Comprehensive study on corrosion protection properties of Al2O3, Cr2O3 and Al2O3–Cr2O3 ceramic coatings deposited by plasma spraying on carbon steel

In this study, individual Al₂O₃ and Cr₂O₃ coatings and Cr₂O₃-25, 50, 75 wt% Al₂O₃ composite coatings were applied on carbon steel by atmospheric plasma spraying method. Corrosion experiments were performed on as-sprayed and epoxy resin sealed coatings including potentiodynamic polarization, electrochemical impedance spectroscopy and long-term immersion in 3.5 wt% NaCl solution. Phase composition and microstructure of the coatings were investigated by x-ray diffraction, optical microscopy and scanning electron microscopy, before and after the corrosion experiment. The results showed that the Cr₂O₃ coating exhibited the best corrosion resistance, due to the densest microstructure and highest adhesion strength. The Cr₂O₃-25 wt% Al₂O₃ coating had the highest interconnected porosities and thus had the least corrosion resistance compared to other coatings. In general, the as-sprayed coatings induced a maximum increase of 3.93 times the polarization resistance (R_p) in the polarization experiment and a 3.5 times increase in the charge transfer resistance (R_ct) in the EIS experiment, which was not significant. Stresses caused by increased volume of corrosion products in the coating-substrate interface resulted in the spallation of Cr₂O₃-25, 50 wt% Al₂O₃ coatings from the substrate over long-term of immersion. The adhesion strength of the coatings was a determining criterion for the long-term durability of the coatings. The sealing treatment resulted in a significant increase in R_p and R_ct.     

The tribological and electrochemical behavior of HVOF-sprayed Cr3C2–NiCr ceramic coating on carbon steel

High Velocity Oxygen Fuel (HVOF) is an excellent approach to prepare a good, wear-resistant lamella of Chromium Carbide-Nickel Chrome (Cr₃C₂–NiCr) on carbon steel for high temperature application. This research investigates the effect of a thin, deposited layer of Cr₃C₂-NiCr on carbon steel in terms of wear and corrosion properties. The microstructure of the HVOF-sprayed Cr₃C₂–NiCr coating was characterized at each step by scanning electron microscopy. Wear testing was performed with a pin-on-disk tester. Wear weight loss was examined by applying different loads over a 9048.96 m sliding distance. Experimental results show that the wear resistance of the coated sample reduced the risk of seizure compared to the uncoated sample. An electrochemical test was also performed and the behavior of the substrate in the coated sample was investigated in 3.5% NaCl for 27 days. Electrochemical Impedance Spectroscopy (EIS) showed that the HVOF coating has high corrosion resistance and protects the substrate from NaCl electrolyte penetration. So deposition this layer of ceramic composite is protected oil piping from synergistic attack of seawater during the transport of crude oil to the refinery.     

Corrosion performance of Al–Al_2O_3 cold sprayed coatings on mild carbon steel pipe under thermal insulation

This paper focused on the corrosion resistance of cold spray Al–Al_2O_3composite coatings used on carbon steel pipe surfaces under thermal insulation. Al–Al_2O_3coatings were produced on the carbon steel pipe surface by cold spray(CS) technology. Experimental apparatus was built to test the corrosion resistance of coatings beneath mineral wool insulation under isothermal, thermal cycling and wet/dry conditions. The results showed that when α-Al_2O_3 was added in spraying powder, the coating could obtain higher hardness and a denser microstructure. From corrosionunder-insulation(CUI) tests, Al–Al_2O_3CS coatings were proven to be efficient in protecting carbon steel pipe from CUI mainly owning to lamellar microstructures of coatings. There was no evidence to show that α-Al_2O_3 might bring any negative effect on corrosion resistance. Al–Al_2O_3CS coatings were sensitive to the chloride ion concentration. When these coatings were exposed to higher concentrations of NaC l, the coating's exhibited faster degradation.     

Development and evaluation of Al2O3–ZrO2 composite processed by digital light 3D printing

Digital Light Processing (DLP) is a promising approach to fabricate delicate ceramic components with high-fidelity structural features. In this work, the alumina and zirconia/alumina ceramic suspensions with low viscosity and high solid loading (40 vol%) were prepared specifically for DLP 3D printing. After debinding and sintering, the final parts were obtained without any defects. The surface morphologies and mechanical properties of alumina (Al₂O₃) and zirconia toughened alumina (ZTA) composites were investigated and the results showed that the final parts exhibited high relative densities and good interlayer combination at the sintering temperature of 1600 °C. Comparing with the Al₂O₃, the ZTA composites exhibited significantly enhanced density (99.4%), bending strength (516.7 MPa) and indentation fracture toughness (7.76 MPa m^1/2).     

