Manufacture and properties of cold spray deposited large thickness Cu coating material for sputtering target

In this study, the manufacture of a large thickness Cu coating layer as sputtering target material via a cold spray coating process was undertaken. The microstructure and properties of the Cu layer as the sputtering target material (before and after the annealing heat treatment) were evaluated, compared, and analyzed. To evaluate the purity, density, grain size and uniformity, microstructure, and properties of the Cu-coated layer as a sputtering target, X-ray diffraction, ICP analysis, SEM, EBSD, porosity analysis, and Vickers hardness tests were performed. The result of the observation of the layer’s purity and microstructure showed that a purity level (99.47%) similar to that of the early powder 2N5 was maintained and that the manufacture of a cold spray deposited, ∼20 mm thick Cu coating material for the sputtering target was performed successfully. As a result of the EBSD mapping, the average grain size near the interface and around the center measured 1.48 μm and 1.49 μm; the grains were small and non-uniform compared with the 1.91 μm size near the surface. Note, however, that the recrystallization and grain growth (caused by annealing) increased the grain size to 1.82 μm (near the interface), 1.83 μm (near the center), and 1.87 μm (near the surface) and improved the level of uniformity. Moreover, through post heat treatment, the overall porosity declined (0.44 % porosity/400 °C/h heat treatment), and the grain texture became uniform. The possibility of controlling the microstructure as a large thickness sputtering target by conducting an annealing heat treatment was also confirmed. Nonetheless, the differences in the porosity and hardness associated with the coating thickness changes were partially maintained. Based on the aforementioned findings, this study suggests that by using cold spray deposition, Cu coating layers with large thicknesses can be applied as a sputtering target.     

Effect of powder alloy composition on the microstructure and properties of kinetic sprayed Cu-Ga based coating materials

This study attempted to manufacture Cu-Ga coating materials via the kinetic spray process and examined the effect of powder alloy composition on the microstructure and properties of the kinetic sprayed Cu-Ga based coating materials. Cu-15 at%Ga, Cu-20 at%Ga, and Cu-30 at%Ga powders were prepared and used. Annealing heat treatments were conducted at 200 °C~800 °C. The results showed that the coating layers could be manufactured with Cu-15 at%Ga and Cu-20 at%Ga powders via the kinetic spray process, except for Cu- 30 at%Ga. A single phase of pure Cu was observed in the Cu-15 at%Ga coating layer and Cu and Cu₃Ga phases in the Cu-20 at%Ga coating layer. A small amount of Ga₂O₃ was also detected between deposited particles in both coating layers. It was difficult to obtain the coating layer due to the shattering of powders during the kinetic spraying with Cu-30 at%Ga powder, which is made up of a variety of inter-metallic compounds. Porosity and hardness decreased as the annealing temperature increased, and porosity decreased into 0.48% (Cu-15 at%Ga), 0.74%(Cu-20 at%Ga) at 800 °C. Annealing heat treatment appeared to be effective in enhancing the density of the coating layers without generating a new phase. This study also considered to suggest the optimal alloy composition of kinetic sprayed Cu-Ga based coating material for sputtering target.     

Effect of preannealing on glass transition and crystallization of gas atomized Cu47Ti33Zr11Ni8Si1 metallic glass powders

Differential scanning calorimetry (DSC), X-ray diffraction (XRD) and transmission electron microscopy (TEM) were used as the main method to investigate the effect of relaxation on the glass transition and crystallization of Cu₄₇Ti₃₃Zr₁₁Ni₈Si₁ metallic glass powders. The preannealing treatments were performed at temperatures close to the experimentally determined glass transition temperature. It was found that the thermal stability is profoundly affected by preannealing since the crystallization temperature is strongly influenced by preannealing and decreases with increase in preannealing temperature. In contrast, the annealing treatment does not change the glass transition temperature. During heat treatment at temperatures around the calorimetric glass transition temperature, T_g, the glassy powder undergoes microstructural alterations as revealed by TEM but not discernible by XRD. Fine nanocrystals of about 4–6 nm homogeneously dispersed in an amorphous matrix are observed by TEM after annealing at 698 K for 60 min. Kissinger analysis reveals that the preannealing decreases the activation energy for nanocrystallization thereby promoting partial crystallization of the glass.     

