Effect of different ion beam energy on properties of amorphous carbon film fabricated by ion beam sputtering deposition (IBSD)

Amorphous carbon (a-C) films were fabricated by ion beam sputtering technique. The influence of sputtering ion beam energy on bonding structure, morphologic, mechanical properties, tribological properties and corrosion resistance of a-C films are investigated systematically. Morphology study shows that lowest surface roughness exists for mid-ion beam energy. Improved adhesion is observed for the films that are prepared under high ion beam energy, attributed to film graphitization, low residual stress and mixed interface. Relatively, a-C films prepared with ion beam energy of 2 keV exhibits optimum sp³ bond content, mechanical properties and corrosion resistance. It is found that the wear rate of DLC films decrease with increased ion beam energy in general, consistent with the varied trend of the H/E value which has been regarded as a suitable parameter for predicting wear resistance of the coatings. The correlation of the sp³ bond fraction in the films estimated from Raman spectroscopy with residual stress, nanohardness and corrosion resistance has been established.     

Effect of swift heavy ion irradiation on the surface morphology of highly c-axis oriented LSMO thin films grown by pulsed laser deposition

A detailed investigation of the surface morphology of the pristine and swift heavy ion (SHI) irradiated La_0.7Sr_0.3MnO₃ (LSMO) thin film using atomic force microscope (AFM) is presented. Highly c-axis oriented LSMO thin films were grown on LaAlO₃ (1 0 0) (LAO) substrates by the pulsed laser deposition (PLD) technique. The films were annealed at 800 °C for 12 h in air (pristine films) and subsequently, irradiated with SHI of oxygen and silver. The incident fluence was varied from 1 × 10¹² to 1 × 10¹⁴ ions/cm² and 1 × 10¹¹ to 1 × 10¹² ions/cm² for oxygen and silver ions, respectively. X-ray diffraction (XRD) studies reveal that the irradiated films are strained. From the AFM images, various details pertaining to the surface morphology such as rms roughness (σ), the surface rms roughness averaged over an infinite large image (σ_∞), fractal dimension (D_F) and the lateral coherence length (ξ) were estimated using the length dependent variance measurements. In case of irradiated films, the surface morphology shows drastic modifications, which is dependent on the nature of ions and the incident fluence. However, the surface is found to remain self-affine in each case. In case of oxygen ion irradiated films both, σ_∞ and D_F are observed to increase with fluence up to a dose value of 1 × 10¹³ ions/cm². With further increase in dose value both σ_∞ and D_F decreases. In case of silver ion irradiated films, σ_∞ and D_F decrease with increase in fluence value in the range studied.     

Growth of silicon nitride films by bombarding amorphous silicon with N ions: MD simulation

In this study, the molecular dynamics simulation method was employed to investigate the growth of silicon nitride films by using N⁺ ions, with energies of 50, 100, 150 and 200 eV, to bombard an amorphous silicon surface at 300 K. After an initial period of N⁺ bombardment, saturation of the number of N atoms deposited on the surface is observed, which is in agreement with experiments. During subsequent steady state deposition, a balance between uptake of N by the surface and sputtering of previously deposited N is established. The Si(N_x) (x = 1-4) and N(Si_y) (y = 1-3) bond configurations in the grown films are analyzed.     

Hydrogen permeation characteristics of some Fe-Cr-Al alloys

Hydrogen permeation data are reported for two Fe-Cr-Al alloys, Type-405 SS (Cr 14-A1 0.2) and a member of the Fecralloy family of alloys (Cr 16-A1 5). The hydrogen permeability of each alloy (in a partially oxidized condition) was measured over a period of several weeks at randomly selected temperatures (between 150 and 850°C) and upstream H₂ pressures (between 2 and 1.5 × 10⁴ Pa). The permeabilities showed considerable scatter with both time and temperature and were 10² to 10³ times lower than those of pure iron, even in strongly reducing environments. The exponent, n, for the relationship between upstream H₂ pressure, P, and permeability, φ, (φ ~ Pⁿ) was closer to 0.7 than to the expected 0.5, indicating a process limited by surface effects (e.g., surface oxide films) as opposed to bulk material effects. Comparison of these results with prior permeation measurements on other Fe-Cr-Al alloys, on Fe-Cr alloys, and on pure iron shows that the presence of a few weight percent aluminum offers the best prospects for achieving low tritium permeabilities with martensitic and ferritic steels used in fusion-reactor first wall and blanket applications.     

