This work focuses on the processing and deposit by suspension plasma spraying (SPS) of ZrO 2 -based ceramic materials for Thermal Barrier Coatings (TBC's) applications. The system of interest is ZrO 2 -16mol%Y 2 O 3 -16mol%Ta 2 O 5 (16YTZ). This ceramic has been reported to keep a non-transformable tetragonal phase (t'-phase), suitable to overcome the thermodynamic limits of the mostly used conventional 7-8wt.% yttria stabilized zirconia (YSZ). The research consists into evaluate the t'-phase stability and performance of the 16YTZ SPS coating. Synthesis of 16YTZ and, the evolution of the resulting microstructure in the dense ceramic and in the coating are a central part of the study. Sintering behavior in dense ceramics prepared from both precursor derived and milled powders is evaluated. Microstructural characterization by XRD, SEM and RAMAN spectroscopy of the as-deposited ceramic coating is presented and discussed.

In biomass boilers, corrosion is a prevalent concern that arises at high temperatures. This is mainly because the fuels consumed in these boilers have a high alkali, chlorine, and other molten salt content that has occasionally led to material depletion, leaks, and unforeseen plant shutdowns. Applying protective coatings using thermal spray techniques is a practical answer to this issue. The current work focused on applying powders of Inconel 625 and Inconel 718 to boiler steel using a high-velocity oxy-fuel spraying method. The samples after coating deposition were subjected to the conditions of a biomass-fired boiler for 15 cycles to study the performance of the coatings in a real environment. The decrease of thickness over time was used to evaluate the erosion-corrosion process. Various characterization techniques were used to examine the as-sprayed and eroded-corroded specimens. The X-ray diffraction (XRD) technique was utilized to analyze the phases, while the surface characteristics of powders, coatings, and samples exposed to erosion-corrosion were investigated through scanning electron microscopy (SEM) combined with energy-dispersive X-ray spectroscopy (EDS). When exposed to the actual boiler environment, the findings showed that Inconel 625-coated steel performed better than Inconel 718-coated steel.

Cavitation is a wear process in engineering systems caused by the energy release of collapsing bubbles leading to the failure of critical components such as valves, pumps, and propellers. Thermally sprayed coatings can be applied to improve the wear resistance of these components. This investigation considers a WC-NiCrBSi coating composition under cavitation wear, where the WC phase provides the strength and the NiCrBSi matrix offers corrosion resistance in seawater. Coatings were deposited on AISI 440C stainless steel discs of 32mm diameter and 8mm thickness using industrially optimized parameters for the HVOF JP5000 system. Indirect cavitation tests were conducted using a modified ASTM G32 testing procedure on coated test coupons in as-sprayed and Hot Isostatic Pressed (HIPed) conditions. Two tests were performed for each coating using natural seawater of pH 8.19 at room temperature, and averaged wear values are reported to compare the cavitation rate and cumulative mass loss of the coatings. Coating microstructural phases in the as-sprayed and HIPed conditions were identified using X-ray diffraction. The microstructure of the coating substrate system and post-cavitation test wear scars were investigated using Scanning Electron Microscopy (SEM) equipped with energy dispersive spectroscopy (EDS). This investigation provides an understanding of the corrosive-cavitation wear behavior and failure modes of coatings. The cavitation erosion rate and cumulative mass loss results showed that the as-sprayed WC-NiCrBSi coatings improve the cavitation wear resistance of the substrate.

Titanium porous transport layers (PTL) are important components in proton exchange membrane water electrolysis (PEMWE) cells. The performance enhancement and the reduction of manufacturing cost of PTLs are of importance for market expansion of PEMWE. Vacuum plasma spraying (VPS) was used to prepare PTL or modify PTL of sintered titanium powders and the PTLs by VPS showed a high performance. Regarding the cost efficiency, it is of great interest to produce PTLs using more economical spray processes than VPS. In this study, high velocity oxy-fuel spraying (HVOF) was used to produce highly porous titanium coatings for this purpose. The spray process was developed to achieve a high porosity of up to Φ = 30 % using three titanium powders with size distributions of fA = -90 +45 μm, fB = -63 +20 μm and fc = -45 +11 μm. The coating structures were examined on the cross sections of the titanium coatings with scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS). The porosity was determined using the image analysis system ImageJ. The deposition efficiency of the titanium powder fC = -45 +11 μm was determined. The results show that the coating structure significantly depends on the titanium powders. Highly porous titanium coatings of Φ = 24 - 40 % can be produced with the titanium powders of fB = -63 +20 μm and fc = -45 +11 μm. Titanium oxides are hardly visible on the cross-sections of the titanium coatings. A high deposition efficiency of approximately DP ≈ 70 % was measured for the titanium powder of fc = -45 +11 μm.

