Symmetry breaking at the phase transitions in ferroelectric pyridinium salts

The phase transitions in ferroelectric pyridinium tetrafluoroborate (PyBF₄) and pyridinium perchlorate (PyClO₄) have been characterized by structural studies. The continuous ferroelectric phase transition at 238.7 K in PyBF₄ appears to be a unique case for multiaxial ferroelectrics, while the first order phase transition in PyClO₄ at 248 K is consistent with the Landau theorem for deducing the character of phase transitions from symmetry considerations. The phase transition in both materials is caused by ordering of the pyridinium cation as well as tetrahedral anions.     

Phase diagram and equations of state of BaSO4

Abstract

The phase diagram and equations of state of BaSO₄, were determined up to 29 GPa and 1000 K in a resistance-heating type diamond anvil cell. At room temperature, barite is the stable form of BaSO₄ which undergoes a reversible phase transition at 10 GPa. The high-pressure form is tentatively determined to be triclinic. At high temperature, a similar phase transition takes place in BaSO₄, but at a pressure higher than that at room temperature. Our results indicate that the phase boundary of the two polymorphs in BasO₄ has a positive slope (dT/dP) of 90 K/GPa. The equations of state for both barite and its high-pressure phase are reported.     

Femtosecond X-ray Studies of Photo-induced Structural Phase Transitions

We summarize recent advancements in the application of femtosecond X-ray scattering to experimental studies of photo-induced, structural phase transitions. Dynamic measurements of atomic rearrangement during solid-liquid and solid-solid transitions, as measured by ultrafast X-ray diffraction using plasma sources of line radiation are reported.     

Phase transitions between orthogonal and tilted hexatic phases

Tilt-driven phase transitions between hexatic smectic phases: SmF-HexB and reversed HexB-SmF have been studied in compounds belonging to two enaminoketone derivative homologue series. The tilt angle order parameter has been measured and its temperature dependence near the phase transition point has been described by applying mean-field model. For both phase sequences the tricritical points have been observed on phase transition lines in binary mixtures of respective materials having first and second order phase transitions between hexatic phases. Received 21 June 1999     

Analysis of K-prime equations of state

In the present communication, we introduce a new K-prime equation of state (EoS), which can be used to understand the interior of the Earth. The newly developed EoS is found to yield similar results as given by Stacey K-prime EoS and Keane EoS, in reference to the seismological data. However, the zero pressure and infinite pressure extrapolation of higher pressure derivatives of bulk modulus are found different for different K-prime EoS.     

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.     

Commensurate incommensurate phase transitions

there are two types of Commensurate-Incommensurate Phase Transitions : t_I between the basic structure and the incommensurate phasis and t_L between the inc. phasis and the lock in phasis. They both have connected structures. So that, they must verify the relation between crystallographic groups in accordance with Landau's Theory. But we have to consider the three phases in the superspace - as we do at an ordered-disordered magnetic transition-because the inc. phasis ins't a crystal in the physical space; e.g., in order to cancel the “middle range order” of the inc. phasis at t_I, we are led to assume the grey (point) group to the basic structure in the superspace. Now both inc. phase and basic structure verify the connection between point-groups in the superspace in the same way as both para and ferro phases do at a ferroic transition in the physical space. We also show that the same type of relation is possible at t_L and we give the order parameter at both t_I and t_L.     

盐石结构MgO的状态方程的第一原理计算

利用平面波密度泛函理论研究了盐石结构MgO的状态方程,所得到的结果与实验值和其他作者的计算值符合很好.同时,还研究了热膨胀系数随温度和压强的变化关系.结果显示:在高压下,温度对盐石结构MgO热膨胀系数的影响很小.     

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.     

Phase transitions in polymesomorphic compounds

Summary The results of a X-ray diffraction study, performed on N(p-n-pentyloxy benzylidene)p′-n-octylaniline (50.8) and N(p-n-pentyloxy benzylidene)p′-n-decylaniline (50.10) are presented. The investigated compounds exhibit smecticB, smecticA and nematic phases in between solid and isotropic liquid phases. In addition, after a thermal cycle the 50.8 compound exhibits a smecticG phase at room temperature. The interlayer and the in-plane intermolecular distances were obtained as functions of temperature through all the mesophases. A phase coexistence has been observed during the solid to smecticB and the smecticB to smecticA phase transitions of the 50.8 compound. The nematic to smecticA phase transitions are found to be of second order for both compounds. Pretransitional effects due to cybotactic-cluster formation in the nematic region are observed.

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Riassunto Si presentano i risultati di uno studio effettuato mediante la diffrazione dei raggi X sul N(p-n-pentilossi benzilidene)p′-n-ottilanilina (50.8) e sul N(p-n-pentilossi benzilidene)p′-n-decilanilina (50.10). Tra le fasi solida ed isotropica i composti esaminati presentano le mesofasiS _B ,S _A e nematica. Inoltre, dopo un ciclo termico il composto 50.8 presenta una faseS _G a temperatura ambiente. Sono state misurate le distanze tra i piani smettici e le distanze laterali tra le molecole in tutte le mesofasi in funzione della temperatura. Una coesistenza di fase è stata osservata durante le transizioni solido →S _B eS _B →S _A del composto 50.8. Le transizioni nematico-S _A sono risultate del second'ordine per entrambi i composti. Nelle fasi nematiche sono stati osservati effetti pretransizionali dovuti alla formazione di gruppi cibotattici.

