The determination of the glass transition temperature by thermally stimulated depolarization currents. Comparison with the performance of other techniques

Several experimental techniques are currently used for the determination of the glass transition temperature, T_g. Thermally stimulated depolarization currents (TSDC) is a thermal analysis technique whose experimental results display a very clean glass transition signature and that, nevertheless, is seldom used as a technique for T_g determination. In the present work we explain how to get the glass transition temperature from TSDC data, and we compare the values obtained for a vast number of glass forming systems (with T_gs in a wide range between ?145 and +180 °C and fragilities between m = 15 and m = 100), with the values obtained by differential scanning calorimetry (DSC) and dielectric relaxation spectroscopy (DRS). We conclude that the T_g determination by TSDC is direct, accurate and reproducible and that the obtained values correlate very well with those obtained by DSC and DRS. This general survey thus suggests TSDC as a valuable alternative technique for determining T_g.     

Effect of Alkyl Side Chain Length on Relaxation Behaviors in Poly(n-alkyl Acrylates) and Poly(n-alkyl Methacrylates)

Dynamic mechanical analysis (DMA) is used to investigate the effect of alkyl side chain length on the relaxation behavior of poly(n-alkyl acrylates) (PnAA) and poly(n-alkyl methacrylates) (PnAMA) above the glass transition temperature (T_g). Master curves and shift factors (log a_T) were obtained using the time–temperature superposition (TTS) principle. The log a_T curves of PnAA and PnAMA exhibit a dynamic crossover from one Vogel–Fulcher–Tammann–Hesse (VFTH) equation to another above T_g. The corresponding temperature was designated as the dynamic crossover temperature (T_c). It is found that T_c/T_g and the apparent activation energy (E_g) increases, e whereas the fragility index (m) decreases with increasing alkyl side chain length. Further analysis shows that m ∝ T_g, E_g∝ , and E_g∝ m² for both PnAA and PnAMA.     

聚丙烯酸酯玻璃化转移温度QSPR的研究

对聚丙烯酸酯的定量构性关系(QSPR)研究具有重要意义。采用分子电性作用失量(MEIV)表征聚丙烯酸酯的分子结构,运用多元线性回归(MLR)建立定量结构玻璃化转移温度相关(QSPR)模型,同时采用逐步回归结合统计检测筛选模型变量,建立了22个聚丙烯酸酯玻璃化转移温度（Tg）与其结构间的多元线性回归方程。另外采用内部及外部双重验证的办法深入分析和检验模型的稳定性。建模的复相关系数(Rcum)、留一法(LOO)交互校验复相关系数(Qcum)和外部样本校验复相关系数(Qext)分别为0.982、0.971和0.922。表明用MEIV对聚丙烯酸酯分子结构信息表达较好,所建QSPR模型的稳定性和预测能力良好。     

环氧树脂高温分子链松弛与玻璃化转变特性

环氧树脂是电力设备中广泛应用的一种绝缘材料, 其介电性能受到分子链运动特性的影响. 本文制备了直径为50 mm、厚度为1 mm的环氧树脂试样, 采用差示扫描量热仪和宽频介电谱仪测试了环氧树脂的玻璃化转变温度和介电特性. 实验结果表明, 环氧树脂的玻璃化转变温度为105 ℃, 在玻璃化转变温度以上, 高频段出现了由分子链段运动造成的松弛过程, 低频段出现了由载流子在材料中迁移造成的直流电导过程. 发现环氧树脂不同尺寸分子链段的松弛时间不同, 其松弛时间分布较宽, 计算得到了分子链段在不同温度下的松弛时间分布特性. 分子链松弛峰频率和直流电导随温度的变化关系服从Vogel-Tammann-Fulcher公式. 拟合实验结果得到分子链松弛峰频率和直流电导的Vogel温度和强度系数. 由Vogel温度计算得到了与差示扫描量热测试结果一致的玻璃化转变温度, 约为102 ℃. 结果表明玻璃化转变温度以上环氧树脂的自由体积增大, 分子链段有足够的空间来响应外电场从而产生分子链松弛极化, 载流子有足够的能量在材料中迁移形成电导.     

