Synthesis & fabrication of lithium-titanate pebbles for ITER breeding blanket by solid state reaction & spherodization

⁶Li produces tritium by (n, α) nuclear reaction, ⁶Li + ¹n → ⁴He + ³H. Lithium titanate (Li₂TiO₃) enriched with ⁶Li, is the most promising candidate for solid test blanket module (TBM) material for fusion reactors. Various processes are reported in literature for the fabrication of Li₂TiO₃ pebbles for its use as TBM material. A process has been developed based on the solid state reaction of lithium-carbonate and titanium-dioxide for the synthesis of lithium titanate and pebble fabrication by extrusion, spherodization and sintering. This paper discusses the sequence of steps followed in this process and the properties obtained. Analytical grade titanium-dioxide and lithium-carbonate were taken in stoichiometric ratio and were milled to ensure thorough intimate mixing and obtain fine particles less than 45 μm before its calcination at 900 °C. Following calcination, the agglomerated product was again milled to fine particles of size less than 45 μm. Aqueous solution of ploy-vinyl-alcohol was added as binder prior to its feeding in the extruder. The extruded strips were spherodized and spherical pebbles were dried and sintered at 900 °C for different duration. Pebbles of desired density and porosity were obtained by suitable combination of sintering temperature and duration of sintering. Properties of the prepared pebbles were also characterized for sphericity, pore size distribution, grain size, crushing load strength, etc. The values were found to be conforming to the desired properties for use as solid breeder. The attractive feature of this process is almost no waste generation.     

Structural and electrical characterizations of n-type implanted layers and ohmic contacts on 3C-SiC

In this work, non-intentionally doped cubic silicon carbide (3C-SiC) epilayers grown on (1 0 0) silicon substrates were implanted using nitrogen (N), phosphorus (P) implantations or their co-implantation (N&P). After annealing from 1150 to 1400 °C, Secondary Ion Mass Spectroscopy (SIMS), Atomic Force Microscopy (AFM), Fourier Transformed InfraRed spectroscopy (FTIR), Scanning Spreading Resistance Microscopy (SSRM) and Scanning Transmission Electron Microscopy (STEM) analysis were performed. Specific contact resistances (ρ_c) of Ti/Ni ohmic contacts were determined using Circular Transfer Length Method (c-TLM) patterns. Our work shows that co-implantation, experimentally investigated for the first time in 3C-SiC, is not beneficial for the doping efficiency.According to the silicon substrate, the post-implantation annealing is limited to 1400 °C. Consecutively to this limit, the total recovering of the lattice does not seem to be possible, whatever are the implanted species. Moreover, as the crystal damages increase when increasing the atomic mass of the implanted species, a comparative study using SSRM measurements proved that, for the same post-implantation annealing treatment, the resistivity of implanted layers depend on the doping species. As a consequence, the lowest ρ_c value (2.8 × 10⁻⁶ Ω cm²) has been obtained (using Ti/Ni 25/100 nm pattern) for a 1400 °C-30 min annealing consecutively to the nitrogen implantation. This value is among the best values obtained on implanted 3C-SiC layers in the literature. Furthermore, for this annealing temperature, a doping activation close to 100% has been evaluated by quantitative SSRM technique which evidences that an efficient dopant activation could be done. The high activation rate obtained on n-type implanted 3C-SiC and the low specific contact resistance achieved with Ti/Ni are very promising for electronic device fabrication.     

Post-annealing effects on the shallow-junction characteristics caused by high-fluence 77 keV BSi molecular ion implantations at room and liquid nitrogen temperatures

In this study, n-type <1 0 0> silicon specimens were liquid nitrogen temperature (LT) and room temperature (RT) implanted with 2 × 10¹⁵ cm⁻² 77 keV BSi molecular ions to produce shallow junctions. Post-annealing methods under investigation included furnace annealing (FA) at 550 °C for 0.5, 1, 2, 3 and 5 h and rapid thermal annealing (RTA) at 1050 °C for 25 s. Post-annealing effects on the shallow-junction characteristics were examined using one-step (FA) and two-step (FA + RTA) post-annealing treatments. Secondary ion mass spectrometry (SIMS), cross-sectional transmission electron microscopy (XTEM), a four-point probe and Raman scattering spectroscopy (RSS) were employed to analyze junction depths (x_j), damage microstructures, sheet resistance (R_s) and damage characteristics, respectively. The results revealed that the shallow-junction characteristics of the LT implant are better than those of the RT one when post-annealing time in FA exceeds 1 h. A post-annealing time of 3 h in FA is needed in order to obtain the optimal one- or two-step post-annealing effects on the shallow-junction characteristics in both the LT and RT implants.     

