Abstract Three different coatings were deposited using the Detonation Gun Spraying (DGS) technology from steel powders alone; and steel powers mixed with Fe3C and SiC particles; respectively. The microstructural characteristics of these coatings were examined and the hardness of each type of coating was studied. The morphology and structure of the feedstock powders were affected by the exposure to high temperature during the spraying process and rapid solidification of steel powders that resulted in the formation of an amorphous structure. The unreinforced steel coating had the highest hardness among the three types of coatings; possibly due to a higher degree of amorphization in the coating compared to the other two samples. The microstructural observation confirmed the formation of dense coatings with a layered structure with good connectivity between layers with minimum defects and porosities in the interfacial regions.

Abstract Since 2004; when it was first isolated; graphene has been the subject of great attention both in scientific research and in various industrial applications; thanks to its excellent physical; chemical and mechanical properties. Recently; studies have shown graphene as a new solid lubricant that improves the tribological performances of materials by lowering the coefficient of friction and increasing the wear resistance. However; the industrial-scale manufacture of graphene has been limited by the lack of a fast; inexpensive and effective coating method for large surfaces. As part of our work; we have developed a versatile inductively coupled plasma technology process in which graphene nanoflakes (GNFs) were synthesized in-flight and uniformly deposited on metallic substrates. The coatings and the quality of the graphene flakes were characterized; and the macroscale tribological performance of the GNFs coating was studied using a ball-on-three-plates tribometer. The results showed that the GNFs coating reduced the coefficient of friction (COF) from 0.6 to below 0.2 compared to an uncoated substrate. The innovative approach to GNFs coating preparation provided in this work is expected to have diverse and important applications in the industry.

Abstract A three-dimensional model of free-surface flows with heat transfer, including solidification, was used to model the build-up of a coating layer in a thermal spray process. The impact of several nickel particles on a stainless steel plate in different scenarios was considered. Particles diameter ranged from 40 to 80 µm and their impact velocity ranged from 40 to 80 m/s. Particles were initially super-heated; their temperature ranged from 1600 to 2000°C. Fast growth of solidification was found to be one cause of particle splashing in thermal spray coatings. Different splat morphologies obtained from the numerical model were comparable with those obtained from the experiments. Simulation of the sequential impact of two nickel particles showed side-flow jetting and particle splashing observed in experiments. The numerical model proved to be capable of simulating different impact scenarios that occur in a thermal spray; this was demonstrated by simulating nine consecutive particles during their impact on the substrate. Several characteristics of a coating layer build-up such as particle splashing and formation of small satellite droplets and rings around the splat could be seen in the numerical results. Particle splashing is one possible cause of porosity formation in thermal spray coatings.

Abstract A model for oxidation of molybdenum particles during plasma spray deposition is developed. The diffusion of metal an-ions or oxygen cat-ions through a thin oxidized film, chemical reactions on the surface, and diffusion of oxidant in gas phase are considered as possible rate-controlling mechanisms with controlling parameters as the temperature of the particle surface, and local oxygen concentration and flow field surrounding the particle. The deposition of molten particle and its rapid solidification and deformation is treated using a Madejski-type model, in which the mechanical energy conservation equation is solved to determine the splat deformation and one-dimensional heat conduction equation with phase change is solved to predict the solidification and temperature evolution. Calculations are performed for a single molybdenum particle sprayed under the Sulzer Metco-9MB spraying conditions. Results show that the mechanism that controls the oxidation of this droplet is the diffusion of metal/oxygen ions through a very thin oxide film. A higher substrate temperature results in a larger rate of oxidation at the splat surface, and hence, a larger oxygen content in the coating layer. Compared to the oxidation of droplet during m-flight, the oxidation during deposition is not weak and can become dominant at high substrate temperatures.

Abstract The crystal structure of the coating depends on the splashing and solidification of the sprayed particles. The splashing of the particles is simulated by commercial software taking temperature dependent parameters like melt viscosity and surface tension into account. This article provides the theoretical background and the experimental verification. The steps of simulation solidification, splashing, and heat and momentum transfer help to develop novel coating systems with defined microstructure and shorten the time to market. Experimental investigations were carried out using Ni and Ni/Cr 80/20 spray powders with a mean particle diameter of about 15 μm. The theoretical investigations to describe the flattening process of a droplet show the influence of particle velocity and temperature. It was shown that different material parameters, as latent heat or surface energy, have a significant influence on the simulation results.

