热喷涂法制备的La3+掺杂纳米TiO2粉末的表征

采用等离子热喷涂法以钛酸四丁酯为主要原料制备出稀土离子掺杂的纳米TiO2光催化剂.通过XRD,XPS,TEM,UV-Vis等检测手段对样品进行表征,同时检测了其光催化性能,并分析了掺杂对TiO2的影响机理.结果表明,所制备的La3 掺杂纳米TiO2是锐钛矿相和金红石相混晶结构,粒径分布在10～50nm之间;La3 掺杂能够促进锐钛矿向金红石的转变,同时抑制TiO2晶粒的长大;La3 掺杂使TiO2紫外-可见吸收光谱发生红移;适量La3 掺杂能显著提高TiO2的光催化活性,最佳掺杂浓度为0.5%(与Ti原子摩尔比),甲基橙降解率在90min内可达到82.4%.比纯TiO2高出13.2%.     

La3+、Ce4+掺杂对纳米TiO2-Fe2O3凝胶相变过程的影响

采用sol-gel法制备了掺杂La3+、Ce4+的TiO2-10wt%Fe2O3复合粉体,利用TG-DTA和XRD分析对凝胶的相变过程进行了表征。结果表明:TiO2-10wt%Fe2O3凝胶在450℃发生非晶态向锐钛矿相的转变,而在500℃煅烧2 h后未发现锐钛矿相向金红石相转变;随La3+、Ce4+掺杂量的增加,锐钛矿晶粒呈现细化→长大的趋势;随La3+掺杂量的增加,对Fe2O3微晶的生成作用呈现促进→抑制的趋势,而对Fe3O4微晶的生成呈现抑制→促进的趋势;随Ce4+掺杂量的增加,对Fe2O3微晶的生成作用随掺杂量的增加呈促进→抑制→促进的趋势,而对Fe3O4微晶的生成呈现抑制→促进的趋势;La3+、Ce4+掺杂对TiO2相变过程有重要影响。     

HF-PCVD法TiO2纳米晶的粒径与晶型控制

以TiCl4和O2为反应体系，采用高频等离子化学气相沉积(HF-PCVD)法制备了晶化完整的锐钛和金红石混晶型TiO2纳米晶，球形体的晶粒分散性良好，分布较为均匀：研究了控制粒径大小和晶相组成的关键反应条件。XPS，TEM，XRD结果显示：增加TiCl4进料量、延长停留时间均利于锐钛相向金红石相转化，但粒径有所增大：添加A1C13使金红石相含量较未掺杂时有较大幅度提高，且粒径随掺铝量增加而减小。本实验条件下，TiO2纳米晶的粒径为25nm～60nm，金红石相含量在12．O％～53．6％间可控。     

等离子喷涂纳米Al2O3/TiO2陶瓷复合涂层高温氧化和热震性能研究

采用等离子喷涂设备在H13热作模具钢表面制备含有不同质量分数TiO2的Al2O3纳米陶瓷复合涂层。采用X射线衍射仪(XRD)、高温氧化试验、热震试验等手段研究等离子喷涂纳米涂层的相组成及其性能。结果表明,等离子喷涂使α-Al2O3转变为亚稳态的γ-Al2O3相,喷涂后涂层中Al2O3由α-Al2O3相和γ-Al2O3相组成,TiO2仍以金红石相存在。纳米AT20涂层比其他涂层具有更好的抗氧化性能;与其他涂层相比,纳米AT13涂层具有最佳的抗热震性能。     

Fe3+掺杂对氧化钛凝胶相变过程的影响

采用溶胶-凝胶法制备不同含量Fe3+掺杂的纳米氧化钛粉体,利用X光衍射仪研究了氧化钛凝胶的相变过程,分析了产物的晶体结构、金红石转变量和锐钛矿晶粒尺度.试验结果表明,Fe3+的掺杂抑制了锐钛矿相变,促进锐钛矿向金红石相的转变;阻碍锐钛矿晶粒的长大.Fe3+掺杂量大于2mol%时,在600℃烧结获得小于40nm的锐钛矿晶体.     

