Characterization and structure study of the anodic oxide film on Zircaloy-4 synthesized using NaOH electrolytes at room temperature

Thick crystalline zirconium oxide films were synthesized on Zircaloy-4 substrates by anodic oxidation at room temperature in NaOH solution with a stable applied voltage (300 V). The film is approximately 4.7 μm in thickness. The XPS and SEM analysis shows that the film is a three-layer structure in water, hydroxide and oxide parts. The thickness of that order is ∼0.01 μm, ∼1 μm, ∼3.7 μm, respectively. The oxide layer is composed of tetragonal and monoclinic phases with the volume ratio about 0.2. Furthermore, the thick anodic film acts as a barrier to oxygen and zirconium migrations. It effectively protects zirconium alloys against the worse corrosion. An extremely low passive current density of ∼0.018 μA/cm² and a low oxidation weight gain of ∼0.411 mg/cm² were also observed in the films.     

Effect of La surface treatments on corrosion resistance of A3xx.x/SiCp composites in salt fog

The influence of the SiC_p proportion and the matrix concentration of four aluminium metal matrix composites (A360/SiC/10p, A360/SiC/20p, A380/SiC/10p, A380/SiC/20p) modified by lanthanum-based conversion or electrolysis coating was evaluated in neutral salt fog according to ASTM B 117. Lanthanum-based conversion coatings were obtained by immersion in 50 °C solution of La(III) salt and lanthanum electrolysis treatments were performed in ethylene glycol mono-butyl ether solution. These treatments preferentially covered cathodic areas such as intermetallic compounds, Si eutectic and SiC_p. The kinetic of the corrosion process was studied on the basis of gravimetric tests. Both coating microstructure and nature of corrosion products were analyzed by scanning electron microscopy (SEM), atomic force microscopy (AFM), energy dispersive X-ray analysis (EDS) and low angle X-ray diffraction (XRD) before and after accelerated testing to determine the influence of microstructural changes on corrosion behaviour during exposure to the corrosive environment. The corrosion process was more influenced by the concentration of alloy elements in the matrix than by the proportion of SiC_p reinforcement. Both conversion and electrolysis surface treatments improved the behaviour to salt fog corrosion in comparison with original composites without treatment. Additionally, electrolysis provided a higher degree of protection than the conversion treatment because the coating was more extensive.     

A novel process of electroless Ni-P plating with plasma electrolytic oxidation pretreatment

A novel Ni based coating - plasma electrolytic oxidation (PEO) pre-treatment followed by electroless nickel (EN) plating - has been developed to produce pore free Ni coatings on AZ91 magnesium alloy. The application of the PEO film between the nickel coating and the substrate acts as an effective barrier and catalytic layer for the subsequent nickel plating. The potentiodynamic tests indicated that the corrosion current density of the PEO + EN plating on AZ91 decreased by almost two orders of magnitudes compared to the traditional EN coating. Salt fog spray testing further proved this improvement. More importantly, the new technique does not use Cr⁺⁶ and HF in its pretreatment, therefore is a much environmentally friendlier process.     

Characterization of microarc oxidation coatings formed on AM60B magnesium alloy in silicate and phosphate electrolytes

Microarc oxidation coatings on AM60B magnesium alloy were prepared in silicate and phosphate electrolytes. Structure, composition, mechanical property, tribological, and corrosion resistant characteristics of the coatings was studied by scanning electron microscope (SEM), X-ray diffraction (XRD) and microhardness analyses, and by ball-on-disc friction and potentiodynamic corrosion testing. It is found that the coating produced from the silicate electrolyte is compact and uniform and is mainly composed of MgO and forsterite Mg₂SiO₄ phases, while the one formed in phosphate electrolyte is relatively porous and is mainly composed of MgO phase. The thick coating produced from a silicate electrolyte possesses a high hardness and provides a low wear rate (3.55 × 10⁻⁵ mm³/Nm) but a high friction coefficient against Si₃N₄ ball. A relatively low hardness and friction coefficient while a high wear rate (8.65 × 10⁻⁵ mm³/Nm) is recorded during the testing of the thick coating produced from a phosphate electrolyte. Both of these types of coatings provide effective protection for the corrosion resistance compared with the uncoated magnesium alloy. The coating prepared from the silicate electrolyte demonstrates better corrosion behavior due to the compacter microstructure.     

