磺酸型聚氨酯离聚物的离子导电性能

本文以多种聚醚为软段，二异氰酸酯（ＭＤＩ和ＴＤＩ）为硬段，合成了多嵌段聚醚聚氨酯，以此聚氨酯为基材，与ＮａＨ及１，３－丙碳酸内酯反应，进一步合成了一系列不同离子化程度的阴离子型碳化聚氨酯离聚物，用交流阻抗谱仪测定了样品的阻抗谱，由此计算出样品的离子电导率。研究结果表明其他条件相同时，以聚乙二醇（ＰＥＧ）为软段的样品具有较高的离子电导率；以聚环氧丙烷（ＰＰＯ）为软段的样品次之，以聚四氢呋喃（ＰＴＭＯ）为软段的样品最低，对于离子化程度不同的聚氨酯离聚物以金属离子和烷氧单元之比为０．０５时导电性能最好。阳离子为Ｌｉ＋和Ｎａ＋的样品具有相近的离子电导率。     

(Me3NEt)[Pd(dinit)2]2和(NEt4)[Pd(dinit)2]2的结构、能带及导电性

合成了导电分子晶体(Me3NEt)[Pd(dmit)2]2和(NEt4)[Pd(dmit)2]2,测定了它们的晶体结构和电导-温度曲线.在能带计算基础上解释了(Me3NEt)[Pd(dmit)2]2的室温电导率(б=58(Ω@cm)-1)高于(NEt4)[Pd(dmit)2]2(б=2.2(Ω@cm)-1)的原因.(Me3NEt)[Pd(dmit)2]2属单斜晶系,P21/m空间群;(NEt4)[Pd(dmit)2]2属三斜晶系,P 1空间群.两种晶体的导电组元皆为平面型配位阴离子[Pd(dmit)2]0 5-,它们以面对面形式的二聚体[Pd(dmit)2]21-存在.凭借肩并肩形式的S…S分子间相互作用,二聚体进一步形成二维导电分子层.两种配合物的二维导电分子层的微小结构差异导致电导率一个数量级的差别.变温电导测定还表明,两种晶体皆为小能隙的半导体.     

(Me_3NEt)[Pd(dmit)_2]_2和(NEt_4)[Pd(dmit)_2]_2的结构、能带及导电性

合成了导电分子晶体(Me3NEt)[Pd(dmit)2]2和(NEt4)[Pd(dmit)2]2, 测定了它们的晶体结构和电导-温度曲线. 在能带计算基础上解释了(Me3NEt)[Pd(dmit)2]2的室温电导率(σ= 58(Ω·cm)-1)高于(NEt4)[Pd(dmit)2]2 (σ= 2.2(Ω·cm)-1)的原因. (Me3NEt)[Pd(dmit)2]2属单斜晶系, P21/m空间群; (NEt4)[Pd(dmit)2]2属三斜晶系, P1 空间群. 两种晶体的导电组元皆为平面型配位阴离子[Pd(dmit)2]0.5-, 它们以面对面形式的二聚体 存在. 凭借肩并肩形式的S…S分子间相互作用, 二聚体进一步形成二维导电分子层. 两种配合物的二维导电分子层的微小结构差异导致电导率一个数量级的差别. 变温电导测定还表明, 两种晶体皆为小能隙的半导体.     

(Me3NEt)[Pd(dmit)2]2和(NEt4)[Pd(dmit)2]2 的结构、能带及导电性

合成了导电分子晶体(Me₃NEt)[Pd(dmit)₂]₂和(NEt₄)[Pd(dmit)₂]₂ , 测定了它们的晶体结构和电导-温度曲线. 在能带计算基础上解释了(Me₃NEt)[Pd(dmit)₂]₂的室温电导率(δ = 58(Ω·cm)^-1)高于(NEt₄)[Pd(dmit)₂]₂ (δ = 2.2(Ω·cm)^-1)的原因. (Me₃NEt)[Pd(dmit)₂]₂属单斜晶系, P2₁/m空间群; (NEt₄)[Pd(dmit)₂]₂ 属三斜晶系, P 空间群. 两种晶体的导电组元皆为平面型配位阴离子[Pd(dmit)₂]^0.5-, 它们以面对面形式的二聚体 存在. 凭借肩并肩形式的S…S分子间相互作用, 二聚体进一步形成二[Pd(dmit)₂]₂^1-维导电分子层. 两种配合物的二维导电分子层的微小结构差异导致电导率一个数量级的差别. 变温电导测定还表明, 两种晶体皆为小能隙的半导体.     

