Comparison of the anti-coking performance of CVD TiN,TiO2 and TiC coatings for hydrocarbon fuel pyrolysis

Previous work has shown that both TiN and TiO₂ coatings can inhibit the metallic catalytic coking effectively, but both of them have their own shortage. In this work, TiC coating was prepared on the surface of SS304 tube using TiCl₄-CH₄-H₂ by CVD method. Its morphology, elemental composition, thickness and oxidation resistance were characterized by SEM, EDX, metalloscopy and TPO tests, respectively. The results show that CVD TiC coating is gray, homogeneous, and dense without cracks or holes. The TiC coating presents a cuboid particle structure with the sizes of about 1.0 µm for the cuboid crystals, and the Ti/C ratio close to 1:1, while the average thickness is about 11.62 µm. TPO results show that the TiC coating begins to react with O₂ and release CO₂ at about 810 °C. Compared with the TiN coating (The initial oxidation temperature of TiN is about 350 °C), the oxidation resistance of TiC coating is improved substantially. As a conclusion, the high oxidation resistance order is TiO₂ coating>TiC coating>TiN coating. Furthermore, the temperature programmed cracking of RP-3 Chinese jet fuel was employed to compare the anti-coking performance of TiN, TiO₂ and TiC coatings. The results show that each of TiN, TiO₂ and TiC coating has obvious anti-coking effect, and the anti-coking performance order is TiN coating=TiC coating>TiO₂ coating.     

Preparation of a thick NiAl/Al2O3 coating by embedding method and its corrosion resistance under supercritical water environment

One of the critical issues in the application of supercritical water oxidation technology is to improve the corrosion resistance of reactor materials. Use of Al₂O₃ coating is one of the most promising methods to address this issue. In this study, thick NiAl/Al₂O₃ coatings on Inconel 625 substrates were prepared by a consecutive pack embedding and in-situ thermal oxidation process. The effect of aluminizing and oxidation temperature on phase structure and coating thickness is studied. Results show the diffusion of Al from the exterior to the interior of the alloy matrix to form intermetallic compounds between Al and metal elements in the matrix (Ni, Cr, Mo, etc.). Moreover, the coating thickness can reach above 300 μm at the aluminizing temperature of 950 °C. Increasing the aluminizing temperature above 950 °C will not increase the coating thickness further. After high temperature oxidation subsequently, only phases of NiAl and Al₂O₃ were detected. The formation of Al₂O₃ layer can be ascribed to the surface oxidization of Al. And the NiAl between the alloy substrate and Al₂O₃ coating provides an interfacial layer that can alleviate the crack or exfoliation of ceramic coating due to the mismatching of thermal expand coefficient. The thick NiAl/Al₂O₃ coatings prepared by aluminizing 950 °C and oxidizing at 1100 °C exhibit satisfied corrosion resistance after supercritical water test. This work would provide a significant method to develop advanced ceramics coating for the corrosion resistance of alloys.     

Al2O3/CrAlSiN multilayer coating deposited using hybrid magnetron sputtering and atomic layer deposition

In this study, Al₂O₃/CrAlSiN multilayer coatings with various periods were prepared using a hybrid process involving overlapping magnetron sputtering of CrAlSiN and atomic layer deposition (ALD) of Al₂O₃. The influence of the number of Al₂O₃ layers on the mechanical properties, corrosion behavior and oxidation characteristics of the coatings was studied using nano/micro indentation, electrochemical corrosion, and high temperature static oxidation tests. The results show that the multilayer structure can effectively prevent crack propagation during the coating and subsequently increase the coating toughness. A substantial improvement in the resistance to electrochemical and oxidation corrosion was observed in the Al₂O₃/CrAlSiN multilayer coatings and increasing the number of Al₂O₃ layers dramatically increases the corrosion durability. The Al₂O₃ ALD layers are expected to inhibit the diffusion of corrosive substances such as ions and oxygen and the increase of the Al₂O₃ layer number decreases the diffusion fluxes of the coating elements to the surface and limit the oxide growth, resulting in the evolution of the oxidation produces from irregular particles to nano-walls/fibers. It is supposed that the PVD/ALD hybrid process may open a new hard coating design concept by providing a superior toughness and corrosion/oxidation resistance.     