Electrochemical characterisation of nickel-based alloys in sulphate solutions at 320 °C

Nickel alloy steam generator tubes of pressurized water reactors (PWR) are sensitive to stress corrosion cracking (SCC) and the possibility of predicting SCC from electrochemical measurements is of considerable interest for nuclear industry. The electrochemical properties of several nickel-based alloys were studied at 320 °C in sulphate solutions at neutral or slightly alkaline pH from corrosion potential measurements, polarisation curves and polarisation resistance (R_p) measurements by linear voltammetry and electrochemical impedance spectroscopy (EIS). The passive layers were much more stable in neutral conditions, due to the presence of chromium oxide, and alloys 600TT and 690 showed the best passivity. R_p measurements confirmed that alloys 600TT and 690 have the lowest corrosion rates. At alkaline pH, the passivation currents were higher than those obtained at neutral pH, and the alloys showed a close behaviour. Reduction of sulphates to sulphides seemed to be possible. Results are in agreement with thermodynamic and surface analysis data of literature. The electrochemical stability did not appear to be directly related to SCC susceptibility since it varied inversely with the pH dependance of SCC in sulphate medium.     

Influence of Nitrogen on Hydrogenated Amorphous Carbon Thin Films Deposited by Plasma Focus Device

To carry out our research, a plasma focus device is used to deposit thin films of nitrogen doped hydrogenated amorphous carbon (a-C:H:N) onto the stainless steel-AISI-304 substrates at room temperature. Thin films are deposited with the same numbers of focus shots, at the same distance from the anode tip and with different partial pressures of nitrogen in the mixtures of acetylene/nitrogen as working gas. The nitrogen contents of deposited films are studied using nuclear reaction analysis (NRA) techniques. The results prove that nitrogen contents of the samples do not increase significantly by increasing partial pressure of nitrogen of the working gas for both sets of the samples. Moreover, NRA results exhibit the limitation of nitrogen incorporated into the samples, when this experimental setup is used. G-peak position and peak intensity ratio of the D-band to G-band (I_D/I_G) are used to investigate the diamond characters. Also, they show that sp² clustering is highly dependent on the nitrogen atomic contents and angular position of the samples. Scanning electron microscopy (SEM) shows the granular surface morphology of the films. Furthermore, it shows that angular position of the samples with respect to the anode axis plays an important role in the grain size of the surface of the samples. The thickness of the films decreases significantly by increasing angular position of the samples, while it decreases slightly by increasing partial pressure of nitrogen of the working gas. The Vickers surface hardness of the thin films exhibits significant dependency on the sp² clustering.     

Change in magnetic properties of MgB2 thin films after irradiation by 200 MeV Au ion beam

The SHI irradiation induced effects on magnetic properties of MgB₂ thin films are reported. The films having thickness 300-400 nm, prepared by hybrid physical chemical vapor deposition (HPCVD) were irradiated by 200 MeV Au ion beam (S_e ∼ 23 keV/nm) at the fluence 1 × 10¹² ion/cm². Interestingly, increase in the transition temperature T_c from 35.1 K to 36 K resulted after irradiation. Substantial enhancement of critical current density after irradiation was also observed because of the pinning provided by the defects created due to irradiation. The change in surface morphology due to irradiation is also studied.     

Positron annihilation on the surfaces of SiO2 films thermally grown on single crystal of Cz-Si

Two-detector coincidence system and mono-energetic slow positron beam has been applied to measure the Doppler broadening spectra for single crystals of SiO₂, SiO₂ films with different thickness thermally grown on single crystal of Cz-Si, and single crystal of Si without oxide film. Oxygen is recognized as a peak at about 11.85 × 10⁻³m₀c on the ratio curves. The S parameters decrease with the increase of positron implantation energy for the single crystal of SiO₂ and Si without oxide film. However, for the thermally grown SiO₂-Si sample, the S parameters in near surface of the sample increase with positron implantation energy. It is due to the formation of silicon oxide at the surface, which lead to lower S value. S and W parameters vary with positron implantation depth indicate that the SiO₂-Si system consist of a surface layer, a SiO₂ layer, a SiO₂-Si interface layer and a semi-infinite Si substrate.     