Proton elastic scattering and proton induced γ-ray emission cross-sections on Na from 2 to 5 MeV

Differential cross-sections for proton elastic scattering on sodium and for γ-ray emission from the reactions ²³Na(p,p′γ)²³Na (E_γ = 440 keV and E_γ = 1636 keV) and ²³Na(p,α′γ)²⁰Ne (E_γ = 1634 keV) were measured for proton energies from 2.2 to 5.2 MeV using a 63 μg/cm² NaBr target evaporated on a self-supporting thin C film.The γ-rays were detected by a 38% relative efficiency Ge detector placed at an angle of 135° with respect to the beam direction, while the backscattered protons were collected by a Si surface barrier detector placed at a scattering angle of 150°. Absolute differential cross-sections were obtained with an overall uncertainty estimated to be better than ±6.0% for elastic scattering and ±12% for γ-ray emission, at all the beam energies.To provide a convincing test of the overall validity of the measured elastic scattering cross-section, thick target benchmark experiments at several proton energies are presented.     

Radiation shielding of concretes containing different lime/silica ratios

The shielding of γ-rays and fast neutrons by concrete has been studied for concretes containing different lime/silica ratios. Calculations were carried out for six different concrete samples. The total mass attenuation coefficients (μ/ρ, cm² g⁻¹) have been computed at photon energies of 1 keV to 100 GeV using the personal computer software package WinXCom. Also the macroscopic effective fast neutron removal cross-sections (Σ_R, cm⁻¹) have been calculated using MERCSF-N program and the removal cross-section database for all required elements. The obtained results showed that the lime/silica ratio of concrete has significant and insignificant effects on μ/ρ and Σ_R values, respectively.     

The interdiffusion and solid-state reaction of low-energy copper ions implanted in silicon

At room temperature, single-crystal silicon was implanted with Cu⁺ ions at an energy of 80 keV using two doses of 5 × 10¹⁵ and 1 × 10¹⁷ Cu⁺ cm⁻². The samples were heat treated by conventional thermal annealing at different temperatures: 200 °C, 230 °C, 350 °C, 450 °C and 500 °C. The interdiffusion and solid-state reactions between the as-implanted samples and the as-annealed samples were investigated by means of Rutherford backscattering spectrometry (RBS) and X-ray diffraction (XRD). After annealing at 230 °C, the XRD results of the samples (subject to two different doses) showed formation of Cu₃Si. According to RBS, the interdiffusion between Cu and Si atoms after annealing was very insignificant. The reason may be that the formation of Cu₃Si after annealing at 230 °C suppressed further interdiffusion between Si and Cu atoms.     

Refinement in the ultrasonic velocity data and estimation of the critical parameters for molten uranium dioxide

Based on the previously reported internal pressure approach and by making use of recent and more accurate experimental measurements on the density, and heat capacity of liquid UO₂ up to ∼8000 K, reliable data on the sound propagation velocity in molten uranium dioxide have been obtained. An equation of state for liquid urania has also been developed which predicts a critical temperature (T_c) ≈ 10 500 K, critical pressure (P_c) ≈ 219 MPa and critical density (ρ_c) ≈ 2510 kg m⁻³.     

Differential cross-section measurements for the C(d, p0)C reaction and applications to surface analysis of materials

This work involves surface analysis by nuclear techniques, which are non-destructive, and computer simulation. The “energy analysis” method for nuclear reaction analysis is used. Energy spectra are computer simulated and compared to experimental data, giving target composition and concentration profile information. Measured values are presented for the differential cross-section of the ¹²C(d, p₀)¹³C reaction in the deuteron energy range 0.81-2.07 MeV for laboratory detection angles of 165° and 135°, using self-supported two-layered targets consisting of high purity thin films of typically 13 μg/cm² natural carbon and 65 μg/cm² gold. The error in the absolute differential cross-section values is generally ∼6%. The method, using these values, is successfully applied to determination of uniform concentration profiles of ¹²C, along considerable depths, for a thick flat target of high purity pyrolitic graphite. It is characterised a thin surface film of carbon on a thick flat quartz target. Uniform concentration profiles of ¹⁶O are also obtained from (d, p) and (d, α) reactions.     

