晶型转变对尼龙11分子链运动的影响

为进一步认识分子链运动与晶型之间的关系,用熔融、冰水淬火和退火等方法制备了α和δ′两种晶型的尼龙11薄膜试样.42Hz～5MHz的介电松弛谱显示了两种不同晶型试样的分子运动特征.不同频率下的介电温度谱显示α型结晶中代表分子链段运动的主松弛较δ′型结晶出现在更高温度,说明退火引起的δ′向α晶型转变使分子链段运动受到了限制.研究结果还显示,α和δ′型结晶中分子链局域松弛运动的活化能基本相同,但α型的松弛时间较δ′型的大,松弛强度则较δ′型的小,表明晶型转变使尼龙11的分子链局域松弛运动也受到了一定程度的抑制.     

限域相变对热致变色环氧绝缘材料介电松弛特性的影响

本文研究了热致变色微胶囊环氧绝缘材料的介电松弛特性及机理.结果表明,热致变色微胶囊环氧绝缘材料表现出非单调介电松弛特性,即在58—66℃温度范围内,介电松弛时间随温度升高而逐渐延长,无法通过传统的Arrhenius或Vogel-Fulcher-Tammann方程进行描述.分析认为,该非单调介电松弛特性主要源于微胶囊内限域相变引发的自由体积变化.随着温度的升高,微胶囊有限空间内发生固-液相变,使得微胶囊内的自由体积逐渐减小,限制了偶极子随外电场的定向过程,导致介电松弛时间逐渐延长.采用限域介电松弛模型拟合了热致变色环氧试样的非单调介电松弛特性,并得到了介电松弛活化能.不同微胶囊含量的热致变色试样的介电松弛活化能均处于相同的数量级,表明其非单调介电松弛过程均发生于热致变色微胶囊内,验证了限域相变对非单调介电松弛特性的作用.     

纳米微粒对低温保护剂溶液玻璃化性质的影响

利用差示扫描量热仪(DSC)研究了加入羟基磷灰石(HA)纳米微粒对低温保护剂溶液玻璃化的影响,实验得到了不同粒径和不同质量浓度的HA纳米微粒加入PVP溶液的玻璃化转变温度与反玻璃化温度.实验结果表明加入纳米微粒能显著的影响低温保护剂溶液的玻璃化性质.且随着纳米微粒质量分数的增加,溶液的玻璃化转变温度与反玻璃化温度均显著...     

1,2-丙二醇协同松弛的DSC研究

利用差示扫描量热法(DSC)研究了1,2-丙二醇在不同降温速率下的协同松弛行为，以曲线拟合方法获得非线性Adam-Gibbs焓松弛参数．结果表明，模型参数强烈依赖于降温速率．在较高降温速率下获得的模型参数和用比热频谱及介电方法得到的结果很接近．利用DSC测得的比热容数据和拟合结果估算了1,2-丙二醇体系非线性AG理论的两个主要微观参数，即协同重排域(CRR)尺寸z*和对应的位形态数量W*．结果表明，如果采用聚合物玻璃推荐的W*，则会导致1,2-丙二醇在玻璃化温度处的CRR中的分子数小于1．而如果采用Johari的方法，则可得到玻璃化温度处的CRR中约有3个1,2-丙二醇分子，但随之产生的W*却异常的大．利用Donth的热力学温度波动公式估算得到的1,2-丙二醇在玻璃化温度处的CRR中的分子数为355，这和Johari方法得到结果难以统一．表明对于小分子氢键液体而言，非线性AG理论中z*的物理意义应重新审视．     

钇掺杂钨酸铅晶体中的极化子和导纳谱

在室温至160 ℃范围内测量了掺钇钨酸铅(PWO∶Y)晶体的直流电导率,证明此时的载流子为极化子.观察到极化子由能带导电到跳跃导电转变引起的电导率极小.在此温区的交流导纳分析给出的交流电导率比直流电导率大三个数量级,说明此时的交流电导率主要是复介电常数的贡献.当样品的电导率和介电常数均随频率而变化时,从交流测量只能得到样品的总的导纳谱，而不能将其中的电导谱和介电谱分开. 关键词： 钨酸铅 电导谱 介电谱 导纳谱 极化子     