Fabrication of TiAl intermetallic phases by heat treatment of warm sprayed metal precursors

Warm Spraying is an atmospheric coating process based on high-velocity impact bonding of powder particles. By decreasing the temperature of combustion gas via mixing with nitrogen the oxidation of feedstock powder can be effectively controlled. This is particularly important for Ti-based coating materials, which rapidly oxidize at elevated temperatures.In this study, Ti–Al composite coatings were fabricated by the Warm Spray process using a mixture of titanium and aluminum powders as a feedstock and applying a two-stage heat treatment at 600 and 1000 °C to obtain intermetallic phases. The microstructure, chemical and phase composition of the deposited and heat-treated coatings were investigated using SEM, EDS and XRD. The experimental results show that TiAl₃ was the first intermetallic phase formed during the first-stage heat treatment. The growth of TiAl₃ layer occurred mainly by diffusion of Al into Ti particles. Significant porosity that developed during the heat treatment was caused mainly by Kirkendall effect. After the second-stage heat treatment, a coating layer with TiAl as the dominant phase was obtained with about 20 vol % porosity.     

Annealing effects on the intermetallic compound formation of cold sprayed Ni,Al coatings

The annealing of Ni and Al coatings under various conditions on substrates fabricated by a cold gas dynamic spray process (CDSP) were investigated. The powder particles were accelerated through a standard De Laval-type nozzle with air used as the main carrying gas. The coatings were annealed at 450–550 °C in either argon or air atmospheres for 4 h. In the case of Ni coatings during annealing both in argon and air atmospheres, intermetallic compound layers such as Al₃Ni and Al₃Ni₂ were observed at the interfaces between the Ni coating and Al substrate. Also, the intermetallic layer formation of Al₃Ni and Al₃Ni₂ at the interfaces depended on the solid-state diffusion and the annealing temperature. The intermetallic compound AlNi was obtained at the interface of Al coating on a Ni substrate by low-temperature annealing under the melting temperature.     

Effect of roll-bonding temperature on the strength and electrical conductivity of an α-brass-clad Cu–1Cr alloy composite

Tri-layered α-brass-clad Cu–Cr-alloy composite plates were prepared by hot roll-bonding. Neither intermetallic-compound layers nor interface defects were observed at the interfaces in the as-rolled and heat-treated α-brass-clad Cu–Cr composite plates. The hardness of the as-rolled α-brass layer was greater than that of the Cu–Cr substrate, since the α-brass was strengthened by strain hardening more efficiently upon rolling. The hardness of the α-brass decreased appreciably upon annealing because of the recovery processes, whereas that of the Cu–Cr layer slightly increased after heat treatment at 450°C due to the precipitation strengthening. After the post-roll-bonding heat treatment at 450°C, the strength of the α-brass-clad Cu–Cr-alloy composite decreased with a significant increase in ductility. The electrical conductivity of the asroll-bonded α-brass clad Cu–Cr alloy composite (47–52% IACS) increased significantly (to 72–74% IACS) after the 1-h heat treatment. The strength and conductivity of the clad composite are dependent on the precipitation strengthening of Cu–Cr and recovery softening of α-brass in the course of the post-roll-bonding heat treatment.     

Effect of heat treatment temperature on the microstructure and actuation behavior of a Ti–Ni–Cu thin film microactuator

Ti–Ni–Cu/SiO₂ two layer diaphragm-type microactuators were fabricated by sputter deposition and micromachining. The influence of heat treatment temperature on the actuation behavior was investigated under quasi-static conditions. The interfacial structure of Ti–Ni–Cu/SiO₂ and internal structure of the Ti–Ni–Cu layer were also investigated using transmission electron microscopy. The reaction layer formed between the Ti–Ni–Cu and SiO₂ layers, and preferentially grew into the SiO₂ side. The reaction layer formed at 1023 K mainly consisted of Ti₄(Ni,Cu)₂O. The maximum height of the diaphragm decreased with increasing heat treatment temperature. The growth of the reaction layer also affected the microstructure of the Ti–Ni–Cu layer. The density of fine platelets and Ti₂Ni precipitates decreased with increasing heat treatment temperature from 873 to 923 K, and they disappeared at 973 K due to the fact that the reaction layer mainly consisted of a Ti-rich phase. The microactuator heat treated at 973 K showed the highest transformation temperature with the lowest transformation temperature hysteresis, which is attractive for high speed actuation.     