Multilayered polypyrrole–SiO2 composite coatings for functionalization of stainless steel: Characterization and corrosion protection behavior

Two different multilayered composite polypyrrole/SiO₂ coatings were synthesized on 304 stainless steel. Electrochemical and electrophoretic depositions were used to grow polypyrrole and SiO₂ layers, respectively. Coatings were characterized by glow discharge optical emission spectroscopy to observe repartition of elements within different layers, by scanning electron microscopy to observe surface morphology and by electrochemistry to investigate corrosion protection behavior. The electrophoretic approach enables good incorporation of SiO₂ particles. This incorporation was more extensive and more homogeneous than for coatings obtained with the mixing method related in previous works. Moreover, incorporation and repartition of SiO₂ particles are greatly enhanced when the silica layer is grown directly on the steel surface. Corrosion protection of the stainless steel substrate was improved when multilayered composite polypyrrole/SiO₂ coatings were used.     

Effects of air annealing treatments on the microstructure,components, and mechanical properties of magnetron sputtered Al2O3–Cr2O3–ZrO2 composite coatings

To investigate the effects of air annealing on the microstructure, components, and mechanical properties of ceramic composite coatings, Al₂O₃–Cr₂O₃–ZrO₂ composite coatings were prepared on silicon substrate using radio frequency magnetron sputtering at room temperature, and then air-annealed in a temperature range of 450–850 °C for 30 min. The results indicated that the phase-structure and superficial characteristics, including morphology and surface roughness, were not visibly altered in the annealed coatings up to 600 °C; the elemental component distributions remained uniform. The improvement in the mechanical properties was attributed to the growth of oxide grains. There were no significant changes in the components of Al, Cr, Zr, and O in the annealed coatings. However, an increase in the Cr component and a decrease in the Zr component occurred on the coating surface; the overall structure of the composite coatings possessed a favorable heat resistance. Upon annealing at 750 °C, the thermally-driven formation of uniform and refined nanoparticles on the coating surface was responsible for the effective enhancement of the mechanical properties. Furthermore, annealing at 850 °C induced the enlargement of the precipitated Cr₂O₃ nanoparticles and the generation of micro-defects, resulting in a drastic morphological evolution, an evident increase in the surface roughness, and a significant decrease in the mechanical properties. This study provides new perspectives on designing novel thermal barrier coatings and understanding the role of high temperature air annealing on the microstructural transformation.     

Preparation and thermal stability investigation of Al2O3–mullite–ZrO2–SiC composite ceramics for solar thermal transmission pipelines

To obtain composite ceramics with excellent thermal shock resistance and satisfactory high?temperature service performance for solar thermal transmission pipelines, SiC additive was incorporated into Al₂O₃?mullite?ZrO₂ composite ceramics through a pressureless sintering process. The effect of the SiC additive on thermal shock resistance was studied. Also, the variations in the microstructure and physical properties during thermal cycles at 1300 °C were discussed. The results showed that both thermal shock resistance and thermal cycling performance could be improved by adding 20 wt% SiC. In particular, the sample with 50 wt% Al₂O₃, 35 wt% Coal Series Kaolin (CSK), 15 wt% partially yttria?stabilized zirconia (PSZ), and 20 wt% SiC additional (denoted as sample A2) exhibited the best overall performance after firing at 1600 °C. Furthermore, the bending strength of sample A2 increased to 124.58 MPa, with an increasing rate of 13.63% after 30 thermal shock cycles. The increase in thermal conductivity and the formation of mullite were the factors behind the enhancement of thermal shock resistance. During the thermal cycles, the oxidation of SiC particles was favorable as it increased the microstructure densification and also facilitated the generation of mullite, which endowed the composite ceramics with a self?reinforcing performance.     

