Zinc Isotope Fractionation on Benzo-15-crown-5 Resin by Liquid Chromatography

Chromatographic fractionation of zinc isotopes was performed on the synthesized benzo-15-crown-5 resin as a column packing material at 323K in the breakthrough manner for both a frontal and a rear bands. Zinc adsorption capacity was affected by anion chloride concentration and solvent dielectric constant. The heavier zinc isotopes were found enriched to the solution phase and the lighter zinc isotope was concentrated on the resin phase. The frontal maximum enrichment ratio for isotopic pair of ⁶⁸Zn/⁶⁴Zn was 1.0081. The isotope separation coefficients for isotopic pair of ⁶⁸Zn/⁶⁴Zn for frontal and rear band, were 5.3 × 10^?4, 4.5 × 10^?4, respectively.     

Zinc Isotope Accumulation in Liquid Chromatography with Crown Ether Resin

Liquid chromatographic separation of zinc isotopes was attempted in the breakthrough manner using benzo-15-crown-5 resin as column packing material at 313 K, and a 20 m long development was successfully achieved. The value of the single-stage separation factor was 1.00035 for the ⁶⁶Zn/⁶⁴Zn isotopic pair, 1.00047 for ⁶⁷Zn/⁶⁴Zn pair, and 1.00060 for the ⁶⁸Zn/⁶⁴Zn pair, which were equivalent to those obtained by a 5 m long chromatographic experiment under the same conditions. Contrary to this, the HETP value was 0.19 cm at the 20m development while it had been 0.09 cm at the 5 m development. Connecting separation columns with polytetrafluoroethylene tubes not packed with the resin may be responsible for this migration distance dependence of the HETP.     

Production of high-purity medical radio isotope 64Cu with accelerator-based neutrons generated with 9 and 12 MeV deuterons

We conducted a feasibility study for producing a high-purity medical radioisotope ⁶⁴Cu from natural zinc with accelerator-based neutrons. ⁶⁴Cu isotopes were produced via the ⁶⁴Zn(n,p) reaction. The accelerator-based neutrons were generated via the C(d,n) reaction using low-energy deuterons of 9 and 12 MeV on a 1-mm-thick carbon target. First, the production purity was estimated using the evaluated nuclear data library JENDL-4.0 and our previously measured thick target neutron yield. We found that even when natural zinc was used as the starting material, significantly high-purity ⁶⁴Cu could be obtained. Next, irradiation experiments for producing ⁶⁴Cu using natural zinc were conducted at Kyushu University Tandem Laboratory, with the amounts of ⁶⁴Cu isotopes and other gamma-emission nuclides measured by a high-purity germanium detector. As a result, high-purity ⁶⁴Cu isotopes of 1.11(49) × 10⁰ and 3.70 (17) × 10⁰ Bq/g/μC were produced with incident deuteron energies of 9 and 12 MeV, respectively.     

Calcium isotope fractionation in liquid chromatography with crown ether resins

Breakthrough mode liquid chromatography was employed to study calcium isotope fractionation. Highly porous silica beads, the inner pores of which were embedded with a benzo-18-crown-6 ether resin or a benzo-15-crown-5 ether resin, were used as column packing material. For both the resins, enrichment of heavier isotopes of calcium was observed in the frontal part of their respective calcium chromatograms. The values of the isotope fractionation coefficient were on the order of 10^?3 and 10^?4 for the benzo-18-crown-6 ether and benzo-15-crown-5 ether resins, respectively. The observed isotope fractionation coefficient was dependent on the concentration of hydrochloric acid in the calcium feed solution; a higher hydrochloric acid concentration resulted in a smaller fractionation coefficient value. The present calcium isotope effects were most probably mass dependent, indicating they came from isotope effects based on molecular vibration. Molecular orbital calculations supported the present experimental results in a qualitative fashion.     

Gadolinium Isotope Separation by Cation Exchange Chromatography

Displacement chromatographies of Gd adsorption band in cation exchange resin were performed to observe the isotope effects in the Gd ion exchange processes involving complex forming reagents. The heavy isotope of ¹⁶⁰Gd was found to be enriched at the front boundary of Gd adsorption band and the lighter isotopes of 1MGd, ¹⁵⁶Gd and ¹⁵⁷Gd were enriched at the rear boundary in both cases of 20.1m elution with EDTA and 14 m elution with malic acid, as predicted in the theoretical relations. Observed separation coefficients are 4.9×10^?5, 4.0×10^?5 and 2.5×10^?5for isotopie pairs of ^{156 160}Gd, ¹⁵⁸Gd and ¹⁶⁰Gd, respectively, in the case of EDTA elution. In the case of malic acid elution, smaller separation coefficients were observed as 1.8×10^?5, 1.6 ⁵O^?5 and 0.92×10^?5 for isotopie pairs of ^{156 160}Gd, ¹⁵⁷Gd and^{158 160} respectively.     

