Relaxation time of water's high-density amorphous ice phase

Dielectric relaxation spectroscopy of pressure amorphized hexagonal ice shows that water's high-density amorphous form relaxes in approximately 1 s at 140 K and 1 GPa and that the relaxation is virtually unaffected by pressure. This indicates that the amorph is an ultraviscous liquid above 140 K, the same as would be obtained by supercooling water at 1 GPa through its ice VI phase boundary, and that the glass transition temperature is independent of pressure and close to that of amorphous solid water produced at atmospheric pressure.     

Super-pressed and super-cooled (?) P(EO)20LiBETI

High pressure conductivity measurements have been carried out on P(EO)₂₀LiBETI from 295 K to 368 K. The decrease of electrical conductivity with pressure is larger in the partially crystalline phase (low temperature and low pressure or high temperature and high pressure) than in the fully amorphous phase (high temperature and low pressure). It is found that if the phase transition is approached from the crystalline phase (decreasing pressure), the pressure of the phase transition varies from 0 to 0.23 GPa as the temperature increases from 336 K to 358 K. The shift of the phase transition temperature with pressure is approximately the same as the shift of the glass transition temperature with pressure for pure PEO. This can be understood in terms of the defect diffusion model. If the material is above 336 K and is in the fully amorphous phase, after pressure is increased above the critical pressure, the material remains in the amorphous phase for extended periods of time before transforming to the partially crystalline phase. This is reminiscent of a super-pressed state but may be an indication of slow crystallization kinetics.     

Size-dependent pressure-induced amorphization in nanoscale TiO2

We investigated the size-dependent high-pressure phase transition behavior of nanocrystalline anatase TiO2 with synchrotron x-ray diffraction and Raman spectroscopy to 45 GPa at ambient temperature. Pressure-induced amorphization results in a high-density amorphous (HDA) form when the starting crystallite size is < 10 mm. The HDA-TiO2 transforms to a low-density amorphous form at lower pressures. Harnessing the nanometer length scale thus provides a new window for experimental investigation of amorphization in poor glass formers and a synthesis route for new amorphous materials.     

聚苯硫醚熔体的压致凝固行为

采用施加压力的方法将聚苯硫醚熔体凝固,凝固后获得的聚苯硫醚样品经过降温和卸压后在常温常压下回收. X射线衍射和差示扫描量热分析表明:约20 ms时间的快速压缩过程可以抑制熔体结晶,制备出非晶态聚苯硫醚块材,样品的表面及中心都是非晶态.非晶态聚苯硫醚的玻璃化转变温度和晶化温度分别为318和362 K.常压下的退火实验表明,非晶态聚苯硫醚在425 K等温结晶的产物为正交相晶型.压致凝固法中熔体的凝固不是靠温度变化,而是靠压力变化,样品表面和内部处在一致的温度下同时受压凝固,避免了热传导对非晶尺寸的影响,因此非常有利于获得结构均匀的大尺寸非晶态材料.     

Exchange bias effect in partially oxidized amorphous Fe-Ni-B based metallic glass nanostructures

The magnetic properties of amorphous Fe-Ni-B based metallic glass nanostructures were investigated. The nanostructures underwent a spin-glass transition at temperatures below 100 K and revealed an irreversible temperature following the linear de Almeida-Thouless dependence. When the nanostructures were cooled below 25 K in a magnetic field, they exhibited an exchange bias effect with enhanced coercivity. The observed onset of exchange bias is associated with the coexistence of the spin-glass phase along with the appearance of another spin-glass phase formed by oxidation of the structurally disordered surface layer, displaying a distinct training effect and cooling field dependence. The latter showed a maximum in exchange bias field and coercivity, which is probably due to competing multiple equivalent spin configurations at the boundary between the two spin-glass phases.     

