Calorimetric investigations of overcritical behaviour in (TEA)2CuCl4 crystals

The results of experimental investigation of molar heat capacity of [N(C₂H₅)₄]₂CuCl₄ - ferroelasto-ferroelectric crystals in a wide temperature range are presented. The typical anomaly for the first order phase transition of order-disorder type at 258 K and additional anomaly with maximum at 195 K has been observed. We suggest that the low temperature anomalies of physical properties of [N(C₂H₅)₄]₂CuCl₄ crystals can be attributed to over critical traces of isomorphous phase transitions (similar to that observed in liquid-gas system). Results of numerical analysis of phenomenological model of phase transition in [N(C₂H₅)₄]₂CuCl₄ crystals are presented and compared with the experimentally determined temperature dependence of the specific heat and entropy changes.     

Ultrasonic investigations of [(CH3)2NH2]5Cd3Cl11

The temperature dependences of ultrasound velocities along the crystallographic a, b and c axis in [(CH₃)₂NH₂]₅Cd₃Cl₁₁ were studied in the vicinity of phase transition at 178.5 K. The results obtained for the longitudinal and shear ultrasonic velocities confirmed clearly the existence of the second-order phase transition at this temperature and the quadratic relation between δV₄ and δV₆ and phase transition parameter was observed.     

A new low-temperature Tcr=101 K phase transition in (NH4)3H(SeO4)2 evidenced by single crystal ESR

Temperature ESR measurements on SeO₃ - radicals in (NH₄)₃H(SeO₄)₂ single crystals disclosed new ESR anomalies at T = 101 K. Below this temperature the hyperfine splitting becomes to be temperature averaged, ESR linewidth shows motional narrowing and an anomaly in forbidden transition intensity is observed. Also the dielectric measurements show an anomaly of the ε at this temperature. We suggest an existence of a new crystal phase VI below T_cr = 101 K with NH₄-groups ordering and slow SeO₄-group dynamics.     

Faraday effect aid birefringence in orthorhombic Li2Ge7O15 near the ferroelectric phase transition

The tensor of the Faraday effect and its temperature derivatives were determined from the temperature dependence of Faraday rotation and indices of refraction of orthorhombic Li₂Ge₇O₁₅ between 120K and 340K, wave length 633nm. A strong anomaly of the Verdet constant V₃₃ and of the index n₃ was observed passing through the transition at 284K. The ratio of the slopes of the Verdet constant V₃₃ above and below the transition is about -2. This value corresponds to a second-order ferroelectric phase transition.     

Phase transition in Sol-Gel processed barium titanate ceramics

Ferroelectric barium titanate (BaTiO₃) ceramics have been prepared from barium acetate [Ba(CH₃COO)₂] and titanium isopropoxide [Ti(CH₃)₂CHO)₄] precursors by sol-gel technique The as-grown powder was found to be amorphous which crystallized to tetragonal phase after annealing at 700°C in air for one hour. The ceramics showed well saturated polarization-field (P-E) hysteresis loops at room temperature. The values of spontaneous polarization(P_s), remanent polarization (P_r) and coercive field (E_c) of the ceramics were found to be19.0, 12.66μC-cm^-2 and 30KVcm^-1 respectively. The room temperature dielectric constant (ε) and loss tangent (tanδ) of the ceramics were found to be 1135 and 0.012 respectively. The dielectric constant and tanδ showed anomaly peaks at 125°C showing ferroelectric to paraelectric phase transition. The polarization parameters also vanish at 125°C confirming the phase transition.     

Uniaxial stress dependence of the elastic wave propagation near normal—incommensurate phase transition in (NH4)2ZnCl4

The effect of uniaxial σ₂ stress on the velocity and attenuation of longitudinal ultrasonic wave propagating along the [001] direction in an NH₄)₂ZnCl₄ crystal was studied in the vicinity of the orthorhombic — incommensurate phase transition. A stress induced shift of the transition temperature is dT₁/dσ₂= 0.2 K/MPa. Application of stress greater that 5 MPa results in the appearance of additional anomalies of velocity and attenuation, which are interpreted as manifestations of a new phase induced by uniaxial Stress.     

Elastic anomalies in ZrTiO4 single crystal

Elastic properties of ZrTiO₄ single crystal have been investigated by ultrasonic and piezoelectric resonance method. The elastic stiffness C^E₄₄ softens around the Tl (normal-incommensurate transition temperature), whereas C₁₁and C₁₂show only small abrupt jumps.     

Phase transition in K2SO4 AT 56 K

Specific heat and dielectric constant of K₂SO₄ were measured below room temperature down to liquid helium temperature. A phase transition was detected at 56 K, which is accompanied with a slight λ-type anomaly in specific heat and a break on dielectric constant vs. temperature curve. Evidence for the incommensurate or super structure was not confirmed by neutron diffraction.     

