The monoclinic and tetragonal phase compositions and distribution in air plasma sprayed (APS) yttria-partially stabilized zirconia (YPSZ) thermal barrier coatings were studied. The coatings were produced from powders with varying phase concentrations, chemical purity and powder production processes. Both the powder and coatings were characterized using X-ray diffraction (XRD) and Raman spectroscopy. The use of environmental scanning electron microscopy (ESEM) and X-ray energy dispersive analysis (EDS) added morphological and elemental information to the study. XRD and Raman spectroscopy were shown to be powerful combined tools and shows an overall decrease in the monoclinic phase within the coatings produced from the different powders. The distribution of both the monoclinic and the tetragonal phases could be highlighted both in the coatings and the individual powder particles. This indicated changes in monoclinic concentration in the less dense areas of some of the coatings and a varying distribution across particles in some of the powders. Raman mapping over small areas also showed how phase surface distribution, on the coatings surfaces, could be assessed.

The major problems with plasma sprayed hydroxyapatite (HA) coatings for hard tissue replacement are severe HA decomposition and insufficient mechanical properties of the coatings. The loss of crystalline HA after high temperature spraying is due mainly to the loss of OH- in terms of water. The present study employed steam to treat HA droplets and coatings during both in-flight and flattening stages. The microstructure of the HA coatings and splats was characterized using scanning electron microscopy, Raman spectroscopy, Fourier transform infrared spectroscopy, and X-ray diffractometry (XRD). Results showed that a significant increase in crystallinity of the HA coating was achieved through the steam treatment (e.g., from 58% to 79%). The Raman spectroscopy analyses on the individual splats and coatings indicate that the mechanism involves entrapping of water molecules by the individual HA droplets upon their impingement. It further suggests that the HA decomposition has already taken place before the impingement of the droplets on pre-deposited materials or the substrate. The improvement in crystallinity and phases, e.g., from tricalcium phosphate and amorphous calcium phosphate to HA, was achieved by reversing the HA decomposition through providing extra OH-ions. Furthermore, the steam treatment during the spraying also accounts for remarkably increased adhesion strength from 9.09 MPa to 23.13 MPa.

Yttria Partially Stabilized Zirconia (YPSZ) coatings are used as Thermal Barrier Coatings (TBCs) because of their capability to improve gas turbine performance by allowing higher turbine inlet temperature and reduced cooling air flow. Usually, YPSZ layers are applied by plasma spray on Ni-based superalloys pre-coated with a bond coat layer of MCrAlY, where M is Co, Ni, or both. In this work we used Raman spectroscopy to study the performance of TBCs during thermal cycling at two different temperature (1273K and 1373K). Raman scattering is capable of detecting monoclinic zirconia and to analyze residual stresses of the coatings with an higher sensitivity than traditional X-ray diffraction measurements. Raman spectra were analyzed by deconvolution methods in order to study the evolution of the relative intensities and position of different bands. We found that the position of the 635 cm-1 band shifts to higher values of wave number during thermal cycling and by comparing this data with those reported in literature, it is possible to retrieve the value of residual stresses in zirconia coating. We also observed a relation between the intensities of the bands at 602 cm-1 and 635 cm-1 band and the number of thermal cycles performed.

The thermal phase stability of plasma sprayed TBC is presented and discussed. TBC phase transformation after various isothermal heat treatment processes was studied via Xray diffraction (XRD) and Raman Spectroscopy methods. The YSZ-Gd-Yb and 20YSZ TBCs demonstrated superior thermal phase stability as compared with the high and standard purity 8YSZ TBCs, although higher purity also helps delay the tetragonal to monoclinic phase transformation. The phase transformation appears to be suppressed by cooling at higher rates. This data presents a qualitative phase stability comparison between the various coatings. However, cooling rate has to be taken into consideration in determining the extent of phase instability during the coating design of aero turbine applications.

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.

