Oxides are chemically stable and wear resistant materials. Because of these properties, they are often applied as protective coatings in harsh environments. However, their chemical and mechanical stability at high temperature in chlorine containing environments is uncharted. These conditions are present in waste-to-energy and biomass boilers in which the currently available metallic and metal matrix composite coatings provide unsatisfactory protection. To be effective in these conditions the coatings should be chemically inert, erosion resistant and act as environmental barriers. For this purpose, this research studies the corrosion behavior and microstructural features of HVOF and APS-sprayed Al 2 O 3 -, Cr 2 O 3 -, TiO 2 -based coatings. Their chemical stability was evaluated by high temperature corrosion testing of self-standing coatings under KCl salt deposit at 550, 650 and 720 °C for the duration of 72 h.

Lowering the thermal energy and increasing the kinetic energy of sprayed particles by newly developed HVAF systems can significantly reduce material decarburization, and increases sliding wear and corrosion resistance of hard metal coatings, making HVAF coatings attractive both economically and environmentally over its HVOFs predecessors. Two agglomerated and sintered feedstock powder chemistries, respectively WC-Co (88/12) and WC-CoCr (86/10/4), with increasing primary carbides grain size from 0.2 to 4.0 microns, have been deposited by the latest HVAF-M3 process onto carbon steel substrates. Respective dry sliding wear behaviours and friction coefficients were evaluated at room temperature via Ball-on-disk (ASTM G99-90) wear tests against Al 2 O 3 counterparts, and via Pin-on-disk (ASTM G77-05) wear tests against modified martensitic steel counterparts in both dry and lubricated conditions. Sliding wear mechanisms, with formation of wavy surface morphology and brittle cracking, are discussed regarding the distribution and size of primary carbides. Corrosion behaviours were evaluated via standard Neutral Salt Spray (NSS), Acetic Acid Salt Spray (AASS), accelerated corrosion test and electrochemical polarization test at room temperature. Optimization of coating tribological properties are discussed regarding the suitable selection of primary carbide size for different working load applications.

This study examines the structural and corrosion properties of Ni and NiCu coatings produced by high-pressure cold spraying. It also assesses the effect of heat treatment. FE-SEM images of coating cross-sections show tightly bonded particles with only a minor presence of open or oxidized boundaries. Polarization measurements in alkaline salt and acid solutions show that the Ni and NiCu coatings have good potential for corrosion protection applications. Corrosion behaviors of as-sprayed and heat treated coatings are compared with corresponding properties of bulk and substrate materials.

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.

This research aims to investigate the effects of employing cryo-milled and milled MCrAlY feedstock powders on the oxidation behaviour of low-pressure plasma sprayed (LPPS) and HVOF-sprayed coatings deposited onto a Ni-based superalloy substrate. Commercially-available powders with three different chemical compositions were selected and sprayed both in standard condition and after milling and cryo-milling processes. The LPPS and HVOF coatings, deposited onto an Inconel substrate, were diffusion-treated at 1080 °C (according to the industrial standard) and subjected to isothermal and cyclic oxidation tests. The outcomes of these tests show that transient oxidation is suppressed in the coatings obtained from milled MCrAlY systems, whose overall resistance to cyclic oxidation (number of cycles to failure) is approximately two times greater than that of standard coatings. This difference is not related to the nanostructural features induced on the powder particles by the milling process, because, after the diffusion treatment, all coatings exhibit identical γ-β two-phase microstructure, with no trace of the original nanostructure. The improvement is ascribed to the fine dispersion of nanometric Al 2 O 3 grains within the milled powder particles: in the sprayed coatings, these nanometric oxides act as nuclei and favour the direct formation of an Al 2 O 3 oxide scale.

HVOF-sprayed WC–10wt%Co–4wt.%Cr coatings were obtained using experimental feedstock powders (manufactured by spray-drying + sintering), containing nanometric carbide particles. Three reference coatings were also deposited using commercially-available powders containing sub-micrometric carbide particles. The coatings obtained from nanostructured powders, although affected by decarburisation phenomena, contained very fine carbide particles (~200 nm size). Those obtained from commercially-available powders simultaneously exhibited sub-micrometric (~400 nm size) and micrometric carbide particles, and were much less decarburised. Sliding wear tests performed at room temperature against sintered Al 2 O 3 balls showed the occurrence of brittle fracture wear (detachment of near-surface material by local brittle cracking) on the nanostructured coatings, which were embrittled by decarburisation. The reference coatings, by contrast, exhibited either ductile wear behaviour (plastic deformation, pull-out of single carbide particles) or a mix of both ductile and brittle wear mechanisms. When the decarburisation of the nanostructured coatings was not too extensive, their wear loss was comparable to that of the reference ones. At 500 °C, the wear behaviour of all coatings was dominated by abrasive grooving, on account of thermal softening. The most decarburised nanostructured coatings, however, still experienced brittle cracking as well.