Density and bond-orientational relaxations in supercooled water

ABSTRACT

Recent computational studies have reported evidence of a metastable liquid–liquid phase transition (LLPT) in molecular models of water under deeply supercooled conditions. A competing hypothesis suggests, however, that non-equilibrium artefacts associated with coarsening of the stable crystal phase have been mistaken for an LLPT in these models. Such artefacts are posited to arise due to a separation of time scales in which density fluctuations in the supercooled liquid relax orders of magnitude faster than those associated with bond-orientational order. Here, we use molecular simulation to investigate the relaxation of density and bond-orientational fluctuations in three molecular models of water (ST2, TIP5P and TIP4P/2005) in the vicinity of their reported LLPT. For each model, we find that density is the slowly relaxing variable under such conditions. We also observe similar behaviour in the coarse-grained mW model of water. Our findings, therefore, challenge the key physical assumption underlying the competing hypothesis.     

Dynamic phase transition in the kinetic Blume--Emery--Griffiths model: Phase diagrams in the temperature and interaction parameters planes

As a continuation of our previously published work, the dynamic phase transitions are studied further, within a mean-field approach, in the kinetic Blume--Emery--Griffiths model in the presence of a time varying (sinusoidal) magnetic field by using the Glauber-type stochastic dynamics. The dynamic phase transitions are obtained and the phase diagrams are constructed in two different planes, namely in the reduced temperature (T) and biquadratic interaction (k) plane and found eight fundamental types of phase diagrams for various values of reduced crystal-field interaction (d) and magnetic field amplitude (h), and in the (T,?d) plane and obtained six distinct topologies for different values of k and h. Phase diagrams exhibit one or two dynamic tricritical points and a dynamic double critical end point, dynamic triple and quadruple points, and besides disordered and ordered phases, three coexistence phase regions exist in which occurring of these strongly depend on the values of d, k and h.     

Effect of Dichloromethane on Transport,Thermal, and Thermal‐Mechanic Properties of Amorphous Glass Poly(Ether Imide) Films

Abstract

In this work the interaction effect of dichloromethane on amorphous glassy poly(ether imide) (PEI) films was analyzed from the correlation between transport, thermal, and mechanical properties. The resulting sorption curves were anomalous two‐stage in the solvent activity range 0–0.34 and pseudo‐Fickian for the solvent activity range 0.40–0.50. From a generalized diffusion equation to describe the combination of Fickian and Case II mechanisms we found that the velocity of solvent penetration (v) was higher than the diffusion coefficient (D) for all solvent activities studied. It was observed from the cluster function and the mean size cluster that solvent–solvent interactions may occur at higher solvent activities. Thermal differential scanning calorimetry (DSC) and thermal gravimetric analysis [(TGA) and thermal mechanical (DMTA)] characterization showed that the solvent clusters may act as an antiplasticizer, increasing the elastic modulus of the PEI matrix by 1.9 times. Therefore, a shifting of the β transition was observed at higher temperatures around the glass transition.     

Short-range order structure and free volume distribution in liquid bismuth: X-ray diffraction and computer simulations studies

ABSTRACT

The structure of liquid bismuth was studied by X-ray diffraction and computer simulation methods. The contraction of the atomic structure within the first coordination sphere in the temperature interval of 575-1225?K is reported. The temperature dependencies of the coordination numbers and of the free volume are analysed. On the basis of the temperature dependencies of the free volume, the temperature dependencies of viscosity and the self-diffusion coefficient were calculated to be in the ranges from 1.17 to 0.86?mPa?s and from 2.18 × 10^?9 to 5.44 × 10^?9?m²/s, respectively. The free volume – extracted results are in fair agreement with the experimental data and with the results obtained in the molecular dynamics simulations.     

