梳状高分子固体电解质的离子导电性研究

深入研究了交替马来酸酐共聚物多缩乙二醇酯（ＣＰ３５０）两种锂盐络合物ＣＰ３５０／ＬｉＡｓＦ＿６和ＣＰ３５０／ＬｉＰＦ＿６的离子传导性能,给出了与复阻抗谱相对应的等效电路．离子电导率随［Ｌｉ］／［ＥＯ］的变化而出现一极大值,室温下,两体系电导率极大值分别为１．３８×１０（－４）,８．３２×１０（－５）Ｓ／ｃｍ．电导率随温度升高而增加．导电行为呈非－Ａｒｒｈｅｎｉｕｓ特征．阴阳离子半径之和（ｒ＿ｃ＋ｒ＿ａ）愈大,离子电导率愈高．     

无定形梳状高分子固体电解质的二重玻璃化转变及典型VTF…

研究了交替马酸酐共聚物多缩乙二醇酯（ＣＰ３５０）－ＬｉＮＯ３络合物的热行为及离子导电性。实验表明：ＣＰ３５０／ＬｉＮＯ３络合物在所研究的［Ｌｉ］／［ＥＯ］配比范围呈均相无定形并具有二重玻璃化转变。２个玻璃化转变温度均随盐含量的增加而上升。离子电导率随盐浓度的变化出现１个极大值，室温电导率最大可达３．７２×１０＾－５Ｓ／ｃｍ。导电行为呈典型ＶＴＦ特征。     

一种梳状高分子固体电解质的分子运动和离子导电性

用交流复阻抗谱和动态粘弹谱等对交替马来酸酐共聚物多缩乙二醇酯衍生物及其ＬｉＣｌＯ４盐复合物进行了研究．结果表明，在Ｌｉ／ＥＯ＝０．０７—０．０４２范围内，从１７３Ｋ到３７３Ｋ，本聚合物一高氯酸锂复合体系的动态粘弹谱存在着两个明显的转变，其中β转变归属于ＰＥＯ的侧链玻璃化转变，转变温度随ＬｉＣｌＯ４盐浓度的增加而增加。α转变归属于主链玻璃化转变，在Ｌｉ／ＥＯ＝０．０２８时有极大值。盐浓度与电导率的关系与通常不一样，在所研究盐浓度范围内观察到两个峰，其一在Ｌｉ／ＥＯ＜０．０１４，另一峰在Ｌｉ／ＥＯ＝０．０２８．电导率与温度的依赖关系不符合Ａｒｒｈｅｎｉｕｓ行为；以ｌｇσ对１／Ｔ－Ｔ０作图，用侧链玻璃化转变温度Ｔβ作Ｔ０时，呈典型的ＶＴＦ行为。该体系室温电导率最高可达６×１０－６ｓ／ｃｍ．     

无定形梳状高分子固体电解质的二重玻璃化转变及典型VTF特征

研究了交替马来酸酐共聚物多缩乙二醇酯(CP350)-LiNO₃络合物的热行为及离子导电性。实验表明:CP350/LiNO₃络合物在所研究的[Li]/[EO]配比范围呈均相无定形并具有二重玻璃化转变。2个玻璃化转变温度均随盐含量的增加而上升。离子电导率随盐浓度的变化出现1个极大值,室温电导率最大可达3.72×10^-5S/cm.导电行为呈典型VTF特征。     

新型梳状高分子固体电解质的研究（Ⅱ）

新型梳状高分子固体电解质的研究（Ⅱ）丁黎明，林云青，梁洪泽，汪东梅，王佛松（中国科学院长春应用化学研究所长春１３００２２）关键词梳状高分子，ＮａＣＩＯ＿４络合物，固体电解质，离子电导率聚环氧乙烷（ＰＥＯ）可以溶解多种碱金属盐并形成络合物，这种络合物具...     

主链玻璃化转变区在室温附近的梳形聚合物电解质

主链玻璃化转变区在室温附近的梳形聚合物电解质＊齐力林云青夏永姚王佛松（中国科学院长春应用化学研究所长春１３００２２）关键词梳状高分子，固体电解质，离子导电性，玻璃化转变，分子运动＊１９９４－１０－３０收稿；１９９５－１２－１０修稿７３２高分子固体电解...     