Due to their promising photocatalytic properties under visible light irradiation, thermally sprayed ZnO-TiO 2 coatings are of interest as substitute for TiO 2 for various industrial applications, like hydrogen production via water splitting or the reduction of organic pollutants in water. Suspension spraying is an effective method to produce coatings in the binary ZnO-TiO 2 system to form Zn 2 TiO 4 in-situ during the spraying process. Aqueous suspensions containing fine dispersed ZnO and TiO 2 particles are mixed at tailored composition and sprayed using the SHVOF and SPS spraying processes. Coatings with homogeneous distribution of elements and different surface structures and phase compositions are obtained. The phase composition is analyzed via XRD. UV-Vis spectroscopy measurements and photocatalytic tests of Rhodamin B degradation are performed. The potential to use appropriate binary suspension feedstock to produce ZnO-TiO 2 -Zn 2 TiO 4 coatings with different microstructures and photocatalytic properties is presented.

Hexavalent chromium has been widely used in the coating industry and more specifically in gas turbine hot end component protection. UK REACH (registration, evaluation, authorization, and restriction of chemicals) have given an end date of September 2024 for the use of hexavalent chromium and as such, the industry must adapt to these regulations. Indestructible Paint LTD have developed a new aluminium diffused slurry coating, CFIPAL, that does not contain hexavalent chromium like its predecessor, IP1041. Both CFIPAL and IP1041 were deposited onto Nimonic 75 alloy and underwent metallurgical and chemical analysis which included scanning electron microscopy, energy dispersive spectroscopy, electron backscatter diffraction, hardness testing, contact angle testing, surface roughness testing and finally, salt spray corrosion testing. The results indicated that CFIPAL is a suitable alternative for hexavalent chromium-containing coatings, such as IP1041.

Light alloys are being investigated as an alternative to ferrous-based engineering components. The manufacturing of such components requires a surface modification step necessary to eliminate the top surface's poor wear and corrosion response for improved functionality. Thermally sprayed cermet coatings offer improved surface resistance to wear and/or corrosion. This work presents a customized composition of WC-CoCr feedstock cut in fine and coarse powder size distribution (PSD) to fabricate different coatings on aluminium alloy and steel substrates using two high velocity spray techniques. The WC-CoCr coatings sprayed using the high velocity air-fuel (HVAF) technique at varied parameters consist of six different coatings (four thick, ~ 200 μm and two thin ones, 60-80 μm) to investigate the relationship between processing conditions, microstructure, and performance. Using scanning electron microscopy (SEM) and electro-dispersive X-ray spectroscopy (EDX) offered a comprehensive characterization of the respective coatings. Micro indentation, dry sliding wear, dry sand abrasion, and cavitation erosion tests conducted on the samples show the performance of the coatings based on the processing techniques and spray conditions. However, despite the similarities in the microstructural makeup of the coatings and the measured micro indentation hardness of the coatings (1000-1300 HV0.1), their respective specific wear rate (SWR) varied based on spray processing techniques and the substrate on which the coatings were deposited. Three of the HVAF coatings showed ~ 60 % more wear on the aluminium alloy substrate compared to the same coating deposited on a steel substrate. However, irrespective of the substrate used the HVAF coatings showed better wear resistance than the HVOF coating. The dry sand abrasion wear results of the two thick HVAF coatings show them superior to the HVOF coating in the three-body wear experiment conducted. The cavitation erosion resistance of the coatings varied based on the processing conditions and the driving mechanisms but the best two were the AF-2 and AF-6 samples.

By approaching the glass transition temperature it was possible to realize well quality metallic coatings on two different glasses using Cold Spray deposition, CS. A roughness is introduced on the glass surface and is proportional to the energy deposited. Using the thermal pressure memory effect of glass, Raman spectroscopy mapping allowed determining that the CS introduced a strong heterogeneity of the glass substrate characterized by zones with different cooling rate and residual stress. Using a simplified Eshelby's inclusion approach, it is demonstrated that the residual stress can be in first approximation explained by the introduction of local density fluctuation induced with high cooling rate of micrometric regions related with the impact of the deposited metallic particles.

