Phase diagram of Bi up to 140 kbars

The phase diagram of Bi has been studied by resistometric techniques in the temperature range of 30 to 300°K up to pressures of 140 kbars. Using the original Bridgman phase notation, the phase transitions I–II, II–III, I–III, III–IV and V–VI were observed. Two new phases, designated VIII and IX were observed in this region. The triple points occurring between I–II–III near 29.5 kbars and 160°K, between IV–V–VIII near 55 kbars and 240°K, between V–VI–VIII near 72 kbars and 255°K and between VI–VIII–IX near 135 kbars and 250°K. Earlier measurements were adjusted to the 1970 Drickamer pressure scale and compared to the present results. A phase diagram is proposed for pressures to 140 kbars. Calculations of the volume changes and latent heats of transformation are made near the triple points I–II–III, IV–V–VIII and V–VI–VIII using the measured volume changes of Bridgman for the I–II, IV–V and V–VI transitions. The latent heat associated with the III–IV transition was calculated using the volume data of Bridgman to be less than ? 2 cal/mol.     

NMR studies of restricted diffusion in lyotropic systems

Tortuosity, 1/alpha, and surface-to-volume ratio, S/V, were determined in aqueous solutions of decylammonium, dodecylammonium and tetradecylammonium chlorides of various concentrations by measuring the apparent diffusion coefficient of water, D(app)(delta). This was found to be much smaller than in the bulk state. Such restricted diffusion is interpreted in terms of the Mitra model, where D(delta) depends on diffusion time and is controlled primarily by S/V. The samples exhibit lamellar (L), hexagonal (H) and isotropic (I) liquid crystalline phases. We observed changes in S/V upon phase transition. In the lamellar and hexagonal phases, the system is ordered, resulting in relatively small S/V ratios, compared to the micellar-isotropic phase. We did not observe a dependence on the diffusion time, delta, in the isotropic phase, because the duration of the experiment was not sufficiently short to observe the change from D(app)(delta) to D(eff). We observed the effective diffusion coefficient of water, which directly probes the tortuosity of the system. The S/V ratios were obtained by fitting the Mitra model, using known values of the bulk water diffusion coefficients, and the assumption that D(app) --> D0 for delta --> 0. S/V is correlated with the type of structure, increasing on transition to the isotropic phase and decreasing on transition to other phases. The change in tortuosity is small, but slightly larger for the isotropic phase.     

Evolution of the commensurate and incommensurate magnetic phases of the S = 3/2 kagome staircase Co?V?O? in an applied field

Single crystal neutron diffraction studies have been performed on the S = 3/2 kagome staircase compound Co(3)V(2)O(8) with a magnetic field applied along the magnetization easy-axis ([Formula: see text]). Previous zero-field measurements (Chen Y et al 2006 Phys. Rev. B 74 014430) reported a rich variety of magnetic phases, with a ferromagnetic ground state as well as incommensurate, transversely polarized spin density wave (SDW) phases (with a propagation vector of [Formula: see text]) interspersed with multiple commensurate lock-in transitions. The magnetic phase diagram with [Formula: see text] adds further complexity. For small applied fields, μ(0)H ≈ 0.05 T, the commensurate lock-in phases are destabilized in favor of the incommensurate SDW ones, while slightly larger applied fields restore the commensurate lock-in phase with δ = 1/2 and yield a new commensurate phase with δ = 2/5. For measurements in an applied field, higher-order scattering is observed that corresponds to the second harmonic.     

Model for processive movement of myosin V and myosin VI

Myosin V and myosin VI are two classes of two-headed molecular motors of the myosin superfamily that move processively along helical actin filaments in opposite directions. Here we present a hand-over-hand model for their processive movements. In the model, the moving direction of a dimeric molecular motor is automatically determined by the relative orientation between its two heads at free state and its head‘s binding orientation on track filament.This determines that myosin V moves toward the barbed end and myosin VI moves toward the pointed end of actin.During the moving period in one step, one head remains bound to actin for myosin V whereas two heads are detached for myosin VI: the moving manner is determined by the length of neck domain. This naturally explains the similar dynamic behaviours but opposite moving directions of myosin VI and mutant myosin V (the neck of which is truncated to only one-sixth of the native length). Because of different moving manners, myosin VI and mutant myosin V exhibit significantly broader step-size distribution than native myosin V. However, all the three motors give the same mean step size of -36nm (the pseudo-repeat of actin helix). All these theoretical results are in agreement with previous experimental ones.     

