Preparation and wear resistance of pulse electrodeposited Ni-W/Al2O3 composite coatings

The aim of this work is to obtain the electroplating parameters for preparation of Ni-W/Al₂O₃ composite coating with high tungsten content, high micro-hardness and excellent wear resistance by pulse plating procedure. Our results showed that the duty cycle is a dominant parameter for the tungsten content in the coating and the tungsten content increases significantly with increasing duty cycle. The further analysis showed the great influence of tungsten content on micro-hardness of the coating. A maximum micro-hardness of about 859 Hv was obtained in pulse electrodeposited Ni-W/Al₂O₃ composite with tungsten content of 40 wt.% at a peak current density of 20 A/dm², a duty cycle of 80%, a pulse frequency of 1000 Hz and a particle loading of 10 g/L alumina in the plating bath. Although the hardness of Ni-W/Al₂O₃ composite coating was only slightly affected by the alumina content of the deposits prepared in present investigation, the alumina content effect on the tribological characteristic of Ni-W/Al₂O₃ composite coatings is significant. The friction coefficient was lowered to 0.25 and the wear loss was reduced to 1.05 mg by setting the control factors according to the values mentioned above for obtaining the coating with the highest micro-hardness.     

Characterization of ceria-yttria stabilized zirconia plasma-sprayed coatings

Ceria-yttria stabilized zirconia (CYSZ) coatings were prepared by air plasma-sprayed on the nickel alloy. The as-sprayed CYSZ coatings and heat-treated CYSZ coatings were characterized by X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The XPS data indicated the coexistence of Ce³⁺, Ce⁴⁺, Y³⁺ and Zr⁴⁺ ions near the surface of the as-sprayed CYSZ coatings and the disappearance of Ce³⁺ ions in the CYSZ coatings after thermal treatment at 1000 °C for 15 h. From the XRD patterns, the solid solution of CeO₂-Y₂O₃-ZrO₂ formed in the CYSZ coatings because of the lack of any features from Y₂O₃ and ZrO₂ single phases. After thermal treatment, the main phases of all the samples were consistent with the characteristic peaks of cubic ZrO₂.     

High performance nanostructured ZrO2 based thermal barrier coatings deposited by high efficiency supersonic plasma spraying

In this paper, the nanostructured zirconia (ZrO₂) based thermal barrier coatings (TBCs) deposited by high efficiency supersonic atmospheric plasma spraying (SAPS), were described. The phase composition, microstructure, thermal conductivity and thermal shock resistance of as-sprayed coating were studied. The results revealed that the as-sprayed coating was composed of tetragonal zirconia and consisted of some unmelted nanoparticles (30-50 nm) and nanograins (60-110 nm), and the latter was the main microstructure of the coating. The nanograins and homogeneously distributed micro-cracks of coating resulted in not only low thermal conductivity, but also high thermal cycling lives. Besides, the failure process of coating during thermal cycles was also investigated in the present work.     

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.     

Microstructure and properties of Ni-Co/nano-Al2O3 composite coatings by pulse reversal current electrodeposition

Ni-Co/nano-Al₂O₃ (Ni-Co/Al₂O₃) composite coatings were prepared under pulse reversal current (PRC) and direct current (dc) methods respectively. The microstructure of coatings was characterized by means of XRD, SEM and TEM. Both the Ni-Co alloy and composite coatings exhibit single phase of Ni matrix with face-centered cubic (fcc) crystal structure, and the crystal orientation of the Ni-Co/Al₂O₃ composite coating was transformed from crystal face (2 0 0) to (1 1 1) compared with alloy coatings. The hardness, anti-wear property and macro-residual stress were also investigated. The results showed that the microstructure and performance of the coatings were greatly affected by Al₂O₃ content and the electrodeposition methods. With the increasing of Al₂O₃ content, the hardness and wear resistance of the composite coatings enhanced. The PRC composite coatings exhibited compact surface, high hardness, better wear resistance and lower macro-residual stress compared with that of the dc composite coatings.     