A high-purity (HP) HOSP (Hollow Oven Spherical Process) PYSZ powder has been evaluated and compared to standard PYSZ powders. The main difference is these two powders is the starting raw material purity. Four TBC systems (2 standard types and 2 high purity versions) were Air Plasma Sprayed (APS) onto CMSX-4 substrates with APS CoNiCrAlY bond coats. Thermal shock testing was performed to 50 % spallation at 1135°C with 1 hour hot cycles with forced air cooling. The as-deposited coatings and those after thermal shock failure were characterized using X-ray diffraction, Raman spectroscopy and scanning electron microscopy. The thermal cycling results show little difference in the thermal shock resistance of the coatings with all failing in an adhesive manner with failures occurring in excess of 180 hot cycles. XRD and Raman data is used to identify the levels of monoclinic and tetragonal phases present in each coating and SEM analysis used to identify differences between PYSZ with a broad particle size distribution and a tighter controlled PYSZ particle size distribution.

Two kind of the feedstock materials were used to produce the atmospheric plasma sprayed coatings. One is the spraying dried powder and the other is the nano-particle dispersed sol precursor. Coating properties were evaluated by the XRD, Raman spectroscopy, SEM and TEM. Also, the photodecomposition efficiency was examined by measuring the decomposition rate of the MB(methylene blue) in a water-cooled solution during the UV radiation and compared to the decomposition efficiency of the optimum coating produced using spraying dried particle. Both the anatase phase fraction and the photodecomposition rate of the coating using the sol precursor were higher than that of the optimum coating using the spraying dried powder.

An ultrasonic nanocrystal surface modification (UNSM) technique was applied to the thermally sprayed yttria-stabilized zirconia (YSZ) ceramic thermal barrier coating (TBC) deposited onto a hot tool steel substrate to improve the mechanical and tribological properties. The surface microstructure of the as-sprayed and UNSM-treated coatings was examined using a scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDS) and Raman spectroscopy, while the hardness of the coatings was measured by Vicker`s hardness tester. The friction and wear behavior of the coatings was assessed using a ball-on-disk tribometer against bearing steel (SAE52100) ball at temperatures of 25 °C and 200 °C under dry reciprocating conditions. Results showed that the UNSM-treated coating had smoother surface, lower friction and higher resistance to wear compared to that of the as-sprayed coating. It was found that hybrid use of thermal spray coating (TSC) and UNSM technique is meaningful to bring together synergy effect of two emerging surface technologies.

Boron carbide has been successfully deposited on Ti alloy by vacuum plasma spraying (VPS). Mechanical properties of the deposited structure were assessed by micro-hardness and nano-hardness indentation. Chemical and phase compositions of the starting powder and the as-sprayed structure were characterized using hot gas extraction (LECO), x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS), scanning transmission electron microscopy (STEM), and Raman spectroscopy. The microstructure consisted of equiaxed boron carbide grains, microcrystalline boron carbide particles, and amorphous carbon regions at the grain boundaries. The amount of boron oxide and amorphous carbon increased during spraying. Carbon segregation to grain boundaries in the as-deposited B 4 C was observed. The measured micro-hardness was slightly higher than values previously reported (1033 ± 2009 HV). There was significant variation of nano-hardness from point to point in the material due to the existence of multiple phases, splat boundaries, and porosity in the deposited structure.

Titanium dioxide coatings were sprayed by a water stabilized plasma gun (WSP) to form robust self-supporting bodies with a photocatalytically active surface. Agglomerated nanometric powder was used as a feedstock. In one case argon was used as a powder-feeding as well as coating-cooling gas whereas in the other case nitrogen was used. Stainless steel was used as a substrate and the coatings were released after the cooling. Over one millimeter thick self-supporting bodies were studied by XRD, HR-TEM, XPS, Raman spectroscopy, UV-VIS spectrophotometry and photocatalytic tests. Majority of the tests was done at the surface as well as at the bottom side representing the contact surface with the substrate during the spray process. Porosity was studied by image analysis on polished cross sections where also microhardness was measured. Dominant phase present in the sprayed samples was rutile whereas anatase was the main minor component. Hydrogen content in the nitrogen assisted coating was higher, but the character of the optical absorption edge remained the same for both samples. Photoelectron spectroscopy revealed differences in the character of O 1s peak between both samples. The photocatalytic activity was tested by decomposition of acetone at UV illumination, whereas also the end products - CO and CO 2 - were monitored. The nitrogen-assisted coating was revealed as more efficient photocatalyst.