Study on spectrum of solvent extraction of chromium( VI) by primary amine

The Cr(VI) solvent extraction in near neutral aqueous solution by primary amine was experimentally studied by the inductively couple plasma-atomic emission spectrometry (ICP-AES), laser Raman spectroscopy, Fourier transform infrared spectroscopy (FTIR) and 1H nuclear magnetic resonance spectroscopy (1H NMR). The ICP-AES analysis of the aqueous phase before and after solvent extraction showed that primary amine could extract Cr(VI) from nearly neutral solution. Laser Raman spectroscopy of loaded organic phase showed that a new peak appeared at 890 cm(-1) after Cr(VI) was extracted by primary amine. FTIR showed the process that primary amine extracted Cr(VI) from nearly neutral aqueous solutions was different from anion exchange mechanism, and the Cr(VI) extracted into the organic phase resulted in the appearance of the peak at 885 cm(-1) of FTIR which justified that the peak at 890 cm(-1) of Raman was caused by Cr(VI). The 1H NMR spectroscopy showed that the value of chemical shift of protons of -NH2 decreased after extraction, and it is believed that primary amine was associated with Cr(VI) through hydrogen bonding. On the basis of the spectroscopic analysis results above, the mechanism of Cr(VI) extraction by primary amine from nearly neutral aqueous solutions was believed to be solvation with molecular association between primary amine and Cr(VI) through hydrogen bonding.     

Microscopic measurement of the linear compressibilities of two-dimensional fatty acid mesophases

The linear compressibility of two-dimensional fatty acid mesophases has been determined by grazing incidence X-ray diffraction. The unit cell parameters of the , , , S and phases of behenic acid and of the phase of myristic acid were determined as a function of surface pressure and temperature. Surface pressure versus molecular area isotherms were reconstructed from these measurements, and the linear compressibility (relative distortion along a given direction for a two-dimensional isotropic applied stress) was determined both in the sample plane and in a plane normal to the aliphatic chain director (transverse plane). The linear compressibilities range over two orders of magnitude from 0.1 to 10 m/N and are distributed depending on their magnitude in 4 different sets which we are able to associate with different molecular mechanisms. The largest compressibilities (10 m/N) are observed in the tilted phases. They are apparently independent on the chain length and could be related to the reorganization of the headgroup hydrogen-bounded network, whose role should be revalued. Intermediate compressibilities are observed in phases with quasi long-range order (directions normal to the molecular tilt in the or phases, S phase, and could be related to the ordering of these phases. The lowest compressibilities are observed in the solid untilted phase and for one direction of the S and phases. They are similar to the compressibility of crystalline polymers and correspond to the interactions between methyl groups in the crystal. Finally, negative compressibilities are observed in the transverse plane for the and phases and can be traced to subtle reorganizations upon untilting. Received: 29 July 1997 / Revised: 14 October 1997 / Accepted: 23 October 1997     

Beam-foil level populations and charge-state fractions

We have measured relative beam-foil excitation functions in S IV, V, VI and Fe V, VI, for levels with one outer-shell excited electron. The ratios of these functions to the charge-state fractions of the corresponding ions have the same dependence on the beam energy, whatever the ion charge is. A simple explanation of the results is proposed.     

Study of the polymorphism of binary solutions of molecular substances in microsamples

Previous studies have shown that certain molecular substances taken in microsamples (droplets of about 1 μm³ in volume dispersed within an emulsion) crystallize into metastable crystalline phases. These compounds are studied in solution with benzene which does not show metastable polymorphism. The binaries benzene-1-2 dichlorobenzene, benzene-chloroform and benzene-nitrobenzene in emulsion are investigated by D.S.C. techniques. Metastable phases appear, too, and it is possible to draw metastable liquidus and locate metastable eutectics in the phase diagrams. In benzene-chloroform solution at least one new metastable phase is detected. In the benzene-nitrobenzene binary a metastable phase is detected, although neither benzene nor nitrobenzene show a metastable crystalline phase when they are pure.     

