Deducing the Fatigue Crack Growth Rates of Natural Flaws in Silicon Nitride Ceramics: Role of R‐Curves

Fatigue failure is a concern when high‐strength, high‐toughness silicon nitride ceramics are used in mechanical components and the growth of natural flaws will determine the usable upper bound strength. In this study a fracture resistance curve (R‐curve) model is incorporated into an established method for deducing natural flaw growth rates from a combination of strength and fatigue life data for smooth specimens. Experimental data for a commercial silicon nitride, SL200, were examined. When compared with results deduced using a constant fracture toughness model, the new method gives more physically realistic growth rate results. Specifically, by incorporating the R‐curve the deduced fatigue threshold is equal to the reported intrinsic toughness for crack propagation of 2.2 MPa√m, whereas the constant fracture toughness model gives a physically unrealistic threshold value. Furthermore, much better agreement is achieved with the growth rates measured using macroscopic compact‐tension specimens. Overall, it is concluded that the R‐curve effect should not be ignored when deducing the fatigue crack growth rates of natural flaws in high‐toughness silicon nitride ceramics.     

Effect of ZnO on Crystallization of Zircon from Zirconium‐Based Glaze

The promotion of zircon (ZrSiO₄) crystallization by ZnO from a zirconium‐based frit glaze was studied and the possible mechanism was discussed. X‐ray diffraction was used to analyze the relative quantities of zircon and other transitional crystals in the samples. The results show that ZnO can significantly decrease the crystallization temperature of zirconium‐based glaze, depress the formation of Ca₂ZrSi₄O₁₂, and promote the devitrification of transitional crystals t‐ZrO₂ and Ca₂ZnSi₂O₇, as well as lead to the formation of more zircon than the ZnO‐free glaze. It was also found that zircon not only can form from the interaction between t‐ZrO₂ and SiO₂ but also can devitrify directly from the glass phase of zirconium‐based glaze.     

Phase Separation and Spatial Morphology in Sodium Silicate Glasses by AFM,Light Scattering and NMR

The morphological and structural properties of sodium silicate (Na₂O–SiO₂) glasses were analyzed using atomic force microscopy (AFM) and light scattering following thermal treatments. AFM observations indicated that the glass surface microstructure evolves during the phase separation mechanisms from continuous interpenetrating phases in the spinodal decomposition process to separated droplets embedded in a continuous matrix for the nucleation/growth one. Raman mapping gave evidence of a phase separation through the nucleation/growth process with formation of silica‐rich clusters characterized by higher polymerization degree as separate droplets. The variations in inhomogeneities versus temperature investigated by Brillouin are exponential for spinodal decomposition and linear in the case of nucleation/growth mechanism. Nuclear magnetic resonance spectroscopy was used to investigate the spatial distribution of the various Q_n species present in thermally treated glasses and allows determining fractal dimension between two and three.     

Weak identification in the ESTAR model and a new model

Determining good parameter estimates in (exponential smooth transition autoregressive) models is known to be difficult. We show that the phenomena of getting strongly biased estimators is a consequence of the so‐called identification problem, the problem of properly distinguishing the transition function in relation to extreme parameter combinations. This happens in particular for either very small or very large values of the error term variance. Furthermore, we introduce a new alternative model – the TSTAR model – which has similar properties as the ESTAR model but reduces the effects of the identification problem. We also derive a linearity and a unit root test for this model.     

COMPARATIVE STUDY OF Ag2O/CO3O4 CATALYSTS PREPARED BY THE SOL-GEL AND CO-PRECIPITATION TECHNIQUES: CHARACTERIZATION AND CO ACTIVITY STUDIES

In this study effects of the preparation method on the characteristic properties and CO oxidation activities of Ag₂O/Co₃O₄ catalysts were investigated. Catalysts were prepared by two different methods: sol gel and co-precipitation. N₂ physisorption measurements, X-ray diffraction, and scanning electron microscopy measurements were used to characterize the catalysts. CO oxidation activity tests were carried out under 1% CO, 21% O₂, and the remainder He feed condition between 20° and 200°C. According to the N₂ physisorption measurements, catalysts prepared by the co-precipitation method have a higher surface area than the catalysts prepared by the sol-gel method. Co₃O₄ and AgCoO₂ phases were obtained from catalysts prepared by both techniques. In addition to these phases, metallic silver peaks were obtained by increasing calcination temperature. SEM micrographs of the catalysts showed that catalysts have uniform particles. Increasing the calcination temperature caused the formation of different-sized agglomerates and an increase in the gaps between agglomerates. The best activity was obtained from the Ag₂ O/Co₃ O₄ catalyst calcined at 200°C and prepared by the co-precipitation method. This catalyst gave 50% CO conversion at 106°C. The other two catalysts gave 100% CO conversion at a higher temperature of 200°C.     