The influence of multilayer structure on mechanical behavior of TiN/TiAlSiN multilayer coating

Nitride coatings have been generally applied on light alloys like titanium and aluminium to promote their multiple performances, including hardness, thermal stability and wear resistance. In this work, TiAlSiN/TiN multilayered (ML) coating and TiAlSiN single-layer (SL) coating were deposited on TC18 (Ti5Al5Mo5V1CrFe) alloy by Multi-arc ion plating technique. The microstructure and chemical composition of the coatings were evaluated by SEM, XRD and XPS. Additionally, hardness, adhesion and wear resistance were measured through nanoindentation, scratch spectrometer and ball-on-disk tribometer. The results present that both ML and SL coating contain three main phases of TiN, Al₂O₃ and Si₃N₄. Nevertheless, the adhesion of ML coating is 62.4 N, compared to that of the SL coating is 51.8 N. The parameter H³/E² as an indication of plastic deformation to evaluate wear resistance shows that the ML coating has high hardness and high toughness concurrently. The tribological study indicated that the wear rate of the ML coated specimen was 1/7 of the SL coated counterpart.     

Tetrahedral amorphous carbon deposited with the pulsed plasma arc-discharge method as a protective coating against solid impingement erosion

The solid impingement erosion resistance of a tetrahedral amorphous carbon (ta-C) coating (sp³ bonding fraction ∼80%, thickness 20 μm) was compared to the erosion resistance of stainless steels, WC–Co hard metal, sintered SiC, sintered Al₂O₃, synthetic ruby (Al₂O₃, grain size of the order of mm) and a commercial TiN coating. The ta-C coating was deposited by the filtered pulsed plasma arc-discharge method on an AISI316L stainless steel sample. All other materials, except the ta-C and the TiN, were in a bulk form. The experiments revealed that the volume removal rate of bulk materials was 1.5–540 times higher than that of ta-C, depending on the material. The extensive chipping of TiN hindered a meaningful comparison of the measured results to those received from bulk materials. The erosion experiments were performed with a test apparatus, which used pressurized air to accelerate angular Al₂O₃ particles (60–77 μm in diameter). The erosion damage was analyzed with a surface profilometer and an optical microscope. The critical thickness for the coating that was able to resist catastrophic delamination under particle exposure, was found to be approximately 1 μm. The extremely low erosion rate of ta-C, when eroded with low values of angle of attack (∼20°), implies that ta-C erodes in a brittle manner.     

Sol–gel derived CeO2/α‐Al2O3 bilayer thin film as an anti‐coking barrier and its catalytic coke oxidation performance

A CeO₂/α‐Al₂O₃ bilayer was coated on a high temperature alloy (Incoloy 800H) by sol–gel dip‐coating and was evaluated for its potential as an anticoking barrier and coke oxidation catalyst. The bilayer effectively functioned as a barrier to metal surface catalyzed coking. The film prevented filamentous catalytic coking via blocking surface active metallic sites on the Incoloy substrate. Furthermore, the bilayer reduced the oxidation temperature of pyrolytic coke deposited on the film surface as compared to a bare oxidized Incoloy substrate, mostly owing to the oxidation catalytic activity of the CeO₂ layer. Finally, it is demonstrated that the presence of the α‐Al₂O₃ buffer layer is critically important to the overall performance. Without the α‐Al₂O₃ layer, a CeO₂ layer nearly completely lost both its barrier and oxidation catalytic functions. It is presumed that metallic species migrating from the substrate during high temperature treatments are responsible for the CeO₂ deactivation, likely by blocking catalytic sites on the CeO₂ surface. © 2018 American Institute of Chemical Engineers AIChE J, 64: 4019–4026, 2018     

