基于基团贡献法和分子动力学预测聚间苯二甲酰对苯二胺的玻璃化转变温度

采用基团贡献法(GC)和分子动力学法(MD)模拟了聚间苯二甲酰间苯二胺纤维(MPDI)和聚对苯二甲酰对苯二胺(PPTA)的玻璃化转变温度, 并与实验值进行了对比. 结果表明, 使用基团贡献法和分子动力学法测得的MPDI和PPTA的玻璃化转变温度与实验值接近, 说明基团贡献法和分子动力学法可以用来预测芳香族聚酰胺的玻璃化转变温度. 在此基础上, 采用GC和MD预测了聚间苯二甲酰对苯二胺(PPIA)的玻璃化转变温度. 在MD模拟中, 对密度、 比体积、 回转半径和非键相互作用随温度的变化规律进行了分析. 结果表明, 自由体积理论能较好地解释PPIA的玻璃化转变现象, 其中非键相互作用随温度的变化是玻璃化转变的本质原因. PPIA的玻璃化转变温度介于MPDI和PPTA之间, 有望成为综合性能介于两者之间的另一种高性能聚酰胺.     

杜仲胶玻璃化转变温度的分子模拟

对杜仲胶的玻璃化转变温度进行了分子动力学模拟。首先,计算了不同聚合度的反式聚异戊二烯的溶度参数,确定了合理的反式聚异戊二烯结构模型的聚合度为20;然后,用分子动力学模拟获得反式聚异戊二烯在不同温度下的比体积,通过对模拟得到的比体积-温度(V-T)作图,求得玻璃化转变温度(Tg)为210 K,采用差示扫描量热(DSC)法实测得到的Tg为203 K,两种结果在误差允许范围内基本一致,其模拟结果与实测值吻合得较好。     

DTA中升温速率及样品热导率对Tg测量值影响的模拟研究

就不同升温速率和实际样品的不同热导率对差热分析(DTA)中高分子材科的玻璃化转变曲线的影响进行了MonteCarlo模拟研究,发现当所有样品刚完成玻璃化转变时,在Tg曲线中该特征点要低于Tg的转变中点.转变中点所对应的样品温度肯定要高于实际的玻璃化转变温度.如果以玻璃化转变曲线的转变中点所对应的样品温度作为该材料的玻璃化转变温度,那么,升温速率越快、样品的热导率越小,所测得的玻璃化转变温度就越大,反之亦然.DTA测得的玻璃化转变温度与升温速率间有很好的线性依赖关系,但与样品热导率间的关系是非线性的.     

DTA中升温速率及样品热导率对T_g测量值影响的模拟研究

就不同升温速率和实际样品的不同热导率对差热分析 (DTA)中高分子材料的玻璃化转变曲线的影响进行了MonteCarlo模拟研究 ,发现当所有样品刚完成玻璃化转变时 ,在Tg 曲线中该特征点要低于Tg 的转变中点。转变中点所对应的样品温度肯定要高于实际的玻璃化转变温度。如果以玻璃化转变曲线的转变中点所对应的样品温度作为该材料的玻璃化转变温度 ,那么 ,升温速率越快、样品的热导率越小 ,所测得的玻璃化转变温度就越大 ,反之亦然。DTA测得的玻璃化转变温度与升温速率间有很好的线性依赖关系 ,但与样品热导率间的关系是非线性的     

黏结剂PLA,PCL及其共聚物与CL-20/TNT共晶黏结性能的分子动力学模拟

运用分子动力学(MD)模拟方法,对绿色黏结剂聚乳酸(PLA)、聚己内酯(PCL)和聚乳酸-己内酯共聚物(P(LA-co-CL))在六硝基六氮杂异伍兹烷/三硝基甲苯(CL-20/TNT)炸药共晶4个晶面(001),(100),(010) H和(010) T上的黏结性能进行了计算研究.对高聚物PLA,PCL和P(LA-co-CL)的密度、体积和玻璃化转变温度进行模拟以验证力场的适用性,结果显示,计算值与实验值吻合较好.分子动力学模拟计算结果表明,组成界面的晶面和高分子极性较高时,润湿性能明显较好;对相关函数计算发现,晶面和黏结剂之间H-O原子对在0. 5 nm范围内数量明显增多.对于极性最小的PCL,在所有晶面上的润湿性能都明显降低.     