聚合物电解质的玻璃化转变温度与离子解离的关系

采用动态力学和数学拟合相结合的方法，研究了聚环氧乙烷环氧丙烷－LiCIO4体系的离子解离与缔合。结果表明：Tg的增加依赖于盐浓度和环氧乙烷（EO）与环氧丙烷（PO）的比例，并且玻璃化转变温度（Tg）的增加可以用一个简单的溶解平衡解释，进而得出平衡常数X和离解度α。     

梳状聚合物电解质的合成与表征

用1H -NMR方法对苯乙烯 /马来酸酐共聚物多缩乙二醇酯的合成进行了表征 ,说明用1H -NMR的方法进行该类化合物的合成研究是简便准确的。并且通过热失重对该电解质的热稳定性进行了研究。     

聚合物单阳离子导体的制备—羧酸型梳状单离子导体

本文报道一种制备聚合物单阳离子导体的新方法。马来酸酐－醋酸乙烯酯及马来酸酐－苯乙烯共聚物以聚乙二醇单甲醚醇解，使酸酐环打开而得到带有聚乙二醇侧链的羧酸型梳状聚合物，其锂盐在加入适当增塑剂成膜后，可作为聚合物单阳离子导体，其结构以非晶态为主，具有较低的玻璃化转变温度及较好的热稳定性，增塑后的室温电导率最高可达１０＾－６Ｓ／ｃｍ。此外还研究了聚合物结构、阳离子半径、增塑剂、温度及外加额率等因素对电导率     

多功能梳状聚合物电解质的合成及其性能

以聚乙二醇单甲醚(PEGME)为侧链,马来酸酐/1-十八碳烯交替共聚物(PMAO)为骨架,制备出具有生物相容性的多功能梳状聚合物(PMAO-PEGME).该聚合物分别与 CH3OH 和LiOH 反应,制得梳状马来酸酐/1-十八碳烯交替共聚物多缩乙二醇酯(PMAO-PEGME-ME)和单离子聚合物电解质(即梳状马来酸酐/1-十八碳烯交替共聚物多缩乙二醇酯羧酸锂 PMAO-PEG-MELi),用FT-IR、1H-NMR、DSC、交流复阻抗谱等对得到的聚合物电解质进行了表征.结果表明:随着 LiClO4浓度的增加,PMAO-PEGME-ME/LiClO4 体系的电导率呈现先上升后下降的变化趋势,符合通常的聚合物电解质电导率与盐浓度的依赖关系.当每千克聚合物中含 1.5 mol Li-ClO4时,电导率达到最大值,室温下为 1.01×10-5S/cm.PMAO-PEGMELi 的室温电导率可达3.57×10-7S/cm.     

三取代过渡金属钨镓杂多配合物的磁性及导电性能研究

合成了过渡金属三取代的钨镓杂多配合物:α-Na~nH~m[GaW~9O~3~7M~3(H~2O)~3]·xH~2O[M=Fe(Ⅲ), Cu(Ⅱ), Co(Ⅱ)]。通过元素分析、红外、紫外、^1^8^3W NMR以及热分析等手段进行了表征, 变温磁化率数据显示了配合物具有反铁磁特征。电导率测定结果表明所合成的配合物是迄今未见文献报道的过渡金属三取代杂多配合物高质子导体, 室温下GaW~9Fe~3的σ值可达10^-^3S·cm^-^1, 其特点是热稳定范围宽, 不易失水, 可望成为能实用化的杂多酸型固体电解质。     

过渡金属离子与明胶相互作用的研究

利用荧光猝灭法,研究了pH值10.0,不同温度下,Mn^2+,Co^2+,Ni^2+,Hg^2+与明胶的相互作用。计算了猝灭常数、螯合平衡常数和结合位点数。紫外光谱和显微红外光谱的测定结果表明,Mn^2+,Co^2+,Ni^2+与明胶分子中的酰胺键发生了作用。确定了猝灭机理。计算得出的热力学函数表明,在Mn^2+,Co^2+,Ni^2+对明胶荧光的猝灭过程中,熵效应起着重要的作用。     

BaxCe0.8Y0.2O3-α固体氧化物燃料电池性能

用高温固相反应法合成了BaxCe0.8Y0.2O3-α（x=1.03,1,0.98)系列固体电解 质，用粉末X射线衍射法研究了样品的晶体结构，用氢及氧浓差电池方法研究了样 品的质子及氧离子导电特性，测定了它们的氢－空气燃料电池的放电性能。结果表 明，各样品均为钙钛矿斜方晶单相结构；质子导电和燃料电池输出电流密度均随样 品中钡离子含量的增加而增大，Ba1.03Ce0.8Y0.2O3-α具有最大的质子导电性和燃 料电池输出电流密度；各样品的氧离子导电性几乎不受钡离子含量影响。     

一种新型24-冠-8醚推动钠离子转移的机理研究

本文应用计时电位法和电流扫描极谱法研究了一种新冠醚, 2,3,14,15-四(邻甲氧基)苯基-1,4,7,10,13,16,19,22-八氧杂-二十四环-2,14-二烯(BDI,1),在两相分配时对水相中Na^+推动转移机理。     