X-ray photoelectron spectroscopy of nano-multilayered Zr-O/Al-O coatings deposited by cathodic vacuum arc plasma

Nano-multilayered Zr-O/Al-O coatings with alternating Zr-O and Al-O layers having a bi-layer period of 6-7 nm and total coating thickness of 1.0-1.2 μm were deposited using a cathodic vacuum arc plasma process on rotating Si substrates. Plasmas generated from two cathodes, Zr and Al, were deposited simultaneously in a mixture of Ar and O₂ background gases. The Zr-O/Al-O coatings, as well as bulk ZrO₂ and Al₂O₃ reference samples, were studied using X-ray photoelectron spectroscopy (XPS). The XPS spectra were analyzed on the surface and after sputtering with a 4 kV Ar⁺ ion gun. High resolution angle resolved spectra were obtained at three take-off angles: 15°, 45° and 75° relative to the sample surface.It was shown that preferential sputtering of oxygen took place during XPS of bulk reference ZrO₂ samples, producing ZrO and free Zr along with ZrO₂ in the XPS spectra. In contrast, no preferential sputtering was observed with Al₂O₃ reference samples. The Zr-O/Al-O coatings contained a large amount of free metals along with their oxides. Free Zr and Al were observed in the coating spectra both before and after sputtering, and thus cannot be due solely to preferential sputtering.Transmission electron microscopy revealed that the Zr-O/Al-O coatings had a nano-multilayered structure with well distinguished alternating layers. However, both of the alternating layers of the coating contained of a mixture of aluminum and zirconium oxides and free Al and Zr metals. The concentration of Zr and Al changed periodically with distance normal to the coating surface: the Zr maximum coincided with the Al minimum and vice versa. However the concentration of Zr in both alternating layers was significantly larger than that of Al. Despite the large free metal concentration, the Knoop hardness, 21.5 GPa, was relatively high, which might be attributed to super-lattice formation or formation of a metal-oxide nanocomposite within the layers.     

Effect of NaAlO2 concentrations on microstructure and corrosion resistance of Al2O3/ZrO2 coatings formed on zirconium by micro-arc oxidation

In this study, Al₂O₃/ZrO₂ composite coatings were prepared on Zr substrates by micro-arc oxidation (MAO) in the NaAlO₂-containing electrolytes, and the effect of NaAlO₂ concentration on the microstructure, bond strength, microhardness and corrosion resistance of coatings was systematically investigated. The study reveals that the adequate NaAlO₂ in the electrolyte (>0.2 M) is essential to the formation of needle-like α-Al₂O₃ in the coatings, and the amount of α-Al₂O₃ rises with the increase of the NaAlO₂ concentration. m-ZrO₂ and t-ZrO₂ are present in all of the coatings, but their relative amount largely depends on the amount of Al₂O₃. It is also found that as the NaAlO₂ concentration increases from 0.2 to 0.3 M, the coating becomes denser and thicker, and its bond strength, maximum microhardness and corrosion resistance increases as well. The coating formed at 0.3 M NaAlO₂ demonstrates the highest bond strength of 52 MPa, the maximum microhardness of 1600 Hv_0.2N and the superior corrosion resistance. However, the overhigh concentration of NaAlO₂ (0.35 M) is found harmful to the coating's microstructure and properties.     

Preparation and characteristics of three-layer YSZ-(YSZ/Al2O3)-YSZ TBCs

Novel three-layer YSZ-(YSZ/Al₂O₃)-YSZ (6 wt.% Y₂O₃ partially stabilized ZrO₂) thermal barrier coatings (TBCs) were successfully prepared on Ni-based superalloy substrate using composite sol-gel and pressure filtration microwave sintering (PFMS) techniques. The coatings were evaluated for the cyclic oxidation resistance, thermal barrier effect and the presences of phases and microstructures. FE-SEM results indicate that the coatings were dense and crack-free. The coatings maintained their structural integrity when they were exposed at 1100 for 100 h. They exhibited superior oxidation resistance, spallation resistance and thermal insulation property compared with single-layer YSZ coatings. Moreover, the detailed mechanisms were discussed in order to understand the improved performance of the three-layer TBCs.     