Detonation spraying provides the opportunity to produce superabrasive diamond grinding tools under atmospheric conditions. In this study, several methods are used to assess the effects of the spraying process on diamond particles, including SEM analysis, energy dispersive X-ray spectroscopy, differential thermal analysis, thermogravimetric analysis, X-ray diffraction, Raman spectroscopy, and friability and fracture force testing. It was found that under optimized conditions, the thermal and mechanical impact of the detonation can remain low enough to ensure the reliability of the diamonds with no adverse effects.

The paper aims at the development of coating having a gradient of crystal grain size. Thick, inner layer was plasma sprayed using coarse TiO 2 powder. This layer has the thickness ranging from 30 to 50 µm. Thin, outer layer of thickness smaller than 10 µm, was plasma sprayed using different aqueous suspensions of fine powders of TiO 2 . The morphology of coarse and fine powders was characterized using scanning electron microscope (SEM) X-ray diffraction (XRD). Electronic emission was tested using home made setup. X-ray diffraction enabled to find out an interesting result which is formation of a mixture of rutile and anatase in suspension sprayed coatings. This was also confirmed by Raman spectroscopy investigations. The technology of suspensions plasma spraying was optimized to obtain homogeneous and dense deposits. The sizes were in the range of tenth to one hundred nanometers in initial powders and get clearly smaller in the coatings sprayed using coarse powder but remained quite similar in suspension sprayed films. X-ray photoelectric spectroscopy (XPS) was used to analyze quantitatively TiO 2 powders and coatings. Electronic emission was correlated with phase composition of the coating and their grain size.

Systematic variation of the induction plasma spray (IPS) conditions, i.e. (i) plasma power, (ii) carrier gas flow rate, and (iii) powder feed rate was performed to deposit TiO 2 coatings using statistical design of experiments (SDE) methodology. The microstructure, surface morphology, and anatase-rutile ratio of the coatings were studied by grazing-incidence X-ray diffraction (GIXD) and surface mapping with micro-probe Raman spectroscopy to determine the spatial phase distribution of anatase and rutile. The photocatalytic activity of the TiO 2 coatings was tested by decomposition of 4-chlorophenol in aqueous solution in the dark and under UV irradiation. The rates of pH changes measured were compared with those of standard Degussa P-25 coatings. The photocatalytic activity of the samples shows a reasonable correlation with the phase content and the plasma processing conditions prevailing during coating deposition.

High velocity oxy-fuel (HVOF) combustion spraying has previously been shown to be a viable method for depositing polymer and polymer/ceramic composite coatings. The addition of hard particulate reinforcing phases to soft polymeric matrices should improve their durability and wear performance. Nano-sized diamond is an ideal reinforcing phase, owing to its high hardness and desirable thermal properties. Composite coatings comprising a Nylon-11 matrix reinforced with nanodiamonds have been successfully produced by HVOF. An important challenge is preserving the structure of the nanoparticles after thermal spray deposition and achieving a uniform dispersion of them within the polymeric matrix. Raman spectroscopy and X-ray diffraction confirmed the presence and retention of nanodiamonds after HVOF deposition. Understanding of the role of variables including the % loading of reinforcing phase in the matrix and powder preparation route are necessary. The coatings exhibited improved sliding wear resistance in macromechanical tests. Nanoindentation studies demonstrated an improvement in deformation behavior and recovery of the HVOF nanodiamond Nylon-11/nanodiamond composites subjected to deformation.

