Elastic phase transitions in metals at high pressures

The elastic phase transitions of cubic metals at high pressures are investigated within the framework of Landau theory. It is shown that at pressures comparable with the magnitude of the bulk modulus the phase transition is connected with the loss of stability relative to uniform deformation of the crystalline lattice. Discontinuity of the order parameter at the transition point and its equilibrium value are expressed through the second-?to fourth-order elastic constants. The second-,third-?and fourth-order elastic constants and phonon dispersion curves of vanadium under hydrostatic pressure are obtained by first-principles calculations. Structural transformation in vanadium under pressure is studied using the obtained results. It is shown that the experimentally observed at P?≈?69?GPa phase transition in vanadium is the first-order phase transition close to a second-order phase transition.     

Data-base for structual phase transitions at high pressures

Abstract

The data on 700 structual phase transitions at high pressure are collected. The 420 fully described phase transitions are reviewed in the form of statistical table showing the number of given change of phase symmetry at the transition. Some other statistical data are presented.     

Theory of elastic phase transitions in metals at high pressures. Application to vanadium

Structural transformations in elementary metals under high pressures are considered using the Landau theory of phase transitions, in which the finite strain tensor components play the role of the order parameter. As an example, the phase transition in vanadium observed at a pressure of 69 GPa is analyzed. It is shown that it is a first-order elastic phase transition, which is close to a second-order transition.     

Structural and magnetic phase transitions in Pr0.7Ca0.3MnO3 at high pressures

JETP Letters - The crystal structure and Raman spectra of Pr0.7Ca0.3MnO3 manganite at high pressures of up to 30 GPa and the magnetic structure at pressures of up to 1 GPa have been studied. A...     

Phase transitions in uranium dioxide at high pressures and temperatures

The melting curve is plotted for uranium dioxide with fluorite structure in a pressure range from ?2.5 to +100 GPa. This curve has a peak at the point 3348 K, 6 GPa, and has a negative derivative at high pressures. The pressure corresponding to a polymorphic transition of uranium dioxide (37 GPa) at a temperature of 1015 K is determined. The slope of the equilibrium curve of the polymorphic transition in UO₂ in the temperature range 300–1000 K is ? 56 K/GPa.     

Structural phase transitions and the equation of state of SnTe at high pressures up to 2 mbar

Synchrotron X-ray diffraction studies of the structure of SnTe have been performed at room temperature and high pressures under the conditions of quasihydrostatic compression up to 193.5 GPa created in diamond anvil cells. Two structural phase transitions have been detected at P ≈ 3 and 23 GPa. The first phase transition is accompanied by a stepwise decrease in the volume of the unit cell by 4% because of the orthorhombic distortion of the initial SnTe-B1 cubic structure of the NaCl type. It has been found that two intermediate rhombic phases of SnTe with the space groups Cmcm and Pnma coexist in the pressure range of 3–23 GPa. The second phase transition at 23 GPa occurs from the intermediate rhombic modification to the SnTe-B2 cubic phase with the CsCl structure type. This phase transition is accompanied by an abrupt decrease in the volume of the unit cell by 8%. The pressure dependence of the volumes per formula unit at room temperature has been determined.     

Pressure effects on the kinetic properties and phase transitions in lithium

The pressure dependences of the electrical resistance and thermal electromotive force of lithium were measured at room temperature. The results substantiated the occurrence of a phase transition caused by increasing pressure (6.7 GPa). A phase transition was detected when pressure was decreased (6.4 GPa). Temperature effects on the pressures of these transitions were studied near room temperature. At pressures above 4 GPa, the pressure dependences of thermal electromotive force and of the velocity of ultrasonic shear waves in BCC lithium exhibited anomalies. The suggestion was made that applying pressure increased the role played by electron-phonon and phonon-phonon interactions in lithium.     

Superconductivity and phase stability of selenium at high pressures

Hexagonal Se shows no indication of a transformation to a metallic, superconducting phase up to 160 kbar. Amorphous Se transforms at about 130 kbar to an unstable metallic, superconducting state which anneals slowly at room temperature toward a non-metallic, non-superconducting phase. Monoclinic Se behaves much like amorphous Se. X-ray diffraction indicates that all samples are in the hexagonal phase after release of pressure.     

Structural and magnetic phase transitions occurring in Pr0.7Sr0.3MnO3 manganite at high pressures

The crystal and magnetic structures and the vibrational spectra of Pr_0.7Sr_0.3MnO₃ manganite are studied within the pressure range up to 25 GPa by methods of X-ray diffraction and Raman spectroscopy. Neutron diffraction studies have been performed at pressures up to 4.5 GPa. The magnetic phase transition from the ferromagnetic phase (T _C = 273 K) to the A-type antiferromagnetic phase (T _N = 153 K) is found at P ≈ 2 GPa. This transition is characterized by a broad pressure range corresponding to the phase separation. The Raman spectra of Pr_0.7Sr_0.3MnO₃ measured under high pressures significantly differ from the corresponding spectra of the isostructural doped A_{1 ? x} A′ _x MnO₃ manganites, (where A is a rare-earth ion and A′ is an alkaline-earth ion) with the smaller average ionic radius 〈r _A〉 of A and A′ cations. Namely, the former spectra do not include clearly pronounced stretching phonon modes. At P ～ 7 GPa, there appears the structural phase transition from the orthorhombic phase with the Pnma space group to the orthorhombic high-pressure phase with the Imma symmetry. In the vicinity of the phase transition, anomalies in the pressure dependences of the lattice parameters, unit cell volume, and phonon frequencies corresponding to the characteristic lattice vibration modes are observed.     

