A thermodynamic connection to the fragility of glass-forming liquids

Although liquids normally crystallize on cooling, there are members of all liquid types (including molecular, ionic and metallic) that supercool and then solidify at their glass transition temperature, Tg. This continuous solidification process exhibits great diversity within each class of liquid-both in the steepness of the viscosity-temperature profile, and in the rate at which the excess entropy of the liquid over the crystalline phase changes as Tg is approached. However, the source of the diversity is unknown. The viscosity and associated relaxation time behaviour have been classified between 'strong' and 'fragile' extremes, using Tg as a scaling parameter, but attempts to correlate such kinetic properties with the thermodynamic behaviour have been controversial. Here we show that the kinetic fragility can be correlated with a scaled quantity representing excess entropy, using data over the entire fragility range and embracing liquids of all classes. The excess entropy used in our correlation contains both configurational and vibration-related contributions. In order to reconcile our correlation with existing theory and simulations, we propose that variations in the fragility of liquids originate in differences between their vibrational heat capacities, harmonic and anharmonic, which we interpret in terms of an energy landscape. The differences evidently relate to behaviour of low-energy modes near and below the boson peak.     

Fragile-to-strong transition and polyamorphism in the energy landscape of liquid silica

Liquid silica is the archetypal glass former, and compounds based on silica are ubiquitous as natural and man-made amorphous materials. Liquid silica is also the extreme case of a 'strong' liquid, in that the variation of viscosity with temperature closely follows the Arrhenius law as the liquid is cooled toward its glass transition temperature. In contrast, most liquids are to some degree 'fragile', showing significantly faster increases in their viscosity as the glass transition temperature is approached. Recent studies have demonstrated the controlling influence of the potential energy hypersurface (or 'energy landscape') of the liquid on the transport properties near the glass transition. But the origin of strong liquid behaviour in terms of the energy landscape has not yet been resolved. Here we study the static and dynamic properties of liquid silica over a wide range of temperature and density using computer simulations. The results reveal a change in the energy landscape with decreasing temperature, which underlies a transition from a fragile liquid at high temperature to a strong liquid at low temperature. We also show that a specific heat anomaly is associated with this fragile-to-strong transition, and suggest that this anomaly is related to the polyamorphic behaviour of amorphous solid silica.     

Violation of the incompressibility of liquid by simple shear flow

In standard fluid dynamics, the density change associated with flow is often assumed to be negligible, implying that the fluid is incompressible. For example, this has been established for simple shear flows, where no pressure change is associated with flow: there is no volume deformation due to viscous stress and inertial effects can be neglected. Accordingly, any flow-induced instabilities (such as cavitation) are unexpected for simple shear flows. Here we demonstrate that the incompressibility condition can be violated even for simple shear flows, by taking into account the coupling between the flow and density fluctuations, which arises owing to the density dependence of the viscosity. We show that a liquid can become mechanically unstable above a critical shear rate that is given by the inverse of the derivative of viscosity with respect to pressure. Our model predicts that, for very viscous liquids, this shear-induced instability should occur at moderate shear rates that are experimentally accessible. Our results explain the unusual shear-induced instability observed in viscous lubricants, and may illuminate other poorly understood phenomena associated with mechanical instability of liquids at low Reynolds number; for example, shear-induced cavitation and bubble growth, and shear-banding of very viscous liquids such as metallic glasses and the Earth's mantle.     

剪切作用对含蜡原油黏弹性的影响规律

为了探索剪切作用对含蜡原油流变性的影响规律,使用高精度的控制应力流变仪测量经历相同降温和不同剪切作用的大庆原油黏弹性参数(储能模量和耗能模量)).用黏性流动能量耗散表示剪切作用.得到了黏弹性参数随剪切作用的变化规律,建立了相应的关系式.观察原油的黏弹性参数随剪切作用和恒温静置时间的变化,发现从黏弹性随恒温静置时间变化的稳定阶段来看,原油在动态降温和静态降温下的黏弹性存在一定差别,不能简单地将静态降温条件下测得的流变数据用于输油管道工艺计算;而剪切作用的变化对原油流变性的影响较小,这对于评价含蜡原油在管道运行和停输期间的流变性具有一定指导意义.     

