Direct observation of molecular cooperativity near the glass transition

The increasingly sluggish response of a supercooled liquid as it nears its glass transition (for example, refrigerated honey) is prototypical of glassy dynamics found in proteins, neural networks and superconductors. The notion that molecules rearrange cooperatively has long been postulated to explain diverging relaxation times and broadened (non-exponential) response functions near the glass transition. Recently, cooperativity was observed and analysed in colloid glasses and in simulations of binary liquids well above the glass transition. But nanometre-scale studies of cooperativity at the molecular glass transition are lacking. Important issues to be resolved include the precise form of the cooperativity and its length scale, and whether the broadened response is intrinsic to individual cooperative regions, or arises only from heterogeneity in an ensemble of such regions. Here we describe direct observations of molecular cooperativity near the glass transition in polyvinylacetate (PVAc), using nanometre-scale probing of dielectric fluctuations. Molecular clusters switched spontaneously among two to four distinct configurations, producing random telegraph noise. Our analysis of these noise signals and their power spectra reveals that individual clusters exhibit transient dynamical heterogeneity and non-exponential kinetics.     

A FeNiMnC alloy with strain glass transition

Recent experimental and theoretical investigations suggested that doping sufficient point defects into a normal ferroelastic/martensitic alloy systems could lead to a frozen disordered state of local lattice strains(nanomartensite domains), thereby suppressing the long-range strain-ordering martensitic transition. In this study, we attempt to explore the possibility of developing novel ferrous Elinvar alloys by replacing nickel with carbon and manganese as dopant species. A nominal Fe_(89)Ni_5Mn_(4.6)C_(1.4) alloy was prepared by argon arc melting, and XRD, DSC, DMA and TEM techniques were employed to characterize the strain glass transition signatures, such as invariance in average structure, frequency dispersion in dynamic mechanical properties(storage modulus and internal friction) and the formation of nanosized strain domains. It is indicated that doping of Ni, Mn and C suppresses γ→α long-range strain-ordering martensitic transformation in Fe_(89)Ni_5Mn_(4.6)C_(1.4) alloy, generating randomly distributed nanosized domains by strain glass transition.     

影响蔗糖溶液玻璃化转变温度的几个因素

以蔗糖溶液为样品，试验研究了退火处理、升温速率、溶液浓度等因素对最大冻结浓缩溶液的玻璃化转变温度Ｔｇ′的影响。结果表明，退火处理对Ｔｇ′值影响较大，而另外两种因素对Ｔｇ′无影响。     

无序材料玻璃相变的关联特性

指出了由极值动力学所导出的活化能为Ngai由实验结果推导的表观活化能，对无序材料的玻璃相变温度区表现出的时间与温度关联性的分析发现：伸展指数的温度行为导致了VFT方程；介电驰豫的减慢来源于伸展行为和因子的温度行为，指出了标度理的适用条件为伸展指数不随温度而变化；提出了伸展指数函数由单一单元的衰减引起；von Schweidler函数由多个单元的共同衰减引起。     

Microscopic origins of entropy, heat capacity and the glass transition in proteins

Internal motion is central to protein folding, to protein stability through the resulting residual entropy, and to protein function. Despite its importance, the precise nature of the internal motions of protein macromolecules remains a mystery. Here we report a survey of the temperature dependence of the fast dynamics of methyl-bearing side chains in a calmodulin-peptide complex using site-specific deuterium NMR relaxation methods. The amplitudes of motion had a markedly heterogeneous spectrum and segregated into three largely distinct classes. Other proteins studied at single temperatures tend to segregate similarly. Furthermore, a large variability in the degree of thermal activation of the dynamics in the calmodulin complex indicates a heterogeneous distribution of residual entropy and hence reveals the microscopic origins of heat capacity in proteins. These observations also point to an unexpected explanation for the low-temperature 'glass transition' of proteins. It is this transition that has been ascribed to the creation of protein motional modes that are responsible for biological activity.     

NVF/DMAM的共聚反应和相应共聚物的玻璃化温度(NVF-体系的共聚反应及其共聚物性能…Ⅳ)

用N-乙烯基甲酰胺与甲基丙烯酸缩水甘油酯进行不同摩尔配比的共聚反应,分析研究不同摩尔配比的共聚反应过程.并对共聚产物进行元素分析,测定相应共聚物的玻璃化转变温度.为N-乙烯基甲酰胺与它的共聚物代替聚丙烯酰胺及其相应系列共聚物的开发提供了实验依据.     