Electrochemical corrosion and materials properties of reactively sputtered TiN/TiAlN multilayer coatings

TiN/TiAlN multilayers of 2 μm thickness were successfully prepared by reactive DC magnetron sputtering method. XRD pattern showed the (1 1 1) preferential orientation for both TiN and TiAlN layers. XPS characterization showed the presence of different phases like TiN, TiO₂, TiON, AlN and Al₂O₃. Cross sectional TEM indicated the columnar growth of the coatings. The average RMS roughness value of 4.8 nm was observed from AFM analysis. TiN/TiAlN coating showed lower friction coefficient and lower wear rate than single layer coatings. The results of electrochemical experiments indicated that a TiN/TiAlN multilayer coating has superior corrosion resistance in 3.5% NaCl solution.     

Composite Ni/Al2O3 coatings and their corrosion resistance

Composite coatings Ni/Al₂O₃ were electrochemically deposited from a Watts bath. Al₂O₃ powder with particle diameter below 1 μm was codeposited with the metal. The obtained Ni/Al₂O₃ coatings contained 5-6% by weight of corundum. The structure of the coatings was examined by scanning electron microscopy (SEM). It has been found that the codeposition of Al₂O₃ particles with nickel disturbs the nickel coating's regular surface structure, increasing its microcrystallinity and surface roughness. DC and AC electrochemical tests were carried out on such coatings in a 0.5 M solution of Na₂SO₄ in order to evaluate their corrosion resistance. The potentiodynamic tests showed that the corrosion resistance of composite coating Ni/Al₂O₃ is better than that of the standard nickel coating. After 14 days of exposure the nickel coating corrodes three times faster than the Ni/Al₂O₃ coating. The electrochemical behaviour of the coatings in the corrosive solution was investigated by electrochemical impedance spectroscopy (EIS). An equivalent circuit diagram consisting of two RC electric circuits: one for electrode, nickel corrosion processes and the other for processes causing coating surface blockage, were adopted for the analysis of the impedance spectra. The changes in the charge transfer resistance determined from the impedance measurements are comparable with the changes in corrosion resistance determined from potentiodynamic measurements.     

Investigation of properties of electric arc ion deposited TiN coating on Al2O3-based ceramic composite

Electric arc ion deposition technique was adopted to deposit TiN coating on Al2O3-based ceramic composite. Scanning electron microscopy and secondary ion mass spectrometry were used to analyze the microstructure, phase constitution, and quality of the TiN coating and the interface. Surface roughness and micro-hardness of the TiN coating were measured to evaluate its quality. Flexural strength of ceramic materials is dependent on both their inherent resistance to fracture and the presence of defects, thus it was used to investigate the effect of electric arc ion deposition technique on the surface modification of Al₂O₃-based ceramic composite. Experimental results show that the higher the deposition bias voltage, the better the coating quality. The TiN coating is homogeneous, with a uniform surface, and free of defects when the deposition bias voltage is 300 V. The TiN coating strongly adheres to the Al₂O₃-based ceramic composite, and the observed elemental interface diffusion strengthens the interface bonding.     

Preparation of YSZ/Al2O3 micro-laminated coatings and their influence on the oxidation and spallation resistance of MCrAlY alloys

YSZ/Al₂O₃ micro-laminated coatings were successfully prepared on the surface of MCrAlY substrates by means of electrolytic deposition and microwave sintering. The as-prepared YSZ/Al₂O₃ coatings were characterized by high-resolution field emission SEM and XRD. Laminated structures of alternate YSZ and Al₂O₃ layers were observed in the coating with the phase composition of Y₂O₃ stabilized t-ZrO₂, α-Al₂O₃ and θ-Al₂O₃. High-temperature cyclic oxidation test at 1000 °C in air was also performed to investigate the oxidation and spallation resistance of such coatings on MCrAlY substrates. The results indicate that such coatings exhibit not only excellent oxidation resistance but also good spallation resistance under thermal cycling due to the structure of multi-sealed Al₂O₃ layers and the preferable high-temperature mechanical properties induced by the designed laminated composite structures, respectively.     

