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.     

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.     

HVOF-Sprayed Coatings Engineered from Mixtures of Nanostructured and Submicron Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-TiO<Subscript>2</Subscript> Powders: An Enhanced Wear Performance

In previous studies, it has been demonstrated that nanostructured Al₂O₃-13 wt.%TiO₂ coatings deposited via air plasma spray (APS) exhibit higher wear resistance when compared to that of conventional coatings. This study aimed to verify if high-velocity oxy-fuel (HVOF)-sprayed Al₂O₃-13 wt.%TiO₂ coatings produced using hybrid (nano + submicron) powders could improve even further the already recognized good wear properties of the APS nanostructured coatings. According to the abrasion test results (ASTM G 64), there was an improvement in wear performance by a factor of 8 for the HVOF-sprayed hybrid coating as compared to the best performing APS conventional coating. When comparing both hybrid and conventional HVOF-sprayed coatings, there was an improvement in wear performance by a factor of 4 when using the hybrid material. The results show a significant antiwear improvement provided by the hybrid material. Scanning electron microscopy (SEM) at low/high magnifications showed the distinctive microstructure of the HVOF-sprayed hybrid coating, which helps to explain its excellent wear performance. 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.     

Microstructural characterization of plasma sprayed Al2O3-40 wt.% TiO2 coatings on high density graphite with different post-treatments

Graphite is one of the candidate materials proposed for application in pyrochemical reprocessing plants involving aggressive molten chloride environment. Post treatments are promising techniques for the improvement of properties of thermal spray coatings for different industrial applications. In the present work, the effect of post treatments like vacuum annealing (VA) and laser melting (LM) on the microstructure and chemical modification of plasma sprayed Al₂O₃-40 wt.% TiO₂ coatings over high density (HD) graphite substrates has been investigated. When compared with sprayed coatings (SC), VA coatings showed cluster morphology and LM coatings exhibited homogenous microstructure. On laser melted surfaces networks of cracks were observed. XRD studies showed that the metastable γ-Al₂O₃ phase present in the SC is transformed to stable α-Al₂O₃ after post treatments. In LM coatings Al₂TiO₅ phase was more predominant in contrast to SC and VA coatings. The microhardness enhancement was observed in case of LM coating compared to the VA and SC. Due to elimination of coating defects in LM samples, there is a considerable reduction in the surface roughness.     

Microstructure and Wear Behavior of Conventional and Nanostructured Plasma-Sprayed WC-Co Coatings

WC-12%Co coatings were deposited by atmospheric plasma spraying using conventional and nanostructured powders and two secondary plasmogenous gases (He and H₂). Coating microstructure and phase composition were characterized using scanning electron microscopy (SEM), transmission electron microscopy (TEM), and x-ray diffraction techniques (XRD) techniques. This study examined wear and friction properties of the coatings under dry friction conditions. SEM was used to analyze abraded surface microstructure. Coating microhardness and fracture toughness were also determined. All coatings displayed strong decarburization as a result of WC decomposition, which gave rise to the formation of secondary phases (W₂C and W). A very fine undissolved WC crystalline dispersion coexisted with these new phases. TEM observation confirmed that the matrix was predominantly amorphous and filled with block-type, frequently dislocated crystallites. Wear was observed to follow a three-body abrasive mechanism, since debris between the ball and the coating surface was detected. The main wear mechanism was based on subsurface cracking, owing to the arising debris. WC grain decomposition and dissolution were concluded to be critical factors in wear resistance. The level of decomposition and dissolution could be modified by changing the plasmogenous gas or feed powder grain size. The influence of the plasmogenous gas on wear resistance was greater than the influence of feedstock particle size.     