Optical simulation, optimized design and fabrication of (ZrO2)x-(Al2O3)1−x composite films with thin inserted TiO2 layers for ArF-line high transmission attenuated phase shift mask blank applications

The tunable optical constants of the stoichiometric (ZrO₂)_x-(Al₂O₃)_1−x composite films with thin inserted TiO₂ layers are simulated as π-phase shifters. The optimized composition range of the superlattices to be used as a high transmission attenuated phase shift mask (HT-APSM) blank is found. The absorption edge shifts to the longer wavelengths when the thickness fraction of the TiO₂ layer increases. The optimized film for ArF-line HT-APSM blank applications must have the lower inspection transmittance for the better inspection and the lower reflectance at the exposure wavelength for a better aerial image as π-phase shifters, and they will be easier to fabricate than a superlattice. In order to find such a film, (ZrO₂)_x-(Al₂O₃)_1−x composite films with various inserted TiO₂ layers are simulated. The optimal deposition processes of such a film are also determined. For example, a (ZrO₂)_0.187-(Al₂O₃)_0.813 composite film with two inserted TiO₂ thin layers is fabricated. The optical properties are as follows: a transmittance of 19.8%, a reflectance of 9.1%, a calculated phase shift of ∼181.5° at the exposure wavelength of 193 nm, and a transmittance of 18.9% at the inspection wavelength of 257 nm. Such a film should be used as an optimized HT-APSM blank.     

Correlation between Al2O3 particles and interface of Al-Al2O3 coatings by cold spray

Al-Al₂O₃ composite coatings with different Al₂O₃ particle shapes were prepared on Si and Al substrate by cold spray. The powder compositions of metal (Al) and ceramic (Al₂O₃) having different sizes and agglomerations were varied into ratios of 10:1 wt% and 1:1 wt%. Al₂O₃ particles were successfully incorporated into the soft metal matrix of Al. It was found that crater formation between the coatings and substrate, which is typical characteristic signature of cold spray could be affected by initial starting Al₂O₃ particles. In addition, when the large hard particles of fused Al₂O₃ were employed, the deep and big craters were generated at the interface between coatings and hard substrates. In the case of pure soft metal coating such as Al on hard substrate, it is very hard to get proper adhesion due to lack of crater formation. Therefore, the composite coating would have certain advantages.     

Microstructure and mechanical properties of Al2O3-Al composite coatings deposited by plasma spraying

Al₂O₃ and Al₂O₃-Al composite coatings were prepared by plasma spraying. Phase composition of powders and as-sprayed coatings was determined by X-ray diffraction (XRD), while optical microscopy (OM) and scanning electron microscopy (SEM) were employed to investigate the morphology of impacted droplets, polished and fractured surface, and the element distribution in terms of wavelength-dispersive spectrometer (WDS). Mechanical properties including microhardness, adhesion and bending strength, fracture toughness and sliding wear rate were evaluated. The results indicated that the addition of Al into Al₂O₃ was beneficial to decrease the splashing of impinging droplets and to increase the deposition efficiency. The Al₂O₃-Al composite coating exhibited homogeneously dispersed pores and the co-sprayed Al particles were considered to be distributed in the splat boundary. Compared with Al₂O₃ coating, the composite coating showed slightly lower hardness, whereas the coexistence of metal Al phase and Al₂O₃ ceramic phase effectively improved the toughness, strength and wear resistance of coatings.     

Role of Ti in the luminescence process of Al2O3:Si,Ti

Al₂O₃:Si,Ti, prepared under oxidizing condition at high temperature, gives PL emission around 430 nm when excited with 240 nm. The Al₂O₃:C, TL/OSL phosphor, also shows emission around 430 nm, which corresponds to characteristic emission of F-center. Thus, to identify the exact nature of luminescent center in Al₂O₃:Si,Ti, fluorescence lifetime measurement studies were carried out along with the PL,TL and OSL studies. The PL and TL in Al₂O₃:Si,Ti show emission around 430 nm and the time-resolved fluorescence studies show lifetime of about 43 μs for the 430 nm emission, which is much smaller than the reported lifetime of ∼35 ms for the 430 nm emission (F-center emission) in Al₂O₃:C phosphor. Therefore, the emission observed in Al₂O₃:Si,Ti phosphor was assigned to Ti⁴⁺ charge transfer transition. Fluorescence studies of Al₂O₃:Si,Ti do not show any traces of F and F⁺ centers. Also, Ti⁴⁺ does not show any change in the charge state after gamma-irradiation. On the basis of the above studies, a mechanism for TSL/OSL process in Al₂O₃:Si,Ti is proposed.     

