Emulsifier-free, organotellurium-mediated living radical emulsion polymerization of Styrene: Initial stage of polymerization

Behavior of the particle formation based on self-assembling in emulsifier-free, organotellurium-mediated living radical emulsion polymerization (emulsion TERP) of styrene was studied from the molecular weight distributions (MWDs) of polystyrene (PS) formed in an initial stage of the polymerization at different temperatures from 50 °C to 70 °C. As the polymerization temperature was decreased, the larger number of poly(methacrylic acid) (PMAA; degree of polymerization, 30)-methyltellanyl (TeMe) (PMAA₃₀-TeMe) participated in the polymerization, resulting in amphiphilic PMAA₃₀-b-PS-TeMe oligomers. Almost all control agents were consumed and a self-assembly nucleation occurred in the initial stage of the polymerization at 50 °C, which lead to depress of particle formation of a homogeneous nucleation. The consumption rate of PMAA₃₀-TeMe affected directly the particle formation. From these results, it is concluded that it is important for the emulsion TERP of styrene with excellent control/livingness that the self-assembly nucleation proceeds without the homogeneous nucleation in the initial stage of the polymerization.     

Strength of Silicon Nitride after Thermal Shock

A water-quenching technique was used to evaluate the thermal-shock strength behavior of silicon nitride (Si₃N₄) ceramics in an air atmosphere. When the tensile surface was shielded from air during the heating and soaking process, the quenched specimens showed a gradual decrease in strength at temperatures above 600°C. However, the specimens with the air-exposed surface exhibited a ∼16% and ∼29% increase in strength after quenching from 800° and 1000°C, respectively. This is because of the occurrence of surface oxidation, which may cause the healing of surface cracks and the generation of surface compressive stresses. As a result, some preoxidation of Si₃N₄ components before exposure to a thermal-shock environment is recommended in practical applications.     

Preparation of highly syndiotactic block copolymers of methyl methacrylate and lauryl methacrylate and their characterization

Summary Highly syndiotactic diblock and triblock copolymers comprising lauryl methacrylate (LMA) and methyl methacrylate (MMA) with narrow molecular weight distributions were prepared by the living anionic polymerization with t-C₄H₉Li/(C₂H₅)₃Al in toluene at low temperature. The block copolymers were soluble in acetone which is a non-solvent for poly(lauryl methacrylate) (PLMA). ¹HNMR and vapor pressure osmometric analyses of the block copolymers indicated the aggregation of the copolymer in acetone through the interaction between PLMA blocks. Stereocomplex formation between the triblock copolymer and isotactic poly(methyl methacrylate) (PMMA) took place more effectively in solution than in the solid state.     

Model Analysis of Multicrack Mechanisms in Ceramic/Superplastic Laminates

Previous experimental results showed that a ceramic/superplastic laminate exhibited multiple cracking in ceramic layers during a three-point bending test. In this work, a model analysis has been developed based on bending theory. It reveals that there are two basic processes that occur after a ceramic layer fractures: one is a relaxation process of the residual stress in the ceramic layer, due to the confinement by the superplastic layers; the other is a shear process of superplastic flow, which originates from the difference in strain rate between the fractured and unbroken ceramic layers. The total stress in an as-fractured ceramic layer is the sum of the residual stress and a shear-accumulated stress, depending on time. When the total stress at a critical distance from the fractured surface exceeds the fracture strength of a ceramic layer, new cracking occurs. There is a critical roller speed below which no multiple cracking occurs, depending on specimen dimensions and material properties. The number of multicracks in one ceramic layer decreases with the progress of the fracture in the laminate, due to the decrease in shear-accumulated stress. The theoretical predications are in good agreement with the experimental results. Moreover, the variations in fracture energy of the laminate due to the multiple cracking are discussed in detail.     

Indentation fracture resistance test round robin on silicon nitride ceramics

Reproducibility of indentation fracture resistance of three commercial silicon nitrides including bearing balls was evaluated by an international round robin with six laboratories. The between-laboratory standard deviations for indentations at 196 N on the perfectly mirror-finished surfaces were in the range of 0.2–0.5 MPa m^1/2, demonstrating an excellent precession of the test results. The scatter in the fracture resistance increased as the indentation load decreased from 196 to 98 N. The errors in measuring crack lengths deduced from the deviation of each laboratory's readings from author's reading for the same indentations tended to increase with a decrease in the magnification of the lab's microscope, which suggested that finding exact crack tips with lower magnification was difficult especially for those samples with insufficiently mirror-finished surfaces indented at 98 N. Observation of indentations at the load of 196 N with powerful optics was advised to ensure the validity of the indentation technique which is used as the quality assessment of Si₃N₄ bearing balls.     