NVF/DMAM的共聚反应和相应共聚物的玻璃化温度(NVF-体系的共聚反应及其共聚物性能…Ⅲ)

用N-乙烯基甲酰胺与N,N-二甲基丙烯酰胺进行不同摩尔配比的共聚反应,分析研究不同摩尔配比的共聚反应过程.并对共聚产物进行元素分析和红外光谱分析,测定了相应共聚物的玻璃化转变温度.为N-乙烯基甲酰胺与它的共聚物代替聚丙烯酰胺及其相应系列共聚物的开发提供了实验依据.     

NVF／DMAM的共聚反应和相应共聚物的玻璃化温度（NVF一体系的共聚反应及其共聚物性能…Ⅲ）

用N-乙烯基甲酰胺与N，N-二甲基丙烯酰胺进行不同摩尔配比的共聚反应。分析研究不同摩尔配比的共聚反应过程．并对共聚产物进行元素分析和红外光谱分析，测定了相应共聚物的玻璃化转变温度．为N-乙烯基甲酰胺与它的共聚物代替聚丙烯酰胺及其相应系列共聚物的开发提供了实验依据．     

Mg-Ni-La非晶合金的玻璃转变动力学研究

用甩带快冷技术制备Mg70(Ni3La)30和Mg70(Ni3.5La)30的非晶合金薄带(宽5mm,厚0.2 mam),采用X线衍射(XRD)和差示扫描量热技术(DSC)对非晶合金的结构和非晶形成能力进行研究;以2种合金的DSC曲线为基础,利用Kissinger方法、Lasocka关系以及原子团族模型等对合金的非晶形成动力学性质进行分析、探讨.研究结果表明:La含量直接影响合金负混合热,对合金的动力学具有重要影响;晶化起始温度Tx的表观激活能和频率因子越小,玻璃转变处Lasocka关系的斜率B越大,则对应Mg-Ni-La体系合金的玻璃形成能力越强,原子结构参数λ对Mg-Ni-La合金非晶形成能力的成分点设计具有很好的指导作用.     

液相—玻璃相转变的渗流模拟中的双曲线近似

借助自由体积理论中的渗流模拟描述液相玻璃相转变；采用双曲线近似将两相转变过程非线性化，并考虑平均淬火速率Ｔ·的影响，求得液相统计权Ｐ（Ｔ，Ｔ·）；最后具体讨论了聚醋酸乙稀酯的液相玻璃相转变，得到一定Ｔ·对应的ＰＴ曲线     

液态结构弛豫动力学非指数性的研究进展

结构弛豫的非指数性是过冷液体3个最基本的动力学特征之一。本文对多种玻璃形成体系在液相区内的结构弛豫非指数性进行了系统研究,涉及到的研究体系包括小分子、金属与合金、高分子、无机网络、离子等5类玻璃形成液体。研究发现,对于绝大部分玻璃形成液体,非指数因子KWW在玻璃转变附近的低频(或低温)区间符合时间-温度叠加原理(TTS);TTS区的宽度与液体的强弱性相关;在弛豫频率接近1011Hz(或者弛豫时间1.6×1012s)时,所有液体的结构弛豫达到纯指数性(KWW=1)。本文讨论了非指数因子与液体强弱性参数和TTS区宽度的关联,以及焓弛豫非指数因子与介电弛豫非指数因子之间的相关性。     

Absence of thermodynamic phase transition in a model glass former

The glass transition can be viewed simply as the point at which the viscosity of a structurally disordered liquid reaches a universal threshold value. But this is an operational definition that circumvents fundamental issues, such as whether the glass transition is a purely dynamical phenomenon. If so, ergodicity gets broken (the system becomes confined to some part of its phase space), but the thermodynamic properties of the liquid remain unchanged across the transition, provided they are determined as thermodynamic equilibrium averages over the whole phase space. The opposite view claims that an underlying thermodynamic phase transition is responsible for the pronounced slow-down in the dynamics at the liquid-glass boundary. Such a phase transition would trigger the dynamic standstill, and then be masked by it. Here we perform Monte Carlo simulations of a two-dimensional system of polydisperse hard disks far within its glassy phase. The approach allows for non-local moves in a way that preserves micro-reversibility. We find no evidence for a thermodynamic phase transition up to very high densities; the glass is thus indistinguishable from the liquid on purely thermodynamic grounds.     

