Structure and properties of plasma sprayed BaTiO3 coatings: Spray parameters versus structure and photocatalytic activity

Plasma spraying enables the creation of layers with thickness in a millimeter range adhering on various substrates. This paper provides a study of phase composition, optical properties and photocatalytic activity of BaTiO₃ coatings prepared by atmospheric plasma spraying. The spraying was carried out by a direct current gas-stabilized plasma gun. BaTiO₃ was fed into the plasma jet as a feedstock powder prepared by a reactive sintering of micrometer-sized powders of BaCO₃ and TiO₂. Microstructure and phase composition are reported and discussed in connection with optical properties and photocatalytic activity. The spraying was carried out by a direct current gas-stabilized plasma gun which normally utilizes spray distance (SD) in frames from 100 to 150 mm. Besides conventional SD 100 mm also extremely high SD 190 mm was used. The color of the sprayed coating is different for each SD and also differs from sintered BaTiO₃. X-ray diffraction and also SAD mode of HR-TEM show certain content of amorphous fraction in the coating. The hydrogen content in the coating was found to be higher in the coatings than in the sintered bulk. The diffuse reflectance was measured by UV–VIS spectrophotometry and corresponding band-gap energy was estimated. X-ray photoelectron spectroscopy confirms specific stoichiometric and structural disorder observed also at bang-gap evaluation and by Raman spectroscopy. HR-TEM images for crystalline and amorphous zones are given. Photocatalytic decomposition of acetone was tested and BaTiO₃ coatings compared with a sintered bulk.     

Effect of spray process on dielectric properties of APS-deposited CaO–B2O3–SiO2 glass-ceramic coatings

Low-dielectric properties are highly desirable for successful realization of thermal spray coatings in electromagnetic wave absorption. Herein, CaO–B₂O₃–SiO₂ (CBS) glass-ceramic coatings are prepared via high-enthalpy atmospheric plasma spraying (HE-APS) method, and the influence of spraying power on physical and dielectric properties of APS-deposited CBS coatings is systematically investigated. Under high-power conditions, the increase in liquid phase hinders the discharge of gases and leads to an increase in the porosity of CBS coatings. The experimental results reveal that the coating density decreases and coating porosity increases with the increase of spraying power. Based on the crystallization behavior of CBS coatings, an excellent low-dielectric crystalline phase (β-CaSiO₃) was obtained after heat treatment at 800 °C. According to the dielectric mixing rule of composite materials, the density and permittivity exhibit the same trend and a minimum permittivity of 5.74 is obtained.     

Analysis of corrosion protection behavior of Al2O3-TiO2 oxide ceramic coating on carbon steel pipes for petroleum industry

Corrosion is the deterioration of materials by chemical interaction with their environment. In the oil and gas industry, corrosion of the pipelines and other equipment is one of the leading causes of failure and the corrosion-related costs are very high. Hence, corrosion protection is an essential requirement. In this study, the objective is to analysis of the corrosion protection behavior of spray Alumina-Titania (Al₂O₃-TiO₂) oxide ceramic coating on carbon steel pipes C45 using two different thermal spray coatings processes. These two different thermal spraying coating, High velocity oxy-fuel (HVOF) and plasma thermal spraying techniques can be used instead of extensive treatment by expensive chemical formation of coatings on pipelines and equipment to improve or restore a component's surface properties or dimensions and to protect them from corrosion. Molten or semi-molten ceramic composite powders are sprayed on the surface in order to produce a dense coating layer. FESEM of coated samples showed that a high temperature of plasma coating method end in melting the ceramic powders and creation of completely melted regions on the coated samples’ surface compared to HVOF coating techniques. Corrosion testing of coated samples in seawater (3.5% NaCl) was conducted within 30 days. Electrochemical impedance spectroscopy (EIS) as well as potentiodynamic polarization outcomes represented that the corrosion resistivity of plasma coating technique for this type of ceramic composite is better than HVOF coating technique. However, both types of coating techniques are protecting the substrate against seawater.     

