Silsesquiazane/organic polymer blends as organic-inorganic hybrid materials

Silsesquiazane (SSQZ), one of the branched forms of polysilazane, was blended with polystyrene (PS), poly(methyl methacrylate) (PMMA), poly(iso-butyl methacrylate) (PBMA), and poly(vinyl acetate) (PVAc) to produce organic-inorganic hybrid materials. The polymers were selected to provide specific interaction, such as ??-?? interaction or hydrogen bonding, with SSQZ. AFM studies revealed that carbonyl containing polymers, PMMA, PBMA, and PVAc were miscible with SSQZ while PS was immiscible. DSC analysis of the hybrids also supported the miscibility behaviours of the system. The glass transition behaviour of SSQZ/PS showed individual transition temperature corresponding to the each component while SSQZ/carbonyl-containing polymers displayed one transition temperature that matched with the theoretically calculated values following the Kwei equation. Among the miscible hybrid system, the interaction with SSQZ increased in the order of PMMA> PBMA> PVAc, as determined by the q value in the Kwei equation. This result was confirmed by determining the degree of hydrogen bonding in FT-IR spectra. Thermal stability of organic polymers was improved by incorporating SSQZ regardless of the miscibility.     

Synthesis and Characterization of Superabsorbent Polymer Based on Carboxymethyl Cellulose-<Emphasis Type="Italic">graft</Emphasis>-Itaconic Acid

Superabsorbent polymers of carboxymethyl cellulose-graft-itaconic acid were synthesized using potassium persulfate as a free radical initiator in the presence of N,N′-methylene bisacrylamide as a crosslinker using solution polymerization technique. The structures of the grafted copolymers were characterized by FT-IR spectroscopy and thermogravimetric analysis. The effect of reaction variables such as concentration of carboxymethyl cellulose, itaconic acid, initiator, crosslinker, and neutralizing agent were optimized to achieve a hydrogel with high swelling capacity of 74 g/g (DI water) and 18 g/g (0.9 wt% NaCl solution). The swelling kinetics of the prepared SAP were analyzed by applying the Fickian diffusion model and the Schott’s pseudo second order kinetics model. The diffusion exponents in the Fickian model, n, showed values of 0.73-0.93, indicating that chain relaxation behavior during absorption had a large effect on total absorbency.     

Ability of surfactant micelles to alter the physical location and reactivity of iron in oil-in-water emulsion

The purpose of this research was to determine how surfactant micelles influence iron partitioning and iron-promoted lipid oxidation in oil-in-water emulsions. Lipids containing ferric ions were used to produce oil-in-water emulsions, and continuous-phase iron concentrations in emulsions were measured as a function of varying continuous-phase polyoxyethylene 10-lauryl ether (Brij) concentrations. Continuous-phase iron concentrations increased with increasing surfactant micelle concentrations (0.1-2.0%) and storage time (1-7 days). At pH 3.0, the concentration of continuous-phase iron was higher than at pH 7.0. Similar trends in iron solubilization by Brij micelles were observed when either hexadecane or corn oil was used as the lipid phase. Lipid oxidation rates, as determined by the formation of lipid hydroperoxides and headspace hexanal, in corn oil-in-water emulsions containing iron decreased with increasing surfactant concentrations (0.5-2.0%). These results indicate that surfactant micelles could alter the physical location and prooxidant activity of iron in oil-in-water emulsions.     

Miscibility and crystallization behaviors of poly(trimethylene terephthalate)/poly(ethylene naphthalate) blends

Poly(trimethylene terephthalate) (PTT)/poly(ethylene naphthalate) (PEN) blends of various compositions were prepared by the solution-blending and melt-blending methods. The changes in miscibility and crystallization behaviors of the blends upon thermal treatment above the melting temperature of the blends at 280°C were investigated by using DSC, DMA,¹H NMR, and SAXS analyses. Without any thermal treatment, the blend systems were not miscible, and the thermal transitions, such as glass transition, cold crystallization, and crystal melting of the individual components were observed in the DSC and DMA analyses. With thermal treatment, though, they became miscible as the thermal transitions of each component disappeared and single glass transition peaks were observed in the thermal analysis. The chain randomness determined using¹H NMR spectroscopy revealed that thermal treatment at 280°C for more than 30 min brought about transesterification reactions between the PTT and PEN segments resulting in an increase in their miscibility. These results were confirmed by the small angle X-ray analysis conducted to determine the long period (L), the thickness of the crystalline lamella stack (l _c ), and the thickness of the amorphous region (l _a ). After short thermal treatment, the melt-blended sample followed the values for the individual components. However, with extended thermal treatment, the blend became homogeneous, possessing different crystalline morphologies which resulted in different values ofL, l _c , andl _a .     

Modification of guar gum through grafting of acrylamide with potassium bromate/thiourea redox initiating system

In the present work, graft copolymers of acrylamide onto guar gum were synthesized by free radical polymerization using potassium bromate/thiourea redox initiating system. The guar gum and guar gum-g-polyacrylamide were characterized by infrared spectroscopy and thermogravimetric analysis. It was found that the guar gum-g-polyacrylamid was thermally more stable than pure guar gum. The grafting ratio, grafting efficiency, add-on, and conversion increased with the concentration of bromate and acrylamide, whereas they decreased with increasing the concentration of guar gum. The grafting ratio and grafting efficiency showed maximum value at the concentration of thiourea and hydrogen ions of 3.2×10^-3 mol dm^-3 and 4.0×10^-3 mol dm^-3, respectively, but decreased with further increasing the thiourea and hydrogen ions concentrations. The increase in temperature from 30 to 45 °C resulted in increasing the grafting ratio while decreasing the conversion. The optimum reaction time for the graft copolymerization was found to be 2 h. Compared to the parent guar gum, the graft copolymer showed higher water swelling capacity and metal ion sorption, as well as better flocculant behaviors.     

Theoretical analysis of kinetic absorption behavior of swellable polymer in solvent

Theoretical equation to predict kinetic absorption behaviors of swellable polymers was developed on the basis of Darcy’s law. The absorption pressure was derived on the model of binary interaction between polymer and solvent. The key variables considered in the equation were the absorption sites of polymer, the concentration of solvent, and the binding order of solvent molecules. The equation was tested with the experimental data of PET in chloroform/hexane mixed solvent from literature. The model equation can simulate the kinetic absorption behaviors and also help to rationalize the experimental results.     

Preparation of inorganic silica nanofibers containing silver nanoparticles

Silica nanofibers containing silver nanoparticles were successfully prepared using sol-gel chemistry and electro-spinning technique. Solution of tetraethly orthosilicate in ethanol containing silver nitrate was aged to have sufficient viscosity and electrospun to form nanofibers. Upon thermal treatment, the gelation reaction between silanols was completed in the prepared silica nanofibers, and at the same time, silver ions in the nanofiber changed to metallic silver or silver oxides. The reduction of silver ions could be also achieved by UV irradiation, and the generated silver nanoparticles were present preferentially on the surface of the silica nanofibers. On testing release behavior of silver ions, it was found that most of silver remained in the silica nanofiber. The silica nanofibers containing silver nanoparticles exhibited excellent antibacterial and deodorant properties.