Protective properties of Al2O3 + TiO2 coating produced by the electrostatic spray deposition method

Mechanical resistance of Al₂O₃ + TiO₂ nanocomposite ceramic coating deposited by electrostatic spray deposition method onto X10CrAlSi18 steel to thermal and slurry tests was investigated. The coating was produced from colloidal suspension of TiO₂ nanoparticles dispersed in 3 wt% solution of Al₂(NO₃)₃, as Al₂O₃ precursor, in ethanol. TiO₂ nanoparticles of two sizes, 15 nm and 32 nm, were used in the experiments. After deposition, coatings were annealed at various temperatures, 300, 1000 and 1200 °C, and next exposed to cyclic thermal and slurry tests. Regardless of annealing temperature and the size of TiO₂ nanoparticles, the outer layer of all coatings was porous. The first five thermal cycles caused a rapid increase of aluminum content of the surface layer to 30–37 wt%, but further increase in the number of thermal cycles did not affect the aluminum content. The oxidation rate of coating-substrate system was lower during the thermal tests than during annealing. The oxidation rate was also lower for smaller TiO₂ particles (15 nm) forming the coating than for the larger ones (32 nm). The protective properties of Al₂O₃ + TiO₂ coating against intense oxidation of substrate were lost at 1200 °C. Slurry tests showed that coatings annealed at 1000 °C had the best slurry resistance, but thermal tests had weakened this slurry resistance, mainly due to decreasing adhesion of the coating.     

Phase composition,structural, and plasma erosion properties of ceramic coating prepared by suspension plasma spraying

Y₃Al₅O₁₂ (YAG), Y₂O₃, and Al₂O₃ ceramic coatings were manufactured to investigate the plasma erosion properties. The X‐Ray Diffraction (XRD) analysis confirmed that YAG coating was synthesized successfully by Y₂O₃ and Al₂O₃ mixture suspension using the plasma spraying method. Meanwhile, metastable phases were found in Y₂O₃ and Al₂O₃ coatings due to the quenching in cooling process of melted droplets. The coating surface morphology and microstructure of cross sections were characterized by SEM. The results reveal that coatings are composed by ultrafine splats and exhibit dense lamellar structure. The plasma erosion properties were evaluated at different etching test power under Ar/CF₄/O₂ plasma gas. The experimental results clarify that both of YAG and Y₂O₃ coatings show the better plasma erosion resistance than Al₂O₃ coatings. The formation of fluorination layer surface prevents the coatings from further erosion with plasma gas. Moreover, the etching rate of coatings depended on the fluorination and removing rate of fluoride layer.     

Evolution behavior of rare-earth yttria modified silicide oxidation-resistant coating at 1700 oC

Yttria-modified silicide (MoSi₂-Y₂O₃) oxidation-resistant coatings with multiple Y₂O₃ contents were prepared using supersonic atmospheric plasma spraying, and the oxidation resistance was investigated at 1700 °C with static atmosphere. Experimental results indicated that the sprayed MoSi₂-Y₂O₃ coating possessed good compactness, which adhered well to the SiC transition layer. Meanwhile, the Y₂O₃ addition greatly enhanced the bonding strength of the coating, and extended its service life at 1700 °C. Wherein the MoSi₂-20 wt.%Y₂O₃ coating exhibited the highest adhesive strength and best oxidation resistance with the lowest mass loss among all the coatings. In practice, the Y₂O₃ changed the microstructures of formed oxide glass scale during oxidation, and then modified the oxidation resistance of the coating. The action mechanism of Y₂O₃ on the oxidation behavior of MoSi₂-Y₂O₃ coating was analyzed.     