Atmospheric plasma spraying coatings from alumina–titania feedstock comprising bimodal particle size distributions

In this work, Al₂O₃–13 wt% TiO₂ submicron-nanostructured powders were deposited using atmospheric plasma spraying. The feedstocks were obtained by spray drying two starting suspensions of different solids content, prepared by adding nanosized TiO₂ and submicron-sized Al₂O₃ powders to water. The spray-dried granules were heat-treated to reduce their porosity and the powders were fully characterised in both untreated and thermally treated state. Comparison with two commercial feedstocks was carried out. Characterisation allowed a temperature for the thermal treatment to be chosen on the basis of the sprayability of the feedstock and the preservation as much as possible of the submicron-sized structure of the unfired agglomerates.Optimisation of the deposition conditions enabled the reconstituted powders to be successfully deposited, yielding coatings that were well bonded to the substrate. The coating microstructure, characterised by SEM, was mostly formed by a matrix of fully molten particles where the presence of semi-molten feedstock agglomerates was also observed.Moreover, microhardness, toughness, adhesion and tribological behaviours were determined, and the impact of the granule characteristics on these properties was studied. It was found that changing the feedstock characteristics allows controlling the coating quality and properties. In general, good mechanical properties were obtained using a feedstock comprising a binary mixture of submicrometric Al₂O₃ and nanometric TiO₂ particles in the spray-dried powder.     

Experiments and transient finite element simulation of γ-Y2Si2O7/B2O3-Al2O3-SiO2 glass coating on porous Si3N4 substrate under thermal shock

A dense γ-Y₂Si₂O₇/B₂O₃-Al₂O₃-SiO₂ glass coating was fabricated by slurry spraying method on porous Si₃N₄ ceramic for water resistance. Thermal shock failure was recognized as one of the key failure modes for porous Si₃N₄ radome materials. In this paper, thermal shock resistance of the coated porous Si₃N₄ ceramics were investigated through rapid quenching thermal shock experiments and transient finite element analysis. Thermal shock resistance of the coating was tested at 700 °C, 800 °C, 900 °C and 1000 °C. Results showed that the cracks initiated within the coating after thermal shock from 800 °C to room temperature, thus leading to the reduction of the water resistance. Based on the finite element simulation results, thermal shock failure tended to occur in the coating layer with increasing temperature gradient, and the critical thermal shock failure temperature was measured as 872.24 °C. The results obtained from finite element analysis agree well with that from the thermal shock tests, indicating accuracy and feasibility of this numerical simulation method. Effects of thermo-physical properties for the coating material on its thermal shock resistance were also discussed. Thermal expansion coefficient of the coating material played a more decisive role in decreasing the tangent tensile stress.     

Mining tailings as a raw material for glass-bonded thermally sprayed ceramic coatings: Microstructure and properties

Magnesium aluminate, MgAl₂O₄, spinel powders for thermal spraying, were synthesized from secondary raw materials by spray drying and subsequent reaction sintering. Talc ore mining tailings and aluminium hydroxide precipitate from aluminium anodizing process were studied. A stoichiometric MgAl₂O₄ spinel coating was prepared as a reference using pure raw materials. Atmospheric plasma spraying resulted in the formation of ceramic coatings. Microstructural investigations revealed that the reference coatings exhibited crystalline lamellar microstructure of MgAl₂O₄ but secondary coatings contained amorphous areas between the crystalline MgAl₂O₄ clusters. Abrasive wear test results revealed considerably lower wear rate for secondary coatings. It is suggested that the different structure of coatings, particularly the high degree of amorphous phase between the isolated crystalline MgAl₂O₄ clusters caused the higher abrasive wear resistance by changing the wear mechanism. The dielectric breakdown strength of the secondary coatings were at the same level, 24 V/μm, as compared to reference coating, 23 V/μm.     

