铜酞菁聚甲基丙烯酸甲酯的合成与表征

以氯甲基化铜酞菁为引发剂,过渡金属卤化物和配位剂(Cu2Cl2/2,2`-联吡啶)为催化体系,进行甲基丙烯酸甲酯原子转移自由基聚合反应,合成出了铜酞菁聚甲基丙烯酸甲酯,并对其进行了结构表征。     

热处理对TiO_2薄膜微观力学性能的影响

采用喷涂法在5mm普通浮法玻璃上制备了纳米级锐钛矿型TiO2薄膜,并进行了不同温度的热处理。采用原子力显微镜、X射线衍射仪和纳米压痕仪分析了薄膜的形貌、结构和微观力学性能。讨论了热处理温度对纳米TiO2薄膜微观力学性能的影响。结果表明:随着热处理温度由20℃升高到500℃,薄膜中TiO2均变为锐钛矿型,平均晶粒尺寸略有增加,薄膜表面平整;随热处理温度从350℃升至500℃,平均粗糙度由12.516nm降低至11.433nm;热处理后纳米压痕硬度和弹性模量均有增加,分别由412.6MPa,14.9GPa增加到908.3MPa,28.4GPa;塑性指数逐渐增大,由0.028增大到0.032;摩擦因数由0.166降低到0.120。     

Hydroxyapatite coating on titanium surface with titania nanotube layer and its bond strength to substrate

A vertically aligned titania nanotube layer on titanium surface was prepared by electrochemical anodic oxidation in an F⁻-containing electrolyte, followed by annealing at 450 °C. Bioactive hydroxyapatite (HA) coatings on as anodized titania nanotube layer were obtained by a biomimetic method without other surface treatment. The morphology, crystal structure, and components of the titania nanotube layer and bioactive coatings were examined by scanning electron microscopy, thin film X-ray diffraction, and Fourier transform infrared spectroscopy. The bond strength between the HA coatings and substrates was tested using a mechanical tester. The diameter of the titania nanotubes was about 100 nm, the wall thickness about 19 nm and the height about 1 μm. HA rapidly deposited on the as anodized nanotube surface after immersion in a biomineral solution only for 1 day. The HA coatings were carbonated apatite and composed of a number of column-like crystals with nanometer size. Tensile test shows that the bond strength between the HA coating and the nanotube layer was larger than 15.3 MPa.     

Use of LINbO3 for Design of Device-type Catalysts with Activity Controllable Functions

A poled ferroelectric LiNbO₃ single crystal with high spontaneous polarization was employed as a catalyst support, and the static and dynamic effects of the polar substrate surfaces on the adsorptive and catalytic properties of thin film catalysts deposited were shown. For the static effect, it was demonstrated that the surface conductivity of copper and metal-free phthalocyanine films increased by the adsorption of NO gas, to a larger extent, when the substrate was the negative polar surface, compared to the positive one. The role of the polar substrates is explained In terms of a band bending model. For the dynamic effect, the Rayleigh surface acoustic wave generated on the LiNbO₃ substrate was shown to enhance the catalytic activity for ethanol oxidation on Cu and Ag thin film catalysts deposited on the propagation path. It is proposed that the catalyst activation is mainly due to an electric Held produced. The use of poled LiNbO₃ is suggested to be effective for the development of a device-type catalyst with activity controllable functions.     

Fe3+掺杂TiO2溶胶的低温制备及其光催化性能

采用溶胶-凝胶法在低温下制备出Fe3+掺杂TiO2(Fe3+/TiO2)溶胶,研究Fe3+掺杂对TiO2催化性能的影响,用TG/DTA技术分析TiO2粉末的热分解过程,用XRD、TEM等表征Fe3+掺杂对TiO2晶型、晶粒尺寸、晶粒形貌的影响,结果表明:Fe3+掺杂会对纳米TiO2晶粒的粒径及晶体形貌产生影响,抑制TiO2晶型由锐钛矿向金红石的转变。将亚甲基蓝作为目标污染物进行光催化降解试验,紫外-可见漫反射吸收光谱分析表明:经适量Fe3+掺杂后的TiO2溶胶光催化活性提高,当硝酸铁与钛酸丁酯的物质的量比为0.20%时,光催化活性最佳。     

Nucleation and Growth of Titania Nanoparticles Prepared by Pulsed Injection Metal Organic Chemical Vapor Deposition from a Single Molecular Precursor

Nanometer-sized titania particles were deposited by the pulsed liquid injection chemical vapor deposition technique from a single molecular metal-organic precursor. A liquid solution of titanium (IV) isopropoxide was used, Ar was the carrier gas, and titania nanoparticles were deposited on the hot wall of the reactor fused quartz tube, under supersaturated conditions. Energy-dispersive spectroscopy, X-ray diffraction (XRD), and transmission electron microscopy studies reveal the formation of amorphous titania-agglomerated nanoparticles (40–50 nm). XRD patterns after different post-annealing processes reveal a high anatase–rutile transformation temperature, comparable to that of micrometer-sized titania, attributed to lattice strains in the nanoparticle structure, as calculated from the X-ray data. The growth dynamics involved in the nucleation and formation of titania nanoparticles is discussed in terms of the so-called chemical vapor synthesis or chemical vapor condensation.     