用三正辛胺-苯萃取分离体系-原子吸收光谱对铬作形态分析

研究了痕量铬形态分析的三正辛胺(TOA)-苯萃取分离体系-原子吸收光谱法。用三正辛胺(TOA)和苯在H₂SO₄介质中把水相中的Cr(Ⅵ)萃入到有机相而Cr(Ⅲ)留在水相中,使两种形态的Cr分离到两相中后对有机相的Cr(Ⅵ)和水相的Cr(Ⅲ)进行AAS测定,可求得Cr(Ⅵ)和Cr(Ⅲ)的含量,该方法对实际水样加标回收率分别在95.0%～102% 和94.8%～103%之间,相对标准偏差分别为2.9%和2.6% ,体系对Cr(Ⅵ)有富集作用,对Cr(Ⅵ)和Cr(Ⅲ)的检出限分别为6.6 μg·L-1和0.20 mg·L-1,TOA对Cr(Ⅵ)的最佳萃取量为4.6 mg·mL-1,该法简单、快速、准确。     

Mixed threefold and fourfold carbon coordination in compressed CO2

Carbon dioxide (CO2) has been recently reported to possess an amorphous form, named "carbonia," structurally similar to other group-IV oxide glasses. By combining ab initio constant pressure molecular dynamics, density-functional perturbation theory, and experimental IR spectra, we show that carbonia, and possibly also phase VI, is not SiO2-like, and that instead it is partially tetrahedral containing also a sizable amount of carbon in threefold coordination, but no sixfold octahedral coordination. Enthalpic considerations suggest that carbonia is a metastable intermediate state of the transformation of molecular CO2 into fully tetrahedral phases.     

Stability and mechanical properties of various Hf-H phases: A density-functional theory study

We performe first-principles density functional theory calculations to investigate the stability and mechanical properties of various Hf Hx(0 ≤ x ≤ 1) phases. For pure Hf phases, the calculated results show that the HCP and FCC phases are mechanically stable, while the BCC phase is unstable at 0 K. Also, as for various Hf Hx phases, we find that H location and concentration could have a significant effect on their stability and mechanical properties. When 0 ≤ x ≤ 0.25, the HCP phases with H at(tetrahedral) T sites are energetically most stable among various phases. The FCC and BCC phases with H at T sites turn to be relatively more favorable than the HCP phase when H concentration is higher than 0.25. Furthermore, our calculated results indicate that the H solution in Hf can largely affect their mechanical properties such as the bulk moduli(B) and shear moduli(G).     

Observation of a pressure-induced first-order polyamorphic transition in a chalcogenide glass at ambient temperature

An apparently first-order polyamorphic transition has been observed with increasing pressure at ambient temperature in a molecular glass of composition Ge(2.5)As(51.25)S(46.25) Raman spectroscopic measurements on pressure-quenched samples and in situ x-ray diffraction measurements indicate that this transition corresponds to a collapse of the ambient-pressure molecular phase to a high-pressure network phase. The high-pressure phase first appears at a pressure of approximately 8-9 GPa and the transformation becomes complete at approximately 14-15 GPa. Calorimetric measurements indicate that the low- and high-pressure phases are thermodynamically distinct and that they coexist in the transition range.     

Phase behavior of symmetric ternary block copolymer-homopolymer blends in thin films and on chemically patterned surfaces

The phase diagram of symmetric ternary blends of diblock copolymers and homopolymers in thin films was determined as a function of increasing volume fraction of homopolymer (phi(H)) and was similar to that for these materials in the bulk. Blends with compositions in the lamellar region of the diagram (phi(H)< or =0.4) could be directed to assemble into ordered lamellar arrays on chemically striped surfaces if the characteristic blend dimension (L(B)) and the period of the stripes (L(S)) were commensurate such that L(S)=L(B)+/-0.10L(B). Blends with compositions in the microemulsion region of the diagram (phi(H) approximately 0.6) assembled into defect-free lamellar phases on patterned surfaces with L(S)> or =L(B), but formed coexisting lamellar (with period L(S)) and homopolymer-rich phases when L(S)相似文献   

M?ssbauer study of contaminated soils by industrial activity in Paramonga city, Region Lima Provinces, Peru

In this work we characterize soils from the Paramonga city, Region Lima Provinces in Peru, which are contaminated by residual chemicals (Br, As and Sr) from sugar and paper industry in the city. Four samples were collected, labelled as S1, S2, S3 and S4 and analized by X-ray diffraction (XRD), energy-dispersive X-ray fluorescence (EDXRF) and M?ssbauer spectroscopy. For all the samples, the chemical analysis by EDXRF revealed the presence of Fe, Mn, Cu, Zn, K, Br, Sr. The XRD detected the presence of quartz as principal phase and copper sulfide and potassium magnesium as secondary phases. The M?ssbauer spectra at room temperature (RT) for all the samples exhibit sextets which reveal the presence of an iron oxide or hydroxide. The fitting M?ssbauer for both samples S1 and S4 have three doublets corresponding to iron in paramagnetic phases and a magnetic component of around 35.50?T corresponding to goethite, α-FeOOH. Sample S2 have two magnetic phases with internal fields of 37?T and 34.6?T which correspond to the goethite and other incorporated element in the structure. The sample S3 have three magnetic fields of H1?=?36.8?T, H2?=?33.6?T and H3?=?34.8?T which correspond to hydroxide iron, pyrrhotite and goethite respectively.     

