Zirconium vacuum arc operation in a mixture of Ar and O2 gases: Ar effect on the arcing characteristics,deposition rate and coating properties

The effect of oxygen and argon partial pressures (P_O2, P_Ar) in a Zr vacuum arc on plasma ion current density J_p, arc voltage V_arc, deposition rate v_d, and selected coating properties was determined. A d.c. arc current of I_arc = 100 A was initiated between a Zr cathode and a grounded anode. Cathode spots produced a plasma jet, which entered a 1/8 torus macroparticle (MP) filter. The plasma was guided by a d.c. magnetic field through an aperture to a glass substrate or a flat disk probe, mounted on a rotatable holder. J_p was measured with the probe, negatively biased to V_b = − 60 V. Coating thickness was measured using a profilometer, and coating properties were investigated using optical microscopy, energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), X-ray diffraction (XRD), nano-indentation and optical analysis.     

Pulsed ion extraction from a hybrid plasma using a shunting arc discharge

A hybrid plasma is generated by combining a burst methane rf (195 kHz) plasma with a carbon shunting arc discharge. The shunting arc discharge triggers the rf methane plasma. As a result, the rf plasma is initiated over a wide range of ambient gas pressure from 0.045 Pa as a base pressure to a methane pressure of 1.26 Pa, at which the rf plasma is not self-ignited. When a target is immersed in the rf- and shunting arc-hybrid plasma, and a negative pulse voltage is applied to the target, carbon ions are extracted from the hybrid plasma. When the carbon shunting arc ionizes the methane gas, an rf plasma is initiated and the ionization of methane is significantly enhanced in the rf plasma. The plasma density in the hybrid plasma increases by a factor of approximately 5-9 compared to that of the shunting arc discharge.     

Formation of zirconium diboride (ZrB2) by room temperature mechanochemical reaction between ZrO2, B2O3 and Mg

A mixture of magnesium, boric oxide and zirconium dioxide were mechanically milled under argon for up to 15 h in a laboratory scale ball mill. X-ray diffraction showed that there was an increasing conversion of ZrO₂ to ZrB₂ with milling time with >98% reaction after 15 h. Differential thermal analysis revealed there were multiple, overlapping reactions all of which seemed to be formation of ZrB₂. The energy evolved decreased with milling time and the sample after 15 h milling showed no thermal reaction. After milling, separation of the ZrB₂ from the coproduct MgO was easily achieved by a mild acid leaching leaving essentially pure ZrB₂ with a crystallite size of 75 nm.     

Effects of oxygen concentration in the Ar/O2 plasma on the bulk structure and surface properties of RF reactively sputtered zirconia thin films

Zirconium oxide is one of the most extensively studied transition-metal oxides for its several attractive properties and the variety of its technological applications. Research was especially stimulated in understanding the factors controlling the structure of ZrO₂ and in identifying the relationship between bulk and surface properties of ZrO₂ thin films. In the present work, ZrO₂ thin films were deposited on Si, without external heating, by RF reactive sputtering from a pure ZrO₂ target in Ar/O₂ plasma with different O₂ concentrations (0 ÷ 20%). Aim of the study was the identification of the effects of the processing parameters - mainly the O₂/Ar ratio in the gas phase - on the film growth and properties. The addition of O₂ was crucial to establish a good stoichiometry, as revealed by Auger depth profiling. The films obtained under O₂-deficient plasma conditions have polycrystalline nanograins whose structure was consistent with either a tetragonal or a cubic phase. Adding O₂ to the gas mixture turns their structure into the stable monoclinic one. Such bulk structural changes were found to affect both their mechanical behaviour and their surface properties: a chemical shift of the Zr3d and O1s core levels to lower binding energies was recorded by XPS analyses, common to all the samples deposited in presence of O₂. This effect was thought to be related to the oxygen induced tetragonal/cubic-to-monoclinic transformation of the oxide structure.     

Effects of water vapour on isothermal oxidation of chromia-forming alloys in Ar/O2 and Ar/H2 atmospheres

Fe9Cr, Fe17Cr and Fe25Cr alloys were subjected to isothermal oxidation in Ar/O₂ and Ar/H₂ atmosphere at 700 °C as high temperature corrosion for 48 h. Oxidation weight change measurement showed increasing Cr content reduced the oxidation rate. The oxidized Cr alloys were analysed using SEM, TEM and XRD. The addition of water vapour accelerates the onset of breakaway oxidation kinetics for Fe9Cr. The presence of water vapour promotes internal oxidation of Cr within Fe9Cr. For Fe17Cr and Fe25Cr, the water vapour effect is not significant due to the large Cr reservoir due to continue growth of Cr₂O₃.     

