Abstract Manufacturing of steel components is often done at high temperatures (HT) posing a serious challenge to components such as forming tools. Thermal spray coatings provide a cost-effective solution for surface protection under HT, corrosive environments and severe wear conditions. Thermally sprayed coatings based on cubic hard materials such as TiC and TiCN can provide an alternative to widely used Cr3C2-NiCr. While the latter possess a superb oxidation resistance and wear resistance at HT, they are prone to degradation in the presence of Mn, an element commonly alloyed in many modern steel grades such as TWIP (twinning-induced plasticity steel). In this study, a (Ti,Mo)(C,N)-29% Ni hardmetal feedstock powder was prepared by agglomeration and sintering. Coatings were deposited using a high velocity air-fuel (HVAF) spray process. The coating was benchmarked against a standard Cr3C2-NiCr coating obtained with the same spray process. Our work comprises analyses of the feedstock powder along with the resulting coating microstructure after deposition and heat treatment. Further, the HT sliding behavior against TWIP steel using a HT pin-on-disc tribometer at 700°C was investigated. The results showed a clear benefit of the TiCN-based coating, with almost no wear detected, while the Cr3C2-coating showed a significant wear loss. Based on these results, the TiCN-based coating is regarded as potential solution for prospective forming applications of modern high Mn steels, such as TWIP.

Abstract Wear protection is one of the major applications of thermally sprayed hardmetal coatings. This paper presents the latest results of a systematic study on the influence of Cr3C2-NiCr feedstock powder characteristics on coating microstructures and economic parameters like deposition rate and deposition efficiency. Four commercial Cr3C2-NiCr powders with spherically shaped particles but different structural features were characterized and deposited by a liquid-fueled and a gas-fueled HVOF and a HVAF process. Deposition rates and efficiencies were determined; all coatings were analyzed in as-sprayed condition and selected samples were heat-treated at 800 °C in argon atmosphere. The effects of the feedstock powders and spray processes on the coating characteristics (microstructure, hardness, Young’s modulus and diffusion processes during heat treatment) were studied.

Abstract In the current study, the tribological properties of TiC-based coatings paired with polycrystalline alumina under unlubricated sliding conditions were investigated in order to demonstrate the technological and engineering potential of such coatings. (Ti, Mo)(C, N)-Co coatings were prepared from an agglomerated and sintered spray powder by HVOF spraying using JP-5000 equipment. Cr 3 C 2 -NiCr coatings were studied for comparison. Sliding wear tests were performed over the temperature range from 23°C to 800°C with sliding speeds in the range 0.3-3 m/s, a wear distance of 5000 m and a normal force of 10 N. Wear rates of coatings and sintered alumina counterparts were measured separately. Compared with Cr 3 C 2 -NiCr coatings, (Ti, Mo)(C,N)-Co coatings showed significantly lower total wear rates, corresponding to those found in the region of mixed/boundary lubrication. With few exceptions, the coefficients of friction were found to be lower for (Ti, Mo)(C,N)-Co coatings than for Cr 3 C 2 -NiCr coatings. After tests were performed, the coating microstructures were studied by optical microscopy and SEM. The oxide scales formed on the coating surfaces were investigated by SEM and X-ray diffraction. Comparison of the total wear rates of the couples consisting of sintered alumina and a (Ti, Mo)(C,N)-Co coating with those of other alumina-ceramic and hardmetal-hardmetal tribological systems demonstrates the immense potential of TiC-based coatings for sliding wear applications.

Abstract Laser-assisted atmospheric plasma spraying (LAAPS) is a new one-step coating process performed in air whereby the laser beam interacts with the plasma torch at the substrate or coating surface during deposition to generate a coating that is metallurgically bonded to the substrate. This hybrid process was developed in order to combine the specific advantages of APS and laser cladding. In this paper, the development of a hybrid gun for coating internal surfaces of tubes and cylinder bores by LAAPS is presented. The process was optimized for spraying AlSi30 coatings on internal surfaces of aluminum alloy cylinder bores. Single-pass coatings with thicknesses of 300-400 µm and metallurgical bonding to the substrates can be realized by applying an optimized parameter set. The dependence of coating microstructure on spray parameters was investigated by metallographic preparation and optical microscopy. Surface pretreatment must be performed to eliminate the strongly adhering oxide layer on the aluminum alloy substrate and to attain metallurgical bonding of coating to substrate.

