Epoxy‐tert‐butyl poly(cyanoarylene ether) blends: Phase morphology,fracture toughness,and mechanical properties

Tert‐butyl hydroquinone–based poly(cyanoarylene ether) (PENT) was synthesized by the nucleophilic aromatic substitution reaction of 2,6‐dichlorobenzonitrile with tert‐butyl hydroquinone using N‐methyl‐2‐pyrrolidone (NMP) as solvent in the presence of anhydrous potassium carbonate in a nitrogen atmosphere at 200°C. PENT‐toughened diglycidyl ether of bisphenol A epoxy resin (DGEBA) was developed using 4,4′‐diaminodiphenyl sulfone (DDS) as the curing agent. Scanning electron micrographs revealed that all blends had a two‐phase morphology. The morphology changed from dispersed PENT to a cocontinuous structure with an increase in PENT content in the blends from 5 to 15 phr. The viscoelastic properties of the blends were investigated using dynamic mechanical thermal analysis. The storage modulus of the blends was less than that of the unmodified resin, whereas the loss modulus of the blends was higher than that of the neat epoxy. The tensile strength of the blends improved slightly, whereas flexural strength remained the same as that of the unmodified resin. Fracture toughness was found to increase with an increase in PENT content in the blends. Toughening mechanisms like local plastic deformation of the matrix, crack path deflection, crack pinning, ductile tearing of thermoplastic, and particle bridging were evident from the scanning electron micrographs of failed specimens from the fracture toughness measurements. The thermal stability of the blends were comparable to that of the neat resin. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 100: 3536–3544, 2006     

Preparation and properties of ABA block polymers of styrene and butadiene or isoprene made with sec-C4H9Li·2(C2H5)2O

ABA-type “tapered” block polymers were prepared from styrene (monomer A) and butadiene or isoprene, using an initiator of sec-butyllithium complexed with two molecules of ethyl ether. The stress–strain curves of polymers containing about 20–50% styrene show the usual resemblance to curves of crosslinked elastomers. The SBS polymers had higher tensile strengths than the SIS polymers. They also had slightly higher tensile strengths than comparable SBS polymers made with sec-butyllithium. The SIS polymers, however, had generally lower tensile strengths than those made with sec-butyllithium. This is probably caused by higher styrene content of the isoprene block, brought about by increased randomization of the styrene–isoprene copolymerization due to the presence of the ether. The A and B blocks become more compatible, producing loss of strength in the polymer. Infrared analyses of polydienes made with the sec-C₄H₉Li·2(C₂H₅)₂O initiator showed a 6% to 8% increase in 1,2-content (for polybutadiene) or 3,4-content (for polyisoprene), compared to polymers made with sec-butyllithium. The polymer microstructures still have high (>80%) total 1,4-content, however. Thus, this amount of ether can be tolerated in the polymerization system without great loss of rubbery properties or block structure in the resultant polymers.     

The reaction of activated vinyl compounds with cotton cellulose via internal catalysis

The reactions of a variety of activated vinyl compounds with cotton cellulose fabric containing quaternary ammonium hydroxide substituents were explored. Each reaction, catalyzed by the basic groups in the cellulose, was followed to or near the point of leveling off. The results are analyzed and discussed in terms of accessibility of the cellulosic compositions and in terms of the efficiency of the quaternary ammonium substituents as catalysts for the addition reactions. Estimates of relative forward rate constants (k_f) and equilibrium constants (K) for the reactions were made. The values of k_f for reactions of the vinyl compounds with the quaternary ammonium celluloses show a relative order which is similar to that for the reactions of the vinyl compounds with simple alcohols. Evidence is presented to indicate that, in some cases, the addition of vinyl compounds is accompanied by anionic-catalyzed graft polymerization.     

Hepatic lipid characteristics and histopathology of laying hens fed CLA or n−3 fatty acids

The effect of dietary CLA and n−3 PUFA on hepatic TAG accumulation, histopathology, and FA incorporation in lipid classes by laying chickens was investigated. One hundred twenty 30-wk-old single-comb white leghorn laying hens were distributed randomly to four treatments (3 replications of 10 birds) and were fed diets containing CLA and animal fat (Diet I), 18∶3n−3 (Diet II), or long-chain n−3 FA (Diet III). A sunflower oil (n−6 FA)-based diet was the control. Feeding Diet I resulted in an increase in hepatic total lipids (P<0.05). The liver TAG content was 32.2, 18.9, 29.4, and 18.7 mg/g for hens fed Diet I, Diet II, Diet III, and the control diet, respectively (P<0.05). The serum TAG was lowest in bilds fed Diet II (P<0.05). Diet I resulted in an increase in the total number of fat vacuoles and lipid infiltration in hepatocytes (P<0.05). The number of cells with 75% or higher lipid vacuolation was observed only in birds fed Diet I. Feeding diets containing CLA resulted in an increase in the content of the c9,t11 CLA isomer in liver TAG and PC (P<0.05). No difference was observed in the CLA concentration of hepatic PE fractions. The content of DHA (22∶6n−3) was higher in the TAG, PC, and PE of hens fed Diet II and Diet III than Diet I and the control (P<0.05). Feeding CLA resulted in an increase in total saturated FA in the TAG and PC fractions (P<0.05). Long-term feeding of CLA in laying birds leads to an increase in liver TAG and may predispose birds to fatty liver hemorrhagic syndrome.     