Improved moisture resistance of SrS:Eu phosphors with nanoscale SiO2 coating

Orange-emitting SrS:Eu²⁺ phosphors were coated with nanoscale SiO₂ and their photoluminescence (PL) degradation behavior in moist air was investigated. The SiO₂ coating was obtained by sol-gel process using diethoxydimethylsilane (DEDMS) and the coating content was varied from 0.5 to 2 wt%. The coatings were composed of a uniform, continuous, and amorphous SiO₂ layer of 30-50 nm thickness and the coating thickness was not varied significantly with the coating content. No peak shift and no decrease of PL intensity were observed after coating. The PL intensity of the coated phosphors decreased to ∼75% of the original value after 10 h exposure to moist air, while the uncoated phosphor decreased to ∼33%, which indicates the improved moisture resistance of the nanoscale SiO₂ coated SrS:Eu²⁺ phosphors.     

Low-temperature oxidation of SiGe by liquid-phase deposition

Low-temperature silicon dioxide (SiO₂) films were grown on silicon germanium (SiGe) surfaces using the liquid-phase deposition (LPD) method. The growth solutions of LPD-SiO₂ are hydrofluorosilicic acid (H₂SiF₆) and boric acid (H₃BO₃). It was found that the growth rate increases with increasing temperature and concentration of H₃BO₃. The Auger electron spectroscopy profile shows that no pileup of Ge atoms occurs at the interface of SiO₂/SiGe after the LPD-SiO₂ growth. Al/LPD-SiO₂/p-SiGe MOS capacitors were prepared to determine capacitance-voltage (C-V) and current-voltage (I-V) characteristics. In our experiments, a low leakage current density of 8.69 × 10⁻⁹ A/cm² under a 2 MV/cm electric field was observed. Such a value is much smaller than those of plasma- and thermal-oxides as a result of no plasma damage and a lower growth temperature. Moreover, lower oxide charges and interface charge densities of 3.82 × 10¹⁰ cm⁻² and 1.12 × 10¹¹ eV⁻¹ cm⁻², respectively, were achieved in our LPD-SiO₂ compared to direct photochemical-vapor-deposition-SiO₂.     

Influence of treating frequency on microstructure and properties of Al2O3 coating on 304 stainless steel by cathodic plasma electrolytic deposition

Alumina ceramic coatings were fabricated on 304 stainless steel by cathodic plasma electrolytic deposition (CPED). Influence of treating frequency of the power supply on the microstructure and properties of the coatings were studied. The results indicated that coatings obtained at various frequencies on 304 stainless steels were all composed of α-Al₂O₃ and γ-Al₂O₃, and α-Al₂O₃ was the dominant phase. The contents of α-Al₂O₃ decreased gradually in a very small rate with increasing the frequency and γ-Al₂O₃ gradually increased. The surface of alumina ceramic coating was porous. With increasing the frequency, the coating surface gradually became less rough and more compact, resulting in low surface roughness. The bonding strength of Al₂O₃ coating was higher than 22 MPa and was not strongly affected by treating frequency. With increasing the frequency, the alumina coated steels showed better and gradually increasing corrosion resistance than the uncoated one in 3.5% NaCl solution. The coating steel with desirable corrosion resistance was obtained at 800 Hz whose corrosion current potential and corrosion density were −0.237 V and 7.367 × 10⁻⁸ A/cm², respectively.     

