Brillouin light scattering study of polymeric glassy sulfur

We present here a study of the acoustic dynamics of polymeric glassy sulfur. The data have been collected in the GHz frequency range by means of Brillouin light scattering for different scattering geometries. The choice of the experimental setup allows us to obtain information on the refractive index, n, that comes out to be close to that corresponding to the high temperature polymeric liquid phase. The longitudinal acoustic excitations have been investigated as a function of temperature from deep into the glassy state up to the glass transition temperature. The temperature dependence of the sound velocity is compared to the one measured in the liquid phase. We find that the sound velocity of the glass can be linearly extrapolated from that of the polymeric liquid measured in the THz frequency range with inelastic X-ray scattering.     

Paramagnons in the PrNi system with an induced magnetic moment

The recent studies of the PrNi system have shown that, at a temperature slightly higher than the ferromagnetic ordering temperature (T _C ～ 21 K), softening of some part of magnetic excitations occurs near the Γ point of the Brillouin zone. The magnetic modes observed have been qualitatively described by a model taking into account the crystal field and the exchang interaction within the mean-field random-phase approximation. To refine the model parameters and obtain a complete set of excitation modes, inelastic neutron scattering measurements on PrNi single crystals and polycrystals have been performed at T = 23 K. An acoustic branch related to the level with high excitation energy has been observed for the first time. The character of its dispersion suggests that the low-energy acoustic mode is responsible for the magnetic phase transition.     

Frequency-modulated stimulated Brillouin spectroscopy in high-refractive-index glasses

Frequency-modulated stimulated Brillouin spectroscopy has been performed for high-refractive-index glasses including heavy-metal oxide glasses, chalcogenide glasses and TeO₂-based and Bi₂O₃-based glasses. Although the Brillouin linewidth in glassy materials is broader in general than that in crystalline materials, we have found that the Brillouin linewidth of Ge₃₃As₁₂Se₅₅ chalcogenide glass is considerably narrow and is comparable to that in crystals.     

Volume and viscosity of Zr–Cu–Al glass-forming liquid alloys

We examined the volume and viscosity of Zr–Cu–Al glass-forming liquid alloys to clarify the origin of a frozen free volume in glassy alloys. Since an excess free volume imparts toughness and ductility to glassy alloys, we attempted to increase this volume in glass structures so that they could be used as engineering materials. The maximum frozen excess free volume was observed in the ternary eutectic composition of the Zr–Cu–Al alloy system; however, its origin remains unclear. We attempted to reveal the mechanism of the formation of the frozen excess free volume in Zr–Cu–Al glassy alloys.     

On the phase diagram of polymorphic ethanol: Thermodynamic and structural studies

It is well known that ethanol exhibits a very interesting polymorphism presenting different solid phases: a fully-ordered (monoclinic) crystal, a (bcc) plastic crystal, which by quenching becomes an orientationally-disordered crystal with glassy properties (hence sometimes named ‘glassy crystal’), and the ordinary amorphous glass. We have carried out calorimetric, X-ray diffraction, and Brillouin-scattering experiments above liquid-nitrogen temperatures and have found several new features that shed more light on the rich and interesting phase diagram of ethanol. Firstly, we have identified up to four different varieties of the monoclinic crystalline phase depending on the thermal history. We also present new specific-heat data of these glassy and crystalline phases below the glass transition temperature up to the melting temperature. Furthermore, we have unexpectedly found that the amorphous phase can also be obtained by the unusual route of a very slow cooling of the liquid in some particular experimental set-ups, evidencing the heterogeneous character of the crystallization kinetics of these molecular glass-formers.     

Mechanical behaviour of highly porous glasses

The mechanical behaviour of highly porous glassy materials (pore volume higher than 85%) is investigated using Hg porosimetry. Because of the small pore size of these materials, Hg liquid cannot enter their porous network and consequently induces an isostatic pressure. Due to the high compliance of the solid network of these materials, compression results in the sample shrinkage. The experiments described in this paper show that an isostatic pressure applied to highly porous glasses induces an irreversible volume shrinkage which can be associated with an unexpected plastic behaviour and structure strengthening. The magnitude of the plastic shrinkage and the increase of the associated mechanical properties depend on the starting bulk density. The irreversible compaction can be explained by siloxane bond formation between clusters constituting the porous glasses, retaining the strained structure. This densification process could offer a new way to synthesise glasses at room temperature.     

