酞菁锌衍生物L—B膜的光电性能研究

用L-B膜方法在SnO_2电极上修饰了不同链长烷氧基取代的酞菁锌化合物(ZnPc C_nH_(2n+1),n=3,9,12,16),分别研究了它们单分子膜成膜性能和转移性能,并测定了修饰在SnO_2电极上的单多层分子膜的光电性能和吸收光谱。研究结果指出链短的取代基即异丙氧基取代的酞菁锌(ZnPcC_3H_7(i))具有较高的转移比及较好的光电性能。     

Ti／SnO2—SbOx—PtOx氧化物电极结构和失效原因的研究

本文用 X 射线衍射,扫描电镜分析研究了 Ti/SnO_2—SbOx—P_tOx 氧化物电极的表面结构,发现 Sb 在 SnO_2中形成固溶体;Pt 能和 Sn 发生相互作用形成 PtSn 金属间化合物。电极中少量的 P_t 能使电极活性和寿命大大提高,主要有两个原因:第一.锡锑掺杂微量铂后涂层的表面积增大。第二.掺杂铂后,导电率增加。从 X 射线衍射图中还看出,Ti 基体能与活性层形成 Ti_6Sn_5金属间化合物,正是由于氧化物间形成了固溶体,界面间形成了金属化合物、使得基底与氧化物之间相互渗透,加强了基底与涂层的附着力。电极失效的原因主要是活性层的溶解和 Ti 基上 Ti 氧化物的形成。Ti 氧化物是在 Ti 基体与涂层之间,起了隔离层的作用,它使电极的导电性大大降低。SnO_2半导体近几年已经被用于电分析化学、电催化和光电化学研究中的工作电极,因为它具有高的导电率,高的机械强度,优良的耐腐蚀性,这些都符合做阳极材料的要求。因此,岩仓千秋等人近来研究了 Ti/SnO_2—SbOx—MOx(M 代表贵金属)电极在 KOH 和NaCl 溶液中的析氧和析氯的电催化活性。在过去的几年中,我们着重对 Ti/SnO_2—S_bOx—PtOx 电极在 H_2SO_4,NaCl 溶液中析氧和析氯,做为阳极材料其制作工艺、组成与它的催化活性以及使用寿命的关系进行了研究。要真正使得该电极能应用于 H_2SO_4介质中的电解及氯碱工业,弄清它的活性层结构及其作用机理是非常重要的。制得的 Ti/SnO_2—SbOx—PtOx 电极,有优良的催化活性,有希望在 NaCl 电解中取代Ru—Ti 电极。为了进一步改进 Ti/SnO_2—SbOx—PtOx 电极的性能,扩大电极的应用范围,找出电极失去活性的原因是十分必要的。国外关于 Ti/SnO_2—SbOx—PtOx 电极失效原因的报导几乎没有,只是日本的岩仓千秋等人对 Ti/SnO_2—SbOx—MOx(RuOx)电极失效的原因提出过一个假设,然而,他们并没有给予实验依据。通过实验,我们发现Ti/SnO_2—SbOx—PtOx 电极失效是一个渐变的过程。电解过程中总是伴随着表面层的溶解,直至最后 Ti 上形成了高阻性的氧化物而导致电极最终失效。     

多级结构SnO_2及其碳复合物的制备与电化学性能

针对SnO_2作为锂离子电池负极材料循环性能和导电性差的问题,采用水热法制备了SnO_2/C复合物。研究了多级结构SnO_2的制备工艺并以此为基础制备了SnO_2/C复合物,通过XRD、SEM、TEM等分析方法表征了材料的结构、组成和形貌;采用循环伏安、恒流充放电等电化学方法表征SnO_2和SnO_2/C复合材料的电化学性能。实验结果表明,在200 mA·g~(-1)恒电流密度充放电时,SnO_2/C复合物电极充放电循环50次后比容量为346.1 mAh·g~(-1),远高于SnO_2电极;与此同时,无定形碳的引入使SnO_2/C复合物电极的倍率性能也显著提高。     

不同锚定分子配位自组装有机太阳能电池

设计了含有三嗪基团的上层锌卟啉ZnPw与含有咪唑基团的锚定卟啉ZnPAim,形成轴向配位自组装体。将这种双层自组装体固定在TiO_2电极表面,构建超分子染料敏化太阳能电池。对自组装ZnPw-ZnPAim电池性能测试,测试结果表明,采用锚定卟啉的自组装体具有较高的光伏性能,其中J_(sc)=5.14 mA/cm~2,η=1.85%。与有机小分子锚定基团相比,双层卟啉自组装体光伏性能高出3.7倍。此外,对锚定卟啉自组装体电池的紫外-可见吸收光谱和双层自组装结构进行了表征。     