Mechanical properties of the plasma-sprayed Al2O3/ZrSiO4 coatings

The mechanical properties of plasma-sprayed Al₂O₃/ZrSiO₄ coatings were investigated by indentation-based techniques. Two types of feedstock were used to prepare the coatings: spray-dried powders and plasma-spheroidized powders. A 100-kW direct current (d.c.) thermal plasma system was employed. The values obtained were found to exhibit a close relationship with the microstructure of the as-sprayed coatings, which composed of zircon, alumina, amorphous silica and tetragonal zirconia. The coatings produced with plasma-spheroidized powders had higher microhardness, Young's modulus and fracture toughness than that produced with the spray-dried powders. The coatings produced with plasma-spheroidized powders by a 100-kW computerized system at 15 kW of net plasma energy had the best mechanical properties, while those deposited at 19 kW of net plasma energy had the worst properties due to the high density of cracks in the coatings.     

Size and pressure effects on solid transition temperatures of ZrO2

Transition temperatures between tetragonal and monoclinic polymorphs of ZrO₂ nanoparticles, thin films and nanostructured materials are calculated by considering energetic contributions of surface (interface) energy and surface stress on total Gibbs free energy. The transition temperatures drop as the size of the nanocrystals decreases, which is consistent with available results.     

Characterization and optimization of a plasma doping process using a pulsed RF-excited B2H6 plasma system

The P+ plasma doping (PLAD) process using B₂H₆/H₂ plasma in a pulsed, RF-excited plasma system has been systematically characterized and optimized. The correlations between the deposition, retained B dose/profile, carrier dose/profile, sheet resistance (R_S) as a function of the pulse voltage, nominal dose, and carrier gas dilution have been extensively investigated. It was found that diluting B₂H₆ with H₂ can be used as a method to control and minimize boron deposition. SIMS and SRP analyses indicate that B and carrier profiles are deeper for higher dilutions up to 5/95 of a B₂H₆/H₂ gas ratio, than they are for lower dilutions due to less B deposition. This results in a higher activation fraction because of the B_SS limit and compensates for the reduction of the retained B dose. The higher dilutions also improved the retained B dose and R_S saturation due to less deposition. The PLAD process of a pulsed, RF-excited plasma system using B₂H₆ diluted with 92.5% to 95% H₂ was found to be an optimal condition for high-dose, boron-doping applications.     

Plasma nitriding of austenitic stainless steel in N2 and N2-H2 dc pulsed discharge

AISI 302/304 austenitic stainless steels have been nitrided in N₂ and N₂-H₂ glow discharge plasmas powered by a high frequency dc pulsed power supply. In a pure nitrogen plasma, no increase in surface hardness from the initial value has been observed. In a N₂-H₂ gas admixture, a 3-4 times increase in hardness has been found, which confirms the necessity of hydrogen gas as a powerful reagent. Grazing incidence X-ray diffraction (GIXRD) shows the presence of three phases of nitride (Fe₃N, Fe₄N and CrN) along with iron oxide (Fe₂O₃). It is found in a N₂ plasma at a sample temperature of 540 °C that at 200 kHz, maximum peak intensity of iron oxide/nitride decreases. In N₂-H₂ plasma treated sample the nitride peak intensity increased in comparison to the intensity in sample nitrided in N₂ plasma. Optical emission spectroscopy (OES) has been used to investigate the active species present during nitriding in the near-cathode region. Emission bands of neutral and ionic molecular species and ionic atomic species of nitrogen have been detected in a nitrogen plasma. In a N₂-H₂ gas admixture, the H_α and H_β lines of Balmer series in addition have been observed. At 20% H₂ addition in nitrogen plasma, a few vibrational state intensities of N₂ and N₂⁺ are observed to be optimized.     