Recently, laser deposition technologies have made significant advancements in their ability to manufacture high temperature metals and ceramics. One of these technologies, known as Direct Energy Deposition (DED), has the potential to deposit a wide range of materials from polymers to refractory materials, ceramics and functionally graded materials. This study evaluates major microstructural characteristics of WC-Co additively manufactured by DED technology. This material is commonly used for deposition of protective coatings due to its high hardness and excellent wear resistance. To this end, hardness and wear resistance of the DED processed samples were also investigated in this study. WC-Co coatings are generally deposited using various thermal spray technologies. However, it is speculated that DED deposited WC-Co could provide superior properties such as higher hardness and wear resistance. A DED manufactured WC-Co sample was examined by Optical Microscopy (OM), Scanning Electron Microscopy (SEM), Energy Dispersive Spectroscopy (EDS), and X-ray Diffraction (XRD). Those studies could provide information about important microstructural features, chemical compositions and phase distribution. All the tests were also repeated on High-Velocity Oxygen Fuel (HVOF) deposited WC-Co with the same composition. Both DED and HVOF produced WC-Co coatings experience decomposition of the carbides into compound phases; however, the DED deposited sample displays unique dendritic and eutectic structures that improve the hardness and wear properties compared to the homogenous HVOF coating. In addition, DED produced samples show higher hardness and relatively better wear resistance compared to the HVOF deposited ones. The obtained results could establish a relationship between microstructural characteristics with hardness and wear properties of both samples.

To achieve higher engine combustion efficiency while reducing emissions, it is necessary to address the challenges posed by elevated operating temperatures. High Entropy Alloys (HEAs) have emerged as promising materials for this purpose, offering exceptional properties at high temperatures, including synergistic effects and excellent resistance to oxidation and corrosion. In this study, a FeCoNiCrAl HEA was investigated as a bond coat material due to its excellent balance of strength and ductility, coupled with outstanding oxidation resistance. It was deposited using HVAF M3 and i7 guns equipped with different nozzles/powder injectors and pressures. Notably, this research marks the first study of the i7 gun globally for the HEA bond coat, coupled with the optimization of HVAF parameters for both i7 and M3 guns. Characterization of both powder and as-sprayed samples was carried out using X-ray Diffraction (XRD), Energy-dispersive X-ray spectroscopy (EDS), and Field Emission Scanning Electron Microscopy (FESEM) techniques. The results revealed the formation of a dense and homogeneous microstructure. Additionally, isothermal oxidation tests were conducted to analyze the behavior of the thermally grown oxide. After 50 hours at 1000 °C, a dense, uniform, and thin alumina TGO layer was observed to have formed. These tests revealed that FeCoNiCrAl HEA exhibits significant potential to enhance oxidation resistance at high temperatures.

In conventional powder processing, there has been considerable work on classifying feedstock powders based on particle size distribution, morphology, microstructure and composition, since these influence processability and final properties. Cold spray is a new application for powders and conventional characterization may be insufficient to assess powder cold sprayability. In particular, metallic powders have an oxide layer, which breaks during impact with the substrate or with another coating layer during cold spray; this fragmentation facilitates bonding. It has been suggested that the thickness of the oxide layer can influence the mechanism of fragmentation; thicker oxides are easier to remove, revealing clean metal surfaces that can metallurgically bond. Consequently, not all high-purity powders or powders that are stored in ambient conditions have the potential to give good coating properties after cold-spray. This work focuses on surface oxidation of the powders, characterizing the variation of oxide film aspects with size and composition of nominally pure copper powders using X-ray Photoelectron Spectroscopy (XPS). The results indicate the presence of Cu (I) and Cu (II) oxide species on the surface of as-received, naturally aged and heat-treated powders; their thickness is determined using the depth profiling feature.

