Toughening and strengthening mechanism of plasma sprayed nanostructured Al2O3–13 wt.%TiO2 coatings

The starting materials of Al₂O₃, TiO₂, ZrO₂ and CeO₂ nanoparticles were agglomerated into sprayable feedstock powders and plasma sprayed to form nanostructured coatings. There were net structures and fused structures in plasma sprayed nanostructured Al₂O₃–13 wt.%TiO₂ coatings. The net structures were derived from partially melted feedstock powders and the fused structures were derived from fully melted feedstock powders. The nanostructured Al₂O₃–13 wt.%TiO₂ coatings possessed higher hardness, bonding strength and crack growth resistance than conventional Metco 130 coatings which were mainly composed of lamellar fused structures. The higher toughness and strength of nanostructured Al₂O₃–13 wt.%TiO₂ coatings were mainly related to the obtained net structures.     

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.     

Plasma spray coating of spray-dried Cr2O3/wt.% TiO2 powder

An agglomerated Cr₂O₃/wt.%TiO₂ powder has been fabricated by the spray drying process under different parameters. The spray-dried powder has well-agglomerated particles of spherical shape. In the conditions of the high slurry feed rate and low binder concentration in the slurry, the powder has large cavities inside some particles and ruggedness over their surface. The optimum plasma spray feed rate has been found by examining the spraying behavior of the powder and melted state of particles. The plasma spray coating has been performed under different process variables such as spraying distance and plasma power. These parameters strongly affect the characteristics of the coated layer: microstructure, hardness, and bond strength.     

Thermal conductivity of titanium dioxide films grown by metal-organic chemical vapor deposition

We studied the effect of the microstructures on the thermal conductivity of the titanium dioxide (TiO₂) films. TiO₂ films were grown by MOCVD, their morphologies were observed using a scanning electron microscope (SEM). The chemical composition was determined through Rutherford backscattering spectroscopy (RBS) and nuclear reaction analysis (NRA) measurements. The thermal conductivity of the in-plane direction was measured using an alternating current calorimetric method (laser-heating Angstrom method) in the temperature range of 300 to 470 K. The authors fabricated a TiO₂ film with extremely low thermal conductivity (~ 0.5 Wm^− 1 K^− 1), in which a feather-like texture is regularly arranged in the direction perpendicular to the heat flow. The origins of the extremely low thermal conductivity were studied from a microstructural viewpoint.     

Laser-induced enhancement of the surface hardness of nanoparticulate TiO2 self-cleaning layer

We here report that the abrasion resistance of nanoparticulate TiO₂ self-cleaning layers can be highly enhanced without a considerable loss of photocatalytic capability. TiO₂ coating layers solution-deposited onto the glass substrate were irradiated by a pulsed ultraviolet (UV) laser at 355 nm, which modified the surface morphologies via laser-induced local melting of TiO₂ nanoparticles. The surface hardness, measured by pencil scratch test, improved with increasing laser power (P). While an unmodified TiO₂ layer revealed a hardness of 6B, it increased to 2H after the surface was irradiated at P = 0.3 W. Almost all of the stearic acid deposited on an unmodified sample disappeared after UV exposure for 12 h. The photocatalytic decomposition was slowed down on laser-irradiated TiO₂ surfaces and this is attributed to the reduction of specific surface areas as a result of the morphological modifications. However, a TiO₂ layer hardened to 2H still exhibited fairly good photocatalytic activity, decomposing more than 75% of the stearic acid after exposure for the same duration.     

Microstructure and adhesion of Cr3C2-NiCr vacuum plasma sprayed coatings

Vacuum plasma spraying (VPS) was used to spray a Cr₃C₂-NiCr coating of ∼ 150, 300 and 450 μm in thickness onto a plain carbon steel substrate, employing a commercially available Cr20Ni9.5C powder. The splat microstructures observed in the coating were found to consist of a NiCr matrix with a predominant Cr₃C₂ phase, besides Cr₇C₃ and Cr₂O₃. The adhesion of the coating to the substrate was evaluated by means of interfacial indentation techniques. It has been found that the interfacial toughness value changes from 7.6 to 10.1 MPa m^1/2 when the thickness increases from 150 to 450 μm. Also, it has been found that the parameter Kca_o, determined by linear regression from the Kca versus 1 / e² curve by means of the interfacial indentation model advanced by Chicot et al., has a value of ∼ 9.8 MPa m^1/2.     