Abstract Extensive research activities were conducted over the last few years on coatings made of titanium oxide, an established material for thermally sprayed coating solutions. Multiple existing and potential applications are closely connected with the existence of different titanium dioxide modifications and the formation of suboxides. This provides a basis for discussions on the Ti-O phase diagram as well as the properties and conditions of formation of relevant phases. Coating microstructures, phase compositions and mechanical properties are discussed as a result of interactions of different spray powders in different spray conditions of atmospheric and vacuum plasma spraying (APS and VPS), as well as of high-velocity oxyfuel (HVOF) spraying. The discussion on applications is focused on electrically conductive coatings, coatings with photocatalytic properties and coatings for wear applications.

Abstract Titanium dioxide (TiO 2 ) has emerged as an excellent photocatalyst material for environmental purification about two decades ago but only recently few works have focused on the photocatalytic properties of sprayed titanium oxide coatings. So far, the role of oxygen deficiency which can appear as a result of the spray process or by use of titanium suboxide powders on the photocatalytic activity has not been investigated. Also the possible influence of the shear plane structure of titanium suboxides (Magnéli phases) on the photocatalytic activity was not taken into consideration. In the present work, the photocatalytic properties of three powders and coatings sprayed from these powders by APS and VPS are investigated: (1) a commercial fused and crushed titanium oxide powder, (2) an agglomerated and sintered titanium suboxide powder consisting predominantly of Magnéli phases Ti 6 O 11 and Ti 5 O 9 , (3) an agglomerated and sintered powder consisting of Ti 2 Cr 2 O 7 and Ti 6 Cr 2 O 15 (Magnéli phases in the TiO 2 - Cr 2 O 3 phase diagram). The phase compositions of the powders and the coatings were investigated by X-ray diffraction. Neither for the spray powders nor for the coatings any ability to reduce the NOx concentration by the photocatalysis was found. From this it is concluded that both oxygen deficiency as well as Magnéli phase structure are not responsible for photocatalytic properties of materials in the Ti-O phase diagram.

Abstract The atmospheric plasma spraying process and the high velocity oxy-fuel (HVOF) spraying process are used to produce ceramic layers from titanium suboxide powder. Titanium suboxide powder is made from commercially fused and ground powders by reduction with hydrogen. Two powder particle sizes, which were produced for both atmospheric plasma spraying and for the HVOF spraying process, were used in tests. Originally melted and crushed powder fractions served as a reference powder. Furthermore, hardness, wear resistance, and electrical resistance were determined. All titanium oxide layers showed high wear resistance, with HVOF-sprayed layers exhibiting higher wear resistance than the layers produced with the atmospheric plasma spraying process. Atmospheric plasma-sprayed layers, on the other hand, are characterized by higher electrical conductivity. Paper includes a German-language abstract.

Abstract This paper provides a short summary of the different concepts related to the structure and preparation of titanium carbide (TiC)-containing wettable powders that could be found in the literature. Empirical composite developments of TiC-containing materials for coating applications are not suitable for fully describing the technical potential of these composites. TiC-containing layers can complete the range of thermal coating solutions based on tungsten carbide and chromium carbide. The development of TiC-based powders that are better than the prior state of the art is the result of a long-term process producing permanent improvements. The processability of different TiC-based powders from alloying steps one and two was tested with various high velocity oxygen fuel installations and different fuel gases. TiC-based coatings offer special advantages through tailoring of the composition to suit requirements in applications in which complex stress profiles exist. Paper includes a German-language abstract.

Abstract Titanium suboxides form a class of ceramic materials possessing such technically interesting properties as electrical conductivity and solid lubrication. Consequently, these materials have a high potential for application as thermally sprayed coatings. In this paper the preparation and characterisation of two spray powders of different composition by agglomeration and sintering with a narrow range of the value n in Ti n O 2n-1 is described. Powders were characterised by X-ray diffraction (XRD), scanning and transmission electron microscopy (SEM and TEM), thermogravimetric measurements (TG), helium pycnometry, nitrogen adsorption and mercury intrusion techniques. The sprayability was tested by plasma spraying. The coating structures were studied by optical microscopy, XRD, TG and TEM. Although the powders were only partially oxidized as a result of the spray process, the crystallographic structure was changed significantly, according to XRD and TEM investigations. As an alternative method of preparation of titanium suboxide spray powders, the reduction of a fused and crushed spray powder with hydrogen is described. Powder particle shape and size distribution are not changed in this process.

