Miniemulsion and conventional emulsion copolymerization of styrene and butadiene: Effect of process on gel content

The properties of styrene/butadiene copolymers obtained by conventional emulsion and miniemulsion polymerizations were studied. Thin layer chromatography with flame ionization detection was used to determine the gel fraction of the copolymer in the latex particles as a function of conversion. It was found that the gel formation began at a higher conversion in the miniemulsion polymerization when compared with that in the conventional process. Also, a lower glass transition temperature was noted at the lowest conversion sampled (～25%), implying a higher initial butadiene monomer concentration within the nucleated miniemulsion monomer droplets when compared with particles formed conventionally. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4616–4622, 2006     

Synthesis and application of core–shell particles as toughening agents for epoxies

Poly(butadiene-co-styrene) [P(B-S)] core-poly(methyl methacrylate) (PMMA) shell particles were prepared using a two-step emulsion polymerization. These core-shell particles were used to toughen an epoxy polymer. The role of particle-epoxy interfaces were studied by systematically varying the shell compositions of the core-shell particles such as PMMA, P[MMA-acrylonitrile (AN)], P[MMA-glycidyl methacrylate (GMA)] and P[MMA-divinyl benzene(DVB)]. Therefore, the nature of the particle-epoxy interfaces is varied in terms of physical interactions and chemical bonding. The fracture toughness values of the toughened epoxies were measured using linear elastic fracture mechanics. Results indicate that the morphology of the dispersed particles in the epoxy matrix plays an important role in the toughening of epoxies. This degree of dispersion can be varied by incorporating AN and GMA comonomers in the PMMA shells or by crosslinking the shell. In summary, nanoscale interactions of the rubber-matrix interface do not directly influence fracture toughness, instead, it was found that the nanoscale interactions could be used to control the blend morphology which has a dramatic effect on toughness. © 1995 John Wiley & Sons, Inc.     

Elucidation of the miniemulsion stabilization mechanism and polymerization kinetics

Styrene/hexadecane miniemulsions were polymerized at 50°C using a redox initiator. The miniemulsions and their corresponding latexes were characterized in terms of size, polymerization rate, and surface properties. The resulting data were analyzed to elucidate the miniemulsion stabilization and polymerization mechanisms. It was found that the free surfactant concentration exceeded the critical micelle concentration when large amounts of surfactant (60 mM sodium lauryl sulfate) were used, resulting in simultaneous micellar and droplet nucleation. Most surfactant was on the surface of the droplets (85%) or particles (95%). The fractional surface coverage was proportional to the surfactant concentration to the 0.55 power. Using a particle diameter equation, the number of particles was calculated to be proportional to the surfactant concentration to the 1.35 power. Through direct particle size measurements, a power of 1.38 was confirmed. The rate of polymerization was determined by reaction calorimetry to be proportional to the number of particles to the 0.59 power, in contrast to classical Smith–Ewart kinetics for conventional emulsions (1.0 power). The average number of radicals per particle was estimated from the rate and number data, and varied with the particle diameter to the 0.97 power. The observed kinetic dependencies were validated through an extension of Smith–Ewart theory. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3987–3993, 2003     

Miscibility of oligomeric poly(dimethyl siloxanes) with long-chain unbranched alkanes: 2. Unsymmetrical cloud point curves

Previously obtained cloud point curves for mixtures of oligomeric poly(dimethyl siloxanes) (weight fraction W₁) with oligomeric polyethylenes have been supplemented by the use of samples of higher molecular weight. Initial flat regions at low-medium W₁ as well as a slight shoulder at extremely high W₁ are now considered to be due to crystallization, since the temperatures at which they occur are the melting points of the oligoethylenes. The actual cloud point curves were of an unsymmetrical dome shape, the form of which could not be simulated by using a concentration-independent interaction parameter g in the Flory-Huggins equation. However, spinodals calculated by assuming a quadratic dependence of g on composition were of the same shape as the experimental cloud point curves. The critical compositions calculated on this basis were also close to the experimental ones.     

Eco‐friendly durable press finishing of cellulose‐containing fabrics

To impart easy‐care properties to cellulose‐containing fabrics along with avoiding any harmful effects of formaldehyde on both the health and the environment, attempts have been made to use citric acid (CA) as an ester crosslinking agent along with different catalytic systems in the absence and presence of certain additives. Further, fixation conditions, type of crosslinking agent, as well as type of substrate have been studied. Results revealed that the enhancement in carboxyl content, performance properties, and the decrease in tear strength (TS) as well as in whiteness indices (WI) of the finished fabric samples were increased by increasing CA concentration up to 80 g/L and by raising thermofixation temperature from 140 up to 180°C for 90 s. Inclusion of triethanolamine hydrochloride (TEA. HCl), decreased the carboxyl content, TS, color strength K/S, as well as oily stain release rating (SRR) of the finished fabric samples along with an increase in bound nitrogen (%N), wrinkle recovery angle WRA, and an improvement in WI without affecting the durable press rating (DP). Within the range examined (0–30 g/L), increasing PEG‐600 concentration improved the wet resiliency, TS, as well as WI properties of the finished samples. Increasing DMDHEU ratio in the CA/DMDHEU crosslinking system gave rise to an increase in %N, WRA (dry and wet), DP, as well as in free CH₂O of finished fabrics, along with a slight improvement in WI values. On the other hand, the TS, carboxyl content, K/S, SRR values of the finished fabric samples were lower at a higher DMDHEU ratio. Increase in carboxyl content, %N, WRA (dry and wet), DP and SRR, as well as extent of post dyeing (K/S) of the treated fabric samples upon using different ester crosslinking agents followed the descending order: citric acid > pyromellitic dianhydride. The opposite holds true for the TS, and WI values. Among the esterifying catalysts used, and for a given set of finishing conditions, NaH₂PO₂ · H₂O proved to be the most effective one, and the following order of effectiveness may be drawn: NaH₂PO₂ · H₂O > K₂HPO₄ > Na₃–citrate > Na₂–tartrate. Inclusion of silicone softener in the finishing formulation brought about an improvement in softeness degree, WRA, %N, DP, TS as well as K/S values along with a decrease in carboxyl content, SRR, and WI values of the treated fabric samples, regardless of the used silicone softener.The performance properties of the finished fabric samples were determined by the type and nature of the substrate. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 2243–2253, 2002     

