非晶物理框架下开展聚合物玻璃化转变教学的思考与探索

玻璃化转变是高分子物理教学中的重要内容.一些高分子物理教科书将聚合物玻璃化转变简单描述为玻璃到高弹态的力学转变,可能局限了学生对玻璃化转变重要科学问题认识的深度、广度和想象空间,甚至造成一些学生认为只有聚合物才存在玻璃化转变.笔者注意到了这一问题,考虑将聚合物玻璃化转变放在非晶物理框架下进行讲授;强调玻璃化转变是非晶物...     

PET类共聚酯的玻璃化转变

用DSC,IR和DLI(解偏振光法)等方法研究了聚(对苯二甲酸/间苯二甲酸)乙二醇酯[P(ET/EI)]和聚对苯二甲酸(乙二醇/丁二醇)酯[P(ET/BT)]系列共聚酯的玻璃化转变.结果表明,共聚酯的玻璃化转变是玻璃态有序结构解序后的一种转变.随ET链段含量的减少,两系列共聚酯的玻璃化转变在DSC中均表现出由拐折渐变为峰形,这是由于需要维持构象转变的ET链段在数量上的减少所致.玻璃态共聚酯的有序结构与分子链末端的游离羟基有关,游离羟基与羰基形成氢键是PET及可结晶共聚酯在结晶时必须经历的一个过程,而不能结晶的共聚酯(IPA30)则因该氢键的形成导致其玻璃化转变的消失.     

含氟聚酰胺酸热亚胺化过程的扭辫分析

用扭辫分析(TBA)研究了含氟聚酰胺酸的热亚胺化过程,用聚合物链段运动有利于小分子生成物的扩散,因而对缩合反应发生影响的观点,解释了剧烈的亚胺化反应总是在玻璃化温度以上发生;还观察到亚胺化反应使聚合物链刚性增加,玻璃化温度逐渐由120℃升高到310℃。因而提出了分段熟化的合理生产工艺。 对TBA谱中的溶剂蒸发,玻璃化转变、玻璃态中的次级转变,予聚物的亚胺化反应等多重转变进行了分析,解释了溶剂和水对亚胺化过程的影响。     

玻璃态PET的有序结构与解偏振光的记忆效应

聚合物的非晶态结构究竟是完全无序的 ,还是局部有序的 ,目前存在两种对立的学说 ,即 Flory的无规线团模型和 Yeh的两相球粒模型 [1] .Siegmann等 [2 ]在研究低于玻璃化转变温度 (Tg≈ 3 4 3 K)下的退火对 PET热谱 (DSC)中玻璃化转变的影响时发现 ,未经退火后的 PET在 Tg范围内仅表现出一个拐折 ,而在 3 2 7K退火时 ,随时间的增加 ,出现了类似于吸热峰的转变过程 ,并认为是由玻璃态中有序程度的增加所致 .本文通过解偏振光方法 (DLI)的研究发现 ,在玻璃态的 PET中确实存在着一定的有序结构 ,与晶态 PET中的有序结构不同的是 ,玻璃…     

环氧树脂的动态力学性能

用声频共振法在25—250℃温度范围内研究了以顺丁烯二酸酐固化的环氧树脂的动态力学性能。杨氏模量及内耗温度谱的实验结果指出:环氧树脂具有典型微少交联高聚物的力学性貭。随着固化程度的不同,大约在150℃左右已固化的环氧树脂由玻璃态转变为高弹态,此时模量急骤下降同时出现内耗峯,在此温度以上试样显示出橡皮高强特征。上述结果与其他一些研究结果一致,然而由内耗峯所确定的玻璃化转变温度却远高于及其同工作者用温度-形变曲綫法所测得的玻璃化转变温度。根据外力对动态力学性能的影响及我们以前的工作,我们认为外力有可能在环氧树脂分子网中产生了某种力化学效应,而动态力学结果与温度形变结果之间的差异可能正是由于此一原因。 根据实验结果还给出了以顺丁烯二酸酐固化的环氧树脂玻璃化转变温度与交联度间的关系,并对结果进行了讨论。     

分子动态模拟研究聚丙烯单链的玻璃化转变

用分子动态模拟法对单链高分子固体微粒的玻璃化转变与主链骨架键的构象态跃迁进行了模拟研究，发展了一种表征单链高分子固体微粒玻璃化转变过程的新方法．     

基于双向滞后方法的Non-Fickian型扩散与溶胀变形分析

在一些玻璃态聚合物中,溶剂分子的运移行为会呈现出不同于经典Fick定律的Non-Fickian扩散性质,且该过程往往伴随着材料溶胀和大变形.类比热传导分析中的非傅里叶效应理论,本文采用双相滞后方法,即引入两个描述玻璃化转变过程中材料性能依赖于浓度的控制参数,以考察Non-Fickian型溶剂扩散与凝胶溶胀变形的行为特征...     

