Structure of Ir-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> coatings obtained by chemical vapor deposition in the hydrogen atmosphere

Chemical vapor deposition is used to obtain Ir and Ir-Al₂O₃ coatings with a thickness of up to 5 μm and growth rate of 2.5 μm/h on steel substrates previously covered with an alumina layer. Tris-acetylacetonates of Ir(III) and Al(III) are used as precursors. The deposition process is carried out at the atmospheric pressure in the presence of hydrogen. The coatings obtained are studied by X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy. A dependence of the structure and composition of coatings on their preparation conditions is found.     

Poly(3-octylthiophene) and polystyrene blends thermally treated as coatings for corrosion protection of stainless steel 304

The effect of thermal annealing of poly(3-octylthiophene) (P3OT) and polystyrene (PS) blend coatings on the corrosion inhibition of stainless steel in a 0.5 M NaCl solution was investigated. P3OT was synthesized by direct oxidation of the 3-octylthiophene monomer with ferric chloride (FeCl₃) as oxidant. Stainless steel electrodes with mirror finish were coated with P3OT/PS blend by drop-casting technique. In order to study the temperature effect on the function like physical barrier against the corrosive species of P3OT/PS polymeric blend, the coatings were thermally annealed at three different temperatures (55?°C, 80?°C, and 100?°C). The corrosion behavior of P3OT/PS-coated stainless steel was investigated in 0.5 M NaCl at room temperature, by using potentiodynamic polarization curves, linear polarization resistance (LPR), and electrochemical impedance spectroscopy. The LPR values indicated that, at 100?°C, P3OT/PS coatings showed a better protection of the 304 stainless steel in 0.5 M NaCl; the corrosion rate diminished in two orders of magnitude with regard to the bare stainless steel. The superficial morphology of the coatings before and after the corrosive environment was researched by atomic force microscopy, optic microscopy, and scanning electronic microscopy. Morphological study showed that the increased temperature benefited the integration of the two polymeric phases, which improved the barrier properties of the coatings. The coating/metal adhesion and the coating thickness were evaluated. The temperature increases the adhesion degree coating/substrate; thus, the coating annealed at 100?°C showed the best adhesion.     

Sol-gel alumina coatings on stainless steel for wear protection

The aluminium oxide films on austenitic steel are prepared from sols of re-dispersed boehmite nano powders in water. After dip-coating of the sol, a heat treatment including drying, calcination and annealing in vacuum at temperatures up to 1100°C is performed to obtain crack-free coatings of a thickness up to 6 μm. XRD measurements detect α- and γ-alumina, a TiO_x-phase at the metal/coating interface and a gradient of phase formation in the coating. The strong adhesion on the substrates is due to the layered assembly and gradient composition of the coating caused by an inter-diffusion of metal cations and oxygen in the metal/oxide interface during heat treatment. Residual stress measurements by X-rays result in compressive stresses of 2–4 GPa in the alumina coatings. The pin-on-disc test shows a remarkable improvement of wear resistance obtained by sol-gel coatings. The α-alumina content and the compressive stress of the coatings correlate with wear resistance of the coatings.     

Layer‐by‐layer deposition of nitrilotris(methylene)triphosphonic acid and Zr(IV): an XPS,ToF‐SIMS,ellipsometry, and AFM study

Layer‐by‐layer assemblies consisting of alternating layers of nitrilotris(methylene)triphosphonic acid (NTMP), a polyfunctional corrosion inhibitor, and zirconium(IV) were prepared on alumina. In particular, a nine‐layer (NTMP/Zr(IV))₄NTMP stack could be constructed at room temperature, which showed a steady increase in film thickness throughout its growth by spectroscopic ellipsometry up to a final thickness of 1.79 ± 0.04 nm. At higher temperature (70 °C), even a two‐layer NTMP/Zr(IV) assembly could not be prepared because of etching of the alumina substrate by the heated Zr(IV) solution. XPS characterization of the layer‐by‐layer assembly showed a saw tooth pattern in the nitrogen, phosphorus, and zirconium signals, where the modest increases and decreases in these signals corresponded to the expected deposition and perhaps removal of NTMP and Zr(IV). Time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS) confirmed the attachment of the NTMP molecule to the surface through PO^?, PO₂^?, PO₃^?, and CN^? signals. Increasing attenuation of the Al signal from the substrate after deposition of each layer was observed by both XPS and ToF‐SIMS. Essentially complete etching of the alumina by the heated Zr(IV) solution was confirmed by spectroscopic ellipsometry, XPS, and ToF‐SIMS. Atomic force microscopy revealed that all the films were smooth with R_q roughness values less than 0.5 nm. Copyright © 2015 John Wiley & Sons, Ltd.     