A comparative study of MoSi2 coatings manufactured by atmospheric and vacuum plasma spray processes

In this work, MoSi₂ coatings were manufactured by atmospheric plasma spraying (APS) and vacuum plasma spraying (VPS) technologies, respectively. Phase composition and microstructure of the coatings were characterized by X-ray diffraction and scanning electron microscopy. Microhardness, void and oxygen content of the coatings were also determined. Oxidation behavior of the coatings at high temperature was examined. The results showed that the surface of VPS-MoSi₂ coating was dense and homogeneous. However, there were many microcracks formed on the surface of APS-MoSi₂ coating. The VPS-MoSi₂ coating also had lower void and oxygen contents, higher Vickers hardness compared with those of APS-MoSi₂ coating. Besides, oxidation resistance of the VPS-MoSi₂ coating was better than that of APS-MoSi₂ at 1500 °C.     

Preparation of nanostructured Gd2Zr2O7-LaPO4 thermal barrier coatings and their calcium-magnesium-alumina-silicate (CMAS) resistance

Nanostructured 30 mol% LaPO₄ doped Gd₂Zr₂O₇ (Gd₂Zr₂O₇-LaPO₄) thermal barrier coatings (TBCs) were produced by air plasma spraying (APS). The coatings consist of Gd₂Zr₂O₇ and LaPO₄ phases, with desirable chemical composition and obvious nanozones embedded in the coating microstructure. Calcium-magnesium-alumina- silicate (CMAS) corrosion tests were carried out at 1250 °C for 1–8 h to study the corrosion resistance of the coatings. Results indicated that the nanostructured Gd₂Zr₂O₇-LaPO₄ TBCs reveals high resistance to penetration by the CMAS melt. During corrosion tests, an impervious crystalline reaction layer consisting of Gd-La-P apatite, anorthite, spinel and tetragonal ZrO₂ phases forms on the coating surfaces. The layer is stable at high temperatures and has significant effect on preventing further infiltration of the molten CMAS into the coatings. Furthermore, the porous nanozones could gather the penetrated molten CMAS like as an absorbent, which benefits the CMAS resistance of the coatings.     

Electromagnetic wave reflection loss and magnetic properties of M-type SrFe12−x(Mn0.5Sn0.5)xO19 hexagonal ferrite nanoparticles in the Ku microwave band

Ferrimagnetic nanoparticles of SrFe_12−x(Mn_0.5Sn_0.5)_xO₁₉ was synthesis by controlling the effective processing parameters of sol-gel techniques. Microwave, magnetic properties and structure of nanosize, high purity sol-gel synthesized SrFe_12−x(Mn_0.5Sn_0.5)_xO₁₉ hexaferrite ferrimagnetic nanoparticles were investigated by vector network analysis, vibrating sample magnetometry, EDS and XRD. 57Fe Mössbauer spectroscopy was employed to find the occupancy sites of incorporated cations. The position of manganese and tin in 12k sites caused reduction in coercivity and magnetization saturation. The values of coercivity and magnetization saturation show that superparamagnetism did not occur in the synthesized products. Results demonstrate that additions of manganese and tin to hexagonal ferrite enhance bandwidth and reflection loss. Such composition could be proposed as a suitable electromagnetic wave absorber in microwave frequencies.     

Microwave absorption study of carbon nano tubes dispersed hard/soft ferrite nanocomposite

Nickel substituted strontium hexaferrite, SrNi₂Fe₁₀O₁₉·(SrFe₁₂O₁₉/NiFe₂O₄) nanoparticles have been synthesized by low combustion method by citrate precursors using sol to gel (S–G) followed by gel to nano crystalline (G–N) conversion. The resulting ‘as-synthesized’ powder is heat treated (HT) at 800 and 1000 °C for 4 h in nitrogen atmosphere. The hysteresis loops show an increase in saturation magnetization from 27.443 to 63.706 emu/g with increasing HT temperatures. The multiwalled carbon nano tubes (CNTs) were synthesized by thermal decomposition of acetylene gas over iron-catalyst deposited on silicon wafer in the temperature range of 750–800 °C. A microwave absorbing medium is prepared by adding CNTs in the nickel substituted strontium hexaferrite nanoparticles. Addition of certain mass of CNTs improves the microwave absorption properties and wave band of SrFe₁₂O₁₉/NiFe₂O₄ absorbent. When 10 wt% CNTs is mixed with SrFe₁₂O₁₉/NiFe₂O₄ nanoparticles to fabricate a composite with 2 mm thickness, the maximum reflection loss reaches to ?36.817 dB at 9.292 GHz and ?10 dB bandwidth reaches 3.27 GHz.     

