Duplex ceramic coating produced by low temperature thermo-reactive deposition and diffusion on the cold work tool steel substrate: Thermodynamics,kinetics and modeling

Specimens of DIN 100MnCrW4 steel (type O1 tool steel) have been cut and prepared for performing a duplex surface treatment involving nitriding and low temperature vanadium thermo-reactive deposition and diffusion (TRD) technique. The TRD process was performed in a molten salt bath at different temperatures of 575, 650 and 725 °C for 1–30 h. The treatment formed a vanadium carbonitride coating with the thickness up to 10.5 μm on a hardened diffusion zone. Characterizations by means of an optical microscope (OM), scanning electron microscope equipped with energy dispersive X-ray spectrometer (SEM–EDS) and X-ray diffraction analysis (XRD) indicated that the compact and dense coating mainly consisted of V(C,N) and V₂(C,N) phases. All the growth processes of the formed vanadium carbonitride layer obtained by TRD followed a parabolic kinetics while the calculated activation energy (Q) for the treatment was 181.1 kJ/mol. An artificial neural network (ANN) based model for predicting the layer thickness of ceramic coatings was presented. Constructing the model, training, validating and testing of experimental results from 72 different specimens were conducted. The data used as inputs in the proposed model were arranged in a format of five parameters that comprised of “pre-nitriding time”, “ferro-vanadium particle size”, “ferro-vanadium weight percent”, “salt bath temperature” and “coating time”. Accordingly, the thickness of duplex coating in each specimen was estimated accurately. Finally, the proposed ANN-based model showed a strong potential for predicting the layer thickness of duplex ceramic coating performed by the TRD technique on the substrate of cold work tool steel.     

Tribological properties of duplex coatings of chromium-vanadium carbide produced by thermo-reactive diffusion (TRD)

Carbide coatings are very important in molding industries due to their good anti-wear properties increasing the life of molds of hot and cold forging, extrusion and powder metallurgy exposing to abrasive forces. Diverse processes are applied to produce carbide coatings. One of them is the thermo-reactive diffusion method (TRD) using a molten salt bath. This process has many advantages including cost-effectiveness over other similar surface coating methods. The aim of this study is the formation of carbide-composite coatings using molten salt baths containing oxides of carbide forming elements individually and in a mixed form on SKD-11 cold work tool steel at 1000 °C. For this purpose, two sets of experiments were considered in this study. In experiment A, a chromium oxide bath and then a mixed chromium oxide and vanadium oxide bath with a molar ratio of Cr to V equal to 0.66 were used. In experiment B, at first a mixed chromium oxide and vanadium oxide bath (Cr/V ratio = 0.66) and next a single bath of vanadium oxide were utilized. To evaluate and compare the produced coatings, FE-SEM, EPMA (point, line and map), XRD analysis, nano-indentation and wear tests were performed. The results showed that the coatings include chromium carbides (Cr₃C₂, Cr₇C₃ and Cr₂₃C₆) and vanadium carbides (V₂C, V₆C₅ and V₈C₇) as well as a carbon-chromium-vanadium triple phase with the composition of Cr₂C₂V. Moreover, the best hardness and abrasion resistance were gained for the coating produced in the molten bath containing chromium oxide and vanadium oxide after experiencing a chromium oxide bath. For the sample, the hardness was between 17.2 and 19.6 GPa and the lowest amount of COF was 0.32.     

High performance environmental barrier coatings, Part I: Passive filler loaded SiCN system for steel

A novel environmental barrier coating system for steel consisting of a perhydropolysilazane (PHPS) bond coat and a polysilazane-based glass/ceramic composite top coat has been developed. After stabilising the coating slurries, double layers were applied on mild and stainless steel substrates by the dip-coating technique. Parameters like pre-treatment of the steel substrates, filler systems, particle size of the fillers or coating thickness were varied to optimize the coatings. The thermal treatment was performed in air at temperatures up to 800 °C. Microstructural analysis by SEM and XRD revealed the formation of a coating system consisting of a SiNO bond coat and a ZrO₂-filled glass/ceramic top coat. A uniform, well adherent, dense and crack-free coating system with a noteworthy thickness up to 100 μm was achieved. Even after cyclic oxidation tests on coated samples at 700 °C the coating system was still undamaged and no oxidation occurred on the mild steel substrates.     