The dry sliding wear behaviour of two HVOF-sprayed Fe-Cr-Ni-Si-B-C (Colferoloy) alloy coatings was studied by ball-on-disk tests performed at room temperature (against alumina and 100Cr6 steel balls), at 400 °C and at 700 °C (against alumina balls only). HVOF-sprayed Ni-Cr-Fe-B-Si-C and Cr 3 C 2 -NiCr layers were also tested for comparison. Under all test conditions, the wear rate of the Colferoloy coatings is lower than that of the Ni-Cr-Fe-B-Si-C coating but larger than that of the Cr 3 C 2 -NiCr cermet. Specifically, at room temperature, the Colferoloy coatings exhibit a combination of mild abrasion, delamination and tribo-oxidative wear against alumina, whereas, against steel, they undergo very limited delamination with negligible wear loss. By contrast, the Ni-Cr-Fe-B-Si-C coating suffers larger wear against steel and undergoes more severe abrasive grooving against alumina. Although the Colferoloy and Ni- Cr-Fe-B-Si-C coatings possess similar microstructure and micro-hardness, their scratch behaviours, which depend on cracking resistance and plastic deformability, differ, thus explaining the micromechanical reason for the different wear mechanisms. At 400°C and 700°C, all of the metal alloy coatings are softened and suffer more severe abrasive grooving; by contrast, the behaviour of the Cr 3 C 2 -NiCr layer at 700 °C is controlled by the formation and delamination of an oxidised layer.

In this study, a TiO 2 (anatase) nanopowder suspension was processed by high velocity suspension flame spraying (HVSFS). The resulting coatings were characterized and compared to conventional HVOF and atmospheric plasma sprayed layers. It is shown that the HVSFS operating parameters can be adjusted to achieve dense titania with a near nanostructure and homogeneous distribution of anatase and rutile phases. These coatings have lower pore interconnectivity and higher wear resistance than the APS and HVOF layers. Alternatively, large unmelted agglomerates of anatase nanoparticles can be embedded in the coating, increasing the porosity and anatase content for enhanced photocatalytic efficiency.

This study shows that thermal spraying is a viable technique for the deposition of barium hexaferrite layers suitable for microwave absorption applications. More specifically, the study shows that impact quenching of molten BaCoTiFe 10 O 19 hinders the crystallization of the hexaferrite phase. Consequently, when spraying conditions induce near-full melting of the feedstock, the coating mostly consists of spinel and a glassy phase, a state with poor magnetic properties. These phases can be converted to hexaferrite by annealing, but in order to obtain enough crystalline hexaferrite in as-deposited layers, a controlled amount of unmelted material must be preserved. Atmospheric plasma spraying proved to be well suited for this purpose, producing layers with excellent magnetic properties, close to those of pure crystalline BaCoTiFe 10 O 19 . In these coatings, dense regions entrain many unmelted agglomerates of micron-sized particles, effectively preserving the hexaferrite phase.

In this study, WC-CoCr coatings were deposited on an aluminum substrate by HVOF spraying. Layer thicknesses between 50 and 150 μm were achieved by stepwise increase of the number of torch scans. The stepwise method is shown to make the coatings not only thicker, but also denser due to peening effects and changes in the splat formation mechanism. It also explains the incremental improvement in coating hardness and corrosion and wear resistance observed over the first few torch scans, the largest of which occurs between the second and third scans. The coatings are also compared to anodized films and were found to have superior wear and impact resistance but less resistance to corrosion.

High temperature thermal fatigue causes the failure of Thermal Barrier Coating (TBC) systems. Due to the difference in thickness and microstructure between thick TBCs and traditional thin TBCs, they cannot be assumed a-priori to possess the same failure mechanisms. Thick TBCs, consisting of a CoNiCrAlY bond coat and Yttria Partially Stabilised Zirconia top coat with different values of porosity, were produced by Air Plasma Spray. Thermal fatigue resistance limit of TBCs was tested by Furnace Cycling Tests (FCT) according to the specifications of an Original Equipment Manufacturer (OEM). TBC systems were analyzed before and after FCT. The morphological and chemical evolution of CoNiCrAlY/TGO microstructure was studied. Sintering effect, residual stress, phase transformation and fracture toughness were evaluated in the ceramic Top Coat. All the tested samples passed FCT according to the specification of an important OEM. Thermal fatigue resistance increases with the amount of porosity in the top coat. The compressive in-plane stresses increase in the TBC systems after thermal cycling, nevertheless the increasing rate has a trend contrary to the porosity level of top coat. The data suggest that the spallation happens at the TGO/Top Coat interface. The failure mechanism of thick TBCs subjected to thermal fatigue was eventually found to be similar to the failure mechanism of thin TBC systems made by APS.

