论材料非晶形成中的焓与熵:竞争亦或协同?

液固Gibbs自由能差是决定材料非晶转变的热力学关键因素,但该参量在预测非晶转变和指导非晶成分设计方面仍有一些基本问题有待解决.其中,一个关键问题是:作为Gibbs能差的两个核心要素,焓与熵,二者在决定和控制非晶转变中关系并不明确.基于课题组系列研究结果,本文就焓与熵在材料非晶转变中的协同性与独立性问题进行了全面探讨,发现二者在决定非晶形成上具有很强的相关性.理论分析和实验测量相结合,展示了材料熔化熵与熔点粘度、混合焓等多个非晶形成经典参量之间的内在关联,证实熔化熵与材料非晶形成之间的密切关联;并从多个角度证实材料低熔化熵有利于非晶形成,纠正了传统上基于经典形核理论得出的高熔化熵有利于非晶形成的认识.研究也发现,决定非晶形成的关键动力学与热力学参量,如粘度和混合焓,均可通过熔化熵得到表达.进而论证了熔化熵在评估非晶形成、指导非晶成分设计中的可靠性和有效性,由此提出熔化熵可作为理解指导材料非晶形成的代表性热力学参量.系列成果为发展非晶形成热力学、深入理解材料非晶形成提供了参考与思路.     

国外物理科普杂志精文提要

 H.谢尔等《输运和弛豫出的时标不变性》1月号在许多无序材料中看到标度不变动力学现象.分散运动可定量解释非晶半导体和绝缘体、聚合物薄膜、分子固溶体和玻璃等材料输运和迁移的测量中的普遍特性.文章讨论无序半导体中的电荷输运,论及它的实验和机制、弛豫规律.最后讨论玻璃材料中的弛豫.由上可见,无序系统中的输运和弛豫特性可归因于事例间时间的长尾分布,而这一分布限制了运动.     

胶体在非晶研究中的应用

胶体玻璃作为一种软物质材料由于其独特的物理化学特性在非晶态物理的研究中有重要的应用.本文简要介绍了胶体玻璃与玻璃材料的联系,并通过具体的研究实例介绍了胶体玻璃在研究非晶结构、动力学以及热力学方面的应用,对胶体玻璃未来的研究进行了展望.     

锆基非晶合金的动态弛豫和应力松弛

非晶合金动态弛豫、变形和微观结构非均匀性之间的关联是非晶态物理领域重要研究内容之一.本文选取玻璃形成能力优良,热稳定性好的Zr₄₈(Cu_5/6Ag_1/6)₄₄Al₈块体非晶合金作为研究载体,借助于动态力学分析及应力松弛实验探究了温度和结构弛豫对非晶合金动态弛豫和变形行为的影响.研究结果表明非晶合金动态弛豫行为对温度极其敏感,随温度升高表现为等构型、老化、玻璃转变和晶化4个阶段.基于玻璃转变温度之下等温测试,结构弛豫行为导致非平衡高能量状态非晶合金向低能量状态迁移,内耗随时间演化规律可用Kohlrausch-Williams-Watts (KWW)扩展指数方程描述.此外,基于KWW方程和激活能谱等方法分析了模型合金应力松弛过程中非均匀结构激活,该过程涉及弹性变形向非弹性变形的转变.由于非晶合金存在微观尺度的结构非均匀性与能量起伏,变形单元的激活并非为单一特征时间,而是服从一定分布.通过考虑对数时间尺度和变形单元激活的特征时间分布分别为对称Gauss分布和非对称Gumbel分布,可...     

非晶合金结构演变影响玻璃形成能力的分子动力学研究

通过分子动力学方法模拟了Ti75Al25、Ni50Zr50和Cu50Zr50非晶合金的玻璃转变过程, 得到并分析了平均原子体积和双体分布函数等结构参数, 并应用Voronoi多面体指数分析法统计了玻璃转变过程中二十面体及类二十面体团簇的数量, 通过分析团簇在玻璃转变过程中种类和数量的涨落趋势, 研究了非晶原子由短程序连接至中程序再至长程无序的动力学演化过程. 结果表明, 非晶合金的玻璃形成能力以及塑性变形能力与动力学演化过程中Voronoi团簇的种类和数量密切相关. 在玻璃转变过程中局部五次对称性高的团簇倾向于连接在一起形成链,从而密排整个空间, 降低系统的动力学行为从而提高玻璃形成能力. 塑性形变倾向于发生在局部五次对称性较低的区域. 在玻璃转变温度附近团簇种类和数量的突变反映出非晶合金的自组织临界行为, 蕴含着丰富的非线性动力学现象.     

