Transformation of tridymite to cristobalite below 1470° C in silica refractories

Because silica refractory has good volume stability and creep properties at high temperature, it has been used in several furnaces. However, silica has three polymorphs (quartz, tridymite and cristobalite) and each polymorph has an- type transformation. It is known that cristobalite is the stable phase of silica between 1470° C and the melting point of silica refractories. However, sometimes cristobalite was found in silica refractories used in the stable temperature region of tridymite. Therefore, the cause and mechanism of this tridymite-to-cristobalite transformation below 1470° C was studied. Although the transformation temperature of tridymite to cristobalite was also 1470° C in the sample used in this research, it decreased on addition of Al₂O₃. The apparent activation energy of the tridymite-to-cristobalite transformation was found to be 787 kJ mol^–1 above 1470° C and 176 kJ mol^–1 below 1470° C with Al₂O₃ by measuring the transformation rate. It was also observed using EPIVIA that the tridymite included CaO; however, CaO and Al₂O₃ were located on the outside of the cristobalite which was produced below 1470°C. Therefore, it is supposed that the liquid phase was produced by the penetration of Al₂O₃, and impurities in the tridymite crystal diffused outside and then silica was precipitated as cristobalite.     

Mechanical properties of a new type of apatite-containing glass-ceramic for prosthetic application

A new type of apatite-containing glass-ceramic in the system MgO-CaO-SiO₂-P₂O₅ can form a tight chemical bond with bones and has a high mechanical strength. The cause for its high mechanical strength was examined by comparing mechanical properties of the glass-ceramics which have an identical chemical composition and different microstructures. It was found that the mechanical strength of the apatite-containing glass-ceramics is considerably increased by the precipitation of-wollastonite crystals due to an increase in fracture surface energy resulting in an increase in fracture toughness.     

NMR Studies on 3He-3He and 3He-4He tunneling motions in solid 3He-4He mixtures

Helium-3 nuclear spin relaxation times T ₁, T ₂, and T ₁have been measured for ³He-⁴He solid mixtures at the exchange plateau region (~0.5K). The ³He concentrations X ₃of the samples were 7.2, 2.9, 1.8, 1.4, 0.67, 0.65, and 0.22%, and their molar volumes varied between 19.9 and 20.9cm³/mole in hcp phase. The spectral density function J() for dipolar field fluctuations was determined in the low-frequency branch from T ₁measurements and in the high-frequency branch from conventional T ₁measurements. It was found that J() is given by J() = cJ()|_3–4 + (1–c)J()|_3–3, where J()|_3–4 is the spectral density function due to the ³He-⁴He tunneling motions, and J()|_3–3 is that due to the ³He-³He tunneling motions. Using the Torrey theory, the correlation frequency of the ³He-⁴He tunneling motions was evaluated from T ₁data, and was found to be in good agreement with Landesman 's theory.Supported in part by the Japan Society for the Promotion of Science through a grant to Y.H.     

Adsorption and decomposition of water-dissolved ozone on high silica zeolites

The adsorption properties of water-dissolved ozone on high silica zeolites were investigated. Adsorbed ozone was desorbed almost reversibly. The adsorption equilibrium relations were described by a linear expression written as q=betaC, where q is the amount adsorbed, C is the equilibrium concentration and beta is the equilibrium constant. Also, the beta values were strongly dependent on the SiO(2)/Al(2)O(3) ratio (mol/mol) and on the pore structure of the high silica zeolites. The larger the SiO(2)/Al(2)O(3) ratio, the larger the value of beta. ZSM-5 (SiO(2)/Al(2)O(3) ratio: 3000), which gave the highest adsorption capacity of water-dissolved ozone, was able to highly concentrate water-dissolved ozone on the adsorbent. The decomposition behavior of adsorbed ozone was also investigated. Ozone adsorbed on high silica zeolite was observed to be a little more stable than ozone existing in bulk water. The decomposition rate was independent of SiO(2)/Al(2)O(3) ratios in the range of 30-3000 or a solution pH in the range of 4-6.     

Formation equation of halogenated organic compounds when water is chlorinated

Various halogenated organic compounds are formed by chlorination of water. In this study, formation of organic compounds halogenated from a reagent humic acid and extract of a leaf mold were examined under various conditions. The following overall formation equation was obtained from empirical data under the practical wide range when free chlorine remained.

[TOX]=k_TOX[TOC][Cl₂]_ot^β.

Here, [TOX] is the concentration of total organic halogen after t h in units of mg chlorine per liter; [TOC] and [Cl₂]_o are concentrations of total organic carbon and dosed chlorine in units of mg per liter; k_TOX is the rate constant and and β are parameters. From the values of k_TOX, and β, the character of organic substances i.e. precursor of halogenated organic compounds, in water can be evaluated. The values k_TOX, and β for humic acid are 0.053, 0.28 and 0.13, and the values for extract of the leaf mold are 0.032, 0.36 and 0.15, respectively. The activation energies are 10 kJ mol⁻¹ and 11 kJ mol⁻¹ for the reactions of humic acid and leaf mold extract, respectively.     

Decomposition of trichloroethene on ozone-adsorbed high silica zeolites

We developed a novel ozonation process for water treatment using high silica zeolites as an adsorptive concentrator of water-dissolved ozone and organic pollutants, resulting in a significant increase in reaction rate. In experiments involving trichloroethene (TCE) decomposition using a tubular flow reactor, TCE decomposition was much greater in the presence of ZSM-5 (SiO(2)/Al(2)O(3) ratio=3000) than in its absence, possibly due to the high concentrations of ozone and TCE inside the adsorbent. The TCE conversion obtained in our experiments was found to reach its theoretically maximum limit.     

