脉冲频率对纯钛微弧氧化膜生长特性的影响

在Na₂CO₃-Na₂SiO₃电解液中, 利用微弧氧化技术在纯钛试样表面制备了氧化膜, 并研究了脉冲频率(500～8000Hz)对膜层生长、相组成及表面形貌的影响. 结果表明: 当脉冲频率<2000Hz时, 膜层的生长速率随频率增加迅速减小, 当>4000Hz时, 其生长速率几乎和频率无关. 微弧氧化膜主要由锐钛矿和金红石相TiO₂及少量不饱和氧化物TiO_2-x(0.022的相对含量与频率无关, 而TiO_2-x随频率的增加而逐渐减少. 氧化膜表面多孔, 随着频率的增加, 膜表面的粗糙度和微孔尺寸逐渐减小, 而微孔的密度逐渐增加.     

Effect of Flame Conditions on Crystalline Structure of TiO2 in Liquid Flame Spraying

Nanostructured TiO2 is a most promising functional ceramic owing to its potential utilization in photocatalytical, optical and electrical applications. Nanostructured TiO2 coating was deposited through thermal spraying with liquid feedstock. Two types of crystalline structures were present in the synthesized TiO2 coating including anatase phase and rutile phase.The effect of spray flame conditions on the crystalline structure was investigated in order to control the crystalline structure of the coating. The results showed that spray distance, flame power and precursor concentration in the liquid feedstock significantly influenced phase constitutions and grain size in the coating. Anatase phase was formed at spray distance from 150 to 250mm, while rutile phase was evidently observed in the coating deposited at 100 mm. The results suggested that anatase phase was firstly formed in the coating, and rutile phase resulted from the transformation of the deposited anatase phase. The phase transformation from anatase to rutile occurred through the annealing effect of spraying flame. The control of the phase formation can be realized through flame condition and spray distance.     

Influence of Electrolytes on the Microstructure of Microarc Oxidation Coatings on Ti—6Al—4V Alloy

Dense ceramic oxide coatings of about 50μm may be prepared on Ti-6Al-4V alloy surface by alternating-current microarc oxidation in aluminate and silicate solutions, respectively.Their phase constituent and microstructure sere characterized using X-ray diffraction (XRD) and scanning electron microscopy(SEM). The results show that the electrolytic ions have incorporated into the interior of the coatings.The coating formed in aluminate solution is composed of the rutile TiO2 and TiAl2O5 phases rather than the rutile, anatase and amorphous SiO2 phases for the coating formed in silicate solution.However,TiAl2O5 content in the outer layer of the two coatings is much higher than in the inner layer.It is suggested that all these oxides may result from a rapid solidification of the molten coating in the microarc discharge zone.     

电参数对Ti6Al4V合金微弧氧化陶瓷膜结构特性的影响

采用交流微弧氧化法于Na₂SiO₃-KOH-(NaPO₃)₆。溶液中在Ti6A14V表面形成了氧化物陶瓷膜.研究了微弧氧化电压与频率对陶瓷膜的生长速率、组织形貌和相组成的影响.结果表明:随电压的升高或频率的减小,膜层的生长速率增加,膜层的表面质量变得粗糙.相对致密均匀的膜层主要由TiO₂(锐钛矿相及金红石相)相组成,电压与频率电参数影响膜层的相组成,随电压的升高和频率的减小,膜层中锐钛矿相TiO₂的相对含量减小,金红石相TiO₂的相对含量增加,并成为主晶相.     

纳米二氧化钛粉体晶相控制实验研究

在水解－沉淀法制备纳米TiO2粉体的过程中，使用不同的沉淀剂获得了晶相不同的纳米TiO2粉体，使用混合沉淀剂，通过控制沉淀剂的比例，制备了晶相组成（金红石与锐钛矿比例）不同的纳米TiO2多晶粉体，采用相同的粉体制备工艺，不同的后续处理工艺，探讨了锐钛矿向金红石转变的相变温度，经分析研究后认为，水解－沉淀法制备的纳米粉体中的锐钛矿向金红石红转变的温度为500－800℃，完全转变的温度在800℃以上；纳米TiO2多晶粉体的晶相组成不仅与沉淀剂的种类，混合沉淀剂中沉淀剂的比例和粉体的煅烧温度有关，而且与粉体的后续处理工艺和粉体表面界面相的稳定性有关。     