O2 plasma treatment of mesoporous and compact TiO2 photovoltaic films: Revealing and eliminating effects of Si incorporation

Radio frequency (13.56 MHz) O₂ plasmas were used to modify the surface of mesoporous and compact TiO₂ films. The effects of substrate location in the plasma, applied rf power, and plasma mode (pulsed or continuous wave) were explored. X-ray photoelectron spectroscopy, contact angle measurements, and scanning electron microscopy were used to characterize changes to the TiO₂ films. For mesoporous materials, O₂ plasma treatment was found to increase oxygen content in the films, but Si content increased with applied rf power as a result of sputtering and redeposition of Si species from the reactor walls. XPS depth profiling using ion sputtering as well as O₂ plasma treatment of dyed materials revealed that Si was deposited throughout the mesoporous network, not as a surface SiO₂ layer. Pulsing the plasma with pulse duty cycles < 40% resulted in the elimination of Si and a reduction of damage in the modified films.     

A mass-spectroscopical study of the decomposition of Ti(NMe2)4 in a mixed Ar–H2–N2 pulsed d.c. plasma

The favourable gas-phase conditions for deposition of TiN have been determined by a mass-spectroscopic investigation of the gaseous species in an ambient of tetrakis(dimethyl-amino)titanium (TDMAT) molecules during pulsed d.c. plasma-enhanced deposition processes. The gas-phase composition was varied, at a pressure of 0.4 Torr, a temperature of 350 °C and a bias voltage of 500 V, based on an Ar, H₂, N₂ ternary diagram. The results reveal that hydrogen plays a key role in the cleavage of –NMe₂ from the central Ti atom. The addition of N₂ to the hydrogen plasma opens up the possibility for transamination reactions by NH_x formation (1<x<3), known by thermal CVD using NH₃. This addition also leads to powder formation, which seems to reach a maximum within a 100% N₂ plasma. In a nitrogen plasma, only relatively small amounts of gaseous species, like HCN, NH₂CN, and CH₃CN, are detected, which indicates that residual hydrocarbon fragments of TDMAT must be incorporated into the powder and coating. Even small amounts of Ar addition to a hydrogen plasma convert TDMAT to powder particles, which is the opposite of the densification purpose of Ar bombarment. No gaseous species, apart from small amounts of HCN, are detected, suggesting hydrocarbon-containing coatings. If Ar:H₂:N₂=1:1:1, no specific mechanism is dominant under the conditions used here. Decreasing the deposition temperature and pressure and increasing the bias voltage seem to favour the cleavage of –NMe₂ ligands.     

Electrophoretic enhanced micro arc oxidation of ZrO2-HAp-TiO2 nanostructured porous layers

Micro arc oxidation (MAO) and electrophoretic deposition (EPD) processes were simultaneously employed to grow ZrO₂-HAp-TiO₂ porous layers on titanium substrates under different conditions. Influence of the electrolyte composition and the growth time on surface morphology, topography, phase structure, and stoichiometry of the layers was investigated. The utilized electrolytes consisted of β-glycerophosphate, calcium acetate, sodium phosphate, and micron sized yttria-stabilized zirconia with different concentrations. AFM and SEM evaluations revealed a rough surface with a porous structure with a pores size of 50-750 nm. The pores size increased with the time and the electrolyte concentration. Based on the XRD and XPS results, the layers consisted of anatase, hydroxyapatite, monoclinic ZrO₂, tetragonal ZrO₂, ZrO, CaTiO₃, and α-TCP phases whose fractions were observed to change depending on the synthesis conditions. The average crystalline size of the HAp phase was determined as ∼54 nm. The nano-sized zirconia particles (d = 20-60 nm) were dispersed not only on surface, but also in depth of the layers. Utilizing thicker electrolytes and prolonging the growth time resulted in decomposition of hydroxyapatite as well as tetragonal ZrO₂ to monoclinic ZrO₂. EDX results also showed that the zirconium wt% in the layers increased with the time. EPD-enhanced MAO (EEMAO) technique was expressed as an efficient route to fabricate ZrO₂-HAp-TiO₂ multiphase systems within short times and only in one step.     

Mechanical and tribological properties of multilayered TiSiN/CrN coatings synthesized by a cathodic arc deposition process