低温高压及高温高压对La80Al20非晶态结构及超导性的影响

用X射线衍射照相、X射线衍射仪及透射电子显微镜分析了用液相淬火技术制备的La₈₀Al₂₀合金样品,结果表明样品是非晶态结构。差热分析(DTA)结果表明,非晶态样品的晶化温度T_cr为280℃左右,玻璃温度T_g为242℃左右。非晶态样品低温高压(流体静压法)试验结果表明:压力从0至4.77kbar,T_c从3.87K提高到4.18K。高压下,超导前的剩余电阻与常压下相比较有明显下降。非晶态样品经高温高压 关键词：     

高压下LiB3O5晶体-非晶体相变的研究

 采用X射线粉末衍射和同步辐射能散X射线衍射技术，对LiB₃O₅（LBO）晶体进行了压致非晶化相变的研究，压力达45.1 GPa。实验结果表明，LBO存在两个中间相变，压力分别为5 GPa和15.8 GPa。而当压力增加到25~31.6 GPa时，LBO出现非晶态，这个非晶化相变是不可逆的。     

非晶物质中的临界现象

非晶态材料有着复杂的原子结构(短程有序、长程无序)和特殊的物理性质,其临界现象和相变问题一直受到学术界关注.非晶合金,又称为金属玻璃,是一种新型的非晶态材料,具有很高的强度和优异的弹性.从微观的角度来看,非晶合金可以看作是一个多粒子系统.临界现象的研究对认识和理解多粒子系统之间的相互作用有深刻的意义.本文主要讨论非晶合金中的临界现象,包括非晶合金从制备过程、微观结构到宏观的力学性能以及磁性方面存在的临界现象,并分析这些临界现象之间的内在联系,进而深入理解非晶合金的微观结构对其宏观性质的影响.这为认识非晶合金的形成本质,提高服役可靠性,探索具有实际应用价值的非晶合金提供理论依据.     

Ultrafast laser-induced phase transitions in amorphous GeSb films

Time-resolved measurements of the spectral dielectric function reveal new information about ultrafast phase transitions induced by femtosecond laser pulses in Sb-rich amorphous GeSb films. The excitation generates a nonthermal phase within 200 fs. The dielectric function of this phase differs from that of the crystalline phase, contrary to previous suggestions of a disorder-to-order transition. The observed dielectric function is close to that of the liquid phase, indicating an ultrafast transition from the amorphous phase to a different disordered state.     

A neutron diffraction study of the glass transition in (KBr)0.47(KCN)0.53

The molecular crystal (KBr)_0.47 (KCN)_0.53 has been investigated by elastic neutron diffraction at the transition from the paraelastic to the orientational glass state. The freezing temperature is characterized by the onset of a momentum transfer dependent broadening of the diffraction lines indicating the transition from a crystalline to an amorphous state.     

Relaxation processes and structural transitions in stretched films of polyvinylidene fluoride and its copolymer with hexafluoropropylene

Relaxation processes and structural transitions in nonstretched and uniaxially stretched films of poly(vinylidene fluoride-hexafluoropropylene) (P(VDF-HFP)) and its homopolymer polyvinylidene fluoride (PVDF) for comparison were investigated with the aim of understanding the electromechanical properties of this lower-modulus ferroelectric copolymer. The mechanical and the dielectric response at the glass transition (?? _a relaxation) exhibit similar temperature dependence of the relaxation time, whereas mechanical and dielectric processes above the glass transition are not related. They represent a continuous softening process within the amorphous phase and the dielectric ?? _c relaxation, respectively. The latter is attributed to conformational changes of VDF segments in lamellae of spherulites constituting the nonpolar crystalline ?? phase. Furthermore, there is a contribution from melting of secondary crystallites formed in the amorphous phase during annealing or storage. Mechanically, this transition appears in nonstretched and stretched films as an accelerated decrease of the elastic modulus that terminates the rubber plateau. Dielectrically, this transition becomes visible as a frequency-independent loss peak only in stretched films, because stretching removes the ?? _c relaxation, which superimposes the transition in nonstretched films. Melting of secondary crystallites is shown to appear in the homopolymer, too, though less pronounced because of more complete primary crystallisation. Stretching increases the modulus above the glass transition only slightly, and it does not significantly influence the softening process. On the other hand, stretching causes a spontaneous polarisation and introduces order within the amorphous phase, rendering it more polar. Melting of secondary crystallites provides an additional contribution to the polarisation. These findings may explain the relatively high electromechanical activity of P(VDF-HFP) but also its relatively low thermal stability. Moreover, they may be important for correct procedure and analysis of temperature-dependent dielectric measurements on partially crystalline polymers, in particular on those with less favourable sterical conditions for primary crystallisation.     