Influence of the vacuum level upon the growth of carbon nanotubes on silicon carbide surface

We have investigated the influence of the vacuum level upon the growth of carbon nanotubes (CNTs) on 6H-SiC () surface.CNTs of about 160 nm in length were formed densely and uniformly on the 6H-SiC surface during annealing at 1700 °C in a high vacuum (∼10⁻² Pa). CNTs of about 1 μm in length were formed during annealing at 1700 °C in an ultra-high vacuum (∼10⁻⁷ Pa). However, CNTs were not formed and SiO₂ layers were formed on the SiC surface at 1700 °C in air. It is found that longer CNTs can grow up in an ultra-high vacuum, moreover, a little aligned and low-density graphite layers, or carbon nanofibers can also grow up.     

On ultra-thin oxide/Si and very-thin oxide/Si structures prepared by wet chemical process

The properties of ultra-thin oxide/Si and very-thin oxide/Si structures prepared by wet chemical oxidation in nitric acid aqueous solutions (NAOS) and passivated in HCN aqueous solutions were investigated by electrical, optical and structural methods. n- and p-doped (1 0 0) crystalline Si substrates were used. There were identified more types of interface defect states in dependence on both post-oxidation treatment and passivation procedure. On samples prepared on n-type Si, continuous spectrum of defect states of 0.05-0.2 eV range and discrete defect traps, ∼E_CB − 0.26 eV and ∼E_CB − 0.39 eV, were found. All mentioned defects are related with various types of Si dangling bonds and/or with SiO_x precipitates. Post-metallization annealing of investigated MOS structures reduced the interface defect density and suppressed the leakage currents. It did not change spectral profile of interface defect states in the Si band gap. In addition, there are presented following two optical phenomena: relation between amplitude of photoluminescence signal of NAOS samples and parameters of chemical oxidation process and quantum confinement effect observed on samples containing Si grains of size less as ∼2 nm.     

Corrosion and wear properties of PEO coatings formed on AM60B alloy in NaAlO2 electrolytes

Coatings with a thickness of 22-32 μm were formed on an AM60B magnesium alloy by plasma electrolytic oxidation (PEO) in electrolytes containing 12.0-24.0 g/l NaAlO₂ and other additives. SEM analyses of the coated samples showed that the coatings were compact with relatively low porosity. X-ray diffraction revealed that the coatings consisted of mainly MgAl₂O₄ and MgO phases. The relative amount of MgAl₂O₄ in the coating increased with increasing NaAlO₂ concentration. The relatively compact and thick coatings provide good corrosion protection for magnesium, as indicated by the results of potentiodynamic polarization tests. In addition, the PEO treatment also significantly improved the wear resistance of the alloy. Pin-on-disk wear tests showed that the PEO treatment reduced the wear volume loss by a factor of 10.     

Nitric acid oxidation method to form SiO2/3C-SiC structure at 120 °C

3C-SiC(0 0 1) surfaces are considerably rough with the roughness root mean square value (R_ms) of 1.3 nm, but the surfaces become considerably smooth (i.e., R_ms of 0.5 nm) by heat treatment in pure hydrogen at 400 °C. Two-step nitric acid (HNO₃) oxidation (i.e., immersion in ∼40 wt% HNO₃ followed by that in 68 wt% HNO₃) performed after the hydrogen treatment can oxidize 3C-SiC at extremely low temperature of ∼120 °C, forming thick SiO₂ (e.g., 21 nm) layers. With no hydrogen treatment, the leakage current density of the 〈Al/SiO₂/3C-SiC〉 metal-oxide-semiconductor (MOS) diodes is high, while that for the MOS diodes with the hydrogen treatment is considerably low (e.g., ∼10⁻⁶ A/cm² at the forward gate bias of 1 V) due to the formation of uniform thickness SiO₂ layers. The MOS diodes with the hydrogen treatment show capacitance-voltage curves with accumulation, depletion, and deep-depletion characteristics.     