A new ternary phase in the system CaO–Al2O3–Cr2O3: Crystal structure and thermal expansion of CaAl2Cr2O7

Polycrystalline material of a novel phase in the system CaO–Al₂O₃–Cr₂O₃ has been obtained by solid-state reactions. Chemical analysis indicated the composition CaAl₂Cr₂O₇. Single-crystal growth of the new compound using borax as a mineralizer was successful. Diffraction experiments at ambient conditions on a crystal with composition CaAl_2.13Cr_1.87O₇ yielded the following basic crystallographic data: space group P 3, a = 7.7690(5) Å, c = 7.6463(5) Å, V = 399.68(6) ų, Z = 3. Structure determination and subsequent least-squares refinements resulted in a residual of R(|F|) = 2.3% for 1440 independent observed reflections and 113 parameters. To the best of our knowledge, the structure of CaAl_2.13Cr_1.87O₇ or CaAl₂Cr₂O₇ represents a new structure type. It belongs to the group of double layer structures where individual double layers contain octahedrally and tetrahedrally coordinated cation positions. Linkage between neighboring sheet packages is provided by additional calcium cations. Furthermore, thermal expansion has been studied in the interval between 29 and 790°C using in situ high-temperature single-crystal diffraction. No indications for a structural phase transition were observed. From the evolution of the lattice parameters the thermal expansion tensor has been obtained. A pronounced anisotropy is evident. The response of structural building units to variable temperature has been discussed.     

Structure and surface properties of Al2O3–TiO2 ceramic coated AZ31 magnesium alloy

Magnesium and its alloys are the engineering materials which have the potential ability to be able to used widely particularly in the automotive, aerospace and in the biomedical sectors, especially thanks to their features such as lightness, specific strength that they have and biocompatibility. However, due to their poor wear resistance and corrosion resistance, the areas of usage are being restricted. This situation prevents Mg alloys to be used without any surface protection despite their good mechanical properties such as high strength/weight ratio. In this study, plasma spraying method is used to improve the poor corrosion resistance of AZ31 Mg alloy. Al₂O₃–13 wt% TiO₂ (AT13) and Al₂O₃–40 wt% TiO₂ (AT40) composite ceramic coatings were coated successfully on the surfaces of AZ31 Mg samples. The wear properties of the AT13 and AT40 coated samples were investigated for tribological applications. Surface morphology and microstructure of the duplex treated samples were analyzed by scanning electron microscopy (SEM) and X-ray diffraction (XRD). The microhardness value of the uncoated AZ31 Mg alloy is 40±3 HV_0.1, while the microhardness values of the AT40 and AT13 coatings are enhanced to 800±39 HV_0.1 and 1500±35 HV_0.1, respectively.     

Preparation of multilayered C–Si–Al2O3 coatings on continuous carbon fibers and C–Si–Al2O3-coated carbon-fiber-reinforced hydroxyapatite composites

Multilayered C–Si–Al coatings with various morphologies were deposited on carbon fibers (CFs) using magnetron sputtering. The thickness of the coatings was increased from 0.5 to 1.5 μm by magnetron sputtering between 90 and 120 min. C–Si–Al coatings of suitable thickness were heat-treated at 600 °C and transformed into C–Si–Al₂O₃ coatings by one-step anodic oxidation (AO). The oxidation time for the one/two-step anodic oxidation and the ratio of oxidation time for the two-step anodic oxidation significantly influenced the morphologies of the C–Si–Al₂O₃(AO) coatings. Al₂O₃ coatings with satisfactory morphologies and structures were prepared by two-step anodic oxidation with a total time of 30 min and a ratio of 1:1 between the initial and secondary oxidation times. The multilayered C–Si–Al₂O₃(AO) coatings were modified to C–Si–Al₂O₃ coatings by secondary heat treatment at 1050 °C. Subsequently, hot-press sintering was used to prepare CFs with multilayered C–Si–Al₂O₃ coating-reinforced hydroxyapatite (CF/C–Si–Al₂O₃/HA) composites. The multilayered C–Si–Al₂O₃-coated CFs demonstrated good resistance to oxidation and thermal shock. This could effectively protect CFs from oxidative damage and maintain its strengthening effect during sintering. The multilayered C, Si, and Al₂O₃ coatings effectively reduced the difference between the coefficient of thermal expansion of the CFs and HA matrixes. The interfacial gaps between the multilayered coatings and HA were reduced. This could enhance the mechanical performance of the composites. The CF/C–Si–Al₂O₃/HA composites exhibited improved mechanical properties with a bending strength of 83.94 ± 12.29 MPa, and fracture toughness of 2.45 ± 0.08 MPa m^1/2. This study can broaden the application of CF/C–Si–Al₂O₃/HA biocomposites as bone-repair materials and help obtain CF-reinforced composites with excellent mechanical properties that are fabricated or serviced at high temperatures.     

