相分离液体在玻璃转变过程中的动力学性质(英文)

近年来,相分离动力学一直受到大家的关注,人们从技术和理论角度进行了研究.一个二元系统从混溶温度开始进行快速冷却,这个过程驱使两个相的形成和生长.这种自发生长过程遵从幂规律R(t)∝t~n,R(t)是在t时刻的相分离域尺寸大小,增长指数n是一个重要的量,有效的反映了相分离域的增长机制.但是对于相分离液体的玻璃转变过程的研究相对较少.本文采用分子动力学(MD)模拟方法,提出了一个新的模型——相分离液体来研究玻璃转变过程.相分离在玻璃转变过程中,过冷液体分离为两个相.我们主要研究了体系的动力学不均匀性.发现两个相的动力学性质是不均匀的,两个相的玻璃转变温度是不一样的.分析得出,相分离液体在玻璃转变过程中存在着一个动力学奇异点.说明相分离可能是引起玻璃转变系统动力学奇异性的一个原因.     

三维颗粒气体相分离现象

颗粒体系是一类复杂的耗散体系.在颗粒气体中,耗散性质会使其内部形成局部的凝聚,类似于真实气体中亚稳分解形成的液滴,因此被认为是颗粒气液两相分离的过程. 零重力环境下二维颗粒气体相分离现象已有成熟的流体静力学理论解释,将该理论模型推广到三维情形,发现相分离现象依然存在且具有同样的不稳定性根源,通过理论计算给出了三维相分离发生的具体条件. 同时,用分子动力学方法模拟检验了理论结果,并给出了三维颗粒气体相分离的新形貌. 关键词： 颗粒气体 耗散 相分离 分子动力学模拟     

分子动力学模拟钠硼硅酸盐玻璃电子辐照诱导的结构演化效应

钠硼硅酸盐玻璃作为高放射废物玻璃固化体的候选材料之一,已有大量实验对该类玻璃开展了电子或重离子的辐照效应研究.然而,在理论计算与模拟方面的工作却很少,目前主要集中于重离子的辐照效应,对电子的辐照效应的模拟尚未见报道.本文利用分子动力学工具提出一种新的方法,以实现对电子辐照诱导的玻璃结构演化进行模拟.该方法基于实验中玻璃的结构变化特点,即实验中的拉曼结果已经证实:在大剂量的电子辐照后的玻璃中存在分子氧的事实,由于这些分子氧不会与其他粒子发生相互作用,因而可以通过从体系中逐步地移除一定数量氧原子的方式,以达到模拟大剂量电子辐照的情形,进而得到电子辐照后的玻璃的结构信息.模拟结果显示:随着移除氧原子的数量增加,玻璃中的Si—O—Si平均键角逐渐减小;而且玻璃中的小环数量会因氧的逐渐减少而逐渐增加;玻璃中部分[BO4]结构会转变为[BO3]结构,最终这种转变会达到饱和;大量移除氧之后,玻璃中的钠元素也出现明显的相分离.这些模拟辐照的玻璃结构特性能较好地与实验中的硼硅酸盐玻璃电子辐照诱导的结构变化符合.因此,本文提出的方法有望为通过分子动力学模拟硼硅酸盐玻璃的电子辐照效应提供新思路.     

二元Lennard-Jones液体的相分离过程及其扩散性质的分子动力学研究

采用分子动力学(MD)模拟方法,研究了二元体系中相分离过程、粒子的扩散系数以及相分离域尺寸大小随温度的变化规律.发现,相分离域随温度的生长过程可以分为两个阶段,分别是温度比较高的快速生长阶段和低温时的稳定生长阶段;相分离体系中系统的扩散激活能不是常数,而是一个随温度变化的函数,并且当温度高于60 K时,满足关系式E(T)=a+bT^c.讨论了组元尺寸的变化对相分离过程的影响.结果表明,随两组元中某一组元 关键词： 相分离 扩散 分子动力学模拟     

液态金属急冷过程中微观结构转变的研究

本文对液态金属Ａｌ在溶态及急冷过程中的微观结构及其转变进行了分子动力学模拟研究。发现在由ＨＡ（Ｈｏｎｅｙｃｕｔ－Ａｎｄｅｒｓｅｎ）健型指数所确定的双锥体原子团结构的数目随急冷温度变化的关系曲线上存在着二个明显的转变点。第一个点与熟知的玻璃转变温度Ｔｇ相吻合；而第二个点则为新发现的低温端相交点Ｔｇ２。这一结果为用分子动力学方法从微观层次上研究结构相变过程提供了一条新途径。     