Effects of the powder manufacturing method on microstructure and wear performance of plasma sprayed alumina-titania coatings

Three Al₂O₃-13wt.% TiO₂ powders, with the same chemical composition but different Al₂O₃-TiO₂ distribution patterns, are plasma sprayed and the resulting coatings are compared in terms of their phase composition, microstructure, hardness, crack growth resistance, and abrasive wear performance. It is demonstrated that the degree of mixing of the Al₂O₃ and TiO₂ ingredients in the feed powder has immense impact on the phase composition, microstructure, hardness, crack growth resistance, and abrasive wear performance of the coatings. A high degree of mixing of Al₂O₃ and TiO₂ in the powder state results in more uniform microstructure, higher hardness, higher crack growth resistance, and consequently better abrasive wear resistance of the coating.     

Modification of TiO2 nanorods by Bi2MoO6 nanoparticles for high performance visible-light photocatalysis

In this work, TiO₂ nanorods were prepared by a hydrothermal process and then Bi₂MoO₆ nanoparticles were deposited onto the TiO₂ nanorods by a solvothermal process. The nanostructured Bi₂MoO₆/TiO₂ composites were extensively characterized by X-ray diffraction, scanning and transmission electron microscopy, X-ray photoelectron spectroscopy and UV-vis diffuse reflectance spectroscopy. The photocatalytic activity of the Bi₂MoO₆/TiO₂ composites was evaluated by degradation of methylene blue. The Bi₂MoO₆/TiO₂ composites exhibit higher catalytic activity than pure Bi₂MoO₆ and TiO₂ for degradation of methylene blue under visible light irradiation (λ > 420 nm). Further investigation revealed that the ratio of Bi₂MoO₆ to TiO₂ in the composites greatly influenced their photocatalytic activity. The experimental results indicated that the composite with Bi₂MoO₆:TiO₂ = 1:3 exhibited the highest photocatalytic activity. The enhancement mechanism of the composite catalysts was also discussed.     

CaCl2作为造孔剂制备泡沫青铜的结构和力学性能

以青铜粉为原料、CaCl_2为造孔剂,采用粉末烧结溶解法制备开孔泡沫青铜。通过改变造孔剂体积分数和粒径成功制备出孔隙率为70%~90%,孔径1~3mm的泡沫青铜试样。研究了孔隙率和造孔剂的关系以及孔隙率、孔径对泡沫试样力学性能的影响,并对其孔结构,相组成和微观形貌进行观察和分析。结果表明:泡沫青铜试样的塑性屈服平台应力随孔隙率增加而减小,当孔隙率为77%~89%时,对应塑性屈服平台应力为12.6~2.6MPa。当应变量为50%时,孔隙率为77%~89%的泡沫青铜单位体积能量吸收值(W)范围为6.21~0.91MJ/m~3。试样的理想吸能效率(I)都接近0.82,说明泡沫青铜可以作为一种理想的吸能材料。     

Microstructural Analysis and Photocatalytic Activity of Plasma-Sprayed Titania-Hydroxyapatite Coatings

