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.

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.

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.

Understanding the alkyl effect of geminal dinitropropyl ester energetic plasticizers on hydroxyl terminated polybutadiene(HTPB):Simultaneous tuning on low temperature behavior and processability

Geminal dinitropropyl ester plasticizers(DNPEPs) possess excellent energetic performances which provide good potentials as insensitive plasticizer. In this study, we design and synthesize DNPEPs with different alkane chain parts, and systematically investigate their structure-property relationships.Results show that DNPEPs have impact sensitivities all higher than 25.2 J, thermal decomposition temperatures all higher than 254 ℃, and glass transition temperatures(T_(g)) lower than-90 ℃.Furthermore, the effects of DNPEPs as plasticizer are studied on hydroxyl terminated polybutadiene(HTPB) in detail, including the viscosity, glass transition temperatures and others. It is noteworthy that 2,2-dinitropropyl nonanoate(DNPNc) among these DNPEPs exhibits the most expected simultaneous tuning effects on both viscosity and T_(g) of HTPB systems, providing favorable potentials to replace the conventional plastizers as dioctyl sebacate(DOS) in the HTPB based propellants and explosives.

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.

基于玻璃化转变的稻谷干燥变温控制系统设计与试验

针对稻谷在变温干燥过程中变温节点不明确、温度波动范围大和响应时间慢等问题,该研究设计了一种基于玻璃化转变的稻谷变温干燥控制系统。根据稻谷玻璃化转变曲线,确定变温控制策略,运用Logistic回归分析建立混配阀门开度和稻谷温度之间的控制模型并通过最小二乘法辨识模型参数。利用遗传算法对模糊隶属度函数进行优化,目标函数值迭代至0.118收敛,寻得最优幅宽。在Simulink仿真试验中,稻谷温度设定为42℃时,模糊PID控制的响应时间为66.43 s,且超调量为3.600%,优化后的模糊PID控制响应时间为37.06 s,且超调量为0.120%;在150 s加入5 s的外部信号干扰,优化后的模糊PID控制比模糊PID控制的调节时间少4.19 s且超调量减小0.050%;在稳态时输入升温信号,优化后的模糊PID控制比模糊PID控制的调节时间少16.79 s且超调量低0.338%。利用自主研制的干燥试验台进行变温试验,在变温响应试验中,优化后的模糊PID控制比模糊PID控制在目标温度和梯度升温调节时间中分别缩短了37.56 s和18.63 s;在温度稳定性试验中,稻谷温度变化范围为41.9~42.1℃,平均相对误差小于0.4%,变异系数小于0.5%;在建三江国家农业高新技术示范区浓江农场进行生产性验证,优化后的模糊PID控制系统响应时间小于30 s,稳态温度误差在±0.15℃,平均相对误差小于0.5%。测试数据表明变温干燥控制系统性能稳定,满足实际干燥作业的生产工艺需求。

籼粳杂交稻变温-缓苏干燥工艺优化及蛋白结构研究

为提升稻谷干燥品质,本实验以籼粳杂交稻为对象,通过爆腰率、整精米率、能耗、干燥时间进行评价,结合单因素、响应面分析优化干燥工艺;同时采用差示扫描量热仪、傅里叶红外光谱、荧光光谱等技术手段,探究了变温-缓苏干燥对籼粳杂交稻蛋白结构及热特性的影响。结果显示:变温-缓苏干燥(变温区间30~60℃)在升温温度5℃、风速1 m/s、缓苏比0.6条件下可使稻谷始终保持在玻璃态,干燥后的爆腰率和整精米率比恒温组(60℃)分别降低79.89%和提高39.54%。在此条件下稻谷蛋白质发生极性减弱、分子间聚集现象,提高了蛋白质热稳定性,α-螺旋含量由16.21%提升至17.64%;扫描电镜结果表明,变温-缓苏干燥未对蛋白质表面结构造成明显影响。实验探究并验证了杂交稻谷变温-缓苏干燥机制,为杂交稻谷高品质干燥研究提供了理论和实践参考。

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.

龙眼果粉的水分吸附特性研究

以龙眼果粉为对象,利用静态测量法测定其在不同温度下的吸湿等温线,探究在不同含水率下龙眼果粉的X射线衍射图谱及玻璃化转变温度,并通过数学方程计算其热力学特性参数,以揭示龙眼果粉的水分吸附特性。结果表明,龙眼果粉的吸湿等温线为Ⅲ型等温线,Peleg模型是龙眼果粉吸湿等温线的最佳拟合模型。在水分活度(water activity,A_(w))>0.69时,龙眼果粉水分吸附量显著增加,导致糖类晶体结构消失。龙眼果粉的吸附过程符合熵焓互补理论,其吉布斯自由能为1586.6 J/mol>0,表明可通过控制环境条件来控制龙眼果粉的吸附过程。干基含水率从0.054 g/g上升到0.350 g/g时,龙眼果粉的玻璃化转变温度起始点从14.6℃降低至-26.5℃,其终点从39.1℃下降至-5.8℃。25℃下龙眼果粉的理论最佳贮藏A_(w)为0.086,对应的干基含水率为0.0495 g/g。该研究结果可为龙眼果粉贮藏条件的选择提供参考。

聚合物复合材料冷冻超薄切片技术——以等规聚丙烯/乙丙橡胶/纳米二氧化硅复合材料为例

真实结构图像对聚合物材料的研究和改性极为重要。冷冻超薄切片技术是聚合物材料进行内部微观结构分析必要的前处理技术。根据聚合物材料分子运动随温度变化这一热力学性质,通过对等规聚丙烯/乙丙橡胶/纳米二氧化硅聚合物复合材料在不同温度下的切片实验,探究切片温度对样品的微观形态和结构的影响规律。实验发现,玻璃化转变温度是影响切片质量变化的关键点。当切片温度设定在材料的玻璃化转变温度附近时,前后所得到样品的微观形态结构呈现出显著的差异。然而,如果切片温度过低,可能会引起严重的卷片现象,不利于显微结构的观察与分辨。玻璃化转变温度是聚合物材料进行切片的最佳温度,不仅能确保获得样品的真实结构,还能够得到高质量且平整的切片。