     

A Study of PMN Crystal Structure Below The Phase Transition Temperature

X-ray diffraction studies of PMN crystal at 103, 183, 203 K show that the disorder in shifts of Pb atoms below T _m develops successively with lowering temperature: from the preferentially uniaxial Pb displacements to equal disordered ones along the axes X, Y, Z. In PMN, in the absence of an external electric field the corresponding rhombohedral ferroelectric phase does not appear in the volume of a whole crystal. The relaxation rotations of oxygen octahedra BO₆ in the vicinity of T _m may be the cause for the appearance of superstructure.     

Three equations of state for solids considering thermal effect

 The Einstein model to consider thermal effect in universal equations of state (UEOS) is modified. It is proposed that the zero-point vibration term should be deleted in a thermal UEOS, and the parameters cannot be directly taken as experimental data at a reference temperature, V_R, B_R, and , but their values at absolute zero temperature, V₀, B₀, and . An approach is proposed to solve V₀, B₀, and from V_R, B_R, and . The approaches are applied to three typical universal EOSs, including the Baonza, mGLJ and Morse EOSs. The numerical results show that the solved values of parameters are almost identical for different EOSs. And the thermo-physical properties predicted through different EOSs are almost identical at zero- and low-pressure conditions, once the same approach and input experimental data are used to solve the parameters. It is concluded that the prediction of thermo-physical properties at zero- and low-pressure conditions cannot be taken as the criteria to judge the applicability of a universal EOS.     

A detonation stability formulation for arbitrary equations of state and multi-step reaction mechanisms

A general normal-mode linear stability formulation of steady planar detonation waves is presented that is valid both for an arbitrary equation of state and for multi-step, multi-species chemical kinetics. The general formulation can be used for many purposes, including an examination of gaseous detonation stability with complex reaction kinetics in which the individual reacting species have variable thermochemical properties. In the present paper, we consider two cases that could not be obtained by previous one-step chemistry, polytropic gas formulations: the first concerns the effect of a difference in heat capacities between product and fuel species, as well as a possible mole change, in a single-step irreversible reaction. The second examines the effects of exothermic or endothermic heat release/absorption in the chain-initiation stage of a model three-step reaction.     

Phase transitions of sulfur at high pressure: Influence of temperature and pressure environment

Abstract

Phase transitions of orthorhombic sulfur were investigated above 10 GPa by Raman spectroscopy using red light excitation. Transitions into several phases that have been reported in previous studies using green light excitation, are confirmed. The phase behaviour is observed to depend strongly on the preparation method. In the presence of a pressure transmitting medium (methanol/ethanol, 4:1), a sequence of phases α-S₈ → [intermediate phase (“ip”) + S₆] → [S₆ + high pressure-low temperature phase (“hplt”)] is described and characterized. Without the use of a pressure transmitting medium, the phase sequence α-S₈ → [“ip” + “hplt”] + “hplt” is observed. In addition, contributions of amorphous sulfur are detected around 10 GPa, i.e. at pressures below the transformation of α-S₈ into the above-mentioned phases. Characteristic Raman spectra of the different phases are extracted and documented over a wide pressure range.     

Phase transitions and metastable states in TlGaSe2

The results of measurements of the dielectric constant of TlGaSe₂ in temperature range of successive phase transitions are presented. An anomaly in the temperature dependence of the real part of dielectric constant in TlGaSe₂ has been observed at about 242?K in addition to anomalies at 115, 108, and also near 65?K as reported in previous publications. The presence of temperature hysteresis effects in temperature interval between 115 and 242?K allowed making a conclusion about possible existence of an incommensurate phase in the mentioned temperature range. A model of succession of the structural phase transitions in TlGaSe₂ has been suggested.     

Dynamics of the Incommensurate Phase of the Fully Deuterated Diacetylene 2,4-Hexadiynylene Bis( p -Toluene Sulfonate)

Inelastic coherent neutron and Raman scattering is used to make a dynamical study of the disubstituted and fully deuterated diacetylene 2,4-hexadiynylene bis( p -toluenesulfonate) ( p TS-D) in a partially polymerized state ( x = 1.5%). The aim of this study is to investigate the dynamics of the incommensurate phase and to make a comparison with the dynamics of the same monocrystal in the high-temperature phase [Even et al. , Phys. Rev ., B52 , 7142.] and the dynamics of the pure monomer p TS-D crystal [Bertault et al ., Adv. Mat. for Optics and Electronics , 6 , 317.]. The phason and amplitudon modes are observed as very damped phonon-like excitations. The effect of polymerization on the critical dynamics in p TS-D is discussed.