DSC法测定PS玻璃化温度的再研究

对Fevotte提出的由DSC曲线构建玻璃化温度谱图的方法进行了改进,将橡胶态含量为0.5时的温度定义为聚合物的Tghr.采用改进Fevotte方法重新研究了PS的玻璃-橡胶态转变,PS的Tghr值比半比热外推法结果Tghc高约4K,当考察热处理时间和降温速率对聚合物玻璃-橡胶态转变的影响规律时,改进方法得到的结果与理论分析更为一致.聚合物的Tghr受热历史影响,随热处理条件改变,通过对不同降温速率冷却后样品滞后焓数据的拟合,推测PS样品的Tghr在377.5～390.9K范围内变化.     

动态化学与材料和非晶物理新关联——金属有机框架玻璃的挑战、进展与新机遇

金属有机框架(简称MOF)玻璃为传统玻璃世界和非晶物理研究带来崭新成员,被视为下一代多孔化学及新型MOF衍生功能材料关键发展方向.作为金属离子或簇核与有机配体通过配位键连接形成的多孔网络,绝大多数MOF还未达到高温熔融态就不可避免地发生热分解,很难通过传统的熔融-淬冷法制备玻璃.面对相关挑战,本综述系统梳理MOF玻璃发展历程及最新进展,提出基于动态化学串联扰动的全新策略用于普适化制备MOF玻璃.基于新的玻璃化方法,发现更多MOF玻璃、阐明结构转变本质并拓展新颖性质功能是从动态化学到材料和非晶物理的重大学科交叉前沿.相关研究孕育系列新机遇,包括从框架/动态化学的设计和调控到MOF玻璃可控制备,从晶态MOF本征性质到其玻璃态的各种潜在性能及新功能应用,以及从MOF多物相多层次结构转换出发更好理解玻璃本质.     

对聚合物玻璃化转变的几点新认识

基于聚合物玻璃化转变的定义,探讨了聚合物宏观单晶体和聚合物单链单晶的玻璃化转变问题,指出玻璃化转变的温度依赖性不服从普适的Arrhenius方程,可以把WLF方程看作是聚合物玻璃化转变的特有温度依赖关系。介绍了二维状态下聚合物可能的玻璃化转变。     

Glass transition. A new approach based on cluster model of glasses

The structure of real glasses has been considered to be microheterogeneous, composed of clusters and connective tissue. Particles in the cluster are assumed to be highly correlated in positions. The tissue is considered to have a truly amorphous structure with its particles vibrating in highly anharmonic potentials. Glass transition is recognized as corresponding to the melting of clusters. A simple mathematical model has been developed which accounts for various known features associated with glass transition, such as range of glass transition temperature,T _g, variation ofT _g with pressure, etc. Expressions for configurational thermodynamic properties and transport properties of glass forming systems are derived from the model. The relevence and limitations of the model are also discussed. Contribution No. 251 from Solid State and Structural Chemistry Unit.     

Glass transition and enthalpy relaxation of ethylene glycol and its aqueous solution

Differential scanning calorimetry (DSC) and cryomicroscopy were employed to investigate the glass transition and enthalpy relaxation behaviors of ethylene glycol (EG) and its aqueous solution (50% EG) with different crystallization percent. Isothermal crystallization method was used in devitrification region to get different crystallinity after samples quenched below glass transition temperature. The DSC thermograms upon warming showed that the pure EG has a single glass transition, while the 50% EG solution has two if the solution crystallized partially. It is believed that the lower temperature transition represents the glass transition of bulk amorphous phase of EG aqueous solution glass state, while the higher one is related to ice inclusions, whose mobility is restricted by ice crystal. Cryomicroscopic observation indicated that the EG crystal has regular shape while the ice crystal in 50% EG aqueous solution glass matrix has no regular surface. Isothermal annealing experiments at temperatures lower than T_g were also conducted on these amorphous samples in DSC, and the results showed that both the two amorphous phases presented in 50% EG experience enthalpy relaxation. The relaxation process of restricted amorphous phase is more sensitive to annealing temperature.     

