QSPR Study on the Glass Transition Temperature of Polyacrylates

Structural parameters of 22 polyacrylic compounds were computed at two levels using Hartree-Fock and DFT methods. Based on the experimental data of glass transition temperature （Tg）, four-parameter （energy of the lowest unoccupied molecular orbital （ELoMO）, the highest positive charge （Qmax^＋）, dipole moments（μ） and the next highest occupied molecular orbital （ENLOMO）） dependent equations were developed using structural parameters as theoretical descriptors. Especially, Tg dependent equation calculated at the HF/6-31G（d） level is more advantageous than others in view of their correlation and predictive abilities. This dependent equation was validated by variance inflation factors （VIF） and t-test methods.

Effects of C60 on the Glass Transition Temperature of Carbazole-based Photorefractive Polyphosphazenes

The bi-functional carbazole-based photorefractive polyphosphazenes with different content of C_（60）-doped were fabricated. The glass transition temperature（T_g） of these polymer composite materials was determined using a differential scanning calorimetric（DSC） method. According to the DSC measurement results with different heating rates, the variation of T_g and the active energy of glass transition（E_g） were analyzed in detail. The analysis results indicate that the transition region shifts to higher temperatures with increasing heating rate, and C_（60） content（below 1.0 wt%） can influence the T_g of photorefractive polyphosphazenes. The T_g first increases and then decreases with the C_（60） content（below 1.0 wt%）. The probable causes of the influence of C_（60） on T_g was proposed.

POLYMER CHAIN DIFFUSION AT A TEMPERATURE BELOW ITS BULK GLASS TRANSITION TEMPERATURE

In this study, it was examined whether the dynamics of polymer chains at a surface is different from that in thebulk, and if so, to what extent they differ in terms of surface glass transition temperature and diffusion coefficient. Obtainedresults clearly indicate that surface chains can travel for a relatively large distance in comparison with the characteristiclength scale of usual segmental motion even at a temperature below its bulk glass transition temperature, T_g^b. This isconsistent with our previous results that the surface glass transition temperature is much lower than the corresponding T_g^b.Also, it was experimentally revealed that there was a gradient of molecular motion in the surface region.

Creep performance of PVC aged at temperature relatively close to glass transition temperature

In order to predict the mechanical performance of the polyvinyl chloride （PVC） at a high operating temperature, a series of short-term tensile creep tests （one- tenth of the physical aging time） of the PVC are carried out at 63 ℃ with a small constant stress by a dynamic mechanical analyzer （DMA）. The Struik-Kohlrausch （SK） formula and Struik shifting methods are used to describe these creep data for various physical aging time. A new phenomenological model based on the multiple relaxation mechanisms of an amorphous polymer is developed to quantitatively characterize the SK parameters （the initial creep compliance, the characteristic retardation time, and the shape factor） determined by the aging time. It is shown that the momentary creep compliance curve of the PVC at 63℃ can be very well fitted by the SK formula for each aging time. However, the SK parameters for the creep curves are not constant during the aging process at the elevated temperatures, and the evolution of these parameters and the creep rate versus aging time curves at the double logarithmic coordinafes have shown a nonlinear phenomenon. Moreover, the creep master curves obtained by the superposition with the Struik shifting methods are unsatisfactory in such a case. Finally, the predicted results calculated from the present model incorporating with the SK formula are in excellent agreement with the creep experimental data for the PVC isothermally aged at the temperature relatively close to the glass transition temperature.

Prediction of Glass Transition Temperatures of Polyarylates Using a Support Vector Machine Model

A three-descriptor quantitative structure-property relationship （QSPR） model, based on the support vector machine （SVM） algorithm, was constructed to predict the glass transition temperatures （Tgs） ofpolyarylates with complex structures. A total of 50 polyarylates were randomly divided into three sets, viz., the training set （30 polymers）, validation set （10 polymers） and prediction set （10 polymers）. By adjusting various parameters by trial and error, the final optimum SVM model based on Austin Model 1 （AM1） calculation is a polynomial kernel with the parameters C of 100, ε of 1.00E-05 and d of 2. The root-mean-square （RMS） errors obtained from the training set, validation set and prediction set are 19.4, 12.8 and 15.5 K, respectively. Research results show that the proposed SVM model has better statistical quality than the previous models. Thus, applying the SVM algorithm to predict Tgs of polymers is feasible.

A NEURAL NETWORK STUDY ON GLASS TRANSITION TEMPERATURE OF POLYMERS

In this paper, an artificial neural network model is adopted to study the glass transition temperature of polymers. In our artificial neural networks, the input nodes are the characteristic ratio C-infinity, the average molecular weight M-e between entanglement points and the molecular weight M-mon of repeating unit. The output node is the glass transition temperature T-g, and the number of the hidden layer is 6. We found that the artificial neural network simulations are accurate in predicting the outcome for polymers for which it is not trained. The maximum relative error for predicting of the glass transition temperature is 3.47%, and the overall average error is only 2.27%. Artificial neural networks may provide some new ideas to investigate other properties of the polymers.