共聚型环氧树脂基高分子染料的制备和表征

合成了环氧基先驱聚合物,采用后重氮偶合反应经一步法在聚合物中同时引入两种不同颜色的偶氮生色团.通过调配重氮盐的比例制备了一系列具有不同颜色及玻璃化转变温度的高分子染料.利用氢核磁共振谱图(1H-NMR)计算了聚合物上两种偶氮生色团的官能化度,采用示差扫描量热仪(DSC)测量了不同高分子染料的玻璃化转变温度(Tg)和分解温度(Td),用分光光度仪对这些聚合物的颜色进行了表征,并在国际照明委员会(CIE)颁布的CIE 1931 Yxy色度图上标出了相应的位置.结果表明:这些聚合物具有良好的溶解性、成膜性强、附着力强,可以应用于彩色滤光片等.     

对高分子体系进行分子动力学模拟方法的研究

以单链聚乙烯为例,研究了多种对高分子体系进行分子动力学模拟的方法.结果表明,不同的力场条件可以导致明显不同的结果.在使用OPLS力场的真空条件下.在100K体系出现了玻璃化现象,在200和300K条件下体系出现了局部结晶现象,而在400和500K体系出现了熔化现象.在给定体系中加入周期性边界和在300K下进行分子动力学模拟,无序和结晶状态都具有一定的稳定性.     

高分子链的去拥挤转变及低温流动

简述了拥挤理论的基本原理,运用拥挤理论来说明高分子链间弱相互作用对高分子链所处的状态的影响,特别是对高分子玻璃化转变的影响.在实验中,采用固体核磁共振方法探测高分子的链间邻近度,并比较了不同链间邻近度的高分子样品在玻璃化转变温度以下的压力诱导流行行为,发现即使测试温度比高分子玻璃化转变温度低132℃,高分子链在压力下依...     

机器学习方法在高分子玻璃化研究中的应用

高分子玻璃的物理性质与其结构和动力学密切相关.揭示高分子玻璃化的微观物理图像对高分子玻璃材料的结构调控和分子设计至关重要.然而,高分子的长链结构和复杂单体结构特征致使目前仍然缺乏普适的理论或者模型来定量解释高分子玻璃化的物理机制.因此,亟需发展更为先进的研究方法从而更深入地理解高分子玻璃化.近年来,国内外学者利用基于数据驱动的信息学方法(例如机器学习)对高分子玻璃化开展了研究,并取得了丰富成果.本综述首先介绍了常用的高分子信息学数据库和机器学习算法.之后,从高分子玻璃化转变温度的预测、新型高分子玻璃材料的研发、过冷液体的结构-动力学关系和玻璃体系相变的确定四个方面总结和评述了机器学习应用在玻璃化研究中的代表性进展.最后,探讨了机器学习方法在高分子玻璃化研究中面临的主要挑战,并对玻璃信息学这一领域的发展进行了展望.     

HTPB/增塑剂玻璃化转变温度及力学性能的分子动力学模拟

为了预测高分子粘结剂端羟基聚丁二烯(HTPB)与增塑剂癸二酸二辛酯(DOS)、硝化甘油(NG)的相容性及HTPB/增塑剂共混物的玻璃化转变温度(Tg)和力学性能,在COMPASS力场条件下采用分子动力学(MD)模拟方法对相容体系(HTPB-DOS)和不相容体系(HTPB-NG)进行了研究.结果表明,通过比较溶度参数差值(Δδ)的大小可以预测HTPB与增塑剂的相容性,即HTPB与DOS属于相容体系,而HTPB与NG不相容.通过温度-比容曲线可以得到HTPB、HTPB/DOS与HTPB/NG的Tg分别为197.54,176.30和200.03K.力学性能分析结果表明,添加DOS增塑剂后使HTPB的弹性模量(E),体积模量(K)和剪切模量(G)下降,材料刚性减弱,柔性增强,力学性能得到改善.本模拟方法可以作为预测聚合物/增塑剂共混物性能的有利工具,也可以为固体推进剂和高聚物粘结炸药的配方设计提供理论指导.     