Influence of Yttria–Alumina Content on Sintering Behavior and Microstructure of Silicon Nitride Ceramics

The present study investigates the influence of the content of Y₂O₃–Al₂O₃ sintering additive on the sintering behavior and microstructure of Si₃N₄ ceramics. The Y₂O₃:Al₂O₃ ratio was fixed at 5:2, and sintering was conducted at temperatures of 1300°–1900°C. Increased sintering-additive content enhanced densification via particle rearrangement; however, phase transformation and grain growth were unaffected by additive content. After phase transformation was almost complete, a substantial decrease in density was identified, which resulted from the impingement of rodlike β-Si₃N₄ grain growth. Phase transformation and grain growth were concluded to occur through a solution–reprecipitation mechanism that was controlled by the interfacial reaction.     

Reactive Hot Pressing of ZrB2–SiC Composites

A ZrB₂–SiC composite was prepared from a mixture of zirconium, silicon, and B₄C via reactive hot pressing. The three-point bending strength was 506 ± 43 MPa, and the fracture toughness was 4.0 MPa·m^1/2. The microstructure of the composite was observed via scanning electron microscopy; the in-situ -formed ZrB₂ and SiC were found in agglomerates with a size that was in the particle-size ranges of the zirconium and silicon starting powders, respectively. A model of the microstructure formation mechanism of the composite was proposed, to explain the features of the phase distributions. It is considered that, in the reactive hot-pressing process, the B and C atoms in B₄C will diffuse into the Zr and Si sites and form ZrB₂ and SiC in situ , respectively. Because the diffusion of Zr and Si atoms is slow, the microstructure (phase distributions) of the obtained composite shows the features of the zirconium and silicon starting powders.     

Catalytic hydrogenation of linoleic acid over platinum-group metals supported on alumina

Catalytic activity and selectivity for hydrogenation of linoleic acid (cis-9,cis-12 18:2) were studied on Pt, Pd, Ru, and Ir supported on Al₂O₃. Stearic acid (18:0) and 10 different octadecenoic isomers (18:1) in the products could be separated completely by using a new capillary column coated by isocyanopropyl trisilphenylene siloxane for gas-liquid chromatography. The monoenoic acid isomers and dienoic acid isomers in the products on the various catalysts showed different distributions. The catalysts exhibited nearly equal selectivity for stearic acid formation. The 12-position double bond in linoleic acid has higher reactivity than the 9-position double bond in catalytic hydrogenation on platinum-group metal catalysts. In addition to hydrogenation products of linoleic acid, geometrical and positional dienoic acid isomers (trans-9,trans-12; trans-8,cis-12; cis-9,trans-13; trans-9,cis-13; cis-9,trans-12 18:2), due to isomerization of linoleic acid during hydrogenation, were contained in the reaction products. Ru/Al₂O₃ exhibited the highest activity for isomerization of linoleic acid with the noble metal catalysts. Conjugated octadecadienoic acid isomers have been observed in products of the reaction on Pt/Al₂O₃, Ru/Al₂O₃, and Ir/Al₂O₃. Catalytic activities of noble metals for positional and geometric isomerization of linoleic acid during hydrogenation decreased in the sequence of Ru ≥ Pt > Ir » Pd.     

A honeymoon‐type adhesive for wood products based on acetoacetylated poly(vinyl alcohol) and diamines: Effect of diamines and degree of acetoacetylation

The honeymoon‐type adhesive for wood products based on acetoacetylated poly(vinyl alcohol) (AAPVA) was investigated focusing on the effect of acetoacetylation on performance, and that of amino compounds as a crosslinking agent. AAPVAs with different degrees of acetoacetylation were synthesized by the addition reaction of diketene in dimethylsulfoxide. Adhesive tests were carried out using aqueous solutions of AAPVA and six kinds of amino compounds, spread separately on test pieces of red meranti selected as the adherend. The mechanical strength of the bonded test pieces was then analyzed. It was found that the adhesive strength increased together with the degree of acetoacetylation at least until 3 h after the application of the adhesives. The degree of acetoacetylation had little effect on water resistance within the range 3.3–37.1%, and as a crosslinking agent, diamines containing primary amino groups were effective, although secondary amines and polyethyleneimine were not. It is assumed that the chemical structure of the amine influenced the crosslinking reaction at the adhesion interface. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2966–2972, 2004     

An authoring technology for multidevice Web applications

The rapid proliferation of mobile computing devices has increased the complexity and cost of cross-platform application development. Multidevice authoring technology (MDAT) lets developers build a generic application common to multiple devices and customize it for specific devices. We developed MDAT an end-to-end development methodology and toolset, to reduce the complexity of creating interactive, form-based Web applications that execute on heterogeneous devices. Web application refers to conventional, servlet-based Web applications as well as portlet applications. A portlet is a Web application component that a Web portal server aggregates with other portlets.