Liquid–liquid structure transition in Sn–3.5Ag–3.5Bi melts

The liquid–liquid structure transition (LLST) as the function of temperature and time in Sn–3.5Ag–3.5Bi melts was investigated with the help of direct current four-probe method. The LLST which occurs during first cycle heating of two cycles heating/cooling experiments can divide into two different structure changes: irreversible LLST of 650°C isothermal and step reversible LLST at 770°C–806°C on subsequent heating process. Obvious kinetic phenomena are observed during isothermal experiments. Irreversible and reversible LLST are analysed from the viewpoint of short-range order. These results will help to understand the law and mechanism of liquid field, and provide some scientific reference for the innovation of lead-free solder manufacturing.     

Reversible Gelation and Phase Transition of Aqueous Solution of Hydrophobically Modified Poly(N‐Isopropylacrylamide)

Abstract

We investigated physical gelation and phase transition of aqueous solutions of hydrophobically modified poly(N‐isopropylacrylamide) (HM‐PNIPAAm) with stearyl acrylate (SA). Aqueous solutions of HM‐PNIPAAm form a reversible gel cross‐linked with hydrophobic aggregations of stearyl groups. The physically cross‐linked HM‐PNIPAAm gel with relatively low SA content shows a two‐step volume transition with increasing temperature. Moreover, overlapping of the reversible gel–sol transition and phase separation results in the phase diagrams of the aqueous solutions of HM‐PNIPAAm, having five distinct regions: dilute sol, gel, gel–sol, sol–sol, and condensed sol regions. The overlapping of the two different phase transitions causes the two‐step volume transition.     

聚酰亚胺电导率随温度和电场强度的变化规律

介质深层充电对航天器安全运行构成了重大威胁.以聚酰亚胺为代表的此类聚合物绝缘介质的电导率受温度影响显著,又因为充电过程中局部产生强电场(10~7V/m量级),因此,其电导率模型需要综合考虑温度和强电场的影响,这对介质深层充电的仿真评估意义重大.已有的两类模型,不是低温区间不适用,就是没有充分考虑强电场的影响.基于跳跃电导理论,本文分析对比了现有电导率模型,提出了适用于较宽温度范围且合理考虑强电场增强效应的电导率新模型,并采用某型聚酰亚胺电导率测试数据做出验证.此外,为了提高新模型在强电场下的低温适用范围,尝试对强电场因子中的温度做变换,取得了满意的效果.参数敏感度分析表明新模型在电导率拟合与外推方面具有参数少、适用性强的优势.     

Electrical conductivity behaviour of pure and polyblends samples of polyvinyl chloride (PVC) and polymethyl methacrylate (PMMA)

Electrical conductivity of pure PVC, PMMA and their polyblends samples has been studied in detail as a function of polarizing fields at constant temperatures. Different plots were drawn to investigate the nature of mechanism responsible for conduction. The nature of all the thermograms is nonlinear but similar for all temperatures. The plots have two slopes, i.e., ohmic conduction with slope of curve ≈1 at lower voltage region and a non-ohmic conduction with slope ≈1.9 at higher voltage region are observed. The increase in the conductivity and decrease in the activation energy, suggest that plasticization effect is taking place between the polymers when they are blended. Fowler–Nordheim plots are not consistent and showing negative and positive slopes simultaneously for lower as well as higher values of applied voltage. Theoretical and experimental values of β_SR and β_PF were calculated and the β_exp of pure and polyblend samples is in agreement with theoretically β_PF. The β_exp value lies close to β_PF, this shows that Poole–Frenkel mechanism is also effective. The calculated metal electrode potential barrier at a constant voltage suggests that the dominant charge carrier mechanism is Schottky–Richardson type. Hence in the present case both SR and PF mechanisms are seem to be operative.     

