This work explains the evolution of phase morphology of polymer blends from pellets to submicron particles in a co-rotating twin-screw extruder. The extruder was opened and blend samples were taken along its length. The major phase component was extracted by means of a selective solvent so that the dispersed phase morphology could be viewed directly by using scanning electron microscopy. The two systems studied were 80:20 polystyrene/amorphous polyamide and 80:20 polystyrene/polypropylene. In both systems, the initial morphology consisted of sheets of dispersed phase. Holes form in the sheets, and these holes grow as a result of interfacial tension forces until they coalesce with each other, forming thin ligaments. These fluid ligaments are unstable and break up via mixer shear forces. Very large changes in dispersed phase size are observed during the softening stage. The particle size changes less after the polymers are completely melted. The extruder results are compared to results from a batch mixer. The same dispersed phase sheeting mechanism is seen in the initial morphology in the batch mixer and the breakup of the dispersed phase domains parallels the breakup seen in the extruder.     

Effects of Stearic Acid on the Injection Molding of Alumina

This research investigated the influence of stearic acid on the injection molding of alumina, by varying the concentration of stearic acid. The interaction between stearic acid and alumina was identified using transmission infrared spectroscopy, indicating stearic acid preferentially adsorbed onto the alumina powder surface. In addition to slightly modifying the intrinsic binder viscosity, stearic acid adsorbed onto the powder surface changed the flow behavior of the mixtures from dilatant flow to pseudoplastic flow at low temperatures. As a result, inhomogeneous distribution of binder in the injection-molded parts was minimized with increased stearic acid concentration. However, the possibility of forming bubbles in the mixtures arising from vaporization of stearic acid was enhanced. Additionally, the binder burnout temperature range was broadened with the increase of stearic acid concentration.     

An SDP Primal-Dual Algorithm for Approximating the Lovász-Theta Function

The Lovász ?-function (Lovász in IEEE Trans. Inf. Theory, 25:1–7, 1979) of a graph G=(V,E) can be defined as the maximum of the sum of the entries of a positive semidefinite matrix X, whose trace Tr(X) equals 1, and X _ij =0 whenever {i,j}∈E. This function appears as a subroutine for many algorithms for graph problems such as maximum independent set and maximum clique. We apply Arora and Kale’s primal-dual method for SDP to design an algorithm to approximate the ?-function within an additive error of δ>0, which runs in time $O(\frac{\vartheta ^{2} n^{2}}{\delta^{2}} \log n \cdot M_{e})$ , where ?=?(G) and M _e =O(n ³) is the time for a matrix exponentiation operation. It follows that for perfect graphs G, our primal-dual method computes ?(G) exactly in time O(? ² n ⁵logn). Moreover, our techniques generalize to the weighted Lovász ?-function, and both the maximum independent set weight and the maximum clique weight for vertex weighted perfect graphs can be approximated within a factor of (1+?) in time O(? ^?2 n ⁵logn).     

Formation of Azobenzenes and Azoxybenzenes from the Aqueous Reactions of Anilines and Ozone

Azobenzenes and azoxybenzenes are two of the products identified from the aqueous reaction of anilines with ozone. Aniline concentration and functional groups on the benzene ring of aniline affected the amount of azobenzenes and azoxybenzenes formed; (1) decreasing the aniline concentration significantly increased azobenzene formation, and (2) electron-withdrawing groups increased the formation of its related azobenzene and azoxybenzene, whereas electron-donating groups had the opposite effect.     

Shear-induced interactions in blends of HMMPE containing a small amount of thermotropic copolyester HBA/HQ/SA

Shear-induced interactions between high molecular mass polyethylene (HMMPE) melt and a thermotropic liquid crystalline copolyester, HBA/HQ/SA (TLCP) were investigated using large amplitude oscillatory shear and capillary shear. Polarized optical microscopy (POM) observations show that the mono-domain nematic TLCP droplets embedded inside a HMMPE melt may be readily elongated using large amplitude oscillatory shear. The HMMPE melt adjacent to the elongated TLCP filament was observed to crystallize faster than that in the matrix away from the interface. TEM analysis on the 1 wt% TLCP/HMMPE blend quenched after capillary shear shows that there are strong interfacial interactions between the elongated TLCP filament and the HMMPE matrix. Long range PE lamellae orientational order up to 2 μm away from the TLCP filament surface were observed, with all the lamellae surface normal parallel to the TLCP fiber. Additionally, a strong interfacial compatibility between the TLCP filament and the HMMPE matrix with an interfacial thickness of ∼30 nm has also been observed. The enhanced interfacial compatibility is attributed to the -CH₂- group interactions due to chain alignment in both components at their interface. These results provide a fundamental insight to other TLCP containing thermoplastics where compatibilities may be present due to segmental interactions.     