Improved interfacial mechanical properties of Al2O3-13wt%TiO2 plasma-sprayed coatings derived from nanocrystalline powders

The interfacial toughness of two types of Al₂O₃-13wt%TiO₂ plasma-sprayed ceramic coatings on steel substrates—“conventional” and “nano”—has been measured using the Rockwell indentation method. The interfacial toughness of the “conventional” coating and the “nano” coating is found to be 22 and 45 J.m⁻², respectively. The “conventional” coating, which was prepared using a fused feedstock powder available commercially, has a microstructure consisting primarily of fully-molten (FM) and solidified “splats”. The feedstock powder for the “nano” coating comprised reconstituted agglomerates of nanocrystalline Al₂O₃ and TiO₂ powders. The microstructure of the “nano” coating, as characterized using scanning and transmission electron microscopy techniques, consists of regions of FM “splats” interspersed with partially-molten (PM) rounded microstructural features. The substructure in these PM features (20–50 μm diameter) consists of α-Al₂O₃ grains (0.5–1 μm) surrounded by a TiO₂-rich amorphous phase. The FM/steel interfaces in both the “conventional” and the “nano” coatings are found to be cracked (before mechanical testing), whereas the PM/steel interfaces in the “nano” coating are found to be adherent. It is believed that the unique bimodal microstructure, together with the presence of the TiO₂-rich amorphous phase at the PM/steel interface, is responsible for the significantly improved interfacial toughness of the “nano” coating. The key differences in the failure modes in the two types coatings are also discussed, with reference to a simple model.     

TEM and DFT investigation of CVD TiN/κ-Al2O3 multilayer coatings

This paper investigates the interfacial structure in hot-wall CVD TiN/κ-Al₂O₃ multilayer coatings using both HREM and DFT modeling. Two multilayers with different thicknesses of the TiN layers (50 and 600 nm) separating the κ-Al₂O₃ layers are analyzed. The general microstructure of the two multilayers is relatively similar. The TiN layer in the thicker TiN/κ-Al₂O₃ coating is thick enough to be several TiN grains high. This means that epitaxial columns, which are often found in the thinner TiN/κ-Al₂O₃ coatings, are not present. However, the orientation relationships at the TiN/κ-Al₂O₃ interfaces are the same in both multilayers. The HREM investigations show that κ-Al₂O₃ (001) planes can grow directly on flat (111) TiN faces, without any other phases or detectable amounts of impurities, such as sulphur, present. Where the TiN layers are more curved, γ-Al₂O₃ can be grown, at least partly stabilized by the cube-on-cube orientation relationship between γ-Al₂O₃ and the underlying TiN. The DFT calculations show very similar adsorption strengths for an O monolayer positioned on Ti-terminated TiC(111) and TiN(111) surfaces, with preferred adsorption in the fcc site. O adsorption on N-terminated TiN(111) is much weaker, with preferred adsorption in the top site. Calculated elastic-energy contributions yield a higher stability for κ-Al₂O₃ on TiN(111) than on TiC(111) and a higher stability for κ-Al₂O₃ than for α-Al₂O₃ on both TiC and TiN. This indicates that the observed higher stability of κ-Al₂O₃ on TiC(111) than on TiN(111) is not due to the lattice mismatch, while the preferred epitaxial growth of κ-Al₂O₃ over α-Al₂O₃ can be partly attributed to the mismatch.     

Effects of critical plasma spray parameter and spray distance on wear resistance of Al2O3-8 wt.%TiO2 coatings plasma-sprayed with nanopowders

Effects of plasma spraying conditions on wear resistance of nanostructured Al₂O₃-8 wt.%TiO₂ coatings plasma-sprayed with nanopowders were investigated in this study. Five kinds of nanostructured coatings were plasma-sprayed on a low-carbon steel substrate by varying critical plasma spray parameter (CPSP) and spray distance. The coatings consisted of fully melted region of γ-Al₂O₃ and partially melted region, and the fraction of the partially melted regions and pores decreased with increasing CPSP or decreasing spray distance. The hardness and wear test results revealed that the hardness of the coatings increased with increasing CPSP or decreasing spray distance, and that the hardness increase generally led to the increase in wear resistance, although the hardness and wear resistance were not correlated in the coating fabricated with the low CPSP. The main wear mechanism was a delamination one in the coatings, but an abrasive wear mode also appeared in the coating fabricated with the low CPSP. According to these wear mechanisms, the improvement of wear resistance in the coating fabricated with the low CPSP could be explained because the improved resistance to fracture due to the presence of partially melted regions might compensate a deleterious effect of the hardness decrease.     