Dynamic light scattering in solid polymers

The viscosity of an amorphous polymeric solid above its glass transition [T _g (T,P)] increases as the temperature of the solid is decreased or the pressure is increased. Under changes in temperature or pressure, molecular subunits in the polymeric solid undergo configurational changes. Such changes or relaxations have a distribution of relaxation strengths and times. As the solid is cooled or as the hydrostatic pressure on the solid is increased, the relaxation strengths increase and the relaxation times increase. These changes in relaxation or dynamic properties are very dramatic as the empirical T _g is approached. Near T _g the polymeric solid is no longer in volume equilibrium; continued cooling or pressuring at a time rate faster than the average relaxation time will produce a polymeric glass. This glass is a nonequilibrium, amorphous solid. If the glass is held at a fixed temperature and pressure very close to, but below, T _g , the volume of the glass will be observed to relax to its equilibrium value. For temperatures and pressures well below T _g , equilibrium is a much more conjectural concept since the relaxation times become extremely long. It has been proposed^1,2 that there is a characteristic temperature T _g at which an amorphous polymer undergoes a second-order transition to an equilibrium glass with zero configurational entropy (i.e., a noncrystallizable solid).     

Mn effect on wurtzite-to-cubic phase transformation in ZnO

Mn doping effect on a wurtzite-to-cubic phase transformation in ZnO has been investigated by in situ high pressure X-ray powder diffraction using synchrotron radiation. Unit cell expansion is clearly observed in Mn-doped ZnO samples. Mn ions sit at Zn site in the wurtzite structure. The onset transition pressure for the wurtzite-to-cubic phase transformation decreases from about 9.5 GPa for pure ZnO to 6 GPa for sintered 2at.% Mn-doped ZnO while the compressibility and volume collapse at transition pressures are not sensitive to the Mn doping in the wurtzite phase. The doping of Mn ions in ZnO increases the onset transition pressure for the cubic-to-wurtzite phase transformation. The results could be explained by a reduction of phase transformation barriers for both transition paths by the Mn doping. The observation of reduction of the wurtzite-to-cubic phase transformation pressure might point out a new direction to synthesize cubic wurtzite phase of ZnO by doping transition element(s).     

高压作用下相分离液体玻璃转变的分子动力学研究

采用分子动力学模拟方法,研究了二元混合液体在不同外压作用下的相分离与玻璃转变过程,计算了相分离液体在玻璃转变过程中的结构和动力学特征.研究发现,外压会促进相分离的产生,并提高玻璃转变温度,会使β弛豫出现的温度更高、存在的时间更长,导致系统扩散性降低.同时还发现,相分离液体的玻璃转变过程存在微观不均匀现象. 关键词： 相分离 玻璃转变 分子动力学模拟 外压影响     

Pressure and Time Dependences of the Supercooled Liquid-to-Liquid Transition in Sulfur

Thermal behavior of bulk amorphous sulfur is investigated by in situ temperature measurements at high pressures of 0.9,1.4 and 2.1 GPa,and under different heating rates of 8,10 and 12K/min at 0.9 GPa.The results show that the onset temperature of the transition from the supercooled liquid to the liquid state for sulfur increases with the pressure and the heating rate.It is deduced that the transition does not follow the Clapeyron equation,indicating considerable coupling of the molecular structure change in the transition.Along with the data at ambient pressure and high pressure,we present a dynamic diagram to demonstrate the relationship between the amorphous solid,supercooled liquid,liquid,and crystal phases of sulfur,and suggest an experimental approach to establish pressure-temperature-time transition diagrams for supercooled liquid and liquid.     

