Application of a transmission line model to evaluate the influence of structural defects on the corrosion behavior of arc-PVD CrN coatings

The effect of bias voltages (40 V, 80 V, and 40/60/80 V) on microstructure and electrochemical properties of arc-PVD CrN coatings were evaluated. Increasing the bias voltage produced microstructural changes, from well-defined columns to columnar grains, and increased defect size. The electrochemical response proved susceptible to the defect type. Nano-droplets promoted the formation of oxides, while large pores allowed the migration of the electrolyte to the substrate/CrN interface. An impedance equivalent circuit based on the Bisquert transmission line was proposed to fit the experimentally obtained impedance spectra. The equivalent circuit allowed correlating the coating electrochemical response to the defect densities and sizes. Samples deposited with 40 V showed the lowest corrosion current (0.05 μA/cm² ± 0.01), which was supported by the highest resistances to the transport of ions through the pores (R_p = 1047 ± 88 kΩ?cm²). Films obtained with 80 V reduced R_p values by two magnitude orders compared to CrN 40 V. The increase of pore resistance in CrN 40 V was associated with the oxidation of nano-droplets (proposed auto-protection phenomenon), which blocks open pinholes due to the smallest average size of defects. Tailoring a gradual increase of the bias voltage (40/60/80 V) preserves the auto-protection mechanism of droplets and improves the surface finish of the coating.     

Preparation of a thick sponge-like structured amorphous silica ceramic coating on 6061 aluminum alloy by plasma electrolytic oxidation in TEOS solution

Plasma electrolytic oxidation (PEO) was performed on 6061 aluminum alloy in organosilicon electrolyte using a stepwise constant potential control method for 23 min. The resulting coating was a sponge-like structured amorphous silica ceramic with a thickness of about 130 μm. Its exceptional wear resistance was attributed to the high hardness of the silica ceramic and the low elastic modulus of the sponge-like structure. The corrosion resistance was enhanced by a dense layer of approximately 2 μm between the coating and the substrate. Impressively, the indentation depth of the PEO coating during nano-indentation tests was only 50–60% of that of 6061 aluminium alloy under varying loads, while the recovery depth of the PEO coating after unloading was 2.5–3.1 times greater than that of 6061 aluminium alloy. Due to its special composition and structure, the PEO coating caused serious wear to the high hardness Si₃N₄ friction balls during the friction and wear test. In the electrochemical tests, the coating reduced the corrosion current density from 1.056 × 10⁻⁵A·cm⁻² to 1.239 × 10⁻⁷A·cm⁻², while extending the passivation region from 0.322 V to 1.032 V.     

Biodegradable magnesium alloy coated with TiO2/MgO two-layer composite via magnetic sputtering for orthopedic applications: A study on the surface characterization,corrosion, and biocompatibility

In this study, a coating of thin TiO₂ layer and a TiO₂/MgO double layer were created on the surface of AZ91D alloy by magnetic sputtering method in order to improve the corrosion and biocompatibility properties of this alloy. The microstructural studies by field-emission scanning electron microscopy (FESEM) and X-ray diffraction (XRD) showed that coatings were formed continuously and homogeneously on the alloy surface. In the double-layer coating, MgTiO₃ and Mg₂TiO₄ compounds were formed at the coating/substrate interface in addition to TiO₂ and MgO phases as the main phases in the coating structure. The results of corrosion test showed that in general, coating improves the corrosion of AZ91D alloy in simulated-body fluid (SBF). The double-layer coating showed the best corrosion resistance at a corrosion current of 5.743 × 10^?7 μA/cm² and a corrosion potential of ?1.513 V due to its cathodic protection of the substrate and blockage of the path of the corrosive solution towards the substrate. In vitro tests showed that considering the good match between the used materials as the coating and body, no toxic material exits which results in improvement in biocompatibility, adhesion, and bone-cell multiplication.     