Stabilization of a very high-k crystalline ZrO2 phase by post deposition annealing of atomic layer deposited ZrO2/La2O3 dielectrics on germanium

The impact of the ZrO₂/La₂O₃ film thickness ratio and the post deposition annealing in the temperature range between 400 °C and 600 °C on the electrical properties of ultrathin ZrO₂/La₂O₃ high-k dielectrics grown by atomic layer deposition on (1 0 0) germanium is investigated. As-deposited stacks have a relative dielectric constant of 24 which is increased to a value of 35 after annealing at 500 °C due to the stabilization of tetragonal/cubic ZrO₂ phases. This effect depends on the absolute thickness of ZrO₂ within the dielectric stack and is limited due to possible interfacial reactions at the oxide/Ge interface. We show that adequate processing leads to very high-k dielectrics with EOT values below 1 nm, leakage current densities in the range of 0.01 A/cm², and interface trap densities in the range of 2-5 × 10¹² eV⁻¹ cm⁻².     

Visible luminescence of Al2O3 nanoparticles embedded in silica glass host matrix

This paper deals with the sol-gel elaboration and defects photoluminescence (PL) examination of Al₂O₃ nanocrystallites (size ∼30 nm) confined in glass based on silica aerogel. Aluminium oxide aerogels were synthesized using esterification reaction for hydrolysis of the precursor and supercritical conditions of ethyl alcohol for drying. The obtained nanopowder was incorporated in SiO₂ host matrix. After heating under natural atmosphere at 1150 °C for 2 h, the composite Al₂O₃/SiO₂ (AS) exhibited a strong PL bands at 400-600 and 700-900 nm in 78-300 K temperature range. PL excitation (PLE) measurements show different origins of the emission. It was suggested that OH-related radiative centres and non-bridging oxygen hole centres (NBOHCs) were responsible for the bands at 400-600 and 700-900 nm, respectively.     

Influences of laser remelting on microstructure of nanostructured Al2O3-13 wt.% TiO2 coatings fabricated by plasma spraying

The effects of laser remelting on microstructure of nanostructured Al₂O₃-13 wt.% TiO₂ ceramic coatings prepared by plasma spraying with agglomerated powders were studied. The microstructure of the feedstock, as-sprayed and laser-remelted coatings were investigated by using scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS) and X-ray diffractometry (XRD). The results indicate that the plasma-sprayed ceramic coating consists of both fully melted regions and partially melted regions. The totally ceramic coating, especially the fully melted regions, has a typical plasma-sprayed lamellar-like structure as the conventional coating, and has some pores. According to the difference of microstructures, the partially melted regions can be divided into liquid-phase sintered regions (a three-dimensional net or skeleton-like structure: Al₂O₃-rich submicron particles embedded in the TiO₂-rich matrix) and solid-phase sintered regions (remained nanoparticles). The lamellar defect of the as-sprayed coating is erased, and the compactness of the coating is improved significantly after laser remelting. The laser-remelted region composed of fine equiaxed grains, which are different from the conventional column-like crystals along the direction of the heat current. Due to the rapid solidification of laser remelting process, there are still some nanoparticles in the remelted region because of an insufficient time for grains growth.     

Microstructure and mechanical properties of alumina coatings prepared by double glow plasma technique

Low-temperature growth (600 °C) of α-Al₂O₃ coatings on the stainless steel substrate by double glow plasma technique was achieved. The compositions and microstructures of the coatings prepared at different oxygen flow rates were characterized, respectively, by X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive X-ray (EDX) spectrometry. A phenomenological mechanism for the formation of the Al₂O₃ ceramic coatings during the oxidation process was proposed on the basis of the experimental results. It was obvious that the oxygen flow rates had a great effect on the surface structure of the prepared Al₂O₃ coatings. The dense and smooth Al₂O₃ coatings were prepared at the oxygen flow rate of 15 sccm. In addition, the correlations between the mechanical properties of Al₂O₃ coating and oxygen flow rates were also discussed. The coating prepared at 15 sccm oxygen flow rate exhibited the best mechanical properties with a maximum hardness of 31 GPa and elastic modulus of 321 GPa. The corresponding critical load of scratch adherence for this sample was 47 N.     