Methods to determine solubility parameters of polymers using inverse gas chromatography

Experimental values of the Flory–Huggins parameter, χ, between polymers and solvents, are frequently used to determine the solubility parameters of the polymers. A method using nonlinear curve fitting of RTχ/V was compared to the linear regression method commonly used. It was found that the formulas for the solubility parameter were the same, but the linear method produced a slightly different entropy term. The nonlinear method gave a lower correlation coefficient and wider confidence intervals and was more effective at distinguishing systems than the linear model. The effect of the deviation of probes in the solubility parameter model is discussed. Using probes with low solubility parameters to measure the polymer solubility parameter gave wider confidence intervals. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2894–2902, 2004     

Phase Diagram for Liquid Crystalline Polymer/ Polycarbonate Blends

A novel mechanism to form binary polymer blends is through phase separation by spinodal decomposition in the unstable region of the phase diagram. The present work investigates the effects of thermally‐induced phase separation by spinodal decomposition on the morphology development of liquid crystalline polymer/polycarbonate blends. Moreover, a thermodynamic binary phase diagram is obtained using a twin‐screw extruder at various processing melt temperatures. Differential scanning calorimetry and scanning electron microscopy were used to study the miscibility of the blends and the resulting morphology. A thermodynamic binary phase diagram exhibiting a lower critical solution temperature was obtained. The droplet size distribution of the blend was also obtained and discussed in light of the Cahn‐Hilliard theory.     

The binding mode of an E-64 analog to the active site of cathepsin B

Two binding modes of the isobutyl-NH-Eps-Leu-Pro inhibitor tocathepsin B have been proposed. Molecular docking using an empiricalforce field was carried out to distinguish between the two modes.The search began with manual docking, followed by random perturbationsof the docking conformation and cycles of Monte Carlo minimization.Finally, molecular dynamics was carried out for the most favorabledocking conformations. The present calculations predict thatthe isobutyl-NH-Eps-Leu-Pro inhibitor preferentially binds tothe S' rather than the S subsites of cathepsin B. The S' bindingmode prediction is supported by the X-ray crystal structureof cathepsin B bound to a closely related ethyl-O-Eps-Ile-Proinhibitor, which was found to bind in the S' subsite with theC-terminal epoxy ring carbon making a covalent bond to the sulfuratom of Cys29. This agreement, in turn, validates our dockingstrategy. Furthermore, the calculations provide evidence thatthe dominant contribution to the total stabilization energyof the enzyme–inhibitor complex stems from the strongelectrostatic interaction between the negatively charged C-terminalcarboxylate group of the ligand and the positively charged imidazoliumrings of His110 and His111. The latter are stabilized and heldin an optimal orientation for interactions with the C-terminalend of the ligand through a salt bridge between the side chainsof His110 and Asp22. By comparison with the crystal structure,some insight into the specificity of the epoxyldipeptide familytowards cathepsin B inhibition has been extracted. Both thecharacteristics of the enzyme (e.g. subsite size and hydrophobicity)as well as the nature of the inhibitor influence the selectivityof an inhibitor towards an enzyme.     

Experimental Simulation of the Reactor Section of Fluid Cokers: Comparison of FCC and Fluid Coke Particles

The hydrodynamics of fluid cokers were studied in a pressurized fully cylindrical cold model of diameter 483 mm, geometrically and dynamically scaled down by a factor of ～20 from commercial units. Differential pressure fluctuations, voidage distributions, solids momentum flux distributions and steady state gas mixing behaviour in the reactor section are compared for the same operating conditions with two kinds of particles, FCC and fluid coke. The voidage distributions and core‐annular flow structures in the reactor section were similar enough that either FCC or fluid coke particles can be used for cold modelling of fluid cokers.     

Improved mechanical properties of shape‐memory polyurethane block copolymers through the control of the soft‐segment arrangement

High‐performance shape‐memory polyurethane block copolymers, prepared with two types of poly(tetramethylene glycol) (PTMG) used as soft segments, were investigated for their mechanical properties. Copolymers with a random or block soft‐segment arrangement had higher stresses at break and elongations at break than those with only one kind of PTMG. Random copolymers with fewer interchain interactions showed higher elongation than block copolymers. All the copolymers had shape‐recovery ratios higher than 80%. In dynamic mechanical testing, the glass‐transition behavior clearly depended on the soft‐segment arrangement: random copolymers had only one glass‐transition peak, whereas block copolymers showed two separate glass‐transition peaks. Overall, the control of the soft‐segment arrangement plays a vital role in the development of high‐performance shape‐memory polyurethane. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 2410–2415, 2004