A molecular dynamics simulation of the melting points and glass transition temperatures of myo- and neo-inositol

The heat of sublimation, density, melting point, and glass transition temperature are calculated for myo- and neo-inositol, using the condensed-phase optimized molecular potentials for atomistic simulation studies (COMPASS) force field and molecular dynamics techniques. Our results show that the calculated heats of sublimation and density are very close to the experimental values for both compounds. Furthermore, our simulated melting temperatures for myo- and neo-inositol also compare very well to the experimentally obtained data. The glass transition temperatures for myo- and neo-inositol have been calculated to be ca. 494 K and ca. 518 K, respectively, and the shape of the volume versus temperature plots produced are typical for a glass transition. As a result, it is our view that the COMPASS force field suitably describes these two compounds in molecular simulations and that molecular dynamics techniques, combined with this force field, can be used to simulate the melt and glass transitions for such molecules.     

Nonlocal viscosity of polymer melts approaching their glassy state

The nonlocal viscosity kernels of polymer melts have been determined by means of equilibrium molecular dynamics upon cooling toward the glass transition. Previous results for the temperature dependence of the self-diffusion coefficient and the value of the glass transition temperature are confirmed. We find that it is essential to include the attractive part of the interatomic potential in order to observe a strong glass transition. The width of the reciprocal space kernel decreases dramatically near the glass transition, being described by a deltalike function near and below the glass transition, leading to a very broad kernel in physical space. Thus, spatial nonlocality turns out to play an important role in polymeric fluids at temperatures near the glass transition temperature.     

Polymer Structures and Glass Transition: A Molecular Dynamics Simulation Study

Full atomistic molecular dynamics (MD) simulations on five polymers with different chain backbone (C—C, Si—O, and C—O) and different side groups (—H, one —CH₃, and two —CH₃) are performed to study the effects of chain flexibility and side groups on the glass transition of polymers. Molecular dynamics simulations of NPT (constant pressure and constant temperature) dynamics are carried out to obtain specific volume as a function of temperature for polyethylene (PE), poly(propylene) (PP), polyisobutylene (PIB), poly(oxymethylene) (POM), and poly(dimethylsiloxane) (PDMS). The volumetric glass transition temperature has been determined as the temperature marking the discontinuity in slope of the plots of V–T simulation data. Various energy components at different temperatures of the polymers are investigated and their roles played in the glass transition process are analyzed. In order to understand the polymer chain conformations above and below the glass transition temperature, dihedral angle distributions of polymer chains at various temperatures are also studied.     

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…     

液态金属铝的热历史对凝固微结构的影响

用分子动力学模拟研究了液态金属Al 系统的热历史对凝固微结构的影响.发现在同一系统中、不同的热历史条件下， 1551 键型和与1551键型相关的二十面体结构(12 0 12 0)在微结构的转变过程中均起着非常重要的作用. 特别有意义的是, 在每个温度的等温运行中能够重复出现的二十面体的数目不随温度的降低而增加, 并有一个极大值.该极大值点正好与其玻璃转变温度Tg相对应, 在不同的热历史条件下极大值的位置是能够移动的.结果还显示出, 热历史条件对微结构转变有严重影响, 且其作用主要是在玻璃转变温度点Tg以后才显示出来. 这就为我们理解和控制凝固过程中的微结构转变提供了一条新途径.     