Abstract Hardmetal-like coatings of the TiC-Ni system are potential for use as wear, corrosion and heat resistant coatings in various operation conditions. Our previous works [1-12] have shown that these materials are well sprayable using different thermal spray processes such as plasma, D-Gun and HVOF spraying. Since HVOF spraying is today the most important process used to apply carbide based coatings, this study was carried out in order to evaluate more systematically the sprayability of these novel spray powders and the influence of HVOF spray parameters on some coating properties. Coating samples were prepared by using DJ Hybrid gun with propane as a fuel gas, and a CDS gun with hydrogen fuel gas. Oxygen flow rate was varied in both cases for changing the flame temperature. Microstructure, phase composition, hardness, and abrasion wear resistance of the coated samples were investigated. The results showed that both HVOF processes used give satisfactory coating properties and that the use of high oxygen flow rates is beneficial for improving the wear resistance of the coatings. Powders with fine particle size are beneficial in the DJ Hybrid process; the use of coarse powders results in coatings with somewhat higher wear rates. The optimum spray condition for the TiC-Ni system powders differs from that typically used for conventional WC-Co and Cr3C2-NiCr powders by a higher flame temperature.

Abstract TiC-based coatings sprayed by different processes, such as detonation gun spraying, high velocity oxy-fuel spraying, atmospheric plasma spraying (APS), and vacuum plasma spraying, using agglomerated and sintered powders have been actively developed over the years. This development is based on the high technical and engineering potential of the hard phase TiC. This paper describes the results of basic studies of the APS for various alloying steps in the production of TiC base coatings from agglomerated and sintered powders as well as the results of the application of APS coatings on piston rings. Paper includes a German-language abstract.

Abstract In this paper the oxidation behaviour of WC, Cr 3 C 2 , and TiC and their composites with binder metals is compared on the basis of literature data and some oxidation experiments. It was found that the oxidation mechanisms in air, which are more or less equal to service conditions of coatings, seem to be totally different from those in the spray process in the case of WC, but similar in the case of TiC and Cr 3 C 2 . Oxide layer scale adhesion strengths and, possibly, the high volatility of WO 3 seem to be responsible for this difference. It can also be assumed, that the problem of oxidation of TiC-based materials and Cr3C2-NiCr is that of local oxidation on the surface of the spray powder particles during the spray process. Cr 3 C 2 -NiCr and TiC-based materials are characterized by a high oxidation resistance in air. Plain WC-Co oxidizes readily in the temperature range 400-600°C, but alloying with Cr, as for instance in WC-CoCr and WC-(W,Cr) 2 -Ni spray powders increases the oxidation resistance.

Abstract Oxide-bonded silicon nitride (OBSN) powders have been developed to address thermal spray problems associated with high temperatures. This paper examines how such powders perform when applied via detonation gun (DGS) and atmospheric plasma spraying (APS) with axial powder injection. All coatings were characterized using optical microscopy and X-ray diffraction with additional tests being performed on DGS coatings. For the first time, relatively dense Si3N4-rich coatings with an oxide binder phase were produced, and some of the DGS coatings were found to be sufficiently wear resistance for industrial use.

Abstract Agglomerated and sintered TiC-Ni based powders were sprayed by detonation gun spray (DGS) and high-velocity oxy-fuel (HVOF) spray processes. Influence of the binder content (20 and 27 vol.-%) and some alloying elements, such as Mo, Co and N on the coating properties were investigated. The coating structures and properties were investigated by optical microscopy, hardness measurements, X-ray diffraction analysis and by rubber-wheel abrasion wear test. It was found that alloying the hard phase with Mo and N leads to an improvement of the coating properties. Alloying of the binder phase with Co did not affect the coating properties. Porosity in the powder granules was found to beneficial in order to melt more efficiently the particles in the DGS process and especially in the HVOF process. HVOF spraying of powders with the higher binder content of 27 vol.-% was found to be advantageous for the preparation of coatings with dense microstructures and good wear resistances.