PVPh/PEO共混物动力学演化过程的NMR研究

聚合物共混物中链段的慢取向运动与其玻璃化转变行为和宏观力学性质密切关联,而基于化学位移各向异性重聚的~(13)C CODEX(centerband-only detection of exchange)固体核磁共振(SSNMR)技术能够有效表征共混物中链段的慢取向运动.该文利用~(13)C CODEX NMR技术详细研究了相容性聚合物共混物聚乙烯基苯酚/聚氧乙烯(PVPh/PEO)中的刚性组分PVPh在较宽温度范围内的慢取向运动特性与玻璃化转变过程的关联.研究表明,在玻璃化转变起始温度以下,PVPh主链的分子运动被冻结,而侧基存在b-松弛的慢取向运动;在玻璃化转变起始温度附近,PVPh主链具有明显的慢取向运动,而且主链和侧基是一种协同的分子运动.该文利用NMR技术揭示了共混物中的玻璃化转变起止温度分别对应于高分子主链慢取向运动CODEX信号的开始和极大值处的温度.     

KLiSO_4单晶的电学性质

我们证实了KLiSO_4为Li离子导体。通过测定样品中的电位分布,确定其载流子为间隙Li离子和Li空位。其电流弛豫在一定时域内遵从负幂次衰减规律。与之对应,在一定频域内存在与频率成负幂次关系的介电色散。在相变温度附近,本底电流、直流电导率和表观介电常数除发生跃变外还出现一个尖锐的小峰。此峰只有在变温速率较慢时才能观察到,表明该相变具有弛豫过程。     

丙三醇浓溶液玻璃化转变与结构松弛参数DSC分析

利用差示扫描量热仪研究了5种高浓度丙三醇水溶液(60%、70%、80%、90%、100%)的玻璃化转变行为,以考察水分含量和升降温速率对其玻璃化转变行为和结构松弛参数的影响.采用4种线性升降温速率(10、15、20、25K/min)获得玻璃化转变的相关参数.利用GordonTaylor方程对玻璃化转变温度的分析结果表明,水对丙三醇增塑常数的计算结果与升降温速率和玻璃化转变温度的读取方法有很大关系.玻璃化转变过程的比热容变化不仅随水分含量的增加而增加,而且与升降温速率也有一定的依赖关系.结构松弛活化能的计算结果表明,随体系水分含量的增加,体系的结构松弛活化能和动力学脆度都逐渐降低.随水分含量的变化,热力学脆度和动力学脆度表现出相反的变化趋势.     

VDF（52）／TrFE（48）铁电共聚物的非晶介电弛豫

用液氮淬火和热处理方法制得结晶度相差较大的铁电共聚物ＶＤＦ（５２）／ＴｒＦＥ（４８）试样。介导弛豫研究提示室温以下共聚物的频率谱由低频和高频两部分组成。低频部由非晶区被冻结分子链段的微布郎运动贡献。符合ＷＬＦ方程；高频部由晶区分子链段较小尺度的局域运动产生，遵从Ａｒｒｈｅｎｉｕｓ规律。分峰拟合结果得到共聚物的玻璃化转变温度为－２４℃，局域弛豫活化能为４６．１ｋＪ／ｍｏｌ．     

KLiSO4单晶的电学性质

我们证实了KLiSO₄为Li离子导体。通过测定样品中的电位分布,确定其载流子为间隙Li离子和Li空位。其电流弛豫在一定时域内遵从负幂次衰减规律。与之对应,在一定频域内存在与频率成负幂次关系的介电色散。在相变温度附近,本底电流、直流电导率和表观介电常数除发生跃变外还出现一个尖锐的小峰。此峰只有在变温速率较慢时才能观察到,表明该相变具有弛豫过程。 关键词：     

Relaxation dynamics and fragility during liquid–glass transitions of poly(propylene glycol)s