等离子喷涂制备TiO2纳米颗粒

采用液料等离子喷涂法，在不同电弧功率条件下，用钛酸丁酯的乙醇溶液作为喷涂原料，制备出了纳米TiO2颗粒。用透射电镜和X射线衍射仪分析了颗粒的显微组织和晶型结构，计算了颗粒中的锐钛矿相和金红石相的含量与晶粒尺寸。研究表明，液料等离子喷涂制备的纳米TiO2颗粒平均粒径为10～50nm，其晶型以锐钛矿为主，且随着电弧功率的增大，锐钛矿含量减少；在文中试验工艺参数下，收集速率为0．8～1．2g／min，收集效率为8％～10％。     

阳极氧化制备TiO_2纳米管阵列的可控相转变及表征

采用电化学阳极氧化法制备TiO2纳米管阵列,分别在O2、N2、5%H2+95%N2(体积分数)和NH3气氛中于400~650℃退火处理,初步实现TiO2纳米管中锐钛矿向金红石相转变的可控制备。采用FESEM、XRD、Raman对退火处理后TiO2纳米管的表面形貌、结构以及相转变等进行表征。结果表明:随着退火温度的升高,在O2气氛退火时,源于Ti基体的吞噬效应(Feeding effect)是导致TiO2相转变的主要原因;在N2和(5%H2+95%N2)气氛退火后,氧空位加速了锐钛矿向金红石相的转变;而在NH3气氛中退火后,N掺杂则有效抑制了锐钛矿向金红石相的转变。在此基础上,对其相转变机理进行了初步探讨,为进一步制备具有可控相含量及微观点缺陷的TiO2半导体和高性能器件提供了有益思路。     

电弧功率对液料等离子喷涂TiO2纳米涂层结构的影响

采用液料等离子喷涂法，在不同电弧功率条件下，用含有0．2w(钛酸丁酯)的乙醇溶液为喷涂材料，制备了TiO2涂层。用扫描电镜、透射电镜和X射线衍射仪分析了涂层的显微组织结构与晶型结构，计算了涂层中的锐钛矿相相对含量与晶粒尺寸。结果表明，液料等离子喷涂TiO2涂层为纳米颗粒堆积形成的纳米结构涂层，涂层由锐钛矿相和金红石相两相构成。涂层中锐钛矿相含量可超过70％，并随着电弧功率的增大而减小。涂层中TiO2晶粒的平均尺寸为20～60nm且随电弧功率的增大而增大。     

Zn掺杂浓度对Zn-TiO_2相变的影响

采用溶胶凝胶法制备了纯TiO_2以及不同浓度Zn掺杂TiO_2纳米粉末。利用XRD、SEM和XPS等对其进行了表面形貌、晶体结构、元素组成与价态研究。讨论了Zn掺杂浓度对TiO_2锐钛矿/金红石相变的影响。结果表明:纯TiO_2在300℃时为锐钛矿,在500℃时出现少许金红石,750℃时全部为金红石;Zn掺杂能细化晶粒并且能促进锐钛矿向金红石的转变,增大Zn掺杂浓度以及提高热处理温度有利于ZnTiO_3的生成。     

球磨纳米TiO2的结构转变

采用X射线衍射研究锐钛矿型纳米TiO2在高能球磨过程中及球磨后的纳米TiO2在退火过程中的结构变化。结果表现在室温常压下高能球磨诱发锐钛矿相转变为金红石相和S相。随着退火温度升高，球磨纳米TiO2粉末的晶粒逐渐长大，锐钛矿相逐渐转变为金红石相，而S相并不直接转变为金红石相而是先转变为锐钛矿相，然后由锐钛矿相转变为金红石相。与未球磨的纳米TiO2相比，高能球磨导致的晶粒细化，显微畸变以及晶格缺陷密度的增加而引起的额外储能使球磨后纳米TiO2的锐钛矿相-金红石相转变温度明显降低。     

Preparation of TiO<Subscript>2</Subscript> Nanopowders by Plasma Spray and Characterizations

TiO₂ powders with the range of 10-60 nm were prepared successfully by plasma spray in the self-developed plasma spray equipment. The prepared nanopowders were characterized by transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The results showed that the prepared TiO₂ nanopowders were the mixture of anatase phase and rutile phase, the main phase was anatase. There were O, Ti, and C elements in powders; Ti element still existed in tetravalent. The photocatalytic degradation of methyl orange indicated that all methyl orange (20 mg/L) can be degraded fully when the addition of prepared TiO₂ nanopowders and illumination time were 1 g/L and 150 min, respectively.     

