高温气相反应合成金红石型纳米TiO2颗粒的研究

在高温气相反应器中,利用掺 ＡｌＣｌ３的 ＴｉＣｌ４氧化反应制备金红石型纳米 ＴｉＯ２颗粒研究了氧气预热温度、反应器尾部氮气流量、反应温度、停留时间等对 ＴｉＯ２颗粒大小的影响结果表明：提高氧气预热温度和加大反应器尾部氮气流量对控制产物粒径有利, ＴｉＯ２粒径随反应温度升高和停留时间延长而增大当反应温度为１３７３Ｋ, ＡＩＣｌ３与ＴｉＣｌ４摩尔比为 ０．２５、停留时间为１．７３ｓ时,纯金红石相纳米ＴｉＯ２颗粒的粒径分布为 ３０－５０ｎｍ．     

氯化法钛白氧化反应器结构分析与模拟

气相氧化反应器是氯化法钛白工艺中的核心技术，对其设备的组成结构进行分析，并讨论气相氧化反应器的模拟进展，提出建立过程控制模型的思路。     

用TiCl4制备纳米TiO2的研究状况

综述了以TiCl4为原料制备纳米TiO2的主要方法:氢氧火焰水解法、气相氧化法、气相燃烧法、液相沉淀法、溶胶-凝胶法、微乳液法和水热法,并对其优缺点做了相应的评论,最后指出了今后研究的方向。     

High-Temperature Oxidation Behavior of Ti-22Al-27(Nb, Zr) Alloys

研究了Ti2Al Nb基合金Ti-22Al-(27-x)Nb-x Zr(x=0,1,6,at%)在650~800℃的氧化行为。采用XRD和SEM等测试技术对此温度区间形成的氧化层特征进行了分析。结果表明,相比Ti-22Al-27Nb,含锆合金具有较好的抗氧化性能。Ti-22Al-(27-x)Nb-x Zr合金在650℃氧化100 h,主要氧化产物为Ti O2,而在800℃氧化100 h,Ti O2,Al2O3和Al Nb O4为主要产物,但是在Ti-22Al-21Nb-6Zr合金中还有Zr O2生成。Ti-22Al-26Nb-1Zr合金具有优异抗氧化性能,归因于氧化产物细化形成了致密的氧化层,而Ti-22Al-21Nb-6Zr合金,虽然在800℃也形成了较多Al2O3,但是氧化层中的Zr O2为氧的快速扩散提供通道,进而导致该合金氧化增重明显。     

氯对TiAl基合金高温氧化行为的影响

研究了表面喷沙少量ＭｎＣｌ２及离子注入氯对ＴｉＡｌ基合金９５０℃恒温氧化行的影 响ＴｉＡｌ合金９５０℃氧化后氧化膜为ＴｉＯ２及Ａｌ２Ｏ３的混合物,表面涂少量ＭｎＣｌ２后, 合金氧化速度降低了４个数量级,氧化膜的成分主要为Ａｌ２Ｏ３,离子注入Ｃｌ在氧化初期也显著降低 了氧化速率,延迟了ＴｉＯ２形成时间。     

TiCl_4水解法制备TiO_2纳米颗粒包覆Ag纳米线阵列结构

采用水热法制备了TiO2纳米颗粒包覆Ag纳米线阵列结构。通过选区电子衍射手段确定了TiO2包覆层的晶体结构为锐钛矿。研究了TiCl4溶液浓度和温度对TiO2/Ag包覆结构形貌的影响,结果显示0.1 mol/L的TiCl4溶液能够得到连续均匀的TiO2包覆层,当TiCl4溶液浓度高于0.1mol/L时,水解产生的HCl在水热环境下会对Ag纳米线造成不同程度的腐蚀。80℃条件下能够得到较为均匀的TiO2包覆层和较高的结晶度;温度过低时,TiO2包覆层的结晶不明显,温度过高时,水解产生的HCl会对Ag纳米线产生腐蚀。     

Effect of La^3＋ on evolution of TiO2 coating layers on lamellar sericite and their pigmentary properties

