一维应变加载下单晶铁结构转变的微观研究

采用嵌入原子势和分子动力学方法,模拟了单晶铁在一维应变条件下由体心立方（bcc）转变为六角密排（hcp）结构的微观过程. 当应变加载至相变临界值时,hcp相开始均匀形核并沿{011}晶面长大为薄片状体系.弹性常数C₃₁和C₃₂在相变前被逐渐硬化,C₃₃则在相变前出现软化行为;当体系完全相变后,上述各弹性常数显示开始随体积压缩而迅速硬化,温度效应对晶格具有软化作用,可削弱C₃₃的硬化和软化过程;样品在压缩过程可出现孪晶结构,孪晶结构使晶格发生剪切变形.混合相中,hcp相势能比bcc相高,最大剪应力方向与bcc相反向;系统的偏应力与hcp相质量分数近似呈线性关系. 关键词： 结构转变 分子动力学 一维应变     

Specific features of the formation of the ferroelectric phase in polytypes of TlGaSe2 crystals

The polytypism of layered crystals of thallium gallium diselenide TlGaSe₂ has been found to substantially affect the temperature of phase transformations and the mechanism of formation of the polar state in these ferroelectrics. In particular, it is shown that the phase transition observed in the C-TlGaSe₂ polytype is an improper ferroelectric phase transition occurring at a temperature T _c ≈ 108 K, whereas the phase transition observed in the 2C-TlGaSe₂ polytype is a proper ferroelectric phase transition occurring at a higher temperature T _c ≈ 111 K. It is concluded that the elucidation of the polytype of a particular sample is a necessary stage of investigation of the TlGaSe₂ crystals.     

Magnetic and structural anomalies of Na<Subscript><Emphasis Type="Italic">n</Emphasis></Subscript>C<Subscript>60</Subscript> (n = 2, 3)

Sodium fullerides Na _n C60 (n = 2, 3) have been synthesized by a liquid phase reaction and investigated with X-ray diffraction (XRD), nuclear magnetic resonance (NMR), electron paramagnetic resonance, and differential thermal analysis. XRD data indicate that the crystal structure of Na₂C₆₀ at 300 K is face centered cubic (FCC). A phase transition from primitive cubic to FCC crystal structure has been observed in this work in Na₂C₆₀ fulleride at 290 K. The transition is accompanied by the step-like change of paramagnetic susceptibility. The crystal structure of Na₃C₆₀ is more complicated than, and different from, what has been reported in the literature. A nearly seven-fold increase of paramagnetic susceptibility with increasing temperature has been observed in the Na₃C₆₀ fulleride at 240–260 K. In the same temperature range, a new line at about 255 ppm appears in the ²³Na NMR spectrum, indicating a significant increase of electron density near the Na nucleus. The observed effect can be explained by a metal-insulator transition caused by a structural transition.     

Phase transitions in crystals of protein amino acids

The temperature dependence of the piezoelectric response of many protein amino acids and their compounds exhibits a sharp increase in the piezoelectric response signals at a certain temperature. It has been shown using the example of the known ferroelectrics without a piezoelectric effect in the paraphase (triglycine sulfate, glycine phosphite, trisarcosine calcium chloride) that such an increase in the piezoelectric response is associated with the structural phase transition to the low-symmetry piezoelectric phase with a large number of piezoelectric coefficients. The specific features of the phase transitions with the symmetry change D ₂-C ₂ have been discussed.     

Low-temperature structural phase transition in a monoclinic KDy(WO4)2 crystal

The low-temperature thermal and magnetic-resonance properties of a monoclinic KDy(WO₄)₂ single crystal are investigated. It is established that a structural phase transition takes place at T _c=6.38 K. The field dependence of the critical temperature is determined for a magnetic field oriented along the crystallographic a and c axes. The initial part of the H-T phase diagram is plotted for H∥a. The prominent features of the structural phase transition are typical of a second-order Jahn-Teller transition, which is not accompanied by any change in the symmetry of the crystal lattice in the low-temperature phase. The behavior of C(T) in a magnetic field shows that the transition goes to an antiferrodistortion phase. An anomalous increase in the relaxation time (by almost an order of magnitude) following a thermal pulse is observed at T>T _c(H), owing to the structural instability of the lattice. A theoretical model is proposed for the structural phase transition in a magnetic field, and the magnetic-field dependence of T _c is investigated for various directions of the field. Fiz. Tverd. Tela (St. Petersburg) 40, 750–758 (April 1998)     