Bi/SnO_(x)@C异质结构材料制备及其钠离子电池性能EI北大核心CSCD

锡基氧化物及其合金具有制备简单和理论比容量高等优点,是一种有前途的钠离子电池负极材料。然而,锡基氧化物及其合金在循环过程中会发生颗粒团聚及体积形变,导致电极粉化、容量衰减和倍率性能差等问题。在此,本工作采用氯化钠模板法合成了Bi/SnO_(x)颗粒锚定在超薄碳层上的复合材料(Bi/SnO_(x)@C),构筑了一种均匀的Bi/SnO_(x)@C异质结构。其中,超薄碳层可以有效抑制Bi/SnO_(x)复合颗粒的团聚并增加电极材料比表面积,提供更多活性位点,同时Bi/SnO_(x)也能够贡献更多的比容量。超薄碳层与Bi/SnO_(x)复合颗粒的协同作用可以有效提高电极材料循环稳定性,对于构筑高性能电极材料具有重要意义。     

硬脂酸二茂铁酯L—B膜修饰SnO2电极的阻抗研究

测定了二茂铁衍生物——硬脂酸二茂铁酯L-B膜修饰SnO_2电极在Fe(CN)_6~(3-/4-)溶液中的阻抗性能,用单纯形法求出了等效电路中的元件参数值,计算了电极反应速度常数K_s。从分析SnO_2电极修饰不同层的硬脂酸二茂铁酯L-B膜的界面阻抗和电极反应的动力学性能,表明与在固相中研究的硬脂酸二茂铁酯L-B膜的阻抗性能明显不同,在Fe(CN)_6~(3-/4-)溶液中表现了电活性分子修饰电极的界面阻抗行为,进一步证实了修饰在SnO_2电极上的硬脂酸二茂铁酯L-B膜在Fe(CN)_6~(3-/4-)的氧化还原电极反应过程中,起电荷传递的中介作用。     

金属酞菁/卟啉分子电催化CO2还原的研究进展

大气中日益增加的CO₂浓度导致了气候变化等环境问题。将CO₂催化转化为有价值的化学品具有重要意义。利用太阳能、风能等可再生能源产生的电能,通过电化学方法将CO₂还原转化为有价值的碳基化合物是最具有应用前景的方式。分子催化剂具有明确的结构和清晰的活性位点,可实现基于机理的性能优化。综述了近年来金属酞菁/卟啉分子在电催化CO₂还原为CO的实验和理论方面的最新研究进展。首先,介绍了金属酞菁/卟啉分子电催化CO₂还原为CO的详细机理。然后,重点介绍了如何通过分子分散和配体修饰提升金属酞菁/卟啉分子电催化CO₂还原为CO的活性和选择性。最后,讨论了金属酞菁/卟啉分子电催化CO₂还原存在的挑战及其可能的解决方案。     

电解催化氧化法处理含酚废水技术及机理研究

以聚合前驱体方法制备了Ti/SnO_2平板电极,用SEM和XRD表征了电极表面涂层形貌及结构。以自制Ti/SnO_2电极为阳极,电解催化氧化法处理100 mg/L的含酚废水,试验表明电催化系统能够产生羟基自由基,自制Ti/SnO_2电极具有良好的催化活性和使用寿命。当电流密度为0.01 A/cm2、极板间距为14 mm、初始p H为4,电解催化时间50 min后,出水苯酚去除率几乎为100%。     

Al/SnO_2/FTO结构双极型电阻开关的制备及其性质研究

通过溶胶凝胶的方法,在FTO衬底上制备得到SnO_2薄膜,并对SnO_2薄膜的晶体结构以及荧光光谱(PL)进行了研究。XRD结果显示SnO_2薄膜为多晶结构,荧光光谱结果表明SnO_2薄膜存在氧空位以及氧填隙等缺陷。通过直流磁控溅射在SnO_2薄膜上面溅射Al作为顶电极,并对Al/SnO_2/FTO结构进行了电阻开关性质研究,测试结果表明器件具有双极型电阻开关性质和良好的阻态保持特性。对器件的电流-电压曲线特征进行了研究,认为SnO_2薄膜内氧离子(氧空位)在电场作用下发生迁移,在Al/SnO_2界面发生氧化还原反应是引起Al/SnO_2/FTO电阻状态改变的原因。     