Poly(4-vinylpyridine) supported acidic ionic liquid: A novel solid catalyst for the efficient synthesis of 2,3-dihydroquinazolin-4(1H)-ones under ultrasonic irradiation

A novel poly(4-vinylpyridine) supported acidic ionic liquid catalyst was synthesized by the reaction of 4-vinylpyridine with 1,3-propanesultone, followed by the polymerization and the addition of the heteropolyacid. Due to the combination of polymer features and ionic liquid, it acted as a heterogeneous catalyst to effectively catalyze the cyclocondensation reaction of anthranilamide with aldehydes under ultrasonic irradiation and afforded the corresponding 2,3-dihydro-4(1H)-quinazolinones compounds in good to excellent yields. In addition, the catalyst could be easily recovered by the filtration and reused six times without significant loss of catalytic activity. More importantly, the use of ultrasonic irradiation can obviously accelerate the reaction.     

Thermoluminescence measurements of liquid crystal azomethines and poly(azomethines) with different shapes as thermo-detectors

We have explored the thermoluminescence (TL) properties of a few series of liquid crystal unsymmetrical and symmetrical azomethines and poly(azomethines) with different shapes. Rod-, bent- and star-shaped compounds were investigated as thermoluminescent detectors. All of the investigated compounds, except ASB3, AG2 and PAZ2, exhibited mesomorphic behavior. The thermoluminescence studies have shown that molecular structure of the compound along with shape influenced the TL properties of azomethines and poly(azomethines). Thermoluminescence intensity (I), temperature of maximum TL (T), activation energy values (E) and frequency factor (s) were detected. For the first time, to the best of our knowledge, thermoluminescence properties of liquid crystalline azomethines and polyazomethines were described and compared in this article.     

液体中静态介电常数随温度渡越行为及其关联特征研究

为了通过液体静态介电常数随温度的变化行为,归纳总结液体中分子间取向关联极化的一般规律,在现有的文献中,筛选了分子的电子极化远小于分子间取向关联极化的18种液体材料,并对其静态介电常数随温度的变化行为进行了分析研究.结果表明,液体中静态介电常数随温度变化存在一个普遍的渡越行为,并且对应于该种渡越,至少存在两种分子之间的取向关联序,一种随温度降低而增强,而另一种则减弱.     

Effect of the competition between relaxation and core hole decay on the Auger-photoelectron coincidence spectroscopy (APECS) spectrum of Ni metal

The valence hole created in Ni metal either by the L2-L3V Coster–Kronig (CK) transition or by the L3V shakeup/off becomes screened out prior to the L3-hole decay. We denote the atomic shell Lx (x = 2, 3) by LX. The metastable two-hole L3V state relaxes to the fully relaxed single L3-hole state before the L3-hole decays. Thus, the coincidence L2-L3(V)-VV(V) Auger-electron spectrum resembles closely the coincidence L3-VV Auger-electron spectrum. The final state of the CK transition preceded Auger transition is a two-hole state rather than a three-hole state. The four-hole satellite about 8 eV below the L3-VV main line in the singles (non-coincidence) Auger-electron spectrum is partly due to the L3VV-VVVV transition and the L2-L3VV-VVVV transition. The valence holes created either by the L2-L3VV transition or by the L3VV double shakeup/off remain localized during the L3-hole decay. The L3-hole lifetime widths of Fe, Co and Ni metals are determined from the APECS spectra. The agreement between experiment and theory (the independent-particle approximation) is poor.     

Many-body effect in the coincidence L3 and M3 photoelectron spectroscopy spectra of Cu metal

The coincidence L₃ and M₃ photoelectron spectroscopy (PES) main lines of Cu metal are calculated by a many-body theory. There is no peak-energy shift between the singles PES main line and the coincidence one. The asymmetric narrowing of the coincidence PES main line on the low kinetic energy (KE) side is very small. This is in accord with recent experimental findings. In Cu metal, the shakeup satellite intensity is small and the main-line satellite separation energy is much larger than the core–hole lifetime width. The interference via the final-state interaction is negligible. In the PES main line, the imaginary part of the self-energy by shakeup excitations, which is very small compared to the core–hole lifetime width, decreases very slowly in linear with photoelectron KE. The branching ratio of Auger decay of a single hole state then increases very slowly in linear with photoelectron KE so that the deviation of the coincidence PES main line from the singles one is very small. The 939 eV structure seen only in the coincidence L₃ PES spectrum of Cu metal is attributed to the enhancement of the inelastic peak of a smaller energy loss due to electrons of a smaller average emission depth measured in coincidence with the elastic Auger peak. The structure will not be enhanced in the singles PES spectrum. The background subtraction in the coincidence spectrum cannot be the same as that in the singles one. Such consideration is necessary before we can conclude about the asymmetric narrowing on the low KE side. A unique capability of APECS by which one can determine the photoelectron KE dependent part of the imaginary part of the self-energy is pointed out.     