Dynamics of supercooled water in confined geometry

As with most liquids, it is possible to supercool water; this generally involves cooling the liquid below its melting temperature (avoiding crystallization) until it eventually forms a glass. The viscosity and related relaxation times (tau) of glass-forming liquids typically show non-Arrhenius temperature (T) dependencies. Liquids with highly non-Arrhenius behaviour in the supercooled region are termed 'fragile'. In contrast, liquids whose behaviour is close to the Arrhenius law (In tau infinity 1/T) are termed 'strong'. A unique 'fragile-strong' transition around 228 K has been proposed for supercooled water; however, experimental studies of bulk supercooled water in this temperature range are generally hampered because crystallization occurs. Here we use broad-band dielectric spectroscopy to study the relaxation dynamics of supercooled water in a wide temperature range, including the usually inaccessible temperature region. This is possible because the supercooled water is held within a layered vermiculite clay-the geometrical confinement and presence of intercalated sodium ions prevent most of the water from crystallizing. We find a relaxational process with an Arrhenius temperature dependence, consistent with the proposed strong nature of deeply supercooled bulk water. Because water that is less supercooled has been established as highly fragile, our results support the existence of a fragile-strong transition.     

Configurational entropy and diffusivity of supercooled water

As a liquid approaches the glass transition, its properties are dominated by local potential minima in its energy landscape. The liquid experiences localized vibrations in the basins of attraction surrounding the minima, and rearranges via relatively infrequent inter-basin jumps. As a result, the liquid dynamics at low temperature are related to the system's exploration of its own configuration space. The 'thermodynamic approach' to the glass transition considers the reduction in configuration space explored as the system cools, and predicts that the configurational entropy (a measure of the number of local potential energy minima sampled by the liquid) is related to the diffusion constant. Here we report a stringent test of the thermodynamic approach for liquid water (a convenient system to study because of an anomalous pressure dependence in the diffusion constant). We calculate the configurational entropy at points spanning a large region of the temperature-density plane, using a model that reproduces the dynamical anomalies of liquid water. We find that the thermodynamic approach can be used to understand the characteristic dynamic anomalies, and that the diffusive dynamics are governed by the configurational entropy. Our results indicate that the thermodynamic approach might be extended to predict the dynamical behaviour of supercooled liquids in general.     

Liquid fragility——A key togoing deep into materials of glassy states

“Liquid fragility“ is a concept that has been widely used in the investigation on the glass community,though it was presented less than two decades ago. The concept enables the comparison between the glass-forming liquids with different dynamic characters by using a general criterion, in which the temperature scale is reduced by the glass transition temperature. In order to illuminate the significance of the concept in the fields of the glass transition,structural relaxation process and the structure of supercooled liquids, the accomplished progress and the faced challenges are summarized from different aspects such as on the correlation between dynamics and thermodynamic characters of condensed matters, on the energy landscape, on the nonexponential relaxation and on the theoretical model of microstructure and medium-range order. The tendency of investigation in “liquid fragility“ is also evaluated.     

落球法测定液体粘滞系数的计算机仿真

用落球法测量液体的粘滞系数,一般是测量粘滞系数较大的液体⒀若要测量粘滞系数很小的液体,由于受到实验条件的限制,根本无法在实验室中进行⒀论文主要介绍如何用计算机来仿真落球法测量粘滞系数很小的液体的粘滞系数,从而对原有实验内容进行了扩展     

气泡粘性对上升运动特性影响的FTM模拟

为了研究气泡粘性对其上升过程的速度、形态以及阻力系数的影响,基于FTM(Front- Tracking Method)模拟了气泡在粘性流体中的运动,通过改变气泡粘性来改变气液粘度比,研究了气泡内的速度分布以及气泡周围粘性剪切应力的分布和变化特点。研究表明：气液粘度比较小时,流场中的粘性耗散很强,气泡的粘度主要影响其平衡速度和形态,气液粘度比较大时,粘性耗散减弱,其平衡速度和形态基本无变化,气泡粘性主要影响气泡内的速度分布;气泡上升过程中的阻力系数随粘度比增大而减小,粘性剪切应力则呈现相反的变化趋势。气泡上升过程中,周围的粘性剪切应力关于中心轴线对称分布,出现最大粘性切应力的区域由气泡两侧逐渐向气泡底部边缘过渡;气泡尾部边缘的形变引起气泡尾部的表面张力不平衡,使得气泡的形态发生改变。     

Water Behaviour: glass transition in hyperquenched water?