Oxidation-induced crack healing and erosion life assessment of Ni–Mo–Al–Cr7C3–Al2O3 composite coating

The present investigation focuses on the effect of Cr₂AlC MAX phase addition on erosion and oxidation-induced crack healing behavior of Ni–Mo–Al alloy. For this, Ni–Mo–Al and 20 wt% Cr₂AlC-blended Ni–Mo–Al powders were coated by Air Plasma Spray (APS). For oxidation-induced crack healing studies, the samples were heat treated at 500, 800, and 1100°C in the air for 5 hours. The heat-treated samples were analyzed by X-Ray Diffraction (XRD) analysis, Scanning Electron Microscopy (SEM), and Energy Dispersive Spectroscopy (EDS) for the phases, morphology, and composition. Erosion behavior studies were carried out at 30, 250, 500, 800, and 1000°C temperatures. The average hardness was obtained to be 400 ± 10 HV for Ni–Mo–Al coating and 580 ± 10 HV for 20 wt% Cr₂AlC-blended Ni–Mo–Al coating. The addition of Cr₂AlC MAX into Ni–Mo–Al matrix reduces the overall erosion rate and improved the crack healing ability. This was attributed to the presence of in-situ-formed Cr₇C₃ and Al₂O₃ phases.     

Influence of layer number and sintering temperature on microstructural,tribological, and corrosion behavior of Al2O3–TiO2 multilayer coatings

The effects of layer number (2, 4, and 6-layer) and sintering temperature (800, 900, 1000, and 1100 °C) on the microstructure, wear, and corrosion properties of Al₂O₃–TiO₂ multilayer coatings deposited on 316L stainless steel plates using the sol-gel dip coating technique were investigated. The wear characteristics were measured through ball-on-disc type dry sliding tests using an Al₂O₃ ball under a 1 N load, whereas the corrosion features were determined by potentiodynamic polarization tests conducted in a 3.5 wt% NaCl solution. Anatase, rutile, α-Al₂O₃, and γ-Al₂O₃ phases were obtained in the hybrid coatings, depending on the sintering temperatures. However, at 1100 °C, the coating did not adhere well to the substrate due to passive oxide film formation on the 316L plate, leading to spalling. Besides, the surface homogeneity deteriorated in the 6-layer coated sample due to higher organic removal and residual stresses. The corrosion rate decreased with the increasing number of layers, but the sensitivity to corrosion varied due to changes in surface properties. The 4-layer coated sample sintered at 1000 °C achieved the highest wear strength (improved by up to 71.1%) and corrosion resistance (increased by up to 90.4%) due to its decreased porosity and homogeneously distributed finer particles.     

Long-sized rods of Al2O3–SiC–TiB2 ceramic composite material obtained by SHS-extrusion: Microstructure,X-ray analysis and properties

Long-sized rods of Al₂O₃–SiC–TiB₂ ceramic composite material were obtained by SHS-extrusion. The material was synthesized by self-propagating high-temperature synthesis (SHS) followed by high-temperature shear deformation. Ceramic samples app up to 465 mm in length and 5 mm in diameter were obtained. According to the results of XRD and SEM the obtained rods have a composite structure. The matrix is Al₂O₃ with distributed titanium diboride and silicon carbide particles. A uniform phase distribution was observed along the entire length of the rod. The microhardness of the matrix was 25–26 GPa, that of the dispersion-strengthening phases - 32–34 GPa. Heat resistance tests showed that during heat treatment at T = 1000 °C for 21 h, the sample specific weight gain and its real rate were 8.3 g/m² and 1 g/(m²∙h), respectively. The density, hardness and electrical resistivity of the samples obtained in this work were 3.27 g/cm³, 19.5 GPa, 3.1∙10⁻⁵ Ohm∙m, respectively.     

Development of novel temperature-stable Al2O3–TiO2-based dielectric ceramics featuring superior thermal conductivity for LTCC applications

A new composition was developed using sintering to improve the dielectric properties of low-temperature co-fired alumina (LTCA) containing CuO–TiO₂–Nb₂O₅–Ag₂O. By substituting some alumina with rutile TiO₂, the second-phase compound could be changed from AgNbO₃ to the rutile phase. Further, low-temperature sintering at temperatures below 960 °C was possible, suppressing Al₂TiO₅ formation during firing. The dielectric characteristics, particularly the temperature coefficient of the resonant frequency (τ_f) and Q × f values, were improved without significantly reducing the sinterability and thermal conductivity. The dielectric properties of the developed 88Al₂O₃–12TiO₂-based ceramic were ε_r: 14.7, τ_f: +0.8 ppm/K, and Q × f: 13,383 GHz (at ～10 GHz) at a firing temperature of 940 °C. The thermal conductivity was 18.5 W/mK, which is the highest value for reported temperature-stable low-temperature co-fired ceramics (LTCCs). These results provide one of the key technologies for the practical application of LTCCs with superior thermal conductivities.     