Study on the formation process of Al2O3-TiO2 composite powders

Fine particles of anatase were suspended in solutions of ammonium alum with Al₂O₃/TiO₂ molar ratios from 0.1:1 to 7:1. By spray drying the suspensions and calcining the spray-dried powders, Al₂O₃-TiO₂ composite particles were obtained. The results show that after the spray drying, coatings of ammomium alum are formed on the surface of the anatase particles, leading to composite precursor powders (CCPs) with larger particle sizes. Upon calcining the CCPs, ammomium alum pyrolyzes to amorphous Al₂O₃ and anatase transforms into rutile. Both are mainly responsible for the observed particle size reductions as well as the densification of each composite particle. The in-situ formed α-Al₂O₃ and rutile may have higher reactivities, forming aluminum titanate at 1150 °C, about 130 °C lower than the theoretical temperature for the formation of Al₂TiO₅ by solid reaction. The reaction between α-Al₂O₃ and rutile starts from the interface between the anatase and the alum coating and mainly takes place in the single particles formed by spray drying. The molar ratio of Al₂O₃ to TiO₂ influences the final crystalline phases in the composite powders, but not stoichiometrically.     

Microstructure and electrical properties of plasma sprayed Gd0.15Ce0.85O2-δ coatings from solution combustion synthesized flowable powders

Powders of Gadolinia doped Ceria (Gd_0.15Ce_0.85O_2-δ (GDC)), a promising electrolyte material for intermediate temperature solid oxide fuel cell has been prepared by solution combustion (SC) synthesis. Variation of fuel to oxidizer ratio in the synthesis results in the GDC powder with varied powder characteristics. Fuel deficient combustion reaction results in GDC powder with smaller crystallites size but with larger agglomerates; whereas reaction with near stochiometric amount of fuel leads to the GDC powder with larger crystallite size and smaller agglomerates. Powders with large agglomerates possess required particle size, shape and flowability characteristics appropriate for plasma spraying. Electrolyte coatings fabricated from the synthesized plasma spray grade powders exhibit superior inter splat adhesion and conductivity (∼0.02 S/cm at 600 °C). Dense nature of the coating is ascribed to the complete melting of the porous GDC particles in the plasma flame. Powders prepared with stochiometric fuel are suitable for tape casting process.     

Gradient MoSi2-borosilicate glass high emissivity coating with enhanced contact and impact damage resistance

High emissivity coatings on fibrous insulation tiles played an important role in thermal protection systems and thereby intrigued many researchers; however, there was little emphasis on the mechanical properties of the coatings. In this study, a gradient MoSi₂-borosilicate glass coating with a dense surface layer and a porous interlayer was designed for mullite fibrous ceramics. Mechanical properties and structure parameters of the coating layers and the substrate were studied. The gradient coating was compared with a monolayer dense coating of the same composition and same surface density in contact damage resistance, impact resistance and emissivity. Compared with monolayer dense coating coated substrates, the gradient coating coated ones exhibited two times higher load bearing capacity in Hertzian indentation test at the same displacement of 1?mm; they appeared to be stiffer and harder at constant load of 20?N, and showed better impact resistance at impact energy range of 0.25–0.75?J in the falling weight test; besides, fatal radial cracks were not observed in gradient coatings after the tests. In addition, the gradient coating had higher emissivity (0.838) than the monolayer dense coating (0.816) because of the significant absorptivity increase and reflectivity decrease by small gradual slopes in the rough surface.     