Dominant microstructural feature over photocatalytic activity of high velocity oxy-fuel sprayed TiO2 coating

TiO₂ photocatalytic coatings were deposited through high velocity oxy-fuel spray using anatase powder and rutile powder as feedstock. The as-sprayed TiO₂ coating was composed of anatase phase and rutile phase. The anatase content in the coating was significantly influenced by fuel gas flow and melting condition of spray powder. A high anatase content of 35% was achieved for the coating deposited using rutile powder. The anatase content in the coating deposited using anatase powder reached 55-65%. The as-sprayed TiO₂ coating was photocatalytically reactive for degradation of acetaldehyde in air. The photocatalytic activity was influenced by spray conditions. The surface morphology and phase structure of coatings deposited at different spray conditions were investigated to clarify the relationship between the coating microstructure and activity. It is found that the photocatalytic activity is significantly influenced by anatase content and surface area.     

Influence of niobium doping on phase composition and defect-mediated photoluminescence properties of Eu-doped TiO2 nanopowders synthesized in Ar/O2 thermal plasma

Nb⁵⁺:Eu³⁺-codoped TiO₂ nanopowders for chemical composition adjustment have been synthesized via Ar/O₂ radio-frequency thermal plasma. X-ray diffraction (XRD) results reveal that all the resultant powders exhibited mixture polymorphs of anatase (mean size: ∼45 nm) as the major phase and rutile (mean size: ∼71 nm). Rutile formation was promoted by the Eu³⁺ doping but suppressed by the Nb⁵⁺ addition. Combined observation using FE-SEM and TEM indicates that all the plasma-synthesized powders had a majority of facet-shaped particles (several nanometers) and a small proportion of nearly spherical crystals (∼150 nm). For the defect-mediated photoluminescence (PL) emission through the energy transfer from the TiO₂ host to the Eu³⁺ activator, the PL intensity originating from the ⁵D₀ → ⁷F₂ electronic transition weakened but that from the ⁵D₀ → ⁷F₁ electronic transition strengthened with increasing Nb⁵⁺ content. This may be a result of the decrease in the oxygen vacancy defects in the TiO₂ host lattice, as revealed by the joint means of UV-vis absorption spectra and excitation and emission spectra.     

Photocatalytic performance of nano-photocatalyst from TiO2 and Fe2O3 by mechanochemical synthesis

Nano-particles of homogeneous solid solution between TiO₂ and Fe₂O₃ (up to 10 mol%) have been prepared by mechanochemical milling of TiO₂ and yellow Fe₂O₃/red Fe₂O₃/precipitated Fe (OH)₃ using a planetary ball mill. Such novel solid solution cannot be prepared by conventional co-precipitation technique. A preliminary investigation of photocatalytic activity of mixed oxide (TiO₂/Fe₂O₃) on photo-oxidation of different organic dyes like Rhodamine B (RB), Methyl orange (MO), Thymol blue (TB) and Bromocresol green (BG) under visible light (300-W Xe lamp; λ > 420 nm) showed that TiO₂ having 5 mol% of Fe₂O₃ (YFT1) is 3-5 times higher photoactive than that of P25 TiO₂. The XRD result did not show the peaks assigned to the Fe components (for example Fe₂O₃, Fe₃O₄, FeO₃, and Fe metal) on the external surface of the anatase structure in the Fe₂O₃/TiO₂ attained through mechanochemical treatment. This meant that Fe components were well incorporated into the TiO₂ anatase structure. The average crystallite size and particle size of YFT1 were found to be 12 nm and 30 ± 5 nm respectively measured from XRD and TEM conforming to nanodimensions. Together with the Fe component, they absorbed wavelength of above 387 nm. The band slightly shifted to the right without tail broadness, which was the UV absorption of Fe oxide in the Fe₂O₃/TiO₂ particle attained through mechanochemical method. This meant that Fe components were well inserted into the framework of the TiO₂ anatase structure. EPR and magnetic susceptibility show that Fe³⁺ is in low spin state corresponding to μ_B = 1.8 BM. The temperature variation of μ_B shows that Fe³⁺ is well separated from each other and does not have any antiferromagnetic or ferromagnetic interaction. The evidence of Fe³⁺ in TiO₂/Fe₂O₃ alloy is also proved by a new method that is redox titration which is again support by the XPS spectrum.     