The technological importance of the crystallographic and surface properties of copper phthalocyanine pigments

New and previously reported results are combined to emphasise the importance of fundamental crystallographic and surface chemical properties on the technology of copper phthalocyanine pigments. Particular attention is paid to undesirable aggregation of pigment crystals and to the changes in aggregate structure and crystal phase which occur during ageing. The two most commercially significant forms of copper phthalocyanine are the α- and β-polymorphs. The crystals of both consist of parallel molecular stacks. In β-phase crystals, the coordinate bonding between adjacent molecules within the stacks promotes crystal growth in the direction of the stacks, producing commonly observed rod-shaped crystals. Moreover, the molecular stacks of the β-phase, being interlocked, are not readily distorted. In contrast, the distortion of lattice planes in the α-phase can accommodate mismatch between contiguous crystals, and promote their fusion into strongly coherent aggregates. Although the strength of aggregation is thus influenced by the crystal lattice, the geometric structure of aggregates is largely determined by crystal shape, brick-shaped crystals being more prone to aggregation than rod-shaped crystals. Aggregates of brick-shaped crystals are porous, and solvent molecules can penetrate some way into their internal structure. Ageing may then occur. Changes in crystal phase and aggregate structure are discussed at some length. New evidence is presented for the existence of an intermediate metastable state in the α-→β-phase transformation induced by solvents. The β-→α-phase change induced by mechanical grinding is shown to start at the surface of β-phase crystals, and then to extend gradually throughout their bulk. Examples are given of different kinds of ageing of aggregate structures. Ageing of aggregates of α-phase crystals in liquid toluene involves not only Ostwald ripening and a transformation to the β-phase, but also crystal fusion (as occurs during ageing in toluene vapour). In liquid n-propanol, on the other hand, the aggregates are converted to highly consolidated structures.     

解析酞菁绿制造中的铜酞菁氯代反应机理

该文解析酞菁绿制造中的铜酞菁氯代反应机理,铜酞菁具有双分子结构,是酞菁绿的氯原子取代度最多只有15个的根本原因.铜酞菁氯代可以在固-固反应体系中进行,三氯化铝将氯气转化为固态,参与反应,反应历程最关键的步骤是生成σ络合物中间体,加入氯化亚铜作用的机理是防止中心离子脱落,加入氯化钠作用的机理是剥开铜酞菁粒子.铜酞菁氯代也可以在液-液反应体系中进行,焦硫酰氯将氯气转化为液态,参与反应,反应历程表明,氯磺酸很容易对铜酞菁进行酰氯化,首先得到磺酰氯基铜酞菁,然后的去SO2是整个反应的控制步骤.     

铜酞菁磺酰胺衍生物对铜酞菁的表面处理

合成了一系列铜酞菁磺酰胺衍生物,并用它们对铜酞菁颜料进行表面处理以改进铜酞菁颜料的分散性、润湿性.通过研究初步认为:添加铜酞菁磺酰胺衍生物能提高铜酞菁颜料在水中的分散性,以添加5%具有短脂肪链的铜酞菁磺酰脂肪胺衍生物组份的分散率为最高.     

解析酞菁绿颜料化加工机理

酞菁绿粗品经过颜料化处理之后,所得到晶体颗粒的一致性越同一,颜色越鲜艳,粒子越细小,着色力越高.酞菁绿的晶型只有一种,颜料化处理不能改变酞菁绿的晶型,只是把粗大的晶体颗粒变成为细小的晶体颗粒,把不规整的晶体结构调整成比较规整的晶体结构.文中介绍了酞菁绿粗品晶体颗粒细化的两种方式：一是重结晶,先将酞菁绿粗大的颗粒完全溶解,然后再重新结晶成适度大小的晶体颗粒;二是机械破碎,在研磨介质、助磨剂的作用下,将酞菁绿粗大的颗粒研磨成适度大小的晶体颗粒.     

增效超分散剂对铜酞菁颜料表面改性的研究

本文合成了几种增效超分散剂，并用于β-型铜酞菁的表面改性，其分散性、流动性和色光均有提高。结果表明，以聚酯为溶剂化链，胺或多胺类为锚基，通过砜基连接到铜酞菁分子上制成增效超分散剂。当超分散剂的用量由0％增加至8％时，体系的流动度由29增加到45；溶剂化链的分子量在1800-8000时，体系的分散性提高明显：在不同的脂肪胺中，多乙烯多胺效果最佳。这类分散剂都具有很好的抗絮凝性能，所制成的油墨长时间置放不分层。     

改性铜酞菁颜料的性质研究

本文研究了带有部分基团取代的α型铜酞菁颜料的合成方法,采用红外光谱、X衍射、电镜扫描对其晶相稳定性进行了研究,并测试了其着色力、比表面积和抗絮凝性能.结果表明:掺入部分—SO_3NR′R、—Br取代及部分聚合铜酞菁,均能使α型铜酞菁在芳香烃溶剂中具有抗晶型转变和抗絮凝的优点.     