Influence of micro-blasting on the microstructure and residual stresses of CVD κ-Al2O3 coatings

Cemented carbides coated with CVD multilayers are commonly used in metal cutting turning and milling operations. For many applications, a micro-blasting finishing procedure based on an impact treatment of the surfaces is carried out in order to smooth the coated surface and reduce sharp cutting edges. In this work, micro-blasting with corundum in aqueous solution at pressures between 0.05 and 0.3 MPa was applied to CVD TiN/Ti(C,N)/κ-Al₂O₃ multilayer coatings deposited onto cemented carbides in order to investigate its influence on the micro-topography, microstructure and residual stresses. The results showed that the micro-blasting reduces the surface roughness and affects the coating thickness. TEM investigations revealed no significant changes on the microstructure of the κ-Al₂O₃ top layer. Synchrotron X-ray investigations showed that the residual stress state of the as-deposited κ-Al₂O₃ top layer is not affected by the micro-blasting treatment under the conditions investigated.     

Preparation and characterization of nanostructured Al<Subscript>2</Subscript>O<Subscript>3</Subscript>-13wt.%TiO<Subscript>2</Subscript> ceramic coatings by plasma spraying

Nanostructured and conventional Al₂O₃-13wt.%TiO₂ ceramic coatings were prepared by plasma spraying with nanostructured agglomerated and conventional powders, respectively. The microstructure and microhardness of the coatings were investigated using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and microhardness measurement. Meanwhile, the friction and wear behaviors were analyzed and compared using a ball-on-disk tribometer. The results show that the conventional coating has lamellar stacking characteristic and has some pores. However, the nanostructured coating shows a bimodal microstructure, which is composed of both fully melted regions and partially melted regions. According to the microstructural difference, the partially melted regions can be divided into liquid-phase sintered regions (a three-dimensional net or skeleton-like structure: Al₂O₃-rich submicron particles embedded in the TiO₂-rich matrix) and solid-phase sintered regions (remained nanoparticles). The microstructural characteristics of the liquid-phase sintered region are formed due to the selective melting of TiO₂ nanoparticles during plasma spraying. On the other hand, the TiO₂ and Al₂O₃ nanoparticles of the solid-phase sintered regions are all unmelted during plasma spraying. Due to the existence of nanostructured microstructures, the nanostructured coating has a higher microhardness, a lower friction coefficient, and a better wear resistance than the conventional coating.     

Characterizations and hot corrosion resistance of Cr3C2-NiCr coating on Ni-base superalloys in an aggressive environment

In the current study, Cr₃C₂-NiCr coating was deposited on the Ni-base superalloys by using high velocity oxyfuel (HVOF) process for high temperature corrosive environment applications. Optical microscopy (OM), x-ray diffraction (XRD), scanning electron microscopy/energy-dispersive analysis (SEM/EDAX), microhardness tester, and electro probe microanalyzer (EMPA) techniques were used to characterize the coating with regard to coating thickness, porosity, microhardness, and microstructure. The thermogravimetric technique was used to establish kinetics of corrosion. The hot corrosion behaviors of the bare and Cr₃C₂-NiCr coated superalloys were studied after exposure to aggressive environment of Na₂SO₄-60% V₂O₅ salt mixture at 900 °C under cyclic conditions. The structure of the as-sprayed Cr₃C₂-NiCr coating mainly consisted of γ-nickel solid solution along with minor phases of Cr₇C₃ and Cr₂O₃. Coating has porosity less than 1.5% and microhardness in the range of 850–900 Hv (Vickers hardness). Some inclusions, unmelted and semimelted powder particles were observed in the structure of the coatings. The Cr₃C₂-NiCr coating has imparted necessary resistance to hot corrosion, which has been attributed to the formation of oxides of nickel and chromium, and spinel of nickel-chromium. This article was originally published inBuilding on 100 Years of Success, Proceedings of the 2006 International Thermal Spray Conference (Seattle, WA), May 15–18, 2006, B.R. Marple, M.M. Hyland, Y.-Ch. Lau, R.S. Lima, and J. Voyer, Ed., ASM International, Materials Park, OH, 2006.     