Abstract Some applications of thermally sprayed coatings need a metallurgical bonding of substrate and coating. This can be reached by laser remelting of a thermally sprayed coating, which causes, on the other hand, a certain dilution of the substrate elements into the coating. This article discusses the influence of reaction enthalpies on the microstructure formation in the alloying systems Ni-Al and Ti-Al. Experimental work and simulation were done to examine the time constants of solidification influenced by laser dwell time and reaction enthalpy. It was observed that, for short dwell times, the reaction heat dominates the solidification process and the microstructure formation.

Abstract Individual splats are the building blocks of any thermal spray coating. Near the coating-substrate interface, they affect coating properties like adhesion strength. This article examines the effect of substrate heating on droplet splashing. Nickel powder was plasma-sprayed onto a polished stainless steel substrate at various temperatures and the resulting splats were analyzed. Droplet splashing was observed experimentally for three different cases: low substrate temperature, high substrate temperature, and droplet-splat interaction. Mechanisms for splashing were explained with the help of computer-generated nickel droplet impacts. The article proposes that the jetting of molten metal is not triggered by the formation of a central splat but rather a solidified ring on the periphery of the splat. It was observed that, on substrates below 350 deg C, splashing is triggered by solidification at the edge of the spreading droplet. Interactions with previously deposited splats also cause droplets to splash.

Abstract Many studies have been devoted to particle flattening and resulting splat cooling. However, if recent models allow to compute the particle flattening time evolution, very few experiments in spraying conditions have been achieved to back such calculations. The aim of this paper is to describe an imaging device allowing the visualization of particle impacts on cold and hot surfaces. This technique makes it possible : • to investigate the "impact mode" : splashing, deposition or rebound, • to link the particle parameters at impact and the substrate parameters to the observed impact mode, • and therefore, to have a better understanding of coating formation. It consists in a controlled atmosphere chamber where is followed the impact of a single particle on a substrate which can be inclined. The particle parameters prior to its impact are measured : its surface temperature by fast (100 ns) two-color pyrometry, its velocity and diameter by Phase Doppler Anenometry (PDA). The particle image during flattening, splashing or rebounding is given by a fast camera (exposure/delay time 100ns to 1ms) with possible multi exposures. The camera is triggered by the PDA and/or the pyrometer. It is then possible to calculate for each molten particle its Sommerfeld parameter characterizing its impact mode (rebounding, deposition or splashing) when no solidification occurs during flattening. The substrate are made of stainless steel 304L rapidly covered by alumina splats resulting in a Ra~5-6µm. They are kept at 300°C, temperature at which splats are disk shaped on smooth substrate (Ra<0.05µm). The very preliminary results obtained show that unmolten or partially molten particles rebound in all directions but not elastically : the rebounding particle velocity is 3 to 5 times lower than that of the impacting one. For fully molten particles, splashing occurs in all cases even for low Sommerfeld numbers. It thus seems that the substrate roughness plays a key role in splashing.

Abstract Stoichiometric cordierite (2MgO-2Al2O3-5SiO2) with additions of titania have been investigated for use as coatings on low thermal expansion refractory concretes. These concretes have coefficients of thermal expansion on the order of 2 ppm/°C. Titania additions of up to 8 mole percent were investigated and the effect of titania in the crystallization of cordierite was examined. Cordierite coatings were air plasma sprayed and both glass and crystalline coatings were produced. The crystalline structure of the coating was found to be dependent upon the preheat temperature of the substrate. Preheats greater than 700 °C produced a mixture of a quartz solid solution and indialite whereas glass coatings were produced at preheats less than 700 °C. Coefficients of thermal expansion for the cordierite materials were dependent upon titania addition and generally increased with addition of titania. In the glass state, the thermal expansion was modestly increased (4.6 to 4.9 ppm/°C) with titania additions, but the quartz and indialite forms of the cordierite increased from 1.2 to 4.7 ppm/°C as the titania addition increased from 0 to 8 mole percent.