Effect of latex conversion on glass transition temperature

We have synthesized styrene-acrylic latex and investigated the effect of such reaction conditions as the dosage of initiator, surfactant and stirring speed on monomer conversion and glass transition temperature (Tg) of polymer by means of orthogonal experiment, then we get the best reaction conditions. Test results prove that the glass transition temperature of the polymer is directly related to the monomer con- version. The improvement of monomer conver- sion can make the glass transition temperature close to the theoretical value. In the case of high final conversion, we can predict the glass transition temperature of the polymers of different composition according to the theoretical relation effectively.

Molecular Dynamic Simulation Study on Glass Transition Temperature of DGEBA-THPA/SWCNTs Composites

Molecular dynamic (MD) simulations were carried out to predict the thermo-mechanical properties of the cured epoxy network composed of diglycidyl ether bisphenol A (DGEBA) epoxy resin and tetrahydrophthalic anhydride (THPA) curing agent and their single-walled carbon nanotubes (SWCNT) reinforced the epoxy matrix composites. Different characters such as the density of the materials and mean square displacements (MSDs) were calculated to estimate the glass transition temperatures (Tgs) of of the materials. 365 K and 423 K of the Tgs were obtained respectively, whereas the latter is much higher than the former. The simulation results indicated that the incorporation of SWCNTs in the epoxy matrix can significantly improve the Tg of the cured epoxy. The approach presented in this study is ready to be applied more widely to a large group of candidate polymers and nanofillers.

High temperature strain glass in Ti–Au and Ti–Pt based shape memory alloys

Strain glass is a frozen short-range strain ordered state found in shape memory alloys recently, which exhibits novel properties around the ideal glass transition temperature T_(0). However, the T_(0) of current strain glass systems is still very low, limiting their potential applications and experimental studies. In this paper, we reported two new strain glass systems with relatively high T_(0). In Ti_(50)Au_(50-x)Cr_(x) alloys, the strain glass appears at x = 25, and exhibits a T_(0) of 251 K, while in Ti_(50)Pt_(50-y)Fey alloys, the strain glass takes place at y = 30, and shows a T_(0) of 272 K. Both of them are comparable with the highest T_(0) value reported so far. Moreover, the phase diagrams of main strain glass systems in Ti-based alloys were summarized. It is found that the influence of the martensitic transformation temperature of the host alloy on the T_(0) of the strain glass is limited. This work may help to design new strain glass systems with higher T_(0) above ambient temperature.

Molecular Dynamics Simulation of Glass Transition Behavior of Polyimide Ensemble

The effect of chromophores to the glass transition temperature of polyimide ensemble has been investigated by means of molecular dynamics simulation in conjunction with barrier analysis. Simulated Tg results indicated a good agreement with experimental value. This study showed the MD simulation could estimate the effect of chromophores to the Tg of polyimide ensemble conveniently and an estimation approach method had a surprising deviation of Tg from experiment. At the same time, a polyimide structure with higher barrier energy was designed and validated by MD simulation.

Ratio of dielectric strength of structural and secondary relaxation close to the glass transition for PPGE and DGEBA

Here, dielectric spectroscopy is used in the fre- quency range from 10-2 Hz up to 107 Hz and we found dynamics of the primary α-and intermolecular Johari–Goldstein β-processes are strongly correlated in diglycidyl-ether of bis-phenol-A and poly phenyl glycidyl-ether (PPGE) over a wide temperature from 193 to 345 K and pressure P range from 0.1 to 600 MPa. In contrast with the widespread opinion of statistical independence of these processes the α-β mutual dependence is quantitatively confirmed in [1] analysing the temperature and pressure behavior of the α-and (JG) β-processes the investigation of the ratio of dielectric strength of two processes close to Tg evidence that the importance of secondary dy namics in relaxing external electric stresses increase in glass formers at high pressures with respect to that of the structural relaxation. We suggest that the thermal agitation, acting above Tg is at the basis of the observed result.

Mixed Alkali-zinc Effects on Thermo-mechanical Properties in Borosilicate Glasses

A series of mixed alkali-zinc borosilicate glasses with various r values(r=molar ratio of[ZnO]/([R^(2)O]+[ZnO]))from 0.00 to 1.00 were fabricated to probe the mixed alkali-zinc effects on thermo-mechanical properties.The nonlinear evolution of glass transition temperature(T_(g))with the addition of ZnO is ascribed to the competition of two converse factors,i e,the T_(g)depression as one of the colligative properties for a solution,on the one hand,and the enhancement of T_(g)due to the higher field strength of zinc cations compared to that of alkali ions.However,the nonlinear evolution of elastic moduli and coefficients of thermal expansion with r is attributed to the variance of intermediate-range clusters,which is confirmed by infrared and Raman scattering spectra.These findings are very helpful in tailoring the performance of borosilicate glasses.