一种新型的可溶性铜酞菁衍生物的合成及其性能研究

通过将铜酞菁氯磺化后 ,与带活性羟基质子的苯酚反应 ,合成了一种与铜酞菁基体色光基本不变 ,但在有机溶剂中溶解度十分大的新型铜钛菁衍生物———铜酞菁磺酸苯酯。用元素分析、IR和热重分析等对其进行了表征。用UV光谱分析了产物的色光。测试了产物的溶解度和凝聚性能     

钛醇盐热解法制备二氧化钛薄膜

以钛酸丁酯为前驱体,研究了旋涂热解法制备二氧化钛薄膜的工艺,在载玻片上获得了负载牢固的透明性较好的二氧化钛薄膜,研究了稳定剂对于二氧化钛薄膜光催化性能的影响,以及不同层数的二氧化钛薄膜的光催化性能,用热分析方法表征了钛醇盐的热解过程,并用XRD对薄膜的晶相结构进行了表征.     

Copper deposition and its replacement by platinum on a gold electrode

The decoration of single crystal gold electrodes with platinum using underpotential deposited copper as an intermediate has been studied in detail. It was found that a significant fraction of the copper is lost in the transfer process from the upd cell to the exchange cell. In addition the surface of the gold is not covered uniformly by the platinum. Nevertheless, acceleration of the electroreduction of oxygen was observed with a loading of 0.14 μg cm⁻². The structure of the decorating layer was studied by scanning electron microscopy and atomic force microscopy.     

WC@TiO2核壳结构纳米复合材料制备与电催特征

Monotungsten carbide and titania nanocomposite with core-shell(WC@TiO2)structure was prepared by a new approach of spray drying and reduction-carbonization reaction,with titania nanopowder and ammonium metatungstate as precursors,methane as carbon source,and hydrogen as reduction gas.The sample was characterized by X-ray diffraction,scanning electron microscope,high resolution transmission electron microscope and X-ray energy dispersion spectroscopy.The results show that its crystal phase is composed of brookite,tungsten and monotungsten carbide.The morphology of the sample particle is irregular sphere-like,with a diameter smaller than 100 nm.Its chemical components are titanium,tungsten,carbon and oxygen.Monotungsten carbide nanoparticles lie on the surface of titania core and form an incomplete shell around titania core in the nanocomposite.The measurement with a microelectrode system of three electrodes shows that the sample is electrocatalytic active to nitrophenol in basic solution at room temperature.Its peak potential is at0.988 V(vs saturated calomel electrode (SCE)),which is more negative than the peak potential,0.817 V(vs SCE),of mesoporous monotungsten carbide, and its peak current is 8.809μA,which is higher than the peak current,4.058μA,of mesoporous monotungsten carbide.The hydrogen generation potential of the sample is at1.199 V(vs SCE),which is more negative than that of pure nanosized monotungsten carbide at1.100 V(vs SCE).These results show that the presence of titania in the sample can lower the peak potential of nitrophenol electrocatalysis and its hydrogen generation potential,and increase its peak current of nitrophenol electrocatalysis in basic solution at room temperature.This indicates a synergistic effect of titania and monotungsten carbide in electrocatalysis.     

Synthesis and Electric Modulus Formalism of Novel Metal-Phthalocyanine Bridged Polymers

Novel nickel and copper phthalocyanine polymers, with uniformly carboxylic end groups and carbonyl groups as bridges linking the phthalocyanine units, were successfully prepared. Structural modelling and atomic absorption spectroscopy confirmed the network polymeric structure and suggested at least nine phthalocyanine units in each polymeric network. The dielectric properties of the prepared polymers were investigated over a wide range of frequencies at room temperature. The electric modulus formalism was used to study the conductivity relaxation in the prepared polymers. The collapsing of the real part of the conductivity function, σ’, at higher frequencies for both materials was observed indicating that the local molecular dynamics is due to the polymer conjugated backbone (functional and/or terminal groups) with no clear effect of the central metal.     

Effect of treatment conditions and titanium source on the hydrothermal synthesis of bismuth titanate particles

Hydrothermal synthesis of bismuth titanate particles was performed using various titanium sources. Uniform particles of titanium hydroxide, hydrous titania, and anatase were prepared respectively as starting materials. They were treated hydrothermally with bismuth nitrates in NaOH aqueous solution. The obtained crystal phases depended strongly upon the phase of the titanium source. Plate-like bismuth titanate particles were obtained at high-treatment temperatures when hydrous titania was used as the starting material. Spherical particles with a spherulite-like structure were obtained at low temperatures and for long treatments.     

Voltammetry of UPD copper and formic acid as characterization of preferentially oriented polycrystalline platinum surfaces

In order to characterize the surface structure of electrochemically modified polycrystalline platinum, the voltammograms of underpotential deposited copper and of formic acid are studied. The operating conditions are chosen in such a way that a direct comparison to results on single crystal platinum electrodes is possible. It is shown that UPD copper in HF solution and formic acid oxidation are well suited to characterize the modified structure of platinum surfaces.