Quantitative determination of the bulk deuterium content of zirconium alloys using nuclear reaction analysis

The use of the D(³He,p)⁴He reaction to study the bulk deuterium concentration in thick Zr alloy targets has been reported previously. In the present paper, we report on new measurements where the technique is extended to larger sample depths using higher projectile energies. This development is important since deuterium is known to concentrate at free surfaces and defects that may occur near surfaces; this effect might yield values unrepresentatively higher than the true bulk concentration. The bulk concentration has been extracted from a detailed comparison of experimental data with simulated proton spectra. In contrast to conclusions reached in an earlier study, the effect of ion beam desorption is unimportant with regard to the measurement of bulk deuterium concentrations when modest ³He fluences are used. Analyses using beams at energies of 2 and 4.5 MeV are consistent and in good agreement with bulk deuterium concentration measured by high vacuum extraction mass spectrometry (HVEMS).     

Effect of induced damage on hydrogen isotope retention of F82H with impurity layer

The effects of induced damage on hydrogen isotope retention in F82H with or without thermal oxidation were investigated using thermal desorption spectroscopy. To induce damage and modify the surface, glow discharge pre-irradiated Ar⁺ ions was examined. In non-oxidized samples, the amount of desorbed deuterium increased with Ar⁺ ion fluence. Oxygen depletion in the surface layer of non-oxidized samples from the Ar⁺ ion irradiation, which resulted in bulk diffusion of deuterium, is responsible for the increase in deuterium retention. A comparison between non-oxidized and oxidized samples clearly indicated that the surface oxide layer greatly influenced deuterium retention/desorption behaviors of F82H.     

Modification of poly(ether ether ketone) by ion irradiation

Poly(ether ether ketone) was irradiated with 3.0 MeV Si²⁺, 3.25 MeV Cu²⁺ and 4.8 MeV Ag²⁺ ions to the fluences from 10¹² to 10¹⁴ cm⁻² and the effects of irradiation were studied using ERDA, RBS and FTIR methods. The irradiation leads to release of hydrogen from the PEEK surface layer modified by the ion beam. The release is mild for low ion fluences but it becomes more pronounced at the ion fluences above 10¹³ cm⁻². At highest ion fluences the hydrogen concentration falls to 20-35% of its initial value. In contrast to hydrogen no significant oxygen release was observed. The kinetic of the hydrogen release is similar for the three ion species. FTIR measurement shows deep structural changes of the polymer structure resulting from the ion irradiation.     

Saturation in deuterium retention of CFC graphite targets exposed to beryllium-seeded plasmas on PISCES-B

ITER strike-plates are foreseen to be of carbon-fiber-composite (CFC). In this study the CFC bulk deuterium retention in ITER-relevant conditions is investigated. DMS 701 (Dunlop) CFC targets were exposed to plasma in PISCES-B divertor plasma simulator. Samples were exposed to both pure deuterium plasma and beryllium-seeded plasma at high fluences (up to ) and high surface temperature (1070 K). The deuterium contents of the exposed samples have been measured using both thermal-desorption-spectrometry (TDS) during baking at 1400 K and ion beam nuclear reaction analysis (NRA). The total deuterium inventory has been obtained from TDS while NRA measured the deuterium depth distribution. In the analysed fluence range at target temperature of 1070 K, no fluence dependence was observed. The measured released deuterium is . In the case of target exposure with beryllium-seeded plasma no change in the released amount of deuterium was found. The deuterium concentration inside the samples is almost constant until the probed depth of ?m, except in the first 1 μm surface layer, where it is 5 times higher than in the bulk. No C erosion/redeposition was observed in the Be-seeded plasma cases. The measured retention, applied to 50 m² of ITER CFC surface, would imply a tritium saturated value of 0.3 gT, much lower than the ITER safety limit of 350 g.     

Oxygen depth profiling in Kr-implanted polycrystalline alpha titanium by means of O(α,α)O resonance scattering

The ¹⁶O(α,α)¹⁶O resonance scattering was applied to study the effects of ion implantation on the oxygen distribution in the near surface region of polycrystalline titanium implanted with 180 keV krypton ions at fluences, ranging between 1 × 10¹⁴ and 5 × 10¹⁵ Kr⁺/cm². Two sample sets were chosen: as-received polycrystalline titanium discs rolled and annealed in half-hard condition which had a thick oxygen layer and similar samples in which this surface layer was removed by polishing. An increase of the mean oxygen concentration observed in both unpolished and polished samples at low fluence suggests a knock-on implantation of surface oxygen atoms. At high fluence, an overall decrease in the mean oxygen concentration and mean oxygen depth suggests an out-diffusion of near-surface oxygen atoms.     

