聚合物压电智能材料研究新进展

聚合物压电材料已经有近 4 0的历史 ,近年来由于被用于智能材料而引起更多研究工作者的关注。本文介绍了聚合物产生压电性能的机制、分类 ,判断、评价聚合物压电性能的基本参数和指标 ,分析了不同形态聚合物压电材料的结构要求及微观机理 ,介绍了材料取向、极化机制与方法。讨论了其主要表征和基本模拟方法 ,并对压电聚合物材料的优良性能、应用与发展前景作出了简要说明     

Ferrocene-containing polymers. I. Radiation-induced polymerization of ferrocenylmethyl methacrylate

γ-Ray-induced polymerizations of ferrocenylmethyl methacrylate (FMMA) in crystalline and amorphous states were investigated with kinetical and ESR methods. In the crystalline state the polymerization of FMMA proceeded slowly and gave low-molecular-weight polymers, whereas in the amorphous state it proceeded rapidly and gave polymers of much higher molecular weight. Molecular weight distributions of these polymers were binodal. The temperature dependence and the dose-rate dependence of the polymerization rates were different between the two states. Wide-line nuclear magnetic resonance (NMR) spectra of the amorphous monomer suggested that the polymerization proceeded in a supercooled state. Electron spin resonance (ESR) spectra of γ-irradiated FMMA and 1,1′-ferrocenyl-di(methyl methacrylate) showed that ferrocene radicals and methacrylic radicals were formed simultaneously at low temperature; with increasing temperature the former radicals disappeared, whereas the latter changed into growing chain radicals. The yields of radicals were relatively low; this means that ferrocene groups in the monomers behave as a radiation energy absorber.     

非晶态与晶态的压电热电铁电高聚物

本文综述了晶态与非晶态两类高聚物的压电性,热释电性和铁电性。这些现象近年来研究得愈来愈广泛。文中以聚氯乙烯作为非晶态高聚物的例子;以PVDF及其共聚物,还有尼龙11作为晶态高聚物的例子。按照偶极子模型,高聚物一般假定需具备四个条件,就可显示出较大的压电性,热释电性和铁电性。本文探讨了上述高聚物的结构与性能,这些对识别材料是很重要的。最后,列举了PVDF及其它材料的压电常数,热释电系数和介电常数,以供读者参考。     

压电高分子材料

本文介绍了有关压电性高分子材料研究的新进展及近几年来对于聚偏腈乙烯、聚酰胺、聚氯乙烯、聚磷腈等压电性的研究结果,并就高分子偶极结构、结晶性等因素与其压电性的关系进行了讨论.     

Piezoelectric properties and molecular motion of poly(β-hydroxybutyrate) films

Piezoelectric, elastic, and dielectric properties of films of poly(β-hydroxybutyrate) (PHB), an optically active natural polymer, were measured as functions of frequency and temperature. In mechanical properties, three relaxation processes were observed at 10 Hz: the α dispersion at 130°C, the β dispersion at room temperature, and the γ dispersion at ?120°C. It was concluded from x-ray diffraction and the thermal expansion coefficient that the α dispersion can be ascribed to thermal molecular motions in the crystalline phase, that the β dispersion is the primary dispersion due to the glass transition, and that the γ dispersion is related to local molecular motion of the main chains in the amorphous phase. Piezoelectric relaxations were also observed in these relaxation regions. It is proposed that the high-temperature process is due to ionic dc conduction. The piezoelectric relaxation at room temperature is ascribed to the increase of piezoelectric activity in the oriented noncrystalline phase, in which the sign of the piezoelectric modulus is opposite to that in the oriented crystalline phase.     

