Encapsulation of titanium dioxide in styrene/n‐butyl acrylate copolymer by miniemulsion polymerization

Miniemulsion copolymerization of styrene/n‐butyl acrylate was investigated as a means of encapsulating hydrophilic titanium dioxide (TiO₂) in a film‐forming polymer. Dispersion studies of the TiO₂ were first carried out to determine the choice of stabilizer, its concentration, and the dispersion process conditions for obtaining stable TiO₂ particles with minimum particle size. Through screening studies of various functional stabilizers and shelf‐life stability studies at both room and polymerization temperatures, Solsperse 32,000 was selected to give relatively small and stable TiO₂ particles at 1 wt % stabilizer and with 20–25 min sonification. The subsequent encapsulation of the dispersed TiO₂ particles in styrene/n‐butyl acrylate copolymer (St/BA) via miniemulsion polymerization was carried out and compared with a control study using styrene monomer alone. The lattices resulting from the miniemulsion encapsulation polymerizations were characterized in terms of the encapsulation efficiencies (via density gradient column separations; DGC) and particle size (via dynamic light scattering). Encapsulation efficiencies revealed that complete encapsulation of all of the TiO₂ by all of the polymer was not achieved. The maximum encapsulation efficiencies were 79.1% TiO₂ inside 61.7% polystyrene and 63.6% TiO₂ inside 38.5% St/BA copolymer. As the density of the particles collected from the DGC increased from one layer to another, both the average particle size and the number of the TiO₂ particles contained in each latex particle increased. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 3479–3486, 2006     

The kinetics of B‐a and P‐a type copolybenzoxazine via the ring opening process

The structure of benzoxazines is similar to that of phenolic resin through thermal self‐curing of the heterocyclic ring opening reaction that neither requires catalyst nor releases any condensation byproduct. These polybenzoxazine resins have several outstanding properties such as high thermal stability and high glass transition temperature. To better understand the curing kinetics of this copolybenzoxazine thermosetting resin, dynamic and isothermal differential scanning calorimetry measurements were performed. Three models, the Kissinger method, the Flynn–Wall–Osawa method, and the Kamal method, were used to describe the curing process. Dynamic kinetic activation energies based on Kissinger and Flynn–Wall–Osawa methods are 72.11 and 84.06 KJ/mol, respectively. The Kamal method based on an autocatalytic model results in a total order of reaction between 2.66 and 3.03, depending on curing temperature. Its activation energy and Arrhenius preexponential are 50.3 KJ/mol and 7959, respectively. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 95: 730–737, 2005     

Phase behavior of ternary polymer blends with favorable interactions

Atactic poly(methyl methacrylate) (aPMMA) and poly(vinyl pyrrolidone) (PVP) with a weight‐average molecular weight of 360,000 g/mol were found to be immiscible on the basis of preliminary studies. Poly(styrene‐co‐vinyl phenol) (MPS) with a certain concentration of vinyl phenol groups is known to be miscible with both aPMMA and PVP. Is it possible to homogenize an immiscible aPMMA/PVP pair by the addition of MPS? For this question to be answered, a ternary blend consisting of aPMMA, PVP, and MPS was prepared and measured calorimetrically. The role of MPS between aPMMA and PVP and the effects of different concentrations of vinyl phenol groups on the miscibility of the ternary blends were investigated. According to experimental results, increasing the vinyl phenol contents of MPS has an adverse effect on the miscibility of the ternary blends. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2064–2070, 2005     

Accurate determination of hexanal in beef bouillons by headspace solid‐phase microextraction gas‐chromatography mass‐spectrometry

