Phase transition in SbCl5 - graphite studied by spin resonance experiments

Conduction Carrier Spin Resonance (CCSR) experiments in stage 3 and 4 acceptor SbCl₅ - Graphite Intercalated Compounds (GICs) reveal an almost stage independent phase transition at T_c ≋ 225K. The CCSR linewidth shows an anomalous broadening below T_c, which is observable only when the sample is kept in a region close to T_c (190–225K); the broadening was not observed for rapid cooling. This broadening has a much faster kinetics for heating than for cooling rum. These thermal hysteresis and kinetics are quite similar to those found in AlCl₃-GICs. We attribute this phase transition to the quasi-2D “solid liquid” transformation experienced by the minority molecules of SbCl₃ present among the intercalated species in SbCl₅-GICs, proposed by Homma and Clarke. For stage 2 data does not show evidences of this phase transition.     

Effect of filler and cooling rate on the glass transition of polymers

Fillers have been reported to raise, have no effect upon, or to lower the glass transition temperature T_gof polymers. In those studies, comparisons have been made between filled and unfilled polymers having equal thermal histories. In the work report here, however, the thermal history (cooling rate) was also varied. Two systems, polystyrene-silica and epoxy-rubber were studied. The glass transitions were measured by using a differential scanning calorimeter and a method of analysis first described by Ellerstein and later elaborated upon by Flynn. The data could be represented by a linear plot of the log of cooling rate versus T_gor T_g ^?1. For the polystyrene system, the filled material had a larger negative slope for the plot of log cooling rate versus T_g ^?1 so that after fast cooling the filled material had a lower T_g than the unfilled material. However, when the cooling rate was lowered, the T_g of the filled and unfilled materials approached each other, and for very slow cooling (annealed samples) the filled material had a higher T_g than the unfilled one. For the epoxy-rubber system, the rubber lowered the T_g by an amount which increased with cooling rate. Thus the extent and even the direction of the change in T_g with filler is shown to be dependent upon thermal history. It is shown that the slope of the plot of log cooling rate versus T_g ^?1 or T_g is related to an activation energy. A new simplified method of correcting T_g for DSC instrument thermal lag is described.     

Mechanical properties of La0.58Sr0.4Co0.2Fe0.8O3-δ membranes

In this paper, we report on the mechanical properties of a La_0.58Sr_0.4Co_0.2Fe_0.8O_3-δ perovskite material. We use ring-on-ring bending tests with disk-shaped samples and depth-sensitive micro-indentation. In particular, the temperature dependency of fracture stress and elastic behavior are addressed. The fracture load is measured to be ～ 40% higher at room temperature (RT) than at 800 °C, which is due to the ferro-elasticity of material at RT. The stiffness shows an increase of about 50% above 600 °C and 700 °C in vacuum and air, respectively. The effect is attributed to a rhombohedral to cubic phase transition, which is not fully reversible upon cooling. The changes in phase composition with temperature are also confirmed by in-situ high temperature XRD. The transition appears to be associated with a change of heat capacity.     

Magnetic and magnetocaloric properties of perovskite manganite Pr0.55Sr0.45MnO3

In this paper, we have studied the magnetic and magnetocaloric properties of the perovskite manganite Pr_0.55Sr_0.45MnO₃. It shows a sharp paramagnetic-ferromagnetic phase transition at 291 K and possesses a moderate magnetic entropy change near room temperature. In addition, a large relative cooling power (143.64 J/kg) and a wide temperature range (84 K) have been found in this material. Compare with the Landau model, we find that the itinerant electrons mainly contribute the larger magnetic entropy change at paramagnetic region.     

The effect of clamped and free boundaries on long range strain coupling in structural phase transitions

In ferroelastic structural phase transitions, the atomic ordering in one cell creates a local strain field which is propagated elastically throughout the material, resulting in an effective or indirect coupling J(R _ij ) between the ordering in cells i and j. With free boundaries on the sample, the J(R _ij ) contains a Zener-Eshelby term J _Z of infinite range, which largely determines the transition temperature T _c. The present paper shows what happens when the boundaries are clamped. On cooling from a high temperature an anomaly takes place at more or less the same temperature as the phase transition for free boundaries. Cooling results in an irregular pattern of domains with positive and negative order parameter whose long range strains cancel. Two cases are distinguished. In the “tweed” case coherent domain boundaries form easily and result in fine lamellar domains. When coherent domain boundaries are not possible (the “non-Sapriel”) case, larger less regular domains are formed. In either case the macroscopic net strain adds up to zero.     