Physicochemical Methods for Prediction of Functional Information for Proteins

Structural genomics initiatives are determining thousands of new protein structures. Many of these structures are of unknown function, and computational methods for the rapid determination of functional information from protein structure are needed. We present details of how functional information is obtained from the structure using THEMATICS (Theoretical Microscopic Titration Curves). THEMATICS is a computational procedure that gives information about chemical reactivity, based on solution of the Poisson-Boltzmann equations for the electrical potential function. We show how anomalies in predicted titration curves are established. We show further that when residues with anomalous predicted titration curves form a cluster in physical space, these residues tend to be very highly conserved across species and such clusters are reliable predictors of the active site. Results are given for ten enzymes; detailed results are shown for the enzymes triosephosphate isomerase (from chicken), 6-hydroxymethyl-7,8-dihydropterin pyrophosphokinase (from E. coli), and papain (from papaya).     

Encapsulation and controlled release in polyacrylamide hydrogels

A novel host–guest system was developed by the encapsulation of simple organic guest molecules in the hydrophilic molecular architecture of crosslinked polyacrylamide hydrogels. The crosslinking agents used for the preparation of the host systems were hexanediol dimethacrylate (HDDMA) and divinyl benzene (DVB). This enabled us to construct hydrogels with different hydrophobic–hydrophilic equilibria. The model guest system used for the studies was benzoic acid. The selections gave simple but excellent host–guest systems with fine polar–apolar balancing. Polyacrylamide hydrogels with encapsulated benzoic acid were prepared with varying crosslink densities (5, 10, 15, and 20 mol %) by the solution polymerization technique. The rate of release of the host from the host–guest assembly was studied in different swelling conditions. The rate of release depended on the interaction forces between the polymer and the solvents. Polar forces, dispersion forces, and hydrogen bonding all played a vital role. The swelling behavior of the host‐polymer system and the host–guest assembly was analyzed and compared by the Flory–Rehner method. The amount of benzoic acid encapsulated in the DVB‐crosslinked polymer was higher than in the HDDMA‐crosslinked polymer, and the rate of release was in the order 5 > 15 > 10 > 20% for the DVB‐crosslinked polymer. The rate of release for the HDDMA‐crosslinked host–guest assembly was in the order 10 > 5 > 15 > 20%. These results were in excellent agreement with those of the Flory–Rehner analysis of the swelling properties. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 93: 1816–1824, 2004     

Rheology of network forming systems

Viscosity and dynamic shear measurements are reported on several network forming systems as a function of reaction time and temperature. Phenolic, epoxy and EPDM rubber systems are examined. Rheological data are related to the reaction kinetics of the systems. With these relations overall activation energies, reaction orders and rate constants are interpreted from the data. These compare favorably with results in the literature. Applications of rheological techniques to processing problems of several network forming systems are described, specifically thermoset injection molding and SBR rubber vulcanization.     

Studies on the cure characteristics and vulcanizate properties of 50/50 NR/SBR blend

Blends of 50/50 natural rubber (NR) and styrene-butadiene rubber (SBR) are vulcanized using several conventional and semi-EV systems. The cure characteristics and vulcanizate properties are compared. The quantity and quality of crosslinks in each case are deciphered by chemical probes to correlated them with the vulcanizate properties.     

Oxidation by UV and Ozone of Organic Contaminants Dissolved in Deionized and Raw Mains Water

Organic contaminants dissolved in deionized pretreated and raw mains water were reacted with ultraviolet light and ozone. Ozone first was used for partial oxidation followed by ozone combined with ultraviolet radiation to produce total oxidation. The reduction of TOC level and direct oxidation of halogenated compounds were measured throughout the treatment process. The rate of TOC reduction was compared for ozone injected upstream and inside the reactor.     

Thermoplastic olefin/clay nanocomposites: Morphology and mechanical properties

Thermoplastic olefin (TPO)/clay nanocomposites were made with clay loadings of 0.6–6.7 wt %. The morphology of these TPO/clay nanocomposites was investigated with atomic force microscopy, transmission electron microscopy (TEM), and X‐ray diffraction. The ethylene–propylene rubber (EPR) particle morphology in the TPO underwent progressive particle breakup and decreased in particle size as the clay loading increased from 0.6 to 5.6 wt %. TEM micrographs showed that the clay platelets preferentially segregated to the rubber–particle interface. The breakup of the EPR particles was suspected to be due to the increasing melt viscosity observed as the clay loading increased or to the accompanying chemical modifiers of the clay, acting as interfacial agents and reducing the interfacial tension with a concomitant reduction in the particle size. The flexural modulus of the injection moldings increased monotonically as the clay loading increased. The unnotched (Izod) impact strength was substantially increased or maintained, whereas the notched (Izod) impact strength decreased modestly as the clay loading increased. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 928–936, 2004