聚对苯二甲酸乙二酯非晶态膜片单轴热——拉伸中的结晶与松弛

用动态力学损耗温度谱作为测试手段,研究了非晶态PET膜片在78—112℃温度范围内的单轴拉伸。实验结果说明,在较低温度下所得结晶的拉伸试样,完全由于应变诱发结晶,发生在应力-应变曲线的屈服后应力开始上升的阶段。在较高温度下(90℃或更高)拉伸可得非晶态而且光学各向同性的试样,是由于分子链的小尺度取向在拉伸过程中已完全热松弛所致,而分子链的大尺度取向要通过高弹态流动而松弛,其速率较慢,用拉伸后试样两端固定时的应力松弛进行了观察。在较低温度下应力松弛后仍为非晶态,在较高温度下应力松弛到起始应力的1O％下才开始结晶。FTIR研究表明在这种状态下的结晶有一结晶诱导期,其时间尺度与应力松弛阶段相当。     

非晶态全同立构聚丙烯玻璃的结晶过程与玻璃化转变

以低于-75℃的干冰-乙醇淬火聚丙烯熔体薄膜,制得了全同立构聚丙烯玻璃。观察此试样在升温过程及等温过程中的比容变化和红外光谱变化,研究它的松弛过程和结晶过程,结果表明在-23℃以下它相当稳定,高于-20℃则有明显的松弛、结晶过程产生。非晶态全同立构聚丙烯的玻璃化转变温度大约稍高于-20℃。     

偏氟乙烯／三氟乙烯共聚物介电松弛的结晶度效应

用改进的介电松弛谱仪（精度２‰）测定了ＶＤＦ／ＴｒＦＥ（７／２７、６５／３５、５２／４８ｍｏｌ％）共聚物溶液成膜、液氮淬火、熔融慢冷和热处理试样在－１２０—１３０℃、１０－２一１０４Ｈｚ范围的复数介电常数．介电松弛研究结果显示低结晶度的淬火试样较高结晶度的熔融慢冷和热处理试样的Ｔｃ高．结晶度上升，居里点处的介电常数增大．室温以下的介电频率谱分别由代表非晶区分子运动的β松弛（低频部）和局域运动的γ松弛（高频部）叠合而成．随结晶度提高，β松弛峰减小，γ松弛峰增大；非晶松弛强度减弱．晶区松弛强度增强．     

蓖麻油基AB交联聚合物的介电性质

在-180℃至140℃范围内,用几个频率测定了蓖麻油基AB交联聚合物的介电松弛谱。对这些聚合物的多重松弛和相行为的研究表明,试样中的两组份在介电松弛谱上显现出相容的或近似互容的特征。试样中的次级松弛归因于聚氨酯组份中链段的局部运动。提出了一个描述界面极化的方法,计算了界面极化松弛活化能,它们同试样中组份间的相容性,界面相互作用大小以及分子链的柔曲性有关。     

拉伸热历史对取向聚对苯二甲酸乙二酯膜在热处理过程中收缩和伸长的影响

弄清取向非晶态聚合物在热处理过程中的收缩和伸长的变化规律,以及所对应的结构变化,有较大的实用意义和科学意义。 对于取向聚对苯二甲酸乙二酯的热收缩和热伸长已有很多研究,但对于拉伸热历史对取向PET在热处理过程中的尺寸变化的影响尚缺乏系统的研究。在热拉伸的过程中发生分子链的取向、热弛豫和结晶三个相互竞争的过程。因此,改变拉伸条件可以得到具有各种不同取向和结晶的PET试样。当非晶态PET膜片在80-105℃以较低     

变温红外法研究聚对苯二甲酸乙二酯分子链的松弛运动及其构象转变

在30～170 ℃范围内逐渐升温过程中,用红外光谱仪原位检测无定形聚对苯二甲酸乙二酯（PET）薄膜红外光谱图的变化情况。通过特征谱带吸光度与温度的变化特点,研究了PET分子链在热变化过程中的松弛运动及冷结晶过程中分子链的构象变化。实验结果表明在冷结晶过程中,随PET结晶的不断完善,对应左右式(gauche)构象的吸收峰减弱,对应反式(trans)构象的吸收峰增强,并计算出CH2面外摇摆振动结晶前和结晶后反式构象和左右式构象的相对百分含量随温度的变化关系,以及玻璃化转变和冷结晶的温区范围。     