Properties of Sodium-Lithium Niobate Solid Solution Ceramics with Small Lithium Concentrations

The structural, dielectric, and piezoelectric properties of the solid solution (Na_1-x,Li_x,)NbO₂ were studied. Solid solution ceramics with x values up to 0.14 occur as a single phase. The phase diagram from 0° to 600°C is given. The low-temperature phase has a perovskite pseudo-monoclinic structure and inverts to a pseudotetragonal structure at a temperature that decreases with increasing x. The high-temperature phase is pseudocubic, and the minimum transition temperature from the pseudotetragonal to the pseudocubic structure is 350° C near x = 0.04. Anomalies in the dielectric constant vs. temperature curve agree well with the transition temperatures, although no anomaly was observed at the temperature of transition from the pseudotetragonal to the pseudocubic phase when x was less than 0.06. Lithium ions in the system facilitate the transformation from the antiferro-electric to the ferroelectric state produced by applying an electric field. A new ferroelectric phase becomes stable when x is greater than 0.07. Poled ferroelectric specimens had a planar coupling coefficient of 0.232, a dielectric constant of 220, and a frequency constant of 3352 kc-mm. The piezoelectric properties disappear not at the transition temperature but at the temperature at which strain exhibits an anomaly when x is greater than 0.07. A perovskite phase with a pseudorhombohedral subcell exists as an intermediate phase for x greater than 0.10, the exact value depending on the preparation method. The phase can be easily converted to pseudomonoclinic when the ceramic is fired at 1180° to 1220°C.     

Structural and Dielectric Investigation of the PbTiO3-BaZrO3 System

Thermal expansion measurements, dielectric measurements, and X-ray diffraction studies were made of the PbTiO₃-BaZrO₃ system. A dielectric constant maximum of 11,300 was found at the Curie temperature for the Pb_0.80-Ba_0.20Ti_0.80Zr_0.20O₃ composition. The transition from a ferroelectric tetragonal phase to a para-electric cubic phase for the 10, 20, and 30 mole % BaZrO₃ in PbTiO₃ compositions was of first order. X-ray diffraction determination of the lattice parameters (25°C) showed that this tetragonal-to-cubic phase transition occurred at a composition of 44 mole % BaZrO₃.     

Coexistence of polar and non-polar phases in ND4DSeO4 crystals

The temperature variation of the dielectric constant has been measured in ND₄DSeO₄ with over 90 mole percent of deuterium content. The grown crystals having P2₁2₁2₁ symmetry at room temperature, after being heated above 367 K, exhibit irreversible phase transition to I2 symmetry. At room temperature the phase I2 is not stable unlike for the crystal with lower degree of deuteration and the crystal returns to P2₁2₁2₁ phase during about 60 hours. A t 275 K occurs the phase transition to I1 but only from I2 phase.     

Raman scatteribg and phase transitions in Cd2Nb2O7

Raman scattering and electric permittivity of Cd₂Nb₂O₇ were studied between 4 and 230 K. Phase transitions at T₆ = 44 K and T₇ = 19 K have been discovered. It is hggested that T₆ = 80 K and T = 44 K correspond to normal-incohmensurate and ihcommensurate-commensurate phase transition points respectively.     

Peculiarities of the ptcr effect in ferroelectrics with diffuse phase transitions

The PTCR effect in ferroelectrics with the diffuse phase transition BaSrNb₂O₆ (BSN) and Na_0.5Bi_0.5TiO₃ (NBT) has some peculiarities: the δ(T) anomaly in BSN is observed below the Curie point, in NBT it doesn't coincide with the anomalies of other electrophysical and optical properties and shows an anomalously large temperature hysteresis. These peculiarities may be explained by the diffuseness of spontaneous polarization temperature dependence. Besides in NBT the percolation effects are of importance.     

Ferroelectricity and phase transitions in highly deuterated NH4HSeO4 crystals

Investigations of dielectric and pyroelectric properties as well as domain structure of 70% deuterated ammonium hydrogen selenate crystals have been carried out. Physical properties of 70% dauterated crystals grown in 12 phase differ considerably from that grown in P2₁2₁2₁ phase. Dielectric anomaly is observed that the paraelectric-incommensurate phase transition.     

High-Pressure Phase Transitions in Zirconia and Yttria-Doped Zirconia

Raman spectroscopy has been utilized to characterize the phase transformations and transition pressures in pure and doped zirconia containing 3, 4, and 5 wt% Y₂O₃. The pressure-induced transformations were investigated to over 6 GPa (at room temperature) using a diamond anvil pressure cell. Pure zirconia single-crystal samples transformed to a "new" tetragonal phase (different from the one obtained at high temperatures at atmospheric pressure) at about 4 GPa. The pressure transformation, like the temperature transition, was reversible and exhibited an approximately 0.45-GPa hysteresis at room temperature. The 3 and 4 wt% Y₂O₃ crystals underwent a monoclinic ( P 2_1/b) to tetragonal ( P 4_{2 nmc}) phase transition similar to that observed at high temperatures. This phase change was found to be irreversible on releasing the pressure. The 5 wt% Y₂O₃ at atmospheric pressure consists of a tetragonal modification in a disordered cubic matrix; a gradual, but reversible, disordering transformation of the tetragonal precipitate takes place with pressure.     