利用神经网络预测聚合物玻璃化温度

分析了影响聚合物玻璃化温度的各种因素，采用合成时进料组成中各组分的摩尔分数、组成成分的重量分数以及聚合度等共计６个变量来表达聚合物结构上的差别，通过神经网络的训练建立了描述硬脂酸乙烯酯＋乙酸乙烯酯＋氯乙烯三元共聚物链结构和组成等６变量空间到玻璃化温度空间的映射关系，进而对未知三元聚合物的玻璃化温度进行预测，预测结果与实验结果与比较吻合。     

保护剂溶液水合和玻璃化性质的DSC研究

利用差示扫描量热仪研究了乙二醇、丙三醇、1,2丙二醇、l,3丁二醇和2,3丁二醇水溶液的水合性质、玻璃化转变温度和反玻璃化转变温度,得出了这些性质与溶液浓度的关系．未冻水含量在低浓度时没有明显的规律性,而在中高浓度则随着溶液浓度的增大而增大．各低温保护剂在水合性质上所表现出的差异性,体现了保护剂的官能团（羟基、甲基）所起的重要作用．保护剂在玻璃化转变温度和反玻璃化转变温度的明显差异,则反映了它们在玻璃化能力方面的强与弱．     

镁基大块非晶玻璃转变的动力学性质

用真空吹铸法制备了直径2 mm的Mg65Cu25Y6Gd4与Mg65Cu25Gd10块体非晶合金棒,采用X射线衍射分析(XRD)、差热分析(DTA)分别对非晶合金的结构和形成能力进行了研究.以Mg65Cu25Y6Gd4与Mg65Cu25Gd10大块非晶合金DTA实验为基础,利用Kissinger方程对其玻璃转变的动力学性质从不同方面进行了研究.分析结果表明:玻璃转变表观激活能与频率因子v0越小,玻璃转变处Lasocka关系的B值越大,则对于同一合金系表现出玻璃形成能力(GFA)越强,这一现象是由于大块非晶合金独特的结构特点所引起的.     

过冷水雾相变传播及温度场的实验研究

实验表明在过冷水雾相变传播过程中伴随有脉冲型单峰形式的温度上升,相变传播速率约为1．2cm/s,温度的波形和峰值以及相变的传播速度与过冷水雾的初始温度基本无关,据此对过冷水雾冰晶机制作了探讨。     

Molecular dynamics simulations on specific heat capacity and glass transition temperature of liquid silver

The embedded-atom method is adopted to simulate the specific heat capacity of liquid silver. The relationship between the specific heat capacity and the temperature above and below melting point is derived. The results show that there exists an anormaly of the specific heat capacity of liquid silver near 950 K. Simulated pair distribution functions show that the liquid-to-glass transition takes place at this temperature.     

动载荷对Zr基非晶合金玻璃化转变及晶化过程影响

采用DMA研究了动态加载条件下Zr62Al8Ni13Cu17大块非晶合金的玻璃化转变和晶化过程，并与无外载荷时相比较，结果表明外加动载荷会缩短晶化孕育期，促进晶化。此外，通过TEM观察加载大小及频率对晶相的影响，发现在一定范围内降低加载频率会导致模量显著下降并促进非晶晶化，加载频率及载荷的大小影响析出晶粒的形状及尺寸。     

The glass transition temperature and microstructure of polyurethane/epoxy resin interpenetrating polymer networks nanocomposites

GLASS TRANSITION TEMPERATURE (TG) HAS BEEN EXTEN- SIVELY STUDIED FOR MANY POLYMERS SINCE IT IS ONE OF THE MOST FUNDAMENTAL FEATURES RELATIVE DIRECTLY TO POLYMER PROPERTIES. IN GENERAL, INORGANIC NANOFILLERS DO NOT DI- RECTLY CONTRIBUTE TO THE TG OF THE MA…     

Influence of pulsing current on the glass transition and crystallizing kinetics of a Zr base bulk amorphous alloy

Based on the thermal analysis, the influence of pulsing current on the glass transition and crystallizing kinetics of Zr41.3Ti14.2CU12.8Ni10.3Be21.4 bulk amorphous alloy has been studied. The obtained results show that after the Zr41.3Ti14.2CU12.8Ni10.3Be21.4 bulk amorphous alloy was pretreated by high-density pulsing current at low temperature, its glass transition temperature Tg, the initial crystallizing temperature Tx and the corresponding exothermic peak of crystallization Tpi were reduced. But the temperature range of supercooled liquid △T=Tx-Tg is almost the same. The calculated results with Kissinger equation show that the activation energy of glass transition of the alloy pretreated is reduced significantly, while the activation energy of crystallization is basically unchanged. The influence of pulsing current on the glass transition and crystallization of theZr41.3Ti14.2CU12.8Ni10.3Be21.4 bulk amorphous alloy is believed to be related with the structure relaxation of the glass caused by the current.