Fatigue of viscoelastic polymers: 2. Fractography

The results of a fractographic study of fatigue failure in viscoelastic polymers is presented. Tests were conducted on a spherulitic low-density polyethylene in reversed loading using non-symmetrical deformation conditions. The microfractographic features have been found to depend on the deformation programme, the temperature of the test and the position on the fracture surface. The latter has been related to the different stages of growth revealed by plotting crack-growth propagation data. As well as interspherulitic fracture, other mechanisms that are sometimes prevalent involve cold-drawing, (fibrillation), and/or lamellar reorientation. The appearance of fatigue fracture surfaces of a non-spherulitic low-density polyethylene, a high-density polyethylene and a plasticized poly(vinyl chloride) corroborate the structural interpretations proposed to account for the observations with the spherulitic low-density polyethylene.     

Melting aspects of filled compounds in a modular co‐rotating twin screw extruder

In the polymer industry, precompounded materials are widely used. Carefully designed melting experiments were carried out to investigate melting mechanisms in master batched polymer compounds, using an intermeshing co‐rotating twin screw extruder. Calcium carbonate or aluminum powder was master batched with linear low‐density polyethylene (LLDPE). The calcium carbonates, which were used in the compounds, have differences in weight fraction and particle size. The compounds containing filler have higher thermal conductivities and viscosities than neat polyethylene. We observed melting initiation and propagation mechanisms of LLDPE compounds by removal and characterization of polymer compound carcasses in the melting region. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 1990–2012, 2006     

Solvent fractionation of petroleum pitch for mesophase formation

Petroleum pitch (Ashland A240) has been subjected to thermal treatment and solvent fractionation to produce refined pitches to be evaluated as impregnants for C-C composites. The solvent fractions were obtained by sequential Soxhlet extraction with solvents such as hexane, benzene, and pyridine. Thermal treatment to 408 °C produced a mesophase pitch (≈50% mesophase); an appreciable portion of the mesophase was soluble in strong solvents. There were substantial differences in chemical composition and in pyrolysis behaviour of the fractions. As the depth of fraction increased, the pyrolysis yield and bloating increased, and the microstructure of the coke became finer until glassy microconstituents were formed in the deepest fractions.     

Using Electrical Capacitance Tomography to Investigate Gas Solid Contacting

An ECT system has been shown to be useful in observing differences in particle behaviour in a bubbling fluidised bed. An image analysis technique is further described that utilises the construction of solids concentration profiles at three key values, x = 0.2, x = 0.5 and x = 0.8, which have been identified as important solids concentrations in a new Bubble Structure Model. Significant differences in the bubble structure are shown to result when the concentration of fine particles is slightly increased in a bubbling fluidised bed. Changes of this type would seriously alter the gas solid contact efficiency in the fluidised bed, which would significantly influence selectivity of in‐bed catalytic reactions and gas residence time.     

Rheological and extrusion characteristics of glass fiber-reinforced polycarbonate

An experimental investigation of the rheological properties of glass fiber-reinforced polycarbonate melts and the extrusion of such compounds through capillary and slit dies is presented. The viscosity–shear rate function seems independent of instrument for cone-plate and capillary investigations. The presence of fibers increases the level of the viscosity. Normal stresses at fixed shear stress are also increased by the presence of fibers. The extrudate swell is decreased by the presence of fibers and surface roughness is increased. Fiber orientation increases and surface roughness decreases with increasing extrusion rate.     

Oxidative stability of soybean oils with altered fatty acid compositions

The oxidative stabilities of one canola oil and six soybean oils of various fatty acid compositions were compared in terms of peroxide values, conjugated dienoic acid values and sensory evaluations. Two of the soybean oils (Hardin and BSR 101) were from common commercial varieties. The other four soybean oils were from experimental lines developed in a mutation breeding program at Iowa State University that included A17 with 1.5% linolenate and 15.2% palmitate; A16 with 2% linolenate and 10.8% palmitate; A87-191039 with 2% linolenate and 29.6% oleate; and A6 with 27.5% stearate. Seed from the soybean genotypes was cold pressed. Crude canola oil was obtained without additives. All oils were refined, bleached and deodorized under laboratory conditions with no additives and stored at 60°C for 15 days. The A17, A16, A87-191039 and A6 oils were generally more stable to oxidation than the commercial soybean varieties and canola oil as evaluated by chemical and sensory tests. Canola oil was much less stable than Hardin and BSR 101 oils by both chemical and sensory tests. The peroxide values and flavor scores of oils were highly correlated with the initial amounts of linolenate (r=0.95, P=0.001). Flavor quality and flavor intensity had negative correlations with linolenate, (r=−0.89, P=0.007) and (r=−0.86, P=0.013), respectively.     

Continuous polymerization of lactam–lactone block copolymers in a twin‐screw extruder

Continuous copolymerizations of ?‐caprolactone with ?‐caprolactam and ω‐lauryl lactam were carried out in a modular intermeshing corotating twin‐screw extruder. Sodium hydride (initiator) and N‐acetyl caprolactam (coinitiator) were used to synthesize lactam–lactone copolymers in a twin‐screw extruder. We consider the variables of feeding order and feed rate of comonomers on the reactive extrusion of lactam–lactone copolymers. It was observed that simultaneous feeding of both monomers with initiator and coinitiator in the first hopper produced a mixture of homopolymers. When we fed the lactam into the first hopper and caprolactone sequentially into the second hopper, we obtained the lactam–caprolactone block copolymers. However, when we fed caprolactone first into the first hopper and the lactam into the second hopper, the extruded product was a mixture of poly(?‐caprolactone) and lactam monomer. We synthesized high molecular weight copolymers of poly(caprolactam‐b‐caprolactone) and poly(lauryl lactam‐b‐caprolactone) with different block lengths by sequential feeding of monomers. The block length of the block copolymer could be adjusted by controlling the feed rate of each monomer during reactive extrusion. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1429–1437, 2003     

Development and evaluation of terminally epoxidized triglycerides for coatings applications

Epoxidized 10-undecenoic acid triglyceride, an experimental seed oil derivative that has a terminal epoxy group on each of the three acyl glyceride segments, has been found to have good reactivity with amine curatives and allows room temperature cures to be obtained. Coatings based on epoxidized 10-undercenoic acid triglyceride have also shown excellent UV stability. As an example, coatings samples placed in a QUVA chamber exhibit no loss in gloss after 3000 hr of a cycled exposure to high intensity UV lamps and moisture at temperatures of 50–60°C. In comparison, coatings based on standard liquid epoxy resins (LERs) and commercially available hydrogenated LERs lose gloss due to chalking/decomposition within 200–800 hr. Presented at the 81 st Annual Meeting of the Federation of Societies for Coatings Technology, November 12–14, 2003, in Philadelphia, PA.     

Propene Oxidation on Ag(111): Spectroscopic Evidence of Facile Abstraction of Methyl Hydrogen

Reactions of propene on an oxygen-modified Ag(111) surface were investigated by means of temperature-programmed reaction spectra and reflection--adsorption infrared spectroscopy (RAIRS) at 100 K. In the presence of oxygen adatoms, interactions of propene with the substrate are strengthened. The reaction between propene and oxygen adatoms (0.086 monolayer) produces not only total oxidation products (CO₂ and H₂O), but also partial oxidation products (CO and acetone). The formation of chemisorbed hydroxyl groups is identified by RAIRS when coadsorbed propene and oxygen adatoms are annealed to 200 K. The formation of hydroxyl is ascribed to the abstraction of methyl hydrogen by oxygen adatoms.