TiO2-coated sericite powders were prepared by the chemical deposition method starting from lamellar sericite and TiCl4 in the presence of La3+. After calcination at 900 ℃ for 1 h, the resultant TiO2 nanoparticles on the sericite surfaces exist in anatase phase. The light scattering indexes of the TiO2-coated lamellar sericite powders are dozens of times higher than those of the naked lamellar sericite powders, varying with different contents of La3+. The presence of La3+ in the deposition solution is beneficial to the formation of the small-sized anatase TiO2 nanoparticles. The presence of La3+ also favors the formation of the dense and uniform island-like TiO2 coating layers in a large range of the mass ratio of TiO2 to sericite from 5% to 20%. XPS analysis shows that when La3+ is absent in the reaction solution, TiO2 coating layers anchor on the sericite surface via Ti-O-Si and Ti-O-Al bonds. The presence of La3+ causes the formation of Si-O-La and Al-O-La bonds on the sericite surface and Ti-O-La bond on the surface of TiO2 coating layers.     

微弧氧化电压对钛基氧化膜成分及生物活性的影响

采用微弧氧化法在纯钛表面制备了多孔钛氧化膜并进行表征。室温条件下,采用200V至350V恒压模式以0.5mol/L磷酸溶液作为电解液进行微弧氧化实验。FESEM分析表明,不同电压下,微弧氧化法制备出的氧化膜层均为多孔结构,孔径分布随电压的升高而增大。XRD和XPS分析表明,在强烈的微弧放电过程中,纯钛表面生成了TiO2和TiP2O7,随着电压的增高,TiO2的结晶度和磷元素的含量逐渐升高。体外实验表明,羟基磷灰石的沉积主要归因于样品表面含有大量可分解成HPO24?的TiP2O7,HPO24?离子被吸附到样品表面成核。约4at%磷元素能促进羟基磷灰石的生成。     

肯尼亚天然金红石矿流化床氯化率的研究

对肯尼亚金红石矿加碳氯化体系的热力学和动力学进行了研究,分析表明,C在固相中过量,体系处于平衡态时,TiCl4和CO是仅有的2个稳定的产物,增加C/TiO2比对产物组成影响不大;高温时,TiO2与C和Cl2生成CO的方程是占主导地位的。本实验提出了一个反应速率模型,得到金红石氯化率的公式,与实验数据吻合较好。反应速率与颗粒初始半径和天然金红石密度有关,在900℃到1000℃温度范围内,表观活化能为10.569 kJ/mol,扩散是反应的主要控制步骤。得到了C-Cl2体系中氯气反应率表达式,氯气反应率取决于反应程度、氯气浓度和焦炭粒径。     

阳极氧化法制备TiO_2纳米管形成机制

采用阳极氧化法在纯Ti表面制备了TiO2纳米管。根据电流-时间(I-t)曲线,结合不同阶段Ti表面的FE-SEM照片,将TiO2纳米管的形成过程分为4个阶段,即氧化膜生成阶段、氧化膜化学溶解和生成阶段、纳米管生成阶段、纳米管稳定阶段。整个过程中发生两个基本的反应,其中TiO2的生成为电化学反应过程,而TiO2的溶解为化学反应过程。通过这两步反应,完成TiO2纳米管形成的一个基本周期。循环发生这两步反应,有序的TiO2纳米管形成。TiO2纳米管成节状,结合上升的生长反应可知,每一节的形成代表上述两个反应循环发生一个周期。     

聚乙二醇对TiO2-SiO2粒子的生成及光催化性能影响

以TiCl4为原料,采用自组装技术制备TiO2-SiO2复合粒子,加入聚乙二醇2000（PEG 2000）,探讨聚乙二醇对TiO2-SiO2粒子生成及光催化降解甲基橙的影响。研究发现：随组装次数的增多,复合粒子表面TiO2 的含量增多;随PEG2000的加入,TiO2颗粒间呈现一定的孔隙,使TiO2层粒子的表面积增加;样品经550 ℃煅烧,得到均为锐钛矿与金红石的混合相,且随着PEG2000含量的增加,锐钛矿的相对含量随之增加;光催化实验表明,PEG2000的掺杂使TiO2-SiO2的光催化性能得以提高。     

Reaction procedure of a graphite fiber reinforced Ti-Al composite produced by squeeze casting-in situ reaction