Anti-cracking mechanism of diatomite asphalt and diatomite asphalt mixture at low temperature

A kind of neat asphalt and three kinds of diatomite asphalt are tested using differential scanning calorimetry（DSC）. The anti-cracking mechanism of diatomite asphalt is analyzed by DSC and the thermal stress restrained specimen test（TSRST） of the asphalt mixtures. The results show that the low temperature performance of diatomite asphalt is better than that of neat asphalt. The glass transition temperature can reflect the low temperature performance of the diatomite asphalt better and has a good relationship with breaking temperatures. Besides, the TSRST, the bending test, the compressing test and the contraction coefficient test are used to study the low temperature performance of the diatomite asphalt mixture. The results prove that the low temperature performance of the diatomite asphalt mixture is better than that of the neat asphalt mixture. The critical bending strain energy density and the compressing strain energy density of the diatomite asphalt mixture are greater than those of the neat asphalt mixture. After adding diatomite to the asphalt mixture, the contraction coefficient is reduced. Based on the above results, the anti-cracking mechanism of the diatomite asphalt mixture is analyzed from the angle of contraction performance and breaking energy.

聚丙烯酸酯类T_g的量子化学-神经网络研究

用密度泛函方法在6-31G(d)基组上优化了38种聚丙烯酸酯类的结构单元,得到了其单元的量子化学参数,探讨了这些参数与聚丙烯酸酯类玻璃化温度(Tg)的关系.计算表明,影响聚丙烯酸酯类Tg的主要因素有结构单元的侧链长度、侧链的分支数、最高占据轨道能级、极化率、偶极矩、等体积热容和热力学能等参数.用模式识别方法(偏最小二乘法)讨论了这些参数与Tg的定性关系,两类Tg大小不同的聚合物基本分布在不同区域,用逐步回归和人工神经网络方法建立了这些参数与Tg的定量关系,2种方法的预测结果与实验值的相关系数分别为0.9753、0.9985,标准偏差分别为18.42、4.25,预报结果与实验值基本一致.

含硝基偶氮苯侧基的丙烯酸酯类液晶聚合物的合成、结构与性质研究——Ⅱ.分子结构对T_g的影响

利用DSC研究了分子结构对含硝基偶氮苯侧基的丙烯酸酯液晶聚合物玻璃化温度的影响。结果表明,随柔性间隔基长度增加,T_g降低;当引入丙烯酸甲酯(MA)作为非晶共聚组分时,T_g降低;T_g真随MA摩尔百分含量增加而降低;当引入丙烯酸作为非晶共聚组分时,T_g升高。

高聚物玻璃化转变温度和分子参数的关系 Ⅲ·聚甲基丙烯酸甲酯立构规整性和T_g的关系

本文研究了聚甲基丙烯酸甲酯(PMAA)的立构规整性与T_8的关系,结果表明立构单元分布和含量均对T_8有显著影响。应用前文导出的理论关系,进一步处理了T_8和构象参数实验数据,用这种简单方法计算得的无扰尺寸温度系数和实验值一致。由此推论,不同立构PMMA链的T_8之差反映了它们局部择优链构象的不同。

木器涂料用环氧-丙烯酸乳液T_g设计及与单体转化率的关系

本试验合成了水性环氧-丙烯酸酯杂化乳液,通过对引发剂用量、乳化剂用量、不同乳化剂配比、种子乳液以及搅拌速度等聚合反应条件的考察,得出了聚合反应的最佳工艺条件,并简单探讨了单体转化率与乳胶膜玻璃化转变温度之间的关系。结果表明,当引发剂质量分数为0.8%、乳化剂质量分数为3%、m(OP-10):m(SDS)=2:1、种子乳液的用量为预乳化液的20%(质量分数)、转速为180r/min时,乳液聚合单体的最终转化率可以达到98%。且最终转化率的提高使乳胶膜玻璃化转变温度更接近于理论计算值。

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 。

异构化PI单体的合成方法及其对PI t_g的影响分析

综述了异构化聚酰亚胺(PI)领域中异构二酐和异构二胺单体的合成方法,其中,异构二酐的合成方法主要以空气氧化法、氧化偶联、Ullmann缩合、芳香族亲核取代法为主;异构二胺的合成方法比较成熟,首先采用硝化或亲核取代方法合成不同结构的二硝基化合物,然后将其还原为二胺。最后讨论了异构单体合成方法对PI玻璃化转变温度(t_g)的影响,由异构二酐单体所得异构化PI的t_g较高,而由异构二胺单体制备的异构化PI,通常是由对位二胺所得PI的t_g最高,间位的最低。