Preparation and characterization of the electrodeposited Cr-Al2O3/SiC composite coating

To increase the SiC content in Cr-based coatings, Cr-Al₂O₃/SiC composite coatings were plated in Cr(VI) baths which contained Al₂O₃-coated SiC powders. The Al₂O₃-coated SiC composite particles were synthesized by calcining the precursor prepared by heterogeneous deposition method. The transmission electron microscopy analysis of the particles showed that the nano-SiC particle was packaged by alumina. The zeta potential of the particles collected from the bath was up to +23 mV, a favorable condition for the co-deposition of the particles and chromium. Pulse current was used during the electrodeposition. Scanning Electron Microscopy (SEM) indicated that the coating was compact and combined well with the substrate. Energy dispersive X-ray analysis of Cr-Al₂O₃/SiC coatings demonstrated that the concentration of SiC in the coating reached about 2.5 wt.%. The corrosion behavior of the composite coating was studied by potentiodynamic polarization and electrochemical impedance spectroscopy techniques. The data obtained suggested that the Al₂O₃/SiC particles significantly enhanced the corrosion resistance of the composite coating in 0.05 M HCl solution.     

Study of La0.8Sr0.2Co0.2Cr0.8O3 − δ as a candidate coating material for the positive current collector in Na/S battery

Perovskite La_0.8Sr_0.2Co_0.2Cr_0.8O_3 − δ (LSCC) ceramic synthesized by the conventional ceramic processing technique was studied as a novel coating material for the cathode current collector in Na/S battery. Its structure, electrical conductivity, density and thermal expansion coefficient (TEC) were investigated. The corrosion performance of LSCC was in particular evaluated by electrochemical techniques in combination with long-term dip-immersion tests. The results indicated that LSCC exhibited excellent corrosion resistance in molten sodium tetrasulfide at 350 °C. The corrosion current density i_corr (0.081 mA cm^− 2) was much lower than that of 316 L stainless steel by approximately two orders of magnitude. The corrosion rate of LSCC deduced from immersion test was as low as about 12 μm year^− 1.     

In vitro corrosion behavior of Ti-O film deposited on fluoride-treated Mg-Zn-Y-Nd alloy

In this paper, a new composite coating was fabricated on magnesium alloy by a two-step approach, to improve the corrosion resistance and biocompatibility of Mg-Zn-Y-Nd alloy. First, fluoride conversion layer was synthesized on magnesium alloy surface by immersion treatment in hydrofluoric acid and then, Ti-O film was deposited on the preceding fluoride layer by magnetron sputtering. FE-SEM images revealed a smooth and uniform surface consisting of aggregated nano-particles with average size of 100 nm, and a total coating thickness of ∼1.5 μm, including an outer Ti-O film of ∼250 nm. The surface EDS and XRD data indicated that the composite coating was mainly composed of crystalline magnesium fluoride (MgF₂), and non-crystalline Ti-O. Potentiodynamic polarization tests revealed that the composite coated sample have a corrosion potential (E_corr) of −1.60 V and a corrosion current density (I_corr) of 0.17 μA/cm², which improved by 100 mV and reduced by two orders of magnitude, compared with the sample only coated by Ti-O. EIS results showed a polarization resistance of 3.98 kΩ cm² for the Ti-O coated sample and 0.42 kΩ cm² for the composite coated sample, giving an improvement of about 100 times. After 72 h immersion in SBF, widespread damage and deep corrosion holes were observed on the Ti-O coated sample surface, while the integrity of composite coating remained well after 7 d. In brief, the data suggested that single Ti-O film on degradable magnesium alloys was apt to become failure prematurely in corrosion environment. Ti-O film deposited on fluoride-treated magnesium alloys might potentially meet the requirements for future clinical magnesium alloy stent application.     