The High-Velocity Suspension Flame Spraying (HVSFS) technique, a recently-developed modification to the standard HVOF process enabling the use of suspension feedstock, was employed in order to deposit Al 2 O 3 coatings from a nanopowder suspension. These coatings were compared to conventional APS and HVOF-sprayed ones. HVSFS coatings possess lower overall porosity and lower pore interconnectivity degree. Indeed, most of the nanoparticles were fully melted by the gas jet, thus forming very thin, well-flattened lamellae, having smaller columnar crystals than conventional coatings. Accordingly, HVSFS coatings possess higher hardness and elastic modulus, as determined from nanoindentation tests. Ball-on-disk tribological tests also indicate that HVSFS coatings possess much better sliding wear resistance than conventional ones, because they are capable of forming denser and more protective surface tribofilms during dry sliding.

Finishing of thermally sprayed metallic, ceramic and cermet coatings is required in order to meet tolerances and requirements on surface roughness in most industrial applications. Conventional machining is a costly and time-consuming process, difficult to automate. Therefore, this study investigates and develops a new technique highly amenable for automation: Fast Regime - Fluidized Bed Machining (FR-FBM). Atmospheric Plasma Sprayed (APS) TiO 2 , Cr 2 O 3 and HVOF-sprayed WC-17%Co and Tribaloy-800 coatings, deposited on AISI 1040 steel substrates, were subjected to FR-FBM treatment. The effects of the leading operational parameters, namely, abrasive size, jet pressure and processing time, were evaluated on all coatings by using a two/three-levels full factorial Design Of Experiments (DOE). The FR-FBM treated surfaces were observed by FE-SEM and their surface finishing was evaluated by contact profilometry. Significant improvements in surface finishing of all the machined thermally sprayed coatings can always be detected, with FR-FBM being able to guarantee the precision and the respect of the closest geometrical tolerances.

Residual stresses in plasma-sprayed Al 2 O 3 and Cr 2 O 3 coatings, deposited using commercial powders, and in HVOF-sprayed ceramic coatings, deposited using conventional Al 2 O 3 and Cr 2 O 3 feedstock and nanostructured- Al 2 O 3 feedstock, were studied by combining X-ray diffraction, substrate chemical removal technique and analytical modelling. The in-situ curvature technique was also employed for HVOF-sprayed Al 2 O 3 coatings, for further verification. Both HVOF-sprayed Al 2 O 3 -based coatings display similar, tensile residual stresses (≈120 MPa) near the top surface and possess moderate through-thickness stress gradients (≈10 - 20 MPa). Plasma-sprayed Al 2 O 3 possesses a smaller through-thickness stress gradient and a larger near-surface stress (≈220 MPa): this latter result seems to be due to higher quenching stresses in APS Al 2 O 3 , as determined by analytical computation The analytical model is validated by its fairly good agreement to the experimental results obtained both by substrate chemical removal and by in-situ curvature. Cr 2 O 3 -based coatings possess a lower near-surface residual stress (≈20 MPa); the HVOF one also exhibits a very large stress gradient (≈80 MPa). Machining and sliding processes (like polishing and dry sliding tribological testing) change their surface residual stresses to compressive ones.

The tribological behaviour of HVOF-sprayed Co-28%Mo- 17%Cr-3%Si coatings, both as-sprayed and after heat treatments at 200°C, 400°C, 600°C for 1h, has been studied. Microstructural and micromechanical properties were characterized by SEM, XRD, depth-sensing indentation (microhardness, elastic modulus, indentation fracture toughness); pin-on-disk dry sliding wear tests were performed against 100Cr6 and sintered alumina spherical pins. The as-sprayed coating contains splat boundary oxide stringers and is mostly amorphous (splat quenching). It has low hardness (≈6.7GPa) and toughness (≈1MPa*m 1/2 ); thus, much adhesive wear occurs against 100Cr6 steel. The friction coefficient increases up to ≈0.9, raising the contact point temperature up to a critical coating oxidation value; then, it decreases, increases again and finally settles. Much of the adhesive wear occurs in the first stage of the test. Abrasive wear prevails with the alumina pin: the coating wear rate is lower because the metallic alloy possesses intrinsically good plasticity. Adhesive phenomena still occur, leading to the same thermal effects. After the 200°C and 400°C heat treatments, no major changes occur. The 600°C treatment causes the formation of some submicrometric crystals. The hardness increases (≈8.8GPa), adhesion to steel pin is prevented, and the friction coefficient soon settles at ≈0.8 with no peaks. The coating undergoes no wear loss and the pin wear rate largely decreases. With the alumina pin, coating and pin wear rates remain quite low. However, adhesion is reduced, so that the friction coefficient has no peaks and its final value is lowered (from 0.84 to 0.75).