The Effect of Heat Treatment on the Oxidation Behavior of HVOF and VPS CoNiCrAlY Coatings

Free-standing VPS and HVOF CoNiCrAlY coatings were produced. The as-sprayed HVOF coating retained the γ/β microstructure of the feedstock powder, and the VPS coating consisted of a single (γ) phase. A 3-h, 1100 °C heat treatment in vacuum converted the single-phase VPS coating to a two-phase γ/β microstructure and coarsened the γ/β microstructure of the HVOF coating. Oxidation of free-standing as-sprayed and heat-treated coatings of each type was carried out in air at 1100 °C for a duration of 100 h. Parabolic rate constant(s), K _p, were determined for free-standing, as-sprayed VPS and HVOF coatings as well as for free-standing coatings that were heat treated prior to oxidation. The observed increase in K _p following heat treatment is attributed to a sintering effect eliminating porosity from the coating during heat treatment. The lower K _p values determined for both HVOF coatings compared to the VPS coatings is attributed to the presence of oxides in the HVOF coatings, which act as the barrier to diffusion. Oxidation of the as-sprayed coatings produced a dual-layer oxide consisting of an inner α-Al₂O₃ layer and outer spinel layer. Oxidation of the heat-treated samples resulted in a single-layer oxide, α-Al₂O₃. The formation of a thin α-Al₂O₃ layer during heat treatment appeared to prevent nucleation and growth of spinel oxides during subsequent oxidation.     

Effect of Heat Treatment on the Microstructure and Microhardness of Nanostructural Al2O3 Coatings

Nanostructural Al₂O₃ coatings were formed on a steel substrate surface using a multichamber detonation sprayer. The Al₂O₃ coatings were characterized by a dense microstructure with porosity below 1% and hardness of 1300 ± 25 HV_0.3. The transition layer between the coating and substrate was up to 15 μm thick, containing Fe-Al-type intermetallic compounds (FeAl₃, Fe₂Al₅). Postdeposition heat treatment of the samples at 850 °C for 3 h was carried out in air and argon environments. The effect of heat treatment on the microstructure and microhardness of the Al₂O₃ coatings was investigated by optical microscopy, scanning and transmission electron microscopy, scanning probe microscopy, x-ray phase analysis, and Vickers hardness testing. A positive impact of postcoating heat treatment on the coating microstructure and microhardness was observed. Heat treatment resulted in an increase in the coating hardness from 1300, to 1350 ± 25 HV_0.3 and 1600 ± 25 HV_0.3 after annealing in air and argon, respectively. Heat treatment in argon led to a more significant increase in the α-Al₂O₃ phase from 47 to 81%.     

Characterization of nanostructured Cr2Nx/Cu multilayers deposited by reactive DC magnetron sputtering

Nitride/metal nanostructured multilayers of Cr₂N_x/Cu were deposited by reactive DC magnetron sputtering with various bilayer periods (2.5-30 nm) and substrate temperatures (25-400 °C). All films had a total thickness of about 470 nm and the overall chemical composition of the chromium nitride layers was close to Cr₂N_0.8. The deposited films were characterized by Rutherford Backscattering (RBS), low-angle X-ray reflectivity (XRR), high-angle X-ray diffraction (XRD) and transmission electron microscopy (TEM). The hardness and elastic modulus were measured by nanoindentation. The films deposited at 25 °C had a well-defined multilayer structure and the chromium nitride layers were found to crystallize into N-deficient fcc CrN_0.4 with traces of hexagonal Cr₂N_0.8. The layers were strongly textured with fcc CrN_0.4[002] and Cu[002] oriented along the growth direction — the fcc CrN_0.4 and Cu grains growing with a cube-on-cube relationship. The measured hardness values were about 8 GPa, and showed no dependence on the bilayer period. Higher deposition temperatures caused the multilayer structure to degrade, and at 400 °C the films were better described as non-textured nanocomposites with the chromium nitride crystallized entirely into the equilibrium hexagonal Cr₂N_0.8 structure. Hardness values of the high-temperature films in the range of 4-8 GPa were measured. Multilayer films deposited at 25 °C were found to be thermally stable against post-deposition annealing at temperatures up to about 400 °C. Annealing at 500 °C caused severe structural changes — the fcc CrN_0.4 phase transformed into hexagonal Cr₂N_0.8 accompanied by degradation of the periodic multilayer structure. The hardness decreased from the originally 8 GPa to about 5 GPa upon annealing.     