The monolayered TiSiN and multilayered TiSiN/CrN were synthesized by cathodic arc evaporation. The Ti/Si (80/20 at.%) and chromium targets were used as the cathodic materials. With the different I_[TiSi]/I_[Cr] cathode current ratios of 1.8, 1.0, and 0.55, the multilayered TiSiN/CrN coatings possessed different multilayer periods (Λ) of 8.3 nm, 6.2 nm, and 4.2 nm. From XRD and TEM analyses, both the monolayered TiSiN and multilayered TiSiN/CrN revealed a typical columnar structure and B1-NaCl crystalline, no peaks of crystalline Si₃N₄ were detected. Among the multilayered TiSiN/CrN coatings, the multilayered coating with Λ = 8.3 nm possessed higher hardness of 37 ± 2 GPa, higher elastic modulus of 396 ± 20 GPa and the lower residual stress of − 1.60 GPa than the monolayered (Ti_0.39Si_0.07)N_0.54 coating(− 7.25 GPa). Due to the higher Cr/(Ti +Cr + Si) atomic ratio, the multilayered TiSiN/CrN with Λ = 5.5 nm possessed the lowest friction coefficient. But the lowest of wear rate was obtained by the multilayered TiSiN/CrN with Λ = 8.3 nm, because of higher H³/E^?2 ratio of 0.323 GPa. The monolayered TiSiN possessed the highest wear rate of 2.87 μm²/min. Therefore, the mechanical and tribological property can be improved by the design of multilayered coating.     

On the wide range of mechanical properties of ZTA and ATZ based dental ceramic composites by varying the Al2O3 and ZrO2 content

In this work the influence of pressureless sintering on the Vickers hardness and fracture toughness of ZrO₂ reinforced with Al₂O₃ particles (ATZ) and Al₂O₃ reinforced with ZrO₂ particles (ZTA) has been investigated. The ceramic composites were produced by means of uniaxial compacting at 50 MPa and the green compacts were heated to 1250 °C using a heating rate of 10 °C min⁻¹, then to 1500 °C at 6 °C min⁻¹ and maintained at this temperature during 2 h. After sintering, relative density over 94%, hardness values between 9.5 and 21.9 GPa, and fracture toughness as high as 3.6 MPa m^1/2 were obtained. The presence of TZ-3Y particles on the grain boundaries suggests that they inhibit notably the alumina grain growth. The grain sizes of pure Al₂O₃ and TZ-3Y as well as Al₂O₃ and TZ-3Y in the 20 wt% Al₂O₃+80 wt% TZ-3Y composite were 1.27 ± 0.51 μm, 0.57 ± 0.12 μm, 0.65 ± 0.19 μm and 0.41 ± 0.14 μm, respectively. The 20 wt% Al₂O₃ + 80 wt% ZrO₂ + 3 mol% Y₂O₃ (TZ-3Y) composite showed a hardness of 16.05 GPa and the maximum fracture toughness (7.44 MPa m^1/2) with an average grain size of 0.53 ± 0.17 μm. On the other side, the submicron grain size and residual porosity seem to be responsible for the high hardness and fracture toughness obtained. The reported values were higher than those obtained by other authors and are in concordance with international standards that could be suitable for dental applications.     

Evaluation of surface and bonding properties of cold rolled steel sheet pretreated by Ar/O2 atmospheric pressure plasma at room temperature

In this study, cold rolled steel sheet for automotive was pretreated by the Ar/O₂ atmospheric pressure plasma at room temperature to improve the adhesive bonding properties. Through the analysis of contact angle and calculation of work of adhesion, the change of surface properties related to the plasma power, treatment time, and flow rate of O₂ gas were investigated before and after plasma treatment. Contact angle was degreased and work of adhesion was increased after plasma treatment. Meanwhile, the changes of surface roughness and morphology were observed by atomic force microscopy (AFM). And the chemical compositions of the steel sheet before and after plasma treatment were characterized by X-ray photoelectron spectroscopy (XPS). Surface roughness was slightly changed and new functional group, oxides, appeared on the surface of steel sheet after plasma treatment. Based on design of experiments and artificial neural network (ANN), the single lap shear test was performed to analyze the effect of plasma treatment parameters gas on adhesive bonding strength. From the result of the single lap shear test, the adhesive bonding strength of joint which was treated by Ar/O₂ atmospheric pressure plasma was improved about 23% compared with that of untreated sheet.     

Influence of niobium doping on phase composition and defect-mediated photoluminescence properties of Eu-doped TiO2 nanopowders synthesized in Ar/O2 thermal plasma

Nb⁵⁺:Eu³⁺-codoped TiO₂ nanopowders for chemical composition adjustment have been synthesized via Ar/O₂ radio-frequency thermal plasma. X-ray diffraction (XRD) results reveal that all the resultant powders exhibited mixture polymorphs of anatase (mean size: ∼45 nm) as the major phase and rutile (mean size: ∼71 nm). Rutile formation was promoted by the Eu³⁺ doping but suppressed by the Nb⁵⁺ addition. Combined observation using FE-SEM and TEM indicates that all the plasma-synthesized powders had a majority of facet-shaped particles (several nanometers) and a small proportion of nearly spherical crystals (∼150 nm). For the defect-mediated photoluminescence (PL) emission through the energy transfer from the TiO₂ host to the Eu³⁺ activator, the PL intensity originating from the ⁵D₀ → ⁷F₂ electronic transition weakened but that from the ⁵D₀ → ⁷F₁ electronic transition strengthened with increasing Nb⁵⁺ content. This may be a result of the decrease in the oxygen vacancy defects in the TiO₂ host lattice, as revealed by the joint means of UV-vis absorption spectra and excitation and emission spectra.     