用微模塑直接在聚合物曲面上制备微图形

用聚二甲基硅氧烷制备的,表面复制有微图形的"弹性印章"直接在聚乙烯,聚丙烯,聚苯乙烯和聚甲基丙烯酸甲酯等热塑性聚合物表面上进行热微模塑,无需复杂设备并可在普通实验室条件下,复制微图形,甚至在小试管外壁的曲面上或在用毛细管形成的微突起表面上也能制备出微曲面图形.讨论了不同聚合物对生成微图形的影响,认为结晶性聚合物以及在温度变化时有较大收缩率的聚合物在微模塑中难以获得清晰图形.无定形聚合物如聚苯乙烯和聚甲基丙烯酸甲酯等能够获得清晰的微结构.     

Studies on the effects of the alkyl group on the surface segregation of poly(n-alkyl methacrylate) end-capped 2-perfluorooctylethyl methacrylate films

The effects of the alkyl group on the surface segregation of poly(n-alkyl methacrylate) end-capped with various numbers of units of 2-perfluorooctylethyl methacrylate (FMA) (PnAMA-ec-PFMA) were investigated by differential scanning calorimetry, angle-resolved XPS analysis, contact angle measurements, and X-ray diffraction (XRD). The results show that with similar numbers of FMA units at the polymer chain end the extent of fluorine segregation (Q) increased with increasing the number of carbon atoms in the side n-alkyl chains of poly(n-alkyl methacrylate). The surface fluorine content within 5 nm deep of the film of poly(n-octadecyl methacrylate) end-capped with one FMA unit (PODMA(160)-ec-PFMA(1.0)) was 208-fold higher than that of the bulk level. These observed differences in Q values were found due to the aggregate structure of the end-capped polymers in the solution, the flexibility, and the crystallinity of the n-alkyl side chains. When the nonfluorinated block was completely amorphous, the molecular aggregate structure of the end-capped polymers in the solution played an important role in the surface segregation of the fluorinated moieties on the resulting film. However, when the nonfluorinated block was crystalline, crystallinity would enhance greatly the segregation of the fluorinated moieties.     

The Nonlinear Viscoelastic Response of Glassy Polymers Subjected to Physical Aging

Constitutive equations are developed for the nonlinear viscoelastic behavior of amorphous glassy polymers in the sub‐yield region. A polymeric glass is treated as an ensemble of cooperatively rearranging regions bridged by links. Stress‐strain relations are derived and verified by comparison with experimental data in static mechanical tests on polycarbonate and poly(methyl methacrylate). We analyze the effects of the straining state (tension, compression and torsion), strain intensity, temperature and time of annealing on stress relaxation. Fair agreement is demonstrated between observations and results of numerical simulation.     

Temperature variation of piezoelectric moduli in oriented poly(γ-methyl L-glutamate)

The real and imaginary components of the complex piezoelectric strain constant, which relates the polarization to the applied stress, have been determined for elongated films of poly(γ-methyl L -glutamate) over the temperature range ?170°C to +170°C at a frequency of 20 Hz. The variation of the piezoelectric constant with temperature is similar for both α-helical and β-form molecular conformations. The sign of piezoelectric polarization is opposite for L and D polymers. A simple model, representing the piezoelectric crystallites as embedded in nonpiezoelectric amorphous regions, is proposed to account for the piezoelectric temperature dispersion curves.     

Highly Transparent and Adhesive Poly(vinylidene difluoride) Films for Self-Powered Piezoelectric Touch Sensors

With the rapid development of internet of things, self-powered touch sensors made of piezoelectric fluorinated polymers have attracted significant interest because they can constantly convert mechanical energy into electrical energy without external power supply.However, it is still challenging to fabricate fluorinated polymer films with good adhesion and high output performance with a large-scale and low-cost method while maintaining high transparency, which are extremely important for simultan...     

The initiation of polymerization by organoaluminium amides

Two organoaluminium amides have been used to initiate the polymerizations of methyl methacrylate, acetaldehyde and n-butyraldehyde. Methyl methacrylate polymerized through the vinyl function to give amorphous products. The aldehydes reacted through the carbonyl group at low temperatures with high degrees of stereospecificity to give polymers with substantial crystallinity. The molecular weight of the polyacetaldehyde is very high.     

