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1.
2.
R.K.B GoverN.D. Withers S. AllenR.L. Withers J.S.O. Evans 《Journal of solid state chemistry》2002,166(1):42-48
SnP2O7 is a member of the ZrP2O7 family of materials, several of which show unusual thermal expansion behavior over certain temperature ranges and which show a number of displacive phase transitions on cooling from high temperature. Here we describe the structural properties of SnP2O7 from 100 to 1243 K as determined by X-ray and neutron powder diffraction. These studies reveal that SnP2O7 shows two phase transitions in this temperature range. At room temperature the material has a pseudo-cubic 3×3×3× superstructure. Electron diffraction studies show that the symmetry of this structure is P213 or lower. On warming to ∼560 K it undergoes a phase transition to a structure in which the subcell reflections show a triclinic distortion; above 830 K the subcell reflections show a rhombohedral distortion. Significant hysteresis in cell parameters is observed between heating and cooling. The structure of SnP2O7 is discussed with references to other members of the AM2O7 family of materials. 相似文献
3.
Varrot A Tarling CA Macdonald JM Stick RV Zechel DL Withers SG Davies GJ 《Journal of the American Chemical Society》2003,125(25):7496-7497
Glycosidases are some of the most ubiquitous enzyme in nature. Their biological significance, coupled to their enormous catalytic prowess derived from tight binding of the transition state, is reflected in their importance as therapeutic targets. Many glycosidase inhibitors are known. Imino sugars are often potent inhibitors, yet many facets of their mode of action, such as their degree, if any, of transition-state "mimicry" and their protonation state when bound to the target glycosidase remain unclear. Atomic resolution analysis of the endoglucanase, Cel5A, in complex with a cellobio-derived isofagomine in conjunction with the pH dependence of Ki and kcat/KM reveals that this compound binds as a protonated sugar. Surprisingly, both the enzymatic nucleophile and the acid/base are unprotonated in the complex. 相似文献
4.
Kabin JA Withers ST Grant CS Carbonell RG Sáez AE 《Journal of colloid and interface science》2000,228(2):344-358
Measurements have been made of the rate of removal of a solid organic film (phenanthrene) from the surface of a rotating disk using emulsions containing water, the nonionic surfactant Tween 20, and d-limonene as the organic phase. The results show that phenanthrene removal initially occurs by the uptake of phenanthrene into the emulsion drops as small aggregates. Simultaneously, the organic phase penetrates into the phenanthrene film, diminishing the adhesive force between the film and the substrate. After sufficient time, the phenanthrene film detaches from the rotating disk surface as a solid. This detachment mechanism accounts for the vast majority of the phenanthrene removal ( approximately 90%). Initial solubilization rates were analyzed using two solubilization models. Both models assume that phenanthrene removal occurs via a mass transfer limited removal of phenanthrene-laden emulsion drops from the phenanthrene film surface into the bulk solution. One model treats the emulsion as homogeneous while the other accounts for the finite size of the emulsion droplets. The latter model was also used to relate the flux of organic phase impacting the phenanthrene film to the detachment times. Copyright 2000 Academic Press. 相似文献
5.
C. S. Withers 《Annals of the Institute of Statistical Mathematics》1991,43(1):147-156
Based on a sample of size n, we investigate a class of estimators of the mean of a p-variate normal distribution with independent components having unknown covariance. This class includes the James-Stein estimator and Lindley's estimator as special cases and was proposed by Stein. The mean squares error improves on that of the sample mean for p3. Simple approximations imations for this improvement are given for large n or p. Lindley's estimator improves on that of James and Stein if either n is large, and the coefficient of variation of is less than a certain increasing function of p, or if p is large. An adaptive estimator is given which for large samples always performs at least as well as these two estimators. 相似文献
6.
Single phase perovskite-based rare earth cobaltates (Ln1−xSrxCoO3−δ) (Ln=La3+, Pr3+, Nd3+, Sm3+, Gd3+, Dy3+, Y3+, Ho3+, Er3+, Tm3+ and Yb3+; 0.67?x?0.9) have been synthesized at 1100°C under 1 atmosphere of oxygen. X-ray diffraction of phases containing the larger rare earth ions La3+, Pr3+ and Nd3+ reveals simple cubic structures; however electron diffraction shows orientational twinning of a local, tetragonal (I4/mmm; ap×ap×2ap) superstructure phase. Orientational twinning is also present for Ln1−xSrxCoO3−δ compounds containing rare earth ions smaller than Nd3+. These compounds show a modulated intermediate parent with a tetragonal superstructure (I4/mmm; 2ap×2ap×4ap). Thermogravimetric measurements have determined the overall oxygen content, and these phases show mixed valence (3+/4+) cobalt oxidation states with up to 50% Co(IV). X-ray diffraction data and Rietveld techniques have been used to refine the structures of each of these tetragonal superstructure phases (Ln=Sm3+-Yb3+). Coupled Ln/Sr and oxygen/vacancy ordering and associated structural relaxation are shown to be responsible for the observed superstructure. 相似文献
7.
A full-field, multi-axial computation technique is described for determining residual stresses using the hole-drilling method with DIC. The computational method takes advantage of the large quantity of data available from full-field images to ameliorate the effect of modest deformation sensitivity of DIC measurements. It also provides uniform residual stress sensitivity in all in-plane directions and accounts for artifacts that commonly occur within experimental measurements. These artifacts include image shift, stretch and shear. The calculation method uses a large fraction of the pixels available within the measured images and requires minimal human guidance in its operation. The method is demonstrated using measurements where residual stresses are made on a microscopic scale with hole drilling done using a Focused Ion Beam – Scanning Electron Microscope (FIB-SEM). This is a very challenging application because SEM images are subject to fluctuations that can introduce large artifacts when using DIC. Several series of measurements are described to illustrate the operation and effectiveness of the proposed residual stress computation technique. 相似文献
8.
Wm. Douglas Withers 《Constructive Approximation》1989,5(1):151-170
The problem of fitting a given function in theL q norm with a function generated by an iterated function system can be rapidly solved by applying Newton's method on the parameter space of the iterated function system. The key to this is a method for calculating the derivatives of a potential function with respect to the parameters. 相似文献
9.
Multilayered BaTiO3(BTO)/Bi0.5K0.5TiO3 (BKT) thin films have been fabricated on Pt/Ti/SiO2/Si substrates using a metalloorganic decomposition process. XRD investigation of the resultant BTO/BKT multilayered thin films shows that they retain a perovskite-related structure type. They also exhibit a well-defined, polarization–electric field hysteresis loop with a measured remnant polarization (2Pr) of 5 µC/cm2 at an applied electric field of 250 kV/cm. The measured dielectric constant and dielectric loss at 10 kHz is 470 and 0.07 respectively. These multilayer BTO/BKT films maintain an excellent fatigue-free character even after 109 switching cycles. The mechanism associated with the enhancement of the electrical properties of the synthesized BTO/BKT films is also discussed. 相似文献
10.
A low-temperature electron diffraction study has been carried out on ThAsSe to search for evidence of structural disorder associated with the low-temperature non-magnetic Kondo effect. A highly structured and extremely complex characteristic diffuse intensity distribution has been observed at low temperature and interpreted in terms of a gradual charge density wave type phase transition upon lowering of temperature involving disordered As-As dimerization within (001) planes. Plausible models of the proposed As-As dimerization have been obtained using a group theoretical approach. 相似文献