纳米柱状多孔WO3- x /TiO2 薄膜的电致变色性能

采用反应磁控溅射在掠射角度α=0°和α=80°的条件下制备氧化钨（WO_3-x）薄膜,然后在其表面沉积二氧化钛（TiO₂）。利用X射线衍射仪（XRD）、场发射扫描电镜（FE-SEM）和X射线光电子能谱仪（XPS）对WO_3-x/TiO₂薄膜的晶体结构、表面/断面形貌以及表面化学成分进行表征。在三电极体系1 mol/L LiClO₄/PC溶液中,采用电化学工作站和紫外-可见分光光度计测试了WO_3-x/TiO₂薄膜的电致变色性能。XRD结果表明,WO_3-x/TiO₂薄膜为非晶态结构,与掠射角度无关。当掠射角度为80°时,获得了纳米柱状多孔薄膜。从 W 4f和Ti 2p的XPS谱图确认氧化钨为亚化学计量比的WO_3-x,而氧化钛为满足化学计量比的TiO₂。与致密薄膜相比,纳米柱状多孔薄膜需要较低的驱动电压且具有较快的响应速度。纳米柱状多孔薄膜的电荷容量为83.78 mC,是致密薄膜电荷容量30.83 mC的2倍以上。在±1.2 V驱动电压下,注入和脱出离子扩散速率分别为D_in=5.69×10^-10 cm²/s和D_de= 5.08×10^-10 cm²/s。与纯WO₃薄膜相比,WO_3-x/TiO₂薄膜的电致变色循环稳定性更好。纳米柱状多孔薄膜在可见光范围内具有较大的光调制幅度,因此其光密度变化（ΔOD）大于致密薄膜。     

Fe2O3-CaO-TiO2 体系下铁酸钙的合成过程及TiO2 和CaTiO3 的影响

为了确定高钛型钒钛磁铁矿烧结过程中铁酸钙的生成是受TiO₂还是TiO₂和CaO形成的CaTiO₃影响,首先利用Fe₂O₃和CaO的纯试剂合成了铁酸钙,并研究了TiO₂和CaTiO₃对钛铁酸钙 （FCT） 形成的影响。在Factsage 7.0软件进行热力学计算的基础上,通过在空气气氛下进行烧结,获得了在1023~1423 K温度范围内、不同烧结时间的不同样品。通过X射线衍射和扫描电镜-能谱分析等表征手段,对烧结样品的物相转变和微观结构变化进行了表征。发现FCT的形成过程主要分为2个阶段：前一阶段为1023~1223 K温度范围内Fe₂O₃与CaO之间的反应,合成产物为Ca₂Fe₂O₅,反应方程式为“Fe₂O₃(s)+ 2CaO(s)= Ca₂Fe₂O₅(s)”;后一阶段为1223~1423 K温度范围内Ca₂Fe₂O₅和Fe₂O₃的反应,主要产物为CaFe₂O₄,反应为“Ca₂Fe₂O₅(s)+ Fe₂O₃(s)= 2CaFe₂O₄(s)”,该阶段尤其是温度为1423 K时,反应速率显著加快,随温度的升高CaTiO₃显著增加。然而,Ti元素在铁酸钙中的固溶很难实现,TiO₂与铁酸钙之间的反应不是形成FCT的有效途径。随着保温时间的延长,CaTiO₃和FCT相界中Fe元素含量增加。FCT主要是通过Fe组分在CaTiO₃中固溶形成的,主要反应是“Fe₂O₃+CaTiO₃(s)=FCT(s)”。     

CC/PANI/TiO2复合材料的制备及其光催化性能研究

先采用原位聚合的方法在碳布上负载聚苯胺,然后利用溶剂热法在制备的碳布/聚苯胺(CC/PANI)复合材料上生长二氧化钛纳米片,得到了可便捷分离的CC/PANI/TiO₂复合光催化材料。通过SEM、XRD、UV、FTIR、XPS等手段对所制备的样品进行了形貌和结构表征,并比较了CC/PANI/TiO₂复合材料和纯TiO₂紫外-可见光条件下催化降解RhB的活性差异,结果表明CC/PANI/TiO₂复合材料具有比TiO₂更优异的光催化活性。光致发光光谱说明CC/PANI/TiO₂复合材料的发光强度比纯TiO₂的弱,有效抑制了光生载流子的复合;瞬态光电流响应和电化学阻抗谱(EIS)证明CC/PANI/TiO₂纳米复合材料更有效促进电子-空穴对分离和提高转移效率;活性物质捕捉实验证实?OH和?O_2^-是复合材料光催化降解RhB过程中的主要活性物质。CC/PANI/TiO₂复合材料循环利用6次后,仍然具有较高的催化活性,显示了其在污水处理领域中的良好应用前景。     