液晶相变的微结构研究

用正电子湮没和差示扫描量热(DSC)变温测量液晶(EBBA)样品的正电子湮没寿命谱及DSC曲线,结果表明正电子湮没的短寿命(τ_s)基本不变,而长寿命(τ₁)和强度(I₁)明显地有两次跳变,其跳变的温度范围与DSC所测定的相转变温度范围基本一致,在加热和冷却过程中样品在晶体相←→向列相之间的相互转变的相转变温度范围显著不同。用正电子湮没的ORE模型讨论了由于液晶相转变所引起的微结构变化,从而提出正电子是研究液晶(EBBA)相变的探针。 关键词：     

Magnetic characterization of Bi2FeMnO6 film grown on (100) SrTiO3 substrate

Single phase Bi₂FeMnO₆ films on (100) SrTiO₃ substrate were fabricated using a pulsed laser deposition method through optimization of the preparation conditions. The magnetic moment is 0.30μ_B at 5 K in the magnetic field of 1 T, indicating that B site cations of Fe and Mn are disordered in the sample. The zero‐field‐cooling (ZFC) and field‐cooling (FC) magnetization curves measured from 2 K to 400 K coincide at 360 K. This is consistent with the observation that hysteresis disappears at 360 K, revealing the antiferromagnetic transition at this temperature. A spin‐glass‐like behaviour was observed at low temperature (～100 K) with a cusp of 25 K. Mn shows multiple valence states in the film. It is possibly because Mn²⁺ and Mn⁴⁺ could decrease the Jahn–Teller effect from Mn³⁺ in the film which results in less lattice distortion. (© 2010 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Cooling by adiabatic (DE)pressurization - the barocaloric effect

Abstract

The barocaloric effect reflects a new cooling principle at low temperatures without the need of liquefied gases nor magnetic fields as used in other cooling techniques. A pressure induced structural and/or magnetic phase transition is used to obtain a significant change in the system's entropy which leads to its cooling if done adiabatically. The effect is illustrated for the two rare earth compounds Pr₁ ? _xLa_xNio₃ and Ce_x(La,Y)₁ ? _xSb using a structural and a magnetic phase transition, respectively. In situ experiments on Ce_x(La,Y)₁?_xSb are presented and reveal a cooling rate of up to 2 K per 0·5 GPa pressure change at working temperatures below 20 K for x=1 and up to 0·42 K per 0·24 GPa for x=0·85 at around 10K.     

Impedance study of BIMGVOX ceramics

The polycrystalline samples of Bi₂V_0.9Mg_0.1O_5.35 were synthesised. The conductivity of the samples with Pt electrodes was determined by non-linear least-squares analysis of the impedance spectra. The total conductivity of the samples exhibits Arrhenius-type dependence on temperature with two straight line sections. In the transition from one linear section to the other a time dependence of conductivity was observed. The conductivity decreases both on heating and cooling during several hours at constant temperature (between 665 and 680K and between 710 and 695K on heating and cooling respectively). During heating at temperatures between 685 and 790K the Arrhenius plot are not linear. It may be expected that a process of slow ordering/disordering of oxygen vacancies is responsible for this phenomenon. The values of conductivity at low temperatures were dependent upon the length of time the sample was allowed to reach equilibrium - the structure of the material seems to be frozen in a metastable state, probably β type. At high temperature region the conductivity do not depend on the thermal history of sample. Paper presented at the 3rd Euroconference on Solid State Ionics, Teulada, Sardinia, Italy, Sept. 15–22, 1996     

Raman analyses of co‐phasing and hysteresis behaviors in V2O3 thin film

We present the studies of the phase transition behaviors of V₂O₃ thin film using temperature‐dependent Raman scattering spectroscopy. Our results show that in both the cooling and heating processes of V₂O₃ thin film, the phase transition occurs gradually but not suddenly, contrary to that in single crystal. The coexistence of both the metal and insulator phases with co‐phasing ΔT_c larger than 30 K is observed in both the cooling and heating processes. We discuss that this large co‐phasing ΔT_c should be distinguished with the large hysteresis ΔT_h reported in nanostructures. In addition, our discussions indicate that co‐phasing ΔT_c and hysteresis ΔT_h would be mainly correlated with stress and defect states in sample, respectively. Furthermore, our Raman analyses suggest that stress would also induce phase transitions in V₂O₃, and the stress (pressure)‐induced phase transitions would behave differently comparing with the temperature‐induced transitions under normal pressure. Copyright © 2012 John Wiley & Sons, Ltd.     