Thermostability,oxidation, and high-temperature tribological properties of nano-multilayered AlCrSiN/VN coatings

In this study, monolithic AlCrSiN, VN, and nano-multilayered AlCrSiN/VN coatings were deposited using a hybrid deposition system combining arc ion plating and pulsed direct current magnetron sputtering. The microstructure, thermostability, mechanical, oxidation and tribological properties of the coatings were comparably investigated. The multilayered AlCrSiN/VN coating exhibited a face-centered cubic (fcc) structure with (200) preferred orientation and showed the highest hardness (30.7 ± 0.5 GPa) among these three coatings due to the multilayer interface enhancement mechanism and higher compressive stress. The AlCrSiN sublayers effectively prevented the V element from rapid outward diffusion to the surface of AlCrSiN/VN coating at elevated temperatures, which improved the oxidation resistance of the coating. Decomposition of V (Cr)–N bonds occurred at annealing temperatures from 800 °C to 1000 °C and V₂N phase appeared at 1100 °C. The AlCrSiN/VN coating showed excellent tribological performance at high temperatures by combining the merits of VN layers for low friction coefficient and AlCrSiN layers for superior oxidation resistance. Compared to VN and AlCrSiN coatings, AlCrSiN/VN coating showed the lowest wear rate of 2.6×10^-15 m³/N·m at 600 °C and lowest friction coefficient of 0.26 at 800 °C with a relativity low wear rate of 39.4×10^-15 m³/N·m.     

Substrate bias effect on structure of tetrahedral amorphous carbon films by Raman spectroscopy

Diamond-like carbon (DLC) films form a critical protective layer on magnetic hard disks and their reading heads. Now tetrahedral amorphous carbon films (ta–C) thickness of 2 nm are becoming the preferred means due to the highly sp³ content. In this paper, Raman spectra at visible and ultraviolet excitation of ta–C films have been studied as a function of substrate bias voltage. The spectra show that the sp³ content of 70 nm thick DLC films increases with higher substrate bias, while sp³ content of 2 nm ultra-thin films falls almost linearly with bias increment. And this is also consistent with the hardness measurement of 70 nm thick films. We proposed that substrate bias enhances mixing between the carbon films and either the Si films or Al₂O₃TiC substrate such that thin films contain less sp³ fraction. These mixing bonds are longer than C–C bonds, which inducing the hardness decreasing of ultra-thin DLC films with bias. But for 70 nm DLC, the effect of mixing layer can be negligible by compared to bias effect with higher carbon ion energy. So sp³ content will increase for thick films with substrate bias.     

Mechanism of diamond nucleation enhancement by electron emission via hot filament chemical vapor deposition

The mechanism of diamond nucleation enhancement by electron emission in the hot filament chemical vapor deposition process has been investigated by scanning electron microscopy, Raman spectroscopy and infrared (IR) absorption spectroscopy. The maximum value of the nucleation density was found to be 10¹¹ cm⁻² with a −300 V and 250 mA bias. The electron emission from the diamond coating on the electrode excites a plasma, and greatly increases the chemical species, as we have seen by in situ IR absorption. The experimental studies showed that the diamond and chemical species were transported and scattered from the diamond coating on the electrode and through the plasma towards the substrate surface, where they caused enhanced nucleation.     

Improvement in corrosion resistance of micro-arc oxidation coating on PVD Ti-coated aluminum alloy 7075

Surface treatments are always needed to enhance corrosion-resistant performance of aluminum (Al) alloys when they are used in seawater environments. The paper aimed to prepare the composite oxide ceramic coating on Al alloy 7075 by combining micro-arc oxidation (MAO) and magnetron sputtering technology. The Al substrate was precoated with titanium (Ti) layer by using the magnetron sputtering technology and then treated by MAO in the alkaline aluminate electrolyte, resulting in a composite MAO coating, which is composed of Al₂O₃ and TiO₂ along with the complex oxide (Al₂TiO₅). The potentiodynamic polarization and electrochemical impedance spectroscopy were carried out to evaluate the corrosion performance of the MAO coatings in 3.5 wt% NaCl solution. Better corrosion resistance was observed for composite oxide coating than the reference MAO coating on the bare Al, as evidenced by the higher corrosion potential of −0.664 V versus Ag/AgCl and the lower corrosion current density of 4.41 × 10^-6 A/cm².     