Properties of High Velocity Suspension Flame Sprayed (HVSFS) TiO2 coatings

TiO₂ coatings were manufactured by the High Velocity Suspension Flame Spraying (HVSFS) technique using a nanopowder suspension. Their microstructure, nanohardness, tribological properties and photocatalytic activity were studied and compared to conventional atmospheric plasma sprayed (APS) and HVOF-sprayed TiO₂ coatings manufactured using commercially available feedstock. The HVSFS process leaves a fairly large freedom to adjust coating properties (thickness, porosity, anatase content, hardness, etc…) according to the desired objective. Layers with higher anatase content and higher porosity can be produced to achieve higher photocatalytic efficiency, better than conventional APS and HVOF TiO₂. Alternatively, dense protective layers can be deposited, possessing lower porosity and pore interconnectivity and better wear resistance than as-deposited APS and HVOF layers. In all cases, HVSFS-deposited layers are thinner (20 µm-60 µm) than those which can be obtained by conventional spraying processes.     

Influence of an oxidation protective coating upon hot corrosion and mechanical behaviour of Ti–48Al–2Cr–2Nb alloy

48-2-2 specimens were coated with Au using electrochemically process and vacuum heat treatment. Au diffused and the coating was composed of TiAlAu₂ and TiAlAu layers from the surface to the bulk alloy. A transition zone between the coating and the sound alloy composed of Au-enriched TiAl is also formed. The oxidation and NaCl salt corrosion behaviours of the coated specimen were investigated through cyclic tests and the effects of coating on mechanical properties of TiAl were assessed by means of creep properties. Au coating was effective in improving the oxidation and NaCl salt corrosion resistances of the coated specimens at 800 °C and 600 °C respectively. This good resistance is attributable to the formation of an Al₂O₃ scale on the surface of the coated specimen. During oxidation, or NaCl salt corrosion, the upper TiAlAu₂ layer of the coating transformed in an Al₂O₃ layer on a TiAu₂ layer. The slightly lower creep properties exhibited by the coated specimens are presumably linked to Cr-enriched phases that segregate at grains boundaries during the vacuum heat treatment. The degradation of creep properties after coating and corrosion is believed to be brought about either by the formation of the brittle TiAu₂ phase or by corrosion or oxygen diffusion through the upper scale.     

Mechanical Properties and Microstructure of VPS and HVOF CoNiCrAlY Coatings

In this study, high velocity oxy-fuel (HVOF) and vacuum plasma spraying (VPS) coatings were sprayed using a Praxair (CO-210-24) CoNiCrAlY powder. Free-standing coatings underwent vacuum annealing at different temperatures for times of up to 840 h. Feedstock powder, and as-sprayed and annealed coatings, were characterized by scanning electron microscopy (SEM), energy dispersive spectroscopy (EDS), and x-ray diffraction (XRD). The hardness and Young’s modulus of the as-sprayed and the annealed HVOF and VPS coatings were measured, including the determination of Young’s moduli of the individual phases via nanoindentation and measurements of Young’s moduli of coatings at temperatures up to 500 °C. The Eshelby inclusion model was employed to investigate the effect of microstructure on the coatings’ mechanical properties. The sensitivity of the mechanical properties to microstructural details was confirmed. Young’s modulus was constant up to ~200 °C, and then decreased with increasing measurement temperature. The annealing process increased Young’s modulus because of a combination of decreased porosity and β volume fraction. Oxide stringers in the HVOF coating maintained its higher hardness than the VPS coating, even after annealing.     