聚对苯二甲酸乙二酯中正电子湮没寿命参数温度效应的研究

对聚对苯二甲酸乙二酯的非晶、低温热处理(54℃)、高温热处理(180℃)以及双轴拉伸等四种不同试样,测量了室温到180℃范围内不同温度在的正电子湮没寿命谱.根据最小二乘曲线拟合解谱结果,可知最长寿命成份的湮没参数τ和I的温度曲线分别灵敏地反映了聚对苯二甲酸乙二酯的玻璃转变过程和结晶过程.据此讨论了正电子湮没寿命参数与PET转变的关联以及PET玻璃转变的有关性质.     

试样两端固定或松弛态结晶对取向非晶态聚对苯二甲酸乙二酯膜结晶的影响

<正> 在研究聚合物的结晶过程中,有时(如在同步辐射法、X-衍射法和红外法的测定中)须将试样两端固定,有时(如研究热处理过程中取向聚合物的尺寸和结构变化)须将试样处于松弛状态。因而研究两端固定或松弛状态对取向聚合物结晶速率和结构的影响引起了人们的兴趣。一些研究结果得出,与松弛状态结晶相比,试样两端固定态结晶使取向聚合物的结晶速率变慢,但有时也出现相反的结果。此外,在上述文献中所用的原始试样都已具有较高的结晶度。为了弄清这一问题,我们用密度、双折射和应力测量等方法对取向程度不同的非晶态PET膜进行了深入和系统的研究。结果表明,试样两端固定与否对结晶速率的影响与试样原始的取向程度有关。     

聚偏氟乙烯的分子运动

本文研究了聚偏氟乙烯(PVDF)的介电、动态力学,热刺激电流和压电性能。在—150℃—120℃范围均观察到四个松弛转变过程,并阐述了它们的机制。 在室温以上,观察到二个松弛峰,与大部分报道不同,而与Kakutani的结果一致,本文还观察到d′_(31)与ε′_3成线性关系,高温下的斜率大于低温的斜率,可能是二种极化机构所致,压电效应的起源与偶极子取向有关。     

1,2-聚丁二烯介电松弛的复平面分析

本文对1,2-聚丁二烯的介电松弛进行了复平面分析.结果表明,在1,2-聚丁二烯的玻璃化转变过程中,ε″(ω)与ε＇(ω)的关系满足Havriliak-Negami方程.由复平面图求出了样品的静态和光频下的介电系数,平均松弛时间和松弛时间分布参数.利用所得数据讨论了1,2-聚丁二烯在玻璃化转变过程中的构象变化、松弛时间分布和平均偶极矩等问题.     

Dielectric relaxation and molecular motion in poly(vinylidene fluoride)

The dielectric properties of poly(vinylidene fluoride) have been studied in the frequency range 10 Hz to 100 kHz at temperatures between ?196 and 150°C. Three dielectric relaxations were observed: the α relaxation occurred near 130°C, the β near 0°C, and the γ near ?30°C at 100 kHz. In the α relaxation the magnitude of loss peak and the relaxation times increased not only with increasing lamellar thickness, but also with decrease of crystal defects in the crystalline regions. In the light of the above results, the α relaxation was attributed to the molecular motion in the crystalline regions which was related to the lamellar thickness and crystal defects in the crystalline phase. In the β relaxation, the magnitude of the loss peak increased with the amount of amorphous material. The relaxation times were independent of the crystal structure and the degree of crystallinity, but increased slightly with orientation of the molecular chains by drawing. The β relaxation was ascribed to the micro-Brownian motions of main chains in the amorphous regions. The Arrhenius plots were of the so-called WLF type, and the “freezing point” of the molecular motion was about ?80°C. The Cole-Cole distribution parameter of the relaxation time α increased almost linearly with decreasing temperature in the temperature range of the experiment. The γ relaxation was attributed to local molecular motions in the amorphous regions.     

