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.     

钛合金微弧氧化膜微晶生长特性的研究

在Na₂CO₃-NaOH溶液中, 采用自制多功能单极性脉冲微弧氧化电源在TC4钛合金上制备了TiO₂薄膜. 利用XRD和SEM分别对氧化膜的相组成和表面形貌进行了分析. 结果表明, 在脉冲频率和电流密度分别固定为5000Hz和20A/dm²时, 氧化膜主要含锐钛矿和金红石相TiO₂,随着处理时间的延长, 金红石TiO₂的相对含量逐渐增加; 氧化膜呈多孔结构, 表面布满了尺寸在300nm～1μm之间的TiO₂颗粒, 随着处理时间的延长, 这些颗粒微孔的尺寸明显变大, 其密度逐渐减小.     

氧化处理时间对Ti6Al4V微弧氧化陶瓷膜的影响

采用交流微弧氧化法于：Na：SiO3-KOH-(NaPO3)6溶液中在％6A14V表面形成了氧化物陶瓷膜．利用扫描电镜、电子探针及X射线衍射研究了陶瓷膜的组织形貌、元素的分布和相组成．研究表明：在恒定的微弧氧化电参数(U =500V，U-=100V和f=600Hz)下，随氧化时间延长，电流密度逐渐降低，膜层厚度不断增加；相对致密均匀的膜分为3层：过渡层、致密层与疏松层．膜层主要由TiO2(锐钛矿和金红石)相组成，延长处理时间，锐钛矿相及金红石相的相对含量发生变化，金红石相TiO2逐渐增多，而锐钛矿相TiO2减小．膜层相的形成过程可分为两个阶段。     

Ti3SiC2-64vol%SiC复相陶瓷高温氧化机理研究

采用热等静压原位合成了高致密的Ti₃SiC₂-64vol%SiC复相陶瓷. 通过热重实验研究其在1100~1450℃中空气气氛的高温氧化行为和机理. 研究显示,复相陶瓷的等温动力学曲线遵循抛物线型氧化或抛物线型直线型氧化规律. SiC (64vol%)的引入显著提高了Ti₃SiC₂-SiC材料的抗氧化能力. XRD及SEM-EDS分析显示,氧化膜由外层金红石型TiO₂和非晶态SiO₂组成,过渡层为TiO₂与SiO₂混合物. 高温下（1400℃）,非晶态SiO₂的形成改变了TiO₂膜的生长形态,形成致密TiO₂膜,有效阻碍了氧的扩散. 长时间氧化其抛物线速率常数比在1200℃下氧化低一个数量级. 材料在1400℃下的抗氧化性能明显优于在1200℃下的抗氧化性能.     

铝合金微弧氧化陶瓷膜形成过程中的特性研究

保持交流电压脉冲幅度不变,对浸在硅酸钠和氢氧化钠溶液中的铝合金样品进行了微弧氧化处理,发现在陶瓷膜形成过程中,样品的电流随时间明显分成五个不同阶段.对应各阶段所制备的陶瓷膜分别用扫描电镜和X射线衍射仪进行了分析,结果表明,铝合金微弧氧化陶瓷膜主要由γ-Al₂O₃和α-Al₂O₃相组成,其含量随氧化时间变化.陶瓷膜内外层α,γ相含量差异主要是由于微弧区熔融的Al₂O₃凝固时冷却速率不同引起的.     

硅基板上Fe掺杂TiO2氧敏薄膜的制备、结构与性能研究

采用溶胶-凝胶法,以Ti(OC₄H₉)₄为前驱体,用提拉法在硅基板上制备了掺Fe的TiO₂氧敏薄膜,对薄膜物相结构进行了X射线衍射(XRD)测定,利用扫描电镜(SEM)对薄膜微结构进行了观察.结果表明:在硅基板上生长的TiO₂薄膜中锐钛矿相为均匀小晶粒分布结构,金红石相以大尺度团聚结构形貌出现.Fe离子的掺杂对硅基板上制备的TiO₂薄膜中金红石相的形成有很大的影响.Fe的掺入降低了金红石相的形成温度约100℃,Fe掺量在6mol% 时,形成金红石相的量达到最大,即析晶能力最强.薄膜中形成晶相的晶格常数在<6mol%的低Fe范围内,随较小的Fe离子取代较大的Ti离子,锐钛矿相和金红石相的晶格常数都随之减小;在>6mol%的高Fe掺量范围内,随Fe掺量的增加,体系缺陷过量增加,晶格结构畸变严重,伴随着畸变能的释放,金红石相的晶格常数c轴逐渐增长,n轴略有下降(或基本不变). TiO₂氧敏薄膜的氧敏性能受金红石相含量和氧空位浓度控制.当Fe离子掺杂浓度为6mol% 时,金红石相及相应氧空位达到最大值,TiO₂氧敏薄膜的氧敏性能也达到最大值,比刚形成金红石相的薄膜的氧敏性能增加近19倍.     

