Chromium carbonitride coatings were deposited by cathodic arc physical vapor deposition technology at a temperature of 300 °C, as were used the reactive gasses CH4 and N2. The structural analysis of the CrN coating showed a polycrystalline structure with mixed CrN and Cr2N phases. All studied coatings, including the CrC exhibits fcc structure. The phases were confirmed by X-ray photoelectron spectroscopy measurements where a surface oxidation was also detected. The increase of the CH4 gas flow during the deposition process leads to a parabolic trend with the highest hardness of 33.5 GPa for the coating deposited at CH4 / N2 = 0.53. At the same time the lowest coefficient of friction for both counterparts Al2O3 and ZrO2 (0.28 and 0.26, respectively) were measured at CH4 / N2 = 1.86. The tribological tests reveal that the wear of the coatings increases with an increasing CH4 flow rate, whereas the coefficient of friction decreases. This observed contradiction is explained by a phenomenon described as the effect of Rebinder.
In the current work, the microstructure, hydrogen permeability, and properties of chromium nitride (CrNₓ) thin films deposited on the Inconel 718 superalloy using direct current reactive sputtering are investigated. The influence of the substrate bias voltage on the crystal structure, mechanical, and tribological properties before and after hydrogen exposure was studied. It was found that increasing the substrate bias voltage leads to densification of the coating. X-ray diffraction (XRD) results reveal a change from mixed fcc-CrN + hcp-Cr₂N to the approximately stoichiometric hcp-Cr₂N phase with increasing substrate bias confirmed by wavelength-dispersive X-ray spectroscopy (WDS). The texture coefficients of (113), (110), and (111) planes vary significantly with increasing substrate bias voltage. The hydrogen permeability was measured by gas-phase hydrogenation. The CrN coating deposited at 60 V with mixed c-CrN and (113) textured hcp-Cr₂N phases exhibits the lowest hydrogen absorption at 873 K. It is suggested that the crystal orientation is only one parameter influencing the permeation resistance of the CrNx coating together with the film structure, the presence of mixing phases, and the packing density of the structure. After hydrogenation, the hardness increased for all coatings, which could be related to the formation of a Cr₂O₃ oxide film on the surface, as well as the defect formation after hydrogen loading. Tribological tests reveal that hydrogenation leads to a decrease of the friction coefficient by up to 40%. The lowest value of 0.25 ± 0.02 was reached for the CrNₓ coating deposited at 60 V after hydrogenation.
Oxidation Behavior of Zr–1Nb Corroded in Air at 400 °C after Plasma Immersion Titanium Implantation
(2018)
In this paper, the influence of plasma immersion titanium implantation into the zirconium alloy Zr-1Nb on the oxidation behavior at 400 °C for 5, 24, 72, and 240 h in air under normal atmospheric pressure (101.3 kPa) was shown. The influence of implantation on the protective properties of the modified layer was shown. The valence of the oxides before and after implantation was analyzed by means of X-ray photoelectron spectroscopy (XPS). Grazing incidence X-ray diffraction (GIXRD) was carried out to examine the phase composition after titanium ion implantation and oxidation. Differential scanning calorimetry (DSC) revealed that titanium implantation exhibited effects of stabilizing the β phase. The formation of the t-ZrO2 and m-ZrO2 was observed during the oxidation of the as-received and modified Zr-1Nb. The measurement of weight gain showed an improvement in oxidation resistance of Ti implanted Zr-1Nb at the oxidation up to 24 h when compared with that of the as-received Zr-1Nb. However, at longer oxidation cycle the oxidation rate of Ti-implanted zirconium alloy is the same with the as-received alloy, which attributed to the layer thickness. Nevertheless, the corrosion of the Ti-implanted alloy is more uniform, while a local corrosion and cracks was detected on the surface of the as-received alloy.
This paper describes the hydrogenation behavior of Zr-1Nb alloy Ti-implanted by plasma immersion ion implantation (PIII). Hydrogen sorption kinetics of the Ti-modified alloy was investigated under gas-phase hydrogenation at 400 °C for 1 h. The influence of implantation time on the protective properties of the modified layer was shown. The lowest hydrogen absorption as well as the highest hydrogen trapping efficiency was achieved after PIII for 30 min. The main contribution to the reduction of hydrogen permeation is the formation of an oxide layer consisting of mixed TiO2 and ZrO2 on the modified surface of the alloy. X-ray photoelectron spectroscopy (XPS) revealed that PIII titanium oxide exists on the surface in the form of TiO2, which transforms to mixed Ti2O3 and TiO2 after hydrogenation. The thickness of the modified layer increases with implantation time that improves the efficiency of hydrogen trapping. All the absorbed hydrogen is gradually distributed in the modified layer and no hydrides are formed after hydrogenation in Ti-modified Zr-1Nb for 15 and 30 min.
Controlled ion bombardment is a popular method to fabricate desirable coating structures and modify their properties. Substrate biasing at high frequencies is a possible technique, which allows higher ion density at the substrate compared with DC current bias. Moreover, high ion energy along with controlled adatom mobility would lead to improved coating growth. This paper focuses on a similar type of study, where effects of coating growth and properties of DC magnetron-sputtered chromium nitride (CrxN) coatings at various substrate bias frequencies are discussed. CrxN coatings were deposited by pulsed DC magnetron sputtering on Inconel 718 and (100) silicon substrates at 110, 160 and 280 kHz frequency at low duty cycle. Coating microstructure and morphology were studied by X-ray diffraction (XRD), atomic force microscopy (AFM), scanning electron microscopy (SEM), scratch adhesion testing and nanoindentation. Results indicate a transformation of columnar into glassy structure of CrxN coatings with the substrate bias frequency increase. This transformation is attributed to preferential formation of the Cr2N phase at high frequencies compared with CrN at low frequencies. Increase in frequency leads to an increase in deposition rate, which is believed to be due to increase in plasma ion density and energy of the incident adatoms. An increase in coating hardness along with decrease in elastic modulus was observed at high frequencies. Scratch tests show a slight increase in coating adhesion, whereas no clear increase in coating roughness can be found with the substrate bias frequency.