Structural,magnetic and superconducting phase transitions in CaFe2As2 under ambient and applied pressure

At ambient pressure CaFe₂As₂ has been found to undergo a first order phase transition from a high temperature, tetragonal phase to a low-temperature orthorhombic/antiferromagnetic phase upon cooling through T ～ 170 K. With the application of pressure this phase transition is rapidly suppressed and by ～0.35 GPa it is replaced by a first order phase transition to a low-temperature collapsed tetragonal, non-magnetic phase. Further application of pressure leads to an increase of the tetragonal to collapsed tetragonal phase transition temperature, with it crossing room temperature by ～1.7 GPa. Given the exceptionally large and anisotropic change in unit cell dimensions associated with the collapsed tetragonal phase, the state of the pressure medium (liquid or solid) at the transition temperature has profound effects on the low-temperature state of the sample. For He-gas cells the pressure is as close to hydrostatic as possible and the transitions are sharp and the sample appears to be single phase at low temperatures. For liquid media cells at temperatures below media freezing, the CaFe₂As₂ transforms when it is encased by a frozen media and enters into a low-temperature multi-crystallographic-phase state, leading to what appears to be a strain stabilized superconducting state at low temperatures.     

热磁预处理对Ni-Mn-Ga单晶磁学和力学性能的影响

研究了预先热磁处理对Ni_503Mn_287Ga₂₁单晶的磁学和力学性能的影响.首先将样品加热到居里温度之上让其冷却,冷却方式分为两种：一种是施加一定大小的磁场从高于居里温度冷却至室温,另一种是在样品经历顺磁-铁磁相变后但还未发生奥氏体-马氏体相变前施加相同大小和方向的磁场并冷却至室温.室温时的拉伸-压缩实验结果表明单晶样品在经历前一种处理后,其可逆应变、磁化强度的变化 （ΔM）比后一种处理的相应值要小很多.在后一种热磁处理的样品中,顺磁-铁磁相变发生后形成了自发磁畴,但这种磁畴不具有择优取向.在顺磁-铁磁相变结束后施加磁场,容易导致择优的马氏体准单畴出现,从而表现出大的可逆应变和ΔM.但对于前者,我们认为样品从居里温度降到室温过程中,其中的磁畴在相同的磁场作用下获得择优生长,形成大磁畴,导致磁诱导的强各向异性.这种择优取向的大磁畴在随后马氏体相变期间影响着马氏体的自发排列方式,不利于马氏体准单畴的出现,结果导致较小的可逆应变和ΔM. 关键词： 磁和力学锻炼 Ni-Mn-Ga单晶 铁磁和马氏体相变     

Solid-State Rb NMR Study in Powdered RbMnCl3

Structural phase transition at 290 K and the implication on the intermediate phase above 290 K in powdered RbMnCl₃ are observed by using a solid-state ⁸⁷Rb NMR spectroscopy. Quadrupole coupling constants (e²qQ/h), the asymmetry parameters (η), and the relative peak intensities for two physically nonequivalent Rb sites, Rb(I) and Rb(II), are determined from nonlinear least-squares fits to the ⁸⁷Rb NMR powder patterns in the temperature range from 260 to 330 K. Quadrupole coupling constants and the asymmetry parameters are examined for the detection of the phase transition resulting in a significant structural change in the Rb(II) site. In addition, changes in the relative peak intensity between the Rb(I) and Rb(II) sites seem to suggest the existence of an anomalous intermediate phase, which is complemented by the differential scanning calorimetry and X-ray diffraction studies.     

一级相变材料Mn1.2Fe0.8P0.4Si0.6的热磁发电性能

本文报道把热能直接转换电能的热磁发电技术所用一级相变新材料Mn_1.2Fe_0.8P_0.4Si_0.6的磁性和热磁发电性能.用高能球磨机械合金化技术和固相烧结合成方法制备了Mn_1.2Fe_0.8P_0.4Si_0.6化合物.磁性测量结果表明,该化合物呈现从铁磁状态变为顺磁状态的一级相变,居里温度为337K,并伴随巨大的磁化强度的变化.根据该材料的这一特性,设计制作了热磁发电演示装置,测定了热流引起材料的相变而产生的电流,并研究了固定磁场中热致磁转变产生的电流随热流温度和样品质量的变化.研究结果表明Mn_1.2Fe_0.8P_0.4Si_0.6化合物具有很好的热磁发电性能,可作为热磁发电材料.     