The in situ reaction procedure and microstructure evolution of a graphite fiber reinforced Ti-Al composite (Grf/Ti-Al) was investigated, and the stability of TiAl3 at high temperature was discussed. As-cast material was prepared by pressing molten pure aluminum into a preform, which was composed of titanium particles and graphite fibers. The in situ reaction procedure of the as-cast material was investigated by differential scanning calorimetry (DSC), and phases in the products were detected by X-ray diffraction (XRD). Experimental results showed that TiAl3 was formed first. With an increase in temperature, TiC and Al4C3 were observed, but TiAl3 decreased. In the final product, Al2O3 and TiO2 were observed. It was considered that the previous forming TiAl3 decomposed, then TiC precipitated, and subsequently, oxidation resulted in the formation of Al2O3 and TiO2.     

Kinetic conditions for the simultaneous formation of oxide and sulphide in reactions of iron with gases containing sulphur and oxygen or their compounds

The scaling of pure iron has been investigated in N₂O₂SO₂ and COCO₂COS mixtures between 700 and 900°C. Simultaneous formation of FeO and FeS at the scale/gas phase boundary is observed when the diffusion in the aerodynamic boundary layer or the reaction at the scale/gas phase boundary is the rate-controlling step of the oxidation in O₂N₂ mixtures or of the sulphidation in COCOS mixtures. In those cases the addition of the second oxidant (SO₂ to O₂N₂ mixtures, and an increased CO₂ to COCO₂COS mixtures) increases the rate of the oxidation or sulphidation reactions. When, however, the diffusion of iron ions and electrons through the oxide or sulphide layer respectively, or the reaction at the metal/scale phase boundary are rate-determining, the thermodynamically stable phase (oxide or sulphide) is formed exclusively and the addition of the second oxidant has no influence on the scaling rate. These results may be understood from an evaluation of the equilibria prevailing at the scale/gas phase boundary.     

Effects of Nb and Si on high temperature oxidation of TiAl

The isothermal oxidation behavior of TiAl based alloys at 900℃ in air with a combination of Nb (5%-10%, mole fraction) and Si (1%-5%, mole fraction) was investigated. The microstructure and the composition of the oxidation scale were studied by using XRD, TEM and EPMA. The results show that the combination of Nb and Si can improve the oxidation resistance of the alloys significantly. The element Si can change the typical microstructure of oxidation scale on TiAl based alloys. In alloys with Si addition, the compact Al2O3 forms in the interior side of oxidation scale. When x (Si)3%, the Ti5Si3 phase forms and the coarse crystal TiO2 forms on Ti5Si3 phase after oxidation. The increase of Nb content in the TiAl based alloys impedes the growth of Ti5Si3 phase, and the formation of TiO2 on surface and on Ti5Si3 phase is also impeded.     

Fe-Cr-Mn合金在湿润环境中的氧化行为研究

研究比较了Fe-13Cr-xMn(x=0.5,1,2) 系列合金在干燥和湿润空气中800 ℃下的氧化行为。结果表明,在干燥气氛中合金表现出良好的抗氧化性能,当Mn含量低于1%时有助于合金表面生成阻碍Cr挥发的 (Mn,Cr)₃O₄尖晶石相;而当Mn含量达到2%,合金表面则会产生Mn₂O₃,从而影响合金的抗高温氧化性能。在含水蒸气气氛中,合金发生了失稳态氧化,表面生成了大量氧化物,合金的氧化速率随Mn含量的增大而减小,主要原因是Mn含量增加导致膜层中形成 (Mn,Cr)₃O₄尖晶石相,从而有效阻碍了水气环境中Cr的挥发,尤其Fe-13Cr-2Mn合金在氧化初期12 h内并没有发生加速腐蚀,Fe-Cr-Mn合金的加速氧化是由表面氧化铬膜与水蒸气发生反应所致。通过SEM,XRD等分析手段深入探讨了合金加速氧化机制以及Mn效应。     

Influence of TiCl4 treatment on performance of dye-sensitized solar cell assembled with nano-TiO2 coating deposited by vacuum cold spraying