Lipid oxidation has great impact on the quality of food products through flavor and taste deterioration, reduction in nutritive value, and potential toxicity of the oxidized food components. Flavor and taste deterioration can be easily perceived and it represents one of the major causes of consumer complaints in the food industry. The deterioration of sensory properties is due to the decomposition products of hydroperoxides that easily isomerize and degrade into volatile compounds. Volatile products are responsible for flavor and taste deterioration. In this study, we present the development of the solid‐phase microextraction gas chromatography‐mass spectrometry (SPME‐GC‐MS) technique to quantify low amounts (μg/g range) of secondary oxidation products, i.e. hexanal. The optimization of SPME parameters is a difficult task because of the possibility of further formation of volatile products during analysis. Different parameters such as type of fiber, exposure time of the fiber to the sample headspace and the optimal temperature of absorption have also been investigated. The complete validation of the method was achieved by the determination of linearity, limits of detection and quantification and repeatability. We demonstrated that the SPME method is a valuable tool for the quantification of low amounts of secondary oxidation products such as hexanal. Therefore, this technique can be used to detect early formation of volatiles.     

Influence of dietary long-chain PUFA on premature baboon lung FA and dipalmitoyl PC composition

One of the major survival challenges of premature birth is production of lung surfactant. The lipid component of surfactant, dipalmitoyl PC (DPPC), increases in concentration in the period before normal term birth via a net shift in FA composition away from unsaturates. We investigated the influence of dietary DHA and arachidonic acid (AA) on lung FA composition and DPPC concentration in term and preterm baboons. Pregnant animals/neonates were randomized to one of four groups: breast-fed (B), term formula-fed (T⁻), preterm formulafed (P⁻), and preterm fed formula supplemented with DHA-AA (P⁺). Breast milk contained 0.68%wt DHA and the P⁺ group formula contained 0.61%wt DHA. In the preterm groups (P⁻ and P⁺), pregnant females received a course of antenatal corticosteroids. At the adjusted age of 4 wk, neonate lung tissue was harvested, and FA composition and DPPC were analyzed. Palmitate was ∼28%wt of lung total FA and no significant differences were found among the four treatment groups. In contrast, DPPC in the B group lung tissue was significantly greater than DPPC in the unsupplemented groups, but not compared with the P⁺ group. The B and P⁺ groups were not significantly different in DHA and AA, but were different compared with the unsupplemented (T, P⁻) groups. These results indicate that LCP supplementation increases lung DHA and AA, without compromising overall lung 16∶0 or DPPC. The shift in FA composition toward greater unsaturation in the groups consuming LCP supported improved surfactant lipid concentration in preterm neonate lungs.     

Oil absorbents based on styrene–butadiene rubber

Four oil absorbents based on styrene–butadiene (SBR)—pure SBR (PS), 4‐tert‐butylstyrene–SBR (PBS), EPDM–SBR network (PES), and 4‐tert‐butylstyrene‐EPDM‐SBR (PBES)—were produced from crosslinking polymerization of uncured styrene–butadiene rubber (SBR), 4‐tert‐butylstyrene (tBS), and ethylene–propylene–diene terpolymer (EPDM). The reaction took place in toluene using benzoyl peroxide (BPO) as an initiator. Uncured SBR was used as both a prepolymer and a crosslink agent in this work, and the crosslinked polymer was identified by IR spectroscopy. The oil absorbency of the crosslinked polymer was evaluated with ASTM method F726‐81. The order of maximum oil absorbency was PBES > PBS > PES > PS. The maximum values of oil absorbency of PBES and PBS were 74.0 and 69.5 g/g, respectively. Gel fractions and swelling kinetic constants, however, had opposite sequences. The swelling kinetic constant of PS evaluated by an experimental equation was 49.97 × 10^?2 h^?1. The gel strength parameter, S, the relaxation exponent, n, and the fractal dimension, d_f, of the crosslinked polymer at the pseudo‐critical gel state were determined from oscillatory shear measurements by a dynamic rheometer. The morphologies and light resistance properties of the crosslinked polymers were observed, respectively, with a scanning electron microscope (SEM) and a color difference meter.     