Transport behavior of oxygen and nitrogen through organasilicon-containing polystyrenes by molecular simulation

Molecular dynamics (MD) simulations have been used to study the transport properties of oxygen and nitrogen in the para-substituted polystyrenes which possess one to four Si atoms in each substituent. The Condensed-phase Optimized Molecular Potentials for Atomistic Simulation Studies (COMPASS) force field was used to construct the polymers. Diffusion coefficients were obtained from molecular dynamics (NVT ensemble) with up to 3 ns simulation times. After molecular dynamic simulation, the trajectories of the small molecules in the polymer matrix were obtained. Then diffusion coefficients have been calculated from the Einstein relationship revealing a considerable agreement between the simulated and the experimental data. And solubility coefficients have been calculated by the Grand Canonical Monte Carlo (GCMC) method. The solubility of oxygen increased with increasing Si content in the polymer membrane. The para-substituted polystyrenes with a branched substituent at the alpha-position showed higher permeability than those of the nonbranched ones. The higher the glass transition temperature (T(g)) of the membrane, the larger the diffusion coefficients of oxygen and nitrogen obtained.     

Molecular simulation of thermophysical properties of aromatic polymers containing oxetane ring in the main chain

Molecular simulation techniques have been applied to newly synthesized aromatic polymers, containing oxetane rings in the main chain, to characterize the shape of rod‐like macromolecules. Single chains and periodic unit cells of a series of aromatic polymers with degree of polymerization 15 were used in the simulations, in accordance with the experimentally obtained one. The total potential energy was minimized and then NVE and NPT molecular dynamics simulations were performed for 1,000 ps at 11 temperatures between 10 and 1,000 K. The coefficient of asymmetry was calculated from the computer‐generated structures. The predictive capability of the NPT molecular dynamics simulation and Polymer Properties modules of Cerius² were used to estimate the orientational properties (order parameter), glass transition temperature, cohesive energy, and decomposition temperature of the polymers simulated. In general, there is a good‐to‐excellent agreement between simulated results and available experimental data of the above investigated properties. © 1999 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 37: 2334–2352, 1999     

Local chain dynamics of a model polycarbonate near glass transition temperature: A molecular dynamics simulation

Constant pressure constant temperature molecular dynamics method is employed to investigate the atomistic scale dynamics of a model Bisphenol A polycarbonate in the vicinity of its glass transition temperature. First, the glass transition temperature and the thermal expansion coefficients of the polymer are predicted by performing simulations at different temperatures. To explore the significance of different modes of motion, various types of time correlation functions are utilized in analyzing the trajectories. In these nanosecond scale simulations, the motion of the chain segments is found to be highly localized with little reorientation of the vectors representing these segments. Detailed analysis of trajectories and the correlation functions of the backbone dihedrals and side methyl groups indicates that they exhibit numerous conformational transitions. The activation energies of the conformational transitions obtained from the simulation are generally larger than the potential barriers for the rotations of these dihedrals, however, both show the same trend. We also have estimated the phenylene ring flip activation energy as 12.6 kcal/mol and the flip frequency as 0.77 MHz at 300 K. These values fall either fall within the range determined by various NMR spectroscopy experiments or slightly out of the range. The study shows that the conformational transitions between the adjacent dihedrals are strongly correlated. Three basic cooperative modes are identified from the simulation. They are: a positive synchronous rotation of two phenylene rings, a negative synchronous rotation of two phenylene rings, and a carbonate group rotation. Above the glass transition temperature, the large scale cooperative motions become much more significant.     

Anharmonicity in a fragile glass-former probed by inelastic neutron scattering

Within the overall understanding of the glass transition, the relationship between microscopic dynamics and fragility is still to be clarified. Decalin is an organic glass former, for which a cis/trans mixture exhibits the highest known degree of fragility in a molecular system. It is therefore an ideal system for the investigation of microscopic dynamics in fragile systems. In the present study, the microscopic dynamics of pure cis-decalin has been measured by inelastic and quasi-elastic incoherent neutron scattering, giving the single particle self-correlation function. The fast relaxation dynamics and low-frequency vibrational modes are reported here. Both in the glass and in the crystal the vibrations show strong anharmonic behavior. In the glass phase, the short time microscopic dynamics evolve rapidly with temperature, however do not exhibit any significant change around the glass transition temperature T(g). The elastic intensity provides a measure of the mean square displacements which are comparable to those measured in other fragile glass formers, in particular, the archetypical fragile glass former orthoterphenyl. It appears that the microscopic relaxation gets unfrozen, relative to T(g), at much lower temperature than in other fragile systems.