Lamellar-to-nematic phase transition in a lipid-surfactant mixture

A lyotropic system, consisting of a lecithin (DMPC) and a non-ionic surfactant (C₁₂E₅) in water was studied. The system exhibits a lamellar-to-nematic phase transition. The nematic phase appears as the temperature is decreased and only exists in a very limited temperature and concentration range, for specific lipid-to-surfactant ratios. While a lamellar phase is found at higher temperatures in both mixed and pure C₁₂E₅ systems, the transition to the nematic phase at lower temperatures coincides with a micellar phase in the pure C₁₂E₅ system. The transition appears to be driven by the strong temperature dependence of the surfactant film spontaneous curvature. The structural properties of the lamellar phase close to the lamellar-to-nematic boundary have been studied by polarised light microscopy and small-angle neutron and X-ray scattering experiments. The signature of a helical defect with Burgers vector of magnitude 2 is apparent in our data, close to the lamellar-to-nematic phase transition. The proliferation of screw dislocations in the lamellar phase might be a plausible mechanism for driving this transition. Received 6 July 1999 and Received in final form 17 April 2000     

High pressure structural phase transition in uranium monochalcogenides

The pressure induced phase transition in uranium monochalcogenides, UX (X = S, Se, and Te) is studied by two-body potential approach. It is found that US, USe and UTe undergo a structural phase transition from NaCl (B1) type to CsCl (B2) type at 78.5, 21 and 9.5 GPa, respectively, which is in good agreement with the recent experimental data. In addition, second-order elastic constants (SOECs) (C ₁₁, C ₁₂ and C ₁₄) have been calculated which can be used to establish the nature of the forces in these materials. The present study shows that the considered two-body potential model can be used to predict the phase transition pressure in UX compounds provided the strength and hardness parameters in B1 and B2 phases are different.     

The hydrogen‐bond effect on the high pressure behavior of hydrazinium monochloride

The first high pressure study of solid hydrazinium monochloride has been performed by in situ Raman spectroscopy and synchrotron X‐ray diffraction (XRD) experiments in diamond anvil cell (DAC) up to 39.5 and 24.6 GPa, respectively. The structure of phase I at room temperature is confirmed to be space group C2/c by the Raman spectral analysis and Rietveld refinement of the XRD pattern. A structural transition from phase I to II is observed at 7.3 GPa. Pressure‐induced position variation of hydrogen atoms in NH₃⁺ unit during the phase transition is attributed to the formation of N―H…Cl hydrogen‐bonds, which play a vital role in the stability and subsequent structural changes of this high energetic material under pressure. This inference is proved from the abnormal pressure shifts and obvious Fermi resonance in NH stretching mode of N₂H₅⁺ ion in the Raman experiment. Finally, a further transition from phase II to III accompanied with a slight internal distortion in the N₂H₅⁺ ions occurs above 19.8 GPa, and phase III persists up to 39.5 GPa. Copyright © 2015 John Wiley & Sons, Ltd.     

Magnetic and structural phase transitions in the shape-memory ferromagnetic alloys Ni2+x Mn1−x Ga

The results of an experimental investigation of the temperature dependences of the magnetic susceptibility and resistivity in the shape-memory ferromagnetic alloys Ni_2+x Mn_1−x Ga (x=0–0.20) are reported. A T−x phase diagram is constructed on the basis of these data. It is shown that partial substitution of Ni for Mn causes the temperatures of the structural (martensitic) T _M and magnetic T _C (Curie point) phase transitions to converge. In the region where T _C =T _M the transition temperature increases linearly with magnetic field in the range from 0 to 10 kOe. The kinetics of a magnetic-field-induced martensitic phase transition is investigated, and the velocities of the martensite-austenite interphase boundary during direct and reverse transitions are measured. A theoretical model is proposed and the T−x phase diagram is calculated. It is shown that there exist concentration ranges where the magnetic and martensitic transitions merge into a first-order phase transition. The theoretical results are in qualitative agreement with experiment. Zh. éksp. Teor. Fiz. 115, 1740–1755 (May 1999)     