Extraction of metals from sulphides using sulphur trioxide in fluidised bed

The kinetics of the reaction of chalcopyrite, iron sulphide, copper sulphide, and nickel sulphide with sulphur trioxide gas were studied using a fluidised bed technique. O₂, N₂, or air was used as a carrier gas for the sulphur trioxide in fluidisation. Binary mixtures of finely ground (0.37–75 μm) samples were reacted with the sulphur trioxide in a Pyrex column at 373–673 K. The reaction products were leached with water and the soluble metals in the solution were determined by atomic absorption spectrometry. The total soluble reaction products were determined gravimetrically. The results obtained showed that a higher yield of soluble salts was obtained when O₂ or air was used as a carrier gas for sulphur trioxide than when an inert gas was used. Higher yields of soluble salts were obtained when the samples were most finely ground. Increase of copper sulphide content in binary mixtures with iron or nickel sulphide led to an increase in the yield of soluble salts. For iron sulphide/nickel sulphide mixtures, the yield of soluble salts increased with the nickel sulphide content. There were maximum values for the soluble metal ratios Ni/Fe and Cu/Ni in the corresponding sulphide binary mixtures and this maximum was at about 50% weight. The soluble Cu/Fe ratio increased with copper sulphide content in mixtures with iron sulphide.     

High PVC film‐forming composite latex particles via miniemulsification,part 1: Preparation

Miniemulsification technology was used to encapsulate TiO₂ particles inside a styrene/n‐butyl acrylate copolymer with high loading levels (11 to 70% PVC (pigment volume concentration)). In this approach, a St/BA copolymer dissolved in toluene in the presence of a costabilizer (hexadecane) was mixed with a dispersion of TiO₂ particles in toluene and sonified, and then emulsified in an aqueous surfactant solution by sonification. The effect of sonification time on both the dispersibility of the TiO₂ particles in the presence of the copolymer and hexadecane and on the encapsulated particle size was investigated. Particle size analysis by dynamic light scattering showed that these composite latexes are quite stable. It was also found that as the TiO₂ loading increased from 11 to 43% PVC, the particle size of the TiO₂ dispersion decreased while the polymer‐encapsulated TiO₂ particle size increased. The effect of surfactant concentration (sodium lauryl sulfate, SLS) on the encapsulated particle size was investigated using four different SLS concentrations in the 11% PVC system. The results showed that as the SLS concentration increased the particle size decreased, as expected. Also it was found that the minimum surfactant concentration that gives stable encapsulated TiO₂ particles is above 10 mM SLS. The role of HD in the recipe was studied for an artificial latex containing no TiO₂ and one prepared at 11% PVC, in terms of particle size before and after solvent stripping, and its effect on the T_g. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 4504–4516, 2006     

Printing cotton fabrics with reactive dyes of high reactivity from an acidic printing paste

The behaviour of reactive dyes of high reactivity during the printing process of 100% cotton fabrics from an alkaline and acidic printing paste was studied in detail. The printing pastes were stored for different periods of time and then the fabrics were printed. The samples were subjected to two methods of fixation, the first by steaming and the second by thermofixation. The effects of different factors such as alkali and acid concentration, storage time of the printing pastes and method of fixation on the K/S values of the prints were investigated. The fastness properties of the printed areas were also measured to determine the improvement obtained by acidic printing with high-reactivity reactive dyes on cotton fabrics.     

Dense Al2O3/ZrO2 Particulate Composites by Free Sintering of Coated Powders

Composite powders, prepared by coating coarse ZrO₂ particles with fine Al₂O₃ powder using a chemical precipitation technique, were compacted and sintered freely at a constant heating rate of 4°C/min to ∼1600°C. Composites containing up to ∼30 vol% inclusions were sintered to nearly full density under the same conditions used for the unreinforced matrix. Furthermore, the sintering kinetics were not influenced significantly by the inclusion volume fraction. The sinterability of the composites formed from the coated powders was significantly better than that for similar composites formed from mechanically mixed powders. The present data provide a further demonstration that the use of coated powders may have widespread applicability for the fabrication, by free sintering, of dense ceramic particulate composites.