Protective coatings for stainless steel for SOFC applications

In this paper, a coating procedure based on spin coating of metal oxide polymer precursors on stainless steel, which decreases the oxide scale growth rate, is evaluated. The yttrium and cobalt solutions were used as polymer precursors, while a ferritic stainless steel Crofer 22 APU was used for the deposition of protective coatings. The thickness of deposited protective film was about ~500 nm. The effectiveness of protective layer was evaluated by cyclic thermogravimetry, oxide scale electrical conductivity, and X-ray diffractometry. The results show that steel coated with yttrium polymer precursor has better properties than uncoated or cobalt-coated sample.     

Elimination of a zero-growth in thickness of Al<Subscript>2</Subscript>O<Subscript>3</Subscript> protective film deposited by cycles of dip-coating method

Multilayered alumina film was deposited onto metallic substrate using cycles of dip-coating method. The film thickness was found not always growing linearly with the increase of the number of dipping cycles, and even a zero-growth in thickness was observed after 20 cycles of dip coatings. This phenomenon was found to be attributed to the dissolving behavior of alumina gel material in original sol. A heat treatment at a temperature higher than 230 °C was found to be able to effectively lower the dissolvability of Al₂O₃ gel material, but an extra high temperature, i.e., 600 °C led to the formation of cracks in the multilayered film due to the increase of interfacial tension force. It was examined by IR and XRD analyses that a heat treatment at 250 °C for 10 min before each coating process could yield an amorphous multilayered film with no crack formed after calcinations at 600 °C. A crack-free Al₂O₃ film with a thickness up to 2 μm after 22 cycles of dip coating process could be produced and it showed an excellent antioxidation performance for steel substrate.     

Structural and electrochemical characterization of sputter-deposited nitrided NiCr alloys

Nickel-based coatings are potential candidates for the protection of electrochemical dissolution of steel surfaces. Such coatings, elaborated by magnetron sputtering in a nitrogen atmosphere, offer good corrosion protection, good adherence as well as stability for metallic structures. NiCr alloys with almost constant composition have been deposited with different nitrogen contents on stainless steel and carbon steel surfaces. The coating uniformity, homogeneity, composition and crystallinity have been studied by scanning electron microscopy, energy-dispersive X-ray spectrometry, atomic force microscopy and X-ray diffraction techniques. The corrosion degradation behavior of all the samples was tested in NaCl and NaCl and CO₂ mixture exposures using electrochemical impedance spectroscopy measurements. Nitrided NiCr alloys on a stainless steel substrate resulted with better adhesion than carbon steel, by delaying the corrosion mechanism when exposed to NaCl and CO₂ solution. A comparison of the corrosion resistive behavior of the substrates (stainless steel, carbon steel) and the coatings is made by using the electrical capacitance concept from a double-layer model for the coating–metal interface.     

Sol-gel ZrO2 coatings for chemical protection of stainless steel

ZrO₂ coatings deposited on 316 L stainless steel sheets were synthesized by sol-gel method using Zr(OC₃H₇)₄ as precursor and isopropanol, glacial acetic acid, and water as solvents for application with ultrasounds. Different solutions for dip-coating were prepared with compositions varying between 0.025 and 0.9 mol/dm³ of ZrO₂. X-ray diffraction shows that the films densified at 800°C are crystalline with a tetragonal structure. The thickness of the coatings varied from 0.35–0.75 m. The influence of the ZrO₂ coatings on the corrosion behavior of stainless steel substrates in aqueous NaCl was studied through potentiodynamic polarization curves at 1 mV/s. The values of the electrochemical parameters allow for an explanation of the role of the films in the increased resistance of steel against corrosion in moderately aggressive environments.     

Biocompatibility Assessment of Insulating Silicone Polymer Coatings Using an in vitro Glial Scar Assay