Hydroxyapatite (HAp Ca₁₀(PO₄)₆(OH)₂) is known to be a biomaterial and an adsorbent for chromatography. In this study, HAp was agglomerated with anatase TiO₂ to manufacture thermal-spray powders to improve the adsorption activity of TiO₂, and then to improve its photocatalytic activity. The microstructures, compositions and photocatalytic activity of plasma-sprayed TiO₂, TiO₂-10%HAp, TiO₂-30%HAp, and HAp coatings were investigated. Due to the low thermal conductivity of HAp compound, not all HAp particles fully melted even under the arc current of 800 A. The addition of HAp inhibited the phase transformation of anatase TiO₂ to rutile. Under the arc current of 600 A, the anatase content in the TiO₂, TiO₂-10%HAp and TiO₂-30%HAp coatings was 11, 20 and 42%, respectively. With the increasing of the spraying distance from 70 to 110 mm, the anatase content in the TiO₂-30%HAp coatings decreased from 34 to 17% under arc current of 700 A. Furthermore, a slight decomposition of HAp to α-Ca₃(PO₄)₂ was found in the TiO₂-30%HAp coatings, it did not decompose to CaO and P₂O₅ according to the XRD and EDAX analysis. The addition of the secondary gas of helium had no significant influence on the melting state of the TiO₂-HAp feedstock powders. Moreover, the HAp in the TiO₂-10%HAp and TiO₂-30%HAp coatings had adsorption characteristic to acetaldehyde. The photocatalytic activity of TiO₂-10%HAp coating was highest among TiO₂, TiO₂-10%HAp, and TiO₂-30%HAp coatings sprayed under the arc current of 600 A for the optimum adsorption property and anatase content. This article is an invited paper selected from presentations at the 2007 International Thermal Spray Conference and has been expanded from the original presentation. It is simultaneously published in Global Coating Solutions, Proceedings of the 2007 International Thermal Spray Conference, Beijing, China, May 14-16, 2007, Basil R. Marple, Margaret M. Hyland, Yuk-Chiu Lau, Chang-Jiu Li, Rogerio S. Lima, and Ghislain Montavon, Ed., ASM International, Materials Park, OH, 2007.     

Impedance spectroscopy of suspension plasma sprayed titania coatings

Two TiO₂ coatings were plasma sprayed, using an aqueous suspension as a feedstock onto initially prepared alumina substrates. Their thickness was about 7 and 15 μm. The coatings were tested using impedance spectroscopy (IS) in the frequency range from 100 Hz to 2 MHz at temperatures ranging from 320 to 1020 K. The measurements allowed to find the Nyquist plots and equivalent circuits of the tested samples. The IS results were interpreted by the microstructural features of the deposits such as chemical composition, atomic structural and phase analysis. The mechanism of electric current conduction in tested coatings was proposed.     

超音速火焰喷涂纳米结构涂层研究进展

超音速火焰(High Velocity Oxy -Fuel,简称HVOF)喷涂具有高速和相对较低的温度两个重要特征,能够获得比普通火焰喷涂或等离子喷涂(Plasma Spray,简称PS)结合强度更高的致密涂层.纳米材料具有独特的表面效应、体积效应及量子尺寸效应,其电学、力学、磁学、光学和热学等性能产生了惊人的变化.随着材料科学技术的深入发展, 在实际生产和生活中运用性能优良的纳米材料倍受人们关注,其中,采用热喷涂技术制备纳米结构涂层是构筑纳米结构材料的最具前途的方法之一.从目前国内外的情况来看,HVOF喷涂纳米结构涂层技术的研究取得了较大的进展.综合国内外文献,总结了HVOF喷涂制备纳米结构涂层的研究现状,着重阐述了热喷涂纳米涂层的基本过程和结合机理,指出了利用HVOF喷涂纳米结构涂层存在的问题,并对热喷涂纳米结构涂层的发展前景作了展望.     

自反应电弧喷涂原位合成Ti(C,N)-TiB2-Al2O3复相陶瓷涂层

以Ti+B4C为反应药芯、Al为外皮材料制备反应型喷涂丝材,探讨利用自反应电弧喷涂技术在45钢基体表面制备复相陶瓷涂层的可行性。以X射线衍射仪(XRD)、扫描电子显微镜(SEM)和能谱仪(EDS)等方法分析、观察了涂层的组织与结构,测试了涂层的主要力学性能。结果表明:利用制备的药芯丝材进行喷涂试验,可获得由TiB2、TiB、TiC0.3N0.7、TiN、Al2O3、AlN等多相组成的复相陶瓷涂层。涂层呈典型的层状结构,其连续的基体相内弥散分布着离散的第二、第三相。涂层与基体间的结合强度为18.9MPa,涂层的平均显微硬度与弹性模量分别为735.4HV0.2和461.4GPa,摩擦因数在0.45～0.50之间,耐磨性能较基体材料提高3倍以上。     