Abstract The surfaces of machine components can be effectively protected against wear by highly resistant hardmetal-like coatings, such as WC-Co and Cr 3 C 2 -NiCr, deposited by different thermal spray processes. These composite materials are characterized by the presence of hard carbide particles embedded in a ductile metal binder matrix which have also found many applications as sintered parts (cutting tools, wear resistant parts, mining drills and others) obtained by a powder metallurgy route. Conclusions on the potentials of the different systems for coating applications can be made on the base of experiences and fundamental research from sintered hardmetals. In this paper a comparison of the properties of sintered parts and thermally sprayed coatings of the WC-Co, Cr 3 C 2 -NiCr and (Ti,Mo)C-NiCo systems is given. The structure and properties of the coatings depend strongly on the technology of spray powder preparation, the combination of spray process temperature and particle velocity, and other spray process parameters. It is shown that the TiC-Ni based system can be significantly improved by alloying. This makes the system suitable for coating applications where simultaneous high wear and corrosion resistance in combination with high temperature stability are required. This system can partially substitute the commercially introduced systems but has also the potential to explore new applications.

Abstract WC-Co-Cr represents an important composition for hardmetal-like coatings which is appHed when simuhaneous wear and corrosion resistance is required. In this paper five commercially available spray powders obtained by various production techniques (sintered and crushed as well as agglomerated and plasma-densified) of the composition WC-10%Co- 4%Cr have been thoroughly characterized and were sprayed by DCS, HVOF (CDS process) and APS. The microstructures of the coatings were characterized and their wear behaviour was investigated by means of an abrasion wear test. For the best of these powders the wear resistance was nearly equal for the DGS and HVOF coatings. Other powders show significant differences with respect to their processabilities in these spray processes. APS coatings from all powders, obtained with an Ar/H2 plasma showed inferior microstructures and significant lower wear resistance. The spray powder compositions, grain sizes and structures were found to determine the processability of the powders and the microstructure and properties of the coatings. COMPOSITE MATERIALS of the type hard phase - metallic binder with WC and CoCr as constituents are widely used for the preparation of hardmetal-like coatings. The chromium addition to the metallic binder is thought to improve its corrosion resistance in comparison with pure WC-Co. This has led to many applications of WC-CoCr coatings where simultaneous wear and corrosion resistance is required. Despite of its significant practical importance only a limited number of publications is devoted to detailed questions of structure and properties of WC-CoCr coatings (1-3). In some comparative studies such coatings have been investigated together with WC-Co and Cr3C2-NiCr coatings (4-8). However, systematic investigations of spray powder compositions and morphologies as well as investigations of the influence of different thermal spray processes on coating structures and properties which have repeatedly been provided for WC-Co (for example (9, 10)) are missing for WC-CoCr. In this paper a short survey of literature on the phase relationships in the WC-CoCr system and the effect of chromium additions on the properties of sintered parts and thermally sprayed coatings compared to WC-Co is given. In the experimental part a systematic study of the influence of the preparation process on composition and morphology of commercially available WC-10%Co-4%Cr spray powders was provided. These powders have been sprayed by DGS, HVOF and APS and the microstructure and basic properties of the coatings have been studied.

Abstract Thermal spraying of silicon nitride has been considered impossible because the high temperatures involved lead inevitably to decomposition/oxidation of the material. To address these issues, improved silicon nitride-based powders were developed, two of which have been tested as reported in this paper. The powders were applied using low pressure plasma spraying (LPPS) and the resulting coatings characterized based on microhardness, adhesion, and cohesion strength. Phase transformations of the powders during spraying were also investigated and preliminary optimization strategies by statistical variation of plasma spray parameters were tested.

Abstract Hardmetal-like coatings on the base of titanium carbide as a hard phase and nickel as a metal binder were prepared from agglomerated and sintered powders by plasma spray, detonation gun spray and high-velocity oxygen-fuel spray processes. The powders used in the spray experiments were plain TiC-Ni type and alloyed (Ti,Mo)C-NiCo type powders with different binder content. The coatings were characterized by optical and scanning electron microscopy, microhardness measurements, XRD analysis and in an abrasion wear test. The results showed that the sprayability of these novel hardmetal-like powders is good in all spray processes studied and the coatings deposited were found to have dense microstructures and good properties. The XRD analysis showed that the coatings have a phase structure similar to that found in the spray powder. The amount of retained carbides in the coatings was high. Some regions in which the carbides had dissolved with the metallic binder phase during spraying were also found, especially in plasma sprayed coatings. In such microstructural regions submicron size reprecipitated carbides were detected. These were clearly detectable in detonation gun sprayed coatings. HVOF sprayed coatings were found to contain a very high content of retained carbide phase. In this process the heat effect to the material seemed to be the lowest. The wear tests clearly showed the importance of alloying the hard phase and the binder phase in order to improve the wear resistance of the coatings. All studied spray processes produced coatings with nearly similar coating wear properties.