This article describes a method of preparing bioactive and porous titanium coatings on titanium-based substrate using vacuum plasma spraying and chemical treatment in alkali solution. The porous titanium coating was fabricated in two-layer structure. The bond strength, average porosity and roughness (Ra) of the porous titanium coating are 55MPa, 30% and 21µm, respectively. The chemical treatment of as-sprayed titanium coatings was carried out in 5.0M NaOH solutions at 40 °C for 24h. The surface morphology and structure of the porous titanium coating before and after chemical treatment were examined by SEM and laser Raman spectroscopy. The treated titanium coating was immersed into SBF to evaluate its bioactivity by examining apatite formation on its surfaces. It was observed by SEM and TF-XRD that apatite was formed on the surface of the treated titanium coating after immersion in SBF. The spherical aggregates gradually grew large by consuming calcium and phosphate ions in SBF and covered the surface with increase in soaking time. Incorporation of CO 3 2- ions into apatite crystal lattice was revealed by FT-IR. The results obtained indicated that net-like sodium titanate formed due to NaOH attack was responsible for apatite nucleation and growth. It is concluded that vacuum plasma spraying and subsequent chemical treatment is an effective way to produce bioactive and porous titanium coatings.

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.

This study investigates the effect of composition on the antibacterial and antiviral properties of hydroxyapatite/titania composite coatings deposited by suspension plasma spraying. Hydroxyapatite is a bioceramic material used as a plasma-sprayed coating to promote osseointegration of femoral stems. TiO2 has promising photocatalytic activity and good efficiency in destroying bacteria, viral species, and parasites. Prior to coating, substrates were grit blasted, ultrasonically cleaned, and heated to enhance adhesion strength. The microstructure of the resulting coatings was then characterized using XRD and Raman spectroscopy. Test results indicated that SPS transformed Ti2O3 into TiO2 with mixed phases. Ti4O7 and Ti3O5 phases were also identified, which show photocatalytic activity due to oxygen vacancies. Antibacterial and antiviral tests were conducted as well.

Titanium dioxide (TiO 2 ) coatings possess high appeal due to self-cleaning properties that can accelerate decomposition of organic pollutants. The global objective is to develop a cold sprayable feedstock powder with an outer titanium dioxide shell that maximises anatase-rutile heterojunctions for enhanced photocatalytic activity under ultraviolet light and the development of cold spray process parameters for successful deposition of this powder into thin photocatalytic coatings. The objective of this reported first step of our global research effort to produce superior photocatalytic TiO 2 coatings by cold spray is to successfully engineer anatase and rutile nanostructure heterojunction shells on pure titanium (CP-Ti) powder known to be easily sprayable by cold spray and then verify its photocatalytic properties through exposure to an organic pollutant, methylene blue (MB). Anatase and rutile heterojunctions are desired due to high activity, stability and broadened bandwidth as opposed to each singular nanostructure. The resulting powder coming out of this first step was characterized using Raman spectroscopy to verify the presence of the desired heterojunctions. The photocatalytic reactivity was tested and evaluated through the degradation of methylene blue upon contact with the TiO 2 powder. Results of this first step showed growth of desired heterojunctions and high reactivity of the produced powder.

Ceramic layers, such as yttria-stabilized zirconia or scandia-stabilized zirconia, used for functional layers of solid oxide fuel cells, i.e. the gas tight oxygen ion conductive electrolyte or as ceramic component in the porous cermet anode, were obtained by the Solution Precursor Plasma Spray (SPPS) process. The influence of different solvent types on microstructure was analyzed by comparison of coatings sprayed with water-based solution to ethanol-based one. Use of solvent with low surface tension and low boiling point enhances splat formation, coating microstructure and crystalline structure. Parameter adjustment to receive coatings from nitrate solutions with ethanol as solvent was carried out. Results of Raman spectroscopy indicate that an intermediate of both nitrates (zirconyl and scandium nitrate hydrate) was deposited.

This study examines the fundamental reactions that, in the solution plasma spraying process, lead to the conversion of the precursor salts to solid material that is deposited onto the substrate. The study specifically focused on the phenomena occurring in-flight and the effect of plasma jet treatment on the mechanical and thermal treatment of the solution injected in the form of a liquid jet. The evolution of precursor droplets in the plasma flow was investigated “in situ” using a shadowgraphy technique. The morphology and structure of material deposited onto smooth stainless steel substrates during single scan experiments were characterized by SEM, GI-XRD and micro-Raman spectroscopy and were correlated to the in-flight observations, in order to evaluate the effect of the plasma-forming gas and solution solvent.