Improvement in performance of indium gallium oxide thin film transistor via oxygen mediated crystallization at a low temperature of 200 °C

We report the fabrication of high-performance polycrystalline indium gallium oxide (IGO) thin film transistors (TFTs) at a low temperature of 200 °C. Growth of a highly aligned cubic phase with a bixbyite structure was accelerated at a certain proportion of oxygen plasma density during deposition of the IGO thin film, which leads to outstanding electrical characteristics. The resulting polycrystalline IGO TFT exhibited a high field-effect mobility of 56.0 cm²/V, a threshold voltage (V_TH) of 0.10 V, a low subthreshold gate swing of 0.10 V/decade, and a current modulation ratio of >10⁸. Moreover, the crystalline IGO TFTs have highly stable behaviors with a small V_TH shift of +0.8 and ?1.0 V against a positive bias stress (V_GS,ST ?V_TH = 20 V) and negative bias illumination stress (V_GS,ST ?V_TH = ?20 V) for 3,600 s, which is attributed to the high quality of the bixbyite crystalline structure.     

Electrodeposited amorphous iron(III) oxides as anodes for photoelectrolysis of water

Deposition of amorphous iron(III)-oxide films on a conducting glass substrate was achieved via a cathodic bias in a 0.1 M hydrated ammonium iron(II) sulfate ((NH₄)₂Fe(SO₄)₂·6H₂O) solution at −1.6 V versus Ag/AgCl. Analysis by X-ray absorption near edge structure confirmed the iron(III) feature of the amorphous films. The deposited films exhibited n-type semiconducting characteristics by showing photoresponses under an anodic bias. The Mott–Schottky method and cyclic voltammetry were employed to characterize the semiconducting properties of the deposited films, which included the band gap (2.2 eV), the potentials of the conduction and valence band edges and flat band (−0.6, +1.6 and −0.58 V versus Ag/AgCl at pH 7, respectively), and the donor density (1 × 10²²/cm³). The deposited iron(III)-oxide films were suitable to serve as an anode for water splitting under illumination.     

Electrophoretic deposition studies of Ba(Zr-Ce-Y)O3 ceramic coating

Electrophoretic deposition (EPD) is now a well established colloidal processing technique which uses electrophoresis mechanism for the movement of suspended charged particles in a suspension in the presence of an electric field. In this work, electrophoretic deposition of BaZr_0.4Ce_0.4Y_0.2O_3-δ (BZCY) in ethanol medium was performed under different conditions on both conducting and non-conducting (porous anode) substrate without using any external additives in a suspension bath. Process parameters such as deposition time, voltage, and rate of deposition of suspended particles were studied under various conditions. Green coating deposited under different potential (30, 50, and 70V) was uniform and crack free, even at extended time of deposition. Surface roughnesses have also been evaluated to correlate it with deposition conditions. It is also found that the rate of deposition on conducting substrate was higher as compared to that on non-conducting substrate (anode). XRD studies of the calcined powder and coating exhibit an expected simple cubic perovskite structure. The deposition yield increases linearly with voltage for each deposition time for both conducting and non-conducting substrates. The coating on non-conducting porous anode heat treated at 1500°C for 2 hours was dense and well adherent to the anode substrate. A film thickness of about 13 μm was obtained at 70V. Such dense BZCY electrolyte coating on BZCY+NiO anode (Half cell) could be well utilized for fabrication of proton conducting SOFC single cell by applying suitable cathode layer on electrolyte film.     

Ir coating prepared on Mo substrate by double glow plasma

Dense and adherent Ir coating was obtained on the surface of the Mo substrate by double glow plasma, which had a deposition chamber and two cathodes. Argon gas was used as the working gas. The bias voltage of Ir target and Mo substrate were −800 and −300 V, respectively. The chamber pressure was 35 Pa. Microstructure of the Ir coating was observed by scanning electron microscopy. The Ir coating had a polycrystalline structure with preferential growth orientation of (220) crystal plane. The deposition rate was ~3.5 μm/h. The good adhesion resulted from the buffer layer between the Mo substrate and the Ir coating. The buffer layer, a combined Ir and Mo, was formed at the beginning of the deposition. The Mo concentration distributed gradiently along the depth of the buffer layer.     