高温氧化对钛合金微弧氧化陶瓷膜组成与结构的影响

针对钛合金不耐高温氧化的问题,在铝酸钠电解液体系中,利用双相脉冲直流微弧氧化技术,在TC4钛合金表面原位生长以Al2TiO5为主晶相的复合氧化物陶瓷膜,研究了1000℃高温氧化对陶瓷膜试样的相组成、结构的影响及膜层增重特点.研究表明,陶瓷膜层试样的高温氧化过程包括Al2TiO5分解、基体氧化和膜层表面形貌变化3个方面.高温氧化后,膜层的主晶相由Al2TiO5变为α-Al2O3和金红石型TiO2,同时,膜层的表面形貌发生显著的变化;由于膜层和基体的热膨胀系数不同和基体钛的氧化,使得高温氧化后膜层在冷却过程中表面出现裂纹和脱壳.陶瓷膜层极大地减少了TC4钛合金在1000℃高温氧化时的增重,因此,陶瓷膜层可用于TC4钛合金的恒温氧化防护.     

Effect of the Oxidation Time on Properties of Ceramic Coatings Produced on Ti-6Al-4V by Micro-Arc Oxidation

Ceramic coatings were prepared on Ti-6AI-4V alloy using ac micro-arc oxidation (MAO) in silicate-hypophosphate solution. Growth regularity and formation mechanism of ceramic coatings were discussed. It was found that during the first stage the growth rate of coatings toward the external surface was larger than that toward substrate and then the coating began to grow mainly towards Ti alloy. When the total coating thickness reaches a certain value, it would no longer increase. In addition, the variations of the composition and microstructure of ceramic coatings according to the depositing time were also investigated with X-ray diffraction (XRD) and scanning electron microscope (SEM). The amount of rutile TiO2 gradually increased, whereas the amounts of the anatase TiO2 and amorphous phases first increased and then decreased slightly.     

Fabrication and characterization of highly crystalline and stable phase-pure rutile nanowires

A homogeneous thin layer of TiO2 has been successfully coated on the surface of multiwalled carbon nanotubes (MWCNTs), which were produced by catalytic chemical vapor decomposition method, via an in situ sol-gel method. The obtained MWCNT-TiO2 composite materials were heat treated in air at high temperatures, attempting to produce highly crystalline pure rutile nanowires. Through comprehensive characterization obtained by scanning electron microscopy (SEM), transmission electron microscope (TEM), energy dispersive X-ray (EDX), and X-ray powder diffraction (XRD), the effect of heat treatment on crystallization and phase transformation was discussed, and the effect of absence of MWCNTs on the morphology of pure rutile nanowires was analyzed. Both anatase and rutile phases exist after heat treatment in 700 degrees C while only rutile phase exists after heat treatment in 800 degrees C. The crystal size of rutile is formed to be significantly larger than that of anatase, and the hollow tubular structure is found to be destroyed which resulted in nanowire structure.     

Preparation of rutile and anatase phases titanium oxide film by RF sputtering

Titanium oxide films were prepared by RF magnetron sputtering onto glass substrates. The effects of RF power and deposition temperature on crystalline structure, morphology and energy gap were investigated, which were analyzed by X-ray diffraction, SEM and UV-Vis spectrometer, respectively. Results show that rutile phase is the favored structure during deposition. Applying RF power in the range of 50-250 W, the amorphous, rutile, and both rutile and anatase phases TiO2 films were obtained in sequence, while the content of anatase is similar in the range of 34-37% although the RF power increases. Increasing the deposition temperature, the anatase phase coexists in the rutile phase in the range of 100-200 degrees C, and the content of anatase increases from 20 to 41% with the deposition temperature. In addition, according to the morphology observation, the granulous surface is found in rutile phase while facetted surface in anatase phase when titanium oxide films deposited at various RF powers and substrate temperatures. The band gap energy of titanium oxide evaluated from (alphahv)1/2 versus energy plots show that the energy gap decreases with RF power increasing.     

电流密度对复合氧化法制备涂层结构的影响

对TiO2薄膜涂层的结构、形貌、元素组成、硬度进行了观察和测量,研究了电流密度对复合氧化法(即预氧化和微弧氧化复合处理)制备多孔TiO2涂层的结构和性能的影响.结果表明:电流密度对多孔TiO2涂层的结构和性能有很大影响.随着电流密度的增加,涂层的锐钛矿型TiO2含量减少,金红石型TiO2含量增加,涂层表面微孔孔径增加,凹凸起伏变得明显,显微硬度增加,钙磷原子比也发生了变化.当电流密度为20,40,60,80和100 mA/cm2时,涂层的钙磷摩尔比为1.22,1.60,1.89,2.01,2.12.在40 mA/cm2电流密度下可得到结构和性能较理想的多孔TiO2梯度涂层.     