Effect of fullerene C60 on the structure and mechanical properties of thin films based on poly(methylmethacrylate) and other carbochain vinyl polymers: A technological aspect

The effect of fullerene C₆₀ on the structure and mechanical properties of poly(methyl methacrylate) films are studied via the methods of X-ray diffraction, mechanics, and optical and atomic-force microscopy. The findings of this study are verified with the use of the data obtained for amorphous and semicrystalline samples of other polymers, primarily carbochain polymers of the vinyl series, such as polyethylene, polypropylene, and polystyrene.     

Mass and momentum transfer in polymers. III. Effects of liquid penetrants on tensile stress relaxation of amorphous polymers

Sorption, diffusion, swelling, and tensile stress relaxation measurements were made at room temperature (23°C) for the systems poly(n-butyl methacrylate) (PBMA) with liquid methanol and ethanol, and poly(methyl acrylate) (PMA) with liquid water. Stress relaxation curves for the fully swollen polymers could be superimposed approximately with those for the dry polymers by appropriate shifting along the long axes. For PMA–water the measured curve for stress relaxation with concurrent sorption could be predicted accurately by using a moving boundary theory with data measurements of stress relaxation of the unswollen and swollen polymer combined with sorption data. The modified moving boundary theory is generalized to include the effects of dimension changes through swelling and the larger effects of plasticization associated with sorption of liquids. This improved theory accurately predicts measured curves of stress relaxation with concurrent sorption for the PBMA–alcohol systems from individual stress relaxation, sorption, diffusion and swelling data. The general approach should be applicable to other amorphous polymer–liquid swelling agent systems. The anisotropic nature of swelling of polymer films and its effect on calculated diffusion coefficients are discussed briefly.     

Study on the concentration effects in size exclusion chromatography VII. A quantitative verification for the model theory of concentration and molecular mass dependences of hydrodynamic volumes for polydisperse polymers

A model theory of concentration effects for polydisperse polymers was proposed in 1988. It is successful in relating the concentration of the injected solution to the effective hydrodynamic volumes of peak, the retention volumes of peak and the polydispersity index (Dc = (Vhcw)/(Vhcn) of hydro-dynamic volume distribution for polydisperse polymers at a given concentration. The dependence of the concentration of injected polymer solution on the effective hydrodynamic volumes, the retention volumes of peak and the polydispersity index of hydrodynamic volume distribution for narrow disperse and polydisperse polystyrene, poly(dodecyl methacrylate), poly(tridecyl methacrylate) and poly(methyl methacrylate) in tetrahydrofuran solvent were studied. The proposed theory was verified by these experimental data. Results show that the proposed theory can predict the concentration effects in GPC for polydisperse polymers quantitatively and can provide a theoretical foundation for the two methods of calibrating the universal calibration curves with polydisperse polymers and of determining the second virial coefficients (A2) of polymers. It is found that the determined values of A2 for narrow disperse and polydisperse polymers by the proposed method are in agreement with those obtained by the LALLS method, and the two universal calibration curves with narrow disperse and polydisperse polymers are in excellent agreement.     

Growth regimes and spherulites in thin-film poly(ɛ-caprolactone) with amorphous polymers

Spherulite ring-band patterns and growth regimes in neat poly(?-caprolactone) (PCL) and its miscible blends were analyzed using polarized-light optical microscopy and differential scanning calorimetry (DSC). Spherulite growth in thin-film forms and transformation of spherulite patterns in different regimes were investigated by comparing neat PCL with its miscible blends. Three miscible diluents in PCL were probed: poly(p-vinyl phenol) (PVPh), poly(benzyl methacrylate) (PBzMA), and poly(phenyl methacrylate) (PPhMA), which represent strong H-bonding and weak polar interactions, respectively. Blending of PCL with miscible amorphous polymers changes the spherulite patterns significantly. The effect of different diluent polymers varies. Inclusion of different amorphous polymers in PCL leads to different extents of suppression in growth rates and induces different spherulitic patterns. The H-bonding interaction leads to that the PCL/PVPh blend shows dendritic crystals and no ring bands. Although PPhMA differs from PBZMA only by a methylene in the chemical structure of repeat unit, the coil-like textures of ring bands in the PCL/PPhMA blend are widely different from the zig-zag ring bands in the PCL/PBzMA blend. Regime plots show that the growth of neat PCL behaves quite differently from any of its blends with amorphous polymers (PVPh, PPhMA, or PBzMA). Regime plots for PCL/PBzMA blend also differ from those for the PCL/PPhMA blend, which correlates with the crystal patterns seen in these two blend systems.     