A comprehensive study of the green hexafluorozirconic acid-based conversion coating

The effect of four practical parameters (deposition temperature, time, bath pH and concentration of Zr) on electrochemical and morphological properties of zirconium based conversion coating (ZrCC) on cold rolled steel (CRS) substrates was investigated. DC polarization and electrochemical impedance spectroscopy (EIS) measurements were used for electrochemical studies. Micro structural characterization was carried out by FE-SEM, AFM and EDS. The optimal conditions were determined as follows: solution temperature 20–30 °C, immersion time 60–120 s, pH = 4 and acid concentration of 4% vol. In such condition, corrosion resistance values were maximum and uniformity was improved. Microscopical observations revealed that ZrCC comprises a two-layered structure. The film formation mechanism of ZrCC was discussed in detail. After achieving the optimum conditions, epoxy nanocomposites were applied on ZrCC treated CRS samples and corrosion performance of fully painted system was investigated. Finally the adhesion strength of subsequently applied organic coating on ZrCC treated substrates was measured by pull-off technique which exhibited considerable high values.     

Deposition behavior and characteristics of hydroxyapatite coatings on Al2O3, Ti,and Ti6Al4V formed by a chemical bath method

A simple chemical bath method was used to deposit hydroxyapatite (HA) coatings on Al₂O₃, Ti, and Ti6Al4V substrates at ambient pressure by heating to 65–95 °C in an aqueous solution prepared with Ca(NO₃)₂·4H₂O, KH₂PO₄, KOH, and EDTA. The deposition behavior, morphology, thickness, and phase of the coatings were investigated using scanning electron microscopy and X-ray diffractometry. The bonding strength of the coatings was measured using an epoxy resin method. The HA coatings deposited on the three kinds of substrates were fairly dense and uniform and exhibited good crystallinity without any additional heat treatment. A coating thickness of 1–1.8 μm was obtained for the samples coated once. By repeating the coating process three times, the thickness could be increased to 4.5 μm on the Al₂O₃ substrate. The bonding strength of these coatings was 18 MPa.     

Porous hydroxyapatite coating on strong ceramic substrate fabricated by low density slip coating-deposition and coating-substrate co-sintering

This study aims at developing a process technique, which can deposit porous scaffold-like hydroxyapatite (HA) coatings on strong ceramic substrates. As a first trial, micro-porous HA coatings on strong zirconia-based substrates are fabricated by the following technique—consisting of low-density HA-slip coating-deposition on the micro-porous substrates pre-sintered at 900 °C, and coating-substrate co-sintering at 1300 °C. The final co-sintering process ensures a strong bonding between the HA coating and the zirconia-based substrate after minimizing the mismatch in thermal expansion coefficients by adding alumina in HA coating and HA in zirconia-based substrate. The presence of porosity in the HA coating also reduces the mismatch. HA decomposition during the co-sintering process is discussed.     

Oxidation resistance of highly porous CVD-SiC coated Tyranno fiber composites

Oxidation tests have been carried out on highly porous ceramic matrix fiber composites consisting of Tyranno Lox M fibers coated with Pyro C and CVD-SiC thin layers. TGA experiments carried out at 900 °C confirm that mass loss rates are higher for materials with thicker Pyro C layers. At higher temperatures (i.e. 1250 °C) such differences are not significant likely due to the interaction between SiC oxidation and Pyro C burnout. These tests clearly show that the oxidation kinetics of Tyranno fibers are much faster than those of CVD-SiC coatings. Therefore, the CVD-SiC coatings protect the Tyranno fibers against oxidation, although this is less effective as the thickness of the Pyro C layer increases. Finally, it has been found that the oxidation kinetics of the CVD-SiC layers are faster as the coating thickness increases and are different for the inner and the outer coating surfaces.     

Microstructure and electrochemical characterization of trivalent chromium based conversion coating on zinc

A trivalent chromium based conversion coating (CCC), based on chromium nitrate solution with Co(II) ions, was developed on Zn substrate. The corrosion resistance of the trivalent CCC, measured in deaerated pH 8.0 borate buffer + 0.01 M NaCl solution using anodic polarization and electrochemical impedance spectroscopy (EIS), was very sensitive to both immersion time and bath pH. Micro-cracks were found on the surface of the CCC. Besides, the density of micro-crack and the coating thickness also depended on immersion time and bath pH. With increasing the coating thickness its pitting potential increased and passive current density decreased. The trivalent CCC formed on Zn for 40 s in pH 1.7 bath showed the best corrosion resistance, and the pitting potential increased significantly from −355 mV_SCE for Zn to 975 mV_SCE for the trivalent CCC on Zn. To explain the corrosion behavior of the trivalent CCC using EIS analysis, a modified equivalent circuit, which considered the micro-cracks in the coating and chromium corrosion product (CCP) deposited in the micro-cracks, was designed and the variation of each electrical parameter was examined. Especially, its corrosion behavior was well described by the variation of the resistance of CCP (R_ccp).     