Preparation of immobilized nano-columnar TiO2 grains by chemical vapor deposition

Nano-columnar TiO2 grains are prepared and immobilized by chemical vapor deposition using TiCl4, H2 and O2 at low temperature. The structure of TiO2 is analyzed by X-ray diffraction (XRD), the morphology is observed by scanning electron microscopy (SEM) and the adhesion is estimated by measuring the critical load in scratch test. Results show that the structure of TiO2 films depend on the deposition temperature changing from amorphous, anatase, rutile, and both anatase and rutile phases as prepared at temperatures of 200, 300, 400 and 500 degrees C, respectively. The nano-columnar TiO2 grains are formed in both rutile and anatase phases, while it could be only rutile phase by increasing TiCl4 flow rate. The morphologies of TiO2 changes from smooth to nano-columnar grains as the deposition temperature increased from 200 to 400 degrees C. Excellent adhesion strength of crystalline TiO2 was obtained and it could be improved by increasing the TiCl4 flow rate in range of 0.3-0.6 sccm, where the critical load of TiO2 increases from 17 to 21 N.     

电压对钛表面微弧氧化陶瓷层特性的影响

为了提高钛表面的生物活性,利用微弧氧化技术在钛表面制备了含有钙磷的多孔二氧化钛陶瓷层。研究了施加电压对多孔微弧氧化层的平均孔径、表面粗糙度、相成分、钙磷含量以及Ca/P原子比的影响。结果表明,随着微弧氧化电压的升高,平均孔径、表面粗糙度、膜层中钙磷含量以及Ca/P原子比都逐渐增大,膜层的相成分由锐钛矿逐渐向金红石转变,并且膜层中逐渐有羟基磷灰石生成。     

Synthesis of nanocrystalline TiO<Subscript>2</Subscript> by tartarate gel method

A gel was formed when a mixture of TiOCl₂ and tartaric acid was heated on a water bath. Ultrafine powders of TiO₂ in the anatase phase were formed, when the gel was decomposed at 623 K and the mole ratio of tartaric acid to titanium was 2. The anatase phase was converted into rutile phase on annealing at higher temperatures, > 773 K. When initial ratio of titanium to tartaric acid was < 2, the decomposition of gel leads to the formation of mixed phases of rutile and anatase. However, pure rutile phase was not formed by the decomposition of gel for any ratio of tartaric acid and titanium. These powders were characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and surface area measurements. The average particle size obtained for anatase phase was 3 nm whereas it was 30 nm for rutile phase. Raman scattering experiments were also performed to confirm both anatase and rutile phases.     

Effects of Current Density on Microstructure of Titania Coatings by Micro-arc Oxidation

In the present study, titania coatings were prepared under different current density conditions in micro-arc oxidation (MAO) process on titanium alloy in NaAlO2 solution. The aim of this work was to study the effects of current density on the microstructure of titania coatings. The morphology and phase composition of the coatings were investigated by field emission scanning electron microscopy (FESEM), X-ray diffraction (XRD) and Raman spectra. The thickness and surface roughness of the coatings were characterized by confocal laser Scanning Microscopy (CLSM). The results showed that the coatings were composed of crystalline anatase and rutile phases of TiO2, and contain a network of evenly distributed small pores. It has also shown that an increase in current density leads to an increase in rutile content.     

Nanocrystalline brookite with enhanced stability and photocatalytic activity: influence of lanthanum(III) doping

Metastable TiO(2) polymorphs are more promising materials than rutile for specific applications such as photocatalysis or catalysis support. This was clearly demonstrated for the anatase phase but still under consideration for brookite, which is difficult to obtain as pure phase. Moreover, the surface doping of anatase with lanthanum ions is known to both increase the thermal stability of the metastable phase and improve its photocatalytic activity. In this study, TiO(2) nanoparticles of almost only the brookite structure were prepared by a simple sol-gel procedure in aqueous solution. The nanoparticles were then doped with lanthanum(III) ions. The thermal stability of the nanoparticles was analyzed by X-ray diffraction and kinetic models were successfully applied to quantify phases evolutions. The presence of surface-sorbed lanthanum(III) ions increased the phase stability of at least 200 °C and this temperature shift was attributed to the selective phase stabilization of metastable TiO(2) polymorphs. Moreover, the combination of the surface doping ions and the thermal treatment induces the vanishing of the secondary anatase phase, and the photocatalytic tests on the doped brookite nanoparticles demonstrated that the doping increased photocatalytic activity and that the extent depended on the duration of the sintering treatment.     