The acoustic and thermal properties of the liquid–glass transitions of propylene glycol and its oligomers, poly (propylene glycol)s, were studied by temperature modulated DSC and Brillouin scattering. The fragility indices were determined from Angell plots using the observed modulation frequency dependence of the complex heat capacity. The variation in the glass transition temperatures is discussed on the basis of the free volume theory. The relaxation time of the structural relaxation obeys the Vogel–Fulcher law, and its high frequency end is in good agreement with the result of the dielectric measurement in the literature. The correlation between the observed thermal expansion coefficients and the glass transition temperature is discussed based on the free volume theory. The sound velocity and attenuation were accurately determined as a function of the temperature by Brillouin scattering by combination with the refractive index measurement. The relaxation dynamics were discussed by considering the relaxation from segmental motions. All of these physical properties were discussed based on the third-order anharmonicity and the Grüneisen parameter.     

Investigation of MWS Relaxation in Nylon 1010 using Dielectric Relaxation Spectroscopy

Maxwell–Wagner–Sillars (MWS) relaxation in nylon 1010, arising from charge carriers accumulated at the interphase between amorphous and crystalline regions, has been investigated by means of dielectric relaxation spectra. In the frequency spectra of nylon 1010, dielectric permittivity showed high values at low frequencies originating from charge carrier movement. For the MWS relaxation, the dielectric strength was independent of temperature. The results revealed that there is a transition temperature, located between 110 and 120°C, resulting in the separation of two different charge carrier movement mechanisms. Below and above this transition temperature, the temperature dependence of the MWS relaxation time follows the Vogel–Tammann–Fulcher type, showing that the charge carrier transport is governed by the motion of the polymer chains. The change of charge carrier movement mechanisms is due to the onset of polymer chain motion in the interphase.     

Segmental dynamics of poly(methyl phenyl siloxane) confined to nanoporous glasses

The effect of a nanometer confinement on the molecular dynamics of poly(methyl phenyl siloxane) (PMPS) was studied by dielectric spectroscopy (DS), temperature modulated DSC (TMDSC) and neutron scattering (NS). Nanoporous glasses with pore sizes of 2.5–20 nm have been used. DS and TMDSC experiments show that for PMPS in 7.5 nm pores the molecular dynamics is faster than in the bulk which originates from an inherent length scale of the underlying molecular motions. For high temperatures the temperature dependence of the relaxation rates for confined PMPS crosses that of the bulk state. Besides finite states effects also the thermodynamic state of nano-confined PMPS is different from that of the bulk. At a pore size of 5 nm the temperature dependence of the relaxation times changes from a Vogel/Fulcher/Tammann like to an Arrhenius behavior where the activation energy depends on pore size. This is in agreement with the results obtained by NS. The increment of the specific heat capacity at the glass transition depends strongly on pore size and vanishes at a finite length scale between 3 and 5 nm which can be regarded as minimal length scale for glass transition to appear in PMPS.     

Mobility in thin polymer films ranging from local segmental motion, Rouse modes to whole chain motion: A coupling model consideration

Large increases of mobility of local segmental relaxation observed in polymer films as the film thickness is decreased, as evidenced by decreases of the glass temperature, are not found for relaxation mechanisms that have longer length scales including the Rouse relaxation modes and the diffusion of entire polymer chains. We show that the coupling model predictions, when extended to consider polymer thin films, are consistent with a large increase of the mobility of the local segmental motions and the lack of such a change for the Rouse modes and the diffusion of entire polymer chains. There are two effects that can reduce the coupling parameter of the local segmental relaxation in thin films. One is the chain orientation that is induced parallel to the surface when the film thickness h becomes smaller than the end-to-end distance of the chains and the other is a finite-size effect when h is no longer large compared to the cooperative length scale. Extremely thin ( ≈ 1.5 nm) films obtained by intercalating a polymer into layered silicates have thickness significantly less than the cooperative length scale near the bulk polymer glass transition temperature. As a result, the coupling parameter of the local segmental relaxation in such thin films is reduced almost to zero. With this plausible assumption, we show the coupling model can explain quantitatively the large decrease of the local segmental relaxation time found experimentally. Received 1 August 2001 and Received in final form 1 December 2001     

Revisiting the Dielectric Relaxation of Ethylene-Vinylacetate Copolymers: Influence of Microstructure