影响离子导电高分子材料性能的内因与外因

材料分子设计离不开结构与性能的关系。分析内因与外因两方面影响因素对材料功能特性的影响有助于优化功能材料的结构。本文以离子型导电功能高分子材料为例,详细分析了各种因素对材料电导率的影响,为离子型导电功能高分子材料的结构设计提供依据。     

钼（Ⅵ）—4—（2—苯并噻唑偶氮）邻苯二酚多元络合物显色体系及其应用…

ｐＨ４．５时，Ｍｏ（Ⅵ）与显色剂４－（２－苯并噻唑偶氮）邻苯二酚反应形成带负电荷的稳定紫红色１：２二元络合物。４０％丙酮水溶液中λｍａｘ为５６０ｎｍ，表观ε５６０为６．３３×１０＾４Ｌ．ｍｏｌ＾－１．ｃｍ＾－１。     

某些铁—硫原子族络合物紫外—可见光谱的研究

本文研究了某些铁－硫原子簇络合物紫外－可见光谱２２０－２３０ｎｍ吸收带λｍａｘ的浓度效应；△λｎｍ随络合物结构对称性增加而减小，随浓度基数增大而变大的变化关系。该类型络合物紫外－可见光谱吸收峰的归属，计算了Ｆｅ＾ＩＩ分裂能△值；配体上的取代基效应，以用在二氯甲烷等溶剂中的溶剂效应。     

掺杂剂对聚乙炔中电荷密度波的影响

用CNDO／2方法研究了各种掺杂剂对聚乙炔中电荷密度波的影响，在掺杂剂附近的碳原子上出现较大的电荷密度，且p型比n型掺杂剂的影响更大，讨论了电荷波与导电性的关系。     

Conductivity of CaF2-MgO composites

Conductivity of CaF₂-(20, 30, 40 vol %) MgO composites was measured as dependent on the temperature and MgO dispersion degree using a standard four-probe dc method. It is shown that the conductivity of composites grows at an increase in the MgO dispersion degree and volume fraction and achieves its maximum at 30 vol % MgO. It is found that the conductivity of CaF₂-30 vol % MgO nanocomposite is higher by two orders of magnitude as compared to pure CaF₂.     

DC Electrical Conductivity of Polymercaptobenzothiazole Disulfide Copper Complex

Polymercaptobenzothiazole disulfide-copper complex PMBTS-Cu has been synthesized by reacting 2-mercaptobenzothiazole disulfide with CuCl₂ in absolute ethanol and dimethyl sulfoxide (DMSO) under reflux for 24 h. PMBTS-Cu has been characterized by several techniques using electronic spectra, elemental analyses, FTIR spectroscopy, and its solubility has been investigated. DC electrical conductivity variation with temperature, in the range 300–500 K, after annealing for 24 h at 100°C, and doping with different ratios of I₂, is determined for comparison. Doping was done in two ways: by mixing and chemically. Activation energies were calculated and the results were interpreted using the band energy model. DC electrical conductivity of I₂doped PMBTS-Cu complex increased with increasing temperature due to the variation of the carrier concentration with temperature as in the case of semiconductors. PMBTS-Cu complex has a copper ion in its backbone and copper salt is known to be a good dopant. Thus, these materials are doped internally, so the doped polymer-Cu complex are only one or two orders of magnitude higher in DC electrical conductivity than the annealed state. However, the energy gap is very small, which suggests suitability in applications like photovoltaic cells.     

分散第二相Al_2O_3对高分子固体电解质电性能的影响

于固体电解质PEO＿NaSCN络合物中加入Al2O3绝缘体作为第二相,分别研究了Al2O3的粒径,含量对该固体电解质电性能的影响.发现当Al2O3的粒径小于1μm时,离子电导率比纯的固体电解质的电导率高,大于1μm时,则比纯样品的低,即临界粒径约为1μm.当Al2O3的含量达到约25%时,电导率达到极大值.此外,样品的高频极化和低频极化也随Al2O3的粒径的增大而越显著.     

ATO包覆TiO2的导电性能研究

采用化学共沉淀法制备了Sb掺杂SnO_2包覆TiO_2的微纳米导电粉体。考察了不同Sb量对粉体的导电性能影响,通过XRD、SEM对粉体进行了表征。将导电粉体制成复合电极片,利用电化学工作站对其进行循环伏安和交流阻抗分析。结果表明,随着扫描速率的增加,氧化峰和还原峰分别向阴极和阳极移动,而且氧化还原峰的形状没有随着扫描速率的增加发生明显的变化;当m(SnCl_4·5H_2O)/m(SbCl_3)=10∶1时,容抗弧半径最小,且斜率最大,电阻最小,导电性最好。此结果与用电阻率测定仪测得电阻率的结果一致,说明利用交流阻抗法和循环伏安法考察导电粉体的导电性是可行的。     

添加提钒尾渣对膨胀石墨/石蜡复合相变材料稳定性和导电性的影响

以不同膨胀石墨(EG-300、EG-350和EG-400)为支撑材料,石蜡(PW)为相变主材,提钒尾渣(VT)为导电强化剂,采用熔融共混法制备复合相变材料,并对复合材料的稳定性和导电性进行测试分析.结果表明,进行60次热循环,EG/PW复合材料质量损失率小于0.03％,VT/EG/PW复合材料质量损失率小于0.08％,...     