High temperature oxidation behavior of MoSi2–Al2O3 composite coating on TZM alloy

A novel MoSi₂–Al₂O₃ composite coating was prepared on Mo-based TZM alloy by slurry sintering method. The oxidation behavior of the coating was evaluated at 1600 °C in static air. Microstructure and phase composition of the as-prepared and oxidized coatings were characterized, and the antioxidant mechanism of the coating at high temperature was discussed. A three-layer structure was observed in the as-prepared coating, consisting of a ～2 μm thick Mo₅Si₃ diffusion layer, a ～65 μm thick MoSi₂ inner layer and a ～36 μm thick outer layer of mixture of MoSi₂ and Al₂O₃. After oxidation at 1600 °C for 5 h, all MoSi₂ phases were completely converted to intermediate silicide Mo₅Si₃ by solid-state diffusion, and the formed Mo₅Si₃ phase would be transformed into Mo₃Si phase with further extending the oxidation time. Furthermore, a dense oxide layer of SiO₂-mullite was formed on the specimen surface, which can effectively protect the material to further oxidation. The MoSi₂–Al₂O₃ coating could protect the substrate effectively at 1600 °C for 20 h without failure. The enhanced oxidation resistance of MoSi₂–Al₂O₃ coating is due to the formation of multi-layer structure containing a SiO₂-mullite composite oxide outer layer with high thermal stability and low oxygen permeability.     

Influence of different introduction modes of metal Ag into plasma sprayed Al2O3 coating on tribological properties

Al₂O₃ coating and Al₂O₃/Ag (10%) composite coating were prepared on the surface of GH4169 superalloy by the atmospheric plasma spraying technology. And an in-situ synthesis method was applied to introduce the Ag particles into a part of Al₂O₃ coatings to obtain Al₂O₃/Ag(synthesis) composite coating. Then, the microstructure and mechanical properties of these three Al₂O₃-based coatings were systematically studied in this work. In order to reveal the lubrication characteristics of Ag, their friction tests were carried out at room temperature (RT), 400 °C, 600 °C and 800 °C, respectively. The results showed that both microstructure and mechanical properties of Al₂O₃/Ag(synthesis) composite coating were better than that of Al₂O₃/Ag (10%) composite coating because many pores and cracks produced during the direct spraying. Although the friction coefficients of two kinds of composite coatings were close to that of Al₂O₃ coatings at RT, their wear rates were both greatly decreased due to the introduction of Ag. In addition, the lubricating performance of Ag was not enough to reduce their friction coefficients when friction temperature is lower than 600 °C. However, the friction coefficients of these composite coatings were both reduced to about 0.3 at 800 °C . At this time, the Al₂O₃/Ag(synthesis) composite coating also exhibited a lower wear rate because of its dense microstructure and excellent mechanical properties.     

Microstructures and oxidation behaviors of Al-modified and Al2O3-modified SiC coatings on carbon/carbon composites via pack cementation

Al₂O₃-modified SiC (AOSC) and Al-modified SiC (ASC) coatings were prepared on carbon/carbon (C/C) composites by one-time pack cementation (PC). Their microstructures and anti-oxidation performances were studied. Compared with ASC coating, AOSC coating shows more conspicuous defects (micro-cracks and holes) and lower densification. ASC coating can offer better oxidation resistance and thermal shock resistance to C/C composites than AOSC coating. Al additive can more efficiently improve the sinterability of SiC, which causes the above results. Besides, Al₂O₃ oxidation product is more stable than SiO₂ (l) of oxidized SiC at 1500 °C based on the thermodynamic analysis.     