First-principles study on the electronic and optical properties of F- and Nb-doped anatase TiO2

We present a comparative study on the electronic and optical properties of Nb- and F- doped anatase TiO₂ by first-principles calculations based on the density functional theory (DFT). Although both TiO₂:Nb and TiO₂:F have a similar band structure, the effective mass of TiO₂:F is larger than that of TiO₂:Nb, and the carriers density in the former is lower than that in the latter, indicating that TiO₂:Nb has better electronic conductivity than TiO₂:F. The interaction between photons and electrons in TiO₂:F is much stronger than that in TiO₂:Nb, resulting in increased photon absorption and reduced transmittance, especially in the visible and near-infrared regions. The results demonstrate that TiO₂:F is not suitable for transparent conductive oxide applications.     

Thermal shock behavior of nanostructured and conventional Al2O3/13 wt%TiO2 coatings fabricated by plasma spraying

The thermal shock behavior of three kinds of Al₂O₃/13 wt%TiO₂ coatings fabricated by plasma spraying was studied in this paper. One kind of those coatings was derived from conventional fused and crushed feedstock powder available commercially; the other two kinds of coatings were derived from nanostructured agglomerated feedstock powders. These two nano coatings possess moderate pores and pre-existing microcracks, they were composed of fused structure and three-dimensional net or skeleton-like structure. For conventional coatings, the pores and pre-existing cracks were bigger, sharp-point and mostly distributed between splats. Thermal shock tests for the three coatings were performed by water quenching method. Testing result showed the two kinds of nano coatings had much higher thermal shock resistance than the conventional coatings. The improved thermal shock resistance for nano coatings could attribute to their improved microstructure and crack propagation mode. The damage evolution and failure mechanism of coatings was quite different at thermal shock temperature of 650 °C and 850 °C, which was explained by a simple model. Different crack propagating modes in nanostructured and conventional coatings during thermal shock tests were due to their different microstructures in these two kinds coatings. The stress state of coating surfaces during the thermal cycles was also discussed in this paper.     

Synthesis and characterization of Y3Al5O12 and ZrO2-Y2O3 thermal barrier coatings by combustion spray pyrolysis

Y₃Al₅O₁₂ and ZrO₂-Y₂O₃ (8 mol% YSZ) coatings for potential application as thermal barrier coatings were prepared by combustion spray pyrolysis. Thermal cycling of as deposited coatings on stainless steel and FeCrAlY bond coat substrates was carried out at 1000 °C and 1200 °C to determine the thermal fatigue response. Structural and morphological studies on Y₃Al₅O₁₂ and 8 mol% YSZ coatings before and after thermal cycling have been carried out. It has been noted that the coatings on FeCrAlY substrates remain intact after 50 cycles between room temperature and 1200 °C, whereas the coatings on stainless steel show some minor damage such as peeling off near the periphery after 50 cycles at 1000 °C. Thermal diffusivity values of Y₃Al₅O₁₂ and 8 mol% YSZ films were measured by using photo thermal deflection spectroscopy and the values are lower than those of coatings produced by conventional techniques such as EBPVD and APS.     

Thermal conductivity and thermal cycle life of La2O3 and HfO2 doped ZrO2-Y2O3 coatings produced by EB-PVD

The effects of La₂O₃ and HfO₂ addition on thermal conductivity and thermal cycle life of EB-PVD YSZ coatings were investigated. La₂O₃ and HfO₂ were selected as additives, because they significantly suppress the sintering of YSZ. The developed coating showed low thermal conductivity as well as high resistance to sintering. Burner rig tests confirmed that the developed coating have a superior thermal insulating effect and have a longer life than that of a coating with conventional composition.