Surface-initiated atom transfer radical polymerization of methyl methacrylate on magnetite nanoparticles

The synthesis of magnetite nanoparticles coated with a well-defined graft polymer is reported. The magnetite nanoparticles with an initiator group for copper-mediated atom transfer radical polymerization (ATRP), 2-(4-chlorosulfonylphenyl) ethyltrichlorosilane (CTCS) chemically bound on their surfaces were prepared by the self-assembled monolayer-deposition method. The surface-initiated ATRP of methyl methacrylate (MMA) was carried out with the CTCS-coated magnetite nanoparticles in the presence of free (sacrificing) initiator, p-toluenesulfonyl chloride. Polymerization proceeded in a living fashion, exhibiting first-order kinetics of monomer consumption and a proportional relationship between molecular weight of the graft polymer and monomer conversion, thus providing well-defined, low-polydispersity graft polymers with an approximate graft density of 0.7 chains/nm². The molecular weight and polydispersity of the graft polymer were nearly equal to those of the free polymer produced in the solution, meaning that the free polymer is a good measure of the characteristics of the graft polymer. The graft polymer possessed exceptionally high stability and remarkably improved dispersibility of the magnetite nanoparticles in organic solvent.     

Preparation of a Near-Infrared Ray Absorption Film from N-Phenylthiocarbamoyl Chitosan Derivative

We recently observed that the decanoylation of N-phenylthiocarbamoyl chitosan (2) with a mixture of decanoic anhydride and pyridine at 60 °C for 24 h afforded N,N-(decanoyl)phenythiocarbamoyl-/2-isothiocynato chitosan decanoate (3b) rather than the expected product N,N-(decanoyl)phenylthiocarbamoyl chitosan decanoate (3a). This result suggested that some of the N,N-(decanoyl)phenylthiocarmbamoyl groups had been converted to isothiocyanate groups during the decanoylation process. The subsequent reaction of compound 3b with aniline gave N,N-(decanoyl)phenylthiocarbamoyl/N-phenylthiocarbamoyl chitosan decanoate (4) in high yield. A solution of compound 4 in CHCl₃ was then added to a solution of copper decanoate (5) in the same solvent, and the resulting mixture was cast onto a glass plate to give a cast film. The film was annealed at 200 °C in an oven to give a greenish film, which showed good near-infrared absorption characteristic in the range of 800–2200 nm.     

Residual stress versus microstructural effects on the strength and toughness of phase-separated PbO–B2O3–Al2O3 glasses

A few authors have reasonably proposed that liquid–liquid phase-separated (LLPS) glasses could show improved fracture strength, S_f, and toughness, K_Ic, as the second phase could provide a barrier to crack propagation via deflection, bowing, trapping, or bridging. Due to the associated tensile or compressive residual stresses, the second phase could also act as a toughening or a weakening mechanism. In this work, we investigated five glasses of the PbO–B₂O₃–Al₂O₃ system spanning across the miscibility gap: Four of them undergo LLPS—three are binodal (two B₂O₃-rich and one PbO-rich) and one is spinodal—and one does not show LLPS (composition outside the miscibility gap). Their compositions were designed in such a way that the amorphous particles are under compressive residual stresses in some and under tensile residual stresses in others. The following mechanical properties were determined: the Vickers hardness, ball on three balls (B3B) strength, and toughness, K_Ic-SEVNB (single-edge V-notch beam [SEVNB]). The microstructures and compositions were analyzed using scanning electron microscopy with energy-dispersive X-ray spectrometry. The spinodal glass showed, by far, the best mechanical properties. Its K_Ic-SEVNB = 1.6 ± 0.1 MPa m^1/2, which embodies an increase of almost 50% over the B₂O₃-rich binodal composition, and 90% considering the PbO-rich binodal composition. Moreover, its fracture strength, S_f = 166 ± 7 MPa, is one of the highest ones ever reported for an LLPS glass. Fracture analyses evidenced that the spinodal composition exhibited the lowest net stress at the fracture point. Moreover, calculations indicate that the internal residual stress level is the lowest in the spinodal glass. The overall results indicate that the microstructural effect of the spinodal glass is the most significant factor for its superior mechanical properties. This work corroborates the idea that LLPS provides a feasible and stimulating solution to improve the mechanical properties of glasses.     