Zinc oxide (ZnO) is known for its rich diversity of microstructures and has been attracting attention for its unique combination of mechanical and physical properties. It has been a material of interest in different areas such as optoelectronics, sensors and the general ceramic industry. It also has been a material of interest in biomedicine due to its antimicrobial characteristics and biocompatibility properties. A simple processing route to produce ZnO micro/nanostructures is the thermal oxidation of zinc, which results in a wide range of ZnO nanostructures depending on the oxidation conditions. The main objective of this study was to investigate the influence of a severe plastically deformed zinc microstructure on the formation of ZnO nanostructures produced by oxidation, with a special attention to the zinc oxide growth mechanism and nanostructures characteristics. For this purpose, the cold spray process was used to produce Zn coatings using different feedstock powders that required different process parameters in order to obtain Zn coatings with severely deformed particles. A non-catalytic thermal oxidation method was then used to successfully produce ZnO nanostructures at the surface of the heavily deformed cold sprayed Zn coatings. The as-grown ZnO nanostructures were investigated in detail using scanning electron microscopy and X-ray photoelectron spectroscopy. These investigations revealed that the chemical fingerprint of the oxides grown in the cold sprayed samples was different from that of conventional ZnO. It was also observed that in the oxidized cold sprayed Zn coatings, the formation of ZnO nanowires was hindered due to the formation of blisters generated during the high temperature exposure, revealing nonoptimized process parameters.

A micro-plasma system was investigated for its capability in additive manufacturing (AM). Micro-plasma AM system has the advantage of lower cost and higher deposition rate over the laser-based AM systems, and generates leaner and cleaner weld deposit than other arc-based AM systems. However, the microplasma system is complex and involves a large number of process variables. In this study, the effects of two arc and wire feed modes on dimensional consistency and hardness were firstly examined. Subsequently, one set of the specimens was further subjected to oxidation tests and the results were compared to that from conventional wrought Inconel 718. It was found that all four processes could produce crack free samples without measurable distortion. Some surface discoloration was observed, ranging from light straw to a purple tint. After heat treatment, the hardness of the samples varies from 403 to 440 HV, with the transverse surface showing slightly lower hardness values. The oxidation tests at 900 °C yielded similar weight change for AM Inconel 718 and its counterpart wrought alloy; however, the rate constant for wrought alloy was slightly higher. Microstructural analysis with SEM and EDS revealed a dendritic structure in the AM Inconel 718 and the presence of Nb-rich compounds in the interdendritic region. The polycrystal grain structure was not delineated in AM material as that in wrought 718. With the increase of exposure time, the oxide layer continues to increase at a higher rate, along with a sublayer of Ni 3 Nb above the metal substrate. In addition, after 200 hours, the wrought alloy developed porous chromia, while AM material exhibited uneven oxide thickness. In consideration of all aspects of the evaluation carried out thus far, it is concluded that the AM material produced by micro-plasma process is equivalent to wrought material in mechanical properties and oxidation performance.

The performance and applicability of thermal barrier coatings (TBCs) depend strongly on the top coat and bond coat interface integrity. The interlayer in TBC systems is often processed prior to top coat spraying to tailor its material properties or surface topography. Both, the bond coat spraying process and the further post-processing may significantly influence the thermally grown oxide (TGO) build-up which is crucial in terms of enhancing the TBC lifetime. In this work, NiCrAlY bond coats were sprayed by means of atmospheric plasma spraying. The as-sprayed bond coats were subjected to laser microtexturing which resulted in different bond coat topographies. Then, the samples were exposed to isothermal oxidation conditions under various oxidation dwell times to see the TGO evolution. The preliminary assessment of the oxidation mechanisms and oxide distribution was done by confocal laser scanning microscopy (CLSM). Scanning electron microscopy with energy dispersive X-Ray spectrometry (SEM/EDS) was used in order to analyze the evolution of bond coat structure and chemical composition during the high temperature oxidation.

Carbides are interesting materials for many wear resistant and high temperature applications, however, the production of coatings with these materials represents a significant challenge as they tend to oxidise or decompose into gaseous phases when they are exposed to extreme thermal spray conditions. An innovative method merging suspension and solution precursors was developed to allow the production of carbide composite coatings. Suspensions of carbides and borides were modified with the addition of oxide precursors to obtain composite coatings by high-velocity oxy-fuel (HVOF) thermal spray. The transformation of these oxides precursors and their subsequent melting during spraying contribute to protect the carbides from oxidising conditions, avoid their degradation during the spray process and support the development of dense coatings, as it was demonstrated by dispersive X-ray spectroscopy and X-ray diffraction analysis. The relationships between processing and microstructure were studied in terms of porosity phase distribution and mechanical properties, proving that this novel approach could be applied to obtain coatings of materials that are prone to decompose during thermal spraying.

