Fabrication, Sinterability, and Mechanical Properties of Lead Zirconate Titanate/Silver Composites

High-toughness and high-strength lead zirconate titanate (PZT) composites that contain fine silver particles were successfully fabricated at low sintering temperatures. Addition of silver to a PZT matrix did not result in unwanted reaction phases; however, some silver diffused toward the perovskite crystal structure. A small quantity of silver accelerated the sinterability of the PZT composites. The formation of oxygen vacancies due to the partial substitution of silver appeared to enhance the sinterability of the PZT. Fracture toughness depended on the size and degree of sphericity of the silver particles, and SEM observations on crack propagation suggested that the toughening mechanism in the PZT/Ag composites involves crack bridging resulting from the ductile behavior of silver particles. It is proposed that high fracture strength in PZT/1 to 5 vol% Ag composites results from the relaxation of transformation-induced internal stress by the silver particles.     

Phase Transformation and Texture in Hot-Forged or Annealed Liquid-Phase-Sintered Silicon Carbide Ceramics

Starting from three powder mixtures of 80 vol% SiC (100α, 50α/50β, 100β) and 20 vol% YAG, liquid-phase-sintered silicon carbide ceramics were prepared by hot pressing at 1800°C for 1 h under 25 MPa, and then by hot forging or annealing at 1900°C for 4 h under an applied stress of 25 MPa in argon. The phase transformation and texture development in the as-hot-pressed, hot-forged, and annealed SiC ceramics were investigated via X-ray diffraction (XRD) and the pole figure measurements. The 6H → 4H polytypic transformation was observed in samples consisting of both α- and β-SiC phases when subjected to compressive deformation but absent in the case of annealing, suggesting the deformation-enhanced solubility of aluminum in SiC. Deformation was also found to enhance the 3C → 4H transformation in the sample containing entirely β-phase, which is due to the accelerated solution-precipitation process assisted by grain boundary sliding. The current study showed that the β- →α-phase transformation had little effect on texture development in SiC. Hot forging generally produced the strongest texture, with the calculated maximum of 2.2 times random in samples started with pure α-SiC phase. The mechanism for texture development was explained based on the microstructural observations.     

Hydrogen and carbon dioxide adsorption with tetra‐n‐butyl ammonium semi‐clathrate hydrates for gas separations

Gas adsorption rates of H₂, CO₂, and H₂‐CO₂ gas mixture (H₂/CO₂ = 3.4) with tetra‐n‐butyl ammonium salt (bromide, chloride, and fluoride) semi‐clathrate hydrate particles were measured at 269 K to assess their properties for gas separation. Equilibrium gas occupancies in the S‐cages of the particles were in order of (high to low) for hexagonal structure‐I, tetragonal structure‐I, and superlattice of cubic structure‐I structures with the maximum fractional occupancy by CO₂ being about 40%. The CO₂ diffusion rate depended on the anion size of the salt, which is attributed to distortion of the S‐cage that is close to the molecular size of CO₂. Simulations of semi‐clathrate hydrate particles with theory showed that H₂/CO₂ selectivities could be as high as 36 (3.0 mol% TBAF) and that selectivities for an ideal membrane (3.3 mol% TBAF) could be >100 (269 K, 0.3–4.5 MPa). Semi‐clathrate hydrates have wide application as separation media for gas mixtures. © 2014 American Institute of Chemical Engineers AIChE J, 61: 992–1003, 2015     

High tensile strength fiber of poly[(R)‐3‐hydroxybutyrate‐co‐(R)‐3‐hydroxyhexanoate] processed by two‐step drawing with intermediate annealing

High tensile strength fibers of poly[(R)‐3‐hydroxybutyrate‐co‐(R)‐3‐hydroxyhexanoate] [P(3HB‐co‐3HH)], a type of microbial polyesters, were processed by one‐step and two‐step cold‐drawn method with intermediate annealing. Thermal degradation behaviors were characterized by differential scanning calorimeter and gel permeation chromatography measurements. Thermal analyses were revealed that molecular weights decreased drastically within melting time at a few minute. One‐step cold‐drawn fiber with drawing ratio of 10 showed tensile strength of 281 MPa, while tensile strength of as‐spun fiber was 78 MPa. When two‐step drawing was applied for P(3HB‐co‐3HH) fibers, the tensile strength was led to 420 MPa. Furthermore, the optimization of intermediate annealing condition leads to enhance the tensile strength at 552 MPa of P(3HB‐co‐3HH) fiber. Wide‐angel X‐ray diffraction measurements of these fibers suggest that the fibers with high tensile strength include much amount of the planer‐zigzag conformation (β‐form) as molecular conformation together with 2₁ helix conformation (α‐form). © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41258.     

