Maximum likelihood estimate for discontinuous parameter in stochastic hyperbolic systems

The purpose of this paper is to study the identification problem of a spatially varying discontinuous parameter in stochastic hyperbolic equations. In previous works, the consistency property of the maximum likelihood estimate (MLE) was explored and the generating algorithm for MLE proposed under the condition that an unknown parameter is in a sufficiently regular space with respect to spatial variables.In order to show the consistency property of the MLE for a discontinuous coefficient, we use the method of sieves, i.e. the admissible class of unknown parameters is projected into a finite-dimensional space. For hyperbolic systems, we cannot obtain a regularity property of the solution with respect to a parameter. So in this paper, the parabolic regularization technique is used. The convergence of the derived finite-dimensional MLE to the infinite-dimensional MLE is justified under some conditions.     

Phase transitions of lanthanide monophosphides with NaCl-type structure at high pressures

Lanthanide monophosphides LnP (Ln = La, Ce, Pr, Nd, Sm, Gd, Tb, Tm and Yb) with a NaCl-type structure have systematically been prepared at high temperatures. Using synchrotron radiation, X-ray diffractions of LnP have been studied up to 61 GPa at room temperature. The NaCl---CsCl transition for CeP is found at around 25 GPa. First-order phase transitions of LnP (Ln = La, Pr and Nd) with the crystallographic change occur at around 24, 26 and 30 GPa, respectively. The structure of the high pressure phases of these phosphides is a body center tetragonal structure (Ln: 0, 0, 0; P: 1/2, 1/2, 1/2; space group P4/mmm), which can be seen as the distorted CsCl-type structure. The Pr---P distance in the high pressure form of PrP is 2.789 Å. This almost agrees with the sum of covalent radii of Pr and P. The Pr---P bond has the covalent character at very high pressures. Similar results are also obtained for LaP and NdP. The pressure-induced phase transitions of SmP, GdP, TbP, TmP and YbP occur at around 35, 40, 38, 53 and 51 GPa, respectively. The structure of the high pressure phase is unknown. The phase transitions of LnP with many f-electrons are not due to the mechanism of the ordinary NaCl---CsCl transition. The transition pressures of LnP increase with decreasing the lattice constants in the NaCl-type structure, which decrease with increasing atomic number of the lanthanide atoms.     

Synthesis of silicon nitride based ceramic nanoparticles by the pyrolysis of silazane block copolymer micelles

Diblock copolymer poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane)‐block‐polystyrene (polyVSA‐b‐polySt) and triblock copolymer poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane)‐block‐polystyrene‐block‐poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane) (polyVSA‐b‐polySt‐b‐polyVSA), consisting of silazane and nonsilazane segments, were prepared by the living anionic polymerization of 1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane and styrene. PolyVSA‐b‐polySt formed micelles having a poly(1,1,3,N,N′‐pentamethyl‐3‐vinylcyclodisilazane) (polyVSA) core in N,N‐dimethylformamide, whereas polyVSA‐b‐polySt and polyVSA‐b‐polySt‐b‐polyVSA formed micelles having a polyVSA shell in n‐heptane. The micelles with a polyVSA core were core‐crosslinked by UV irradiation in the presence of diethoxyacetophenone as a photosensitizer, and the micelles with a polyVSA shell were shell‐crosslinked by UV irradiation in the presence of diethoxyacetophenone and 1,6‐hexanedithiol. These crosslinked micelles were pyrolyzed at 600 °C in N₂ to give spherical ceramic particles. The pyrolysis process was examined by thermogravimetry and thermogravimetry/mass spectrometry. The morphologies of the particles were analyzed by atomic force microscopy and transmission electron microscopy. The chemical composition of the pyrolysis products was analyzed by X‐ray fluorescence spectroscopy and Raman scattering spectroscopy. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 4696–4707, 2006     

Fully automated micro- and nanoscale one- or two-dimensional high-performance liquid chromatography system for liquid chromatography-mass spectrometry compatible with non-volatile salts for ion exchange chromatography