Radiation-induced polymerization of vinyl monomers adsorbed on inorganic substances. VI. Temperature dependence and effects of additives on methyl methacrylate–silica gel system

To elucidate the reaction mechanism of radiation-induced polymerization of methyl methacrylate adsorbed on silica gel, the temperature dependence and effects of acetone and pyridine were investigated. It was found that even at ?78°C the polymerization rate was quite fast. The amounts of high molecular weight GPC peaks of both graft polymers and homopolymers increased with increasing irradiation temperature. The activation energy of the adsorbed state polymerization was low compared with that of bulk polymerization. The low molecular weight peaks of homopolymers decreased with acetone addition but were almost unaffected by pyridine. The low molecular weight peaks of homopolymers were thus polymerized by an anionic mechanism. In the methyl methacrylate–silica gel system both radical and anionic polymerization take place at the same time in formation of graft polymers and homopolymers. A reaction mechanism for the methyl methacrylate–silica gel system was proposed based on the results obtained to date.     

压电晶体传感器的研究进展

本文简要介绍了压电晶体传感器的基本原理,以及基于质量、粘度、电导率变化的溶液分析法。重点介绍了电化学石英晶体微天平（EQCM）、压电生物传感器;对具有很大发展潜力和重要应用价值的串联式压电传感器（SPQC）、串联式表面声波电导传感器（SAW）、液隔电极式压电传感器（ESPS）等也作了简要说明。     

Piezoelectric detectors coated with liquid-crystal materials

The usefulness of liquid crystals as coating materials for quartz resonators in piezoelectric detectors of air-pollution has been tested. The concentration characteristics of the detector with respect to benzene, toluene, chlorobenzene, o- and m-dichlorobenzene, nitrobenzene, and o-, m- and p- diethylbenzene have been determined with the use of 4-pentyl-4'-cyanodiphenyl, 4-pentyl-4'-propylazo-benzene, 4-propyl-4'-methylazoxybenzene, and cholesteryl oleylcarbonate as coating materials. The effects of the quantity of coating material and of temperature on the sensitivity of the piezoelectric detector have been tested. The influence of the ordered structure of the liquid-crystal coating materials on the selectivity of the detector is discussed. Experiments have been performed to test the usefulness of the detector with liquid-crystal coating for detecting organophosphorus pesticides (DDVP and Phosdrin).     

压电胰岛素-C肽微阵列免疫传感器研究

以AT切型、基频10MHz的镀金膜石英晶体作为换能器,将抗人胰岛素和C肽单克隆抗体固定在石英晶体电极表面,用2×5检测池固定夹具构建一种新型压电胰岛素-C肽微阵列免疫传感器.研究了抗体固定方法、抗体工作浓度、固定量、一致性以及传感器的响应参数如检测温度、时间和特异性等的影响.该微阵列传感器在胰岛素浓度为2.5～160.0mIU/L、C肽浓度为0.375～12.0ng/mL范围内响应特性良好,压电晶体频率偏移值与胰岛素和C肽浓度呈良好的线性关系.将此微阵列传感器用于人血清标本的测定,结果与放射免疫法符合(r为0.92和0.94).此微阵列传感器具有灵敏度高、特异性好,低密度阵列结构,检测通量较高,不需标记,操作简单、能实时在线检测和重复使用等优点,能用于临床实验诊断,具有临床推广应用价值.