Diluent effects on carbonate mobility in bisphenol-A polycarbonate in the solid state

The effect of miscible low molecular weight additives on the mobility of the carbonate group in bisphenol-A polycarbonate (BPAPC) has been studied using n.m.r. and dielectric relaxation experiments in the solid state. Proton-enhanced dipolar-decoupled carbon-13 n.m.r. spectra of BPAPC, isotopically enriched at the carbonate position, are obtained without magic-angle sample spinning. The resolved chemical shift anisotropy allows study of nuclear spin relaxation for the carbonate groups in the polymer that have different orientations relative to the static magnetic field in the laboratory frame. The spin-lattice relaxation time in the rotating frame (T_1?) is measured at a motional-probe frequency of 50 kHz for the undiluted polymer and for BPAPC-diluent blends containing either dibutylphthalate or dinitrobiphenyl. The T_1? exhibits some dependence on orientation in all systems studied. In the blend containing dibutylphthalate (DBP), T_1? is decreased by a factor of two for all orientations of the carbonate group. This implies that DBP substantially increases the spectral density of 50 kHz motions in the carbonate region of the polymer at ambient temperature. In contrast, dinitrobiphenyl does not significantly alter the Fourier component of thermal fluctuations at 50 kHz. Dielectric relaxation measurements at 10 kHz reveal that the primary (T_g) and secondary (β) motional processes in BPAPC are affected by low molecular weight additives. An intermediate relaxation process appears in the temperature interval between the glass transition temperature (T_g) and the sub-T_g β-relaxation (T_β) in the polymer-diluent blends. The n.m.r. spin-lattice relaxation rate in the rotating frame, T^?1_1?, correlates well with the relative magnitude of the dielectric dissipation factor (tan δ_ε) between T_g and T_β.     

锰掺杂对PNW-PMS-PZT压电陶瓷结构和性能的影响

采用传统陶瓷工艺制备了Pb(Ni1/2W1/2)O3-Pb(Mn1/3Sb2/3)O3-Pb(Ti，Zr)O3-xMnO2压电陶瓷，分析了经1150℃烧结2h制备的陶瓷样品的相结构组成。实验结果表明：所有陶瓷样品均为钙钛矿相，未发现其它晶相。随着锰掺杂量的增加，陶瓷晶粒逐渐长大。研究了不同剂量的锰掺杂对压电陶瓷介电和压电性能的影响。结果表明：随着锰掺杂量的增加，材料逐渐变“硬”，当MnO2掺杂量少于0．2％(按质量计，下同)时，相对介电常数εr、压电常数d33和机械品质因数Qm逐渐增加，介电损耗tanδ减小；当MnO2掺杂量多于0．2％时，εr、d33和Qm逐渐降低，tanδ增加。随着锰掺杂量的增加，机电耦合系数kp和Curie温度θc逐渐减小。MnO2掺杂量为0．2％的压电陶瓷适合制作大功率压电陶瓷变压器。其压电性能为：εr=2138，tanδ=0．0058，kp=0．613，Qm=1275，d33=380pC／N和θc=205℃。     

Dielectric properties of polyarylate (PAr) around the glass transition

Dielectric characterization of the α-relaxation in polyarylate (PAr) has been carried out by means of a dielectric spectroscopy technique in a frequency range of 10–30 kHz. Complementary thermally stimulated depolarization currents (TSDC) and differential scanning calorimetry d.s.c.) measurements have also been performed. The results are interpreted in terms of the standard Cole-Cole plot and Havriliak-Negami distribution for the dielectric relaxation times. Information about the temperature and frequency dependence of a.c. conductivity is also obtained from the experimental curves. However, the behaviour of the main dielectric relaxation time is deduced from the experimental data in a wide range of temperature around the glass transition. This behaviour results in close agreement with the theoretical predictions of a free-volume approach for the dielectric α-relaxation recently proposed by the authors.     

聚酰亚胺/二氧化硅杂化膜的制备与介电性能的研究

采用溶胶-凝胶法制备了BTDA-ODA聚酰亚胺/SiO2杂化膜,利用红外分光光度计（FTIR）、热重分析仪（TGA）和透射电镜（TEM）研究了杂化膜的微观结构和热性能,并对杂化膜的介电常数（e）和介电损耗（tand）随SiO2粒子含量和电场频率的变化进行了分析和讨论。结果表明：杂化膜的介电常数和介电损耗随SiO2粒子含量的增加而增大,随电场频率的升高而逐渐降低,用考虑到粒子的形状因素和两相间相互作用的EMT模型可以预测聚酰亚胺/SiO2杂化膜的介电常数。     

Stochastic defect diffusion model for relaxation effects in crystalline polyethylene

It is suggested that some relaxation processes observed in crystalline polyethylene are consequences of the diffusive motion of a particular defect called a point dislocation or twist dispiration loop along the polyethylene stems in lamellar crystals. The motion of the defect, characterized by a diffusion coefficient and a mobility, is described by solutions of the Smoluchowski diffusion equation with boundary conditions that constrain the defect to move along routes that produce experimentally observable results. The fact that passage of the defect causes both a 180° rotation of the chain and moves an extra CH₂ group in the direction of the chain axis is important to the interpretation of the data according to this model. The diffusion coefficient for a defect is estimated to be around 2 × 10^?9 cm² s^?1 at 70°C. This value is shown to be reasonable both from the viewpoint of detailed computer modelling of defect motion and contemporary ideas about scaling.     