Vapor‐deposited silicone coatings are attractive candidates for providing insulation in neuroprosthetic devices owing to their excellent resistivity, adhesion, chemical inertness and flexibility. A biocompatibility assessment of these coatings is an essential part of the materials design process, but current techniques are limited to rudimentary cell viability assays or animal muscle implantation tests. This article describes how a recently developed in vitro model of glial scar formation can be utilized to assess the biocompatibility of vapor‐deposited silicone coatings on micron‐scale wires. A multi‐cellular monolayer comprising mixed glial cells was obtained by culturing primary rat midbrain cells on poly(D ‐lysine)‐coated well plates. Stainless steel microwires were coated with two novel insulating thin film silicone polymers, namely poly(trivinyltrimethylcyclotrisiloxane) (polyV₃D₃) and poly(trivinyltrimethylcyclotrisiloxane–hexavinyldisiloxane) (polyV₃D₃–HVDS) by initiated chemical vapor deposition (iCVD). The monolayer of midbrain cells was disrupted by placing segments of coated microwires into the culture followed by immunocytochemical analysis after 7 d of implantation. Microglial proximity to the microwires was observed to correlate with the amount of fibronectin adsorbed on the coating surface; polyV₃D₃–HVDS adsorbed the least amount of fibronectin compared to both stainless steel and polyV₃D₃. Consequently, the relative number of microglia within 100 µm of the microwires was least on polyV₃D₃–HVDS coatings compared to steel and polyV₃D₃. In addition, the astrocyte reactivity on polyV₃D₃–HVDS coatings was lower compared to stainless steel and polyV₃D₃. The polyV₃D₃–HVDS coating was therefore deemed to be most biocompatible, least reactive and most preferable insulating coating for neural prosthetic devices.

     

Sol-enhanced triple-layered Ni–P–TiO2 composite coatings

A novel coating process, TiO₂ sol enhanced Ni–P electroless composite coatings on carbon steel, is presented in this paper. Transparent TiO₂ sol was added into the electroless plating Ni–P solution at a controlled rate, leading to in situ synthesis of a triple-layered Ni–P–TiO₂ composite coating, i.e. the inner, transition and outer layers. The inner layer has a thickness of ~3 μm, mainly composed of Ni and P elements. The transition layer of the coating has a relatively high content of TiO₂ with a thickness of ~500 nm and a columnar-structure. The thickness of the outer layer was ~7 μm, with almost evenly distributed Ni, P and TiO₂. The hardness and Young’s modulus of the composite coating were greatly improved to ~10 and ~200 GPa, respectively, compared to ~6 and ~110 GPa of the traditional Ni–P coating.     

TOF-SIMS depth profiling and element mapping on oxidized AlCrVN hard coatings

V-alloyed AlCrN hard coatings were deposited on silicon wafers (Si (100)) by reactive arc evaporation in a commercial coating system at 500 °C for 10 min, resulting in a coating thickness of ∼500 nm. The chemical composition of the stoichiometric coatings is constant at approximately Al_0.70Cr_0.05V_0.25N regardless of the applied bias voltage during deposition. Coatings synthesized at a low bias of −40 V show a dual-phase structure (hexagonal close-packed and face-centered cubic (fcc)), whereas coatings deposited at a high bias of −150 V have a metastable single-phase structure (face-centered cubic). All samples were oxidized for 15 min under 20 mbar O₂ atmosphere and at four different temperatures (550, 600, 650, and 700 °C). The oxidized coatings were subject to depth profiling and element mapping by a time of flight secondary ion mass spectrometry instrument, equipped with a Bi-cluster analysis gun and Cs⁺-sputter gun. The evaluation of the in-depth distribution of several elements and species points out distinctive differences in the oxidation behavior of the two different coatings, whereas element mapping shows the formation of islands made of oxidized vanadium and aluminum species as the top-most layer of the single-phase (fcc) coating at temperatures above 650 °C.     

Electrochemical behaviour of SiO2 sol-gel coatings on stainless steel

SiO₂ coatings onto stainless steel substrates have been prepared by sol-gel in order to study the performance and mechanism of attack in different corrosive solutions. The electrochemical behaviour of the samples has been evaluated by Electrochemical Impedance Spectroscopy using NaCl and HCl as electrolytes. Comparative tests have been performed on samples with one and two silica layers as well as on uncoated ones. SiO₂ coatings produce no important protection of stainless steels subjected to electrochemical corrosion. This behaviour may be explained by micropores and microcracks produced during the coating sintering.     

Structure of Ir and Ir-Al<Subscript>2</Subscript>o<Subscript>3</Subscript> coatings obtained by chemical vapor deposition in the presence of oxygen

By chemical vapor deposition Ir and Ir-Al₂O₃ coatings are obtained with a thickness of up to 40 fum on steel substrates precoated with a layer of Al₂O₃. Tris-acetylacetonates of iridium(III) and aluminium(III) are used as precursors. The deposition processes are carried out at atmospheric pressure in the presence of oxygen. The obtained coatings are studied by X-ray diffraction, X-ray photoelectron spectroscopy, and scanning electron microscopy. The dependences of coating structures and compositions on the preparation conditions are found. An increase in the deposition temperature results in the formation of Ir coatings with loose discontinuous structure, an increase in the size of metal crystallites, and the growth of the oxygen concentration in their composition. An increase in the concentration of precursor vapors in the deposition zone at a constant deposition temperature results in the formation of Ir coatings that consist of differently structured layers (compact, columnar, and granular). Mixed Ir-Al₂O₃ coatings which composed of metal Ir and amorphous Al₂O₃ crystallites, which exhibit a pronounced iridium texture in the [111] direction, have the most perfect compact structure. The introduction of the oxide phase in the coating composition halves the Ir crystallite size.     