Nano-Blast Synthesis of Nano-size CeO2–Gd2O3 Powders

CeCl₃·7H₂O and GdCl₃·6H₂O that were dissolved in water were precipitated with urea (NH₂CONH₂) to produce matrix agglomerates for three-component nano-reactors. Mixing hexamethylenetetramine with dilute nitric acid resulted in the formation of well-dispersed nano-particles of cyclotrimetilene trinitramine (C₃H₆N₆O₆) (RDX) in the solvent. Nano-reactors were produced by impregnating the nano-C₃H₆N₆O₆ into the matrix agglomerates of an intermediate complex of cerium and gadolinium compounds. Blast initiation of the C₃H₆N₆O₆ resulted in extremely rapid detonation and gaseous products formation at temperatures of 2000°–5000°C, which were compressed into a volume nearly equal to the initial volume of each RDX nano-particle. Multiple "nano-blasts" occurred in the volume of each nano-reactor. The impact of the blast waves led to fragmentation of the surrounding matter. The evolution of a large volume of gaseous products dissipated the heat of the process and limited temperature increase, thus reducing the possibility of local sintering among the primary particles. The short-term high temperature generated during the blasts enhanced the solid solubility of the metal oxides. Uniform aggregates of 22∼74 nm consisting of 6∼14 nm crystallites of gadolinia in ceria solid solution were synthesized.     

Chemical‐Free Approach for Z‐Isomerization of Lycopene in Tomato Powder: Hot Air and Superheated Steam Heating above the Melting Point of Lycopene

Z‐isomers of lycopene exhibit higher bioavailability and antioxidant capacity than those of the all‐E‐isomer. Therefore, it is important to develop an efficient and environmentally friendly procedure for Z‐isomerization. The current methods for Z‐isomerization of (all‐E)‐lycopene use toxic chemicals such as organic solvents and catalysts. This study is aimed to develop a chemical‐free method for Z‐isomerization of (all‐E)‐lycopene in tomato powder by hot air and superheated steam heating. The Z‐isomerization reaction is promoted by heating above the melting point of lycopene. When heated with superheated steam, the thermal decomposition of lycopene is suppressed compared to that when heated with hot air. When tomato powder is heated at 240 °C for 5 min by superheated steam, the total Z‐isomer content and remaining lycopene are 69.0% and 90.7%, respectively, while with hot air heating, the total Z‐isomer content and remaining lycopene are 69.9% and 68.0%, respectively. These results indicate that the thermal Z‐isomerization of lycopene occurs in the molten state and heating in a low oxygen atmosphere suppresses the thermal decomposition of lycopene. Practical Applications: Tomato powder rich in lycopene Z‐isomers is an important ingredient for the food and animal feed industries. Since Z‐isomers of lycopene are more soluble in solvents including ethanol which is a low‐toxicity and environmentally friendly solvent, the efficiency of lycopene extraction with ethanol can be improved by using the Z‐isomer‐rich tomato powder as a raw material. The obtained Z‐isomer‐rich extract has a high added value because the Z‐isomers have higher bioavailability and antioxidant capacity than those of the all‐E‐isomer. In addition, since lycopene Z‐isomers exhibit higher accumulation efficiency and better color improvement in hen egg yolks than those of the all‐E‐isomer, Z‐isomer‐rich tomato powder is an effective animal feed.     