Isotopic composition of boron secondary ions as a function of ion-beam fluence

We have examined the effects of target mass on sputtered material using 100 keV argon and neon to sputter an elemental target comprising the two naturally occurring isotopes of boron. At low beam fluences (≈ 1 × 10¹⁵ions/cm²) a light-isotope secondary enhancement is observed relative to steady-state secondary ion yields collected at higher beam fluences. The enhancement (46.1%o for Ne⁺ irradiation and 51.8%o for Ar⁺ irradiation) is large compared to the predictions of analytical theories and is independent of variations in surface potential, chemical effects, and surface impurities. This effect is consistent with an explanation based on an energy and momentum asymmetry in the collision cascade.     

Implanted Deuterium Retention and Release in Carbon-Coated Beryllium

Deuterium implantation experiments have been conducted on samples of clean and carbon-coated beryllium. These studies entailed preparation and characterization of beryllium samples coated with carbon thicknesses of 100, 500, and 1000 Å. Heat treatment of a beryllium sample coated with carbon to a thickness of approximately 100 Å revealed that exposure to a temperature of 400°C under high vacuum conditions was sufficient to cause substantial diffusion of beryllium through the carbon layer, resulting in more beryllium than carbon at the surface. Comparable concentrations of carbon and beryllium were observed in the bulk of the coating layer. Higher than expected oxygen levels were observed throughout the coating layer as well. Samples were exposed to deuterium implantation followed by thermal desorption without exposure to air. Differences were observed in deuterium retention and postimplantation release behavior in the carbon-coated samples as compared with bare samples. For comparable implantation conditions (sample temperature of 400°C and an incident deuterium flux of approximately 6 × 10¹⁹ D/m²-s), the quantity of deuterium retained in the bare sample was less than that retained in the carbon-coated samples. Further, the release of the deuterium took place at lower temperatures for the bare beryllium surfaces than for carbon-coated beryllium samples.     

Severe surface spalling and blistering in Mo Single crystals subjected to high fluence He bombardments

Single crystals of Mo were implanted at room temperature with 200 keV He⁺ ions to fluences high enough to produce two layers of exfoliation. The first layer of exfoliation occurs by the entire spalling of the crystal surface at a critical fluence of ≈ 10¹⁸/cm². This is followed by subsequent blistering and blister rupturing on the already spalled surface. The exfoliation mechanisms are discussed with relation to the microstructure which develops during implantation and the attendant property changes. The implanted regions were studied by SEM, TEM, and by ion beam channeling.     

Deuterium implantation in graphite

A study has been made of deuterium ion implantation in polycrystalline graphite over the temperature range 100 K to 450 K. Deuterium depth profiles are obtained using a method based on observing the energy spectra of the tritons and protons from D-D reactions initiated with a 200 keV probing deuteron beam. In marked contrast to the low adsorption for gaseous hydrogen previously reported, graphite is found here to retain large concentrations of implanted deuterium with atomic loadings exceeding unity in the deeper regions of a cold target. The amount of deuterium retained continues to decrease with increasing temperature until at 150°C the retention has fallen to approximately half that at −160°C. No evidence is found for a layer of surface deuterium of the type seen in metals such as copper. Scanning electron micrographs of irradiated areas show no observable surface deformation for doses of up to 2.4 × 10¹⁹ deuterons/cm².     