Electrochemical evaluation of the corrosion protectiveness and porosity of vacuum annealed CrAlN and TiAlN cathodic arc physical vapor deposited coatings

The corrosion behavior of cathodic arc physical vapor deposited CrAlN and TiAlN coatings were examined in 1 M HCl solution before and after vacuum annealing at 700, 800, 900, and 1000 °C. Electrochemical impedance spectroscopy (EIS) and potentiodynamic polarization (PDP) methods were used to study the corrosion behavior and porosity of the coatings in comparison with the bare steel substrate (304SS). Structural and mechanical characterization of the coatings were also conducted. It is found that with increasing annealing temperature, the mechanical properties of TiAlN increased due to age hardening caused by spinodal decomposition while the hardness of CrAlN decreased as result of relaxation. Similarly, EIS and PDP results revealed that the as‐deposited and annealed coatings offer higher corrosion resistance as compared to the bare 304SS substrate. The coatings susceptibility to corrosion is reduced after annealing as indicated by the increasing nobility of E_corr. Both PDP and EIS tests revealed that CrAlN coating annealed at 1000°C exhibited superior corrosion resistance properties. It is found that the reduced current density for CrAlN coating annealed at 1000°C was due to the reduction in the porosity. Annealed TiAlN coating follows similar behavior until an optimum annealing temperature of 800°C. Beyond this temperature, porosity enlargement and an increase in the number of pores subsequent to structural changes deteriorated the corrosion resistance of TiAlN coating.     

Fabrication and properties of the superhydrophobic ceria-based composite coating on magnesium alloy

A superhydrophobic ceria-based composite coating is developed to improve anticorrosion properties of AZ61 magnesium alloy, fabricating via chemical conversion method followed by hydrothermal treatment. The cerium conversion coating has a block structure with microcracks. After the hydrothermal treatment, a dense CeO₂ layer, porous CeO₂ nanorods, and stearic absorbing layers are grown stepwise on the conversion coating. And the composite coating is hydrophobic or even superhydrophobic and has almost no microcracks. As the hydrothermal reaction time increases, the water contact angle of the composite coating first increases and then decreases, and it reaches the maximum value of 152° after hydrothermal treatment for 4 h. Both the dense CeO₂ layer and the superhydrophobic stearic absorbing layer can effectively prevent the electrolyte from contacting the substrate; the corrosion current density of the superhydrophobic composite coating is lower than that of the hydrophilic composite coating and the cerium conversion coating, and has the best corrosion resistance.     

Elaboration and characterization of nanocrystalline TiO2 thin films prepared by sol–gel dip-coating

Nanocrystalline TiO₂ thin films were deposited on a ITO coated glass substrate by sol–gel dip coating technique, the layers undergo a heat treatment at temperatures varying from 300 to 450 °C. The structural, morphological and optical characterizations of the as deposited and annealed films were carried out using X-ray diffraction (XRD), Raman spectroscopy, Atomic Force Microscopy (AFM), visible, (Fourier-Transform) infrared and ultraviolet spectroscopy, Fluorescence and spectroscopic ellipsometry. The results indicate that an anatase phase structure TiO₂ thin film with nanocrystallite size of about 15 nm can be obtained at the heat treatment temperature of 350 °C or above, that is to say, at the heat treatment temperature below 300 °C, the thin films grow in amorphous phase; while the heat treatment temperature is increased up to 400 °C or above, the thin film develops a crystalline phase corresponding to the titanium oxide anatase phase. We have accurately determined the layer thickness, refractive index and extinction coefficient of the TiO₂ thin films by the ellipsometric analysis. The optical gap decreases from 3.9 to 3.5 eV when the annealing temperature increases. Photocatalytic activity of the TiO₂ films was studied by monitoring the degradation of aqueous methylene blue under UV light irradiation and was observed that films annealed above 350 °C had good photocatalytic activity which is explained as due to the structural and morphological properties of the films.     