Ultrafine grain formation and coating mechanism arising from a blast coating process: A transmission electron microscopy analysis

This article examines the substrate/coating interface of a coating deposited onto mild steel and stainless steel substrates using an ambient temperature blast coating technique known as CoBlast. The process uses a coincident stream of an abrasive blast medium and coating medium particles to modify the substrate surface. The hypothesis for the high bond strength is that the abrasive medium roughens the surface while simultaneously disrupting the passivating oxide layer of the substrate, thereby exposing the reactive metal that then reacts with the coating medium. The aim of this study is to provide greater insight into the coating/substrate bonding mechanism by analysing the interface between a hydroxyapatite coating on both mild and stainless steel substrates. The coating adhesion was measured via a tensile test, and bond strengths of approximately 45 MPa were measured. The substrate/coating interface was examined using transmission electron microscopy and selected area diffraction. The analysis of the substrate/coating interface revealed the presence of ultrafine grains in both the coating and substrate at interface associated with deformation at the interface caused by particle impaction during deposition. The chemical reactivity resulting from the creation of these ultrafine grains is proposed to explain the high adhesive strength of CoBlast coatings.     

Time‐of‐flight SIMS characterization of hydrolysed organofunctional and non‐organofunctional silanes deposited on Al,Zn and Al–43.4Zn–1.6Si alloy‐coated steel

In this paper Al, Zn and Al–43.4Zn–1.6Si (AlZn) alloy‐coated steel have been treated with the organofunctional silane γ‐mercaptopropyltrimethoxysilane (γ‐MPS) and the non‐organofunctional silane 1,2‐bis(triethoxysilyl)ethane (BTSE). Also, a two‐step treatment of metal substrates was performed: the metal substrates were treated with the BTSE silane followed by a γ‐MPS treatment. The influence of metal substrate and the pH value of the silane film properties were investigated using time‐of‐flight secondary ion mass spectrometry (ToF‐SIMS). The results show that the BTSE silane is fully hydrolysed but the γ‐MPS silane is not. The presence of negative ions of the type HSi_xO_y^? indicates that both types of silane films are highly cross‐linked via Si–O–Si bonds. The two‐step treatment gave a γ‐MPS silane layer on top of the BTSE silane layer but the thickness of the total silane film become thinner than for a single BTSE film, indicating that some of the BTSE is dissolved during the γ‐MPS deposition step. Furthermore, the ToF‐SIMS results show that the thiol group of the γ‐MPS silane is oxidized. Finally, no major influence, either in the positive or the negative mass spectra, from the different metal substrates could be detected for the silane films investigated. Copyright © 2003 John Wiley & Sons, Ltd.     

Structure of rhenium coatings obtained by CVD

By chemical vapor deposition in the hydrogen atmosphere from Re₂(CO)₁₀ and Re(CO)₃(Cp) on steel and ceramic (C/SiC) substrates, rhenium coatings are obtained with an average thickness of 3–13 μm, when Re₂(CO)₁₀ is used, and of 2–8 μm when depositing from Re(CO)₃(Cp). The coatings are studied by X-ray diffraction and scanning electron microscopy. It is shown that when Re₂(CO)₁₀ is used, an increase in the deposition temperature results in the growth of textured coatings with preferred orientation of crystallites in the [0 0 2] direction. At the same time, a tendency for decreasing the size of rhenium crystallites is observed. With the change of evaporator temperature, the structure of Re coatings obtained from Re(CO)₃(Cp) on steel substrates changes considerably: from compact non-layered without the obvious growth direction (T _evaporator = 120°C) to a three-layer structure, where the initial layer has a compact structure followed by columnar and powdered layers (T _evaporator = 110°C). A fine compact coating is formed on ceramic substrates at an evaporator temperature of 110°C.     