Dielectric properties of some semiconducting polyazophenylenes

The dielectric properties of a series of semiconducting polyazophenylenes were studied as a function of temperature and molecular weight in the temperature range 293–600°K and for molecular weights between 5,100 and 62,800 at a constant frequency of 1 kHz. The compounds studied included poly-2,4-diaminotoluene, poly-2,4-diaminoanisole, and poly-2,5-diaminotoluene. The dielectric properties are presented in the usual way in terms of a complex dielectric constant ε^* = ε′—jε″. Activation energies of relaxation processes were evaluated from the areas and widths of the dielectric loss factor, ε″, against reciprocal temperature at constant frequency. The dielectric activation energies were found to be roughly equal to the activation energies from the DC conductivity. This indicates that the conduction mechanism is based on rotational movements of molecules or parts of molecules.     

Phases confirmation of cloudy Silwet L-77 aqueous solution by dielectric relaxation spectroscopy

<正>The phase transition of Silwet L-77(a kind of siloxane surfactant) dilute aqueous solution with temperature was investigated by dielectric relaxation spectroscopy.In the initial heating process,a dielectric relaxation was found at about 10~6 Hz,which was considered as the interface polarization ascribed to the interface between water and liquid phases(W and L_1).With the temperature increasing further,a new dielectric relaxation was observed at about 10~4 Hz,which was assigned to the appearance of liquid crystal phase(L_α).According to the dielectric parameters fitted by Cole-Cole equation,the coexistence temperature of W,L_1 and L_αwas determined at about 37.0℃.     

拉伸取向尼龙1010样品的抗张回复

研究了拉伸取向尼龙 10 10的抗张回复现象 .残存应变ε′表征了由链滑移而产生的永久形变 ,回复应变(ε -ε′)表征了键角变化和链段取向产生的形变 .当拉伸温度T=18℃ (T 相似文献   

Dielectric and conductivity relaxations in poly(hema) and of water in its hydrogel

The dielectric permittivity ε′ and loss ε″ of anhydrous poly(2-hydroxyethyl methacrylate) and its 38.6 w/w% hydrogel have been measured in the frequency range from 12 Hz to 200 kHz and the temperature range from 77 to 273 K. The former has a sub-T_g relaxation with a half-width of 4.5 decades for the loss spectra, whose strength increases with temperature, and an activation energy of 62.5 kJ/mol. The dielectric relaxation time of the α process of supercooled water in the hydrogel is 53 s at its calorimetric T_g of 135 K. The half-width of the relaxation spectrum is 2.85 decades and, in the narrow temperature range, its apparent activation energy is 60.8 kJ/mol. Heating of the hydrogel causes crystallization of water which begins at about 207 K and becomes readily detectable as a second dielectric loss peak at about 230 K. For each temperature between 207 and 267 K, supercooled water in the hydrogel coexists with its crystallized form, with the amount of the crystallized solid increasing with increasing temperature. These results are discussed in terms of “bound” and “free” states of water in the hydrogel.     

Conductivity measurement and dielectric,impedance and modulus spectroscopic studies on bis (P-nitrophenol) melaminium monohydrate

The present work is aimed to study the dielectric and electrical characteristics of bis (P-nitrophenol) melaminium monohydrate (BNPM) over the temperature and frequency ranges of 333–453 K and 50 Hz–5 MHz, respectively. The dielectric properties such as dielectric constant (ε′), dielectric loss (ε″), ac-conductivity (σ_ac), real (M′) and imaginary part (M″) of dielectric modulus were investigated as a function of temperature and frequency. The impedance analysis has been carried out using Cole-Cole plots to elucidate the electrical conduction mechanism. Further, observations indicated that the grain boundaries are more resistive and capacitive than the grains, inducing inhomogeneity in the material, which, in turn, causes broad frequency-dependent dielectric anomalies. The observed frequency-dependence of the AC conductivity validated the Jonscher power law. Further, an asymmetric dispersion peak in the imaginary part of the electrical modulus (M”) was noticed, indicating that the fabricated material exhibits non-Debye relaxation behavior.     