Influence of Nb concentration in the α-matrix on the corrosion behavior of Zr-xNb binary alloys

The influence of the Nb concentration in the α-matrix on the corrosion behavior of Zr-xNb (x=0-0.6 wt%) binary alloys was evaluated using a static autoclave in the temperature range from 300 to 500 °C. Corrosion tests and precipitate analysis of Zr-xNb binary alloys showed that corrosion resistance increased with the increase of the Nb concentration in the α-matrix, and the best corrosion resistance was obtained when the Nb concentration was nearly at its equilibrium solubility limit at all test temperatures. The alloys containing a higher Nb concentration than their equilibrium solubility also showed good corrosion resistance, which could be attributed mainly to the formation of Nb-precipitates, resulting in an equilibrium Nb concentration in the α-matrix. These results imply that the corrosion resistance of Nb-containing Zr-alloys can be controlled by the Nb concentration in the α-matrix rather than the Nb-precipitates.     

核级不锈钢焊接接头钝化膜耐蚀性能和半导体特性研究

采用电化学阻抗谱(EIS)、场发射扫描电子显微镜(SEM)、Auger扫描能谱仪(AES)以及容抗测试技术(M-S曲线),研究了316LN/316L不锈钢焊接接头在模拟压水堆一回路高温高压水中形成的钝化膜的耐蚀性能和半导体特性。结果表明,焊缝区、热影响区和母材区形成的钝化膜的耐蚀性能不同,热影响区钝化膜开路电位及电化学阻抗等均低于其他区域,说明热影响区钝化膜的耐蚀性能最差,这主要与钝化膜的致密程度、厚度及Cr氧化物的含量有关。M-S曲线表明,母材区钝化膜平带电位为-0.7V,较其他区域(-0.4V)负移,表明有BO-3等阴离子在钝化膜表面吸附,加之具有较低的施主和受主浓度,可排斥侵蚀离子的腐蚀,使之较其他区域有更强的耐蚀性能。     

Spectroscopic studies of homogeneous thin carbon erosion films on mirrors and flakes with a high deuterium content formed in tokamak T-10

Redeposited hydrocarbon films on plasma facing elements in tokamaks accumulate hydrogen isotopes. In the present study such films were made to redeposit on stainless steel mirror substrates as thin films and without any substrate as bare flakes with high deuterium content, under deuterium-plasma discharges inside T-10 tokamak vacuum chamber. These films were subjected to spectral characterizations through Fourier-transform infrared (FT-IR), electron paramagnetic resonance (EPR), and photoluminescence techniques. IR spectra showed the presence of two main deuterium states as observed by the CD_2,3 sp³ stretching modes at 2100–2200 cm⁻¹ and the CD₂ sp³ bending modes at 600–1100 cm⁻¹. Among these, CD₃ stretching mode at 2217 cm⁻¹ may serve as a control for deuterium desorption during the cleanup process of the reactor. As a comparative measure, C60 films were also studied, the luminescence excitation spectrum of which showed similarity in peak positions with tokamak bare flakes pertained to sp² luminescence centers. The observed spectral differences are mainly due to more localized sp² states for C60 and sp³ states for tokamak flakes. EPR spectra of the bare flakes showed the defective states with a high spin density, ∼10¹⁹ cm⁻³ which serve as luminescence quenching centers, and provide a path for hydrogen isotopes adsorption.     

Effect of 4MeV electron beam irradiation on carbon films

Pulsed KrF excimer laser is used to deposit tetrahedral amorphous carbon (ta-C) thin films on Si (1 1 1) single crystal substrates at room temperature under vacuum ∼10⁻⁶ mbars. The pristine deposited films are then irradiated by 4 MeV electron beam at doses varying from 1000 to 4000 cGy. Analysis through AFM illustrates that the irradiation of electron has induced cluster formation on the film surface and increased the surface roughness. Optical properties (n, α and Tauc optical band gap) measured by spectroscopic ellipsometry and electrical resistivity measured by four probe technique are found to depend strongly on electron dose. High electron doses cause significant alteration in order/disorder or sp² states in the film which is the main cause of modifying band gap in the carbon films. The electrical conductivity of the films also increases by increasing electron dose which is due to tunneling of charge carriers through neighbouring conductive chains. The present electron irradiation process at varying electron doses proved to be successful to modulate the optical and electrical properties of carbon films.     