Abstract A brief feasibility study was performed to produce thermal spray coatings using gas atomized powders of Cu47Ti34-xZr11Ni8Six, where x=0 and 1. These alloys have previously been shown to be capable of forming metallic glasses having thick (1-2 cm) cross sections because they can be cooled from the melt at relatively low cooling rates (e.g., 100-102Ks-1). The properties of these metallic glasses include high strength, high elasticity and high fracture toughness. Amorphous plasma arc sprayed coatings were produced which were close in composition to the starting powders, and exhibited comparable glass transition and crystallization behavior. The amorphous structure of the as-sprayed coatings was used as a source for forming a range of partially devitrified and fully crystallized structures. The average hardness of the coatings increased from around 6 GPa to near 10 GPa as the degree of crystallization increased.

Abstract Layers of high-purity copper and iron produced by cold gas-dynamic spraying have been thermally processed to induce recrystallization and grain growth. In the case of copper deposits, the as-sprayed structure could be "pinned" by arrays of Cu2O particles present on the surfaces of the feedstock powder, however copper powders of higher purity and sphericity yielded sprayed structures which could be annealed to induce recrystallization and grain growth. The higher purity copper compacts exhibited a morphological change in fracture from a brittle, intraparticle mode in the as-deposited condition, to a ductile, "cup-and-cone" morphology in the annealed condition. For compacts produced from water atomized iron, annealing at sub-critical temperatures produced recrystallization and grain growth as found with copper, and thermal processing in the austenitic region resulted in altogether new and coarser grain structures upon cooling. Ease of thermal processing of cold-sprayed materials may offer additional processing routes for engineered surfaces and functional devices produced in this manner.

Abstract This paper presents a one-dimensional heat transfer model which predicts the solidification and cooling of a plasma-sprayed alumina splat after the flattening process is completed. A heterogeneous nucleation process taking place on the substrate surface was assumed. The density and average size of the formed nuclei were determined from the integration of the nucleation rate calculated from the classical kinetic theory for nucleation. This rate depends on the activation energy required for nucleation which takes into account the effect of the surface via a wetting angle between the growing nucleus and the catalytic surface. This contact angle was estimated from the comparison of the computed grain density with the density observed on splat surface using an atomic force microscope. When 67% of the splat surface in contact with the substrate are covered by grains, a planar solidification front was assumed to move through the melt. The theoretical model accounted also for the selection of the crystalline phase. Calculations were performed for various substrate materials at different initial temperatures. Results are expressed in terms of nucleation temperature, nucleation rate, density and grain size distribution.

Abstract A study was performed to examine the effects of starting powder composition, substrate thermal conductivity, and substrate temperature on the composition and structure of individual Al-Cu-Fe splats formed during thermal spraying. The fraction of quasicrystalline phase which formed was found to depend on the chemistry and solidification history of the splats. Due to evaporative loss of Al during spraying, an initial powder composition higher in Al produced splats closer to the desired composition, which yielded more of the quasicrystalline phase. Deposition onto lower thermal conductivity surfaces resulted in an increase in the quasicrystalline phase, as did solidification onto higher temperature substrates.

Abstract Different mechanisms of splashing of droplets impacting onto the substrate surface during thermal spraying are considered. It is shown that supercooling formed in the flattening droplet consists of the thermal supercooling and that arisen due to the high pressure developed upon the droplet impact. Solidification starts when the supercooling exceeds some critical value. With a "cold" substrate when its temperature is less than a transition temperature the marked contribution to the supercooling is due to its high pressure part. In this case a regular disc-shaped splat will be formed in the central part of the flattening droplet and splashing will occur in the periphery. With a "hot" substrate when its temperature exceeds the transition temperature the thermal supercooling is high enough, no splashing occurs and a regular disc-shaped splat is formed. Theoretical results agree with the experimental observations.