Metal ion implantation in inert polymers for strain gauge applications

Metal ion implantation in inert polymers may produce ultra-thin conducting films below the polymer surface. These subsurface films are promising structures for strain gauge applications. To this purpose, polycarbonate substrates were irradiated at room temperature with low-energy metal ions (Cu⁺ and Ni⁺) and with fluences in the range between 1 × 10¹⁶ and 1 × 10¹⁷ ions/cm², in order to promote the precipitation of dispersed metal nanoparticles or the formation of a continuous thin film. The nanoparticle morphology and the microstructural properties of polymer nanocomposites were investigated by glancing-incidence X-ray diffraction and transmission electron microscopy (TEM) measurements. At lower fluences (<5 × 10¹⁶ ions/cm²) a spontaneous precipitation of spherical-shaped metal nanoparticles occurred below the polymer top-surface (∼50 nm), whereas at higher fluences the aggregation of metal nanoparticles produced the formation of a continuous polycrystalline nanofilm. Furthermore, a characteristic surface plasmon resonance peak was observed for nanocomposites produced at lower ion fluences, due to the presence of Cu nanoparticles. A reduced electrical resistance of the near-surface metal-polymer nanocomposite was measured. The variation of electrical conductivity as a function of the applied surface load was measured: we found a linear relationship and a very small hysteresis.     

Investigation of thermally stimulated properties of SHI beam irradiated polycarbonate/polystyrene double layered samples

The double layered samples of polycarbonate/polystyrene (PC/PS) have been prepared by solvent casting method and irradiated with 55 MeV C⁵⁺ beam at different ion fluences range from 1 × 10¹¹ to 1 × 10¹³ ion/cm². The effect of swift heavy ion (SHI) beam in interfacial phenomena, phase change, dielectric relaxation, degradation temperature, stability, charge storage and transport mechanism of PC/PS pristine and irradiated double layered samples have been investigated by thermally stimulated discharge current (TSDC), differential scanning calorimetry (DSC) and thermogravimetric analysis (TGA). TSDC show α, β-relaxation peaks shifted to the lower temperatures side with increase of fluence. The activation energy and relaxation time decrease, while the depolarization current and charge released increase with increase in the ion fluences. DSC curve show the glass transition temperature (T_g) and heat capacity decreases with increase in the ion fluences. The TGA characteristics represent the thermal stability, which is found to be decreased with increase in the ion fluences.     

Radiation damage (blistering) in Al,Cu, Si by exposure to a plasma focus discharge

Plates of Al, Cu (polycrystalline) and Si (monocrystal) have been irradiated with beams of D⁺ ions (keV to MeV) and other radiation by exposure to a single discharge of a 5–10-kJ Plasma Focus in deuterium. Scanning electron microscope and elemental X-ray energy dispersive analysis are used for diagnostics. The nonuniformity of the ion beam causes a nonuniform damage with formation of clusters of blisters. A statistical analysis of blister parameters (diameter and skin thickness) is used to investigate the internal structure of a deuteron beam ejected from the plasma. The value K ～ 10–20 keV is obtained as the typical ion energy for the bulk of the deuterons and an ion energy E ～ 200–230 keV is typical for individual ion groups (ion strings) forming the high-energy deuteron beam.     

Surface modifications and deuterium depth profiles in molybdenum irradiated with low-energy D ions

Depth profiles of deuterium trapped in single crystal Mo, polycrystalline Mo, and molybdenum trioxide film on polycrystalline Mo irradiated with 200 eV D ions have been measured up to a depth of 8 μm using the D(³He,p)⁴He nuclear reaction at a ³He energy varied from 0.69 to 4.0 MeV. For the D ion irradiation at 323 K to the highest ion fluence of 5 × 10²⁴ D/m², the D concentration decreases from several at.% in the near-surface layer to bulk values below 10⁻⁴ at.% for single crystal Mo and about 10⁻² at.% for polycrystalline Mo. The maximum D concentration in molybdenum trioxide film differs little in value from that for polycrystalline Mo. Blister formation at high fluences is observed for polycrystalline Mo and molybdenum trioxide film, but not for single crystal Mo. As the irradiation temperature increases from 323 to 493 K, the D retention in the polycrystalline Mo decreases from about 3 × 10²¹ down to about 2 × 10¹⁸ D/m².     

Temperature dependence of surface morphology and deuterium retention in polycrystalline ITER-grade tungsten exposed to low-energy,high-flux D plasma

Surface topography and deuterium retention in polycrystalline ITER-grade tungsten have been examined after exposure to a low-energy (38 eV/D), high-flux (10²² D/m² s) deuterium plasma with ion fluences of 10²⁶ and 10²⁷ D/m² at various temperatures. The methods used were scanning electron microscopy equipped with focused ion beam, thermal desorption spectroscopy, and the D(³He,p) ⁴He nuclear reaction at ³He energies varied from 0.69 to 4.0 MeV. During exposure to the D plasma at temperatures in the range from 320 to 815 K, small blisters of size in the range from 0.2 to 5 μm, depending on the exposure temperature and ion fluence, are formed on the W surface. At an ion fluence of 10²⁷ D/m², the deuterium retention increases with the exposure temperature, reaching its maximum value of about 10²² D/m² at 500 K, and then decreases below 10¹⁹ D/m² at 800 K.     