It has been unclear whether amorphous glassy water heated to around 140-150 K remains glassy until it crystallizes or whether instead it turns into a supercooled and very viscous liquid. Yue and Angell compare the behaviour of glassy water under these conditions to that of hyperquenched inorganic glasses, and claim that water stays glassy as it heats up to its crystallization point; they also find a 'hidden' glass-to-liquid transition at about 169 K. Here we use differential scanning calorimetry (DSC) heating to show that hyperquenched water deposited at 140 K behaves as an ultraviscous liquid, the limiting structure of which depends on the cooling rate--as predicted by theoretical analysis of the liquid-to-glass transition. Our findings are consistent with a glass-to-liquid transition-onset temperature (T(g)) in the region of 136 K (refs 3,4), and they indicate that measurements of the liquid's properties may clarify the anomalous properties of supercooled water.     

玻璃形成液体其内在结构中的二十面体

采用分子动力学模拟(molecular dynamics简称MD)的方法,并利用势能曲面(potential energy landscape简称PEL)理论对玻璃形成液体进行研究.在模拟中,键角分布序参数(An)被首先应用于描述二元玻璃形成液体其内在结构(Inherent Structure简称IS)中的结构序.通过计算An,得出了一般液体和IS液体中六面体、八面体和二十面体结构随温度的变化情况.在IS液体中二十面体序所占比例明显多于一般液体.在IS液体中,六面体、八面体的结构随温度的变化不是很明显,而二十面体结构随着温度的变化呈现出一定的规律.得出了二十面体是IS的主要变化的结构.玻璃转变是一般液体接近IS的过程,同时也是二十面体增多的过程.     

Negative wake behind bubbles in non-newtonian liquids

GAS bubbles rising by gravity in non-newtonian elastic liquids(1-4) are different to gas bubbles in viscous newtonian fluids in at least two ways. First, the bubbles in the non-newtonian liquids often have a peculiar tip at the rear pole, and second, the terminal rise velocity versus volume curve often has a discontinuity at a certain 'critical' volume. To investigate this unusual flow situation further we have used laser-Doppler anemometry(5) to measure the liquid velocity in the wake behind air bubbles in a non-newtonian liquid. The measurements described here reveal the unexpected result that the liquid velocity behind the bubbles is in the downwards direction away from the rising bubbles (the velocities are referred to an observer at rest with respect to the liquid far from the bubbles). Thus the liquid velocity is opposite to the velocity in the usual wake behind objects moving in viscous newtonian fluids and we have called the phenomenon 'negative wake'.     

Ice-free cryopreservation of mouse embryos at -196 degrees C by vitrification

The failure of complex mammalian organs, such as the kidney, to function following freezing to low temperatures is thought to be due largely to mechanical disruption of the intercellular architecture by the formation of extracellular ice. Classical approaches to the avoidance of ice formation through the imposition of ultra-rapid cooling and warming rates or by gradual depression of the equilibrium freezing point during cooling to -80 degrees C have not been adequate. An alternative approach relies on the ability of highly concentrated aqueous solutions of cryoprotective agents to supercool to very low temperatures. At sufficiently low temperatures, these solutions become so viscous that they solidify without the formation of ice, a process termed vitrification. When embryo suspensions are cryopreserved using conventional procedures, this supercooling behaviour allows intracellular vitrification, even in the presence of extracellular ice. We have therefore used mouse embryos to examine the feasibility of obtaining high survival following vitrification of both the intra- and extracellular solutions and report here that in properly controlled conditions embryos seem to survive in high proportions after cryopreservation in the absence of ice.     