An evaluation of plasma-sprayed coatings based on Al2O3 and Al2O3–13 wt.% TiO2 with bond coat on pure titanium substrate

In this study, the effects of bond coat on the properties of Al₂O₃ and Al₂O₃–13 wt.% TiO₂ coatings, which is plasma sprayed onto a commercial pure titanium substrate with and without Ni–5 wt.% Al (METCO 450 NS) as bond coating layer were investigated in terms of microhardness, bonding strength and surface roughness. Optical and scanning electron microscopy (SEM) examinations revealed that there is a uniform coating layer with no spalling and delamination. However, there is a little amount of porosity. The results indicated that the application of bond coat layer in the plasma spraying of Al₂O₃ and Al₂O₃–13 wt.% TiO₂ on pure titanium substrate has increased the hardness and bonding strength of coatings. While the adhesive bonding is dominant without bond coat, the cohesive bonding is dominant with the application of the bond coating layer. It has been observed that percentage of cohesion strength was about three times higher than that of adhesion strength.     

TiO2–ZnO/Ni–5wt.%Al composite coatings on GH4169 superalloys by atmospheric plasma spray techniques and theirs elevated-temperature tribological behavior

Ni–based composite coatings with different amounts of TiO₂–ZnO were fabricated by atmospheric plasma spraying (APS) to protect GH4169 superalloy substrates against excess wear and friction at elevated temperatures. In addition, the influence of the simultaneous addition of the oxides on the microstructure, microhardness, and wear behaviour was investigated. According to the results, the simultaneous addition of TiO₂/ZnO provides anti-friction and wear inhibition over 600 °C. In particular at 800 °C, the TiO₂–ZnO/Ni–5wt.%Al composite coating (10 wt% TiO₂ and 10 wt% ZnO were incorporated within Ni–5wt.%Al matrix) exhibits a superior lubricity and wear resistance compared to the Ni–5wt.%Al based coatings. The XRD, Raman, and TEM characterisations reveal the formation of a glaze oxide layer consisting of NiO, TiO₂, ZnO and the in-situ production of ternary oxide (Zn₂TiO₄), which was primarily responsible for the tribological performance of the sliding wear contacts at the specific temperature.     

Determination of surface area and porosity of sol–gel derived ceramic powders in the system TiO2–SiO2–Al2O3

The surface characteristics of ternary ceramic powders in the system TiO₂–SiO₂–Al₂O₃ prepared by a sol–gel technique were studied through nitrogen gas adsorption at liquid nitrogen temperature and application of the Brunauer–Emmett–Teller (BET) equation. The total surface area, total pore volume and pore radius of the powders were calculated through the construction of plots relating the amount of nitrogen gas adsorbed V₁ and the thickness of the adsorbed layer t (V₁−t plots). These results permitted the detection of the different types of pores present in the samples. In a first approximation, the V₁−t plots seem to demonstrate the correctness of the results obtained for the total specific area of the investigated samples. The influence of thermal treatment (drying, calcination) on the surface characteristics of the investigated powders was assessed.     

Low thermal expansion behavior and thermal durability of ZrTiO4–Al2TiO5–Fe2O3 ceramics between 750 and 1400 °C

The thermal-shock-resistant materials in the system Al₂TiO₅–ZrTiO₄ (ZAT) were synthesized by oxide process. The range of ZAT compositions investigated had showed very low thermal expansions of 0.3∼1.3×10⁻⁶/K compared to 8.29×10⁻⁶/K of pure ZrTiO₄ and 0.68×10⁻⁶/K of polycrystalline Al₂TiO₅, respectively, compared with the theoretical thermal expansion coefficient for a single crystal of Al₂TiO₅, 9.70×10⁻⁶/K. The composites also had high thermal durability between 750 and 1400° for 100 h. The low thermal expansion and high thermal durability are apparently due to a combination of microcracking caused by the large thermal expansion anisotropy of the crystal axes of the Al₂TiO₅ phase and the limitation of grain growth Al₂TiO₅ by the ZrTiO₄. The microstructural degradation of the composites is presented here analyzed by scanning electron microscopy, X-ray diffraction, and dilatometry.