A one- or two-dimensional high performance liquid chromatography system for electrospray ionization mass spectrometers has been developed that is optimized for ion exchange and reversed phase separations. A unique and simple valve configuration permits the use of a variety of non-volatile salts; ammonium sulfate was used in an example of strong cation exchange separations. The system was designed and evaluated for both micro- and nanoflow chromatography. The peptide detection limit was approximately 100 fmol for micro- and 20 fmol for nanoflow, demonstrating the concentration and mass sensitivity improvements expected with nanoelectrospray ionization. The 1D/2D-HPLC MS system is fully automated for routine peptide analyses, compatible with direct injection of proteolytic digests, and exhibits chromatographic reproducibility and sensitivity. Software permits operator selection of either a 1D or 2D configuration with corresponding system parameters as required for individual samples. The hardware elements and resulting performance are described in this paper.     

Recent progress of high-power negative ion beam development for fusion plasma heating

A negative-ion-based neutral beam injector (N-NBI) has been constructed for JT-60U. The N-NBI is designed to inject 500 keV, 10 MW neutral beams using two ion sources, each producing a 500 keV, 22 A D⁻ ion beam. In the preliminary experiment using one ion source, a D⁻ ion beam of 13.5 A has been successfully accelerated with an energy of 400 keV (5.4 MW) for 0.12 s at an operating pressure of 0.22 Pa. This is the highest D⁻ beam current and power in the world. Co-extracted electron current was effectively suppressed to the ratio of Ie/I_D⁻ < 1. The highest energy beam of 460 keV, 2.4 A, 0.44 s has also been obtained. To realize 1 MeV class NBI system for ITER (International Thermonuclear Experimental Reactor), demonstration of ampere class negative ion beam acceleration up to 1 MeV is an important mile stone. To achieve the mile stone, a prototype accelerator and a 1 MV, 1 A test facility called MeV Test Facility (MTF) were constructed. Up to now, an H⁻ ion beam was accelerated up to the energy of 805 keV with an acceleration drain current of 150 mA for 1 s in a five stage electrostatic multi-aperture accelerator.     

Selective chemical vapor deposition synthesis of double-wall carbon nanotubes on mesoporous silica

Double-wall carbon nanotubes (DWNTs) have been selectively synthesized over Fe/Co loaded mesoporous silica by catalytic chemical vapor deposition of alcohol. Several silica materials with desired pore diameter and morphology have been investigated for the DWNT growth. The diameter distribution and selectivity of the DWNT are found to depend on the reaction temperature, pore size, and thermal stability of the support material. A high-yield synthesis of DWNTs has been achieved at 900 degrees C over high-temperature stable mesoporous silica. The outer diameter of DWNTs is found to be in the range of 1.5-5.4 nm with a "d" spacing of 0.38 +/- 0.02 nm between inner and outer layers, which is much larger than those of multiwall carbon nanotubes.     

NMR studies of phosphinenickel(0) complexes of ethyl methacrylate Ni(PR3)2(CH2=C(CH3)COOC2H5)

¹³C NMR data are given for a series of phosphinenickel(0) complexes of ethyl methacrylate (ema), Ni(PR₃)₂(CH₂=C(CH₃)COOC₂H₅) (PR₃ = PPh₃ (Ia), PEtPh₂ (Ib), PEt₂Ph (Ic), PMe₂Ph (Id), PEt₃ (Ie)). The olefinic carbon signals of ema shift upfield by 71.5–86.5 ppm on coordination, the magnitude of the upfield shift increasing with increase in the bacisity of the phosphine ligand. The effect of the basicity of PR₃ is discussed on the basis of the back-bonding from Ni to ema. Variable temperature¹H NMR studies reveal that the ema of Id, the complex having the least sterically demanding phosphine ligands, exchanges with free ema in toluene on the NMR time scale. The dependence of the rate of exchange on the concentration of ema shows that the exchange proceeds through anS_N2 mechanism. The activation parameters are: ΔH₂₇₃^≠ 2.75 kcal/mol, ΔG₂₇₃^≠ 12.7 kcal/mol, ΔS₂₇₃^≠ ?37 e.u. The³¹P NMR spectra of the complexes show two doublets when the exchange is frozen out, indicating the inequivalence of the two phosphine ligands in the ema-coordinated complex. The difference in the³¹P chemical shifts of the two coordinated tertiary phosphines increases with increase in the basicity of the PR₃ ligand.