Effect of partial pressure of reactive gas on chromium nitride and chromium oxide deposited by arc ion plating

The effects of reactive gas partial pressure on droplet formation, deposition rate and change of preferred orientation of CrN and Cr2O3 coatings were studied. For CrN coatings, as nitrogen partial pressure increases, the number and size of droplets increases, the deposition rate initially increases obviously and then slowly, and the preferred orientation of CrN changes from high-index plane to low-index one. For Cr2O3 coatings, with the increase of oxygen partial pressure, the number and size of droplets decreases, the deposition rate decreases and the （300） becomes the preferred orientation. These differences are ascribed to the formation of CrN （with a lower melting point） and Cr2O3 （with a higher melting point） on the surface of Cr target during the deposition of CrN and Cr2O3. Complete coatings CrN or Cr2O3 film can be formed when reactive gas partial pressure gets up to 0. l Pa. The optimized N2 partial pressure for CrN deposition is about 0.1-0.2 Pa in order to suppress the formation of droplets and the suitable 02 partial pressure for Cr2O3 deposition is approximately 0.1 Pa for the attempt to prevent the peel of the coating.     

Microstructure and tribological behavior of suspension plasma sprayed Al2O3 and Al2O3-YSZ composite coatings

Several alumina and alumina-zirconia composite coatings were manufactured by suspension plasma spraying (SPS), implementing different operating conditions in order to achieve dense and cohesive structures. Temperatures and velocities of the in flight particles were measured with a commercial diagnostic system (Accuraspray®) at the spray distance as a function of the plasma operating parameters. Temperatures around 2000 °C and velocities as high as 450 m/s were detected. Hence, coatings with high amount of α-alumina phase were produced. The microstructure evolution according to the spray parameters was studied as well as the final tribological properties showing efficient wear resistance.     

Influence of O2/Ar flow ratio on the structure and optical properties of sputtered hafnium dioxide thin films

Hafnium dioxide (HfO₂) thin films were deposited on a quartz substrate by RF reactive magnetron sputtering. The influence of O₂/Ar flow ratio on the deposition rate, structure and optical properties of HfO₂ thin films were systematically studied using X-ray diffraction (XRD), scan electron microscopy (SEM) and UV-visible spectroscopy. The results show that the deposition rate decreases obviously when the O₂/Ar flow ratio increases from 0 to 0.25 and then, decreases little as the O₂/Ar flow ratio further increases to 0.50. The HfO₂ thin films prepared are all polycrystalline with a monoclinic phase. The thin film deposited with pure argon shows a preferential growth and has considerably improved crystallinity and much larger crystallite size. Meanwhile, after oxygen is introduced into the deposition, the thin films prepared have random orientation, weakened crystallinity and smaller crystallite size. The refractive index is higher for the thin film deposited without oxygen and increases as the O₂/Ar flow ratio increases from 0.25 to 0.50. The band gap energy of the thin film increases with an increasing O₂/Ar flow ratio.     

In-situ TiB2-Al2O3 formed composite coatings by atmospheric plasma spraying: Influence of process parameters and in-flight particle characteristics

In the present study, mechanically alloyed Al-12Si, B₂O₃ and TiO₂ powder was deposited onto an aluminum substrate using atmospheric plasma spraying (APS). The effects of mechanical alloying (MA) time and plasma parameters (arc current and primary/secondary/carrier gas flow rate) on in-situ reaction intensity and in-flight particle characteristics (temperature and velocity) have been investigated. It has been observed that MA time has a remarkable effect on powder morphology and relative amount of in-situ formed TiB₂ and γ-Al₂O₃. In-flight particle diagnostic measurements demonstrate that among the plasma parameters arc current has the strongest effect on in-flight particle velocity and temperature. Also, results indicate that in-flight particle velocity is more dominant than temperature on the relative amount of in-situ formed phases.