Coupling of orientational and translational modes in solid C60 and C70

The orientational phase transitions in solid C₆₀ and C₇₀ are accompanied by quite different anomalies in the crystalline strains. In solid C₆₀ the phase transition Fm3m→Pa3 is primarily an orientational effect (antiferro-rotational), which is driven by the condensation of orientational modes belonging to X₅ ⁺ irreducible representation (irreps) of Fm3m. These modes are the primary order parameters (oops) and their number is equal to the number of irreps of T_2g and T_1g symmetry within the manifolds under consideration. Taking into account irreps up to the manifold 1=12, we have studied the rotation-rotation-translation (RRT) coupling between the oops and the lattice displacements. We have investigated the resulting lattice contraction and the change of the elastic constant c₁₁ at the phase transition. In solid C₇₀ (fcc-phase) we investigate the bilinear coupling of orientational fluctuations of T_2g symmetry to transverse acoustic lattice displacements. This coupling is the driving mechanism for the ferroelastic phase transition Fm3m → R3m. Finally we investigate the transition from the rhombohedral phase to a low temperature monoclinic phase. This transition in antiferro-rotational.     

On the second-order phase transition initiated by a strong electron-phonon interaction

A model of a crystal with a strong electron-phonon interaction that initiates a second-order phase transition has been considered. The purpose of the study is to determine the temperature dependence of the thermodynamic potential of the symmetric phase in the temperature range in the immediate vicinity of the transition temperature T _C for this model. The problem has been solved using the quantum Matsubara Green’s function approach, which takes into account the influence of both thermal and quantum fluctuations. It has been demonstrated that fluctuation coherent deformations of the crystal lattice with the same symmetry as in the ordered phase appear to be energetically favorable at T > T _C due to the interaction with the electronic subsystem. The results obtained have made it possible to construct the model of the second-order phase transition near the Curie point T _C.     

Structural and magnetic phase transitions in Pr<Subscript>0.7</Subscript>Ca<Subscript>0.3</Subscript>MnO<Subscript>3</Subscript> at high pressures

The crystal structure and Raman spectra of Pr_0.7Ca_0.3MnO₃ manganite at high pressures of up to 30 GPa and the magnetic structure at pressures of up to 1 GPa have been studied. A structural phase transition from the orthorhombic phase of the Pnma symmetry to the high-pressure orthorhombic phase of the Imma symmetry has been observed at P ∼ 15 GPa and room temperature. Anomalies of the pressure dependences of the bending and stretching vibrational modes have been observed in the region of the phase transition. A magnetic phase transition from the initial ferromagnetic ground state (T _C = 120 K) to the A-type antiferromagnetic state (T _N = 140 K) takes place at a relatively low pressure of P = 1 GPa in the low-temperature region. The structural mechanisms of the change of the character of the magnetic ordering have been discussed.     

Ferroelectric phase transitions of the 0.32PIN-0.345PMN-0.335PT single crystals studied by temperature-dependent Raman spectroscopy,dielectric and ferroelectric performance

The ferroelectric phase transition characteristics of the 0.32Pb(In_1/2Nb_1/2)O₃-0.345Pb(Mg_1/3Nb_2/3)O₃-0.335PbTiO₃ (0.32PIN-0.345PMN-0.335PT) single crystals were studied by the temperature-dependent Raman spectroscopy and some electrical properties. Ferroelectric monoclinic phase was confirmed at room temperature by the numbers of the Raman modes. Successive ferroelectric phase transitions, i.e. ferroelectric monoclinic phase to ferroelectric tetragonal phase transition (FE_M-FE_T) and ferroelectric tetragonal phase to paraelectric cubic phase transition (FE_T-P_C), are evidenced by the anomalies of Raman modes line width, peaks intensity and their ratios around T_M-T and T_C/T_m temperatures. The temperature dependent permittivity derivative ξ = d?/dT not only provides further evidence of the successive ferroelectric phase transitions, but also demonstrates the second-order transition characteristic of the FE_M-FE_T phase transition and the first-order transition feature of the FE_T-P_C phase transition. The FE_M-FE_T phase transition is also confirmed by the abnormal narrowing of the P-E loops, decrease of the P_r and E_c values, and extremums of the pyroelectric performance.     

Characterisation of the high-pressure structural transition and elastic properties in boron arsenic

This paper carries out the First principles calculation of the crystal structures (zinc blende (B3) and rocksalt (B1)) and phase transition of boron arsenic (BAs) based on the density-functional theory. Using the relation between enthalpy and pressure, it finds that the transition phase from the B3 structural to the B1 structural occurs at the pressure of 113.42GPa. Then the elastic constants C₁₁, C₁₂, C₄₄, bulk modulus, shear modulus, Young modulus, anisotropy factor, Kleinman parameter and Poisson ratio are discussed in detail for two polymorphs of BAs. The results of the structural parameters and elastic properties in B3 structure are in good agreement with the available theoretical and experimental values.     