冷却速率对Lennard-Jones体系凝固过程中结构与动力学性质的影响

用分子动力学模拟方法研究了五种不同冷却速率对Lennard-Jones体系凝固过程中结构与动力学性质的影响.采用两种不同的方法来确定玻璃转变温度Tg,并且对结晶温度Tc、径向分布函数g(r)、均方位移函数MSD与扩散系数D、平均配位数进行比较分析.结果表明:冷却速率影响Lennard-Jones体系凝固过程中的结构.当使用足够高的冷却速率冷却时,体系发生玻璃化转变,而且冷却速率越快,玻璃转变温度越高;当冷却速率较小时,体系形成晶体,而且冷却速率越慢,结晶温度越高,结晶程度也越高.同时发现,冷却速率对扩散系数和平均配位数也有很大影响,二者在体系发生玻璃转变时都有一个缓变的过程,表明了过冷液相区的存在.     

金属玻璃液体中的强脆转变现象

强脆转变是玻璃形成液体在从低温到高温升温过程中由强性液体转变为脆性液体的现象,反之从高温到低温冷却过程即为脆强转变.由于其意味着液体的结构发生了某种快速、非连续的变化,强脆转变现象成为异常动力学的典型代表.自1999年《Nature》杂志首次报道了水的强-脆转变现象之后,液体的强脆转变现象就作为凝聚态物理和材料科学领域中的前沿和热点问题被广泛关注.越来越多的研究表明,强脆转变现象在金属玻璃形成液体中普遍存在.为阐明金属玻璃强-脆转变现象对于深入理解玻璃转变本质、探讨液固遗传微观结构特征、揭示晶化过程相互竞争规律、提高玻璃形成能力、促进金属玻璃制备和处理工艺标准化等方面的重要意义,综合评述了强脆转变现象在金属玻璃形成液体中的普遍性、特殊性、定量表征、热力学表现以及结构起源等研究领域的最新进展,并指出了该领域今后的发展方向.     

Fe_50Cu_50合金熔体相分离过程的分子动力学模拟

基于镶嵌原子势,采用分子动力学模拟的方法探讨了Fe50Cu50合金熔体在1823 K下液-液相分离过程.结果发现:熔体中同类原子配位数随弛豫时间的延长逐渐增大,而异类原子配位数逐渐减少;由BhatiaThornton结构因子SCC(q)获得的相关长度随时间的变化也呈现出明显的递增趋势,表明该合金熔体在该温度下发生了液—液相分离.原子轨迹的可视化显示结果发现,相分离的初期,体系呈明显的网络状组织,随时间的延长,异类原子逐渐分离,最终形成富Fe和富Cu的相分离组织,符合调幅分解特征.与Fe75Cu25合金熔体的相分离过程对比发现,Fe与Cu原子数目相差越小,相分离行为越剧烈,形成稳定分层结构所需的时间越短.以上研究从原子尺度上表征了金属熔体的相分离过程.     

应力诱发NiAl单晶马氏体相变的分子动力学模拟

利用嵌入原子势（EAM）,对NiAl单晶在外应力作用下的动态拉伸过程进行了分子动力学模拟.应力-应变曲线分析以及原子构型分析表明外应力诱发NiAl合金发生了马氏体相变,原子结构由B2相转变为L1₀相.通过研究原子构型的演化过程,发现马氏体相变是通过多个{110}孪晶面的扩展和湮灭作用来完成的.同时探讨了马氏体相变的微观机理. 关键词： 马氏体相变 NiAl 分子动力学模拟     

过冷Fe85Ni15熔体的结构及动力学研究

基于嵌入原子势(EAM),采用分子动力学(MD)模拟的方法探讨了过冷液态Fe85Ni15合金的微观结构及动力学性质.对B-T结构因子(SF)与相对长度(Correlation length)的分析发现：Fe85Ni15熔体具有相分离的趋势,但不十分明显.配位数(CN)及F-Z结构因子的计算结果证实了体系的短程序对应着二十面体结构.均方位移(MSD)的计算结果表明：Fe85Ni15合金属于脆性液体.将获得的扩散激活能与其它合金系进行对比发现扩散激活能并不能反映熔体的玻璃形成能力,熔体中的二十面体结构不利于非晶的形成.     

