纳米管结构聚苯胺的电阻率和磁化率

研究了用自组装法制备的质子酸掺杂的纳米管结构聚苯胺的电阻率(ρ)和磁化率随温度变化的依赖关系，讨论了质子酸掺杂浓度、不同对阴离子以及苯胺单体与质子酸聚合时反应浓度对纳米管结构聚苯胺电学性质的影响.实验结果表明，lnρ和T-1/2呈线性关系，不同对阴离子对聚苯胺的电阻率影响很大，随着质子酸掺杂浓度以及苯胺单体与质子酸聚合时反应浓度的增大，聚苯胺的电阻率明显减小；而且，其磁化率可以表示为与温度无关的泡利顺磁性和符合居里定律的顺磁性之和.     

钙钛矿氧化物CaRu0.5Ti0.5O3中Ti掺杂诱导的铁磁性和自旋玻璃态

有钙钛矿结构的钌氧化物是一种典型的电子关联体系, 对其化学掺杂后将表现出丰富的新奇磁学性质. 我们采用传统的固相反应法制备了钙钛矿型 CaRu0 .5Ti0 .5 O3 块材(CRTO) . 相比于母体材料 CaRuO3 的顺磁性,CRTO 表现出截然不同的铁磁-顺磁转变, 居里温度为45 K. 根据对 CRTO 的晶体结构分析, 我们发现 Ti 元素的掺杂会导致氧八面体旋转畸变的减弱, 可能导致 Ru 离子之间的交换作用变强. 我们同时还进行了场冷-零场冷条件下的磁矩-温度测量和交流磁化率测量, 发现该体系出现了类自旋玻璃态.     

第一性原理计算和Monte Carlo算法耦合对共掺杂稀磁半导体磁学性质的研究

将第一性原理计算和Monte Carlo算法耦合,对共掺杂稀磁半导体进行模拟,预测其磁学性质,并与同种过渡金属原子单掺杂稀磁半导体相比较进行分析.首先用第一性原理计算掺杂原子间的磁相互作用强度,作为后面Monte Carlo模拟的输入参数;然后利用Monte Carlo方法结合海森堡自旋模型和磁相互作用强度来模拟体系热力学磁化强度和磁化率,由此得到居里温度;用同样的方法模拟掺杂磁性体系的磁滞回线.计算结果显示,对应于掺Co、Al-Co、Fe、Al-Fe的ZnO基稀磁半导体的居里温度分别为346 K、450 K、743 K、467 K,与实验值很吻合;模拟这四种掺杂情况得到的磁滞回线也很符合理论分析和实验结果,且呈现和居里温度相同的变化规律.     

储锂硅材料的ESR谱研究

采用了电化学方法制备储锂硅材料,并用电子自旋共振(ESR)方法进行研究. 实验结果表明, 储锂前的硅ESR行为符合居里自旋的ESR特征, ESR信号主要来源于硅材料中的晶格缺陷、 表面悬空键等局域化自旋中心. 储锂后硅材料中产生了泡利自旋,居里自旋的强度比储锂前增大2～3倍. 此外,对硅和储锂硅ESR谱线的g因子和ΔH_pp随温度的变化情况也进行了分析. 硅材料电化学储锂时,与锂离子中和的电子主要参与形成Li-Si共价键,对ESR信号贡献很小.     

钙钛矿La0.8Ca0.2MnO3多晶样品的制备及低温磁学特性

我们利用固相反应法制备了粉末状La0.8Ca0.2MnO3样品,其空间群为pnma,样品中存在超顺磁性粒子,其截止态和超顺磁态的转变温度为185K,从dσ/dT的负峰得到铁磁-顺磁相变居里温度为210K,在顺磁领域线性拟合而得到顺磁居里温度为216.4K,分子式有效磁矩为6.25μB,低温领域磁化曲线服从布洛赫T32定律,其自旋波劲度系数为49.2meV2.     