TiO2与SiO2掺杂对Al2O3相转变的研究

通过球磨混合法,制备TiO2、SiO2和TiO2+SiO2掺杂的Al2 O3粉体,经不同温度煅烧后进行X射线衍射(XRD)测试,比较研究这三种掺杂对Al2 O3粉体相转变温度的影响.研究结果表明,TiO2、SiO2掺杂对γ-Al2 O3向α-Al2 O3的相转变均有促进作用.在掺杂质量分数为0.5％的情况下,二者可分别...     

Effects of Amorphous and Crystalline SiO2 Additives on γ-Al2O3-to-alpha-Al2O3 Phase Transitions

This paper focused on the effects of various phases of SiO₂ additives on the γ-Al₂O₃-to-α-Al₂O₃ phase transition. In the differential thermal analysis, the exothermic peak temperature that corresponded to the theta-to-α phase transition was elevated by adding amorphous SiO₂, such as fumed silica and silica gel obtained from the hydrolysis of tetraethyl orthosilicate. In contrast, the peak temperature was reduced by adding crystalline SiO₂, such as quartz and cristobalite. Amorphous SiO₂ was considered to retard the γ-to-α phase transition by preventing γ-Al₂O₃ particles from coming into contact and suppressing heterogeneous nucleation on the γ-Al₂O₃ surface. On the other hand, crystalline SiO₂ accelerated the α-Al₂O₃ transition; thus, this SiO₂ may be considered to act as heterogeneous nucleation sites. The structural difference among the various SiO₂ additives, especially amorphous and crystalline phases, largely influenced the temperature of γ-Al₂O₃-to-α-Al₂O₃ phase transition.     

Characteristics and Formation Mechanism of BaTiO3 Powders Prepared by Twin-Fluid and Ultrasonic Spray-Pyrolysis Methods

Spherical fine (micrometer and submicrometer in size) homogeneous BaTiO₃ powders were synthesized from ethanol: water solutions of BaCl₂ and TiCl₄ using the spray-pyrolysis technique. Two different atomizers—twin-fluid and ultrasonic, with a resonant frequency of 2.5 × 10⁶ Hz—were used for mist generation. Hollow spherical particles containing a certain amount of unreacted BaCl₂ phase and having a mean particle diameter of 2.5 μm were obtained at 1173 K using a twin-fluid atomizing system. Decomposition of precursors and their transition to the cubic BaTiO₃ phase occurred, even at 973 K in the case of the ultrasonic atomizing system. For the initial droplet size of 2.2 μm and residence time of ∼60 s, spherical BaTiO₃ particles with the mean particle diameter of 0.53 μm were obtained. A BaTiO₃ formation mechanism has been proposed as a reaction between TiO₂ and BaCl₂ rather than a reaction of oxides.     

Thermodynamic and Structural Properties of Sodium Lithium Niobate Solid Solutions

Thermodynamics of the Na_1−xLi _x NbO₃ system is investigated by high-temperature drop-solution calorimetry in molten 3Na₂O–4MoO₃ solvent at 973 K. Standard molar enthalpies of formation are derived. The estimated heats of transition between hypothetical and stable structures, lithium niobate and perovskite for NaNbO₃ and vice versa for LiNbO₃ are −6 kJ/mol and −10 kJ/mol, respectively. X-ray diffraction studies at room temperature showed for 0 ≤ x ≤ 0.14 there are three phases based on different ordering of the perovskite type lattice: orthorhombic with a quadrupled reduced perovskite cell at 0 ≤ x ≤ 0.02, orthorhombic with a doubled reduced perovskite cell at 0.015 ≤ x ≤ 0.14, and rhombohedral at 0.08 ≤ x ≤ 0.13. There are two two-phase (morphotropic) regions with coexistence of the two orthorhombic phases at 0.015 ≤ x ≤ 0.02 and with the second orthorhombic phase coexisting with the rhombohedral phase at 0.08 ≤ x ≤ 0.13. A reproducible anomaly in specific heat at ∼600 K, not reported previously, has been observed in pure NaNbO₃. Heat-capacity measurements confirm a phase transition at 553 K for 0.07 ≤ x ≤ 0.09. With increasing lithium concentration, a gradual disappearance of high-temperature phase transitions associated with tilting of oxygen octahedra has been observed.     

CO2水合物浆在水平圆管中的传热特性

在CO₂水合物浆流动传热特性测试实验系统上,采用套管式电加热的方法对CO₂水合物浆进行了分解实验,并对CO₂水合物浆的流动传热特性进行了分析。对CO₂水合物浆的相变特性进行了研究,得到CO₂水合物浆的相变温度在8～12℃。研究了在固相体积分数为13.2%以及流速为0.45m/s的条件下CO₂水合物浆在内径为8mm的水平不锈钢管中的传热特性,计算得到CO₂水合物浆在不锈钢水平圆管中的对流传热系数为1500～1800 W/(m²·K),并且其在流动传热过程中呈现先增大随后趋向平稳的趋势,在水合物的相变区相应的对流传热系数表现最大。研究了分解加热功率对管壁温和对流传热系数的影响,发现加热功率对管壁温度的影响较强。在实际应用中可利用CO₂水合物浆的相变作用来增强传热,提高传热效率。