Solution Preparation of Li(Co,Fe)O2 Coatings for Molten Carbonate Fuel Cell Components

An aqueous solution process has been used for dip coating onto substrates of 316L stainless steel. Coatings of LiCoO₂, Li(Co_0.5Fe_0.5)O₂ and LiFeO₂ were applied and heat treated to 650°C for 3 hrs. Thermal analysis, X-ray diffraction analysis, and SEM analysis were carried out to characterize the microstructure of the coatings. Results showed that the coatings transformed from a gel to a porous, crystalline layer between 270 and 350°C. Microhardness measurements at low load (50 g) were used as an indication of the surface coverage. Samples subjected to 10 thermal cycles at 10°C/min to 650°C and back to ambient, to simulate use in a molten carbonate fuel cell, showed no decrease in microhardness.     

Silica-Zirconia Sol–Gel Coatings Obtained by Different Synthesis Routes

Homogeneous xSiO₂-(1−x)ZrO₂ coatings have been prepared onto glass-slides, monocrystalline Si and stainless steel (AISI 304) using sols prepared via acid and basic catalysis. Zirconium tetrabutoxide (TBOZr), zirconium n-propoxide (TPZ), tetraethoxysilane (TEOS) and methyltriethoxysilane (MTES) were used as precursors of zirconia and silica, respectively. The different parameters involved in the synthesis procedure, as molar ratios H₂O/alkoxides, NaOH/alkoxides, and sintering temperature have been analysed, correlating the stability and rheological properties of the sols. The evolution and structure of the sols and coatings have been studied by FTIR. Coatings have been prepared by dipping from acid and basic sols. Electrophoretic Deposition (EPD) technique has also been used to prepare coatings onto stainless steel from basic particulate sols in order to increase the critical thickness. A maximum thickness of 0.5 μ m was reached by both dipping and EPD process for 75SiO₂: 25 ZrO₂ composition. The critical thickness decreases with ZrO₂ amount depending strongly of the drying conditions. Si–O–Zr bonds have been identified by FTIR, indicating the existence of mixed network Si–O–Zr in the coatings obtained by the different routes. Crystallisation of ZrO₂(t) was only observed at high sintering temperature (900^∘C) by FTIR and confirmed by DRX.     

Sol–gel-derived nanocomposite coatings filled with inorganic fullerene-like WS<Subscript>2</Subscript>

Silica coatings filled with nanoscaled inorganic fullerene-like tungsten disulphide (IF-WS₂) have been prepared through a sol–gel process on stainless steel substrates, and the structure and mechanical properties have been investigated. The precursor was prepared from a mixture of colloidal silica, 3-glycidoxypropyltrimethoxysilane (GLYMO), water and ethanol, adjusted to pH 4 with HNO₃. In this solution WS₂ is dispersed and in some cases immediately before coating ethylenediamine (ED) is added. The stainless steel substrates are dip-coated, dried in air and heat-treated in the temperature range of either 150–360 °C in air or up to 900 °C in vacuum. The solidification process is followed by differential thermal analysis (DTA). The resulting brown coloured coatings have a thickness of 1.5–4 μm. Scanning electron microscopy investigations (SEM) show that the WS₂ nanoparticles are embedded as small aggregates in a hybrid silica matrix. X-ray diffraction (XRD) measurements prove that most of the tungsten disulphide embedded in the matrix can be protected against oxidation even after curing the samples at temperatures up to 900 °C. Hardness and modulus of the hybrid silica films were measured through an instrumented indentation test. Increasing the temperature of the heat treatment yields an increase of hardness from 0.3 to 1 GPa and of modulus from 3 to 17 GPa. The amount of up to 10 wt.% WS₂ in the coatings has no remarkable influence on hardness and modulus of the samples.     

Synthesis of HAP coating on galvanostatically treated stainless steel substrates by sol–gel method

Producing bioactive hydroxyapatite coatings on metallic implant materials combines the mechanical advantages of implant materials and biological affinity of the hydroxyapatite surface to the natural tissue. In this work, hydroxyapatite was synthesized on 316L stainless steel substrates via sol–gel method by using Ca(NO₃)₂·4H₂O and C₆H₁₅O₃P. In order to improve adherence of the coatings produced, the surface of the substrate was initially modified by electrodepositing nucleus of calcium phosphate compounds. Effect of aging time for preparation of the sol solution and coating characteristics were investigated. The phase compositions and structures of the coatings were characterized by X-ray diffractometry, and scanning electron microscopy was used to determine morphological characteristics of the coatings. Adhesion between the hydroxyapatite coating and the substrate was investigated by using scanning scratch tester. The coating produced on the modified surface by the sol solution aged for 24 h was found to prove better morphological and adhesion properties.