Influence of plasma nitriding treatment on the adhesion of DLC films deposited on AISI 4140 steel by PVD magnetron sputtering

Duplex surface treatments composed of diamond like carbon (DLC) coating followed by plasma nitriding have drawn attention for a while. In this study, AISI 4140 steel substrates were plasma nitrided at different treatment temperatures and times. Then, DLC films were deposited on both untreated and plasma nitrided samples using PVD magnetron sputtering. The effect of different plasma nitriding temperatures and times on the structural, mechanical and adhesion properties of DLC coatings was investigated by XRD, SEM, microhardness tester and scratch tester, respectively. It was found that surface hardness, intrinsic stresses, layer thickness values and phase distribution in modified layers and DLC coating were the main factors on adhesion properties of duplex coating system. The surface hardness and residual stress values of AISI 4140 steel substrates significantly increased with both DLC coating and duplex surface treatment (plasma nitriding + DLC coating). Increasing plasma nitriding temperature and time also increased the diffusion depth and the thickness of modified layers. Hard surface layers led to a significant improvement on load bearing capacity of the substrate material. However, it was also determined that the process parameters, which provided lower intrinsic stresses, improved the adhesion properties of the duplex coating system.     

Effect of arc current on microstructure,texturing and wear behavior of plasma sprayed CaZrO3 coatings

In order to enhance the biocompatibility of metallic implants, various ceramic coatings are currently in vogue. CaZrO₃, a promising candidate material, was deposited through plasma spraying on stainless steel (316L) substrates at arc currents of 400, 500 and 600 A. The coatings were characterized using a SEM, XRD, surface profilometers and a tribometer. It was found that the arc current had profound effects on the thickness, microstructure, phase evolution, crystallinity and wear behavior of the coatings. The cross-sectional images and fractographic analysis showed that a denser coating with better inter-splat fusion was produced at arc current of 600 A. The average roughness (Ra) of the coatings increased from 3.62 to 6.68 μm as the arc current was increased from 400 to 600 A. The feedstock (powder) and the coatings were predominantly composed of CaZrO₃ along with a minor amount of CaZr₄O₉ phase. The rise in the arc current resulted in a slight increase in the relative proportion of the CaZrO₃ phase. Also, the coating produced at arc current of 600 A exhibited highest crystallinity. The detailed XRD analysis of (002) and (200) reflections of the ferroelectric CaZrO₃ revealed the preferred orientation of crystals in the coatings. The presence of this texture is explained on the basis of shifting the unstable Zr⁴⁺ ion in oxygen octahedral cage preferably in one direction. The increase in the arc current decreased the coefficient of friction and, as a result, relatively better wear resistance was observed for the coating produced using higher arc current. Moreover, the coating fabricated using arc current of 600 A reduced the volumetric weight loss by 13 times during the wear test as compared to the substrate. Plasma sprayed CaZrO₃ coating not only enhanced the wear resistance of the stainless steel but also showed the potential to furnish a bioactive surface.     

Glass–ceramics as oxidation resistant bond coat in thermal barrier coating system

Thermal barrier coating (TBC) system consisting of yttria stabilized zirconia (YSZ) top coat, glass–ceramic bond coat and nickel base superalloy substrate was subjected to static oxidation test at 1200 °C for 500 h in air. Oxidation resistance of this TBC system was compared with the conventional TBC system under identical heat treatment condition. Both the TBC systems were characterized by SEM as well as EDX analysis. No TGO layer was found between the bond coat and the top coat in the case of glass–ceramic bonded TBC system while the conventional TBC system exhibited a TGO layer of about 16 μm thickness at the bond coat-top coat interface region.     

Improvement of the electrochemical behavior of steel surfaces using a TiN[BCN/BN]n/c-BN multilayer system