Hydrothermal fabrication of p-Cu2O−n-ZnO films and their properties for photodegradation and ultraviolet sensors

This article reports spin coating and hydrothermal approaches to the synthesis of Cu₂O seed layer−ZnO and Cu₂O film−ZnO heterojunction films on fluorine-doped tin oxide substrates. Cu₂O seed layers and an ethylene glycol (EG) reducing agent were employed to obtain pure, uniform, and adhesive Cu₂O films on the substrate. Transmission electron microscopy validated the heterojunctions with clear interfaces between each component on the p-Cu₂O film−n-ZnO (with EG) sample, the conductive types of which were determined through Mott−Schottky measurements. Constructed energy band diagrams supported the Mott−Schottky result, manifesting favorable conduction band positions for the generation of •O₂⁻ radicals for all constituent materials and indicating smooth charge carrier transport for the p-Cu₂O film−n-ZnO (with EG) sample. Furthermore, abundant p−n junction interfaces synergistically enabled the sample to exhibit the most satisfactory photodegradation capability (rate constant ≈ 8.9 × 10⁻³ min⁻¹), which was attributable to the predominance of •OH radicals. The sample's rectifying (diode) behavior with a ratio of the current density (J) at +3 V (forward bias) to that at −3 V (reverse bias) of approximately 27 was observed without ultraviolet illumination. Moreover, the J at −3 V is under illumination approximately 80 times that without illumination, implying the suitability of the sample for UV detectability.     

Microstructures,mechanical properties and corrosion resistance of sprayed Ca–P coating for micropatterning carbon/carbon substrate surface

Carbon/carbon (C/C) surface micropatterning is a method of modifying the surface into the complete and regular geometry. In this work, we introduce a positive effect on bonding strength between sprayed Ca–P coating and surface micropatterning C/C substrate. Interestingly, C/C substrate coated by Ca–P coating provides textured surface for a new bone ingrowth. The sprayed Ca–P coating is then subjected to microwave-hydrothermal (MH) treatment with the aim of eliminating surface defects and obtaining a uniform purity phase. These objectives were achieved in our previous study by the MH method. The molar ratio of Ca/P in the coatings is nearly close to 1, which is far below that of Ca/P for hydroxyapatite (Ca₁₀(PO₄)₆(OH)₂, HA, 1.67). The purpose of this article is to transform the phases in the sprayed Ca–P coating, which owns the better bioactivity and high corrosion resistance. In order to raise the molar ratio of Ca/P, the coatings are treated under high-temperature (around 700 °C). They are analyzed by scanning electron microscopy (SEM), X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), and a fourier transform infrared spectra (FTIR). The bonding strength (coating/substrate), biological activity and corrosion resistance of the coatings are investigated. The resulting coatings own the different microstructures and phase compositions from the original sprayed Ca–P coating. Especially, results show that the shear strength of the sprayed Ca–P coating deposited on surface micropatterning C/C substrate increases by 61% which is more than that of the coating on non-surface micropatterning C/C substrate. Additionally, high-temperature treated coating presents a good biological activity and an excellent corrosion resistance of current density (1.3078 × 10^-6 A/cm²) and potential (−0.17 V_SCE).     

Optimization of wear–corrosion properties of a–C:N films using filtered cathodic arc deposition

Applying a 4-factor (negative substrate bias voltage, arc current, Ar flow and N₂/Ar ratio) 3-level (L9) orthogonal array design using the Taguchi method to optimize the wear–corrosion properties of a–C:N in Filtered Cathodic Vacuum Arc (FCVA) deposition was investigated. The influence of N₂/Ar ratio, over the range of 1/6 to 2/3, is shown by the increase in the following: the wear–corrosion current density changes from 36 to 78 nA/cm², and the friction coefficient changes from 0.042 to 0.086. A higher N₂/Ar ratio induces the a–C:N film's structure to reduce the sp³ content (sp² rich) which implies the formation of loose networks due to N₂ incorporation. Based on the analysis, the N₂/Ar ratio is the most significant control factor as its percentage contribution is 69% for wear–corrosion current density and 32% for frictional coefficient, respectively. There is a tendency for a higher friction coefficient by increasing the following three factors; level of negative substrate bias voltage, Ar flow and N₂/Ar ratio. We observed an increase of N content and sp² bonding which correlated to the decrease of hardness and an also rougher a–C:N surface with increasing the factors level. Over the design range of 4 factors, the optimum wear–corrosion properties and friction coefficient obtained from the Taguchi analysis were obtained using a 20 V negative substrate bias, 30 A arc current, 30 sccm Ar flow and 1/6 N₂/Ar ratio respectively. Overall, the results show an optimum design when compared with the current design as it was able to reduce 84% of the wear–corrosion current density (35.7 down to 5.6 nA/cm²) and 58% of the frictional coefficient (0.060 down to 0.025), respectively.     