Corrosion behavior of Ni-based structural materials for electrolytic reduction in lithium molten salt

In this study, the corrosion behavior of new Ni-based structural materials was studied for electrolytic reduction after exposure to LiCl-Li₂O molten salt at 650 °C for 24-216 h under an oxidizing atmosphere. The new alloys with Ni, Cr, Al, Si, and Nb as the major components were melted at 1700 °C under an inert atmosphere. The melt was poured into a preheated metallic mold to prepare an as-cast alloy. The corrosion products and fine structures of the corroded specimens were characterized by scanning electron microscope (SEM), Energy Dispersive X-ray Spectroscope (EDS), and X-ray diffraction (XRD). The corrosion products of as cast and heat treated low Si/high Ti alloys were Cr₂O₃, NiCr₂O₄, Ni, NiO, and (Al,Nb,Ti)O₂; those of as cast and heat treated high Si/low Ti alloys were Cr₂O₃, NiCr₂O₄, Ni, and NiO. The corrosion layers of as cast and heat treated low Si/high Ti alloys were continuous and dense. However, those of as cast and heat treated high Si/low Ti alloys were discontinuous and cracked. Heat treated low Si/high Ti alloy showed the highest corrosion resistance among the examined alloys. The superior corrosion resistance of the heat treated low Si/high Ti alloy was attributed to the addition of an appropriate amount of Si, and the metallurgical evaluations were performed systematically.     

Computer simulation of sputtering at the low index (1 0 0), (1 1 0) and (1 1 1) surfaces of Ni3Al in a STEM

The present study is relevant to the preferential Al sputtering and/or enhancement of the Ni/Al ratio in Ni₃Al observed by the scanning transmission electron microscopy fitted with a field emission gun (FEG STEM). Atomic recoil events at the low index (1 0 0), (1 1 0) and (1 1 1) surfaces of Ni₃Al through elastic collisions between electrons and atoms are simulated using molecular dynamics (MD) methods. The threshold energy for sputtering, E_sp, and adatom creation, E_ad, are determined as a function of recoil direction. Based on the MD determined E_sp, the sputtering cross-sections for Ni and Al atoms in these surfaces are calculated with the previous proposed model. It is found that the sputtering cross-section for Al atoms is about 7-8 times higher than that for Ni, indicating the preferential sputtering of Al in Ni₃Al, in good agreement with experiments. It is also found that the sputtering cross-sections for Ni atoms are almost the same in these three surfaces, suggesting that they are independent of surface orientation. Thus, the sputtering process is almost independent of the surface orientation in Ni₃Al, as it is controlled by the sputtering of Ni atoms with a lower sputtering rate.     

Sputtering of clusters from copper-gold alloys

Polycrystalline Cu, Cu₂₀Au₈₀, Cu₄₀Au₆₀, Cu₈₀Au₂₀ and Au samples were bombarded with 15 keV Ar⁺, and the resulting secondary neutral yield distribution was studied by non-resonant laser post-ionisation mass spectrometry. Neutral clusters containing up to 15 atoms were observed for the targets. The yield of neutral clusters, Cu_mAu_n−m, containing n atoms, Y_n, was found to follow a power in n, i.e. Y_n∝n^-δ, where the exponent δ varied from 5.2 to 10.1. For a fixed n, the cluster yields showed a variation with number of copper atoms, m, much greater than expected for a binomial distribution suggesting that the clusters are not formed randomly above the surface and a component of preformed cluster emission occurs. In addition, the cluster compositions from the sputtered alloys were indicative of sputtering from a copper rich surface.     