ET类分子导体3d轨道对晶体能带及导电性的影响

采用扩展休克尔 -紧束缚方法 (EHTB)研究了ET类分子导体 [ET =bis (ethylenedithio) tetrathiafulvalene]的能带 .讨论了硫原子 3d轨道对能带结构的影响 ,添加 3d轨道导致ET分子柱间的横向作用大为增强 ,并与纵向作用处于同一数量级 ,这一结论解释了晶体二维导电性的实验结果 .计算得到 (ET) 2 C3 H5SO3 ·H2 O ,(ET) 2 HgCl3 ·TCE两个晶体的带隙分别为0 5 79,0 .5 72eV ,与实验得到的导电激活能 0 .3 19,0 .3 0 8eV符合较好 .     

Electrical field-effect of polyvinylidenefluoride (PVF2)

Summary By means of modified field-effect measurements the properties of space charge distribution in polymers at the polymer-metal interface have been investigated. In general, these properties are due to excess charge and/or dipole orientation. The superposition of both effects is investigated in PVF₂ (phase-II) in order to show whether the conformational PVF₂ properties in the crystalline or in the noncrystalline regions control the space charge distribution. In the temperature region 60 °C <T < 90 °C and for times greater than 60 sec the space charge properties are significant influenced by additional dipole relaxations which result from the beginning chain mobility within the crystallites of PVF₂. In the time interval 1 sec <t < 60 sec charge carrier injection at the PVF₂-gold contact can be described by the Richardson-Schottky theory. Based on this theory, a plot of reduced current versus reduced field is presented displaying all experimental data obtained at various temperatures and field-strength on a single curve. No clear distinction can be given in this case between bulk-limited and electrode-limited processes.With 6 figures     

稀土添加剂对超细ZrO2织构、结构的影响

Pure zirconia and zirconia containing Y or Ce were prepared by Supercritical Drying Method (SCD) followed by calcination in air at temperature up to 700℃. It was found that the zirconia containing Y or Ce possessed much higher specific surface area and larger pore volume than that of pure zirconia. The BET surface area of 3.4Y2O3-96.6ZrO2 without calcination and that calcined at 700℃ were 376.2 m2﹒g-1 and 80.0 m2﹒g-1 respectively, while the corresponding values of pure zirconia were 248.0 m2 ﹒g-1 and 47.8 m2﹒g-1 respectively. It was postulated that the better textural properties of zirconia containing Y or Ce were resulted from preventing zirconia particles sintering in the presence of Y or Ce additive. All of these samples made by SCD had a well-developed mesoporous texture.     

CuO/SiO2制备过程中吸附质相间分配比的调控及其对粒径影响的研究

吸附相反应过程中, 吸附层是反应的场所, 吸附质在吸附层和本体溶液中的分配对吸附层中的反应和粒子的形成、生长过程有重大影响. 通过定义相间分配比的概念, 研究了不同吸附质种类、不同温度和水量条件下吸附质相间分配比的变化规律. 采用XRD和TEM等手段考察了不同条件下制备所得样品的粒子大小、形貌等, 并与相间分配比的变化趋势相比较, 得到了相间分配比对粒径的调控规律. 研究发现不同吸附质在相间分配比上存在的差异导致了晶粒粒径的变化, Cu(OAc)₂的相间分配比大于NaOH的相间分配比, 因此以Cu(OAc)₂为吸附质制备得到的CuO粒子较小. 同时在常温(0～40 ℃)和低水量条件下时, 相间分配比的变化也是导致粒径变化的主要因素, 温度升高和水量增加均导致相间分配比变大进而导致粒径变小.     

Time—resolved Microwave Conductivity Studies on the Chemical Treatment of the Nanocrystalline Porous TiO2 Films

Effect of Ti(iso-C3H7O)4 treatment on the photoinduced charge carrier kinetics of nanocrystalline porous TiO2 films is studied by time-resolved microwave conductivity measurements. Analysis of the transient photoconductivity decays indicates that Ti(iso-C3H7O)4 treatment leads to an increased concentration of photogenerated charge carriers and a fast interfacial transfer rate of holes via the surface modification of the fleshly growing TiO2 nanocrystallites.