Cathodic plasma electrolytic deposition of ZrO2/YSZ doped Al2O3 ceramic coating on TiAl alloy

ZrO₂/yttria-stabilized zirconia (YSZ) doping Al₂O₃ ceramic coating was fabricated via cathodic plasma electrolytic deposition (CPED) technique. The microstructures and the chemical and phase compositions of the doped coating were characterized, the mechanical properties and the high temperature oxidation resistance were evaluated, and the doping mechanism was also discussed in detail. The results showed that, doped Zr⁴⁺ and Y³⁺ ions could effectively reduce the working voltage during CPED process and increase the content of metastable γ-Al₂O₃ in the coating. Accordingly, the doped ZrO₂/YSZ significantly refined the grain size of Al₂O₃, as well as remarkably improved the high temperature oxidation resistance, the micro-structural compactness and hardness of the Al₂O₃ CPED coating. This study displayed here constructed an efficiently method for the fabrication of multifunctional coating on the surface of TiAl alloy.     

Properties of TiN–Al2O3–TiCN–TiN,TiAlN, and DLC-coated Ti(C,N)-based cermets and their wear behaviors during dry cutting of 7075 aluminum alloys

In the work, TiAlN for physical vapor deposition (PVD), multilayer TiN-Al₂O₃-TiCN-TiN for chemical vapor deposition (CVD), and diamond-like carbon (DLC) for plasma-enhanced chemical vapor deposition (PECVD) were deposited on the cermet inserts. Characteristics and wear behaviors of the three coated cermets during dry cutting of 7075 aluminum alloys were observed. The results show that TiN-Al₂O₃-TiCN-TiN coatings have highest adhesion strength and hardness. At the cutting speed of 1100 r/min, the depth of 0.2 mm, and the feed rate of 0.1 mm/r, the three coated inserts show the best wear-resistant properties. In this case, TiN/Al₂O₃/TiCN/TiN shows the worst wear-resistant properties (value of the flank wear [VBB] = 0.062 mm), while DLC coatings show the most excellent wear-resistant properties (VBB = 0.046 mm). During the cutting of aluminum alloys, which have high plasticity and low melting point, adhesive wear dominate on the flank of the inserts. The thickest coating of TiN/Al₂O₃/TiCN/TiN results in the bluntest cutting edge, which form the most serious adhesive worn zone. For the TiAlN and DLC coatings, due to a smaller cutting force, the two coatings have much better wear resistance. Further, the self-lubricating properties of DLC show excellent effect on protecting the inserts. Thus, the DLC-coated cermets have the best wear-resistant properties. Further, the TiAlN-coated cermets have the widest wear-affected zone while the DLC coating has the narrowest.     

Electrolytic deposition of Ni-Co-Al2O3 composite coating on pipe steel for corrosion/erosion resistance in oil sand slurry

To improve the resistance of the hydrotransport pipe steel to corrosion and erosion in oil sand slurry, a Ni-Co-Al₂O₃ composite coating was fabricated by electrolytic deposition on X-65 pipe steel substrate. Potentiodynamic polarization curve and electrochemical impedance measurements show that the deposited coating significantly improves the corrosion resistance of the steel in water-oil-sand solution that simulates the chemistry of oil sand slurry. The corrosion resistance of the coating increases with the increasing Al₂O₃ particle concentration in electrolyte, cathodic current density, electrode rotating speed and temperature. However, a maximum value of corrosion resistance as a function of the depositing parameters is observed, indicating that the optimal electrodepositing parameters and operating conditions are essential to the maximization of the corrosion resistance of the coated steel in oil sand slurry. The optimal depositing conditions are suggested in the given system. The morphology, structure and composition of the coatings were characterized by scanning electron microscopy and energy-dispersive X-ray analysis. The Ni-Co-Al₂O₃ composite coating develops a compact, uniform, nodular structure with an average thickness of 50-200 microns. The Al₂O₃ amount in the coating increases with the increasing Al₂O₃ concentration in electrolyte, which also enhances the co-deposition of Ni and Co. The micro-hardness and wear resistance of the composite coatings are much higher than the steel substrate and increase with the increasing Al₂O₃ particle amount in the coating.