Yb2O3 and Gd2O3 doped strontium zirconate for thermal barrier coatings

Yb₂O₃ (10 mol%) and Gd₂O₃ (20 mol%) doped SrZrO₃ was investigated as a material for thermal barrier coating (TBC) applications. The thermal expansion coefficients (TECs) of sintered bulk Sr(Zr_0.9Yb_0.1)O_2.95 and Sr(Zr_0.8Gd_0.2)O_2.9 were recorded by a high-temperature dilatometer and revealed a positive influence on phase transformations of SrZrO₃ by doping Yb₂O₃ or Gd₂O₃. The results for the thermal conductivities of Sr(Zr_0.9Yb_0.1)O_2.95 and Sr(Zr_0.8Gd_0.2)O_2.9 indicated that both dopants can reduce the thermal conductivity of SrZrO₃. Mechanical properties (Young's modulus, hardness, and fracture toughness) of dense Sr(Zr_0.9Yb_0.1)O_2.95 and Sr(Zr_0.8Gd_0.2)O_2.9 showed lower Young's modulus, hardness and comparable fracture toughness with respect to YSZ. The cycling lifetimes of Sr(Zr_0.9Yb_0.1)O_2.95/YSZ and Sr(Zr_0.8Gd_0.2)O_2.9/YSZ double layer coatings (DLC), which were prepared by plasma spraying, were comparable to that of YSZ at operating temperatures <1300 °C. However, the cycling lifetime of Sr(Zr_0.9Yb_0.1)O_2.95/YSZ DLC was 25% longer, whereas Sr(Zr_0.8Gd_0.2)O_2.9/YSZ DLC had a shorter lifetime compared to the optimized YSZ coating at operating temperatures >1300 °C.     

Correlation between microstructure,chemical components and tribological properties of plasma-sprayed Cr2O3-based coatings

The wear resistance of chromium oxide (Cr₂O₃) coatings could be improved by doping modification and changing the structural scale, etc. In this study, micrometric Cr₂O₃ coatings were doped with different additives, CeO₂ and Nb₂O₅. Moreover, Cr₂O₃ coatings were deposited from nanostructured feedstock by the combination process of plasma spraying and dry-ice blasting. The correlation between the microstructure, chemical components and tribological properties of plasma-sprayed Cr₂O₃-based coatings was discussed based on the investigation of their porosity, hardness and friction behaviors. The results showed that the composite coatings doped with additives exhibited a higher microhardness, corresponding to a lower porosity than pure Cr₂O₃ coating under the identical plasma-spray condition. CeO₂ constituent was found to improve the wear resistance of Cr₂O₃ coating while Nb₂O₅ incorporation corresponds to a steep rise in the friction coefficient. The mismatch of coefficient of thermal expansion (CTE) between Cr₂O₃ and Nb₂O₅ lamellae facilitated the origin of fatigue cracks and the formation of microfracture pits. Although the combination process promotes a porosity reduction, the nanostructured Cr₂O₃ (n-Cr₂O₃) coatings present a lower microhardness than micrometric coatings, due to their loosen microstructure from insufficient plasma power compared to microscaled coatings. The wear mechanisms of both the micro- and nanometric Cr₂O₃ coatings are fatigue cracks and material transfer.     

Effect of powder particle size on vibration damping behaviour of plasma sprayed alumina (Al2O3) coating on AISI 304 stainless steel substrate

The damping capacity of plasma sprayed alumina (Al₂O₃) coatings on AISI 304 stainless steel was investigated in this study as a function of particle size of the starting alumina powder. The coatings were prepared from different sizes alumina powder using commercial air plasma spraying (APS) technique. The damping properties of coated samples were characterized by damping capacity (Q^?1) measured experimentally using dynamic mechanical analyzer (DMA). The surface morphology of the coatings was studied using scanning electron microscope (SEM). The results revealed that the coating was porous and was able to improve the damping capacity of bare substrate. It was also observed that the powder particle size had a significant effect on the damping characteristics of the coatings. The damping values were found to be increased with the increase in particle size in the measured strain range. This behaviour was correlated with the microstructure investigated by SEM.     