La基非晶合金β弛豫行为:退火和加载应变的影响

β弛豫行为是理解非晶合金扩散、塑性变形和玻璃转变行为的重要切入口.本研究以具有显著β弛豫行为的(La_0.6Ce_0.4)₆₅Al₁₀Co₂₅非晶合金为研究载体,利用动态力学分析仪,研究了加载频率、退火以及加载应变等因素对非晶合金β弛豫行为的影响.结果表明,随着加载频率的升高,非晶合金β弛豫峰向高温段移动.低于玻璃转变温度退火导致非晶合金β弛豫峰内耗值降低,非晶合金“缺陷”浓度降低,玻璃体系向更稳定状态迁移.随加载应变幅值增大,非晶合金β弛豫强度增大.本研究为进一步厘清非晶合金β弛豫起源提供新思路.     

块体非晶合金 Zr55Cu30Al10Ni5 结构弛豫的研究

应用同步辐射小角x射线散射和差示扫描量热分析对块体非晶合金Zr55Cu30Al10Ni5结构弛豫进行了研究.实验结果表明:经340℃、不同时间退火后的非晶内部的电子密度涨落随退火时间的延长先增大而后减小;玻璃转变温度附近焓弛豫峰的表观激活能则随退火时间的延长先减小而后增大.结果反映了随退火时间的延长,块体非晶合金内部类液体区不断减少及类固体区不断增加的过程.     

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     

非晶合金中的流变单元

非晶合金是一类具有诸多优异性能的先进金属材料,同时也是研究非晶态物质的模型体系.最近,大量的实验和模拟证据显示,在非晶合金中可能存在类似晶体中缺陷的"流变单元",这些动力学单元和非晶合金的的流变、物理、力学性能密切关联.本文主要综述了流变单元提出的背景、实验证据、流变单元的特征、激活与演化过程、相互作用以及相关的理论.文中提供了大量实验证据证明流变单元模型不仅可以帮助理解非晶态物质中如形变、玻璃转变、弛豫动力学以及非晶结构和性能的关系等重要的基本物理问题,而且可以指导非晶合金性能的调控和设计,获得性能优异的非晶合金材料.     

不同力学激励形式探索La基非晶合金微观结构非均匀性

非晶合金力学行为与其微观结构非均匀性之间本征关联,是固体力学研究领域至今未能很好解决的重要科学问题之一.单一力学激励形式并不能有效地描述非晶合金微观结构非均匀性,特别是结构与动力学的关联.如何探索非晶合金结构信息,须将诸多因素综合,在不同力学激励下研究非晶合金微观结构非均匀性与变形机理.本研究以La₆₂Cu₁₂Ni₁₂Al₁₄非晶合金为模型体系,利用动态力学分析仪研究非晶合金动态弛豫行为.基于准点缺陷模型,对模型合金体系α弛豫和β弛豫进行了分离.借助于拉伸应变率跳实验,探索非晶合金高温流变行为.确定非晶合金塑性流变过程中弹性、滞弹性以及塑性变形的贡献.本研究从非晶合金动态力学弛豫行为和宏观塑性流变行为出发,尝试揭示微观非均匀性对非晶合金在不同激励形式中缺陷的激活、扩展和融合的物理本质.     

Local heating and quenching effects on amorphous selenium configurational disorder,during reactor neutron irradiations

A new observation about the influence of reactor neutron bombardment on the configurational disorder of glasses has been drawn from enthalpy change diagrams (DSC) performed near Tg on amorphous selenium.

The irradiation was done at low temperature (30 K) and fission and capture effects were shielded by enclosing samples in NB cells.

Near Tg (320 K) a progressive change is observed from a stabilized relaxation state (initial state) to a highly quenched state in the bulk, as a function of the neutron dose.

A local heating and quenching effect induced by deposited energy spikes, is assumed and calculated to explain the apparent 300 K temperature incursion in the material, followed by fast cooling of configurational state through the liquid-glass transition.     

The orientational glass transition in pentachloronitrobenzene: a study by differential scanning calorimetry and thermally stimulated currents

The orientational disorder that is a feature of the crystalline pentachloronitrobenzene above ∼−82 °C, can be frozen by cooling to produce an orientational glass. The number of degrees of freedom frozen on cooling, or released on heating, in this orientational glass transition is low, so that the heat capacity change associated with this transition is expected to be small. In the present work, we show that the calorimetric signature of this orientational glass transition is in fact very weak. Conversely, since the molecular motions associated with this relaxation drag strong dipoles, the technique of thermally stimulated depolarisation currents (TSDC) provides a very strong signature of this transition. The orientational glass transition in pentachloronitrobenzene was studied by TSDC and, from this study, it was shown that this orientational glass belongs to the class of very strong glasses in the fragility scale proposed by Angell.     

Hysteresis in vortex glass transitions of the first order

The distribution of relaxation times in a glass is very broad. As a result the free energy of a glass slowly approaches its equilibrium value but never reaches it. This slow relaxation explains why, in the hysteresis cycle, the melting tempetature is higher than the solidification temperature.