The aim of this work is to improve the electrochemical behavior of AISI 4140 steel substrates by using a TiN[BCN/BN]_n/c-BN multilayer system as a protective coating. We grew TiN[BCN/BN]_n/c-BN multilayers via reactive r.f. magnetron sputtering technique, systematically varying the length period (Λ) and the bilayer number (n), maintaining constant the total thickness of the coating and all other growth parameters. The coatings were characterized by FTIR spectroscopy that showed bands associated to h-BN bonds, and c-BN stretching vibrations centered at 1385 cm^− 1 and 1005 cm^− 1, respectively. Film composition was studied via X-ray photoelectron spectroscopy where typical signals for C1s, N1s and B1s are shown. The electrochemical properties were studied by electrochemical impedance spectroscopy and Tafel curves. In this work, the maximum corrosion resistance for the coating with (Λ) equal to 80 nm was obtained, corresponding to n = 25 bilayers. The polarization resistance and corrosion rate were around 10.1 kOhm cm² and 0.22 mm/year; these values were 83 and 15 times higher, respectively, than uncoated AISI 4140 steel substrate (0.66 kOhm cm² and 18.51 mm/year). Optical microscopy was used for surface analysis after corrosive attack. The improvement of the electrochemical behavior of the AISI 4140 coated with this TiN[BCN/BN]_n/c-BN multilayer system can be attributed to the presence of several interfaces that offer resistance to diffusion of Cl⁻ of the electrolyte toward the steel surface.     

Adhesion characteristics and corrosion stability of epoxy coatings electrodeposited on phosphated hot-dip galvanized steel

The influence of hot-dip galvanized steel (HDG) surface pretreatment with phosphate coatings on the corrosion stability and adhesion characteristics of epoxy coatings electrodeposited on HDG steel was investigated. Phosphate coatings were deposited on hot-dip galvanized steel from baths with different concentrations of NaF (0.1, 0.5 and 1.0 g dm⁻³) and at different temperatures (50, 65 and 80 °C). The influence of fluoride ion concentration in the phosphating bath, as well as the deposition temperature of the bath, on the adhesion characteristics and corrosion stability of epoxy coatings on phosphated HDG steel was investigated. The dry and wet adhesions were measured by a direct pull-off standardized procedure, as well as indirectly by NMP test, while corrosion stability was investigated by electrochemical impedance spectroscopy (EIS).     

Electrophoretic deposition of bioactive wollastonite and porcelain–wollastonite coatings on 316L stainless steel

Wollastonite and porcelain–wollastonite coatings on stainless steel were obtained by electrophoretic deposition using acetone as dispersive medium. A direct electric current of 800 V for 3 min was used for obtaining the single wollastonite coating. A well-sintered layer was observed after heat treatment at 1050 °C for 1 h in air. The two-layer coating was obtained by depositing dental porcelain at 400 V for 30 s followed by the deposition of wollastonite at 400 V for 3 min. After forming the two layers, this complex coating was heat treated at 800 °C for 5 min. Under these conditions, strong bonds of both the interface wollastonite–porcelain and that of porcelain–metallic substrate were observed. The in vitro bioactivity assessment of the coatings was performed by immersing the deposited substrates in simulated body fluid (SBF) for 21 days. All the materials showed to be highly bioactive through the formation of a homogeneous apatite layer.     

Assembly of 8YSZ nanoparticles into gas-tight 1-2 μm thick 8YSZ electrolyte layers using wet coating methods

The application of a thin film electrolyte layer with a thickness in the micrometer range could greatly improve current solid oxide fuel cells (SOFCs) in terms of operating temperature and power output. Since the achievable minimal layer thickness with conventional powder coating methods is limited to ∼5 μm, a variety of thin film methods have been studied, but results on regular large-scale anode substrates are still lacking in the literature. In this paper, a wet coating process is presented for fabricating gas-tight 1-2 μm thick 8YSZ electrolyte layers on a regular NiO/8YSZ substrate, with a rough surface, a high porosity and a large pore size. These layers were deposited in a similar way as conventional suspension based layers, but the essential difference includes the use of coating liquids (nano-dispersion, sol) with a considerably smaller particle size (85 nm, 60 nm, 35 nm, 6 nm). Successful deposition of such layers was accomplished by means of an innovative coating process, which involves the preparation of a hybrid polyvinyl alcohol/8YSZ membrane by dip-coating or spin-coating and subsequently burning out the polymer part at 500 °C. Results from He leak tests confirmed that the sintered layers posses a very low number of defects and with values in the range 10⁻⁴-10⁻⁶ (hPa dm³)/(s cm²) the gas-tightness of the thin film layers is satisfactory for fuel cell operation. Moreover, preliminary results have also indicated a potential reduction of the sintering temperature from 1400 °C to the range 1200-1300 °C, using the presented coating process.     