Effect of sintering conditions on the microstructure and mechanical properties of ZrN as a surrogate for actinide nitride fuels

Pellets of sintered ZrN were studied to optimize the mechanical properties and microstructures needed in nitride fuel pellets, using ZrN as a surrogate for actinide nitrides and as potential component in low fertile and inert matrix fuels. Samples were prepared via sintering in either Ar or N₂ (with and without 6% H₂) and at 1300 °C or 1600 °C. A significant difference in the hardness was measured ranging from 1000 (Kg/mm²) in samples sintered at 1600 °C in argon to 100 (Kg/mm²) in samples sintered at 1300 °C in nitrogen. Samples with 6% hydrogen added to the sintering environment experienced a decrease in hardness, as well as an increase in intergranular cracking as compared to samples sintered without hydrogen, suggesting hydrogen embrittlement. Grain size was more uniform in samples sintered in pure Ar as compared to Ar-H₂, while the latter had a larger fraction of high angle grain boundaries than the former. Cracking around indents had a clear tendency to follow high angle boundaries, which were found to be intrinsically weak in ZrN.     

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.     

Direct carbothermic reduction of actinide oxalates: Example of Nd(III) oxalate-carbon mixtures conversion

Mixed uranium-plutonium monocarbide was obtained by carbothermic reduction of mixture of UO₂, PuO₂ and C at around 1500 °C under vacuum or argon for 4 h followed by sintering at around 1650 °C under mixture of Ar + 8%H₂ for 10 h. Moreover, PuO₂ was synthesized by oxalic precipitation followed by calcination at around 700 °C (PUREX process). This work deals with a process simplification, i.e. fabrication of carbide by calcination of actinide oxalate, precipitated in presence of carbon, at 1600 °C for 13 h under argon. In this preliminary study, neodymium was used as a surrogate of actinides. No carbon influence was noticed during calcination of neodymium oxalate into oxide. Carbon content was the same before and after calcination making possible conversion to carbide directly from mixture of neodymium oxalate and C.     

Interferences in electron emission from O2 by 30 MeV O impact

Interference structures in the ejected electron spectra for 30 MeV O^5,8+ + O₂ are investigated. The measured electron yields were studied for electron energies from 5 to 400 eV and observation angles of 30°, 60°, 90°, 120° and 150° with respect to the incident beam direction. Experimental molecular cross-sections were normalized to theoretical molecular one-center cross-sections revealing oscillatory structures suggestive of secondary interferences as evidenced by the independence on the observation angle. An oscillation interval for 30 MeV O^5,8+ + O₂ of Δk ∼ 4 a.u. is found, a value two times larger than that previously observed for 3 MeV H⁺ + N₂. No obvious evidence for primary Young-type interferences was seen.     

Neutron irradiation-induced dimensional changes in MEMS glass substrates

A study is made of radiation-induced expansion/compaction in Pyrex^® (Corning 7740) and Hoya SD-2^® glasses, which are used as substrates for MEMS devices. Glass samples were irradiated with a neutron fluence composed primarily of thermal neutrons, and a flotation technique was employed to measure the resulting density changes in the glass. Transport of Ions in Matter (TRIM) calculations were performed to relate fast (∼1 MeV) neutron atomic displacement damage to that of boron thermal neutron capture events, and measured density changes in the glass samples were thus proportionally attributed to thermal and fast neutron fluences. Pyrex was shown to compact at a rate of (in Δρ/ρ per n/cm²) 8.14 × 10⁻²⁰ (thermal) and 1.79 × 10⁻²⁰ (fast). The corresponding results for Hoya SD-2 were 2.21 × 10⁻²¹ and 1.71 × 10⁻²¹, respectively. On a displacement per atom (dpa) basis, the compaction of the Pyrex was an order of magnitude greater than that of the Hoya SD-2. Our results are the first reported measurement of irridiation-induced densification in Hoya SD-2. The compaction of Pyrex agreed with a previous study. Hoya SD-2 is of considerable importance to MEMS, owing to its close thermal expansivity match to silicon from 25 to 500°C.     