The dielectric relaxation behavior of a series of ethylene-vinylacetate (EVA) copolymers was investigated by measuring the complex dielectric permittivity in a broad frequency and temperature range. Crystallinity of EVA copolymers was estimated by differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS). The shape of the higher temperature relaxation, appearing above the glass transition temperature T _g depends on the VA content. It was found that this relaxation was asymmetric for VA concentrations higher than 40 wt% and changed to a symmetric shape at lower VA values. Concurrently, as the VA content decreased, a major broadening of the relaxation over a wide frequency range was observed. It is found that the dielectric relaxation was preserved on going through the melting range of the semicrystalline samples, although it exhibited changes of its characteristic parameters that are typical for segmental relaxation appearing at T _g. This finding allows one to associate this relaxation to the segmental motions at T _g in the amorphous phase and not to the existence of interfacial regions.     

Glassy dynamics of polymers confined to nanoporous glasses revealed by relaxational and scattering experiments

The glassy dynamics of poly(propylene glycol) (PPG) and poly(dimethyl siloxane) (PDMS) confined to a nanoporous host system revealed by dielectric spectroscopy, temperature-modulated DSC and neutron scattering is compared. For both systems the relaxation rates estimated from dielectric spectroscopy and temperature-modulated DSC agree quantitatively indicating that both experiments sense the glass transition. For PPG the segmental dynamics is determined by a counterbalance of adsorption and confinement effect. The former results form an interaction of the confined macromolecules with the internal surfaces. A confinement effect originates from an inherent length scale on which the underlying molecular motions take place. The increment of the specific-heat capacity at the glass transition vanishes at a finite length scale of 1.8 nm. Both results support the conception that a characteristic length scale is relevant for glassy dynamics. For PDMS only a confinement effect is observed which is much stronger than that for PPG. Down to a pore size of 7.5 nm, the temperature dependence of the relaxation times follows the Vogel-Fulcher-Tammann dependence. At a pore size of 5 nm this changes to an Arrhenius-like behaviour with a low activation energy. At the same pore size vanishes for PDMS. Quasielastic neutron scattering experiments reveal that also the diffusive character of the relevant molecular motions --found to be characteristic above the glass transition-- seems to disappear at this length scale. These results gives further strong support that the glass transition has to be characterised by an inherent length scale of the relevant molecular motions.Received: 1 January 2003, Published online: 14 October 2003PACS: 64.70.Pf Glass transitions - 77.22.Gm Dielectric loss and relaxation - 61.25.Hq Macromolecular and polymer solutions; polymer melts; swelling     

