苯胺与二苯胺共聚物的合成与表征

以过硫酸铵(APS)为氧化剂，合成了苯胺和二苯胺的共聚物。利用元素分析、傅立叶变换红外光谱(FTIR)、紫外-可见光谱(UV—vis)和电导率测定等手段，研究了介质组成、单体配比等对聚合产率及共聚物结构和性能的影响。结果表明，得到的产物是苯胺和二苯胺的无规共聚物，介质中有机溶剂(乙醇)比例的增加，有利于二苯胺的聚合，随着共聚物中二苯胺结构单元的增加，共聚物的电导率下降，而溶解率升高，在二甲基甲酰胺(DMF)中的溶解率最大可以达到79．0％。     

聚邻甲氧基苯胺薄膜对pH的光学响应

在盐酸介质中,应用循环伏安法通过电聚合在氧化铟锡(ITO)透明导电玻璃上形成聚邻甲氧基苯胺薄膜.用紫外可见光谱方法测定了聚合物薄膜在不同pH下的特征吸收光谱,聚邻甲氧基苯胺薄膜的λmax在557～746nm之间,作出了相应的滴定曲线.结果表明,在pH为1～12范围内聚合物薄膜对pH的变化表现了极高的光学敏感性,其表观pKa约为6.4.应用聚邻甲氧基苯胺薄膜测定了不同pH的溶液,其测定结果与精密酸度计相比误差＜±4%.     

甲氧基取代三苯胺的合成及其性能研究

通过Ullmann反应合成了4-甲氧基三苯胺（MeO-TPA）和4,4＇-二甲氧基三苯胺（DMeO-TPA）两种具有良好溶解性的甲氧基取代三苯胺,通过FFIR、^1H NMR和元素分析等手段对其进行了表征,并采用循环伏安（CV）结合UV-Vis吸收光谱测试了其能级结构.以甲氧基取代三苯胺为电荷传输材料,TiOPc为电荷产生材料制备了双层光电导体,测试了其光敏性.结果表明MeO-TPA和DMeO-TPA具有较三苯胺（TPA）更为优良的空穴传输性能.     

层状二氧化锰/苯胺-邻甲氧基苯胺共聚物复合材料的制备与性能研究

采用软化学合成法合成出基面间距为0.70nm的层状二氧化锰(bir-MnO2),并利用表面吸附技术制备了层状二氧化锰/苯胺-邻甲氧基苯胺共聚物复合材料(bir-MnO2/P(An-co-oAs)),借助FTIR、XRD、SEM、TGA、四探针和充放电循环实验等测试手段对样品的结构与性能进行表征.结果表明,P(An-co-oAs)的引入,对复合材料中bir-MnO2的层状结构破坏较小,P(An-co-oAs)通过氢键和静电作用吸附在bir-MnO2的表面.与bir-MnO2相比,复合材料的电导率提高2个数量级.首次放电比容量由bir-MnO2的188mAh/g提高到复合材料的202mAh/g.     

苯胺电聚合条件研究

采用表面增强拉曼散射(SERS)技术和循环伏安法研究了H_2SO_4介质中苯胺在Au电极上的电聚合过程。探讨了电解液pH、苯胺浓度、聚合电势和时间对聚苯胺链结构的影响,提出了苯胺电聚合适宜条件,讨论了苯胺电聚合初期分子偶合反应机理。     

合成吡咯-苯胺共聚物亚微米颗粒及增强的超电容性

采用简单的化学氧化聚合直接合成吡咯-苯胺(Py-An)共聚物亚微米颗粒。所得共聚物的产率和电导率受聚合条件如共单体配比、聚合温度和氧单比的影响。当n(Py)/n(An)=7/3,氧单比为1,共聚温度为20℃时,共聚物具有相对较高的产率(57.5%)和电导率(2.61S/cm)。红外光谱(FT-IR)的分析结果表明,共聚物分子链由吡咯和苯胺链段构成,并随着共单体配比的不同而变化。扫描电镜(SEM)显示Py-An(7/3)共聚物呈现亚微米尺度的无规则颗粒状形貌,粒径约300~500nm。相对均聚物来说,Py-An(7/3)共聚物显示出更好的溶解性和赝电容特性。循环伏安(CV)的研究表明Py-An(7/3)共聚物的质量比电容为256F/g,且1 000次循环后仍能保持初始比电容的97.6%。     

界面聚合法樟脑磺酸掺杂苯胺/邻甲苯胺共聚物电极材料的制备与性能

采用界面聚合法,以大分子掺杂酸樟脑磺酸为掺杂剂,合成了苯胺/邻甲苯胺共聚物。利用红外光谱(FT-IR)和紫外光谱(UV-vis),对该共聚物成分和结构进行了表征。通过循环伏安和恒流充放电技术考察了该共聚物的电化学电容行为。结果表明,制备的活性电极材料樟脑磺酸掺杂苯胺/邻甲苯胺共聚物在1mol/LH2SO4溶液中呈现一定的电化学电容行为。随着扫速从3mV/s增大到10mV/s,峰电流从5mA增大11mA,表明该聚合物具有较快的电流响应。在电流密度为1.5mA/cm2时,单电极比电容达到275F/g,表明该材料在电化学电容器中有一定的应用前景。     