F2 laser induced oxidation of inorganic material

Transparent SiO₂ thin films were selectively fabricated on Si wafer by 157 nm F₂ laser in N₂/O₂ gas atmosphere. The F₂ laser photochemically produced active O(¹D) atoms from O₂ molecules in the gas atmosphere; strong oxidation reaction could be induced to fabricate SiO₂ thin films only on the irradiated areas of Si wafer. The oxidation reaction was sensitive to the single pulse fluence of F₂ laser. The irradiated areas were swelled and the height was approximately 500-1000 nm at the 205-mJ/cm² single pulse fluence for 60 min laser irradiation. The fabricated thin films were analytically identified to be SiO₂ by the Fourier-transform IR spectroscopy. The SiO₂ thin films could be also removed by subsequent chemical etching to fabricate micro-holes 50 nm in depth on Si wafer for microfabrication.     

Enhancement of surface mechanical properties by using TiN[BCN/BN]n/c-BN multilayer system

The aim of this work is to improve the mechanical properties of AISI 4140 steel substrates by using a TiN[BCN/BN]_n/c-BN multilayer system as a protective coating. TiN[BCN/BN]_n/c-BN multilayered coatings via reactive r.f. magnetron sputtering technique were grown, systematically varying the length period (Λ) and the number of bilayers (n) because one bilayer (n = 1) represents two different layers (t_BCN + t_BN), thus the total thickness of the coating and all other growth parameters were maintained constant. The coatings were characterized by Fourier transform infrared spectroscopy showing bands associated with h-BN bonds and c-BN stretching vibrations centered at 1400 cm⁻¹ and 1100 cm⁻¹, respectively. Coating composition and multilayer modulation were studied via secondary ion mass spectroscopy. Atomic force microscopy analysis revealed a reduction in grain size and roughness when the bilayer number (n) increased and the bilayer period decreased. Finally, enhancement of mechanical properties was determined via nanoindentation measurements. The best behavior was obtained when the bilayer period (Λ) was 80 nm (n = 25), yielding the relative highest hardness (∼30 GPa) and elastic modulus (230 GPa). The values for the hardness and elastic modulus are 1.5 and 1.7 times greater than the coating with n = 1, respectively. The enhancement effects in multilayered coatings could be attributed to different mechanisms for layer formation with nanometric thickness due to the Hall-Petch effect; because this effect, originally used to explain increased hardness with decreasing grain size in bulk polycrystalline metals, has also been used to explain hardness enhancements in multilayered coatings taking into account the thickness reduction at individual single layers that make up the multilayered system. The Hall-Petch model based on dislocation motion within layered and across layer interfaces has been successfully applied to multilayered coatings to explain this hardness enhancement.     

Effect of current density on the microstructure and corrosion behaviour of plasma electrolytic oxidation treated AM50 magnesium alloy

Plasma electrolytic oxidation (PEO) of an AM50 magnesium alloy was accomplished in a silicate-based electrolyte using a DC power source. Coatings were produced at three current densities, i.e. 15 mA cm⁻², 75 mA cm⁻², and 150 mA cm⁻² and were characterised for thickness, roughness, microstructural morphology, phase composition, and corrosion resistance. Even though the 15 min treated coatings produced at higher current density levels were thicker, they showed poor corrosion resistance when compared to that of the coatings obtained at 15 mA cm⁻². Short-term treatments (2 min and 5 min) at 150 mA cm⁻² yielded coatings of thickness and corrosion resistance comparable to that of the low current density coatings. The superior corrosion resistance of the low thickness coatings is attributed to the better pore morphology and compactness of the layer.     

Thermal oxidation temperature dependence of 4H-SiC MOS interface

The thermal oxidation temperature dependence of 4H-silicon carbide (SiC) is systematically investigated using X-ray photoelectron spectroscopy (XPS) and capacitance-voltage (C-V) measurements. When SiC is thermally oxidized, silicon oxycarbides (SiC_xO_y) are first grown and then silicon dioxide (SiO₂) is grown. It is identified by XPS that the SiO₂ films fall into two categories, called SiC-oxidized SiO₂ and Si-oxidized SiO₂ in this paper. The products depend on thermal oxidation temperature. The critical temperature is between 1200 and 1300 °C. The interface trap density (D_it) of the sample possessing Si-oxidized SiO₂, at thermal oxidation temperature of 1300 °C, is lower than SiC-oxidized SiO₂ at and below 1200 °C, suggesting that a decrease of the C component in SiO₂ film and SiO₂/SiC interface by higher oxidation temperature improves the metal-oxide-semiconductor (MOS) characteristics.     

