高温超导体中的相分离

对高温超导体中的一种特殊现象———相分离作了简要介绍和讨论，希望有助于对高温超导体从其母体———反铁磁绝缘体到金属（超导态）的转变以及与此相关的高温超导体的物理性质的了解．文章分四部分：高温超导体的电子相图；高温超导体中相分离研究的内容及现状；有关相分离的物理机制；高温超导体中的条纹相．     

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     

La0.7-xGdxSr0.3MnO3体系中的相分离

采用固相反应法制备了样品La0.7-xGdxSr0.3MnO3(x=0.00,0.20,0.30,0.40,0.50).通过测量样品的M～T曲线,ESR曲线,研究了La0.7-xGdxSrO0.3MnO3,体系中的相分离现象及相分离与CMR之间关系.结果表明:当x=0.30,0.40时,在PM-FM相变区产生相分离,并且磁电阻MR得到增强.研究结果表明:La0.7-xGdx Sr0.3MnO3中的相分离与Gd在A位的占位情况紧密相关,磁电阻MR的增强是在外磁场作用下,铁磁区扩大顺磁区减小引起的.     

复杂氧化物中电子相分离的量子调控

复杂氧化物可以呈现出高温超导、庞磁阻以及多铁效应等诸多新奇的物理现象.这类材料中的电荷/自旋/轨道和晶格自由度之间的强耦合相互作用,可以导致多种相互竞争且能量非常接近的电子态的空间共存,这就是电子相分离现象.如果可以将材料的空间尺寸缩小到电子相分离的特征长度,其物理性质甚至电子关联作用本身都会发生根本的变化,从而有可能实现复杂氧化物中的量子调控.本文综述了我们课题组在过去几年中针对复杂氧化物中电子相分离的量子调控取得的进展,内容包括：发现了锰氧化物边缘电子态,通过氧化物微纳加工技术,实现了量子态空间分布的调控,提高了庞磁阻锰氧化物的临界温度;研究了当材料空间尺度小于其电子相分离特征尺度时电子相分离的表现,确定了在电子相分离消失以后体系的磁结构;通过超晶格生长技术调控了材料中的掺杂有序度,对锰氧化物中大尺度的电子相分离的物理机理从实验上给出了解释.     

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     

聚氰丙基甲基硅氧烷-聚脲嵌段共聚物的NMR表征及研究

用高分辨NMR对聚甲基硅氧烷-聚脲嵌段共聚物以及聚氰丙基甲基硅氧烷-聚脲嵌段共聚物结构进行表征,对NH形成的各种氢键进行详细的研究,同时观察了氢键在力学性能中的作用,结果发现氢键强烈地影响着力学性能。用固体¹H宽线研究这类材料的相分离状况,并总结影响相分离的因素。保持硬段含量不变,增加软段分子量使相分离程度增加;保持软段分子量不变,增加硬段含量使相分离程度降低。软、硬段之间的相互作用(如氢键)使相分离程度降低。     

聚氰丙基甲基硅氧烷—聚脲嵌段共聚物的NMR表征及研究

用高分辨NMR对聚甲基硅氧烷-聚脲嵌段共聚物以及聚氰丙基甲基硅氧烷-聚脲嵌段共聚物结构进行表征,对NH形成的各种氢键进行详细的研究,同时观察了氢键在力学性能中的作用,结果发现氢键强烈地影响着力学性能。用固体~1H宽线研究这类材料的相分离状况,并总结影响相分离的因素。保持硬段含量不变,增加软段分子量使相分离程度增加;保持软段分子量不变,增加硬段含量使相分离程度降低。软、硬段之间的相互作用(如氢键)使相分离程度降低。     

螺旋管内气液固三相流颗粒相分布规律

为了深入认识螺旋管多相流相分离现象,并为新型螺旋管除砂器设计提供指导,本文应用马尔文粒度仪,测量了螺旋管气水砂三相流底部水平段液膜中的颗粒浓度和粒度分布。研究表明:在泡状流和分层流条件下,螺旋管底部水平段可形成稳定的连续液膜流动;在宽广的气速范围内,液膜中的颗粒浓度分布规律均为内弯侧较低、外弯侧较高,说明螺旋管除砂器对于实际生产中流动工况的变化具有良好的适应性;泡状流中提高气速有利于分离;分层流中在中等气速条件下外弯侧颗粒浓度最大,中等气速是相分离的最佳操作工况。     

超导金属玻璃Zr_(78)Co_(22)Ⅰ-Ⅴ曲线上的台阶结构

测量了非晶态超导合金 Zr_(78)Co_(22)的 I-V 特性,观察到了电压阶跃现象.基于超导相分离模型,提出了电流拨动机制.理论分析结果表明,这种超导相之间的拨流会导致电压阶跃的出现,从而完美地解释了实验现象.     

