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The effect of low energy plasma immersion ion implantation and deposition of titanium on microstructure, defect structure and hydrogen trapping in zirconium alloy Zr-1Nb was studied. Defect structure and distribution were analyzed by Doppler broadening using slow positron beam. The surface microstructure after modification is represented by nanostructured Ti grains with random orientation. The gradient distribution of titanium as well as vacancy type defects were analyzed. The concentration of vacancy type defects is rising with increasing bias voltage. Gas-phase hydrogenation of the Ti-modified Zr-1Nb alloy was performed at 400 °C for 60 min. The strong interaction of hydrogen with vacancy type defects was demonstrated. Two different changes in the defect structure after hydrogenation were observed: when a titanium film is formed on the surface (after deposition at 500 V) hydrogen trapping occurs with the formation of titanium hydride phases, while in the implanted layer (deposition at 1000 and 1500 V) hydrogen is trapped due to interaction with vacancy type defects. The physical basis of Ti diffusion and its influence on the evolution of defect structure after surface modification and hydrogenation were discussed.
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.
The influence of plasma-immersion titanium-ion implantation on the hydrogen saturation of E110 zirconium alloy is described. Titanium ions are implanted from the metal plasma of an arc discharge at an accelerating-pulse bias potential of 1.5 kV (the pulse-repetition frequency is 100 kHz, and the pulse length is 5 μs) for 30 min. The phase composition, morphology, and valence state of the alloy surface layer are studied. Comparative analysis of changes in the hardness and wear resistance of the alloy subjected to implantation is performed. It is demonstrated that the rate of hydrogen penetration into the surface-doped alloy decreases substantially at a gas-phase hydrogenation temperature of 400°C.
Oxidation behavior of Zr–1Nb in air at 400°C after Titanium Plasma Immersion Ion Implantation
(2018)
Zirconium alloys have been widely used in nuclear reactors due to low thermal neutron capture cross-section, excellent corrosion resistance and acceptable mechanical properties [1, 2]. Nowadays several methods apply for improving hydrogen and corrosion resistance such as addition of stabilizing additives (yttrium) [3, 4], deposition of thin solid films [5, 6], micro-arc oxidation [7] and modification of the surface by electron beam [8, 9]. Despite the multiplicity of the methods hydrogen embrittlement is still a pressing issue. Previous results [10, 11] have shown the positive influence of plasma immersion titanium implantation on the hydrogenation behavior of Zr–1Nb and Zr–2.5 Nb. After Ti implantation hydrogen preferably accumulates in the modified surface layer comprising the implanted Ti. Furthermore, the hydrogen concentration is considerably less inside the zirconium modified sample than in the as-received samples.
The integration of elements into the zirconium lattice can influence the valence of the surface and change corrosion and oxidation rates of the alloys. So it is very important not to decrease the zirconium oxidation resistance due to Ti implantation. Therefore, the purpose of this research is to study of the influence of Ti implantation on surface morphology, oxidation rate and phase structure of the Zr–1Nb alloy after oxidation on air at 400 0C for 5, 24, 72 and 240 h. The surface structure of the samples and their elemental composition were investigated with the scanning electron microscope Mira II XMH (Tescan) with energy dispersive x-ray spectroscopy system (EDS). X-ray photoelectron spectroscopy (XPS), differential scanning calorimetry (DSC) as well as X-ray diffraction (XRD) was used to characterise the influence of titanium implantation on the oxidation behaviour. The results show that the oxidation kinetics after Ti modification of the zirconium alloy changed. Although the weight gain of the implanted sample remains approximately the same, it can be considered that Ti implantation stabilizes the oxide layer and has beneficial influence on the oxidation protection of Zr-1Nb.
In the current study, the properties of the CrₓN coatings deposited on the Inconel 718 superalloy using direct current reactive magnetron sputtering are investigated. The influence of working pressure on the microstructure, mechanical, and tribological properties of the CrₓN coatings before and after high-temperature hydrogen exposure is studied. The cross-sectional scanning electron micrographs indicate the columnar structure of the coatings, which changes from dense and compact columns to large columns with increasing working pressure. The Cr/N ratio increases from 1.4 to 1.9 with increasing working pressure from 300 to 900 mPa, respectively. X-ray diffraction analysis reveals a change from mixed hcp-Cr₂N and fcc-CrN structure to approximately stoichiometric Cr₂N phase. After gas-phase hydrogenation, the coating deposited at 300 mPa exhibits the lowest hydrogen absorption at 600 °C of all investigated coatings. The results indicate that the dense mixed cubic and hexagonal structure is preferential for hydrogen permeation resistance due to the presence of cubic phase with higher packing density in comparison to the hexagonal structure. After hydrogenation, no changes in phase composition were observed; however, a small amount of hydrogen is accumulated in the coatings. An increase of coating hardness and elastic modulus was observed after hydrogen exposure. Tribological tests reveal that hydrogenation leads to a decrease of the friction coefficient up to 20%–30%. The best value of 0.25 was reached for hydrogen exposed CrₓN coating deposited at 300 mPa.