二维CdO的低晶格热导率研究

寻求具有较小晶格热导率k_lat的高热电性能的二维材料具有重要意义。基于从头计算和声子玻耳兹曼输运理论,该研究首先对二维CdO结构进行优化,并通过计算声子谱验证了单层CdO的动力学稳定性。在此基础上详细研究了单层CdO的声子输运性质。计算表明在室温下单层CdO的晶格热导率k_lat约为5.7 W/(m·K),低于单层石墨烯、磷烯、黑磷和MoS₂等二维材料的晶格热导率。其中,Z方向声学模式(Z-direction acoustic, ZA),横声学支(transverse acoustic,TA),纵声学支(longitudinal acoustic, LA),Z方向光学模式(Z-direction optical, ZO),横光学支(transverse optical, TO),纵光学支(longitudinal optical, LO)对k_lat的百分比贡献分别为73.7％、13.9％、3.7％、2.8％、4.7％和1.2％。研究发现,ZA、TA、LA声学支和光学支之间的强散射是导致单层CdO低热导率的原因。本文计算结果可用于指导基于CdO的低维热电器件的设计。     

2H NMR studies of supercooled and glassy aspirin

Acetyl salicylic acid, deuterated at the methyl group, was investigated using ²H NMR in its supercooled and glassy states. Just above the glass transition temperature the molecular reorientations, studied using stimulated-echo spectroscopy, demonstrated a large degree of similarity with other glass formers. Deep in the glassy phase the NMR spectra look similar to those reported for the crystal and below 20 K they are indicating that rotational tunneling plays a role. Measurements of the spin–lattice relaxation times for temperatures below 150 K reveal a broad distribution of correlation times in the glass. The dominant energy barrier characterizing the slow-down of the methyl group motion is significantly lower than the well-defined barrier in the crystal.     

EXAFS studies of glassy and liquid ZnCl2: A comparison with vitreous GeO2

The Zn-EXAFS (extended X-ray absorption fine structure) above its K-absorption edge has been measured for glassy ZnCl₂ at low temperature, through T_g (375 K), and into the supercooled and normal liquid state (mp = 593 K) at 673 K. By Fourier filtering and fitting the normalized glass spectra using α-ZnCl₂ as a model compound, the Zn²⁺Cl^? distance was determined to be (2.34 ± 0.01) Å and the average coordination number about the Zn²⁺ was found to be 5.1 ± 0.8. The latter value agrees with the value of 4.7 nearest neighbors obtained by the molecular dynamics computer simulation study of Woodcock et al., for liquid ZnCl₂ just above its melting point. The agreement is supportive of the notion that short-range order in the glass is reflective of that of the corresponding liquid from which it was quenched. Spectral measurement as a function of temperature indicates that there is considerable dynamic decoupling of the Zn²⁺ from its nearest Cl^? neighbor even below T_g. This is contrasted with similar data in glassy GeO₂ which show that the motion of Ge is strongly coupled with its four oxygen neighbors all the way to T_g. This difference in dynamic disorder substantiates the notion that glassy ZnCl₂, as well as vitreous BeF₂, provides a further weakened structural analog for glassy GeO₂ and SiO₂.     

Sound velocity in liquid and glassy selenium

The speed of longitudinal sound waves at 7 and 22 MHz has been measured in liquid, supercooled, and amorphous selenium, including the region around the glass transition temperature, T_g, near 35 °C. In amorphous selenium the speed of shear waves at 7 MHz was also measured. The experiments were performed with high purity Se (99.9999%) hermetically sealed in an evacuated silica ampoule. Four temperature regions with strongly different relaxation times can be distinguished between room temperature and the melting point: (1) a glassy state below T_g, which is stable on the time scale of the experiments, (2) a glassy state above T_g, which is metastable on the time scale of the experiments, (3) a region where homogeneous crystal nucleation occurs, and (4) a supercooled liquid, which is stable on the time scale of the experiments. Each region is marked by a change in the slope of the temperature dependence of the sound velocity. Near the glass transition temperature the velocities of longitudinal and transverse sound exhibit hysteresis with a step-like drop on heating and a more continuous rise on cooling. The step-like anomaly in sound velocity may be a general property of the glass transition.     

Elastic properties of zinc tris(thiourea) sulphate in a wide temperature range studied by Brillouin spectroscopy

The elastic properties of the zinc tris (thiourea) sulphate crystal were studied by Brillouin spectroscopy in the range 80 – 300 K. The measurements were made on single crystals obtained by the isothermal method. The temperature dependences of the Brillouin shift were determined for the crystal in the principal directions and in a few mixed directions on a tandem type spectrometer. The results revealed anomalies in the bulk wave propagation rate and in a few elastic constants at about 138 K. (© 2007 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Optical properties of KGd(WO4)2 single crystals studied by Brillouin spectroscopy