微波原位制备作为锂离子电池电极材料的石墨烯/TiO2 纳米复合物

通过改造的家用微波炉,实现了原位高效制备石墨烯/TiO₂纳米复合物。结果表明：微波辅助法能够在商用锐钛矿型TiO₂纳米颗粒表面均匀制备石墨烯纳米片,通过SiO₂/Si的剧烈电晕放电,其制备时间仅需数分钟（最短3 min）。石墨烯纳米片的尺寸大约为50 nm且缺陷很少。TiO₂晶体结构仍为锐钛矿型,主要归功于极短的制备周期和较低的反应温度（600~700 ℃）。石墨烯具有优异的电导率,可以提升锂离子扩散速率、提高电子传输速率并降低接触电阻。在1 C（170 mA·g^-1）条件下石墨烯/TiO₂纳米复合物的电池放电比容量提高了2倍。与商业化锐钛矿型TiO₂纳米颗粒相比,在1 C到5 C的不同充放电倍率下,石墨烯/TiO₂纳米复合物的比容量差距显著扩大。     

Zr1-xCoNbx (x = 0-0.2)合金吸放氢性能及抗歧化机制研究

采用真空电弧熔炼法制备了Zr_1-xCoNb_x (x = 0,0.05,0.1,0.15,0.2)合金,研究了Nb掺杂对合金晶体结构、吸放氢及抗歧化性能的影响。XRD结果表明：Zr_1-xCoNb_x (x = 0-0.2)合金主相为ZrCo相,含有少量ZrCo₂杂相;其氢化物为ZrCoH₃和ZrCo₂相。Nb掺杂极大地提高了合金吸氢动力学性能,ZrCo吸氢反应活化时间为7690 s,Zr_0.8CoNb_0.2缩短至380 s。ZrCo吸氢反应活化能为44.88 kJ mol^_-1 H₂,Zr_0.8CoNb_0.2降低至32.73 kJ mol^_-1 H₂,有利于吸氢反应动力学性能。DSC测量结果表明：ZrCo放氢温度为597.15 K,Zr_0.8CoNb_0.2降低至541.36 K,放氢温度降低,有利于抗歧化性能。ZrCo合金放氢反应活化能为100.55 kJ mol^_-1 H₂,Zr_0.8CoNb_0.2降低至84.58 kJ mol^_-1 H₂。合金歧化程度随着Nb掺杂量增加而降低,798 K保温10 h,ZrCo歧化83.68%,Zr_0.8CoNb_0.2仅歧化8.71%,Nb掺杂降低8f₂和8e位置氢原子数量,减小岐化反应驱动力。     

TiO2和Al2O3对CaO-SiO2-CaF2基础焊接渣系熔化特性的影响

研究了TiO₂和Al₂O₃对CaO-SiO₂-CaF₂基础焊接渣系黏度、熔化温度、表面张力等熔化特性的影响，并利用XRD和拉曼光谱分析四元焊渣的物相和结构特征.结果表明，TiO₂含量增加会显著降低焊接熔渣黏度、熔化温度及表面张力，提升熔渣流动性；Al₂O₃含量增加会使焊接熔渣黏度、熔化温度及表面张力先略有升高后明显降低.CaO-SiO₂-CaF₂-TiO₂和CaO-SiO₂-CaF₂-Al₂O₃四元焊渣完全熔化后，其黏度均在0.2 Pa·s以下，继续升温对黏度无显著影响，低于熔化温度后，焊渣随温度降低迅速凝固，呈明显的短渣特性.经XRD和拉曼光谱分析可知，四元焊接熔渣中主要含具有硅酸盐网络结构的Ca₄Si₂O_...     