High entropy alloys (HEAs) constitute a new class of advanced metallic alloys that exhibit exceptional properties due to their unique microstructural characteristics. HEAs contain multiple (five or more) elements in equimolar or nearly equimolar fractions compared to traditional alloy counterparts. Due to their potential benefits, HEAs can be fabricated with thermal spray manufacturing technologies to provide protective coatings for extreme environments. In this study, the AlCoCrFeMoW and AlCoCrFeMoV coatings were successfully developed using flame spraying. The effect of W and V on the HEA coatings were investigated using X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, and micro-hardness testing. Furthermore, performance of the coating under abrasive loading was investigated as per ASTM Standard G65. Microstructural studies showed different oxides with solid-solution phases for all the HEA coatings. Hardness results were higher for the AlCoCrFeMoV coatings followed by AlCoCrFeMoW and AlCoCrFeMo coatings. Lower wear rates were achieved for the AlCoCrFeMoV coatings compared to AlCoCrFeMoW and AlCoCrFeMo coatings. The evolution of multiple oxide phases and underlying microstructural features improved the resistance to abrasive damage for the AlCoCrFeMoV coatings compared to other HEA coatings. These results suggest that the flame-sprayed HEA coatings can be potential candidates for different tribological interfaces while concurrently opening new avenues for HEA coating utilization.

Process monitoring and control methods during direct metal deposition (DMD) are used to ensure a consistent manufacturing quality of the process. In the optical regime, naturally occurring process emission provides therefore selective and specific element lines, which can be obtained by optical spectrometers. However, DMD processes are in the heat conduction regime and superimposed broad spectral emissions dominate the wavelength specific signals. The aim of this work is to investigate the occurrence of different elemental lines in DMD processes as well as deposition track cross-sectional dimensions. Therefore, experiments were simultaneously conducted by using a high-resolution spectrometer (resolution = approx. 47 pm FWHM at 522 nm and 55 pm FWHM at 407.5 nm) and a medium resolution spectrometer (resolution = 0.73 nm FWHM), which were coupled by a bifurcated optical fibre. A parameter study of 27 single track DMD experiments using Co-Cr-based (MetcoClad21) powder on low-alloyed tool steel C45W (1.1730) substrate material, varying laser power, scan velocity and powder feed rate was conducted. Series of spectra were obtained for all sets of parameters with a scan rate of 100 Hz. The individual wavelength spectrum was analysed and classified by an algorithm into two types. Type-A spectra, with specific element emission lines and Type-B spectra, without significant emission lines with mostly predominant thermal emission radiation. Each deposition track was coupled to cross-sectional dimensions, including height, welding depth and melted areas. In addition, certain elemental lines contained in Type-A spectra were verified by using data from the NIST atomic spectra database. The investigation indicates that the relative number of Type-A spectra with respect to the total quantity of spectra, correlates significant to the process parameters. All detected and identified element lines occurred to be non-ionised elements, especially Cr I, Fe I and Mn I lines were frequently observed.

In this study, hydroxyapatite, titania, and HA-TiO 2 composite layers are deposited by suspension plasma spraying on titanium substrates and assessed by means of SEM and XRD analysis, Raman spectroscopy, and acoustic emission testing. The coatings exhibited dense microstructures with low porosity and good interfacial bond strength. The main phase in the HA and composite coatings was found to be similar to the peak of the feedstock powder. In the composite and titania coatings, besides rutile and anatase, a significant percentage of thermally stable Ti 3 O 5 was observed, which is favorable for photocatalytic performance.

In this work, binder-free Co 3 O 4 films with in-situ oxygen vacancies are deposited in a one-step process by solution precursor plasma spraying (SPPS). It is believed to the first time Co 3 O 4 layers composed of hexagonal flakes were synthesized through the SPPS route. Specific capacitances up to 1700 F/g were obtained at a scan rate of 5 mV/sec, almost 97% of which was retained after 13,000 cycles at 20 mV/sec. This supercapacitor-like performance is attributed to the synergistic effects of a binder-free composition with in-situ oxygen vacancies and porous nanostructures.

In plasma spraying, hydrogen is widely used as a secondary working gas. Under low-pressure conditions, even small amounts of hydrogen can have a significant effect on the plasma jet as mechanisms such as diffusion and recombination come into play. This study investigates the influence of Ar-H 2 mixtures on electron densities, temperature distributions, and local composition in the plasma jet using optical emission spectroscopy. Several mechanisms reported in the literature are consulted to explain the observed phenomena.