Structural studies of silicon oxynitride layers formed by low energy ion implantation

Silicon oxynitride (Si_xO_yN_z) layers were synthesized by implanting ¹⁶O₂⁺ and ¹⁴N₂⁺ 30 keV ions in 1:1 ratio with fluences ranging from 5 × 10¹⁶ to 1 × 10¹⁸ ions cm⁻² into single crystal silicon at room temperature. Rapid thermal annealing (RTA) of the samples was carried out at different temperatures in nitrogen ambient for 5 min. The FTIR studies show that the structures of ion-beam synthesized oxynitride layers are strongly dependent on total ion-fluence and annealing temperature. It is found that the structures formed at lower ion fluences (∼1 × 10¹⁷ ions cm⁻²) are homogenous oxygen-rich silicon oxynitride. However, at higher fluence levels (∼1 × 10¹⁸ ions cm⁻²) formation of homogenous nitrogen rich silicon oxynitride is observed due to ion-beam induced surface sputtering effects. The Micro-Raman studies on 1173 K annealed samples show formation of partially amorphous oxygen and nitrogen rich silicon oxynitride structures with crystalline silicon beneath it for lower and higher ion fluences, respectively. The Ellipsometry studies on 1173 K annealed samples show an increase in the thickness of silicon oxynitride layer with increasing ion fluence. The refractive index of the ion-beam synthesized layers is found to be in the range 1.54-1.96.     

Ti-Mo互扩散界面吸氢同位素效应的离子束分析研究

为探究Ti-Mo互扩散对金属吸氢的影响,本文采用离子束分析方法对Ti-Mo薄膜的膜-基互扩散界面的吸氢同位素（H和D）效应进行了研究。通过氩离子刻蚀减薄的方法有效降低了表面碳、氧杂质对样品吸氢的影响。吸氢结果表明,对于表面洁净的样品,氢化后固相中氢或氘的浓度均沿着深度随钼原子含量的增加而减小。在单一气体吸氢实验中,氢原子浓度减小的趋势较氘原子缓慢;而在氢氘混合气体吸氢实验中,当容器中的氢氘压强比p(H2)∶p(D2)≥05∶1时,固体中氘氢浓度之比随钼浓度的增加而降低,但当p(H2)∶p(D2)<05∶1时,氘氢浓度之比随钼浓度的增加而升高。因此,由于Ti Mo界面的互扩散,吸氢出现了显著的氢同位素效应,钼的存在不利于体系对氢同位素气体的吸收。     

Recharging processes, radiation induced strain and changes of OH bands under H ion implantation in Ti doped lithium niobate

A systematic analysis of variations in structural and optical characteristics of Z-cut plates of titanium doped congruent lithium niobate single crystals implanted with 120 keV proton beam at various fluences of 10¹⁵, 10¹⁶ and 10¹⁷ protons/cm² is presented. Through, high resolution X-ray diffraction, atomic force microscopy, Fourier transform infrared and UV-visible-NIR analysis of congruent lithium niobate, the correlation of properties before and after implantation are discussed. HRXRD (0 0 6) reflection by Triple Crystal Mode shows that both tensile and compressive strain peak are produced by the high fluence implantation. A distinct tensile peak was observed from implanted region for a fluence of 10¹⁶ protons/cm². AFM micrographs indicate mountain ridges, bumps and protrusions on target surface on implantation. UV-visible-NIR spectra reveal an increase in charge transfer between Ti³⁺/Ti⁴⁺ and ligand oxygen for implantation with 10¹⁵ protons/cm², while spectra for higher fluence implanted samples show complex absorption band in the region from 380-1100 nm. Variations of OH⁻ stretching vibration mode were observed for cLN Pure, cLNT2% virgin, and implanted samples with FTIR spectra. The concentration of OH⁻ ion before and after implantation was calculated from integral absorption intensity. The effect of 120 keV proton implantation induced structural, surface and optical studies were correlated.     