p，n型掺杂剂与Mn共掺杂GaN的电磁性质

采用基于密度泛函理论的第一性原理平面波赝势法计算Mg,Zn,Si,O和Mn共掺GaN,分析比较共掺杂后的电子结构和磁学性质,并分别用平均场近似的海森伯模型和Zener理论估算共掺杂后体系的居里温度（T_C）.计算表明：共掺杂后体系均在能隙深处产生自旋极化杂质带,具有半金属性,能产生自旋注入.p型共掺杂（GaN：Mn-Mg＼Zn）后体系具有较GaN：Mn更稳定的FM态且能使T_C升高;而n型共掺杂（GaN：Mn-Si＼O）后体系FM态稳定性 关键词： Mg Zn Si O和Mn共掺GaN 第一性原理 T_C）')" href="#">居里温度（T_C）     

Lal-xTexMnO3晶格结构的X射线粉末衍射分析

通过X射线粉末衍射数据,用Rietveld精修方法分析了Te部分替换LaMnO3中La后,其晶格参数及其结构对称性所发生的变化.结果表明:Te掺杂LaMnO3系列样品具有R(3)C的晶格结构对称性,其MnO6八面体晶格还产生了伸张畸变,畸变程度随Te掺杂量的增加而增大.此外根据Mn-O-Mn键角、eg电子能带的带宽、A位离子平均半径及A位离子尺寸失配度等的变化特点,推测Te掺杂LaMnO3样品除居里温度等相变物理量将随x增加而非线性变化外,还可能产生自旋玻璃态、相分离等宏观现象.     

质子辐照聚苯胺的Raman与红外光谱研究

本文用Raman与红外光谱表征质子辐照聚苯胺的结构。聚苯胺的红外光谱的主要吸收峰经低能和高能质子辐照后分别向高频移动2—12cm~(-1)和5—26cm~(-1)。在1228,1344,1380和1444cm~(-1)处的Raman带在低能质子辐照后分别移到1236,1348,1392和1456cm~(-1),在804,1588和1620cm~(-1)处的Raman带,经高能质子辐照后分别移到808,1592和1624cm~(-1)。醌型结构的拉曼线1588cm~(-1)也上移4cm~(-1)。这些结果表明,质子辐照不同于质子酸的掺杂(质子化过程)而是引起聚苯胺中分子链的断裂。     

钴掺杂二氧化锡纳米粉的光致发光和磁学性质

研究了钴掺杂对二氧化锡纳米粉的光致发光性质和磁学性质的影响,发现钴掺杂对发光带的位置影响很小,但紫外发光带与蓝色发光带的强度之比随掺杂含量的增加而下降.当钴掺杂含量达到0.02时,样品中的铁磁性被完全破坏.讨论了样品中的磁相互作用的机理,认为掺杂离子的不均匀分布、自旋极化子与掺杂离子之间的耦合都可能导致反铁磁性的相互作用,这种反铁磁性的作用破坏了铁磁性. 关键词： 钴掺杂二氧化锡 光致发光 磁学性质     

钾掺杂对三联苯的超导特性探寻

新型超导材料的设计合成及其超导机理的探索是目前凝聚态物理学领域的重要研究方向. 本文采用高真空热烧结方法制备了钾掺杂对三联苯粉末材料并表征了它们的晶体结构、分子振动、磁学及超导特性. X射线衍射图谱和拉曼光谱表明在烧结样品中除存在钾掺杂对三联苯和KH外, 还含有苯环重组的C₆₀和石墨成分. 拉曼光谱中部分峰位的红移进一步证实钾成功掺入对三联苯分子晶体中并将4 s电子转移到C原子上. 零场冷却磁性测量结果表明: 多数样品在整个温度测量区间表现为居里顺磁性, 但少数样品呈现出抗磁性, 而且在17.86, 10.00 和6.42 K三个温度点出现磁化率突降的反常行为, 其中17.86 K处的突降很可能源于钾掺杂C₆₀引起的超导转变, 而后两者可能与钾掺杂对三联苯导致的超导相关. 研究结果有助于理解金属掺杂芳香烃有机超导体这一新兴超导家族的晶体生长和物理特性, 同时也提供了一种低温制备C₆₀和石墨的新方法.     