航空复合材料及其基体树脂的太赫兹光谱特性研究

现如今各类航空复合材料大量应用在航空飞机制造领域,而不同基体树脂的复合材料具有不同的性能优势,其物理性能关系到复合材料的设计、使用与检测。为研究不同种类的航空玻璃纤维复合材料及其基体树脂在太赫兹频段的光谱特性与介电性能,利用太赫兹时域光谱技术(THz-TDS)在0.2~1.0 THz频段内研究了3类不同航空玻璃纤维复合材料及其基体树脂：环氧树脂3238A/玻璃纤维EW180A,氰酸酯树脂9915/玻璃纤维QW120A,双马来酰亚胺树脂QY8911/玻璃纤维ZW100A的光谱吸收和介电色散特性,计算得到了不同航空复合材料及其基体树脂的折射率ｎ、吸收系数α、介电常数实部ε′和介电常数虚部ε″,并结合改性添加剂进行了基体树脂的对比分析,以及结合增强体玻璃纤维进行了复合材料的对比分析,在此基础上,使用Debye模型对树脂体系中偶极子的弛豫过程进行了理论计算,并对实验结果进行了拟合分析。研究表明,对于ε″和α,均以QW120A/9915＜ZW100A/QY8911＜EW180A/3238A和9915＜QY8911＜3238A的顺序增大,这是由于在树脂体系中含有的极性官能团和分子越多,偶极子取向极化引起的弛豫运动则会越剧烈,介电耗损就越大;随着交变电场频率的增加,偶极子因弛豫运动落后于电场的变化,需要更多的能量克服材料内粘滞阻力,引起介电耗损增大,导致ε″和α随之增大,并且均未有明显的吸收峰;由于树脂体系中分子链结构和极性基团的含量不同,对于各类复合材料和浇注料,氰酸酯树脂的ε′和n均最小,介电性能最好也最稳定,双马来酰亚胺树脂和环氧树脂介电性能次之,稳定性稍差,顺序为QW120A/9915＞ZW100A/QY8911＞EW180A/3238A和9915＞QY8911＞3238A;在聚合物树脂内部,偶极子的极化行为由于弛豫运动而受阻尼影响,滞后于交变电场的周期性变化,导致取向极化的程度相对减弱,ε′和ｎ呈现反常的色散现象,即ε′和ｎ随频率的增大而降低,而对于复合材料,玻璃纤维作为无机非金属材料弱化了聚合物树脂中极化行为的影响,均未出现反常色散现象;由于混合型树脂体系中不同极性的基团发生极化响应的机制不同,导致实际介电耗损高于拟合结果,而ε′和ｎ并不受影响,因而在使用Debye方程进行拟合时,ε″和α的拟合结果稍有误差。首次报道了不同航空复合材料及其基体树脂在太赫兹频段的介电性能差异、光谱特性及其规律,给出了环氧、氰酸酯和双马来酰亚胺三种不同航空树脂及其玻璃纤维复合材料在太赫兹频段的基础参数,为太赫兹频段下固体电介质材料透波性能的研究补充了新的内容,为航空复合材料的太赫兹无损检测提供了重要参考,并且对航空复合材料性能改进、吸波复合材料、光电半导体材料、太赫兹超材料和高性能雷达罩等研究具有重要意义。     

Dynamic light scattering in solid polymers

The viscosity of an amorphous polymeric solid above its glass transition [T _g (T,P)] increases as the temperature of the solid is decreased or the pressure is increased. Under changes in temperature or pressure, molecular subunits in the polymeric solid undergo configurational changes. Such changes or relaxations have a distribution of relaxation strengths and times. As the solid is cooled or as the hydrostatic pressure on the solid is increased, the relaxation strengths increase and the relaxation times increase. These changes in relaxation or dynamic properties are very dramatic as the empirical T _g is approached. Near T _g the polymeric solid is no longer in volume equilibrium; continued cooling or pressuring at a time rate faster than the average relaxation time will produce a polymeric glass. This glass is a nonequilibrium, amorphous solid. If the glass is held at a fixed temperature and pressure very close to, but below, T _g , the volume of the glass will be observed to relax to its equilibrium value. For temperatures and pressures well below T _g , equilibrium is a much more conjectural concept since the relaxation times become extremely long. It has been proposed^1,2 that there is a characteristic temperature T _g at which an amorphous polymer undergoes a second-order transition to an equilibrium glass with zero configurational entropy (i.e., a noncrystallizable solid).     

Thermal and mechanical properties and micro-mechanism of SiO2/epoxy nanodielectrics

In addition to electrical insulation properties, the thermal properties of nanodielectrics, such as glass transition temperature, thermal expansion coefficients, thermal conductivity, and mechanical properties, including Young's modulus, bulk modulus, and shear modulus, are also very important. This paper describes the molecular dynamics simulations of epoxy resin doped with SiO₂ nanoparticles and with SiO₂ nanoparticles that have been surface grafted with hexamethyldisilazane (HMDS) at 10% and 20% grafting rates. The results show that surface grafting can improve certain thermal and mechanical properties of the system. Our analysis indicates that the improved thermal performance occurs because the formation of thermal chains becomes easier after the surface grafting treatment. The improved mechanical properties originate from two causes. First, doping with SiO₂ nanoparticles inhibits the degree of movement of molecular chains in the system. Second, the surface grafting treatment weakens the molecular repulsion between SiO₂ and epoxy resin, and the van der Waals excluded region becomes thinner. Thus, the compatibility between SiO₂ nanoparticles and polymers is improved by the grafting treatment. The analysis method and conclusions in this paper provide guidance and reference for the future studies of the thermal and mechanical properties of nanodielectrics.