Characteristics of fine size Fe-Ni alloy powders directly prepared by spray pyrolysis

Fe-Ni alloy powders with composition of Fe_0.25Ni_0.75 were directly prepared by spray pyrolysis. The powders prepared at temperatures of 1200 and 1400 °C had peaks of pure Fe-Ni₃ alloy phase. The alloy powders with a spherical shape and dense structure were prepared at a temperature of 1400 °C by melting the powders. The composition ratio of Fe and Ni components in the alloy powders prepared at a temperature of 1400 °C coincided well with that of the spray solution. The mean sizes of the alloy powders changed from 0.20 to 0.74 μm when the concentrations of the spray solution changed from 0.02 to 1 M. The alloy powders prepared from the spray solution with a concentration of 0.5M had a maximum saturation magnetization and minimum coercivity values as 96.95 emu g^?1 and 34.67 Oe, respectively.     

Fe掺杂TiO2纳米材料的合成及光催化性能

以钛酸丁酯为钛源,Fe(NO3)3·9H2O为铁源,采用溶胶-凝胶法制备Fe/TiO2纳米粉体,利用溶胶结合静电纺丝技术制备Fe/TiO2纳米纤维,从材料改性及形貌改善两个角度共同提高TiO2纳米材料的光催化活性及实用性。借助XRD、SEM、TEM等分析技术,探究了Fe/TiO2纳米材料在可见光区的光催化活性,分析了煅烧温度及掺铁量对Fe/TiO2纳米材料光催化性能的影响。结果显示,铁的掺入及形貌的改善有助于提高TiO2的光催化性能。     

Nanoindentation study of the mechanical and damage behaviour of suspension plasma sprayed TiO2 coatings

TiO₂ coatings can be used as self-cleaning surfaces owing to their photocatalytic and hydrophilic properties. Suspension plasma spray (SPS) has proven to be a feasible and cheap technique for producing self-cleaning surfaces with acceptable photo-activity. This paper presents a nanoindentation study of the mechanical properties (hardness, Young's modulus and scratch resistance) of photoactive layers of suspension plasma sprayed TiO₂ coatings applied on to glass substrates. Microstructure observation showed that the rutile grains were surrounded by fine anatase crystals. Under the same spraying conditions, the resulting anatase/rutile concentrations varied depending on the cooling rate (the substrate being either cooled with water or in air). The results showed that higher concentrations of anatase, which is softer than rutile, reduced the scratch damage and increased the friction coefficient.     

Electrodeposition of composite Fe–TiO<Subscript>2</Subscript> coatings from methanesulfonate electrolyte

The process of electrodeposition of an iron–titania composite electrochemical coating from methanesulfonate electrolyte is studied. TiO₂ Degussa P 25 nanopowder (a mixture of crystalline modifications of rutile and anatase, with the latter prevailing) is used for preparation of suspension electrolyte. The dispersed phase content in the composition coating increases at a decrease in current density and increase in TiO₂ in the suspension. It is shown that kinetics of codeposition is adequately described by the improved Guglielmi model. It is shown that inclusion of TiO₂ particles into an iron matrix results in an increase in microhardness of the coating due to dispersion strengthening. Fe–TiO₂ (anatase+rutile) coatings manifest photocatalytic activity with respect to the reaction of destruction of the methyl orange dye in aqueous solutions under exposure to UV radiation, and this activity is higher than in the case of similar coatings containing TiO₂–rutile particles.     

Comparison of the structure and wear resistance of Al2O3-13 wt.%TiO2 coatings made by GSP and WSP plasma process with two different powders

The goal of this study is to compare two Atmospheric Plasma Spraying (APS) systems for elaborating alumina/titania coatings with good wear resistance. Both torches used were a common d.c. current Gas-Stabilized Plasma gun (GSP) with argon and hydrogen as plasma forming gases, and a Water-Stabilized high-throughput Plasma gun (WSP) working with water as plasma forming substance. The feedstock were either cladded alumina/titania powder or a mixture of conventional fused and crushed Al₂O₃ powder with agglomerated TiO₂ nanometric particles, the resulting mean size in both cases being about 50 µm. Feedstock material phases were α-alumina and anatase titanium dioxide and the composition of both powders was 13 wt.% of TiO₂ in Al₂O₃. Coatings obtained were analyzed by scanning electron microscopy (SEM). They presented lamellar structures with titania uniformly distributed in the alumina matrix, for both spray techniques. X-ray diffraction showed that anatase phase of titania was converted into rutile phase. The wear resistance tested by slurry abrasion (SAR) has shown that the best coating was that obtained with cladded powder sprayed by GSP process. This finding matched with the highest microhardness of this coating (Vickers indentation). It is worth noting that with these two relatively dissimilar torches similar results were obtained for the wear resistance of alumina-13 wt.% titania coating.