Preparation of a-C:H/a-C:H:Si:O and a-C:H/a-C:H:Si multilayer coatings by PACVD

Carbon based multilayer coatings were prepared by plasma assisted chemical vapor deposition (PACVD) using methane (CH₄) and hexamethyldisiloxane (HMDSO) or methane and tetramethylsilane (TMS) as precursors. These coatings were deposited in a modified plasma nitriding plant operated at relatively high working pressures of 20 Pa. The multilayer design consisted of a-C:H and a-C:H:Si:O or a-C:H and a-C:H:Si single layers, respectively. The number of single layers and the material of the top layer were varied at constant total coating thicknesses. These multilayer coatings were investigated with regard to their morphology and composition as well as indentation hardness, abrasive wear, lubricant free friction and wetting behavior via contact angle measurements. The multilayer coatings exhibited lower wear rates and higher hardness values than a-C:H:Si:O or a-C:H:Si single layers and lower friction coefficients than pure a-C:H coatings under unlubricated test condition. Utilizing duplex processes, combining plasma nitriding pre-treatment and a following coating deposition, the adhesion of the multilayer coatings on high speed and cold working steel substrates could be considerably improved.     

Microstructural Studies of Cold Sprayed Copper,Nickel, and Nickel-30% Copper Coatings

Cold spraying enables to produce metallic coatings with low porosity level and low oxygen content. Several material properties such as electrical conductivity and corrosion resistance rely on these properties. Aim of this study was to characterize microstructural properties of cold sprayed copper, nickel, and nickel-30%copper coatings. Microstructures, denseness, and deformation of particles were investigated. SEM analysis and corrosion tests were done to get information of through-porosity. Open porosity has an important role on protectiveness of anodically protective coatings, such coating materials like copper and nickel. In this study, cold-sprayed Cu coating was fully dense. However, cold-sprayed Ni and Ni-30%Cu coatings seemed to be microstructurally dense but some porosity in some areas of the coatings especially in some parts of particle boundaries was noticed after corrosion tests. Furthermore, effect of annealing to microstructure and corrosion test behavior was studied. Cold sprayed Ni coating became denser during heat treatment.     

Post-heat Treatment Effects on Cold-Sprayed Aluminum Coatings on AZ91D Magnesium Substrates

Commercially pure aluminum (CP-Al) powder was deposited by the cold spray process onto AZ91D magnesium (Mg) substrates that had been subjected to three different heat-treatment conditions: namely, as-cast (F), homogenized (T4), and artificially aged (T6). The substrate hardness was measured to be 80.7?±?1.8, 73.7?±?4.0, and 103.6?±?7.4 HV_0.025 for the F-, T4-, and T6-Mg alloy substrates respectively. Thick (~400???m) and dense (below 1% porosity) Al coatings have been obtained. After post-deposition heat treatment at 400?°C, the intermetallic Mg₁₇Al₁₂ (??) and Al₃Mg₂ (??) phases with different thicknesses were found to have formed at the coating/substrate interface depending on the holding time. While no significant thickness differences of the intermetallic layers were detected in the cases of F- and T6-AZ91D substrates, thicker layers formed on the T4-AZ91D substrate. It is believed that the higher Al concentration in the T4-AZ91D solid solution within the ??-Mg could diffuse and contribute more easily to the growth of the intermetallic phases. The hardness of the ??- and ??-phase was measured to be 260.5?±?10.7 HV_0.025 and 279.6?±?13.7 HV_0.025, respectively. Shear strength test results revealed lower adhesion strength after heat treatment, which is attributed to the presence of brittle intermetallic layers at the coating/substrate interface.     

Behavior of porosity and copper oxidation in W/Cu composite produced by plasma spray

A spherical tungsten (W)/copper (Cu) composite powder was plasma-sprayed onto a boron-nitride-coated graphite substrate to produce heat sink material for the electronic packaging by atmospheric plasma spray using different input powers. At the surface of the deposited layer, Cu became oxidized to cuprite (Cu₂O). The degree of oxidation at the surface layer did not vary significantly with input power. Very little Cu₂O was detected at the inner layers after grinding off the 70 μm from the surface. The input powers had a strong effect on the porosity in the deposit layers. The porosity in the deposit layers at 25 kW was very small, about 3 vol%. The microstructures of W/Cu composite were discussed.