The results of a study of KGd(WO₄)₂ single crystals by Brillouin scattering method are presented. The Brillouin spectra for the acoustic phonons propagating in the [100], [010], [001], [110] and [101] directions, taken in 90° and 180° scattering geometry at room temperature have been recorded. Using the Brillouin spectroscopy the refractive indices for some directions of KGd(WO₄)₂ crystals were determined. The refractive indices were also calculated for the same directions by the rotation transformation of the principal optical axes of the optical indicatrix to the crystallographic directions of KGd(WO₄)₂ crystals. Moreover, some anomalies of the acoustic phonons propagating connected with birefringence of KGd(WO₄)₂ crystals were discussed. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Unusual Glassy Smectic-G Liquid Crystal: Heat Capacity of N-p-n-Pentyloxybenzylidene-p'-n-butylaniline between 11 and 393 K

Abstract

The heat capacities of the title compound (C₃H₁₁,O—C₆H₄,- CH=N—C₆H₄,—C₄H₉, abbreviation 5O ? 4) with a purity of 99.92 mole percent have been measured with an adiabatic-type calorimeter between 11 and 393 K. The transition temperature and the enthalpy and entropy of phase transition for stable crystal → S_G, S_G → N and N → isotropic liquid were T _c = 299.69 K/ΔH = 22.68 kJ mol^?1/ΔS = 75.70 JK^?1 mol^?1, 325.72/7.11/21.79 and 342.48/1.78/5.22, respectively. The crystal which melts at 285.5 K is a metastable modification. The S_A phase hitherto reported in between S_G and N does not exist. The glassy So state was realized by rapid cooling of the specimen from the So phase. The molar enthalpy of the glassy S_G state at 0 K was by (10.1±0.1) kJ mol^?1 higher than that of the stable crystalline state and the residual entropy of the glassy state was (9.40±0.83) JK^?1 mol^?1. The relaxational heat-capacity anomaly was observed from as low as 100 K and double glass transition phenomenon occurred around 200 K; a quite unusual phenomenon which has never been observed for the glassy states of nematic and cholesteric liquid crystals. The present results give a fair evidence that the unusual glass transition phenomenon previously found for the S_G state of 6O?4 (a homologous compound) is not exceptional at all but common to the smectic glasses; at least common to the glassy S_G states. Two possible origins responsible for the double glass transitions have been discussed.     

Polymer electrolyte liquid crystal mixtures as phase-dependent thermoelectric materials

Organic thermoelectric materials have gained a trajectory in recent years given its advantages of processability, low cost and flexibility. In this paper, polymer electrolyte liquid crystal (PELC) mixtures composed of polyvinyl alcohol, potassium iodide, and 4-Cyano-4'-pentylbiphenyl (5CB) liquid crystal are fabricated, the 5CB acts as a ‘temperature switch’, i.e., a strong correlation between the thermoelectric properties and the transition from Ne-Iso transition of the 5CB, is observed. The electrical conductivity and Seebeck coefficient of the PELC mixtures both decrease above the Ne-Iso transition temperature. This thermoelectric behavior is discussed in terms of the carrier concentration, carrier mobility, and order-disorder transition.     

Conformation and segmental mobility of a diluted single polymer chain simulated with bond fluctuation model

The conformation of a single long polymer chain has been modelled using the Bond Fluctuation Model. The interaction between non-bonded segments has been introduced in the model by means of a Lennard-Jones potential while two energy potentials depending on bond length and bond angle took into account intramolecular interactions. The effect on chain configuration of varying bond angle potential, which tends to extend the polymer chain, was studied. The chain was allowed to equilibrate at high temperature, adopting a random coil conformation. When the system was subjected to a cooling ramp, its energy and dynamically accessible volume decreased but the system maintained the liquid conditions up to a temperature range in which the glass transition yielded a glassy coil with very restricted but not null segmental mobility. The remaining mobility in the glassy state, as well as its conformation, characterised through correlation functions, also depended significantly on the strength of bond angle potential. Further isothermal annealing yielded very compact structures, always amorphous with particular shapes depending on annealing temperature.     

基于第一性原理的单层WS2热输运特性研究

二维WS₂是一种层状过渡金属硫化物，因其具有特殊的层状结构、可调带隙及稳定的物理化学性质而备受关注。结合玻尔兹曼输运方程(BTE)和密度泛函理论(DFT),利用第一性原理研究了单层WS₂声子的输运特性，分析了声子的谐性效应和非谐性效应对WS₂晶格热导率的影响机理，计算了其声子的临界平均自由程，提出通过调整阻断频率的方法来调控WS₂的晶格热导率。研究结果表明：单层WS₂在300 K时的本征晶格热导率为149.12 W/(m·K),且随温度的升高而降低；从各声子支对总热导率的贡献来看，声学声子支起主要作用，特别是纵向声学(longitudinal acoustic, LA)声子支对单层WS₂热导率的贡献百分比最大(44.28%);单层WS₂声学声子支和光学声子支之间的较大带隙(声光学声子支之间无散射)导致其具有较高的晶格热导率。本文研究可为基于单层WS₂纳米电子器件的设计和改进提供借鉴和理论指导。     