纤维状Fe_2O_3/SnO_2复合电极材料的制备及性能研究

以乙酰丙酮铁和氯化亚锡为反应原料,以聚丙烯腈和N,N-二甲基甲酰胺混合液为溶剂,采用静电纺丝法制备纤维状Fe_2O_3/SnO_2复合电极材料。利用XRD和XPS对材料的晶型和元素组成进行分析,借助SEM和TEM对材料结构进行表征,结果显示制备材料直径为纳米级的纤维状结构;通过恒流充放电、循环伏安测试、交流阻抗测试等方法对材料进行电化学性能测试,结果表明Fe_2O_3/SnO_2复合材料较之纯的Fe_2O_3和SnO_2具有更好的电化学性能,且当Fe_2O_3和SnO_2质量比为2∶5时,Fe_2O_3/SnO_2复合电极材料循环充放电性能最好,以0.1 A/g电流密度在0.01～3 V循环100次后仍保持675.3 mAh/g的比容量。     

Minimum wet thickness for double‐layer slide‐slot coating of poly(vinyl‐alcohol) solutions

A combined slide‐slot coating die, with the slide coating on top, was designed and built to investigate the double‐layer coating of poly(vinyl‐alcohol) solutions. The operating coating windows were examined as a function of flow rates and viscosities of the two coating layers. The top coating layer could be made much thinner as compared to the double‐layer coating so long as a stable thin film could be formed on the slide. A minimum wet thickness of the top layer was found to be as thin as 5 μm or less. A large viscosity ratio of the two layer solutions appears to be helpful in expanding the coating windows. Addition of a small quantity of polymer, such as carboxymethyl cellulose, can further enhance the coating speed and reduce the top layer thickness. A flow visualization technique was employed to observe the coating bead region. It was found to be easier to change the flow direction in the slide‐slot coating die than the double‐layer slot die, resulting in a more stable coating flow and much thinner top layer. POLYM. ENG. SCI., 45:1590–1599, 2005. © 2005 Society of Plastics Engineers.     

Structure formation mechanisms in consolidating pigment coatings—Simulation and visualisation

Microstructure development in consolidating pigment coating layers was studied in terms of particle flocculation and clustering mechanisms utilising a 3D particle dynamics model. The model includes hydrodynamic forces, colloidal interactions as well as the Brownian motion. The influence of colloidal interactions and drying strategy on the coating layer thickness development and internal solid concentration gradients, was investigated. A low particle surface potential resulted in the formation of porous particle networks, which impeded the shrinkage of the coating layer. At higher surface potentials particles arranged into denser structures, whereby the solids concentration profile could be controlled by the drying. Low electrostatic double layer thicknesses allowed sharp concentration gradients to form as result of the applied drying strategy. At high double layer thicknesses, the structure formation was similar regardless of drying strategy. This work elucidates the combined effect of drying conditions and colloidal suspension properties on coating microstructure development. Furthermore, the results aid in the understanding of how coating suspension additives may influence the structure development of the coating layer.     

Effect of the incorporation of SiC nanowire with double protective layers on SiC coating for C/C composites

To maintain the thermal stability of SiC nanowires during SiC coating fabrication process, carbon and SiC double protective layers were covered on the surface of nanowires. And SiC nanowires with double protective layers toughened SiC coating were prepared by pack cementation. The results showed that after introducing the SiC nanowires with double protective layers, the fracture toughness of the SiC coating was increased by 88.4 %. The coating protected C/C for 175 h with a mass loss of 3.67 %, and after 51 thermal shock cycles, the mass losses of the oxidized coating were 3.96 %. The double protective layers are beneficial to improve the thermal stability of nanowires, leading to good fracture toughness and thermal shock resistance of SiC coating. SiC nanowires consume the energy of crack propagation by fracture, pullout and bridging, leading to an increase in fracture toughness.     

Facile fabrication of high-efficiency near-infrared absorption film with tungsten bronze nanoparticle dense layer

An excellent transparent film with effective absorption property in near-infrared (NIR) region based on cesium-doped tungsten oxide nanoparticles was fabricated using a facile double layer coating method via the theoretical considerations. The optical performance was evaluated; the double layer-coated film exhibited 10% transmittance at 1,000 nm in the NIR region and over 80% transmittance at 550 nm in the visible region. To optimize the selectivity, the optical spectrum of this film was correlated with a theoretical model by combining the contributions of the Mie-Gans absorption-based localized surface plasmon resonance and reflections by the interfaces of the heterogeneous layers and the nanoparticles in the film. Through comparison of the composite and double layer coating method, the difference of the nanoscale distances between nanoparticles in each layer was significantly revealed. It is worth noting that the nanodistance between the nanoparticles decreased in the double layer film, which enhanced the optical properties of the film, yielding a haze value of 1% or less without any additional process. These results are very attractive for the nanocomposite coating process, which would lead to industrial fields of NIR shielding and thermo-medical applications.