The high-pressure phase diagram of ammonia dihydrate

We have investigated the P–T phase diagram of ammonia dihydrate (ADH), ND3·2D₂O, using powder neutron diffraction methods over the range 0–9 GPa, 170–300 K. In addition to the ambient pressure phase, ADH I, we have identified three high-pressure phases, ADH II, III, and IV, each of which has been reproduced in at least three separate experiments. Another, apparently body-centred-cubic, phase of ADH has been observed on a single occasion above 6 GPa at 170 K. The existence of a dehydration boundary has been confirmed where, upon compression or warming, ADH IV decomposes to a high-pressure ice phase (ice VII or VIII) and a high-pressure phase of ammonia monohydrate (AMH V or VI).     

Magnetic-field switching of crystal structure in an orbital-spin-coupled system: MnV2O4

We studied the magnetic and structural properties of spinel MnV2O4, which has S=5/2 spin with no orbital degrees of freedom on the Mn2+ site and S=1 spin and three orbital degrees of freedom on the V3+ site. We found that the ferrimagnetic ordering at TN=56.5K and the structural phase transition at Ts=53.5K are closely correlated in this compound and found a switching of crystal structure between cubic and tetragonal phases by the magnetic field. This phenomenon can be explained by the coupling between orbital and spin degrees of freedom in the t2g states of the V site.     

Modelling of dynamical processes in a molecular crystal by NMR

In this contribution we report on the plastic crystal 1-chloroadamantane dynamics via conventional frequency dependent (¹H and ¹³C) and field cycling NMR measurements. A suitable microscopic dynamical model, worked out from from X-ray analysis is developed and the molecular motions are interpreted in terms of: self diffusion and dipolar molecular axis combined with uniaxial rotation. In the rotator phase the molecules execute a bimodal reorientation process whereas the uniaxial rotation solely persists in the low temperature phase. In both phases, the residence times exhibit an Arrhenius temperature dependence. The results confirm the existence of a dynamic crossover transition predicted by molecular dynamics simulation.     

Phase transitions in a nonuniformly stressed state of matter

The nucleation of a new phase of a substance in a nonuniform stress field created during measurements of rigidity is considered. The phase diagram of silicon containing the Si I, II, and V phases are considered. The high-pressure boundaries of the phases formed near the indenter are found using the finite elements method.     

三种具有Keggin结构的硅钨氧簇化合物的光谱研究

合成了三种具有Keggin结构的硅钨氧簇化合物：K₃H[SiWⅥ₁₂O₄₀]·3H₂O(Ⅰ),(H₃O)₄[H₃SiWⅥ₉WⅤ₃O₄₀]·2H₂O(Ⅱ)和[(CH₃)₄N]₄[SiWⅥ₁₂O₄₀]·4.5 H₂O(Ⅲ),用FTIR,NIR FT-Raman,UV-Vis和荧光光谱等研究手段进行了光谱研究,探讨其结构与性能的关系。在这些化合物中, 阴离子相同或类似,具有孤立的[SiW₁₂O₄₀]簇骼基元,通过静电作用和弱的氢键与阳离子及水相连。它们的FTIR和NIR FT-Raman光谱研究表明：硅钨酸盐的特征振动频率与其结构相关,由于化合物Ⅱ中的部分W6+已被还原成W5+,使ν_as(WO_d)振动频率降低,且簇阴离子电荷大小也明显地对ν_as(W—O_c—W),ν_as(Si—O_a),δ(O_a—Si—O_a)等产生影响;化合物Ⅰ和Ⅱ的UV-Vis光谱显示,在200和250 nm左右有紫外吸收谱带;化合物Ⅰ的稳态荧光光谱观察到分别以220,350和440 nm激发时,相应在350,440和520及675 nm左右产生一个或两个发射峰。