室温下过搀杂Bi2212高温超导单晶的化学相分离

我们用高灵敏度的交流磁强计研究了Bi2212高温超导单晶的超导转变行为,发现对过搀杂的单晶样品,高温退火处理后立即测量,磁化表现为陡峭的超导转变.但是放置一段时间(数周)后,磁化曲线出现多个转变,并且再次高温退火能将其恢复为单一转变.说明即使是很均匀的单相,随着时间的推移,也会出现相分离现象.这一结果表明,在室温下,单晶中的氧原子仍然能够移动,而且倾向于重新排布形成不同的相.新形成的相的的磁化曲线有约瑟夫森弱联的特征,暗示新相是以小的团簇形势存在,团簇之间以约瑟夫森弱联耦合起来.另一方面,对最佳搀杂的单晶样品,没有观察到相分离现象.     

Numerical Simulation of Phase Separation Kinetic of Polymer Solutions Using the Spectral Discrete Cosine Transform Method

A spectral discrete cosine transform (DCT) method was used to solve numerically the spatio-temporal nonlinear Cahn-Hilliard equation for a temperature-induced phase separation process of a polymer solution. The properties of a high molecular weight polystyrene solution were used in the model to reflect the behavior of a real world polymer system. Based on the value of the initial concentration, three different final morphologies of the phase separated system, granular, interconnected, and microcellular, were identified. It was shown that the initial concentration is the main factor to determine the high rate of the phase separation when the phase separation time is the primary desired parameter. The degree of phase separation, as a quantitative measure of the phase separation process, indicates the rate and amount of separated polymer material for practical applications. The model is capable of providing quantitative information of morphology evolution during phase separation processes for microstructure control purposes. The structure factor profile was extracted as a theoretical output that enables comparison with scattering experiments observations as the finger-print of phase separation morphological evolution. It is shown that the DCT method is a very suitable and feasible method for solution of the nonlinear partial differential equation of phase separation kinetics.     

Dynamics of transient metastable states in mixtures under coupled phase ordering and chemical demixing

We present theory and simulation of simultaneous chemical demixing and phase ordering in a polymer-liquid crystal mixture in conditions where isotropic-isotropic phase separation is metastable with respect to isotropic-nematic phase transition. In the case the mechanism is nucleation and growth, it is found that mesophase growth proceeds by a transient metastable phase that surround the ordered phase, and whose lifetime is a function of the ratio of diffusional to orientational mobilities. In the case of spinodal decomposition, different dynamic regimes are observed depending on the mobility ratio: metastable phase separation preceding phase ordering, phase ordering preceding phase separation, or simultaneous phase ordering and phase separation. Not only the overall dynamics but also the final structure of the material can be different for each kinetic regime.     

Impurity and electronic phase separation in high-T C superconductors and other quasi-two-dimensional degenerate magnetic semiconductors

Both electronic phase separation occuring at impurity frozen, and the impurity phase separation occuring at mobile impurity are investigated for the case of quasi-two-dimensional degenerate magnetic semiconductors to which HTSC's belong. The optimum geometry for the electronic phase separated state is found, and its energy is evaluated. According to these evaluations, the electronic phase separation is not forbidden for HTSC's. The impurity phase separation is calculated with the aid of the jellium model for the impurity metal generalized for the two-dimensional case. At realistic parameters both the impurity-magnetic phases arising as a result of phase separation may be high-conducting or even superconducting.     

Phase separation in colloidal suspensions induced by a solvent phase transition

A colloidal suspension of macroparticles in a solvent is considered near a solvent first-order phase transition. The solvent phase transition is described by a Ginzburg-Landau model with a one-component order parameter which is coupled to the macroparticles coordinates. Wetting of the macroparticle surface by one of the two coexisting phases can induce phase separation of the colloidal particles. This phase separation is first explained by simple thermodynamic arguments and then confirmed by computer simulation of the Ginzburg-Landau model coupled to the macroparticles. Furthermore a topological diagnosis of the interface between the stable and metastable phase is given near phase separation and possible experimental consequences of the phase separation are discussed.     