Ti-Al-N coatings were deposited on high-speed steel substrates by filtered vacuum arc deposition (FVAD) during evaporation of aluminum and titanium cathodes. Distribution of elements, phase composition, and mechanical properties of Ti-Al-N coatings were investigated using Auger electron spectroscopy (AES), X-ray diffraction (XRD), transmission electron microscopy (TEM) and nanoindentation, respectively. Additionally, tribological tests and scratch tests of the coatings were performed. The stoichiometry of the coating changes from Ti0.6Al0.4N to Ti0.48Al0.52N with increasing aluminum arc current from 70 A to 90 A, respectively. XRD and TEM showed only face-centered cubic Ti-Al-N phase with preferred orientation of the crystallites in (220) direction with respect to the sample normal and without precipitates of AlN or intermetallics inside the coatings. Incorporation of Al into the TiN lattice caused shifting of the (220) reflex to a higher 2θ angle with increasing Al content. Low content and size of microdroplets were obtained using coaxial plasma filters, which provides good mechanical and tribological properties of the coatings. The highest value of microhardness (36 GPa) and the best wear-resistance were achieved for the coating with higher Al content, thus for Ti0.48Al0.52N. These coatings exhibit good adhesive properties up to 30 N load in the scratch tests.
Zirconium alloys are the main construction materials of water-cooled nuclear reactors. Zirconium is used in the core of nuclear reactors as fuel element claddings due to low thermal-neutron capture cross section. Hydrogen is released in the process of water radiolysis or high-temperature oxidation of fuel claddings under loss of coolant accident (LOCA) conditions. The penetration and accumulation of hydrogen in zirconium alloys lead to degradation of their physical and mechanical properties caused by hydrogen embrittlement and delayed hydride cracking [1, 2]. Plasma immersion ion implantation (PIII) is widely used to improve the mechanical properties, corrosion and erosion resistance as well as to decrease hydrogen absorption rate of zirconium [3, 4]. During PIII, a plasma ions are accelerated by high voltage pulsed bias applied to the target. The accelerated ions penetrate in the bulk of the target and modify the deeper layers of materials. Previous studies shown that PIII of titanium improves the protection properties of Zr-2.5Nb alloy from hydrogenation [5]. Moreover, the microdroplets and ion energy have significant impact on hydrogen absorption of the alloys. However, it is necessary to understand the mechanism of hydrogen interaction with the modified layers depending on the time of implantation. In this study, titanium ions were implanted into Zr-1Nb alloy target using filtered vacuum arc source and high frequency short pulser. Coaxial plasma filter was used to reduce the number and size of microdroplets evaporated from the cathode spots. The implantation parameters are: 70 A arc current, 0.15 Pa argon pressure, 1500 V pulsed bias, 100 kHz repetition frequency, 5 μs pulse length and 5-30 min implantation time. Gas-phase hydrogenation was performed at 623 K and 2 atm. hydrogen pressure for 60 min. Surface morphology, phase composition and depth distribution of elements were investigated using scanning electron and atomic force microscopies (SEM and AFM), X-ray diffraction and glow-discharge optical emission spectroscopy (GDOES). It was revealed that the microdroplets and craters with the size of several microns are formed after titanium implantation. The number and size of craters are increased with implantation time from 5 to 30 minutes. It is assumed that the presence of craters on the surface caused by bombardment of an accelerated ion clusters, which is formed due to incorporation (condensation) and ionization of evaporated atoms near the cathode region. Furthermore, the surface becomes rougher and the microstructure changes to fine-grained with an average grain size of 50-100 nm with increase of implantation time. Hydrogenation behaviour depends on the implantation time and differs from the non-treated Zr-1Nb alloy. Hydrogen absorption rate decreases by two times with increase in implantation time from 5 to 30 min. Furthermore, hydrogen preferably accumulates in the modified layer at higher implantation time. The distribution of hydrogen tends to decrease in the depth of implanted layer. The phase state of the alloy has not changed after implantation, however, the extensive distortions of the crystal lattice are observed after hydrogenation of the non-treated and implanted for 5 min Zr-1Nb alloys.