聚1-萘胺纳米颗粒的合成及表征

采用界面聚合法合成了聚(1-萘胺)纳米颗粒.利用红外光谱(FT-IR),紫外可见吸收光谱(UV-vis),电子扫描显微镜(SEM),投射电镜(TEM),X射线衍射(XRD),循环伏安(cyclic voltammogram)等测试方法,对聚合物进行了表征并对聚合物形貌、结构及性能进行了初步探讨.结果表明,界面聚合法合成的聚(1-萘胺)呈现直径在100nm内的颗粒状分布;XRD结果显示,聚(1-萘胺)为半结晶态聚合物;界面聚合法合成的聚(1-萘胺)具有一定的电化学活性.     

聚(苯胺-邻六氟羟基苯胺)共聚物的合成及其性能表征

采用过硫酸铵作为引发剂,通过化学氧化聚合法制备了一系列可溶性的聚(苯胺-邻六氟羟基苯胺)(PAH)的共聚物。利用傅里叶红外光谱(FTIR)、核磁共振氟谱(19F-NMR)、核磁共振氢谱(1H-NMR)、凝胶渗透色谱(GPC)、紫外光谱(UV)和场发射扫描电子显微镜(FESEM)等对共聚物的化学结构和形貌等进行了表征和分析。结果表明,邻六氟羟基苯胺(HAFIP)成功导入了共聚物主链中,共聚物的数均分子量Mn介于6.51×10~4与9.04×10~4之间。HAFIP的存在抑制了共聚物的醌式结构n→π*跃迁,随着共聚物中邻六氟羟基苯胺(HAFIP)摩尔分数的增大,共聚物形貌逐渐由纳米纤维向纳米颗粒变换。与聚苯胺难于溶解于一般有机溶剂不同的是,当邻六氟羟基苯胺(HAFIP)的摩尔分数超过0.5时,共聚物可以完全溶解于四氢呋喃、乙醇、N-甲基吡咯烷酮、N,N-二甲基甲酰胺等有机溶剂中,表明HAFIP的导入,可以大幅改善聚苯胺的溶解性能,从而扩展聚苯胺的应用范围。     

苯胺及吡咯的共聚合研究进展

综述了苯胺及吡咯的共聚合机理、共聚物结构和共聚研究现状。着重讨论了取代基对聚合过程和聚合物性能的影响，以及在与其它共轭单体和非共轭单体共聚时的工艺方法．     

Novel synthesis of nanorod ZnO and Fe-doped ZnO by the hydrolysis of metal powders

Fe-doped ZnO nanorods have been synthesized by a novel process employing a hydrolysis of metal powders. Zn and Fe nano-powders were used as starting materials and incorporated into distilled water. The solution was refluxed at 60 degrees C for 24 h to obtain the precipitates from the hydrolysis of Zn and Fe. X-ray diffraction patterns for all the samples showed a pure wurtzite single phase, without any segregation of the Fe into the particulates within the instrumental resolution limit. The TEM results for ZnO with and without an Fe-doping showed that the produced powders had a rod-like shape. The rod shape was attributable to the zinc oxide from the hydrolysis of Zn. With an increasing Fe content, the UV-vis spectra were shifted to a long wave length and this result indicates that the band gap was changed by an Fe-doping.     

Improvements in methods for measuring the volume conductivity of electrically conductive carbon powders

Electrically conductive carbon powders are commonly used as filler materials in polymers to create electrically semi-conductive composite materials for use in battery electrodes and anti-static applications. Current methods for characterizing the conductivity of these powders use two pistons to compress the powders. Two-piston methods are known to underestimate conductivity. This study develops a guard-electrode method based on ASTM D257 to better characterize the bulk conductivity and impedance spectra of electrically conductive powders. The conductivity and impedance spectra of a highly conductive powder (copper powder) and a low conductivity powder (cellulose) were used to bound the conductivity of carbon black, graphite, and biochar. Powders were measured through a full range of compression with both the two-piston and the guard-electrode method. In all cases, measurements using the guard-electrode method have higher conductivity and lower impedance than the same powders measured using the two-piston method. The grain conductivity of the particles is obtained through fitting the relationship of conductivity versus packing fraction using the GEM equation. The guard-electrode method is shown to be more similar to established conductivity values as measured via a four-probe technique for copper and graphite then the two-piston method.     