Cr^3^+的水解聚合作用IV.两种"根+节"体系之间的过渡状态

The hydrolytic polymerization of chromium (III) ion in 0.040, 0.060, 0.080 and 0.160M Cr(NO3)3 solutions was studied pH-metrically in the medium of 0.5M NaNO3 at 40+/-1 C. The average number of OH- bound per Cr^3^+ at different pH was designated as Z, the gighest value of Z was found to be about 1.0. A family of curves of Z(pH)B, each at a definite concentration B of Cr(NO3)3, was obtained. The values of both B and pH were determined from the curves and a linear relationship between -lgB and pH was found for each value of Z. From the slope of each curve of-lgB(pH)z, a value of t was obtained, which increased from 1.51 to 2.06 when Z increased from 0.10 to 1.0. This implied that the polymerized hudrolysis products were of mixed types. The data of different Z value were treated by three different methods, namely, "core + links" method, project strip method and "homoligand formation constant" method. The results obtained showed the existence of "core + links" compounds not only with two hydroxyl bridges as Cr (Cr(OH)2)n^(^3^+^n^)^+(n = 1,2,3) but also with both one and two hydroxy bridges as Cr3(OH)3, indicating that the present system was a transition from t = 2 to t = 1. The hydrolysis constants of the above compounds are as follows: lgβ = -4.19, lgβ33 = -5.28, lgβ = -8.23, lgβ64 = 12.28. The above results are in agreement with those obtained at low and medium concentration of Cr(NO3)3. Furthermore, the constants obtained by means of different methods are in good agreement with each other as well as with those reported in previous papers.     

A two dimensional coordination polymer based on drug ligand enoxacin and transition metal ion

A two-dimensional coordination polymer, [Mn(Enox)₂]·4H₂O, 1 (H-Enox?=?1-ethyl-6-fluoro-1,4-dihydro-4-oxo-7-(1-pierazinyl)-1,8-naphtyridine-3-carboxylic acid), has been rationally designed and synthesized under hydrothermal conditions. Compound 1 is self-assembled from bifunctional drug ligand enoxacin and transition metal ion Mn(II) through covalent coordination bonds and hydrogen bondings.     

A study on the glass transition behavior and morphology of semi-interpenetrating polymer networks

The epoxy resin/polyurethane semi-IPN was prepared and the glass transition behavior of the semi-IPN was discussed with DSC and DMA methods. The results show that the two glass transition temperatures (T_g) referring to epoxy resin and polyurethane respectively get closer. Between the two T_g there exists another T_g related to the interface between the two polymers. SEM indicates that this semi-IPN has a two-phase continuous structure which changes with different weight compositions. This is also proved by testing the Young's modulus. It is found that the IPN system has a cellular structure. Comparatively, the compatibility between the two polymers is the best when the weight ratio of EP/PU is 70/30. © 1996 John Wiley & Sons, Inc.     

The effect of glass transition on the self-oscillation regime of tensile drawing of a polymer

The effect of the transition of a polymer into its rubbery state at the glass-transition temperature on the character of the excitation of self-oscillation neck propagation is studied with numerical methods. To describe the rate of plastic yielding near the glass-transition temperature, the Eyring equation is modified by the introduction of the temperature dependence of the parameter related to the free volume. There are three intervals of strain rates. At low strain rates when the yield stress increases with an increase in the strain rate, neck propagation is stable and no oscillations are excited. At high strain rates, when the glass-transition temperature is achieved during stationary neck propagation, the excitation of oscillations shows a mild character and there exists a certain critical length of the samples below which no oscillations are excited. In the intermediate interval of strain rates, the excitation shows a severe character. In this case, the oscillations are excited when, in the transition region, the glass-transition temperature of the polymer is achieved owing to excitations. In strain-rate-sample-length coordinates, the diagram describing the regions of various oscillation behaviors of the samples is constructed.     

Effect of particle agglomeration and interphase on the glass transition temperature of polymer nanocomposites

In this article, we utilize finite element modeling to investigate the effect of nanoparticle agglomeration on the glass transition temperature of polymer nanocomposites. The case of an attractive interaction between polymer and nanofiller is considered for which an interphase domain of gradient properties is developed. This model utilizes representative volume elements that are created and analyzed with varying degrees of nanoparticle clustering and length scale of interphase domain. The viscoelastic properties of the composites are studied using a statistical approach to account for variations due to the random nature of the microstructure. Results show that a monotonic increase in nanofiller clustering not only results in the loss of interphase volume but also obstructs the formation of a percolating interphase network in the nanocomposite. The combined impacts lead to a remarkable decrease of T_g enhancement of clustering nanofillers in comparison with a well‐dispersed configuration. Our simulation results provide qualitative support for experimental observations that clustering observed at high nanofiller concentrations negatively impacts the effects of the nanofiller on overall properties. © 2011 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys, 2011     

高分子量聚全氟乙丙烯(Fs-46)耐辐照性质的研究

本文针对聚全氟乙丙烯(Fs-46)树脂的耐辐照性质, 对照研究了普通Fs-46树脂与分子量大于20万Fs-46树脂的耐辐照及抗热老化性质。在190±2℃饱和水蒸汽0.2~3.0kPa压力下, 经(γ-射线(1×10^6库仑)照射后, 再于200℃经4320小时的热老化模拟试验, 后者机械强度基本不变, 前者的机械强度明显下降。结果表明分子量大于20万的Fs-46树脂具有比普通树脂Fs-46更好的耐辐照和抗热老化性能。