We estimate the width of this hysteresis for a general type of transition into the glassy state. We apply these estimates to the special case of the vortex melting transition and find good agreement with recent experiments. We show how strong disorder changes the character of the vortex melting transition and evaluate the position of the tricritical point.     

丙三醇浓溶液玻璃化转变与结构松弛参数DSC分析

利用差示扫描量热仪研究了5种高浓度丙三醇水溶液(60%、70%、80%、90%、100%)的玻璃化转变行为,以考察水分含量和升降温速率对其玻璃化转变行为和结构松弛参数的影响.采用4种线性升降温速率(10、15、20、25K/min)获得玻璃化转变的相关参数.利用GordonTaylor方程对玻璃化转变温度的分析结果表明,水对丙三醇增塑常数的计算结果与升降温速率和玻璃化转变温度的读取方法有很大关系.玻璃化转变过程的比热容变化不仅随水分含量的增加而增加,而且与升降温速率也有一定的依赖关系.结构松弛活化能的计算结果表明,随体系水分含量的增加,体系的结构松弛活化能和动力学脆度都逐渐降低.随水分含量的变化,热力学脆度和动力学脆度表现出相反的变化趋势.     

Isoconfigurational elastic constants and liquid fragility of a bulk metallic glass forming alloy

Samples of Zr(46.25)Ti(8.25)Cu(7.5)Ni(10)Be(27.5) were isothermally annealed and quenched near the glass transition temperature and studied by the pulse-echo overlap technique. The shear modulus G of the samples shows a strong reversible dependence on annealing temperatures and, thus, on the specific configurational potential energy of the equilibrium liquid. The low-T dependence of G of the configurationally frozen glasses shows linear temperature dependence as expected by Debye-Grüneisen theory. The T dependence of G in the liquid state is directly related to the viscosity and fragility of the liquid.     

金属Cu熔化结晶过程的分子动力学模拟

采用常温、常压分子动力学模拟技术,研究了在周期性边界条件下,由８６４个Ｃｕ原子构成的模型系统的熔化、结晶过程。原子间相互作用势采用ＥＡＭ势。模拟结果表明：在连续升温过程中,金属Ｃｕ在１５２０Ｋ熔化;以不同的冷速进行冷却,在较慢冷却条件下,液态Ｃｕ在１０１０Ｋ结晶;当冷速较快时,液态Ｃｕ形成非晶态。分析了升降温过程中熔体偶分布函数、原子体积、能量、ＭＳＤ随温度的变化特征。     

Accelerated aging in ultrathin films of a molecular glass former

We report the thermodynamic measurement of the enthalpy released during the aging of supported films of a molecular glass former, toluene, at temperatures well below the glass transition temperature. By using microfabricated devices with very short equilibration times (below 1 s), we evidence a remarkable variation of the relaxation rate on decreasing film thickness from 100 nm down to a 7 nm thick film. Our results demonstrate that surface atoms are more efficient than bulk atoms in attaining low energy configurations within the potential energy landscape.     

大块金属玻璃Zr41Ti14Cu12.5Ni10Be22.5的流变行为研究

采用静态拉伸方法在连续升温条件下动态地测量了大块金属玻璃Zr41Ti14Cu12.5Ni10Be22.5（Vit1）的黏度随温度的变化关系.在应变速率与温度的关系曲线中，观测到了与玻璃转变和晶化过程相联系的多个应变速率峰.在玻璃转变温度Tg以上，大块金属玻璃Zr41Ti14Cu12.5Ni10Be22.5的过冷液体呈现Newton流体特征，其黏度与温度的关系符合Vogel Fulcher-Tammann (VFT)关系式，拟合得到脆度D*＝36，VFT温度T0＝319K，脆度参数m＝30，这说明Zr41T 关键词： 大块金属玻璃 应变速率 剪切黏度 自由体积     

The kinetics of the structural relaxation process in PHEMA-silica nanocomposites based on an equation for the configurational entropy

The enthalpy relaxation of polymer-silica nanocomposites prepared by simultaneous polymerization of poly(2-hydroxyethyl methacrylate) (PHEMA) and tetraethyloxysilane, TEOS, a silica precursor, is investigated. Both the glass transition temperature, T_g, and the temperature interval of the glass transition, ΔT _g , increase as the silica content in the sample does. Structural relaxation experiments show that the temperature interval in which conformational motions take place broadens as the silica content in the hybrid increases. A phenomenological model based on the evolution of the configurational entropy during the structural relaxation process, the SC model, has been used for determining the temperature dependence of the relaxation times during the process. The results show an increase of the fragility of the polymer as the silica content increases, a feature that can be related to the broadening of the distribution of relaxation times characterized by the β parameter of the stretched exponential distribution. On another hand the silica content increase produces a significant change of the relaxation times in the glassy state.