Indentation-induced ductile behavior of glass–ceramics involving layered aluminosilicates

Contact damage in materials is critical in engineering applications because it influences mechanical resistance, such as wear, erosion, and impact failure. Indentation tests were performed using a tungsten carbide ball indenter (Hertzian contact) on the surfaces of glass–ceramics containing hexagonal CaAl₂Si₂O₈ or mica crystals (fluorophlogopite), both of which have a layered structure. The stress–strain relation and the permanent deformation on the surface, as well as the observation of the microcrack zone by X-ray computed tomography using synchrotron radiation, revealed that the glass–ceramic with hexagonal CaAl₂Si₂O₈ showed ductility similar to the quasi-plastic behavior previously observed in the mica glass–ceramic. The yield stresses of the glass–ceramics were estimated from the stress deviating from the stress–strain relation assuming complete elastic response between the ball and the sample. The ratio of the yield stress to Young modulus (Y/E) of the glass–ceramic with hexagonal CaAl₂Si₂O₈ was determined to be higher than that of the mica glass–ceramic.     

Binary phase behavior of 1,3-distearoyl-2-oleoyl-sn-glycerol (SOS) and 1,3-distearoyl-2-linoleoyl-sn-glycerol (SLS)

The binary phase behavior of SOS (1,3-distearoyl-2-oleoyl-sn-glycerol) and SLS (1,3-distearoyl-2-linoleoyl-sn-glycerol) was examined by using DSC and conventional and synchrotron radiation X-ray diffraction. The solid-solution phases were observed in the metastable α and γ forms in all concentration ranges. Results indicated that the miscible γ form did not transform to the β′ form when the mixtures were subjected to simple cooling from a high-temperature liquid to a low-temperature solid phase. However, and α-melt-mediated transformation into β′ and β₂ resulted in the formation of immiscible phases in concentration ranges of SLS below 30%. By contrast, at SLS concentration ranges above 30%, the α-melt-mediated transformation caused crystallization of only the γ form, and β′ and β₂ crystals did not appear. These results show that the specific interactions between SOS and SLS are operative in the phase behavior of the mixture states of SOS and SLS.     

AFM observation of polyethylene single crystals: selective handedness of screw dislocations in a chair type

The three-dimensional morphology of polyethylene single crystals grown from dilute solution has been examined by atomic force microscopy. Single crystals were deposited on a soft ground of aqueous solution of poly(vinyl alcohol) (PVA) to avoid the collapse of thin lamellar crystals with thickness of 10 nm. The observation of single crystals on dried PVA clarifies the morphology of a chair type crystal as well as well-known hollow pyramidal type. It has been confirmed that the screw dislocations in the chair type follow a selection rule of the handedness in a manner to relieve the distortion in the chair type.     

Control of Oxidation State of Eu Ions in Na2O–Al2O3–SiO2 Glasses

Glasses doped with well‐controlled Eu³⁺ and Eu²⁺ ions have attracted considerable interest due to the possibility of tuning the wavelength range of the emitted light from violet to red by using their ⁵D₀→⁷F_j and 5d–4f electron transitions. Glasses were prepared to dope Eu³⁺ ions in a Na₂O–Al₂O₃–SiO₂ system, and the changes in the valence state of Eu³⁺ ions and the glass structure surrounding the Eu atoms during heating under H₂ atmosphere were investigated using fluorescence spectroscopy, X‐ray absorption fine‐structure spectroscopy, and ²⁷Al magic‐angle spinning solid‐state nuclear magnetic resonance spectroscopy. The reduction behavior of Eu³⁺ ions was dependent on the Al/Na molar ratio of the glass. For Al/Na < 1, the Al³⁺ ions formed the AlO₄ network structure accompanied by the Na⁺ ions as charge compensators; the Eu³⁺ ions occupied the interstitial positions in the SiO₄ network structure and were not reduced even under heating in H₂ gas. On the other hand, in the glasses containing Al₂O₃ with the Al/Na ratio exceeding unity, the Eu³⁺ ions commenced to be coordinated by the AlO₄ units in addition to the SiO₄ network structure. When heated in H₂ gas, H₂ gas molecules reacted with the AlO₄ units surrounding Eu³⁺ ions to form AlO₆ units terminated with OH bonds, and reduced Eu³⁺ ions to Eu²⁺ via the extracted electrons.     

Thermal Stability of Polycarbosilane-Derived Silicon Carbide Fibers under Reduced Pressures

Three types of polycarbosilane-derived SiC fibers—Nicalon, Hi-Nicalon, and Hi-Nicalon S—were exposed at temperatures of 1573–1773 K under a reduced pressure of 1.3 Pa. The thermal stability of the fibers was investigated through examinations of the gas evolution, grain growth, specific resistivity, fiber morphology, and tensile strength. The thermal decomposition of the silicon oxycarbide phase began at 1523 K; then, active oxidation of the β-SiC crystallites occurred at >1673 K. The active oxidation caused serious damage to the fiber structure, which resulted in significant degradation of the fiber strength. Hi-Nicalon had a tensile strength of ∼0.5 GPa after exposure at 1773 K, although Nicalon and Hi-Nicalon S fibers completely lost their strength, even after exposure at 1673 K. Hi-Nicalon fiber had relatively good thermal stability under reduced pressure.     