Photoconduction investigations in 75 MeV oxygen ion irradiated kapton-H polyimide

Photoconduction behaviour of 75 MeV oxygen ion irradiated (Fluences: 1.8 × 10¹¹, 1.8 × 10¹² and 1.8 × 10¹³ ions/cm²) kapton-H polyimide film in the visible region has been investigated at different temperatures ranging 400-2500 °C and at various electric fields ranging 40-600 kV/cm. A photoinduced exciton formation is the major source for providing charge carriers through thermolization and field-assisted dissociation processes. An attempt has been made to fit the field dependence of the steady state photocurrent to one of the several possible conduction mechanisms. In the high and low fluence (1.8 × 10¹³ and 1.8 × 10¹¹ ions/cm²) irradiated samples there exists a possibility of Poole-Frankel type of photoconduction mechanism, whereas at intermediate fluence (1.8 × 10¹² ions/cm²) a Schottky type photoconduction mechanism may be operative. The log I_ps versus 1/T plots consist of two straight lines with a knee point around 800-1000 °C. The activation energy estimated from the slope of these lines is field dependent varying from 0.40 to 0.73 eV and 0.18 to 0.23 eV above and below the knee point, respectively. This indicates the presence of more than one type of trapping levels in irradiated kapton-H polyimide.     

Neutron flux determination in irradiation sites of an Am–Be neutron source at NNRI

Neutron flux measurements and flux distribution parameters for two irradiation sites of an Am–Be neutron source irradiator were measured by using gold (Au), zirconium (Zr) and aluminum (Al) foils. thermal neutron flux Φ_th = 1.46 × 10⁴ n cm⁻² s⁻¹ ± 0.01 × 10², epithermal neutron flux Φ_epi = 7.23 × 10² n cm⁻² s⁻¹ ± 0.001, fast neutron flux Φ_f = 1.26 × 10² n cm⁻² s⁻¹ ± 0.020, thermal-to-epithermal flux ratio f = 20.5 ± 0.36 and epithermal neutron shaping factor α = −0.239 ± 0.003 were found for irradiation Site-1; while the thermal neutron flux Φ_th = 4.45 × 10³ n cm⁻² s⁻¹ ± 0.06, the epithermal neutron Φ_epi = 1.50 × 10² n cm⁻² s¹ ± 0.003, the fast neutron flux Φ_f = 1.17 × 10 n cm⁻² s⁻¹ ± 0.011, thermal-to-epithermal flux ratio f = 29.6 ± 0.94, and epithermal neutron shaping factor α = 0.134 ± 0.001 were found for irradiation Site-2. It was concluded that the Am–Be neutron source can be used for neutron activation analysis (NAA). The Am–Be source can be used for neutron activation analysis thereby reducing the burden on GHARR-1 and increasing the research output of the nation.     

Structural characterization of buried nitride layers formed by nitrogen ion implantation in silicon

The synthesis of buried silicon nitride insulating layers was carried out by SIMNI (separation by implanted nitrogen) process using implantation of 140 keV nitrogen (¹⁴N⁺) ions at fluence of 1.0 × 10¹⁷, 2.5 × 10¹⁷ and 5.0 × 10¹⁷ cm⁻² into 〈1 1 1〉 single crystal silicon substrates held at elevated temperature (410 °C). The structures of ion-beam synthesized buried silicon nitride layers were studied by X-ray diffraction (XRD) technique. The XRD studies reveal the formation of hexagonal silicon nitride (Si₃N₄) structure at all fluences. The concentration of the silicon nitride phase was found to be dependent on the ion fluence. The intensity and full width at half maximum (FWHM) of XRD peak were found to increase with increase in ion fluence. The Raman spectra for samples implanted with different ion fluences show crystalline silicon (c-Si) substrate peak at wavenumber 520 cm⁻¹. The intensity of the silicon peak was found to decrease with increase in ion fluence.     

Synthesis and characterization of PEFC membranes based on fluorinated-polymer-alloy using pre-soft-EB grafting method

Polymer electrolyte fuel cell (PEFC) membranes based on thin film of crosslinked perfluorinated polymer-alloys (RX-FA) have been fabricated by soft electron beam (soft-EB) grafting with styrene monomers using soft-EB irradiation under nitrogen atmosphere at room temperature (RT). The characteristic properties of styrene-grafted materials (GRX-FA) and sulfonated materials (SRX-FA) have been measured by differential scanning calorimetry (DSC) and FT-IR spectroscopy, ionic conductivity and so on. The glass transition temperatures (dry state) of all obtained SRX-FA were about 105 ± 1 °C, which are higher than Nafion^®. The ion exchange capacities of SRX-FA have been achieved about 3.3 meq/g (dry). The ionic conductivity of obtained SRX-FA has showed about 0.17 S/cm at 60 °C with relative humidity (RH) of ∼95%. The ionic conductivities of the obtained SRX-FA were higher than that of conventional perfluoro-sulfonic acid membranes (PFSA). Fabricated membrane electrode assemblies (MEAs) based on the obtained SRX-FA have shown encouraging performance in the PEFC, compared with the conventional PFSA. The power density of obtained MEAs based on the SRX-FA was about 330-340 mW/cm² under 500 mA/cm² at 60 °C operation. Moreover, the maximum power densities of obtained MEAs based on the SRX-FA shows about 630 mW/cm² at 60 °C. On the other hand, the power density at 500 mA/cm² and maximum power density of MEA based on Nafion^®112 were about 320 and 590 mW/cm² at 60 °C. Thus, the power density of the obtained SRX-FA was higher than that of conventional PFSA.     