High-pressure effect on the ferroelectric-paraelectric transition in PbTiO<Subscript>3</Subscript>

The crystal structure of lead titanate PbTiO₃ was investigated by energy dispersive X-ray diffraction at high pressures up to 4 GPa in a temperature range of 300–950 K. At the ambient conditions, the PbTiO₃ structure is tetragonal with the space group P4mm (ferroelectric phase). A structural phase transition into the cubic phase with a space group Pm[`3]mPm\bar 3m is observed at T = 747 K. It was found that the phase transition temperature decreases upon applying the high pressure with the coefficient dT _C /dP = -65 K/GPa. Dependences of parameters and volume of the unit cell on the pressure and temperature was found, and the bulk modulus and thermal expansion coefficients for the tetragonal and cubic phases of lead titanate have been calculated.     

Magnetostructural phase transitions in manganese arsenide single crystals

The effect of an external magnetic field with a strength up to 140 kOe on the phase transitions in manganese arsenide single crystals has been investigated. The existence of unstable magnetic and crystal structures at temperatures above the Curie temperature T _C = 308 K has been established. The displacements of manganese and arsenic atoms during the magnetostructural phase transition and the shift in the temperature of the first-order magnetostructural phase transition in a magnetic field have been determined. It has been shown that the magnetocaloric effect in a magnetic field of 140 kOe near the Curie temperature T _C is equal to ??T ?? 13 K. A model of the superparamagnetic state in MnAs above the temperature T _C has been proposed using the data on the magnetic properties and structural transformation in the region of the first-order magnetostructural phase transition. It has been demonstrated that, at temperatures close to T _C, apart from the contribution to the change in the entropy from the change in the magnetization there is a significant contribution from the transformation of the crystal lattice due to the magnetostructural phase transition.     

Role of vacancies of a strongly strained crystal in the melting process

It has been shown that, apart from classical vacancies formed as a result of the thermal fluctuations, a crystal can contain so-called nonclassical vacancies of nonfluctuation nature. The latter vacancies appear when the temperature exceeds a critical value T _C . The factor responsible for their formation is a mechanical instability of an ideal crystal. The temperature T _C is a second-order phase transition point. The vacancies formed as a result of this phase transition are joined together into small clusters with sizes of the order of several atoms. The above transition makes a substantial contribution to the premelting process observed experimentally.     

Incommensurate cooperative tilting modes of MnF6 octahedra relatedto the structural phasetransitions in BaMnF4

The structural phase transitions of the layer compound BaMnF₄ were studied by high-resolution X-ray diffraction using synchrotron radiation. The intensities and profiles of two kinds of superlattice reflections having incommensurate reduced wave vectors q ₁= (～ ± 1/5,0,0) _p and q ₂ =(～ ± 2/5,1/2,1/2)_p, respectively, were measured as a function of temperature from 25 K to 280 K. These temperature dependencies show that incommensurate structural phase transitions of second order occur at 234 K and 244 K. These structural phase transitions are interpreted as successive condensations of a folding-screen-like incommensurate plane-distortion mode and a commensurate anti-ferro-distortive tilting mode of the MnF₆ octahedra around the primitive a₀ - and b₀ -axes, when cooled down. It is also found that there is another structural phase transition at about 45 K related to a precursor structural distortion for the antiferromagnetic transition occurring at about 26 K.     

Structure and phase transitions in Cu2P2O7

X-ray diffraction studies of the temperature variation of the Cu₂P₂O₇ crystal structure were performed in the vicinity of the transition from the α-phase (C2/c space group) to the β-phase (C2/m space group). These results as well as those of Raman spectroscopy studies and temperature variation of the electric capacitance point to the existence of an intermediate phase in the temperature range 347–363?K.     

Magnetic phase transitions and magnetocaloric effect in the Fe-doped MnNiGe alloys

The magnetic phase transition and magnetocaloric effects in Fe-doped MnNiGe alloys are investigated. The substitution of Fe for Ni decreases the structural transition temperature remarkably, resulting in the magnetostructural transition occurring between antiferromagnetic and ferromagnetic states in MnNi_{1 - x}Fe_xGe alloy. Owing to the enhanced ferromagnetic coupling induced by the substitution of Fe, metamagnetic behaviour is also observed in TiNiSi-type phase of MnNi_{1 - x}Fe_xGe alloys at temperature below the structural transition temperature.