Thermal design and its on-orbit performance of the AKARI cryostat

The AKARI satellite (formerly known as ASTRO-F) is Japan’s first infrared astronomical satellite. AKARI is equipped with the infrared camera (IRC) and the far-infrared surveyor (FIS), which are cooled below 7 K. The AKARI’s 68.5 cm telescope, which is made of SiC, is also cooled below 7 K. A unique feature of the AKARI cryostat is that it uses both cryogen and mechanical coolers. Using mechanical coolers, the helium lifetime can be greater than one year with 170 L of liquid helium. AKARI was launched on February 21, 2006 (UT), from the Uchinoura Space Center (USC). It has been performing successfully in orbit.     

Sound Velocity Measurements in the Low and the High Field Phases of the Nuclear-Ordered bcc Solid 3He in Magnetic Fields

We have measured the temperature and magnetic-field dependences of the sound velocity for one longitudinal and two transverse waves in the low field phase (LFP) and the high field phase (HFP) of nuclear spin ordered bcc solid ³He crystals with a single magnetic domain along the melting curve. From sound velocity measurements for various crystal orientations as a function of the sound propagation direction, we determined the elastic stiffness constants, c _ij (T,B). In the LFP with tetragonal symmetry for the nuclear spin structure, we extracted six nuclear spin elastic stiffness constants Δc _ij ^ℓ (T,0.06 T) from the temperature dependence of the sound velocity at 0.06 T and Δc _ij ^ℓ (0.5 mK,B) from the magnetic-field dependence of sound velocity at 0.5 mK. In the HFP with cubic symmetry for the nuclear spin structure, we extracted three Δc _ij ^h (T,0.50 T) at 0.50 T and Δc _ij ^h (0.5 mK,B) at 0.5 mK. At the first-order magnetic phase transition from the LFP to the HFP at the lower critical field B _c1, large jumps in sound velocities were observed for various crystal directions and we extracted three . Using the thermodynamic relation between Δc _ij and the change in the internal energy for the exchange interaction in this system, ΔU _ex(T,B), Δc _ij are related to the generalized second-order Grüneisen constants Γ _ij ^X ≡∂ ²ln X/∂ ε _i ∂ ε _j as Δc _ij (T,B)=Γ _ij ^X ΔU _ex(T,B), where X represents some physical quantity which depends on the molar volume and ε _j is the j-th component of a strain tensor. In the LFP, the Δc _ij ^ℓ (T,0.06 T) were proportional to T ⁴, and Δc _ij ^ℓ (0.5 mK,B) were proportional to B ². We extracted for the spin wave velocity in the LFP, s ^ℓ , from Δc _ij ^ℓ (T,0.06 T) and for the inverse susceptibility, 1/χ ^ℓ from Δc _ij ^ℓ (0.5 mK,B). In the HFP, Δc _ij ^h (T,0.50 T) were proportional to T ⁴ and Δc _ij ^h (0.5 mK,ΔB) were proportional to ΔB(≡B−B _c1). We obtained for the spin wave velocity in the HFP, s ^h , from Δc _ij ^h (T,0.50 T) and for B _c1 from Δc _ij ^h (0.5 mK,ΔB). The values obtained for and were compared with the Multiple Spin Exchange model (MSE) with three parameters by using analytic expressions for s ^ℓ and χ ^ℓ . The three-parameter MSE does not agree with the observed Δc _ij in the LFP.      

Quantum Fluid Dynamics of Rotating Superfluid 3He in Aerogel

Superfluid ³He A-like and B-like phases in 98% aerogel have been studied under rotation up to 2π rad/s by using cw-NMR and Homogeneous Pressing Domain (HPD) NMR at 29 mT and 3.0 MPa. Triplet superfluid ³He has continuous symmetries whose degeneracies are lifted by small perturbations of magnetic field, boundary condition of the sample cell, counterflow and global anisotropies of aerogel. We report NMR results of the two typical samples in aerogel under rotation, which are almost identical in the phase diagram, T _c and the critical velocity of the multiplication of vortex but are very different in textures and responses to the flow with each other. One samples (S-D) is slightly compressed by squeezing and thermal stress and thus has global anisotropic deformation along the sample axis. The other cell (S-H) has randomly(not uniaxially)-oriented global anisotropy. In the S-D, we observed a large negative shift in cw-NMR and spin wave and HPD in the B-like phase. Comparing textures determined by NMR and its response to the counterflows between two samples, we discuss how the long-range order of the continuous symmetry and textures are controlled by orientation effects due to global anisotropy in aerogel.      

Solid-state amorphization of Cu + Zr multi-stacks by ARB and HPT techniques

A series of CuZr binary alloys with wide composition range were fabricated through ARB and HPT techniques using pure Cu and Zr metals as the starting materials. Bulk alloy sheets with thickness of about 0.8 mm after ARB process and alloy disks with 0.30 mm in thickness and 10 mm in diameter after HPT process can be obtained, respectively. The structures of all the alloys were found to be gradually refined with the increase of ARB cycles or HPT rotations. As a result, nanoscale multiple-layered structure was formed for the 10 cycled ARBed specimens, which could partially transform into amorphous phase during subsequent low temperature annealing. While for the as-HPTed sample, the alloy was completely amorphized after 20 rotations without any heat treatment. The thermal stabilities of the amorphous alloys were studied. The deformation behavior and the amorphization mechanism during the ARB and HPT process were put forward and discussed.