Role of crystal orientation on the magnetic properties of CoFe2O4 thin films grown on Si (1 0 0) and Al2O3 (0 0 0 1) substrates using pulsed laser deposition

We report the influence of crystal orientation on the magnetic properties of CoFe₂O₄ (CFO) thin films grown on single crystal Si (1 0 0) and c-cut sapphire (Al₂O₃) (0 0 0 1) substrates using pulsed laser deposition technique. The thickness was varied from 200 to 50 nm for CFO films grown on Si substrates, while it was fixed at 200 nm for CFO films grown on Al₂O₃ substrates. We observed that the 200 and 100 nm thick CFO-Si films grew in both (1 1 1) and (3 1 1) directions and displayed out-of-plane anisotropy, whereas the 50 nm thick CFO-Si film showed only an (1 1 1) orientation and an in-plane anisotropy. The 200 nm thick CFO film grown on an Al₂O₃ substrate was also found to show a complete (1 1 1) orientation and a strong in-plane anisotropy. These observations pointed to a definite relation between the crystalline orientation and the observed magnetic anisotropy in the CFO thin films.     

Mechano-thermal nanoparticulate coatings for enhancing the cycle stability of LiCoO2

A mechano-thermal coating method was adopted for obtaining LiCoO₂ coated particles with pre-formed pseudo-boehmite nanoparticulate, followed by calcination at 723 K for 10 h. From X-ray diffraction (XRD) analysis it was seen that the coated cathode materials did not show any extraneous phase peaks corresponding to the pseudo-boehmite and the crystal structure, α-NaFeO₂, remained the same as pristine LiCoO₂. Scanning electron micrograph (SEM) of the coated samples showed that above the 1.0 wt.% coating level, the excess pseudo-boehmite got glued to the coated cathode particles as spherules. TEM images showed that the Al₂O₃ particles derived from pseudo-boehmite formed ∼20 nm thickness coating layer on the LiCoO₂ particles. The XPS/ESCA results revealed that the presence of two different O 1s corresponds to the surface coated Al₂O₃ and the core material. The electrochemical performance of the coated materials by a cycling study suggest that 1.0 wt.% coated Al₂O₃ derived from pseudo-boehmite on the two commercial LiCoO₂ samples improved cycle stability by a factor of five and 11 times over the pristine LiCoO₂ cathode material. Cyclic voltammetry revealed that the hexagonal-monoclinic-hexagonal phase transformations were retained for the coated cathode materials upon continuous cycling.     

The electrical properties of dielectric stacks of SiO2 and Al2O3 prepared by atomic layer deposition method

We produced dielectric stacks composed of ALD SiO₂ and ALD Al₂O₃, such as SiO₂/Al₂O₃, Al₂O₃/SiO₂, and SiO₂/Al₂O₃/SiO₂, and measured the leakage currents through the stacks in comparison with those of the single oxide layers. SiO₂/Al₂O₃ shows lowest leakage current for negative bias region below 6.4 V, and Al₂O₃/SiO₂ showed highest current under negative biases below 4.5 V. Two distinct electron conduction regimes are observed for Al₂O₃ and SiO₂/Al₂O₃. Poole-Frenkel emission is dominant at the high-voltage regime for both dielectrics, whereas the direct tunneling through the dielectric is dominant at the low-voltage regime. The calculated transition voltage between two regimes for SiO₂ (6.5 nm)/Al₂O₃ (12.6 nm) is −6.4 V, which agrees well with the experimental observation (−6.1 V). For the same EOT of entire dielectric stack, the transition voltage between two regimes decreases with thinner SiO₂ layer.     

Influence of preparation technology on the microstructure and anti-oxidation property of SiC-Al2O3-mullite multi-coatings for carbon/carbon composites

Oxidation protective SiC-Al₂O₃-mullite multi-coatings for carbon/carbon (C/C) composites were prepared with a two-step pack cementation process. The influence of preparation temperature and SiO₂/Al₂O₃ ratio of the pack powder on the phase, microstructure and oxidation resistance of the multi-coatings were investigated. It showed that the multi-coatings that contained mullite could be produced at 1700-1800 °C. A denser coating surface was acquired with the decrease of SiO₂/Al₂O₃ ratio in the pack chemistries while a little damnification to the interface of the coating and C/C substrate. The as-prepared coating could effectively protect C/C composites from oxidation at 1600 °C for 81 h.