Electroless polymerization of aniline on platinum and palladium surfaces

Aniline was found to polymerize slowly and spontaneously on the platinum and palladium metal surfaces in an aqueous acid solution of the monomer. The phenomenon was thus equivalent to an “electroless polymerization” process. The polyaniline (PANI) so-deposited were characterized by X-ray photoelectron spectroscopy (XPS), Fourier transform infrared (FTIR) spectroscopy, and atomic force microscopy (AFM). The chemical state of the electroless deposited PANI film was near to that of the 75% intrinsically oxidized nigraniline (NA) state of PANI. The electrolessly deposited PANI films exhibited similar protonation–deprotonation behavior as that of the aniline homopolymer. The amount of the PANI deposited on the metal surface was affected by the monomer concentration, the nature of the acid medium, and the oxygen content in the reaction medium.     

磁性聚苯胺纳米微球的合成与表征

报道了具有核壳结构的Fe3 O4 聚苯胺磁性纳米微球的合成方法和表征结果 .微球同时具有导电性和磁性能 .在优化的实验条件下 ,可得到饱和磁化强度Ms 为 5 5 .4emu/g ,矫顽力Hc 为 6 2Oe的磁性微球 .微球的导电性随着微球中Fe含量的增加而下降 .微球的磁性能则随着Fe含量的增加而增大 .Fe3 O4 磁流体的粒径和磁性聚苯胺微球的粒径均在纳米量级 .纳米Fe3 O4 粒子能够提高复合物的热性能 .实验表明 ,磁流体和聚苯胺之间可能存在着一定的相互作用 ,但这种相互作用较为复杂 ,难于研究 .     

Surface modification of polyacrylonitrile film by anchoring conductive polyaniline and determination of uricase adsorption capacity and activity

Polyacrylonitrile (PAN) films were modified with chemical polymerization of conductive polyaniline (PANI) in the presence of potassium dichromate as an oxidizing agent. The effect of aniline concentration on the grafting efficiency and on the electrical surface resistance of PAN and (PAN/PANI)-1-3 composite film was investigated. The surface resistances of the conductive composite films were found to be between 6.32 and 0.97 kΩ/cm. As the amount of grafted PANI increased on the PAN films, the electrical resistance of composite film decreased. The PAN/PANI composite films were also characterized using SEM and FTIR. The changes in the surface properties of the films were characterized by contact angle measurements. As expected, the PAN, PAN/PANI and PAN/PANI-uricase immobilized films, exhibited different contact angle values and surface free energy due to different interactive functional groups of the films.The conductive films were well characterized and used for immobilization of uricase. The amount of adsorbed enzyme increases with the increase of surface concentration of grafted fibrous polyaniline polymer. The maximum amount of immobilized enzyme onto composite film containing 2.4% PANI was about 216 μg/cm² (i.e., PAN/PANI-3). The immobilized uricase was reused 24 times in batch wise assay in a day. Finally, the immobilized uricase enzyme system was successfully fabricated and applied to determine the uric acid level in human serum samples.     

压力对聚苯胺导电性的影响

 导电高聚物聚苯胺薄膜经过定向拉伸后，其有序度、电导及跃迁势垒都发生了很大变化。本文研究了准静水压力对定向拉伸前后，聚苯胺薄膜电学性质的影响。发现未定向拉伸的聚苯胺薄膜的电导随压力单调增加，跃迁势垒T₀随压力单调减少，而定向拉伸后的聚苯胺薄膜则在0.47 GPa出现电导的极大值，在0.35~0.71 GPa之间出现T₀的极小值，这个异常行为与聚乙炔、聚噻吩等导电高聚物均不相同。     

Spectroscopic Studies on Threonine Doped Polyaniline Composites

The structural and magnetic properties of polyaniline (PANI)- and threonine (T)-doped polyaniline composites were characterized by using FTIR, UV-Vis, and electron paramagnetic resonance (EPR) spectroscopic techniques. The FTIR, UV-Vis, and X-band EPR spectra were recorded for PANI- and threonine-doped polyaniline (PANI-T) composites. The increased intensity of the IR bands in PANI-T composites is due to the increasing dopant concentration. The observed red shift corresponding to the N-H ··· N mode indicates the hydrogen bond formation in between the PANI and threonine molecule. The observed decrease in spectral intensity of the UV-Vis spectrum of the PANI-T composite confirms the occurrence of the protonation at the imine nitrogen sites. The EPR parameters such as line width, g factor, line asymmetry parameter, signal intensity, and spin concentration values were estimated. The EPR spectrum of PANI clearly indicates the presence of unpaired polaron. The EPR signal intensity and spin concentration values decrease with increasing dopant concentration, which reveals the polaron to bipolaron formation in PANI-T composites. EPR lineshape analysis showed that the absorption profile was Gaussian shape. The Gaussian-shaped line is generally due to the dipole–dipole interactions in the PANI and PANI-T composites. The line asymmetry parameter and g values indicated the isotropic nature of PANI and PANI-T composites.     