Characterization of high energy ion implantation into Ti-6Al-4V

Ion implantation is a surface modification process that can improve the wear, fatigue, and corrosion resistance for several metals and alloys. Much of the research to date has focused on ion energies less than 1 MeV. With this in mind, Ti-6Al-4V was implanted with Al²⁺, Au³⁺, and N⁺ ions at energies of 1.5 and 5 MeV and various doses to determine the effects on strengthening of a high energy beam. A post heat treatment on the specimens implanted with Al²⁺ samples was conducted to precipitate Ti_xAl type intermetallics near the surface. Novel techniques, such as nanoindentation, are available now to determine structure-mechanical property relationships in near-surface regions of the implanted samples. Thus, nanoindentation was performed on pre-implanted, as-implanted, and post heat treated samples to detect differences in elastic modulus and hardness at the sub-micron scale. In addition, sliding wear tests were performed to qualitatively determine the changes in wear performance. The effect of this processing was significant for samples implanted with Al²⁺ ions at 1.5 MeV with a dose higher than 1 × 10¹⁶ ions/cm² where precipitation hardening likely occurs and with N⁺ ions.     

Study of the behavior of 3d-shell electrons in binary Nd-Fe alloys

The behavior of 3d electrons in binary Nd-Fe alloys with different Nd content from 7 to 13 at.% has been studied by using positron coincidence Doppler broadening techniques. It has been found that the 3d electron signal in Nd₂Fe₁₇ alloy is relatively high as compared with other alloys. In Fe-rich Nd₂Fe₁₇ alloys, as the content of Fe increasing, the phase boundaries between α-Fe and Nd₂Fe₁₇ phases will increase, which gives rise to the decrease in the probability of positron annihilation with 3d electrons. In Nd-rich Nd₂Fe₁₇ alloys, with the decrease of Fe content, the d-d interactions are weakened, and the probability of positron annihilation with 3d electrons will decrease. The coercivity JH_c and remanence Jr of the Nd-Fe alloy increase with the d-d interaction.     

Modification of Ti6Al4V Corrosion Property by Nitrogen Ion Implantation

In this project the effect of nitrogen ion implantation on the corrosion resistance of Ti6Al4V alloy is studied. Nitrogen ions are implanted with four fluences from 8 × 10¹⁷ to 5 × 10¹⁸ ions/cm² in the Ti6Al4V substrates. The effect of ion implantation on surface morphology and roughness is investigated with Atomic Force Microscopy. X-ray diffraction is used for phase analysis of the samples and as a result Ti₂N(105) in the fluence of 1 × 10¹⁸ ions/cm² and TiN in fluence of 2 × 10¹⁸ ions/cm² are observed. For corrosion resistance analysis in one molar sulfuric acid a potansiostate device is used and the best corrosion resistance is obtained for the fluence 2 × 10¹⁸ ions/cm². Moreover corrosion resistance variation is explained by microstructure considerations.     

The long-term behaviors of passivation and hydride layer of commercial grade pure titanium in TRU waste disposal environments

Preservation of the passivity under reducing environmental conditions for extended periods of time and the behavior of hydrogen evolution as the results of the preservation of the passivity of several candidate commercial grade pure titanium related to the small amount of palladium addition, such as Ti–Gr.17 for metallic containers to be buried under deep ground for disposing of transuranic (TRU) waste is investigated. The present investigation has revealed the following corrosion paths for the titanium alloys investigated. The passivity of the alloys is preserved as the result of repeated destruction and recovery of the surface films on the alloys. The long-term corrosion rate under the preserved passivity is of the order of 10⁻⁶–10⁻⁸ my⁻¹ with evolution of hydrogen. The substrate alloys absorb parts of the hydrogen generated to form lath-type hydride phase before forming hydride layers at the final stage.     

Ab initio study of hydrogen related defect in ZrO2: Consequences on dry and aqueous oxidation

Zirconium alloys are used as fuel cladding in nuclear reactors, where they are subject to corrosion. In this article, based on first-principles calculations, we examine the effect of hydrogenation on the thermodynamic stability of various defects in ZrO₂ oxide in dry and aqueous environments. We found a defect complex consisting of an oxygen vacancy and a hydrogen atom, V_O-H, to be particularly stable for a wide range of Fermi levels for all the environmental conditions tested. We suggest that this V_O-H complex may be responsible for the increase in the kinetics of oxidation of zirconium alloys frequently observed in aqueous environments.