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     

Effect of Nanoparticles on the Phase Behavior of Polystyrene/Poly(vinyl methyl ether) Blends with Different Polydispersities

Effects of two kinds of silica nanoparticles on the phase behavior of blends of poly (vinyl methyl ether) (PVME) and two kinds of polystyrene (PS), with the same number average molecular weight but different polydispersities, were studied by using optical microscopy. The addition of both the hydrophilic A200-SiO₂ and hydrophobic R974-SiO₂ nanoparticles made the miscibility become worse. The decrease in the phase separation temperatures of PS/PVME with polydisperse PS (pPS) was larger than that of PS/PVME with monodisperse PS (mPS) in the presence of A200-SiO₂; the shifts of the phase separation temperatures of mPS/PVME and pPS/PVME were comparable for the incorporation of R974-SiO₂. The addition of both kinds of silica accelerated the phase separation during the nonisothermal phase separation. The domain size changes of the phase morphology of mPS/PVME (50/50) and pPS/PVME (50/50) were almost the same during the nonisothermal phase separation in the presence of nanoparticles. During the isothermal phase separation, the introduction of silica slowed down the phase separation dynamics by hindering the phase structure transition. The morphology changes of pPS/PVME (50/50) were more evident than those of mPS/PVME (50/50) with the incorporation of SiO₂.     

Magnetically induced phase separation in the Co–Cr binary system

Direct evidence of phase separation in the Co-rich corner of the Co–Cr binary system, the transformation of high-temperature FCC α-Co into a ferromagnetic α_f phase and a paramagnetic α_p phase, has been experimentally obtained by using diffusion couple technique, scanning electron microscopy with energy dispersion analysis of X-ray (SEM-EDX), analytical transmission electron microscopy, optical microscopy and X-ray diffraction. Thermodynamic calculation, on the basis of the presently obtained phase equilibrium data, has verified that this phase separation arises from magnetic ordering, and that a similar phase separation appears in the HCP phase below 469°C which is transformed into a ferromagnetic ε_f phase and a paramagnetic ε_p phase. It is therefore concluded that magnetically induced phase separation must be responsible for the microscopic composition modulation of Cr in the CoCr thin film magnetic recording media.     

Effect of electron flux on electronic-excitation-induced phase separation in GaSb nanoparticles

We studied the effect of electron flux on phase separation induced by electronic excitation in GaSb nanoparticles, in order to see whether the phase separation is characterized as a cooperative phenomenon, in which a nonlinear relation may be found between density of excited states introduced and the efficiency of the phase separation or not. The phase separation to two phases consisting of an antimony core and a gallium shell proceeds abruptly after incubation time with increasing electron dose and does only at the flux above a threshold value. It is suggested that such nonlinear behaviors take place as a cooperative phenomenon among electronic-excitation effect, nano-size effect and temperature.     

红外显微化学图像技术在空心微球制备中的应用

在考察聚苯乙烯(PS)与聚乙烯基苄氯(PVBCl)相容性及干涉效应对测量结果影响的基础上,使用红外显微化学图像技术研究表征了PS与PVBCl混合物薄膜和微球的相分离情况,对比分析了不同处理条件下制备的微球半球壳中两种聚合物的相分离红外显微化学图像。研究结果表明建立的研究方法可以用来定性或半定量的分析球壳内PS和PVBCl两聚合物的分相情况,在测试中样品的干涉效应会对测量造成较大的不确定度,在不同温度下获得的聚合物微球样品中,40℃条件下两聚合物的分相情况更为理想。该研究为探索非均相双半球型聚合物微球制备条件以及红外显微化学图像法表征聚合物相分离提供了一种直观可行的表征方法,但受空间分辨率的影响,该方法不适合于6.25μm×6.25μm以下尺寸样品的分析。     

Preparation of lotus-like superhydrophobic fluoropolymer films

Styrene and 2,2,3,4,4,4-hexafluorobutyl methacrylate copolymers were synthesized by bulk polymerization, and the superhydrophobic copolymer films were prepared subsequently using phase separation technique. The copolymer was dissolved in tetrahydrofuran, and then added ethanol into the solution thereafter, to induce phase separation. The microstructures of the polymer films were controlled by the degree of phase separation, which was enhanced properly by the concentration of ethanol. The surface morphology of the films, observed by environmental scanning electron microscope, is similar to that of the lotus leaf. The contact angle and sliding angle were measured as 154.3° and 5.8°, respectively. The excellent superhydrophobic property demonstrated that the phase separation technique is useful for preparing lotus-like fluoropolymer films.