Self organized nano crystallinity of magnetite precipitated from a 4.9Na2O · 33.3CaO · 17.1Fe2O3 · 44.7B2O3 glass

Glasses with the mol% composition 4.9Na₂O · 33.3CaO · 17.1Fe₂O₃ · 44.7B₂O₃ were melted, rapidly quenched using a twin roller technique, and subsequently tempered in the range from 550 to 620 °C. This led to the crystallization of magnetite with mean crystallite sizes in the 10-20 nm range. Using higher temperatures resulted in a larger quantity of formed crystallites and slightly larger mean crystallite sizes. Larger tempering times did not lead to substantial crystal growth. The time law of Ostwald ripening was not followed. This is explained by an increase in viscosity of the residual glassy phase during nucleation and crystal growth. Here, the smaller iron concentration near the crystals leads to higher viscosities and to the formation of a diffusional barrier around the crystals, which reduces further crystal growth. The crystallization stops, if T_g of the residual glassy phase is equal to the tempering temperature. Magnetite nano crystals with sizes in the 10-20 nm range offer a wide range of applications, such as the preparation of ferrofluids or of materials for medical diagnostics and therapy.     

Fictive temperature measurement of amorphous SiO2 films by IR method

The structure and properties of amorphous materials, in general, change with their thermal history. This is usually explained using the concept of fictive temperature, i.e., the temperature at which the super-cooled liquid state turned into a glassy state. In earlier studies, a simple IR method was used to determine the fictive temperature of silica glasses, both bulk and fiber. In the present study the applicability of the same technique for thin amorphous silica films on silicon was examined. It was found that the IR absorption as well as reflection peak wavenumber of the silica structural band can be used to determine the fictive temperature of amorphous silica films on silicon with an unknown thermal history. Specifically, IR absorbance spectra of an amorphous silica film of thickness greater than 0.5 μm grown on silicon can be taken before and after etching a thin surface layer of 20–30 nm and the peak wavenumber of the difference signal can be compared with the pre-determined calibration curve to convert the peak wavenumber to the fictive temperature. For a film thicker than ∼2 μm, IR reflection peak wavenumber can be converted directly to the fictive temperature of the film by using the calibration curve.     

Preparation of zirconia mullite flakes via a plasma rapid solidification process using starting materials derived from a sol–gel technique

Flakes of zirconia–mullite with different zirconia contents varying from 3 to 24 wt% were produced from sol–gel derived raw materials via a plasma melting method followed by a rapid solidification process using a rotating copper roll. The morphology, phase constitution and microstructure development of the as-prepared flakes and of the flakes after various heat treatments were investigated by means of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM) and energy dispersive spectroscopy (EDS). It was found that the starting materials could be transformed from the initial irregular-shaped powders into flakes which consisted of mullite, zirconia phase, a relatively large amount of glassy phase and pores. Using TEM, it was shown that the crystalline phases consisted of zirconia polymorphs and mullite. The glassy phases consisted of Al₂O₃–SiO₂ solid solution supersaturated with zirconia. Firing at 1500 °C or 1700 °C resulted in full crystallisation of the flakes and a fairly homogeneous distribution of zirconia particles in terms of size and shape dispersed in the mullite matrix, which contained both intra-granular and inter-granular precipitates. The microstructural characteristics of the flakes may provide promising physical properties for applications in high temperature thermal insulation materials.     

弛豫铁电0.24PIN-0.47PMN-0.29PT单晶声表面波性能研究

随着信息技术的迅速发展,对声表面波器件的要求也进一步提高。为寻找性能更加优异的声表面波器件基底材料,本文利用分波解法对室温下[001]_c及[011]_c极化弛豫铁电0.24PIN-0.47PMN-0.29PT单晶的声表面波性能进行研究。利用[001]_c及[011]_c极化弛豫铁电0.24PIN-0.47PMN-0.29PT单晶的弹性、压电及介电性能参数,通过求解克里斯托弗方程计算了晶体声表面波相速度、机电耦合系数及能流角随传播角度的变换关系。结果表明,沿[011]_c方向极化的0.24PIN-0.47PMN-0.29PT单晶声表面波性能要优于沿[001]_c极化的单晶。[011]_c极化0.24PIN-0.47PMN-0.29PT单晶的声表面波机电耦合系数显著高于沿[001]_c极化单晶。同时沿[011]_c极化0.24PIN-0.47PMN-0.29PT单晶的声表面波能流角的最大值也明显小于[001]_c极化单晶。因此,沿[011]_c方向极化的0.24PIN-0.47PMN-0.29PT单晶兼具优异的声表面波性能及温度稳定性,更适合于实际应用。