Raman scattering and SEM studies of graphite and silicon carbide surfaces bombarded with energetic protons,deuterons and helium ions

Experimental investigations on the chemical and physical effects of 10–15 keV H₁⁺, D₁⁺ and He⁺ ion bombardments to fluences up to 10¹⁹ ions/cm² on graphite and SiC have been conducted using the techniques of Raman scattering and scanning electron microscopy (SEM). Raman scattering data for ion bombarded graphite reveal the formation of an amorphous surface layer as indicated by the appearance of a broad band in the spectrum centered at 1525 cm which replaces the bands due to microcrystalline carbon at 1585 cm^?1 and 1360 cm^?1. The microcrystalline structure could be partially restored upon vacuum annealing at 1040°C for several hours. A weak, broad band centered at 2150 cm also appears after bombardment which is indicative of the formation of ?C = C? bonds. Surfaces of “KT” SiC were also amorphized on ion bombardment as indicated by changes in the Raman spectra. Chemical trapping of the incident h₁⁺ and D₁⁺ ions to form bulk C-H, C-D and Si-H species was observed. Preferential sputtering of Si leaving a carbon rich surface region also occurred. Blister formation was observed in the SEM studies.     

Effects of ion beam treatment on atomic and macroscopic adhesion of copper to different polymer materials

Low-energy ion irradiation of polymer induces different phenomena in the near surface layer, which effect strongly the metal-polymer interface formation and promotes adhesion of polymers to metals. Low-energy argon and oxygen ion beams were used to alter the chemical and physical properties of different polymers (PS (polystyrene), PαMS (poly(α-methylstyrene), BPA-PC (bisphenol-A-polycarbonate) and PMMA (poly(methyl methacrylate)), in order to understand the adhesion phenomena between a deposited Cu layer and the polymers. The resulting changes were investigated by various techniques including X-ray photoelectron spectroscopy, measurements of the metal condensation coefficient and a new technique to measure cross-linking at the polymer surface. Two types of practical adhesion strengths of Cu-polymer systems, measured using 90° peel tests, were observed: (i) peel strength increased at low ion fluences, reached a maximum and then decreased after prolonged treatment and (ii) no improvement in the peel strength on treated polymer surfaces was recorded. The improvement in the metal-polymer adhesion in the ion fluence range of 10¹³-10¹⁵ cm⁻² is attributed to the creation of a large density of new adsorption sites resulting in a larger contact area and incorporation of chemically active groups that lead to increased interaction between metal and polymer by metal-oxygen-polymer species formation. XPS analysis of peeled-off surfaces showed that in most cases the failure location changed from interfacial for untreated polymers to cohesive failure in the polymer for treated surfaces. These observations and measurements of the metal condensation coefficients suggest that bonding is improved at the metal-polymer interface for all metal-polymer systems. However, the decrease in the peel strength at high ion fluences is attributed to the formation of a weak boundary layer in polymers. The correlation between sputter rate of polymers and altering in the peel strength for moderate ion fluences was determined. It was observed that the metal-polymer adhesion could be improved for PS and BPA-PC, which have a low sputter rate and preferentially formed cross-links in the treated surface. For degrading polymers, like PαMS and PMMA, chain scission rather than cross-linking dominates, low molecular weight species are formed and no adhesion enhancement is observed.     

Effect of surface oxide layer on deuterium permeation behaviors through a type 316 stainless steel

Effect of surface oxide layer on the hydrogen isotope permeation was studied. Iron oxide was uniformly formed in the oxide layer, although chromium was limited at the interface between the oxide layer and bulk SS-316. The permeation behavior of deuterium for oxidized SS-316 was compared with that for unoxidized SS-316 at temperature range of 333–673 K. The deuterium permeability for the oxidized SS-316 was reduced 1/10–1/20 times as high as that for unoxidized one. However, the activation energy of deuterium permeation as gas form for oxidized SS-316 was almost the same as that for unoxidized SS-316 and was 0.64 eV, which was almost consistent with the sum of activation energies for diffusion and solubility. This fact indicates that the deuterium permeation is diffusion limited. The permeability of deuterium as water form was almost constant even if heating temperature is high, showing that the deuterium was permeated through bulk SS-316 and react with oxygen at the oxide layer as water desorption, which is controlled by the permeation flux of deuterium and oxygen concentration on the surface of oxide layer in downstream side.