Dynamic Fragility of α‐Olefin Molecular Bottlebrushes

The glass transition temperature, dynamic fragilities, and flow activation energy of a series of well‐entangled poly(α‐olefin) (PαO) molecular bottlebrushes were measured as a function of side chain length (N_sc ). The PαO bottlebrushes studied here have side chain lengths, N_sc , ranging from 4 (poly(1‐hexene)) to 10 (poly(1‐dodecene). A linear polyolefin (polypropylene), with Nsc = 1, was included in this study as a reference. The observed glassy dynamics behavior in the PαO bottlebrushes is opposite to that observed in linear polymers, namely, the glass transition temperature, the dynamic fragility, and the activation energy of structural relaxation are decreasing functions of the backbone rigidity. This anomalous behavior is due to a decrease in correlation between adjacent backbones, which is directly related to their cooperativity in the α‐relaxation, as N_sc and the concomitant distance between backbones increase. This change in conformation is also manifested as an increase in free volume and the consequent decrease in monomeric friction coefficient. © 2019 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2019 , 57, 1293–1299     

A model for the fragility of the melts

The concept of fragility has been used widely to characterize the temperature dependence of the viscosity of glass forming materials. However, the physical background that determines the degree of fragility is still not well understood. In the present study an expression for the fragility is derived based on a simple model of the melt. According to the model, the fragility is determined by the relaxation of structural units that form the melt, and is described in terms of the bond strength (E ₀), coordination number (Z ₀), and their fluctuations (ΔE and ΔZ). It is shown that a strong system is characterized by large value of total bond strength (Z ₀ E ₀) and small value of its fluctuation ((ΔZ)²(ΔE)²). On the other hand, a fragile system is characterized by small value of total bond strength and large value of its fluctuation. This revised version was published online in August 2006 with corrections to the Cover Date.     

Zr-Al-Ni-Cu(Nb,Ti)大块非晶玻璃转变的动力学性质

以Zr-Al-Ni-Cu (Nb,Ti)大块非晶合金差示扫描量热分析实验为基础,利用Lasocka方程、Kissinger方程及Vogel-Fulcher-Tamman(VFT)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越小,则晶化转变激活能越大,表现出相反的难易程度,且玻璃转变表观激活能数值远较传统非晶要小,验证了大块非晶合金独特的结构特点及玻璃形成能力(GFA)强的原因.利用VFT方程对玻璃转变弛豫时间与升温速度的VFT曲线 进行了拟合,所算得的玻璃脆性参数m均在30左右,反映了Zr-Al-Ni-Cu (Nb,Ti)非晶合金强 的脆性属性.玻璃转变处Lasocka关系的B值、原子表观激活能及玻璃脆性参数均反映了相同的GFA大小趋势,从不同方面进一步揭示了非晶合金玻璃转变区间的动力学行为与GFA之 间的密切联系,可作为判断非晶合金GFA强弱的重要依据. 关键词： 玻璃转变 玻璃形成能力 表观激活能 玻璃脆性参数     

基于可拓方法我国银行体系脆弱性的评价

在银行体系脆弱性评价中借助物元的概念,建立了银行体系脆弱性评价模型,并采用较为客观的评价方法——可拓方法对该模型进行评价,介绍了一种新的银行体系脆弱性评价方法.消除了其它主观评价方法带来的偏差,从而为我国银行体系脆弱性的监管决策提供有益参考.     

The relationship between viscosity and glass forming ability of Al-(Ni)-Yb alloy systems

The dynamic viscosity of Al-Yb and Al-Ni-Yb superheated melts was measured using a torsional oscillation viscometer. The results show that the temperature dependence of viscosity fits the Arrhenius law well and the fitting factors are calculated. The amorphous ribbons of these alloys were produced by the melt spinning technique and the thermal properties were characterized by using a differential scanning calorimetry (DSC). E (the activation energy for viscous flow), which reflects the change rate of viscosity, has a good negative relation with the GFA in both Al-Yb and Al-Ni-Yb systems. However, there is no direct relation between liquidus viscosity (ηL) and GFA. The superheated fragility M can predict GFA in Al-Yb or Al-Ni-Yb alloy system.     