1,2-丙二醇水溶液玻璃化转变与结构松弛

为了考察水含量对1, 2-丙二醇水溶液玻璃化转变和结构松弛参数的影响, 用差示扫描量热法(DSC), 测量了5种高浓度1, 2-丙二醇水溶液(60%、70%、80%、90%、100%, w)玻璃化转变区域的表观比热容. 用5种降温速率(1、2、5、10、20 K·min-1)和10 K·min-1的升温速率获得玻璃化转变的相关参数. 玻璃化转变温度分析结果表明, 虽然水含量增加能从总体上降低体系的玻璃化转变温度, 但与纯羟基类多元醇相比, 水对1, 2-丙二醇的增塑作用并不显著. 结构松弛活化能计算结果表明, 体系水含量的增加能明显降低结构松弛活化能. 脆度分析结果表明, 随着体系水含量增加, 动力学脆度逐渐降低, 但热力学脆度是先升高后降低, 在80%左右达到最大值. 结构松弛协同重排域计算结果表明, 当浓度由60%增加至100%时, 玻璃化转变特征长度由2.79 nm增加至3.57 nm.     

Molecular Dynamics Simulation of Glass Transition Behavior of Polyimide Ensemble

The prediction of glass transition temperature from chemical structure has a great significance to select and design new high-properties materials. However, for the estimation and correlation methods, the deficiency of parameters for newer groups will lead to invalidity of Tg prediction or greater deviation from experiment. In the present work, we predicted Tg for a polyimide (PI) ensemble with rigid moieties, and analyzed structural factor that regards to the rotation barrier of the bridging…     

Glass transition and state diagram for freeze-dried horse mackerel muscle

Glass transition temperatures of freeze-dried horse mackerel muscle conditioned at various water activities at 25 °C were determined by differential scanning calorimetry (DSC). High moisture content (>0.33 g/g, d.b.) samples obtained by adding liquid water into freeze-dried samples, were also analyzed. The state diagram was composed of the freezing curve and the glass transition line, which were fitted according to Clausius–Clapeyron model and Gordon–Taylor model, respectively. The state diagram yielded maximally freeze-concentrated solutes at 0.786 solids with the characteristic temperature of glass formation being −83.1 °C. The state diagram of horse mackerel muscle developed in this work could be used to predict the stability during frozen storage and in dried conditions as well as in designing drying and freezing processes.     

不同结晶度的乙二醇及其水溶液玻璃化转变与焓松弛

为了考察晶体成分对无定形成分玻璃化转变和结构松弛行为的影响,利用差示扫描量热法(DSC),结合低温显微技术,研究了乙二醇(EG)及其50％水溶液在不同结晶度时的玻璃化转变和焓松弛行为.采用等温结晶方法控制骤冷的部分结晶玻璃体中的晶体份额.DSC结果表明,对于部分结晶的EG,只有单一的玻璃化转变过程,而对于50％EG,当结晶度不同时,不同程度地表现出两次玻璃化转变（无定形相Ⅰ和无定形相Ⅱ）.相Ⅰ的玻璃化转变温度和完全无定形态的含水EG的玻璃化转变温度相一致;相Ⅱ的玻璃化转变温度要比此温度约高6 ℃.低温显微观察结果印证了DSC实验结果.DSC等温退火的实验和KWW(Kohlrausch-Williams-Watts)衰变函数分析结果表明,EG无定形和50％EG中的两种无定形有不同的焓松弛行为.     

Glass transition of semi-crystalline PLLA with different morphologies as studied by dynamic mechanical analysis

Poly(l-lactic acid) was crystallized from the glassy state at different temperatures to produce fully transformed semi-crystalline specimens exhibiting different lamellar morphologies. The materials were tested by dynamic mechanical analysis, where a T _g decrease was found with an increasing crystallization temperature. Considering a three-phase model, this tendency was related to the corresponding increase in the thickness of the rigid amorphous phase. It is suggested that this phase could, in some extent, accommodate through local translational/rotational motions the cooperative motions taking place within the mobile amorphous phase. This could be due to the non-compact structure of the cooperatively rearranging regions, which can present a string-like or fractal structure in their edges. The width of the loss factor peak associated to the glass transition increases with increasing crystallization temperature, suggesting an increase in the broadness of the distribution of relaxation times. The drop in the storage modulus across T _g varies systematically with the crystallization temperature in the different materials and could be correlated with the crystalline content. Above T _g, the loss factor exhibits a plateau-like behaviour at significantly high values, which seems to be a rather general behaviour in semi-crystalline systems that could be related to the contribution of pure irreversible flow in the overall viscoelastic behaviour.     

氯乙烯/N-苯基马来酰亚胺共聚物的玻璃化温度研究

研究了单体配比、聚合温度、转化率和加料方式对氯乙烯(VC)/N-苯基马来酰亚胺(PMI)共聚物的玻璃化温度的影响.用序列模型模拟了玻璃化温度与转化率的关系,可较好地反映变化趋势.分批加料可使共聚物的耐热性能提高,却使其颗粒特性变差.