A detailed study of the d + B system for nuclear reaction analysis - Part A: The B(d,p)B reaction in the energy region Ed,lab = 900-2000 keV

The differential cross-sections of the ¹⁰B(d,p_{0,1,2,3,4-5,6}) reactions for the determination of the depth distribution of boron in near-surface layers of materials have been determined in the projectile energy region E_d,lab = 900-2000 keV. The experiment was carried out in energy steps of 25 keV and for eight detector angles between 135° and 170° (in steps of 5°). The obtained experimental data are suitable for nuclear reaction analysis (NRA) studies. A qualitative discussion of the observed cross-section variations through the strong influence of overlapping resonances in the d + ¹⁰B system is also presented.     

Effect of 200 MeV Ag ion irradiation on structural and electrical transport properties of Fe3O4 thin films

Thin films of Fe₃O₄ have been deposited on single crystal MgO(1 0 0) and Si(1 0 0) substrates using pulsed laser deposition. Films grown on MgO substrate are epitaxial with c-axis orientation whereas, films on Si substrate are highly 〈1 1 1〉 oriented. Film thicknesses are 150 nm. These films have been irradiated with 200 MeV Ag ions. We study the effect of the irradiation on structural and electrical transport properties of these films. The fluence value of irradiation has been varied in the range of 5 × 10¹⁰ ions/cm² to 1 × 10¹² ions/cm². We compare the irradiation induced modifications on various physical properties between the c-axis oriented epitaxial film and non epitaxial but 〈1 1 1〉 oriented film. The pristine film on Si substrate shows Verwey transition (T_V) close to 125 K, which is higher than generally observed in single crystals (121 K). After the irradiation with the 5 × 10¹⁰ ions/cm² fluence value, T_V shifts to 122 K, closer to the single crystal value. However, with the higher fluence (1 × 10¹² ions/cm²) irradiation, T_V again shifts to 125 K.     

Oxidation kinetics and oxygen diffusion in low-tin Zircaloy-4 up to 1523 K

This paper deals with the study of oxidation kinetics and the identification of oxygen diffusion coefficients of low-tin Zy-4 alloy at intermediate (973 K ? T ? 1123 K) and high temperatures (T ? 1373 K). Two different cases were considered: dissolution of a pre-existing oxide layer in the temperature range 973 K ? T ? 1123 K and oxidation at T ? 1373 K. The results are the following ones: in the temperature range 973-1123 K, the oxygen diffusion coefficient in α_Zr phase can be expressed as D_α = 6.798 exp(−217.99 kJ/RT) cm²/s. In the temperature range 1373-1523 K, the oxygen diffusion coefficients in α_Zr, β_Zr and ZrO₂, were determined using an ‘inverse identification method’ from experimental high temperature oxidation data (i.e., ZrO₂, and α_Zr(O) layer thickness measurements); they can be expressed as follows: D_α = 1.543 exp(−201.55 kJ/ RT) cm²/s, D_β = 0.0068 exp(−102.62 kJ/ RT) cm²/s and D_ZrO2=0.115exp(−143.64kJ/RT)cm²/s. Finally an oxygen diffusion coefficient in α_Zr in the temperature range 973 K ? T ? 1523 K was determined, by combining the whole set of results: D_α = 4.604exp(−214.44 kJ/RT) cm²/s. In order to check these calculated diffusion coefficients, oxygen concentration profiles were determined by Electron Probe MicroAnalysis (EPMA) in pre-oxidized low-tin Zy4 alloys annealed under vacuum at three different temperatures 973, 1073 and 1123 K for different times, and compared to the calculated profiles. At last, in the framework of this study, it appeared also necessary to reassess the Zr-O binary phase diagram in order to take into account the existence of a composition range in the two zirconia phases, α_ZrO2 and β_ZrO2.