基于位形熵模型的山梨醇玻璃焓松弛的量热分析

利用DSC技术考察了无定形山梨醇体系的焓松弛行为, 在10 K•min^－1的升温速率下测定了经历不同降温速率(0.5～20 K•min^－1)的山梨醇在玻璃化转变(T_g)前后的比热容[c_p(T)]. 利用基于位形熵演变的焓松弛现象学模型(GR模型)模拟了实验数据. 不论是否假设松弛过程存在一个亚稳极限态, 模型参数均能很好地重现经历不同热历史体系的升温c_p(T)曲线. 在物理意义明确的模型参数组中, 除了非指数参数随降温速率的增加而增加外, 其余均不随热历史的变化而变化. 拟合较低降温速率下c_p(T)曲线获得的GR模型参数的预测力明显好于在较大降温速率下获得的结果. 由于松弛时间对拟合过程中选择的“固定参数”的取值很敏感, 因此模型能否预测体系的比热容不能看成确定松弛时间的唯一依据. 在利用GR模型分析无定形山梨醇体系的脆度时, 如果选择极限假想温度作为T_g, 会导致计算结果明显小于文献值.     

地震和风耦合作用下连体高层建筑联合易损性分析方法研究

近年来,城市地标建筑的建设中,高层连体建筑越来越受到青睐,在其服役期内不可避免地受到风和地震等多种灾害作用。而单一灾害作用下的结构失效概率低估了结构损伤乃至倒塌的可能性,迫切需要多灾害作用下的结构安全性能评价方法。本文以苏州国际会议酒店的连体高层建筑为对象,开展了地震和风耦合作用下的联合易损性分析方法研究。首先,建立了地震和风耦合作用下的多灾害易损性函数和结构性能需求函数,形成了多灾害联合易损性分析方法。随后,选取了地震动记录,开展了基于数值风洞的结构风荷载模拟,并进行了单一灾害作用下的结构易损性分析。最后,基于均匀分布抽样了100组地震和风耦合作用的荷载组合,开展了结构多灾害联合易损性分析。结果表明,结构易损性随着PGA和风速的增大而增大;相比单一灾害作用,地震与风耦合作用下,结构各破坏状态的失效概率均有所增加;当风速达40 m/s时,罕遇地震作用下结构轻微破坏、中等破坏、严重破坏和倒塌破坏的概率相比仅地震作用时分别增加了1.13%,35.67%,84.00%和98.33%。本文研究为复杂高层建筑多灾害安全性能评价提供了可用工具和参考。     

α‐ and β‐Relaxations in neat and antiplasticized polybutadiene

Dielectric spectroscopy was carried out to measure the α‐relaxation (local segmental motion) and the higher frequency, secondary relaxation (β‐mode) in 1,4‐polybutadiene, both neat and containing a nonpolar diluent, mineral oil. The α‐relaxation shifted to lower frequencies (antiplasticization) in the presence of the diluent, suggesting the glass temperature of the latter is higher than the T_g of the polymer (i.e., >187K). The T_g of neat mineral oil cannot be determined directly, due to crystallization. While the diluent increased the magnitude of the α‐relaxation times, it had no effect on the β‐relaxation. Moreover, neither the shape of the α‐relaxation function nor its temperature dependence was influenced by the diluent. From this we conclude that the main effect of the mineral oil was to increase the local friction, without changing the degree of intermolecular cooperativity of the molecular motions. We also find that near the glass temperature, there is rough agreement between the time scale of the secondary relaxation process and the value of a noncooperative relaxation time estimated from theory. This approximate correspondence between the two relaxation times also holds for 1,2 polybutadiene. However, the β‐process cannot be identified with the noncooperative α‐relaxation, and the relationship between them is not quantitative. © 2000 John Wiley & Sons, Inc.* J Polym Sci B: Polym Phys 38: 1841–1847, 2000     

La55Al25Ni10Cu10大块金属玻璃结构弛豫过程中的焓变

用铜模吸铸法制备直径为4 mm的La55Al25Ni10Cu10大块金属玻璃非晶棒。采用差示扫描量热仪（DSC）研究了金属玻璃结构弛豫行为,并运用Stretched-Exponential弛豫方程对焓弛豫动力学进行描述。结果表明：La55Al25Ni10Cu10金属玻璃在玻璃转变温度Tg以下不同时间等温退火中会发生焓弛豫,用Stretched-Exponential弛豫方程能很好地描述焓弛豫动力学行为,得到Kohlrausch指数β=0.78,弛豫激活能E=60.8kJ.mol^-1。La55Al25Ni10Cu10金属玻璃形成液体的脆性指数为54,其玻璃形成液体属于强液体。