Mechanical properties of MWPECVD diamond coatings on Si substrate via nanoindentation

The mechanical properties of polycrystalline diamond coatings with thickness varying from 0.92 to 44.65 μm have been analysed. The tested samples have been grown on silicon substrates via microwave plasma enhanced chemical vapour deposition from highly diluted gas mixtures CH₄-H₂ (1% CH₄ in H₂). Reliable hardness and elastic modulus values have been assessed on lightly polished surface of polycrystalline diamond films.The effect of the coating thickness on mechanical, morphological and chemical-structural properties is presented and discussed. In particular, the hardness increases from a value of about 52 to 95 GPa and the elastic modulus from 438 to 768 GPa by varying the coating thickness from 0.92 to 4.85 μm, while the values closer to those of natural diamond (H = 103 GPa and E = 1200 GPa) are reached for thicker films (> 5 μm). Additionally, the different thickness of the diamond coatings permits to select the significance of results and to highlight when the soft silicon substrate may affect the measured mechanical data. Thus, the nanoindentation experiments were made within the range from 0.65% to 10% of the film thickness by varying the maximum load from 3 to 80 mN.     

Self-organisation of nanoscaled pores in anodic oxide overlayer on stainless steels

The nanoscaled morphology of the overlayer covering stainless steels after electropolishing in perchloric acid-based electrolyte was explored mainly by AFM and SEM. Two kinds of stainless steels were tested. For the austenitic one (AISI 304L), a quasi-periodic arrangement of pores in this overlayer has been observed. Depending on the experimental conditions, the distance between neighbouring pores ranged from 20 nm up to 230 nm. This inter-pore distance varied either with the applied voltage or with the current density for a constant voltage. From XPS spectra performed on the nanostructured surfaces, analysis of the energy shifts of Cr and Fe 2p levels showed that the anodic overlayer was enriched in Cr atoms compared to the 304L steel bulk composition. For the austeno-ferritic duplex stainless steel, the electropolished surface exhibited nanoscaled pores, which had grown and self-organised on both phases but with different characteristic dimensions.     

Electrochemical polymerization of phenol on 304 stainless steel anodes and subsequent coating structure analysis

Anodic oxidation was carried out using 304 stainless steel anodes in neutral 0.1 mol/L phenol solution with an electrolyte composed of 0.1 mol/L sodium sulfate. This oxidation generated a yellow brown polyphenol coating on the steel anode surface. The reaction conditions discussed in this report relate to the methods of linear scanning, cyclic voltammetry and constant current oxidation. The proper anodic electrode potential for polyphenol deposition was observed to be 1.45 V, with a bath voltage of 2.5 V. The chemical structure of the polyphenol coating was analyzed by infrared spectroscopy and the molecular weight of the soluble part of the coating was detected by gel permeation chromatography. A scanning electron microscope was used to analyze the microstructure of the polyphenol coating, taking advantage of the partial solubility of the polyphenol in tetrahydrofuran. The observed linear and flake-layer modes of the polyphenol coating growth are summarized herein.     

Scaled-up self-assembly of carbon nanotubes inside long stainless steel tubing

The self-assembly of carbon nanotubes (CNTs) on the inside wall of a relatively long stainless steel tubing for applications such as separations and chromatography, is reported in this paper. The CNTs were deposited by the chemical vapor deposition (CVD) using ethylene as the carbon source and the iron nanostructures in the stainless steel as the catalyst. The coating consisted of a layer of CNTs aligned perpendicular to the circumference of the tubes, often with an overcoat of disordered carbonaceous material, which could be selectively oxidized by exposing the CNT layer below to pure O₂ at 375 °C. Variation in uniformity in terms of the thickness and morphology of the deposited film and surface coverage were studied along the length of a tube by scanning electron microscopy (SEM). The effects of process conditions, such as flow rate and deposition time on the coating thickness, were studied. The catalytic effect of the iron nanostructures depended on surface conditioning of the tubing. It was found that the pretreatment temperature influenced the quality of the nanotube coating. The morphology of the CNT deposit supported the base-growth scheme and VLS (vapor-liquid-solid) growth mechanisms of CNTs.     

Composite anticorrosion coatings for AZ91D magnesium alloy with molybdate conversion coating and silicon sol–gel coatings

This study evaluated the corrosion resistance of AZ91D magnesium alloy coated by composite coatings which consisted of a molybdate conversion coating and three layers of silicon sol–gel coatings. For molybdate conversion treatment, various conditions including the pH of the molybdate baths, immersion time and bath temperature were investigated using electrochemical measurements. The corrosion resistance of the AZ91D magnesium alloy was improved to some extent by the conversion coating with the optimal conversion parameters (7.3 g/L (NH₄)₆Mo₇O₂₄·6H₂O solution with pH 5 for 30 min at 30 °C).