Effect of H2 flow rate and stand-off distance on the formation of phases in plasma-sprayed Al2O3 coatings

Plasma-sprayed Al₂O₃ coatings contain both metastable and stable phases of Al₂O₃. The formation of these phases is influenced by various process parameters, such as stand-off distance (SOD), gas flow rates, nozzle diameter and is also dependent on the melting and solidification behaviour of feedstock particles, as these help in controlling the weight fraction of different phases formed in the coating. The present work reports the investigation on the effect of two major plasma spray parameters, namely secondary gas (H₂) flow rate and SOD, on the formation of phases in plasma-sprayed Al₂O₃ coating. The phases were identified by X-ray diffraction analysis and to quantify those phases, the Rietveld refinement method was used. The influence of α-phase on the mechanical properties of the Al₂O₃ coatings was evaluated, and it has been observed that α-phase content decreases with the increase in secondary gas flow rate. With the increase in SOD, the α-Al₂O₃ phase content first decreases and then increases.     

Microstructure, spallation and corrosion of plasma sprayed Al2O3–13%TiO2 coatings

The electrochemical corrosion behaviours of the steel substrates coated with three different plasma sprayed Al₂O₃–13%TiO₂ coatings were studied in this paper. The three kinds of Al₂O₃–13%TiO₂ coatings were conventional ME coating, nanostructured NP coating and NS coating. There were micro cracks, laminar splats and straight columnar grains in ME coating. For the two nanostructured coatings, the laminar microstructure and columnar grains were not obvious. The NP coating had the highest hardness and spallation resistance. Electrochemical corrosion behaviour of the three coatings was mainly investigated by potentiodynamic polarization and electrochemical impedance spectroscopy (EIS) in aqueous Na₂SO₄ solution.     

The effect of plasma spray parameters on the cavitation erosion of Al2O3-TiO2 coatings

This paper reports a study of how the choice of plasma spray parameters, used during deposition of Al₂O₃-13%TiO₂ coatings on carbon steel, influences the cavitation erosion properties of such coatings. The parameters studied are the power feeding rate and hydrogen flow rate. The surface and cross section of coatings before and after cavitation were also observed by scanning electron microscopy (SEM). The phases present in the coatings were characterized by X-ray diffraction method (XRD). The microscopic observations were used to study the inter-lamellar connection, porosity, unmelted particles and so on inside the coating. We also measured the roughness, microhardness, adhesion strength and cavitation erosion of the coatings. The XRD results showed that the coating includes different allotropes of Al₂O₃ such as α and γ. The cavitation erosion studies of the coatings were conducted by ultrasonic cavitation testing on the basis of ASTM G32 standard. It was found that cavitation erosion is accelerated around the unmelted particles and porosities. The results reveal that the cavitation resistance of the coating is determined by its microstructure and that increasing discontinuities (inside the coating) reduce its cavitation resistance. We have found that the coating obtained at hydrogen gas flow rate of 16 L/min and powder feeding rate of 20 g/min has the best cavitation resistance.     

Characterisation and oxidation of LVOF sprayed Al2O3–40%TiO2 coating on superni 601 and superni 718 superalloys at 800 and 900°C

Failure of components due to high temperature oxidation is the major degradation mechanism in boiler and gas turbine industries. Superalloys having superior mechanical properties and creep resistance are used in these applications but lack resistance to oxidation under aggressive environments. Protective coatings are used to improve their oxidation resistance in such applications. In the present investigation, Al₂O₃–40%TiO₂ coating was deposited on superni 718 and superni 601 superalloys by low velocity oxy fuel process. The as sprayed coating was characterised for microhardness, surface roughness, scanning electron microscopy and X-ray diffraction analysis. High temperature oxidation behaviour of Al₂O₃–40%TiO₂ coated and uncoated superni 718 and superni 601 superalloys has been evaluated at the elevated temperatures of 800 and 900°C for total duration of 50 cycles under cyclic conditions. Each cycle consisted of keeping the samples for 1 h at the elevated temperature followed by 20 min cooling in ambient air. Al₂O₃–40TiO₂ coating in the as sprayed condition showed the presence of Al₂O₃–TiO₂, α-Al₂O₃, TiO₂ as the main phases. Al₂O₃–40%TiO₂ coating on superni 718 and superni 601 superalloys has shown a lower oxidation rate as compared to those of uncoated superalloys. However, the oxidation rate of the coating was not steady due to the occurrence of spallation/sputtering at various stages. The coating was found adherent on the substrate superalloys throughout the study.     