Effect of pressure on the secondary relaxation in a simple glass former

We have studied dielectric spectra of the glass-forming liquid metafluoroaniline under hydrostatic pressure up to 700 MPa. Its glass transition pressure p(g) increases approximately linearly with temperature. Above p(g)(T), a well pronounced secondary relaxation, the Johari beta peak, is observed showing activated behavior. The activation energy rises proportionally to pressure and, consequently, proportionally to the glass transition temperature T(g)(p). The activation volume is independent of temperature but exhibits different values for pressures higher and lower than the pressure where the liquid left the ergodic regime. The activation volumes are about 1/10 and 1/6 of the molecular volume of fluoroaniline, respectively, suggesting that there are two different species of clusters.     

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.     

Thermally stimulated currents in poly(vinyl chloride): Tacticity and molecular weight influence

Thermally stimulated currents (TSC) have been measured in several samples of poly(vinyl chloride) differing in tacticity and molecular weight as a result of polymerizing them at different temperatures. This has allowed us to characterize the relaxation behavior of PVC. No dielectric relaxation can be observed by this experimental technique at temperatures between liquid helium and liquid nitrogen. The β relaxation is observed around 173°K, with similar parameters in all samples studied. Around the glass transition the relaxation times isolated in the α peak follow a compensation law. Molecular weight and tacticity have a strong influence on the temperature of the maximum and the intensity of this relaxation, respectively.     

The evolution of the molecular relaxation parameters described by the Cole–Cole model at the isotropic-nematic phase transition*

This paper presents the dielectric properties of the isotropic liquid and nematic phase at the phase transition. One strong molecular relaxation is observed in both phases. It is interpreted as related to the relaxation around a short molecular axis, due to the fact that molecules possess a strong longitudinal dipole moment. In the isotropic liquid the relaxation is described by the Debye model, while after entering the nematic phase (at cooling) relaxation becomes described by the Cole–Cole model. The distribution parameter of the Cole–Cole model changes from 0.05 (10 degrees above the temperature of the Iso-N transition) to 0.09 (exactly at the phase transition Iso-N), and finally, it reaches 0.35 (10 degrees below the Iso-N transition). Additionally, we observe that ion contribution to the dielectric response is not influenced by the phase transition. All relaxation parameters are discussed within the context of the phase transition phenomena.     

非晶材料玻璃转变过程中记忆效应的热力学

低温下处于非平衡态的非晶材料升温到玻璃转变以上,要先后发生弛豫和回复最终达到平衡过冷液态,其中弛豫过程中释放的能量在回复过程中以等量的方式获取,表现出明显记忆行为.本文基于氧化物、金属与小分子等多种非晶形成体系,全面探讨了在围绕玻璃转变的一个冷却加热循环过程中的焓弛豫特征,建立了弛豫谱,发现弛豫焓在数值上与熔化焓密切相关.基于弛豫焓与非晶材料动力学Fragility之间的关联,展示了非晶体系在动力学极限(m=175)条件下的玻璃转变热力学基本特征,与热力学二级相变进行了对比.研究深化了对非晶弛豫与玻璃转变热力学的理解.     

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).     

Investigation into the dielectric relaxation of vinylidene fluoride copolymers with hexafluoropropylene

Four relaxation processes and one ferroelectric-paraelectric phase transition are revealed in vinylidene fluoride-hexafluoropropylene copolymers with different ratios of the components in the temperature range from ?100 to 150°C. The relaxation process occurring at the lowest temperature is associated with the local mobility of the chains, whereas the relaxation process at a higher temperature is due to micro-Brownian motion of segments in the amorphous phase in the glass transition range. A smeared relaxor phase transition from the polar modification of the α phase of vinylidene fluoride units to the paraelectric phase is observed in the temperature range 50–70°C. At higher temperatures, there occurs an intensive relaxation process that can be attributed to space-charge relaxation or manifestation of the normal relaxation mode.     

Spectroscopy of II–VI nanocrystals at high pressure and high temperature

We review experimental measurements of CdS, CdSe, and CdS_xSe_{1 − x} nanocrystals which address the properties and phase stability of both powder and embedded nanoparticles under extreme conditions. We address the high pressure phase transition of wurtzite or zincblende phase to the rock salt structure; the high temperature solid to liquid phase transition; and the homogeneous nucleation of nanoparticles in glass from dissolved reactants. We also review the use of high pressure optical measurements to study electronic states.