Modifying ability of Ql-free coal-tar pitch to develop optical anisotropy in co-carbonizations

Carbonization properties of a Ql-free coal-tar pitch (CTP-ASM) prepared by selective precipitation were studied to evaluate it as a source for needle-coke. Its modifying ability for production of needlecoke in co-carbonizations with principal carbonizing substances which gave cokes of mozaic texture in single carbonizations was estimated by changing mixing ratios. The shape and size of the anisotropic optical texture in the co-carbonized coke were measured by point counting. CTP-ASM and Ashland A240, of eight additives, had the highest modifying ability in the co-carbonizations with Khafji vacuum residue. Both contained ca. 6% benzene-insolubles (Bl), and had f_a values of ≈0.9. Other additives of either lower or higher Bl or f_a showed less modifying ability. The modifying susceptibility of principal carbonizing substances varies with their structure and properties. Based on a systematic investigation of co-carbonizations the compatibility between a principal carbonizing substance and an additive is discussed from a viewpoint of their structural parameters.     

Synthesis of High‐Purity Ti3SiC2 by Microwave Sintering

High‐purity ternary laminated compound Ti₃SiC₂ was successfully synthesized by a microwave heating method in the flowing argon for the first time. The mixtures of titanium, silicon, and graphitic carbon (C_gc) or activated carbon (C_ac) with different molar ratios were used to investigate the reaction mechanisms. It was confirmed that Ti₃SiC₂ with high purity of 98 vol.% was achieved without the aids of Al. The optimum experimental parameters were determined as Ti/Si/C_gc having the molar ratio of 3/2.2/2, first holding at 1480°C for 30 min, and subsequent dwelling at 1300°C for 60 min.     

Optical assessment of silicon nanowire arrays fabricated by metal-assisted chemical etching

Silicon nanowire (SiNW) arrays were prepared on silicon substrates by metal-assisted chemical etching and peeled from the substrates, and their optical properties were measured. The absorption coefficient of the SiNW arrays was higher than that for the bulk silicon over the entire region. The absorption coefficient of a SiNW array composed of 10-μm-long nanowires was much higher than the theoretical absorptance of a 10-μm-thick flat Si wafer, suggesting that SiNW arrays exhibit strong optical confinement. To reveal the reason for this strong optical confinement demonstrated by SiNW arrays, angular distribution functions of their transmittance were experimentally determined. The results suggest that Mie-related scattering plays a significant role in the strong optical confinement of SiNW arrays.     

Preparation of regioisomers of structured TAG consisting of one mole of CLA and two moles of caprylic acid

TAG (MLM) with medium-chain FA (MCFA) at the 1,3-positions and long-chain FA (LCFA) at the 2-position, and TAG (LMM) with LCFA at the 1(3)-position and MCFA at 2,3(1)-positions are a pair of TAG regioisomers. Large-scale preparation of the two TAG regioisomers was attempted. A commercially available FFA mixture (FFA-CLA) containing 9-cis, 11-trans (9c, 11t)- and 10t,12c-CLA was selected as LCFA, and caprylic acid (C₈FA) was selected as MCFA. The MLM isomer was synthesized by acidolysis of acyglycerols (AG) containing two CLA isomers with C₈FA: A mixture of AG-CLA/C₈ FA (1∶10, mol/mol) and 4 wt% immobilized Rhizomucor miehei lipase was agitated at 30°C for 72 h. The ratio of MLM to total AG was 51.1 wt%. Meanwhile, LMM isomer was synthesized by acidolysis of tricaprylin with FFA-CLA: A mixture of tricaprylin/FFA-CLA (1∶2, mol/mol) and 4 wt% immobilized R. miehei lipase was agitated at 30°C for 24 h. The ratio of LMM to total AG was 51.8 wt%. MLM and LMM were purified from 1,968 and 813 g reaction mixtures by stepwise short-path distillation, respectively. Consequently, MLM was purified to 92.3% with 49.1% recovery, and LMM was purified to 93.2% with 52.3% recovery. Regiospecific analyses of MLM and LMM indicated that the 2-positions of MLM and LMM were 95.1 mol% LCFA and 98.3 mol% C₈ FA, respectively. The results showed that a process comprising lipase reaction and short-path distillation is effective for large-scale preparation of high-purity regiospecific TAG isomers.