Removal of nitrogen oxides from air by chemicals-impregnated carbons

Fixation of nitrogen oxides (NO_x) in air onto granular activated carbon impregnated with chemicals was attempted to improve removal efficiency of NO_x by activated carbon adsorption. Nitric oxide (NO) and nitrogen dioxide (NO₂), were tried to remove by a flow test. Fixed-bed adsorption breakthrough curves were obtained when some kinds of carbon were used. The amount adsorbed of NO₂ changed with the amount and kinds of metallic salts impregnated. Chemicals-impregnated carbons were prepared from a commercial activated carbon. Among obtained carbons, the one which showed the highest selectivity for NO_x was chosen, and its performance with the change in humidity was determined. Removal mechanism of NO₂ was estimated, and the carbon impregnated with potassium hydroxide was found to be superior to any other carbon tested. The amount of the adsorbed NO and that produced by the reduction of NO₂ were determined from the breakthrough curves.     

Fabrication and Mechanical Properties of Continuously Graded MoSi2–ZrO2(2Y) Materials Using Wet-Molding

Continuously graded MoSi₂-ZrO₂(2Y) materials with high density (97.5% of theoretical) have been fabricated by uniaxial wet-molding, followed by hot pressing (1000°C/1 h/30 MPa) and hot isostatic pressing (1400°C/2 h/196 MPa). Their composition profiles are greatly influenced by the viscosity of mixed solutions of glycerin and ethanol used as a dispersion medium; a linear compositional gradient from MoSi₂/ZrO₂(2Y) 70/30 to 20/80 mol% is obtained from the solution (50/50 vol%) with a viscosity of 20 mPa s. Vickers hardness (Hv) and fracture toughness (KIC) increase from 9.7 to 12.4 GPa and from 5.1 to 12.5 MPa m1/2, respectively, with increasing ZrO₂(2Y) composition.     

Numerical simulation of particle breakage in dry impact pulverizer

A novel method to simultaneously simulate particle motion and its breakage in a dry impact pulverizer was developed. The motion of particles in the pulverizer was calculated using a discrete phase model (DPM)‐computational fluid dynamics (CFD) coupling model. When the particle impacts against a vessel wall, impact stress acting on the particle is calculated from Hertz's theory as a function of the impact velocity. At the same time, the particle strength as a function of the particle size is calculated from Griffith's theory. If the impact stress is larger than the particle strength, the particle is broken and replaced with smaller fragments. The size distribution of the fragments is obtained from a breakage function proposed. The motion of the fragments is calculated again by using the DPM‐CFD coupling model. By repeating the above calculations over the whole particles, the grinding phenomenon can be simulated. The calculated results showed good agreement with the experimental one, and validity of the proposed method was confirmed. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3601–3611, 2013     

Synthetic Molecular Gear Based on Double-Decker Porphyrin Complexes

New rotary molecular machines (1 and 2) were synthetically constructed from two distinct porphyrin-based rotors, a cerium(IV) bis(porphyrinate)s double-decker (CeDD) and a porphyrinatorhodium(III)-based rotor. These rotors are adjacently mounted on rotational axes aligned to near vertical as resembling the bevel-gear-shaped structure. Structural study using NMR analysis reveals that these distinct rotors are connected through a coordination bond between rhodium(III) and a pyridyl group. At temperature from 193 to 393 K, each rotor represents rotational motion driven by heat fluctuation without decomposition into the corresponding precursors in dichloromethane-d ₂ and tetrachloroethane-d ₄. Importantly, the mechanical interaction between the teeth of these rotors is strongly dependent on the central metal atom in a DD rotor and the teeth structure in a porphyrinatorhodium(III)-based rotor. Understanding such relationship between the chemical structures and mechanical interaction is of importance for generating cooperative motion in the hybrid machinery system.     

Fracture toughness of silica particulate‐filled epoxy composite

The relationship between the postcuring conditions and fracture toughness on three silica particulate‐filled epoxy composites was investigated. The glass transition temperature, T_g, and the fragility parameter, m, derived from the thermo‐viscoelasticity, were used to characterize the composites, which were postcured under various conditions. The glass transition temperature and fragility both depended on both of the curing conditions and the volume fraction of silica particles. The glass transition temperature increased with the postcuring time and temperature, while the fragility generally decreased as the volume fraction increased. There was no direct correlation between the glass transition temperature and fragility. The fracture toughness depended on both the glass transition temperature and fragility. The composites with a high glass transition temperature and low fragility had high fracture toughness. These results indicate that the glass transition temperature and fragility are useful parameters for estimating the fracture toughness of the silica particulate‐filled epoxy composites. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 2261–2265, 2002