TY - CHAP A1 - Kashkarov, Egor B. A1 - Sutygina, Alina A1 - Nikitenkov, Nikolay A1 - Syrtanov, Maxim S. A1 - Obrosov, Aleksei ED - Tiwari, Ashutosh T1 - Microstructure changes and hydrogenation behaviour of Zr-1Nb alloy after plasma immersion titanium implantation at different time of exposure T2 - American Advanced Materials Congress 2016 N2 - 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. KW - implantation KW - titanium KW - zirconium KW - hydrogenation KW - microstructure Y1 - 2016 SN - 978-91-88252-03-6 PB - VBRI Press CY - Linköping ER - TY - GEN A1 - Kashkarov, Egor B. A1 - Nikitenkov, Nikolay A1 - Sutygina, Alina A1 - Laptev, Roman A1 - Bordulev, Yuriy A1 - Obrosov, Aleksei A1 - Liedke, Maciej O. A1 - Zak, Andrzej A1 - Weiß, Sabine T1 - Microstructure, defect structure and hydrogen trapping in zirconium alloy Zr-1Nb treated by plasma immersion Ti ion implantation and deposition T2 - Journal of Alloys and Compounds N2 - 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. KW - Zirconium KW - Ion implantation KW - Titanium KW - Diffusion KW - Surface modification KW - Hydrogen trapping KW - Microstructure KW - Slow positrons KW - Doppler broadening KW - Defects Y1 - 2018 UR - http://www.sciencedirect.com/science/article/pii/S0925838817335879 U6 - https://doi.org/10.1016/j.jallcom.2017.10.151 SN - 0925-8388 VL - 732 SP - 80 EP - 87 ER - TY - GEN A1 - Kashkarov, Egor B. A1 - Nikitenkov, Nikolay A1 - Sutygina, Alina A1 - Obrosov, Aleksei A1 - Manakhov, Anton A1 - Polčak, Josef A1 - Weiß, Sabine T1 - Hydrogen absorption by Ti-implanted Zr-1Nb alloy T2 - International journal of hydrogen energy N2 - 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. KW - Zirconium KW - Titanium implantation KW - Hydrogenation KW - X-ray photoelectron spectroscopy KW - Glow discharge optical emission spectroscopy KW - X-ray diffraction Y1 - 2018 UR - https://www.sciencedirect.com/science/article/pii/S0360319917346359 U6 - https://doi.org/10.1016/j.ijhydene.2017.12.003 SN - 0360-3199 VL - 43 IS - 4 SP - 2484 EP - 2491 ER - TY - GEN A1 - Kashkarov, Egor B. A1 - Nikitenkov, Nikolay A1 - Sutygina, Alina A1 - Syrtanov, Maxim S. A1 - Zakharchenko, S. A1 - Obrosov, Aleksei T1 - Influence of Plasma-Immersion Titanium-Ion Implantation on the Kinetics of Hydrogen Penetration into E110 Zirconium Alloy T2 - Journal of Surface Investigation: X-ray, Synchrotron and Neutron Techniques N2 - 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. KW - ion implantation KW - zirconium KW - titanium KW - hydrogen sorption KW - wear resistance KW - X-ray photoelectron spectroscopy Y1 - 2018 UR - https://link.springer.com/journal/11700 U6 - https://doi.org/10.1134/S102745101803031X SN - 1819-7094 VL - 12 IS - 3 SP - 570 EP - 575 ER -