非线性耗散方程Cauchy问题整体解的存在性

运用能量方法及局部解延拓方法,解决了粘性弹性力学、流体力学中一类非线性拟双曲型方程初值问题经典解的整体存在唯一性,并获得了解的衰减渐近性。     

基于能量准则的SDOF阻尼减震结构最大地震位移

粘滞阻尼耗能能减小结构地震反应。根据振动等能量准则 ,由地震动力能量方程推导了单自由度 (SDOF)弹性体系的地震最大位移反应与阻尼比的关系。与地震动力时程数值分析方法计算得到的结果对比表明 :该文理论结果较好地反映了 SDOF结构的最大地震位移反应。在地震动特征周期处产生类共振时阻尼减震效果更为显著。利用振动等能量准则方法可较为简便地确定阻尼减震结构体系的最大位移反应和进行减震设计。     

定向井有杆抽油系统井下耗能分析

针对现有抽油系统井下能耗计算公式难以确定杆液、杆管间摩擦耗能的缺陷,提出一种比较精确的分析方法。首先,对杆管间库仑摩擦力以及杆柱各节点的弹性运动速度进行了计算;其次,对抽油系统中库仑摩擦力、粘滞阻尼力以及盘根盒摩擦力在一个抽油周期内的耗能进行了分析,并根据悬点功图计算出一个抽汲周期内井下输入功,进而对井下效率进行了计算;最后给出了计算实例。计算结果表明,杆柱弹性运动速度引起的粘滞阻尼力耗能不能忽略。     

羟乙基甲壳素水溶液的流变性能研究

质量分数为1.0 %～2.8%的羟乙基甲壳素水溶液为剪切变稀的假塑性流体,流动曲线符合幂律定律,利用多元线性回归方法对实验数据进行处理,获得恒定温度下稠度因数和非牛顿指数的经验关系式。在 25℃～45℃温度范围,求出不同质量分数的溶液的流动活化能为4～16kJ/mol,得出黏流活化能与质量分数的经验关系式。用“剪切静置法”研究了pH值和加入不同价态的电解质对溶液的触变性的影响,均表现出正触变性。     

工程结构粘滞流体阻尼器减振新技术及其应用

介绍了结构控制和消能减振技术的减振机理和减振设计方法，对不同结构构造的粘滞流体阻尼器的耗能原理进行了研究，研制出了一种性能稳定的双出杆型工程结构减振粘滞流体阻尼器，研究表明，研制的粘滞流体阻尼器是一种无刚度的速度相关型阻尼器，阻尼器的阻尼力与活塞的运动速度近似呈线性关系，对一栋顶部设置有钢塔的高层建筑实施了减振控制，计算结果表明，流体阻尼器可有效地降低结构在强震和大风下的振动反应，是一种性能良好的消能减振装置。     

First-order transition in confined water between high-density liquid and low-density amorphous phases

Supercooled water and amorphous ice have a rich metastable phase behaviour. In addition to transitions between high- and low-density amorphous solids, and between high- and low-density liquids, a fragile-to-strong liquid transition has recently been proposed, and supported by evidence from the behaviour of deeply supercooled bilayer water confined in hydrophilic slit pores. Here we report evidence from molecular dynamics simulations for another type of first-order phase transition--a liquid-to-bilayer amorphous transition--above the freezing temperature of bulk water at atmospheric pressure. This transition occurs only when water is confined in a hydrophobic slit pore with a width of less than one nanometre. On cooling, the confined water, which has an imperfect random hydrogen-bonded network, transforms into a bilayer amorphous phase with a perfect network (owing to the formation of various hydrogen-bonded polygons) but no long-range order. The transition shares some characteristics with those observed in tetrahedrally coordinated substances such as liquid silicon, liquid carbon and liquid phosphorus.     

改进型蜡基粘结剂的喂料流变性能

研究了改进型蜡基粘结剂体系和Fe-2Ni粉混合制备的喂料的流变性能.结果表明,喂料是一种假塑性流体,其非牛顿指数n较大,150℃时n为0.52,恒剪切速率粘流活化能△Eη=53.8Kj·mol