纯钛微弧氧化阳极工艺过程模型的建立及实验研究

对纯钛微弧氧化陶瓷膜在工艺过程中的生长规律进行了实验研究,分析了陶瓷层表面形貌、厚度、相结构等不同生长阶段的特点。基于微弧氧化工艺过程阳极等效电路,建立了电极电压、电流密度、频率、占空比、时间等工艺参数对陶瓷膜性能影响的理论模型。模型分析结果表明:在陶瓷层成膜后,随着膜层厚度的增加,金红石相TiO2相对含量增加;膜层厚度不变时,工艺过程趋于停止。模型分析与实验结果是吻合的,为提高陶瓷膜层性能并改善微弧氧化工艺提供了理论基础。     

阴/阳极电压对钛合金微弧氧化膜特性影响的研究

在Na2CO3-Na2SiO3溶液中,采用正负不对称交流微弧氧化电源在钛合金上制备出了多孔金红石TiO2薄膜.利用X射线衍射仪(XRD)和扫描电镜(SEM)分别研究了钛合金微弧氧化陶瓷膜的相组成和微观结构,实验结果表明,氧化膜主要由大量金红石和少量锐钛矿TiO2组成;膜表面布满了尺寸不到4μm的小孔,膜截面没有明显的疏松层和致密层之分.对微弧氧化样品在3.5%NaCl溶液中的抗点腐蚀测试表明,阴极峰值电压与样品的耐腐蚀性能密切相关,当阴、阳极峰值电压和处理时间分别为45、320V和30min所制备的钛合金微弧氧化样品其抗点腐蚀能力最强.     

反应时间对LY12铝合金微弧氧化膜层组织及性能的影响

在K₂ZrF 电解液体系中, 利用微弧氧化方法在LY12铝合金表面制备了氧化锆陶瓷膜. 结果表明, 膜层主要由t-ZrO₂、m-ZrO₂组成, 还含有少量的γ-Al₂O₃和KZr₂(PO₄)₃. 随着反应时间的延长, 膜层晶相物质的含量增多; 膜层表面粗糙度增大, 致密性提高; 膜层的厚度近似线性增加, 硬度增大, 耐腐蚀性提高, 抗热震性减弱. 磨损实验表明, 带有氧化锆陶瓷膜的试样耐磨损性能大幅度提高, 铝合金的摩擦系数约为膜层的2/3, 随着反应时间的延长膜层的磨损量先降低后升高, 摩擦系数减小.     

钛合金微弧氧化陶瓷膜微观特性的分析

微弧氧化膜存在微米量级宏孔,这些宏孔对氧化膜特征的研究非常重要.研究了微弧氧化中电流密度对微弧氧化膜的生长速率、结构形貌及相组成的影响,并对氧化膜进行了离子束抛光处理,分析了氧化膜和微孔的组织结构.研究表明:电源频率固定为1 500 Hz/5 μs和氧化膜厚为10 μm时,随着氧化电流密度的增大,氧化膜的生成速度和孔径都随之增大,但同一膜厚的氧化层组成成分金红石型TiO2和锐钛矿型TiO2的相对含量无明显变化;离子束抛光后的氧化膜膜层外疏内密,放电通道内表面更是淀积了电解液溶质、氧化膜颗粒及基材等多种物质的纳米微颗粒.     

Structural Characteristics of TiO2 Ceramic Coating by Micro-Plasma Oxidation

TiO2 ceramic coatings with thickness of 20 μm were formed on the surface of pure titanium by micro-plasma oxidation. Their micro-structures were investigated by by using X-ray diffraction and their surface images were detected by using scan electronic microscope. There were three kinds of TiO2 coatings, pure anatase type TiO2 phase, mixed phases consisted of rutile type TiO2 phase and anatase type TiO2 phase, pure rutile type TiO2 phase. The coating surface with the pure anatase type TiO2 phase is rough, while the coating surface with the pure rutile type TiO2phase is smooth. The upper coating surface with the mixed type TiO2 phases is anatase type TiO2 structure and the subsurface of the TiO2 coating is rutile type TiO2structure.     

Ag掺杂对TiO2粉末结构的影响

采用溶胶-凝胶工艺制备了Ag掺杂的TiO2粉末。通过XRD、SEM、EDX、DSC-TG、BET氮吸附法等研究了Ag掺杂对TiO2结构的影响，结果发现掺杂的Ag降低了TiO2锐钛矿向金红石相转变的温度，促进了相转变。适量掺杂时，Ag抑制了锐钛矿粒子的生长，结果使锐钛矿粒子的粒径降低，TiO2粉末的比表面积增加。     

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.     

Effects of Additive AlCl3 on Crystal Phase, Particle Size and Microstructural Parameters of Nanocrystalline TiO2 Prepared by HF-PCVD

Nanocrystalline TiO2 was prepared by high frequency plasma chemical vapor deposition (HF-PCVD). The effects of additive AlCl3 on crystal phase, particle size and microstructurai parameters of TiO2 nanocrystallites were investigated by X-ray diffraction(XRD) and transmission electron microscopy (TEM). The nanocrystallites obtained experimentally are mixture of anatase and rutile, the uniform diameters of particles are about 30 nm. The phase transformation from anatase to rutile was accelerated by AlCl3, and rutile content is increased from 26.7 wt pct to 53.6 wt pct with increasing of addition of AlCl3 from 0.0 wt pct to 5.0 wt pct. The particle size is reduced and the size distribution becomes very narrow. The crystal lattice constants have the trend to decrease, and celi volumes appear as shrinkable     

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。     

煅烧温度对二氧化钛纳米晶性能的影响

研究了不同煅烧温度下,锐钛矿相、混晶和金红石相二氧化钛纳米晶的 粒径、比表面积和吸收光谱的变化。经相同的温度煅烧后,金红石相二氧化钛纳米晶的生长速率和比表面积下降速率均大大高于锐钛矿相,表明高温反应或煅烧难以获得金红石相纳米晶,真空热处理的金红石相二氧化钛纳米晶可以保持较高的比表面积和较小的粒径,但易导致非化学配比、晶格缺陷并降低了粉体的性能。     

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.     

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.     

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.