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     

Coal liquefaction in nitrogen compounds

Model compound studies have shown that 1,2,3,4-tetrahydroquinoline is an exceptionally good coal solvent. In the pure compound, subbituminous coal conversion to THF-soluble products approaches 100% under relatively mild reaction conditions. The effectiveness of tetrahydroquinoline for coal conversion appears to be related to its concentration relative to coal. The unique behaviour of tetrahydroquinoline is ascribed to its being a highly active H-donor; the fact that it is regenerable under reaction conditions by the reaction of hydrogen and quinoline; and that its polarity allows penetration of the coal structure and aids in dispersion of the dissolved coal. It has been found that, during reaction with coal, tetrahydroquinoline and other nitrogen compounds undergo extensive condensation reactions which result in an increase in the nitrogen content of the high boiling and non-distillable liquefaction products.     

Wrinkling of epoxy powder coatings

Differential scanning calorimetry (DSC) and mechanical profilometry were used to study wrinkle formation in curing epoxy powder coatings. Powder coating formulations were studied that contained solid epoxy resins, methylene disalicylic acid (MDSA) crosslinker, and an amine‐blocked Lewis acid catalyst. Both the crosslinker (MDSA) and the amine‐blocked catalyst are required for wrinkle formation. Evaporation of the blocking amine from the free surface of the coating generated a depthwise gradient in the extent of polymerization and crosslinking, and hence in the degree of solidification, as evidenced by the formation of a mechanical skin prior to wrinkling. It is hypothesized that compressive elastic stress develops in the still swellable skin when unreacted low‐molecular‐weight material from beneath diffuses up into the monomer‐ or oligomer‐depleted crosslinking skin and swells it. This compressive stress, if above a critical value, buckles the skin to produce wrinkles. Experimentally observed compositional requirements for wrinkle formation were consistent with the proposed mechanism. The size of the wrinkles can be controlled by varying formulation parameters such as the amount of catalyst or crosslinker. Increasing the amount of catalyst decreased both the wavelength and the amplitude of the wrinkle pattern. Increasing the amount of crosslinker initially increased the amplitude of the wrinkles; after reaching a maximum level, the wrinkle amplitude decreased. DSC was a useful tool to understand the critical reactions responsible for wrinkling in this system. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 116–129, 2005     

Thin-Layer Dielectrics in the Pb[(Mg1/3Nb2/3)1-xTix]O3 System

Thin layers of Pb[(Mg_1/3Nb_2/3)_{1– x} Ti _x ]O₃ (PMNT) were prepared by spin casting alkoxide-based solutions on platinized Si. The effects of additives, heat treatment, and composition ( x = 0 to 0.9) on perovskite phase development, ceramic microstructure, and dielectric properties are reported. Depending upon the processing conditions, ceramic thin layers could be formed in a nonferroelectric pyrochlore phase (A₂B₂O₆) or in a ferroelectric perovskite phase (ABO₃). The dimensions of the pyrochlore and perovskite units cells were related and increased with Mg and Nb contents. To minmize pyrochlore formation, the most effective processing method involved rapid heat treatment between successive solution depositions. Phase development and microstructure were also affected by solution additives. Additions of benzoic acid were found to affect the structure in solution and the later organic pyrolysis behavior from thin layers. The effect of composition on the dielectric and ferroelectric properties is also reported.     

Ultimate properties of blown films of linear low density polyethylene resins as affected by alpha-olefin comonomers

Blown film samples of linear low density polyethylene resins copolymerized with butene, hexene, and octene were characterized in terms of various mechanical and optical properties which included tensile, impact, tear, puncture, haze, and gloss. The microstructure development aspects were also investigated employing crystallinity and density, infrared dichroic ratio, and birefringence, and focusing on various positions along the circumference of the bubble. The ultimate properties, and the microstructure of the blown film samples, were found to depend strongly on the extent of short chain branching and on the comonomer employed.     

Qualitative and quantitative analysis of multilayer coextruded and laminated films

The packaging industry is undergoing a period of rapid expansion in the use of multilayer and coextruded containers. This presents a challenge to the analytical chemist, who must characterize these extremely complex structures. The state of the art for the production of the new generation of containers, including methods, materials and structures, will be briefly reviewed. The applications of such containers and the motivations for the analysis of the structures involved will also be reviewed. The methods for the analysis of these multilayer and coextruded structures will then be considered in detail. The characterization of the surfaces involved will be emphasized. Techniques to identify, quantify, and determine the orientation of the structures will be discussed. The use of infrared spectroscopy (with emphasis on internal reflection spectroscopy) for the identification of the materials in these structures will be discussed. Also, the use of infrared spectroscopy in quantitatively determining the composition and orientation of the structures will be presented. The use of optical microscopy and combined microscopy/infrared spectroscopy for the quantification of the layer structures will be discussed. The use of auxiliary techniques for the completion of the analysis of the complex layer structures will be presented.     

Polydimethylsiloxane based polyurethane and its composite with layered double hydroxide: Synthesis and its thermal properties

This investigation reports the synthesis of a new class of polyurethane (PU) based on bis(hydroxyalkyl) polydimethylsiloxane (PDMS) as diol and isophorone diisocyanate as diisocyanate followed by the preparation of PU/layered double hydroxide (PU/LDH) nanocomposite via ex-situ technique. Nuclear magnetic resonance and Fourier-transform infrared spectroscopy studies confirm the formation of PU and incorporation of PDMS into the PU backbone. Thermogravimetry analysis revealed that thermal stability of the composite improves significantly with incorporation of LDH into the PU matrix. This may be accredited to the barrier effect rendered by the LDH layers. Differential scanning calorimetry study reveals that with the incorporation of LDH, glass transition temperature (T_g) of the composite increases for an optimum level of loading beyond which it remains constant.