High pressure phase transitions in organic solids II: X-ray diffraction study ofp-dichlorobenzene at high pressures

X-ray diffraction experiments onp-dichlorobenzene at high pressures show a transition at ～ 0.3 GPa, to a new phase, the diffraction pattern of which cannot be indexed on the anticipated low temperature monoclinic crystal structure. We have instead found an orthorhombic cell, very closely related to the low temperature monoclinic cell, for this new phase. This structure, which also occurs inp-diiodobenzene at ambient conditions, has cell constantsa =14.02,b = 6.06,c = 7.41Å andZ = 4. The space group is Pbca. This new phase has a non-β herring-bone structure, in contrast with the initialα phase which has aβ-structure with ribbon-like arrangement of molecules, with Cl-Cl contacts of ～ 4A between adjacent molecules. This implies that with pressure the halogen-halogen interaction in this compound plays a less dominant role in crystal engineering.     

Stable phase of metallic hydrogens at high pressures

The stable phase of metallic hydrogens at zero temperatures is studied by the structural expansion. A number of structural transitions are predicted to occur with increase of the pressure.     

Structural and magnetic phase transitions in gadolinium under high pressures and low temperatures

High pressure structural transition studies have been carried out on rare earth metal gadolinium in a diamond anvil cell at room temperature to 169?GPa. Gadolinium has been compressed to 38% of its initial volume at this pressure. With increasing pressure, a crystal structure sequence of hcp?→?Sm-type?→?dhcp?→?fcc?→?dfcc?→?monoclinic has been observed in our studies on gadolinium. The measured equation of state of gadolinium is presented to 169?GPa at ambient temperature. Magnetic ordering temperature of gadolinium has been studied using designer diamond anvils to a pressure of 25?GPa and a temperature of 10?K. The magnetic ordering temperature has been determined from the four-point electrical resistivity measurements carried out on gadolinium. Our experiments show that the magnetic transition temperature decreases with increasing pressure to 19?GPa and then increases when gadolinium is subjected to higher pressures.     

Optical properties of methanol at high pressures

The pressure dependence of the refractive index of methanol has been measured in a diamond-anvil cell up to 5·6 GPa at room temperature. These experiments cover the liquid phase of methanol (below 3·6 GPa) as well as the ‘superpressed fluid’ phase above 3·6 GPa. We have extracted the polarizability of methanol from our experimental data and the equation of state by using the Lorentz-Lorenz equation.     

Electron microscopy of phase transitions

The possibilities of electron microscopy for the study of phase transitions are briefly outlined and illustrated by some particular aspects of phase transitions in Pb₃V₂O₈, Ba₂NaNb₅O₁₅ and Au3+xZn. Lead orthovanadate is used as an example for the application of a procedure to distinguish between the static or dynamic nature of diffuse intensity in diffraction patterns occurring near the transition temperature. For Ba₂NaNb₅O₁₅ the behaviour of the discommensurations in the vicinity of the ferroelastic transition has been studied and the low-temperature transition around 105 K is proven to be due to a doubling of the baxis and not to a restoration of the fourfold symmetry. The decomposition mechanism of the metastable <2³3> type long period super-lattices in the binary Au_3+xZn alloys is described in terms of the withdrawal of nodes of four <3> domains.     

Thermodynamics of melting of lithium,potassium and rubidium at high pressures

Volume measurements of liquid and solid Li, K and Rb in the vicinity of their melting curves have been carried out using a piston piezometer method. From the experimental results the volume, entropy and internal energy changes upon melting of the metals are calculated. The obtained data are analyzed along with the results for Na and Cs.It is stated that the anomalies in the melting curves of K, Rb and Cs are most probably connected with a s-d electron transition.     

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.     

Mg2Si化合物在静水压下的电子输运性能研究

本文基于第一性原理采用全电势线性缀加平面波方法和波尔兹曼理论运算了在静水压下Mg₂Si的电子和热电性能. 研究发现, 对于n型载流子控制Mg₂Si输运性质, 应变达到0.02时, 室温情况下, 热电性能参数得到了明显提高, 其塞贝克系数增幅为26%, 功率因数增幅47%; 高温时, 功率因数增幅45%. 而对于主要载流子为空穴时, 其热电系数最值出现在应变为0.01时. 但其数值与未施加静水压的结构相比提高不多, 表明对于p型Mg₂Si半导体应变对其输运性能的影响不大. 并且结合电子能带结构图解释这些现象.     

Electron and magnetic transport in the diluted magnetic semiconductor CdGeAs2<Mn>at high pressures

In CdGeAs₂<Mn>, a metamagnetic phase transition and a negative magnetic resistance induced by high pressure were found and studied.