Observation of a pressure-induced first-order polyamorphic transition in a chalcogenide glass at ambient temperature

An apparently first-order polyamorphic transition has been observed with increasing pressure at ambient temperature in a molecular glass of composition Ge(2.5)As(51.25)S(46.25) Raman spectroscopic measurements on pressure-quenched samples and in situ x-ray diffraction measurements indicate that this transition corresponds to a collapse of the ambient-pressure molecular phase to a high-pressure network phase. The high-pressure phase first appears at a pressure of approximately 8-9 GPa and the transformation becomes complete at approximately 14-15 GPa. Calorimetric measurements indicate that the low- and high-pressure phases are thermodynamically distinct and that they coexist in the transition range.     

磁通格子的有序-无序相变和反向熔化

考虑了无序钉扎、热涨落和磁通互作用, 用Monte Carlo分子动力学模拟方法研究二维磁通格子在无序钉扎强度和温度空间的相图, 以及由布拉格玻璃相到非晶磁通玻璃相和到磁通液体相的有序-无序相变.为了决定磁通格子的序，计算了静态结构因子和磁通格子位形的有限尺寸指数.计算结果表明，Bragg玻璃相在低温的无序磁通玻璃相和高温的磁通液体相之间 , 表现出磁通格子的反向熔化行为.分析后认为，这一反向熔化行为起因于磁通之间互作用的温度效应. 关键词： Ⅱ类超导体 磁通格子 相图 结构因子 反向熔化     

Structural stability and phase transitions in K8Si46 clathrate under high pressure

The structural stability of type-I K8Si46 clathrate has been investigated at high pressure by synchrotron x-ray diffraction. In contrast to that observed in the Na-doped structure-II analogue [A. San-Miguel, Phys. Rev. Lett. 83, 5290 (1999)]], no phase separation into the beta-Sn Si structure was identified at 11 GPa. Instead, K8Si46 is found to undergo a transition to an isostructural positional disordered phase at around 15 GPa. Ab initio phonon band structure calculations reveal a novel phenomenon of phonon instabilities of K atoms in the large cavities is responsible for this transition. Above 32 GPa, the new structure transforms into an amorphous phase.     

Influence of tensile deformation on the crystalline organization of ethylene copolymers

The influence of tensile deformation on the crystalline properties of ethylene copolymers (ethylene-vinyl acetate [EVA] copolymers) was investigated by differential scanning calorimetry (DSC). The consequence of drawing on the mobility of the amorphous phase also was investigated through the study of the glass transition temperature. The results indicate that more disorganized crystals, melting at a lower temperature, are present after the tensile deformation, reducing the mobility of the amorphous chains, as shown by an increase of the glass transition temperature. For the lowest molecular weight copolymer. less crystalline changes are observed after the tensile test, probably due to the fact that no stiffening appears during the drawing.     

Crystallization of a Mechanically Activated CuTi Alloy

The atomic structure and amorphous-crystalline transition dynamics in CuTi metallic glass synthesized by high-energy ball milling have been studied. Using high-resolution transmission electron microscopy (HRTEM), it has been shown that the initial amorphous phase contains crystalline inclusions, which are up to 8 nm in size and may serve as crystallization centers. In contrast to the earlier studied amorphous CuTi alloys synthesized by melt spinning, the process of crystallization in the mechanically generated amorphous alloy begins at a lower temperature (250°C) and lasts for 20–30 s. A conclusion about the diffusion mechanism of crystallization in this material has been made.