Titanium tetrachloride (TiCl4) treatment was employed to TiO2 coating deposited on fluoride-doped tin oxide (FTO) conducting glass and indium oxide doped tin oxide (ITO) conducting glass, respectively. The nano-crystalline TiO2coating was deposited using a composite powder composed of polyethylene glycol (PEG) and 25 nm TiO2 particles by vacuum cold spraying (VCS) process. A commercial N-719 dye was used to adsorb on the surface of TiO2 coating to prepare TiO2 electrode, which was applied to assemble dye-sensitized solar cell (DSC).The cell performance was measured under simulated solar light at an intensity of 100 mW·cm-2.Results show that with an FTO substrate the DSC composed of a VCS TiO2 electrode untreated by TiCl4 gives a short-circuit current density of 13.1 mA·cm-2 and an open circuit voltage of 0.60 V corresponding to an overall conversion efficiency of 4.4%. It is found that after TiCl4 treatment to the VCSTiO2 electrode with an FTO substrate, the short circuit current density of the cell increases by 31%, the open-circuit voltage increases by 60 mV and a higher conversion yield of 6.5% was obtained. However, when an ITOsubstrate is used to deposit TiO2 coating by VCS, after TiCl4 treatment, the conversion efficiency of the assembled cell reduces slightly due to corrosionof the conducting layer on the ITO glass by TiCl4.     

聚吡咯包覆二氧化钛纳米自修复微胶囊制备及其形成机制

目的以聚吡咯为有机囊壁、纳米二氧化钛为无机囊芯制备粒径均一的纳米级自修复微胶,并探讨其形成机制。方法采用化学氧化法于超声环境中制备出有机/无机复合自修复微胶囊,利用SEM、FT-IR和XRD等方法,研究了不同制备工艺对微胶囊粒径、形貌、结构的影响。结果阴离子型表面活性剂更有利于聚吡咯在二氧化钛颗粒表面包覆,在十二烷基苯磺酸钠(SDBS)和超声波作用下,吡咯单体以纳米二氧化钛为核心聚合,形成具有纳米晶结构的聚吡咯囊壁,进而获得粒径均一、直径约为100 nm的球形PPy-TiO_2复合纳米微胶囊。结论由于阴离子表面活性剂在二氧化钛粉体表面的化学吸附,形成了有机修饰层,从而可在有效抑制纳米二氧化钛自身团聚的同时,促进吡咯单体在其表面的包覆聚合。     

扩散铝涂层的制备及其对γ-TiAl基体的防护

采用电弧离子镀在γ-TiAl基体上镀铝后进行扩散处理,制备出了扩散铝涂层,涂层与基体结合良好,无贯穿性裂纹,EDX和XRD分析表明涂层由厚的TiAl3外层和薄的TiAl2内层构成．900℃空气中的高温氧化实验结果显示：γ-TiAl氧化后生成了疏松多层的Ti和Al氧化物的混合物,其抗高温氧化性能很差;施加扩散铝涂层后,高温下生成了一层连续致密的Al2O3膜,抗氧化性能显著提高,同时讨论了涂层的氧化和退化机制．     

溅射Ni-Cr-Al-Ti涂层高温氧化过程中组织变化对生成TiO_2的影响

观察了溅射 Ni- 9.7Cr- 5 .5 Al- 7Ti(质量分数 )纳米晶涂层在高温氧化过程中的组织变化 ,探讨了溅射涂层表面氧化膜以及涂层预氧化 90 min后磨去生成的氧化膜再重新氧化生成氧化膜中 Ti O2 的生长 ,认为溅射涂层氧化过程中 Ni3(Al Ti)相的析出与 Ti O2 的生成长大有着密切关系 ,对两种不同情况下 Ni3(Al Ti)相对 Ti O2 生长的影响机制进行了分析。     

钛合金切削过程氧化膜特性研究

高速切削钛合金时，在加工表面会产生氧化膜，对钛合金的力学性能造成影响。对钛合金Ti-6Al-4V进行单因素车削试验，研究切削表面变形特性并对氧化膜表面进行物相分析。结果表明：切削表面会产生严重塑性变形，变形层的厚度随着进给量的增大而增大，切削表面发生氧化反应，形成氧化膜，表面呈现不同的颜色，其成分主要为Al2O3、锐钛矿型 TiO2 和金红石型 TiO2。