氢化TiO2纳米棒的制备及其对Q235碳钢的光生阴极保护特性

随着海洋开发的逐步推进,海洋工程中的金属防腐蚀问题显得愈加重要。目前,可利用半导体的光电效应实现对金属的光生阴极保护,为改善常用的TiO₂光电极材料的弱光吸收和低转换效率问题,文中利用水热法在FTO导电玻璃表面构建一维有序TiO₂纳米棒阵列,并通过氢化处理提高TiO₂对太阳光的吸收和光电流密度。考察了氢化TiO₂纳米棒阵列在海水环境下对Q235碳钢的光生阴极保护特性,结果表明氢化TiO₂纳米棒的光电流密度达到了2.12 mA/cm²,且稳定性良好;当Q235碳钢耦连于模拟太阳光照下的氢化TiO₂纳米棒电极时,其界面反应电阻变小,电极电位较原先的腐蚀电位降低约349 mV,说明氢化TiO₂纳米棒阵列能够对碳钢产生良好的光生阴极保护效应,且该效应在无光条件下能保持至少7 h。     

TiO2/膨润土复合光催化材料的常温制备及性能研究

采用改进的溶胶-凝胶法,在以水为主要溶剂的反应体系中,控制钛酸四丁酯充分水解、缓慢聚合,在 常压、低温(70℃)的温和条件下制备出稳定的TiO₂纳米晶溶胶,并利用TiO₂纳米晶溶胶在膨润土表面负载,获得TiO₂/膨润土复合光催化材料。采用 X 射线衍射、扫描电镜、比表面积测定等研究手段对样品的结构形貌进行了表征,并考察了其光催化活性。结果表明：较高的水用量有利于TiO₂晶体形成,当去离子水:钛酸四丁酯摩尔比大于167:1时,在溶胶体系中出现了锐钛矿型TiO₂纳米晶体;TiO₂纳米晶主要负载于膨润土表面,并未嵌入到膨润土层间结构,但相对于单一膨润土,TiO₂负载显著提高了材料比表面积;当去离子水:钛酸四丁酯摩尔比=192:1时,在紫外光照射下,复合光催化材料表现出最高的光催化活性,对亚甲基蓝的降解率达到93.8%。     

FeTiO3-Fe2O3固溶体合成及其碳热还原研究

为明确Fe₂O₃固溶对FeTiO₃还原过程的影响机理,本文基于粉末煅烧法合成(1-x)FeTiO₃?xFe₂O₃固溶体(0≤x≤1),研究了非等温碳热还原条件下固溶体的还原行为,并采用X射线衍射仪(XRD)和扫描电镜-能谱仪(SEM-EDS)对合成固溶体及还原产物进行表征。结果表明,实验合成固溶体质地均匀,纯度较高,且x越大,FeTiO₃晶格畸变程度越大。固溶体开始还原温度和还原速率(还原度α的增大速率)均随着x值的增加而增加。固溶Fe₂O₃能够促进FeTiO₃还原,且在还原过程中存在过渡相Fe₂TiO₄和Fe₃Ti₃O₁₀。固溶体-石墨交界面首先形成浮士体(FeO)、钛铁尖晶石(Fe₂TiO₄)和TiO₂,进一步还原生成金属Fe和Ti₂O₃。非等温碳热还原过程动力学计算分析,得出表观活化能为295.54 kJ/mol。     

Al2O3/Ti2AlN复合材料在900℃,1000℃和1100℃空气中的氧化行为

利用综合热分析仪、背散射扫描电镜(BSE)和能谱分析(EDS)对Al₂O₃/Ti₂AlN复合材料在900 ℃,1 000 ℃和1 100 ℃/20 h空气中连续氧化20h后的氧化增重及氧化层截面进行了研究。结果表明：Al₂O₃/Ti₂AlN复合材料在空气中的氧化行为符合抛物线规律,在900 ℃,1 000 ℃和1 100 ℃/20 h氧化增重分别为2.78×10_-2 kg/m₂、10.4 ×10_-2 kg/m₂、21.9 ×10_-2 kg/m₂,抛物线速率常数相应为1.08×10_-8 kg₂/m₄s、1.44×10_-7 kg₂/m₄s、6.56×10_-7 kg₂/m₄s,氧化激活能为274 kJ/mol。氧化层主要由TiO₂和Al₂O₃组成的,连续的Al₂O₃次外层可以提高其抗氧化性能。氧化层结构的改变是由于氧化温度对Ti₄₊、Al₃₊由基体表面向外扩散和O_2-向内扩散的影响,以及TiO₂和Al₂O₃在不同温度下的形核生长速率导致的。对Al₂O₃/Ti₂AlN而言,控制材料与氧化气氛的界面是提高该材料抗氧化性能的关键。     