D,L-乳酸、L-乳酸、羟基乙酸的均聚物及共聚物的结晶性能研究

合成了高分子量的聚Ｄ,Ｌ－乳酸、聚Ｌ－乳酸、聚羟基乙酸、Ｄ,Ｌ－乳酸和共聚物以及乙酸和Ｄ,Ｌ－乳酸共聚物。以ＷＡＸＤ、ＦＴ－ＩＲ、ＤＴＡ表征了上述系列聚合物的结晶性能,分析了单体种类和共聚物中单体的比例对聚合物中结晶性能的影响,并对该系列聚合物的晶区结构作了描述。用万能拉力计测试了ＰＬＡ系列聚合物的力学性能,以ＤＴＡ测定了ＰＧＬＡ系列聚合物的热性能,探讨通过调整聚合物的组成以改变其结晶特性来调控聚     

Preparation of nanoscale iron and Fe3O4 powders in a polymer matrix

The synthesis of the title matrix-mediated nanocomposite was performed in both poly(4-vinylpyridine) homopolymer and vinylstyrene-4-vinylpyridine copolymers. NH2–NH2 was used as the reducing agent to prepare the polymer-supported metallic particles which were later converted into fine oxide powders by oxidation. The structure and morphology of the products were studied by Fourier transform infrared spectroscopy, wide angle X-ray diffraction, transmission electron microscopy as well as electron spectroscopy for chemical analysis and magnetic measurements. The wide angle X-ray diffraction patterns contained reflections that could be assigned to Fe3O4 particles while no reflections were observed that correspond to ultrafine iron powders. The magnetization behaviour of the nanocomposite was determined by the degree of loading of Fe in the polymer matrix.     

Effects of different sintering atmosphere on the structure and properties of Cu-doped ZnO powders prepared by sol–gel method

Cu-doped ZnO powders have been successfully synthesized by the sol–gel method in different sintering atmospheres, including argon and air, respectively. The effects of the sintering atmosphere on the structure, magnetic and optical properties of Cu-doped ZnO were investigated in detail by X-ray diffraction, X-ray photoelectron spectroscopy, X-ray absorption spectroscopy, vibrating sample magnetometer and photoluminescence measurements. The results showed that the Cu-doped ZnO powders sintered in Ar had a hexagonal wurtzite structure without any secondary phase, however, CuO was observed in the sample sintered in air. From the magnetic and photoluminescence spectra, it could be seen that the sintering atmospheres strongly influenced the magnetic and optical properties of the powders.     

主链型液晶共聚酯的研究

以2,2-双(4-羟基苯基)丙烷(双酚A)、1,10-癸二醇与含液晶基元的缩聚单体2-甲基-1,4-苯撑双(4-氯甲酰)苯甲酸酯通过溶液缩聚反应合成了一系列含液晶性和非液晶性两种序列结构的共聚酯,采用DSC、偏光显微镜和X-衍射方法研究了共聚物的液晶行为,发现除共聚物10外所有的共聚物均具有较好的结晶性和热致液晶性。随双酚A用量的改变,共聚物的特性粘数和熔点呈规律性变化。     

Influence of copolymer composition on the transport properties of conducting copolymers: poly(aniline-co-o-anisidine)

The effect of different compositions of monomers on the transport properties of copolymers by various techniques such as optical, electrical and magnetic has been investigated and compared with the homopolymers. The UV-visible absorption spectra show a hypsochromic shift with an increase in the o-anisidine content in copolymers indicating a decrease in the extent for conjugation (i.e. an increase in the bandgap). From temperature dependence of electrical conductivity the transport parameters such as charge localization length and average hopping distance are calculated and also the effect of the monomeric composition on the coherence length has been discussed. The magnetic studies show the paramagnetic and diamagnetic nature of homopolymers and copolymers. The X-ray diffraction pattern indicates that the copolymers are of amorphous nature.     

Ge取代P型高锰硅合金的晶粒细化及其热电性能

采取悬浮熔炼法制备Ge取代的高锰硅试样Mn(Si1-xGex1).733(x取0.004,0.006,0.008,0.010,0.012),采用甩带法得到快凝高锰硅合金粉末,XRD分析表明快速凝固能够减少MnSi金属相的含量,Ge对Si位的取代产生晶格畸变,使得衍射峰向低角区偏移;将悬浮熔炼和快速凝固所得试样进行放电等离子烧结,测试并比较其热电性能。结果显示,快速凝固有效地降低了材料的热导率,Ge取代则使得有效载流子浓度增加,提高了电导率,从而提高材料的热电性能。实验范围内,当Ge取代量x=0.010时,ZT值最高,悬浮熔炼试样在850K时ZT值为0.53,快速凝固试样在750K时ZT值达到0.55。     

气-液界面沉淀法制备锑掺杂氧化锡（ATO）纳米粉体

以2SnCl4·5H2O和SbCl3为原料,采用气-液界面法制备纳米ATO粉体,用粒度分析仪、X射线衍射仪、x射线光电子能谱仪及透射电子显微镜研究不同掺杂量下粉体组成、分布情况以及尺寸形貌;采用宽频介电阻抗谱仪测量不同掺杂比例样品的电性能,研究表明,采用气-液界面法制备的ATO纳米粉体粒径小、分布窄,掺杂剂分布均匀,表现出优异的电性能。当掺杂量为10At％时,所制备的粒径为10nm左右,表现出最佳的导电性能,电导率达到1．64×10-2S·cm-1。该制备方法对于其他复合纳米粉体的合成制备具有重大借鉴意义。