Effects of pH value and temperature on the corrosion behavior of a Ta2N nanoceramic coating in simulated polymer electrolyte membrane fuel cell environment

To improve the corrosion resistance and electrical conductivity of Ti-6Al-4V bipolar plates used in polymer electrolyte membrane fuel cells (PEMFCs), a novel electro-conductive Ta₂N nanoceramic coating was developed by reactive sputter-deposition using a double cathode glow discharge plasma technique. The microstructure of the coating consisted of fine equiaxed Ta₂N grains with an average grain size of ∼13 nm, which exhibited a strong (101) preferred orientation. To explore the influence of both pH values and temperatures on the corrosion resistance of the coating, the electrochemical behaviors and electronic properties of passive films grown on the Ta₂N coating were systematically investigated using different electrochemical techniques in simulated PEMFC operating environment. It was shown that either increasing the acidity or the temperatures of the solution, the corrosion potential (E_corr) decreased and the corrosion current density (i_corr) increased. At a given temperature or pH value, the Ta₂N coating had a higher E_corr and lower i_corr as compared with uncoated Ti-6Al-4V. The results of EIS measurements showed that with increasing temperature or acidity of the solution, the resistance of the passive film (R_p) formed on the Ta₂N coating decreased slightly, being of the order of magnitude of 10⁷ Ω cm², which was an order of magnitude higher than that of uncoated Ti-6Al-4V. The interfacial contact resistance (ICR) values were found to increase with increasing pH value or decreasing solution temperature, and the ICR values of the Ta₂N coating were markedly lower than that of uncoated Ti-6Al-4V, due to the thinner thickness of passive films. Furthermore, the Ta₂N-coated Ti-6Al-4V is more hydrophobic than bare Ti-6A1-4V, which was favorable for both the simplification of water management and improving corrosion resistance in PEMFC operating environment.     

Solution-based fabrication and electrical properties of CaBi4Ti4O15 thin films

Ferroelectric CaBi₄Ti₄O₁₅ (CBT) thin films were prepared by spin coating technology using solution-based fabrication. The as-deposited CBT thin films were crystallized below 600 °C and the layered perovskite were crystallized at 700 °C using CFA processing in air. The enhancement of ferroelectric properties in CBT thin films for MFIS structures were investigated and discussed. Compared the Bi₄Ti₃O₁₂ (BIT), the CBT showed the better physical and electrical characteristics. The 700 °C annealed CBT thin films on SiO₂/Si substrate showed random orientation and exhibited large memory window curves. The maximum capacitance, memory window and leakage current density were about 250 pF, 2 V, and 10^?5 A/cm², respectively.     

Structural,optical and photocatalytic properties of ZnO nanorods: Effect of aging time and number of layers

ZnO thin films were prepared by sol–gel dip coating method onto glass substrates. The effects of aging time of the starting solution (2, 10 and 30 days) and the number of coats (2, 5 and 10 coatings) on structural, morphological and optical properties were investigated. Photocatalytic efficiency was also assessed. X-ray diffraction analysis indicates that all the films exhibit a Zincite-type structure with a preferred grains orientation along the [002] direction. The preferred orientation factor (POF) increases with aging time while the crystallite size decreases. The field emission scanning electron microscopy observations reveals nanorods morphology. The length of ZnO nanorods increase with increasing number of layers whereas their length decreases as a function of aging time while adopting a random orientation. A high optical transparency is observed for all ZnO thin films, ranging from 90 up to 96%. Methylene Blue (MB) dye photocatalytic degradation was found increases with aging time, reaching almost 94% after 10 h under UV irradiation. The apparent reaction rate (K_app) obtained by Langmuir-Hinshelwood model increases with increasing aging time from, from 0.218 h⁻¹ for 2 days to reach a steady state around 0.270 h⁻¹. Nevertheless, a small variation of K_app was recorded when varying the number of coats; 0.223–0.226 h⁻¹.     