Hygrothermal aging of rubber‐modified and mineral‐filled dicyandiamide‐cured DGEBA epoxy resin. III. Dielectric spectroscopy investigation

The effects of moisture absorption on the dielectric properties of a rubber‐modified, mineral‐filled, epoxy resin based on the diglycidyl ether of bisphenol A cured with dicyandiamide are reported. Samples of the resin were aged by immersing in deionized water, or 5% w/w NaCl solution, at elevated temperatures. Dielectric measurements were carried out over the frequency range 10^?1 to 6 × 10⁵ Hz. A featureless dielectric spectrum was observed with both real and imaginary dielectric permittivity increasing with the amount of absorbed water. The change in the dielectric properties with absorption of water was independent of presence of salt, temperature of exposure, and aging history, although a hysteresis of the hydration–dehydration process was observed at low frequencies. Two types of absorbed water were observed—water molecularly dispersed within the epoxy matrix and clustered water in spherical microcavities. The time dependence of the real dielectric permittivity measured at 10 kHz was found to closely resemble that of the water absorption, which allowed the activation energy of diffusion to be calculated from both dielectric and gravimetric data. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 1011–1024, 2002; DOI 10.1002/app.10368     

New approach for the preparation of nanoporous polyorganosilicate low‐k films

The distribution of pores and the mechanical properties of materials are the key factors in preparing satisfactory low‐k films. In the present study, a kind of silsesquioxane‐polyethylene glycol (SSQ‐PEG) was synthesized and used as a template to make the distribution of pores more even in the low‐k films. The crosslinking density of films could be adjusted by the sol‐gel of tetramethoxysilane/dimethoxydimethylsilane with various proportions. The porosity of films could also be adjusted with different proportions of pendant PEG chains introduced. A dielectric constant as low as 2.1 had been achieved for nanoporous polyorganosilicate films with good tenacity. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 1238–1243, 2007     

Effect of the matrix crystallinity on the percolation threshold and dielectric behavior in percolative composites

Through the use of polyethylenes with different crystallinities as matrices, the effects of the matrix crystallinity on the percolation threshold and dielectric behavior of percolative composites have been investigated. The results suggest that the percolation threshold is negatively related to the matrix crystallinity, whereas the enhancement of the dielectric constant is positively related to the matrix crystallinity. A two‐dimensional diagram is proposed to illustrate such relationships. In addition, it has been found that the insulator–conductor transition is much flatter in low‐crystallinity‐matrix‐based composites, and this may be favorable for preparing threshold composites with a high dielectric constant and a low loss tangent. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2007     

The Effects of Phenyltrimethoxysilane Coupling Agents on the Properties of PTFE/Silica Composites

A study on PTFE reinforced with SiO₂ was described. This study included the manufactural process of SiO₂-reinforced PTFE and the effects of the content of silane (Z6124) on the properties of the composites material, such as thermal, dielectric properties, tensile strength and morphology, etc. PTFE/silica composites of 60 wt% SiO₂ loaded with a different coupling agent content were mixed by a high-speed dispersion machine and prepared by a two-roll milling machine. Our results show that the sample treated with 3 wt% silane has the highest tensile strength and optimum dielectric properties. Furthermore, the tensile strength and coefficient of thermal expansion (CTE) increase, and the water absorption decreases, with an increasing silane content. These experiments reveal that silane treatment can reduce the overall hydrophilicity of the composites. Finally, predictions on dielectric and CTE properties are discussed. It has been found that experimental values of the dielectric constant agree well with those predicted by the rule of mixture.     

Silicon‐containing heterocyclic polymers and thin films made therefrom

Thin films, in the range of tens of micrometers thickness, have been prepared by casting onto glass plates the chloroform or N‐methylpyrrolidone solutions of polyimides or poly(imide‐amide)s containing silicon and phenylquinoxaline units in the main chain. The polymers have been synthesized by solution polycondensation reaction of aromatic diamines having preformed phenylquinoxaline rings with bis(3,4‐dicarboxyphenyl)dimethylsilane dianhydride or with a diacid chloride resulting from the reaction of this dianhydride with p‐aminobenzoic acid. The polymers were easily soluble in polar aprotic solvents and showed high thermal stability. The free‐standing films exhibited good mechanical properties with tensile strengths in the range of 48–86 MPa, tensile modulus in the range of 1.25–2.22 GPa and elongation at break in the range of 3–37%. Electrical insulating properties of some polymer films were evaluated on the basis of dielectric constant and dielectric loss and their variation with frequency and temperature. The values of the dielectric constant at 10 kHz were in the range of 2.94–3.08 for polyimides and 3.89–4.49 for poly(imide‐amide)s. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3062–3068, 2006