Preparation of barium hexaferrite coatings using atmospheric plasma spraying

Thick coatings of barium hexaferrite with the compositions BaFe₁₂O₁₉ and BaCoTiFe₁₀O₁₉ were prepared using atmospheric plasma spraying (APS) technology. The coatings were prepared from pre-reacted powders of the desired composition. The as-deposited coatings were poorly crystallized, but their crystallinity was improved with a subsequent annealing. The crystallization mechanism of the sprayed hexaferrites was studied during annealing up to 1300 °C, using X-ray powder diffraction combined with thermal analysis and with electron microscopy including microanalysis. Single-phase coatings were obtained after annealing treatments at 1100–1300 °C. Their magnetic properties showed that they would be suitable for absorbers at microwave and mm-wave frequencies, depending on the coating phase's composition, the crystallinity and the thicknesses.     

Influence of Ca/Al ratio on physical and dielectric properties of Al2O3/CaO-B2O3-SiO2 glass-ceramics composite coatings prepared by high enthalpy atmospheric plasma spraying

The dielectric layer plays a key role in regulating electromagnetic wave broadband scattering based on meta-surface technology. Herein, the physical properties of composite powder, prepared by spray drying of CaO-B₂O₃-SiO₂ (CBS) glass-ceramic powder and Al₂O₃ in different mass ratios, are systematically investigated. Meanwhile, a high enthalpy atmospheric plasma spraying equipment is utilized to prepare CBS/Al₂O₃ composite coatings, and the morphology, physical properties and dielectric properties of the composite coating are analyzed. The XRD and DSC data of the composite coating reveal that the crystallization behavior of β-CaSiO₃ and CaB₂O₄ gradually disappear with the increase of Al₂O₃ content. Hence, only CaAl₂Si₂O₈ phase is observed during heat treatment. The experimental results confirm that the dielectric properties of CBS/Al₂O₃ composite coating conform to the rule of mixture for composite materials. Also, the dielectric properties are affected by porosity and crystallization rate.     

Preparation of plasma sprayed nanostructured GdPO4 thermal barrier coating and its hot corrosion behavior in molten salts

Nanostructured GdPO₄ coatings, designed as the outer layer of double-ceramic-layer thermal barrier coatings (DCL-TBCs), were produced by air plasma spraying (APS). The coatings have close chemical composition to that of the agglomerated particles used for thermal spray. Nanozones with porous structure are embedded in the coating microstructure, having a percentage of ~30%. Hot corrosion tests of the coatings were carried out in V₂O₅ and Na₂SO₄+V₂O₅ salts at 900 °C for 4 h. Results indicate that dense reaction layers, consisting of GdVO₄ and Gd₄(P₂O₇)₃, form on the coating surfaces, which could suppress further penetration of the molten salts. In the V₂O₅ molten salt, the reaction layer is thicker and less molten salt trace could be found beneath the layer.     

Infrared radiative performance and anti-ablation behaviour of Sm2O3 modified ZrB2/SiC coatings

To improve the emissivity of ZrB₂/SiC coatings for serving in more serious environment, ZrB₂/SiC coatings with varying contents of high emissivity Sm₂O₃ were fabricated using atmospheric plasma spraying. The microstructure, infrared radiative performance and anti-ablation behaviour of the modified coatings were investigated. The results showed that as the content of Sm₂O₃ increased, the density of the coatings increased because of the low melting point of Sm₂O₃. When the content of Sm₂O₃ was 10 vol%, the coating had the highest emissivity in the 2.5–5 μm band at 1000 °C, up to 0.85, because of the oxygen vacancies promoting additional electronic transitions. Due to the high emissivity, the surface temperature of the coating modified with 10 vol% Sm₂O₃ decreased by 300 °C, which led to little volatilisation of the sealing phase. Further, the mass ablation ratio of the above coating was 3.19 × 10^?4 g/s, decreasing 31% compared to that of a ZrB₂/SiC coating. The formed dense surface structure of the coatings showed considerable oxygen obstructive effects. These findings indicate that the modified coatings show considerable anti-ablation performance, which provides effective anti-ablation protection for the C/C composite substrate.