Microstructure and tribological behavior of TiAlSiN coatings deposited by deep oscillation magnetron sputtering

Development of pulsed‐techniques aimed to generate highly ionized target species and high plasma density opens up a new way to tailor composition, structure, and properties of coatings. In this work, TiAlSiN coatings have been deposited at various negative substrate biases (V_s) using deep oscillation magnetron sputtering by sputtering a TiAlSi compound target in Ar/N₂ mixtures. The increase in V_s from ?30 to ?120 V resulted in a decrease in (111)‐preferred orientation and grain size, together with the increase in residual stress and rough morphology. The nc‐TiAlN/a‐Si₃N₄ nanocomposite structure was obtained in coatings. The highest hardness and Young's modulus reached 42.4 and 495 GPa at ?120 V, respectively. However, at ?60 V, the coatings with the highest H/E* and H³/E*² ratios of 0.095 and 0.332 exhibited excellent adhesion with above HF1 level, the lowest coefficient of friction (COF) of 0.35 and specific wear rate of 2.1 × 10^?7 mm³ N^?1 m^?1. Wear mechanism changed from the mixture of severe adhesive, oxidative and abrasive wear to mild oxidative wear to severe oxidative wear. TiAlSiN coatings with high hardness and H/E* and H³/E*² ratios exhibited the decrease in COF and wear rate due to refined grains in uniform distribution, which well promoted oxide layers formed on sliding contact surface.     

Structure of the hydroxyapatite plasma-sprayed coatings deposited on pre-heated titanium substrates

Plasma spraying is the most commonly used thermal spray method for the application of hydroxyapatite (HA, Ca₁₀(PO₄)₆(OH)₂) coatings. In the present study, the HA coatings were plasma spraying deposited onto plates of titanium pre-heated to 20 °C, 300 °C and 550 °C. The obtained HA coatings were investigated by means of X-ray diffraction and scanning electron microscopy. It is found that the coatings, in addition to HA, contain the tetracalcium phosphate (TTCP, (Ca₄(PO₄)₂O) phase (~10%) and a small amount of CaO (<2%). Crystal structure of HA in the coatings is revealed to be distorted. The PO4 tetrahedrons are deformed (Baur distortion coefficient D1(TO) ~0.2). The distances Ca1-O1 and Ca1-O2 are changed as compared to these in stoichiometric hydroxyapatite. These distortions are considered as a result of internal stresses, which are demonstrated in the broadening of peaks on X-ray diffraction pattern of HA. Microstructure of coatings consisting of flattened splats was formed by fully molten particles. The axial base texture was developed in the coatings. Ultrastructure is columnar with a preferred orientation of c-axes of the crystals parallel to the normal of plane coating n. The heating of substrate has a marked effect on the ultrastructure of coatings: the domain size increases from 790 to 1100 Å, the strain Δ decreases from 1.6·10^-3 to 1,2·10^–3, TTCP content diminishes from 12% to 7%. These results show that the effects due to heating of the substrate may be associated with partial recovery of HA microstructure.     

Fabrication of Mn–Co Spinel Coatings on Crofer 22 APU Stainless Steel by Electrophoretic Deposition for Interconnect Applications in Solid Oxide Fuel Cells

This study investigates the microstructure, oxidation kinetics, and electrical behavior of Mn–Co spinel coating for interconnect applications in solid oxide fuel cells. A relatively dense, uniform, and well‐adherent Mn–Co (Mn_1.5Co_1.5O₄) spinel coating with good oxidation resistance and stable conductivity was successfully prepared on the surface of Crofer 22 APU stainless steel using electrophoretic deposition followed by sintering at 1150°C. During further thermal treatment at 800°C, the chromium oxide (Cr₂O₃) sublayer formed at the substrate/coating interface during sintering showed a very slow growth, and no chromium penetration was detected in the Mn–Co coating. The oxidation kinetics of the Mn–Co‐coated substrate obeyed the parabolic law with the a parabolic rate constant k_p of 5.20 × 10^?15 g²/cm⁴/s, which was 1–2 orders of magnitude lower than that of the uncoated Crofer 22 APU stainless steel substrate. For oxidation (at 800°C) times ≥50 h, the area‐specific resistance of the Mn–Co‐coated Crofer 22 APU substrate became ~17 mΩ·cm² and was almost constant after further oxidation.