Microstructure and mechanical properties of Al2O3-Cr2O3 composite coatings produced by atmospheric plasma spraying

Al₂O₃, Al₂O₃-Cr₂O₃ and Cr₂O₃ coatings were deposited by atmospheric plasma spraying. Phase composition of powders and as-sprayed coatings was determined by X-ray diffraction. Electron probe microanalyzer was employed to investigate the polished and fractured surface morphologies of the coatings. Mechanical properties including microhardness, fracture toughness and bending strength were evaluated. The results indicate that the addition of Cr₂O₃ is conducive to the stabilization of α-Al₂O₃. Compared with the pure Al₂O₃ and Cr₂O₃ coatings, Al₂O₃-Cr₂O₃ composite coatings show lower porosities and denser structures. Heterogeneous nucleation of α-Al₂O₃ occurs over the isostructural Cr₂O₃ lamellae and partial solid solution of Al₂O₃ and Cr₂O₃ might be occurring as well. Furthermore, grain refining and solid solution strengthening facilitate the mechanical property enhancement of Al₂O₃-Cr₂O₃ composite coatings.     

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.     

Deposition, microstructure and properties of texture-controlled CVD α-Al2O3 coatings

The influence of nucleation on the microstructure and properties of CVD Al₂O₃ was investigated. The experimental α-Al₂O₃ layers were deposited (a) without nucleation control and (b) with nucleation steps resulting in pronounced , and growth textures. The experimental layers were characterised using X-ray diffraction, scanning electron microscopy and transmission electron microscopy. Wear properties of the textured coatings were evaluated in turning. The chemistry of the nucleation surface appeared to be an important factor in pre-determining the phase content and growth textures of the Al₂O₃ layers. Optimised nucleation resulted in substantially improved wear properties and these kinds of α-Al₂O₃ layers were typically composed of relatively small, defect-free grains exhibiting no porosity. The textured α-Al₂O₃ layer showed the best wear resistance.     

Development and Application of Binary Suspensions in the Ternary System Cr<Subscript>2</Subscript>O<Subscript>3</Subscript>-TiO<Subscript>2</Subscript>-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> for S-HVOF Spraying

Compositions in the system Cr₂O₃-TiO₂-Al₂O₃ are among the most used ceramic materials for thermally sprayed coating solutions. Cr₂O₃ coatings present good sliding wear resistance; Al₂O₃ coatings show excellent insulation behavior and TiO₂ striking corrosion properties. In order to combine these properties, coatings containing more than one oxide are highly interesting. The conventional spraying process is limited to the availability of binary feedstock powders with defined compositions. The use of suspensions offers the opportunity for tailor-made chemical compositions: within the triangle of Cr₂O₃-TiO₂-Al₂O₃, each mixture of oxides can be created. Criteria for the selection of raw materials as well as the relevant aspects for the development of binary suspensions in the Cr₂O₃-TiO₂-Al₂O₃ system to be used as feedstock for thermal spraying are presented. This formulation of binary suspensions required the development of water-based single-oxide suspensions with suitable behavior; otherwise, the interaction between the particles while mixing could lead up to a formation of agglomerates, which affect both the stability of the spray process and the coating properties. For the validation of this formulation procedure, binary Cr₂O₃-TiO₂ and Al₂O₃-TiO₂ suspensions were developed and sprayed using the S-HVOF process. The binary coatings were characterized and discussed in terms of microstructure and microhardness.     

Y2O3对原位自生TiC增强Ni基涂层组织和性能影响

采用氩弧熔覆的方法,以Ni60A自熔性合金粉末为粘结相,添加Ti粉、C粉和不同含量的稀土氧化物Y₂O₃,在16Mn钢基体上制备出TiC陶瓷颗粒增强金属基熔覆涂层. 运用XRD, SEM等手段对复合涂层的显微组织进行表征和分析,并对熔覆涂层的硬度及耐磨性进行了测试. 结果表明,适量添加Y₂O₃可以使涂层组织中枝晶的方向性减弱、同时细化涂层组织,使涂层组织更加均匀,涂层的硬度和耐磨性有显著提高. 添加2% Y₂O₃熔覆涂层的组织为最细,涂层具有较高的显微硬度和良好的耐磨性能.