Structure and properties of nitrile rubber (NBR)–clay nanocomposites by co‐coagulating NBR latex and clay aqueous suspension

Nitrile rubber (NBR)–clay nanocomposites were prepared by co‐coagulating the NBR latex and clay aqueous suspension. Transmission electron microscopy showed that the silicate layers of clay were dispersed in the NBR matrix at the nano level and had a planar orientation. X‐ray diffraction indicated that there were some nonexfoliated silicate layers in the NBR–clay nanocomposites. Stress–strain curves showed that the silicate layers generated evident reinforcement, modulus, and tensile strength of the NBR–clay nanocomposites, which were significantly improved with an increase in the amount of clay, and strain‐at‐break was higher than that of the gum NBR vulcanizate when the amount of clay was more than 5 phr. The NBR–clay nanocomposites exhibited an excellent gas barrier property; the reduction in gas permeability in the NBR–clay nanocomposites can be described by Nielsen's model. Compared with gum NBR vulcanizate, the oxygen index of the NBR–clay nanocomposites increased slightly. The feasibility of controlling rubber flammability via the nanocomposite approach needs to be evaluated further. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 3855–3858, 2003     

Spinning and drawing properties of ultrahigh‐molecular‐weight polyethylene fibers prepared at varying concentrations and temperatures

The concentrations and temperatures of ultrahigh‐molecular‐weight polyethylene (UHMWPE) gel solutions exhibited a significant influence on their rheological and spinning properties. The shear viscosities of UHMWPE solutions increased consistently with increasing concentrations at a constant temperature above 80°C. Tremendously high shear viscosities of UHMWPE gel solutions were found as the temperatures reached 120–140°C, at which their shear viscosity values approached the maximum. The spinnable solutions are those gel solutions with optimum shear viscosities and relatively good homogeneity in nature. Moreover, the gel solution concentrations and spinning temperatures exhibited a significant influence on the drawability and microstructure of the as‐spun fibers. At each spinning temperature, the achievable draw ratios obtained for as‐spun fibers prepared near the optimum concentration are significantly higher than those of as‐spun fibers prepared at other concentrations. The critical draw ratio of the as‐spun fiber prepared at the optimum concentration approached a maximum value, as the spinning temperature reached the optimum value of 150°C. Further investigations indicated that the best orientation of the precursors of shish‐kebab‐like entities, birefringence, crystallinity, thermal and tensile properties were always accompanied with the as‐spun fiber prepared at the optimum concentration and temperature. Similar to those found for the as‐spun fibers, the birefringence and tensile properties of the draw fibers prepared at the optimum condition were always higher than those of drawn fibers prepared at other conditions but stretched to the same draw ratio. Possible mechanisms accounting for these interesting phenomena are proposed.     

Effect of amino acid deletions in the O-glycosylated region of Aspergillus awamori glucoamylase

Aspergillus awamori glucoamylase (GA) contains globular catalyticand starch-binding domains (residues 1–471 and 509–616,respectively). A heavily O-glycosylated sequence comprises twoparts. The first (residues 441–471) in the crystal structurewraps around an /-barrel formed by residues 1–440. Thesecond (residues 472–508) is an extended, semi-rigid linkerbetween the two domains. To investigate the functional roleof this linker, we made internal deletions to remove residues466–512 (GA1), 485–512 (GA2) and 466–483 (GA3).GA2 and GA3 were expressed in Saccharomyces cerevisiae culturesupernatants at 60 and 20% the wild-type level, respectively,while GA1 was almost undetectable. Western blots comparing extracellularand intracellular fractions indicated that the region deletedin GA3 was critical for secretion, while the region deletedin GA2 contributed to the production of a stable enzyme structure.The activities of purified GA2 and GA3 on soluble and insolublestarch were similar to those of wild-type GA, indicating thatfor soluble starch their deletions did not affect the catalyticdomain and for insoluble starch the linker does not coordinatethe activities of the catalytic and starch-binding domains.The deletions had a significant negative effect on GA2 and GA3thermos tabilities.