Effect of B2O3 content on viscosity and structure of SiO2−MgO−FeO-based slag

The effect of B₂O₃ content on the viscosity of SiO₂?MgO?FeO-based molten slag system was investigated using the rotating cylinder method. The evolution process of the melt structure under different contents of B₂O₃ was comprehensively studied via FTIR spectroscopy and a model for calculating the degree of polymerization was developed. The results showed that the viscosity of the molten slag decreased with the addition of B₂O₃, which had a slight effect when its content exceeded 3 wt.%. As the addition of B₂O₃ increased from 0 to 4 wt.%, the break temperature of the slags decreased from 1152 to 1050 °C and the apparent activation energy decreased from 157.90 to 141.84 kJ/mol. The addition of B₂O₃ to the molten slag destroyed the chain silicate structure to form a more cyclic borosilicate structure. The Urbain model was improved to calculate the viscosity of the SiO₂?MgO?FeO-based slags, and the values were in good agreement with the experimentally measured values.     

Effect of Bi2O3 on structure and wetting studies of Bi2O3-ZnO-B2O3 glasses

Glasses with different Bi₂O₃ contents (37-42 mol%) have been prepared by conventional melt quench technique. The IR and Raman studies indicate that these glasses are made up of [BiO₆], [BiO₃], [BO₃] and [BO₄] basic structural units. The vibrations of [BiO₃] and [BO₃] become stronger as the content of Bi₂O₃ increases, which makes glass structure loosened. Viscosity of the glasses was measured by using a Rheotronic III paralleled plate rheometry, which shows that the viscosity of glass samples decreased when the content of Bi₂O₃ increased at the same temperature (400-460 °C). The temperature range which suits for glasses sealing was calculated by using the approximation of Arrhenian behaviour. The wetting performance of Bi₂O₃-ZnO-B₂O₃ glasses was described by using high-temperature microscope, which also proves that the structure of investigated Bi₂O₃-ZnO-B₂O₃ glasses become loosened due to the increasing of the content of Bi₂O₃.     

Effect of B2O3 on the Structure and Viscous Behavior of Ti-Bearing Blast Furnace Slags

This study provided a fundamental analysis of the viscous behavior and structure of Ti-bearing blast furnace slags modified by different B₂O₃ additions with a basicity (CaO/SiO₂) range of 0.5–0.9. The viscosity of slag melts was measured by rotating cylinder method, and the results showed that both slag viscosity and apparent activation energy for viscous flow remarkably decreased with B₂O₃ addition. To connect the viscosity variation of slags to the melt structure, Fourier transformation infrared spectroscopy analysis was performed. The results indicated that B₂O₃ acted as a typical network forming oxide, which was introduced into the network and existed dominantly as a two-dimensional structure, BO₃ triangular. With the increase of B₂O₃ content, the stretching vibration of BO₃ triangular gradually became more pronounced, which resulted in a simpler and less complex structure and caused the decrease of slag viscosity.     

Precipitation selectivity of boron compounds from slags

The effects of slag composition, additive agents and heat treatment on the crystal morphology, the precipitation behavior and the efficiency of extraction of boron (EEB) from slags were investigated. The EEB varied with the slag composition; the further the slag composition deviated from the line between the borate 2MgO·B₂O₃ and the silicate 2MgO·SiO₂ in the MgO–B₂O₃–SiO₂ system, the lower the EEB. The EEB varied with the temperature of heat treatment, the highest EEB appeared at 1100°C. During the solidification of molten slags the behavior of the boron compounds involved two steps: phase separation and crystal precipitation. The micrographs of the phase separation were described using the fractal dimension which was 1.87–1.92. The result of computer simulation indicated that the mechanism of the phase separation was Spinodal decomposition. The fractal dimension of the crystalline phase 2MgO·B₂O₃ whose micrographs showed fractal characteristics was 1.62. The result of computer simulation showed that the growth of the borate 2MgO·B₂O₃ was dependent on the DLA model. The additives TiO₂ and MO_x decrease the activation energy of crystallization and make the boron compounds precipitate in the form of the crystalline phase more easily, thus the EEB was increased. The structure of slag was modified by addition of TiO₂. A lot of [B₂O₅] and [BO₃] clusters, which were favorable to make crystals of 2MgO·B₂O₃ and 3MgO·B₂O₃ precipitate, were formed in the slags.     