DEVELOPMENT OF SYNERGISTIC HEAT STABILIZERS FOR PVC FROM ZINC BORATE-ZINC PHOSPHATE

The importance of flame-retardant and smoke-suppressed poly(vinyl chloride) (PVC) compositions is increasing gradually in the polymer industry since PVC releases smoke and toxic gases (hydrogen chloride, HCl) during heating at temperatures above 140°C with the result of dehydrochlorination reaction. In this study, the synergistic effects of zinc borate (ZB)-zinc phosphate (ZP) on the thermal stability of PVC were investigated using thermal techniques. The induction and stability time values of PVC plastigels were obtained at 140° and 160°C. The results revealed that PVC plastigels having only ZP and ZB retarded dehydrochlorination of PVC compared with the unstabilized sample. However, the plastigels with both ZB and ZP had a superior synergistic effect on char formation of PVC. Since the induction periods of the samples having both ZB and ZP were higher than those of the unstabilized samples having only ZB or only ZP, the synergistic effect was observed.     

HEAT AND MASS TRANSFER IN THE ADSORBENT BED OF AN ADSORPTION HEAT PUMP

The heat and mass transfer equations governing an adsorbent bed in an adsorption heat pump and the mass balance equation for the adsorbent particles in the adsorbent bed were solved numerically to simulate the cycle of a basic adsorption heat pump, which includes isobaric adsorption, isosteric heating, isobaric desorption, and isosteric cooling processes. The finite difference method was used to solve the set of governing equations, which are highly nonlinear and coupled. The pressures of the evaporator and condenser were 2 and 20 kPa, respectively, and the regeneration temperature of the bed was 403 K. Changes in the temperature, adsorptive pressure, and adsorbate concentration in the adsorbent bed at different steps of the cycle were determined. The basic simulated cycle is presented in a Clausius-Clapeyron diagram, which illustrates the changes in average pressure and temperature of the adsorbent bed throughout the cycle. The results of the simulation indicated that the most time-consuming processes in the adsorption heat pump cycle were isobaric adsorption and isobaric desorption. The high thermal resistance of the bed slows down heat transfer, prolonging adsorption and desorption processes.     

Highly efficient and versatile one-pot synthesis of substituted thienylidene compounds

A novel, efficient, and very mild one-pot synthesis of methyl 2-[(Z)-4-aryl-5-morpholino-3-oxo-2,3-dihydrothiophen-2-ylidene]acetate derivatives under kinetic control has been developed. The title compounds were prepared by the reaction of thioacetomorpholides with dimethyl acetylene-dicarboxylate (DMAD) in the presence of K₂CO₃ in a non-polar solvent with excellent yields.     

Hydrolysis of freshly prepared wheat starch fractions and commercial wheat starch using α-amylase

The enzymic hydrolysis of commercial wheat starch and freshly prepared wheat starch fractions was studied in batch and flow systems. Fresh starch was prepared by wet separation of wheat flour into starch milk and gluten, followed by processing the starch milk using a serially connected hydrocyclone system to produce underflow and overflow streams. The underflow stream consisted mainly of the larger (> 30 w m) granules, while the overflow stream contained only the smaller (< 10 w m) granules. In batch system, the hydrolysis behavior of wheat starch fractions was investigated under the action of Sigma f -amylase ( Bacillus licheniformis ), either as soon as they were prepared or after spray drying. The two fractions of fresh wheat starch showed different hydrolysis behavior, the difference getting larger as the separation improves. Underflow streams were found to be much more susceptible to hydrolysis than overflow streams, regardless of whether the hydrolysis was carried out right away or on dried samples, and also regardless of whether rinsing was applied. In flow system, dried underflow stream and commercialwheat starch were hydrolyzed using Orbamil-T ( Bacillus licheniformis ), Orbamil-BHT ( Bacillus stearothermophilus ), and Sigma f -amylase ( Bacillus licheniformis ). Hydrolysis of fresh starch was found to be significantly faster than commercial wheat starch. Commercial f -amylase Orbamil-T was found to be almost as effective as the purified Sigma f -amylase.