PACS

78.67.Sc; 78.67.Bf; 81.15.-z     

重防腐环氧粉末涂料在西部管道工程中的应用

西部原油、成品油管道工程涉及的范围很宽,地形复杂、气候多样。通过对腐蚀与防护问题的研究,采用目前较先进的防护涂层,即单层重防腐环氧粉末涂料及重防腐环氧粉末涂料作为底层的三层防腐结构相结合,最大限度地保护管道,阻缓管道腐蚀,通过对各种防护对策比较着重阐述防腐环氧粉末涂料制造,三层PE熔结环氧粉末涂料结构的特点及工艺。     

Undec-10-ene-1-thiol multifunctional molecular layer as a junction between metallic zinc and polymer coatings on steel

The present work provides the formation of a new duplex system by combination of different layers on steel. Electrodeposition of zinc coating is performed as a first step and serves as a platform for molecular self-assembly and polymer coatings. Undec-10-ene-1-thiol molecule is used as layer junction between zinc surface and the polydimethylsiloxane (PDMS) film. Thiol function interacts by chemisorption with Zn surface while the terminal double bond takes place in the hydrosylilation reaction and thus increases the adhesion of PDMS to the zinc coating. Improvement of corrosion inhibition is evaluated by electrochemical methods at each stage of modification and particularly for the multilayer coating.     

Superposed structure of double-ceramic layer based on YSZ/LaMgAl11O19 thermal barrier coating

The superposed structure of double ceramic layer (SDCL) could be an effective means to develop long-life thermal barrier coating (TBC) at high temperatures. In this study, YSZ/LaMgAl₁₁O₁₉ TBC system with double-ceramic layer (DCL) and SDCL structures were prepared on nickel-based superalloy substrates by atmospheric plasma spraying. The thermal cycling behavior of the coatings was investigated using a furnace at 1000 °C and burner-rig facility at 1375 ± 25 °C on the coating surface. Results showed that the thermal cycle life of the SDCL structure was increased by 7.2% for the furnace and 13.2% for the burner-rig facility compared with that of the DCL structure. The relatively long thermal cycle life of the SDCL structure was attributed to the blocking of the propagation of cracks in the LMA layers by the YSZ ceramic layer and the release of residual thermal stresses by the formation of cracks in the LMA layers.     

铝电解用炭素阳极抗氧化涂层的性能研究

采用过渡层、阻挡层、封填层相结合的具有协同作用的涂层结构形式,涂覆在炭素阳极表面以阻止(减少)氧化性气体与碳阳极接触,从而阻止(减少)阳极的消耗。通过对单一涂层结构和功能组合层结构的氧化失重率测试分析以及涂层表面形貌的SEM分析对比结果表明,采用最优配方制备的复合结构涂层阳极,可使氧化损失比裸样(未涂覆抗氧化涂层试样)减少70%左右,抗氧化效果显著。     

Oxidation protective multilayer coatings for carbon-carbon composites

An oxidation protective double layered coating was deposited on a carbon-carbon composite (C/C) using a simple and low cost method. A surface modification of the C/C was obtained by direct reaction of liquid silicon with the C/C, promoting the formation of a 5-10 μm β-SiC layer on the composite surface. The inner layer, in contact with the C/C, is a composite made with a barium borosilicate glass matrix (SABB) and boron carbide particles; the outer layer is another composite layer formed by a SABB glass matrix and yttrium oxide particles. The layers are deposited by a slurry technique. Oxidation tests were carried out in a furnace in air, in order to verify the coating stability and its effectiveness. No mass loss of the C/C composite was observed after 100 h at 1200°C, while after 150 h at 1300°C the C/C mass loss did not exceed 1%.     

Layered particle-based polymer composites for coatings: Part II—Stone chip resistant automotive coatings

Especially in the course of modern automotive coatings comprising a reduced number of layers the resistance towards the stone chipping is becoming an issue. Layered double hydroxide (LDH)-based polymer composites are readily accessible materials and suitable to impart impact resistance to coatings, provided that an accurate understanding of the structure property relations both of the platelets and the composites is achieved.Incorporated into aqueous polymer dispersions the LDH particles are found in the resultant composites in the form of aggregated clusters, polymer intercalated stacks or exfoliated platelets depending on their size and the type of the intercalated anions.In addition LDH particles are found to be effective in the control of the coating layer architecture by affecting the spinodal phase separation of the incompatible polymers.Applied as a primer layer the LDH-based composites provided an excellent stone chip resistance to an automotive coating system.