Improvement in mechanical and optical properties of vapour chopped vacuum evaporated PANI/PMMA composite thin film

PANI/PMMA composite was synthesized by emulsion polymerization pathway and the composite thin film was obtained by vacuum evaporation. The effect of vapour chopping and varying PMMA concentration was also studied. The FTIR spectra showed that the PANI/PMMA composite thin film deposited as a short chain oligomers. Increase in transmittance and decrease in refractive index was obtained with increasing concentration of PMMA, which further increased the adhesion and decreased intrinsic stress. The vapour chopping improved its optical as well as mechanical properties and produced smoother surface morphology. Increase of PMMA made the film more amorphous and does not change its band gap.     

磁性薄膜的晶格结构和磁性

采用Monte-Carlo模拟方法对六边形、正方形和三角形晶格结构磁性薄膜的磁学特性及磁畴结构进行了模拟,结果表明,磁性薄膜的磁性特征及其磁相变温度和薄膜结构密切相关并存在临界膜厚,当薄膜厚度大于临界膜厚时薄膜磁性特征稳定.在低温区,不同结构磁性薄膜的磁滞回线均出现台阶现象,结果同相关实验一致.     

Positron beam studies on polyaniline and Ag-coated polyaniline

The effect of doping of the polyaniline emeraldine base (PEB), with Ni as well as Ni over layer coating has been investigated using variable low energy positron beam. Depth-resolved Doppler S-parameter measurements have been performed on undoped, Ni-doped polyaniline (PANI), and Ag (40 nm) film deposited PANI samples. Significant variation in S-parameter is observed for undoped and Ni-doped PANI. The size of the free volume hole has shifted to lower values upon doping with Ni as compared to that of undoped PANI, which is consistent with the conductivity measurements. For Ag-coated PANI systems, the S vs. E_p curves show distinct changes at the surface and interior regions. These results are discussed in the light of changes in free volume hole size distribution.     

聚苯胺/ZnO纳米线薄膜材料作为发光层的柔性光电器件 及其发光机理

综合氧化锌纳米线(ZnO NWs)的光学活性与聚苯胺(PANI)的空穴传输特性,设计并制备了一种聚合物/ZnO纳米线电致发光材料,并对其发光特性进行了研究。通过高分子络合软模板法,将有序的单晶ZnO NWs均匀生长在覆有铟锡氧化物(ITO)涂层的柔性聚乙烯对苯二甲酸乙二醇酯(PET)衬底上并嵌入PANI薄膜,获得了电致发光薄膜材料和有机/无机异质结实验器件ITO/(ZnO NWs-PANI)。有机/无机异质结器件电致发光可调,在相对低的开启电压下呈现室温蓝紫外发光,并且ZnO NWs表面覆盖PANI增加了蓝紫外发光的强度和稳定性;而无PANI的ZnO NWs阵列具有450 nm处的缺陷发射峰,这可能是电子从扩展态锌间隙Zn_i到价带的跃迁引起的。这些结果表明,基于PANI/ZnO纳米线的复合材料在柔性光电器件方面的应用极具潜力。     

X-ray reflectivity studies on glass transition of free standing polystyrene thin films

We have studied thermal expansion of free standing polystyrene thin films using X-ray reflectivity to elucidate the glass transition temperature and the thermal expansivity. We found that the glass transition temperature T_g decreased with the film thickness, depending on molecular weight. The reduction in the free standing films is much larger than in the supported films on Si substrate, suggesting that some segmental motions are activated due to free surfaces on both sides in the free standing films. We also found that the thermal expansivity in the glass and the melt decreased with the film thickness. This decrease must be attributable to chain confinement effects.