KINETICS OF REDUCTION IRON OXIDE IN CaO-SiO_2-Al_2O_3-Fe_tO SLAGS WITH CARBON SATURATED IN MOLTEN IRON

1.IntroductionItisimportanttoinvestigatethekineticsofreductionofironoxideinslagswithcarbonsaturatedinmoltenironforunderstandingboththeslag-metalreactioninthehearthofblastfurnaceandthefinalreductionbehavioursofprereductionironorepelletscontainingcarboninironbathreactor.Theprevious.......h..sll--7]focusedtheirattentionsmainlyonthereductionrateofpureironoxideortheredlltionrateofironoxideinsimpleslags.Thoseresultsarenotconsistentwiththatoftilerealsituation.Throughanalyzinggascompositionattheoutlet…     

Optimum composition of blast furnace slag as deduced from liquidus data for the quaternary system CaO-MgO-Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-SiO<Subscript>2</Subscript>

On the basis of liquidus measurements in the system CaO-MgO-Al₂O₃-SiO₂ and previously published data, diagrams have been constructed at 5 pct Al₂O₃ intervals from 5 to 35 pct Al₂O₃. Liquidus temperatures and primary phase fields are shown. The optimum composition of a blast furnace slag for a given alumina content is indicated. At the optimum point, ordinary slags will be entirely liquid and will have maximum desulphurization potential and minimum viscosity. The relation of optimum composition of slags to the “plateau region” of the liquidus surface, and the application of these data on synthetic quaternary slags to actual slag compositions are discussed. Index of refraction of glasses is given as well as composition, temperature, and phase data for each mixture.     

Coordination polymers with [Au(CN)4]- building blocks: a 1-d chain of molecular NiII2AuIII2 squares

A new coordination polymer utilizing the neglected cyanoaurate anion [Au(CN)₄]- building block is reported. Reaction of a Ni(II) salt, diethylenediamine (dien) and K[Au(CN)₄] yields Ni(dien)[Au(CN)4]₂, which consists of a unique bimetallic Ni(II)₂/Au(III)₂ supramolecular square through cis N(cyano) bridging of the [Au(CN)₄]- building block to [Ni(dien)]²⁺ cations. These squares further aggregate into a 1-D chain via Au-N(cyano) interactions; no Au(III)-Au(III) interactions are observed. Within the square, the magnetic coupling between the Ni(II) centres is very weak, indicating that the [Au(CN)₄]- unit is a poor mediator of magnetic exchange in this system.     

Synthesis and crystal structure of Ba3Si4C2

SiC powder prepared by the Na flux method at 1023 K for 24 h and Ba were used as starting materials for synthesis of tribarium tetrasilicide acetylenide, Ba₃Si₄C₂. Single crystals of the compound were obtained by heating the starting materials with Na at 1123 K for 1 h and by cooling to 573 K at a cooling rate of −5.5 K/h. The single crystal X-ray diffraction peaks were indexed with tetragonal cell dimensions of a = 8.7693(4) and c = 12.3885(6) Å, space group I4/mcm (No.140). Ba₃Si₄C₂ has the Ba₃Ge₄C₂ type structure which can be described as a cluster-replacement derivative of perovskite (CaTiO₃), and contains isolated anion groups of slightly compressed [Si₄]⁴⁻ tetrahedra and [C₂]²⁻ dumbbells. The electrical conductivity measured for a not well-sintered polycrystalline sample was 2.6 × 10⁻²–7 × 10⁻³ S cm⁻¹ in the temperature range of 370–600 K and slightly increased with increasing temperature. The Seebeck coefficient showed negative values of around −200 to −300 μV K⁻¹.     

Primary investigation of corrosion resistance of Ni-P/TiO2 composite film on sintered NdFeB permanent magnet

In this paper, an electroless nickel plating and sol-gel combined technique used to prepare the Ni-P/TiO₂ composite film on sintered NdFeB permanent magnet is described and the composite film was characterized by X-ray diffraction (XRD), environmental scanning electron microscopy (ESEM), and energy dispersive X-ray spectrometer (EDX). The corrosion resistance of Ni-P/TiO₂ film was studied by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) techniques. The self-corrosion current density (i_corr) of Ni-P/TiO₂ composite film is 2.38μA/cm² in 0.5mol/L H₂SO₄ solution about 33% of that of Ni-P coating and 0.22μA/cm² in 0.5mol/L NaCl solution about 14% of that of Ni-P coating, respectively. In 0.5mol/L H₂SO₄ and 0.5mol/L NaCl solutions, the polarization resistance (Rp) of the composite film is 12.5kΩ cm² and 120kΩ cm², about 1.6 and 2 times that of Ni-P coating, respectively. The results indicate that Ni-P/TiO₂ composite film has a better corrosion resistance than Ni-P coating.