Abstract Some of the recent research progress concerning the structure and properties of thermal sprayed coatings are reviewed. Structures of coatings are classified into three classes of hierarchy, i.e., layer structures, inter-splat structures and intra-splat structures. Important progress in the study and coatings development in each class is described. These include coatings developed to take advantage of the microstructure due to rapid solidification, such as amorphous and extension of solid state solubility, and characterization of porosity and how it is affected by process parameters. Then, stress generation during thermal spray is compared between plasma spray and HVOF spray. Particular attention is given to the importance of thermal and mechanical interactions of sprayed particles with the substrate and coating surface, which determine the nature of interlamellar bonding and that of microscopic stress.

Abstract Spinel powders of different compositions were fabricated for their good properties of chemical resistance. These powders were plasma sprayed on steels and their microstructure was investigated by scanning electron microscopy (SEM), microanalysis, X-ray diffraction and transmission electron microscopy (TEM). Due to the powder fabrication process, coatings were very heterogeneous in composition, but had the spinel structure. TEM observations pointed out that splat solidification occurred with a cooling rate gradient leading to different crystallization inside a lamella. Young's moduli by the coatings were measured by the resonant frequency method and the correlation with coating microstructure was discussed.

Abstract This paper examines the stress state of plasma-sprayed amorphous coatings of Fe-B with additions of Ni, Cr, and Mo. Internal stresses depend on the type of plasma gas used, the thickness and composition of the coating, and the material and temperature of the substrate. In this study, additional cooling of the substrate was found to be the most efficient way to reduce internal stresses. Amorphous coatings were also found to improve fatigue strength by as much as 25-30%, which is attributed to the formation of compressive stresses in the coating layers adjoining the substrate.

Abstract Within the framework of a scientific collaboration between the University of Limoges, France and the State University of New York, Stony Brook, USA, a joint work has been conducted on microstructure development and properties of plasma-sprayed molybdenum coatings. This first part of the work is devoted to the study of the effect of substrate nature and temperature on splat cooling, solidification and crystalline structure. They were investigated by means of a heat transfer model in the splat and the substrate, and the observation of splats by a scanning electron microscope and an atomic force microscope. The model takes into account melt undercooling, nucleation and crystal growth, as also a possible melting and re-solidification of the substrate. It has the capability to predict the grain size distribution under assumptions that the quality of contact between the splat and the underlying layer is uniform, nucleation takes place only on the substrate surface, crystal grains grow perpendicular to the substrate surface and no grain coalescence occurs during crystal growth.

Abstract Experimental apparatus simulating a horizontal belt caster has been constructed for the study of thin strip casting of steels and light metal alloys. In this apparatus, the solidifying metal is deposited onto a moving substrate. The substrate was flame sprayed with various commercial coatings while its speed and the thicknesses of strip produced matched industrial values. The main objective of the present work was to determine the influence of various operational variables on local cooling rates and final microstructures. To this end, experiments were carried out to study the effects of various types of coating, roughness of the substrate, initial superheat, and strip thickness on heat fluxes. An interesting feature of this equipment is that the strip is subjected to different rates of cooling at the lower and upper surfaces, allowing two different rates of solidification to be studied simultaneously.

Abstract Directed light fabrication (DLF) is a rapid fabrication process that fuses gas delivered metal powders within a focal zone of a laser beam to produce fully dense, near-net shape, 3D metal components from a computer generated solid model. Computer controls dictate the metal deposition pathways, and no preforms or molds are required to generate complex sample geometries with accurate and precise tolerances. The DLF technique offers unique advantages over conventional thermomechanical processes or thermal spray processes in that many labor and equipment intensive steps can be avoided to produce components with fully dense microstructures. Moreover, owing to the flexibility in power distributions of lasers, a variety of materials have been processed, ranging from aluminum alloys to tungsten, and including intermetallics such as M05Si3. Since DLF processing offers unique capabilities and advantages for the rapid fabrication of complex metal components, an examination of the microstructural development hhas been performed in order to define and optimize the processed materials. Solidification studies of DLF processing have demonstrated that a continuous liquid/solid interface is maintained while achieving high constant cooling rates that can be varied between 10 to 10 5 Ks-1 and solidification growth rates ranging up to 10-2 ms-1.