Dynamic Mechanical Properties and Adhesive Joint Strengths of Emulsion Polymers Produced by Power Feed Technique. III. Adhesive Joint Strengths of Grafted Power Feed Copolymer

Power feed copolymers were synthesized using styrene and n-butyl acrylate through non-uniform feeding emulsion polymerization. Poly(vinyl alcohol) (PVA) was used as a protective colloid, onto which vinyl monomers were grafted. Power feed copolymer had a very broad glass transition temperature compared with random copolymer, even if grafting and/or crosslinking were introduced to the system. This tendency was almost the same as the non-grafted power feed copolymer where only low molecular weight surfactant was used.

Adhesive joint strengths of power feed copolymers were evaluated compared with random copolymers. In the case of usual linear power feed copolymer, the adhesive joint strengths were not higher than those of random copolymer, which was considered to be due to the lower film strengths of the power feed copolymer. Power feed copolymer having grafting showed slightly higher adhesive joint strengths over a wide range of temperatures than random copolymer. When crosslinking was introduced to the system, power feed copolymer showed much higher adhesive joint strengths over a wide temperature range.     

Miscibility Between Ethylene Vinyl Acetate Copolymers and Tackifier Resins

A series of ethylene vinyl acetate copolymer (EVA) were blended with various kinds of tackifiers and the miscibility between the components was investigated. The miscibility of the blend is illustrated as a phase diagram. The EVA and modified rosin systems tended to have a phase diagram with lower critical solution temperature (LCST), whereas the EVA and petroleum resin systems tended to have that with upper critical solution temperature (UCST). The phase diagrams of EVA/tackifier resins systematically changed as VAc content in the copolymer increased, which is accounted for by the classical Flory-Huggins theory.     

deNOx Performance and Reaction Mechanism of the Di-Air System

The detailed reaction mechanism of Di-Air, which showed the unprecedented high deNO_x performance at high temperature conditions, was studied in this work. Since the Di-Air phenomenon occurs with continuous short pulse injections of hydrocarbons over NSR (NO_x storage and reduction) catalyst, this study focused on the specific function of HC as an effective reductant for NO_x reduction reaction. As a first step, the deNO_x performance was compared with three different reductant gases including CO, H₂ and C₃H₆ in a modified synthetic gas bench equipped with a gas injector which enables continuous small amount of injections. At inlet gas temperature of 450 °C C₃H₆ showed the best deNO_x performance whereas H₂ was the best at 150 °C. Moreover the result of temperature programmed desorption showed that intermediate species represented by –NCO (isocyanates) produced from C₃H₆ was thermally more stable than that produced from CO. These results confirmed that the injected HC reacts with adsorbed NO_x on NSR catalyst generating thermally stable intermediates, which could contribute the high deNO_x performance at high temperature conditions.     

Removal of lignin in a liquid system by an isolated fungus

The screening of a strain which could perform lignin removal was carried out. Based on taxonomic study the isolated strain (LM‐2) was identified as Penicillium sp. LM‐2 could decolorize 0.6 g dm^?3 lignin within 4 days in a shaking culture at 25 °C. The efficiency of decolorization of the lignin was over 80% in the pH range of 4.0–6.0, but was low above pH 6.2. The rise of temperature had a slight adverse effect on the lignin decolorization in the range of 25–35 °C. Lignolytic enzymes such as lignin peroxidase, manganese peroxidase and laccase were not detected in the culture broth or within the fungal cells. The lignin was removed from the high molecular weight fraction mainly by adsorption and accumulation inside the cells. © 2001 Society of Chemical Industry     

Preparation and properties of transparent cellulose hydrogels

Highly transparent cellulose hydrogels with physical crosslinkage were prepared from nonaqueous organic cellulose solutions and viscose by coagulating and regenerating cellulose in an aqueous solution containing a water‐miscible organic solvent. Nonaqueous organic cellulose solutions used were LiCl/dimethylacetamide, paraformaldehyde/dimethyl sulfoxide, and triethylammonium chloride/dimethyl sulfoxide. Preparation conditions and physical properties of the transparent cellulose hydrogels were studied. The transparency of the cellulose hydrogels depended on the composition of the aqueous solution containing the organic solvent. Furthermore, transparent cellulose hydrogels from viscose showed high tensile strength. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3020–3025, 2003