Plasma sprayed oxides are effective coatings against wear and corrosion. Low particle velocity in the plasma jet causes a limited interlamellar cohesion. HVOF-sprayed ceramic coatings emerged as an improved alternative. In this paper, microstructural characteristics and tribological performances of HVOF sprayed Al 2 O 3 , nanostructured Al 2 O 3 and Cr 2 O 3 coatings are compared to reference plasma-sprayed Al 2 O 3 and Cr 2 O 3 . The microstructure is analysed by SEM, EDS and XRD. Hardness and fracture toughness are investigated by instrumented indentation and elastic modulus by 3-point bending. Steel wheel and rubber wheel tests have been used to assess dry particle abrasion resistance. Sliding wear resistance is tested by pin-on-disk at room temperature and at 400°C, against SiC and 100Cr6 steel balls. HVOF-sprayed coatings are denser and have better interlamellar cohesion thanks to increased particle velocity. They are harder, tougher, possess a higher elastic modulus and lower porosity. Dry particles abrasion resistance is definitely superior to plasma-sprayed ceramics due to higher toughness; sliding wear resistance is higher, particularly at 400°C.

HVOF-sprayed coatings (WC-17Co, WC-10Co-4Cr, Co-28Mo-17Cr-3Si) have been compared with various kinds of industrially manufactured hard chrome coatings (HCC), whose substrate preparation, deposition process, post deposition treatments greatly affect their characteristics. Microstructure, micromechanical properties, tribological behaviour and corrosion resistance (electrochemical polarization tests and Corrodkote test) have been studied. HVOF-sprayed cermets are harder but less tough than HCC, Co-28Mo-17Cr-3Si are less hard than HCC. Splats detachment causes a comparable or higher mass loss in three-body abrasion than HCC coatings. Forming a uniform surface film, cermet coatings definitely overcome HCC in two-body sliding, while Co-28Mo-17Cr-3Si has insufficient hardness to display good sliding wear resistance. HVOF coatings show no passivation in corrosive media but cermets posses more noble corrosion potentials than HCC, and undergo generalized corrosion in HNO 3 and HCl, with similar corrosion current densities (I C ). HCC passivate and resist well in HNO 3 0.1N, but undergo pitting corrosion in 0.1N HCl. Definitely different E C and I C are recorded for various HCC in HCl. HVOF-sprayed cermet coatings show lower I C in 0.1N HCl solution than several kinds of HCC. No visible damage occurs on HVOF-sprayed coatings after the Corrodkote test, while non de-hydrogenated HCC suffered pitting corrosion.

Plasma-sprayed ceramic coatings were deposited on refractory substrates to improve their chemical resistance to molten glass. Mullite, coarse and fine alumina powders were employed. Different layers with step-wise varying compositions were deposited in order to avoid dilatometric incompatibility troubles. In all the samples, the top coating consisted of plasma-sprayed fine alumina powders, to achieve low porosity and confer adequate chemical resistance, while mullite was used to match the low thermal expansion coefficient of the porous refractory substrates. The coatings were characterized by SEM, XRD, fracture toughness, abrasion resistance, thermal shock resistance and resistance to chemical attack. Since the overall thermo-mechanical and chemical behaviour is greatly affected by microstructural features, such as porosity amount, stacking sequence of layers and their composition, a FEM simulation of the thermo-mechanical properties (with particular regard to thermal stresses-induced cracking) has been conducted and compared to the experimental results.

Plasma-sprayed alumina-waste glass composite coatings on ceramic substrates were produced. Two kinds of alumina powders, different alumina volume fractions, and two glass powders particle size distributions were tested. Post-process thermal treatments were performed. The coatings were characterized by SEM, XRD, Vickers microhardness, fracture toughness, abrasion resistance tests. Coatings superior to traditional tile glazes were obtained with as high as 50 vol.% of waste glass. Fine glass powders (<45µm) must be employed to achieve adequate toughness. A low-cost spray-dried alumina can be used instead of the expensive commercial powders. The thermal treatment enhances the coating properties. A FEM thermo-mechanical simulation was performed. Elastic modulus calculations show a definite coating anisotropy (higher mechanical properties in the longitudinal direction). Compressive residual stresses in the alumina and tensile ones in the glass are developed after the thermal treatment. Crack propagation studies based on Griffith model show cracks initiating from larger pores and propagating easily through the glass, thus explaining the coating toughening achieved through the employment of finer glass powders. Cracks are stopped by alumina; this effect is enhanced in the thermally treated coatings. The numerical and experimental (from indentation fracture toughness test) crack propagation patterns are in good agreement.