Synthesis, characterization of ceria-coated silica particles and their chemical mechanical polishing performance on glass substrate

Nano-sized ceria particles were coated on the silica surface by the precipitation method using ammonium cerium nitrate and urea as precipitant with poly(vinylpyrrolidone) (PVP) as assistant. The structures and compositions of ceria-coated silica particles were characterized using X-ray diffraction (XRD), field-emission scanning microscopy (FE-SEM), energy dispersive spectroscopy (EDS), transmission electron microscopy (TEM) and dynamic light scattering (DLS) measurements. The results show that nano-size ceria particles were coated uniformly around the surface of silica particles when PVP was used as assistant during coating process, while without PVP, the ceria particles were grown sparsely on the silica particle surface and many ceria particles grow up through independent nucleation in the solution. Then, the chemical mechanical polishing (CMP) behaviors of the as-prepared ceria-coated silica particles on glass substrate were investigated. The CMP test results suggest that the as-prepared ceria-coated silica particles exhibit higher removal rate than pure silica particles without deteriorating the surface quality. In addition, online coefficient of friction (COF) was conducted during the polishing process. The COF data indicate that the COF values of ceria-coated silica particles are larger than those of pure silica particles due to their surface properties.     

Novel aspects of charge and lattice dynamics in the hole-doped manganite La0.67Sr0.33MnO3

Previous infrared studies on the hole-doped manganite La_0.67Sr_0.33MnO₃ (LSMO) have analysed its charge dynamics in terms of one type of charge carrier despite evidence of both electron and hole Fermi surfaces. Here, we investigate the charge dynamics of an LSMO film with infrared and optical spectroscopy in order to provide a complete picture of metallic conduction. In the ferromagnetic metallic phase, the low-frequency optical conductivity is best explained by a two-carrier model comprising electrons and holes. The number densities, effective masses and relaxation response of the delocalized electrons and holes are quantified. We discover that only one-third of the doped charges are coherent and contribute to the dc transport. Metallic LSMO cannot be classified as a bad metal at low temperatures because the mean free path of the coherent, mobile charge carriers exceeds the Ioffe–Regel–Mott limit. The incoherent spectral response of the doped charges manifests itself as a broad mid-infrared feature. We also report the first observation of splitting of an infrared-active phonon due to local Jahn–Teller distortion in the vicinity of the thermally driven transition to the nonmetallic, paramagnetic phase in LSMO. This demonstrates that infrared spectroscopy is capable of detecting the presence of local lattice distortions in correlated electron systems.     

Crystallinity,relaxational transitions,and free volume in high-density polyethylene

Most of the procedures employed so far in the literature for obtaining the amorphous volume of a polymer below its melting point have been based upon some kind of ad hoc assumptions. In this paper the principle of corresponding states, whose validity has been established for a number of polymers, is applied for obtaining the amorphous volume of polyethylene in the experimentally inaccessible region. The degree of crystallinity as a function of temperature is then calculated in a typical case using the actual sample volume data of Quinn and Mandelkern and the ideal crystal volume values obtained from X-ray measurements. Our results indicate the onset of a prominent relaxational transition at T₁ = 152°K. A careful analysis of the volume-temperature relationship indicates a much weaker transition at T₂ = 233°K. By making use of the isoprene volume concept, it is shown that the Simha-Boyer relation is valid in a more general form.