Nitric acid oxidation of Si (NAOS) method for low temperature fabrication of SiO2/Si and SiO2/SiC structures

We have developed low temperature formation methods of SiO₂/Si and SiO₂/SiC structures by use of nitric acid, i.e., nitric acid oxidation of Si (or SiC) (NAOS) methods. By use of the azeotropic NAOS method (i.e., immersion in 68 wt% HNO₃ aqueous solutions at 120 °C), an ultrathin (i.e., 1.3-1.4 nm) SiO₂ layer with a low leakage current density can be formed on Si. The leakage current density can be further decreased by post-metallization anneal (PMA) at 200 °C in hydrogen atmosphere, and consequently the leakage current density at the gate bias voltage of 1 V becomes 1/4-1/20 of that of an ultrathin (i.e., 1.5 nm) thermal oxide layer usually formed at temperatures between 800 and 900 °C. The low leakage current density is attributable to (i) low interface state density, (ii) low SiO₂ gap-state density, and (iii) high band discontinuity energy at the SiO₂/Si interface arising from the high atomic density of the NAOS SiO₂ layer.For the formation of a relatively thick (i.e., ≥10 nm) SiO₂ layer, we have developed the two-step NAOS method in which the initial and subsequent oxidation is performed by immersion in ∼40 wt% HNO₃ and azeotropic HNO₃ aqueous solutions, respectively. In this case, the SiO₂ formation rate does not depend on the Si surface orientation. Using the two-step NAOS method, a uniform thickness SiO₂ layer can be formed even on the rough surface of poly-crystalline Si thin films. The atomic density of the two-step NAOS SiO₂ layer is slightly higher than that for thermal oxide. When PMA at 250 °C in hydrogen is performed on the two-step NAOS SiO₂ layer, the current-voltage and capacitance-voltage characteristics become as good as those for thermal oxide formed at 900 °C.A relatively thick (i.e., ≥10 nm) SiO₂ layer can also be formed on SiC at 120 °C by use of the two-step NAOS method. With no treatment before the NAOS method, the leakage current density is very high, but by heat treatment at 400 °C in pure hydrogen, the leakage current density is decreased by approximately seven orders of magnitude. The hydrogen treatment greatly smoothens the SiC surface, and the subsequent NAOS method results in the formation of an atomically smooth SiO₂/SiC interface and a uniform thickness SiO₂.     

Formation of atomically smooth SiO2/SiC interfaces at ∼120 °C by use of nitric acid oxidation method

Conventional thermal oxidation of SiC requires heating at ∼1100 °C. In the present study, we have developed a method of oxidizing SiC at low temperatures (i.e., ∼120 °C) to form relatively thick silicon dioxide (SiO₂) layers by use of nitric acid. When 4H-SiC(0 0 0 1) wafers are immersed in 40 wt% HNO₃ at the boiling temperature of 108 °C and the boiling is kept for 5 h after reaching the azeotropic point (i.e., 68 wt% HNO₃ at 121 °C), 8.1 nm thick SiO₂ layers are formed on the SiC substrates. High resolution transmission electron microscopy measurements show that the SiO₂/SiC interface is atomically flat and the SiO₂ layer is uniform without bunching. When SiC is immersed in an azeotropic mixture of HNO₃ with water from the first, the SiO₂ thickness is less than 0.3 nm. The metal-oxide-semiconductor (MOS) diodes with the SiO₂ layer formed by the nitric acid oxidation method possess a considerably low leakage current density.