Dielectric properties of selected laterally fluoro-substituted 4,4′′-dialkyl,dialkoxy and alkyl-alkoxy [1:1′;4′:1′′]terphenyls

Measurements of the complex permittivity, ε*?=?ε′ – iε″, within the frequency range 200 Hz to 10 MHz for 15 laterally fluoro-substituted terphenyls have been conducted. In most cases the substances exhibited the nematic phase over a broad temperature range. All substances were characterised by negative dielectric anisotropy, and are potentially useful for vertical alignment mode systems. The static permittivity tensor components have been analysed in relation to the dipole structure of the molecules. Dielectric relaxation processes observed in the liquid crystalline (LC) and solid rotator (R) phases (obtained by slow cooling of the samples) are characterised by calculation of the relaxation times and activation barriers. The rotation motions around the short axes are typical for LC phases, whereas rotations about the long axes, accompanied in some cases by internal motions, are present in the R phase.     

Dielectric relaxations in PEEK by combined dynamic dielectric spectroscopy and thermally stimulated current

The molecular dynamics of a quenched poly(ether ether ketone) (PEEK) was studied over a broad frequency range from 10^?3 to 10⁶ Hz by combining dynamic dielectric spectroscopy (DDS) and thermo-stimulated current (TSC) analysis. The dielectric relaxation losses ε′′_KK has been determined from the real part ε′_T(ω) thanks to Kramers–Kronig transform. In this way, conduction and relaxation processes can be analyzed independently. Two secondary dipolar relaxations, the γ and the β modes, corresponding to non-cooperative localized molecular mobility have been pointed out. The main α relaxation appeared close to the glass transition temperature as determined by DSC; it has been attributed to the delocalized cooperative mobility of the free amorphous phase. The relaxation times of dielectric relaxations determined with TSC at low frequency converge with relaxation times extracted from DDS at high frequency. This correlation emphasized continuity of mobility kinetics between vitreous and liquid state. The dielectric spectroscopy exhibits the α_c relaxation, near 443 K, which has been associated with the rigid amorphous phase confined by crystallites. This present experiment demonstrates coherence of the dynamics of the PEEK heterogeneous amorphous phase between glassy and liquid state and significantly improve the knowledge of molecular/dynamic structure relationships.     

Phthalocyanine with a giant dielectric constant

Compound 1 has been prepared by the reaction of 4-nitrophthalonitrile and trans-2-methoxy-4-(2-nitrovinil)phenol by the common method of nucleophilic substitution of an activated nitro group in an aromatic ring. The metallophthalocyanines 2, 3 were prepared by the reaction of a dinitrile derivative with Co(OAc)(2) or Zn(OAc)(2) in DMSO. The lutetium bis-(phthalocyaninato) complex 4 was obtained by treating the dinitrile derivative with lutetium acetate and DBU in 1-hexanol. The new compounds were characterized by elemental analyses, FT-IR, (1)H-NMR, MALDI-TOF MS and UV/Vis spectral data. The spectroscopic data of the new compounds were in accordance with the structures. The temperature and frequency dependence of dielectric and conduction properties of the spin coated film of compounds (2-4) have been studied by fabricating metal-Pc-metal structures. The results show that compound 2 has giant dielectric constant. At a low range of frequency and room temperature, ε' is found to be equal to 2.33 × 10(6), 1.53 × 10(4) and 1.03 × 10(4) for 2, 3 and 4, respectively. The giant dielectric behavior of 2 is mainly attributed to Maxwell-Wagner polarization. The obtained results also indicated that the frequency dependence of the dielectric permittivity, ε'(ω), exhibits non-Debye type relaxation for all temperatures investigated. The ac conductivity results gave a temperature dependent frequency exponent s. The results were compared with the prediction of the Quantum Mechanical Tunneling and Correlated Barrier Hopping models.