添加磷酸根对纳米二氧化钛晶相的控制

以TiCl4为前驱体添加磷酸盐通过水热法制备了纳米TiO2。通过X射线衍射仪、差热分析仪、扫描电子显微镜、比表面仪(BET)和光化学反应器等手段对所制备的TiO2的颗粒晶型、失重、形貌、比表面和降解罗丹明B的能力进行了表征。结果表明,随着磷酸根的添加,TiCl4水解生成的TiO2的晶型由纯金红石型向锐钛矿型转换,且所合成的锐钛矿和金红石的混晶样品的光催化活性明显高于单独晶相的光催化活性。     

TC4钛合金微弧氧化因素对生物陶瓷膜中Ca,P相对含量的影响

为了提高钛合金陶瓷膜的生物相容性,采用微弧氧化技术在TC4钛合金表面制备了一层富含Ca,P的生物活性陶瓷膜。采用SEM,EDS,XRD研究了电流密度、溶液中Ca,P摩尔比、添加剂EDTA.2Na浓度对膜层中Ca,P相对含量(原子分数)及Ca,P摩尔比的影响及微弧氧化生物陶瓷膜层的形貌及组成。结果表明:随着电流密度的增大,膜层中的Ca,P相对含量增加,Ca,P摩尔比也逐渐增加;增大溶液中Ca,P摩尔比,膜层中Ca相对含量有所增加,Ca,P摩尔比也逐渐增加;当加入添加剂EDTA.2Na时,膜层中的Ca相对含量显著增加,从而使膜层中Ca,P摩尔比显著增加;氧化膜由致密的内膜层和多孔的外膜层构成,主要由Ca,P,O,Ti,V元素组成,其相成分主要为金红石和板钛矿型TiO2,并含有一定量的非晶相Ca,P化合物。     

混晶结构纳米TiO2粉的光催化活性

以钛酸四丁酯为钛源制备混晶结构纳米TiO2粉，研究了纳米TiO2的光催化活性与颗粒晶相结构之间的关系．结果表明，当金红石相的质量分数少于18．53％，光催化活性随着金红石相的增多而降低；当金红石相的质量分数为18．53％-28．2％时，随着金红石相的增多，光催化活性逐渐增强，在28．2％附近具有最高的光催化活性，与纯锐钛矿结构纳米TiO2粉的光催化活性相当；金红石相含量继续增加，则光催化活性逐渐降低．适量金红石相的存在有利于锐钛矿相中的电荷分离，使光催化活性提高．     

Ti靶及TiO2靶溅射TiO2薄膜微观形貌、结构及光学性质研究

利用射频磁控溅射技术通过Ti靶及TiO2靶在氩氧气氛中同时溅射制备TiO2薄膜,并对所得的样品进行不同温度的退火处理。采用X射线衍射、扫描电子显微镜、拉曼光谱和吸收谱研究了不同的靶材及退火温度对TiO2薄膜晶体结构、微观形貌及光学性质的影响。结果表明:由于靶材的不同,Ti靶溅射时氧分压较低,造成薄膜中存在大量的氧缺陷,晶相发育不完善,颗粒相比TiO2靶溅射时较小,从XRD和拉曼光谱来看,Ti靶溅射得到的TiO2薄膜更有利于金红石相的形成。薄膜的透过率随退火温度的升高而降低,TiO2靶材溅射的薄膜的光学带隙随温度升高而明显降低,而Ti靶得到的薄膜的光学带隙对退火温度的依赖关系不明显。     

微弧氧化TC4钛合金与金属电偶的腐蚀行为

为了减小钛合金与金属偶合的接触腐蚀,采用微弧氧化技术,在TC4钛合金表面生成了一层主要由Al2TiO5相、锐钛矿TiO2相及金红石TiO2相组成的多孔膜.研究了TC4钛合金微弧氧化前后与45钢、LY12铝合金和紫铜偶合的电偶腐蚀行为.结果表明:3种金属分别与TC4钛合金偶合时,45钢会发生严重的电偶腐蚀,LY12铝合会...