Wet‐Etching Induced Abnormal Phase Transition in Highly Strained VO2/TiO2 (001) Epitaxial Film

The metal–insulator transition (MIT) behavior in vanadium dioxide (VO₂) epitaxial film is known to be dramatically affected by interfacial stress due to lattice mismatching. For the VO₂/TiO₂ (001) system, there exists a considerable strain in ultra‐thin VO₂ thin film, which shows a lower T_c value close to room temperature. As the VO₂ epitaxial film grows thicker layer‐by‐layer along the “bottom‐up” route, the strain will be gradually relaxed and T_c will increase as well, until the MIT behavior becomes the same as that of bulk material with a T_c of about 68 °C. Whereas, in this study, we find that the VO₂/TiO₂ (001) film thinned by “top‐down” wet‐etching shows an abnormal variation in MIT, which accompanies the potential relaxation of film strain with thinning. It is observed that even when the strained VO₂ film is etched up to several nanometers, the MIT persists, and T_c will increase up to that of bulk material, showing the trend to a stress‐free ultra‐thin VO₂ film. The current findings demonstrate a facial chemical‐etching way to change interfacial strain and modulate the phase transition behavior of ultrathinVO₂ films, which can also be applied to other strained oxide films.     

Effect of magnetic field on the TC and magnetic properties for the aligned MnBi compound

In the compound MnBi, a first-order transition from the paramagnetic to the ferromagnetic state can be triggered by an applied magnetic field and the Curie temperature increases nearly linearly with an increase in magnetic field by ∼2 K/T. Under a field of 10 T, T_C increases by 20 and 22 K during heating and cooling, respectively. Under certain conditions a reversible magnetic field or temperature induced transition between the paramagnetic and ferromagnetic states can occur. A magnetic and crystallographic H-T phase diagram for MnBi is given. Magnetic properties of MnBi compound aligned in a Bi matrix have been investigated. In the low temperature phase MnBi, a spin-reorientation takes place during which the magnetic moments rotate from being parallel to the c-axis towards the basal plane at ∼90 K. A measuring Dc magnetic field applied parallel to the c-axis of MnBi suppresses partly the spin-reorientation transition. Interestingly, the fabricated magnetic field increases the temperature of spin-reorientation transition T_s and the change in magnetization for MnBi. For the sample solidified under 0.5 T, the change in magnetization is ∼70% and T_s is ∼91 K.     

聚丁二烯中的等待时间效应

测量了高聚物材料聚丁二烯的比热,发现在温度T_g=178K出现玻璃转变且转变点附近的比热与降温过程有关。在降温过程中,若控制样品在某一温度T_wg等待时间t_w,则升温比热测量表明,T_g处的比热跃变△c_p存在明显的等待时间效应,即△c_p随t_w的增大而增大。在T_w=169K条件下,△c_p(t< 关键词：     

Effect of regimes of cooling in a magnetic field on the magnetization of a La0.9Sr0.1MnO3 single crystal

Magnetization measurements were performed on a lanthanum manganite La_0.9Sr_0.1MnO₃ single crystal in the temperature interval 4.2–300 K and magnetic field interval 50 Oe-55 kOe in two sample cooling regimes: 1) cooling down to 4.2 K in a high (55 kOe) magnetic field, and 2) cooling in a “zero” field. It is shown that the temperature dependences of the magnetization M(T) are substantially different in these regimes. Pronounced anomalies of M(T) were observed at temperatures T*=103 K and T _c =145 K. The first anomaly is attributed to a structural transition, while the second one corresponds to a ferromagnet-paramagnet phase transition. The magnetization of a La_0.9Sr_0.1MnO₃ single crystal in the cooling regimes studied shows typical “spin-glass” behavior. Pis’ma Zh. éksp. Teor. Fiz. 68, No. 1, 39–43 (10 July 1998)     

Comparison of the ferromagnetic phase transitions in La0.7Ca0.3MnO3 and single crystal nickel by micromagnetic imaging

There is considerable controversy surrounding the nature of the paramagnetic to ferromagnetic phase transition in La_0.7Ca_0.3MnO₃. We have used transmission electron microscopy to perform micromagnetic imaging in order to determine whether the phase change is first or second order. On warming through the transition point, the ferromagnetic phase retreats from the sample surface as it is replaced by the paramagnetic phase. This coexistence of ferromagnetic and paramagnetic phases indicates a primarily first-order transition. However, there is also a continuous loss of magnetization which precedes the phase transition. We compare this with the ferromagnetic transition in nickel which displays a purely continuous phase change. We discuss the accuracy and range of applicability of the micromagnetic imaging techniques of electron holography and Fresnel imaging which were used in this investigation.     

Specific heat and latent heat of KMnF3 ferroelastic crystal

The specific heat and the heat flux exchanged by a single crystal of KMnF₃ have been measured simultaneously while cooling the sample at constant rate of 0·06 K/h through the phase transition at T ₀= 186 K. The phase transition is weakly first order and close to a tricritical point. The temperature dependence at T185 K of the excess specific heat and the excess entropy follow very well the predictions of a Landau potential at a tricritical point.