Room-Temperature Reactor Packed with Hydrophobic Catalysts for the Oxidation of Hydrogen Isotopes Released in a Nuclear Facility

A room-temperature reactor packed with hydrophobic catalysts for the oxidation of hydrogen isotopes released in a nuclear facility will contribute to nuclear safety. The inorganic-based hydrophobic Pt catalyst named H1P has been developed especially for efficient oxidation over a wide concentration range of hydrogen isotopes at room temperature, even in the presence of saturated water vapor. The overall reaction rate constant for hydrogen oxidation with the H1P catalyst in a flow-through system using a tritium tracer was determined as a function of space velocity, hydrogen concentration in carriers, temperature of the catalyst, and water vapor concentration in carriers. The overall reaction rate constant for the H1P catalyst in the range near room temperature was considerably larger than that for the traditionally applied Pt/Al₂O₃ catalyst. Moreover, the decrease in reaction rate for H1P in the presence of saturated water vapor was slight compared with the reaction rate in the absence of water vapor due to the excellent hydrophobic performance of H1P. Oxidation reaction on the catalyst surface is the rate-controlling step in the range near room temperature and the rate-controlling step is shifted to diffusion in a catalyst substratum above 313K due to its fine porosity. The overall reaction rate constant in the range near room temperature was dependent on the space velocity and hydrogen concentration in carriers. The overall reaction rate constants in the range of 1;000=T greater than 3.2 correlated to k _overall[s^?1] = 5.59 × 10⁷ × SV[h^?1] × exp (?67.7 [kJ/mol]/R_gT), where the space velocity range was from 600 to 7,200 h^?1.     

Heat Capacity of Thorium Nitrides from 450 to 850K

The throium nitrides (ThN and Th₃N₄) were prepared by solid-gas reaction with thorium hydride and nitrogen.

The heat capacity of these samples were measured from 450 to 850K by a high-temperature double- adiabatic calorimeter and were determined as functions of temperature as follows:

Th₃N₄: C _p=41.30–8.47×10^?3 T-6.37×10⁵ T ^?2

ThN: C _p=12.50–2.66×10^?3 T-2.44×10⁵ T ^?2     

Behavior of Helium Release from Simulated Radioactive Waste Glasses

Rates of He release from two kinds of simulated high-level radioactive waste glasses were measured in the temperature range from 573 to 753K by a mass spectrometric method. Diffusion coefficients of He in the glasses were determined from the fractional release data. The diffusion coefficients were given as a function of temperature by the equations:

D/(m²·s^?1) = 2.3 × 10^?6 exp (?71.1±2.1 kJ/RT) for P0798 glass

=9.8 × 10^?7 exp (?60.2±2.1 kJ/RT) for P0504 glass.

In addition, solubilities of He in the glasses were determined from the measurement of the total amount of released He and found to be

S/(atoms/m³) = 2.0 × 10²² for P0798 glass

=2.2 × 10²² for P0504 glass.

at 693 K and 1.7 × 10⁵ Pa He.

The diffusivities and solubilities of He in the glasses were, respectively, several and an order of magnitude lower than silica, alkali silicate and Pyrex glasses, which properties are notable for the radioactive waste glasses.     

Strontium Isotope Effect in Liquid-Liquid Extraction of Strontium Chloride Using a Crown Ether

Isotope effects in a liquid-liquid extraction of strontium with dicyclohexano-18-crown-6 (DC18C6) were investigated. Unit mass enrichment factors were observed to increase with concentrations of strontium salt in an aqueous phase. Isotope distinguishing ability of DC18C6 to strontium isotopes was calculated as an intrinsic separation factor to be K _c =1.00051±0.00004. An odd mass number isotope, ⁸⁷Sr, was recognized to behave differently from even mass number isotopes, ⁸⁴Sr, ⁸⁶Sr and ⁸⁸Sr. The enrichment factor induced by a nuclear property (odd or even mass number) other than the mass difference was ε_O/E = ?8.0 × 10^?4 which was observed with 3.2M Sr aqueous solution. Isotope shift of energy state for 5S-orbital of strontium produces the isotope shift in vibrational energy between the strontium ion and the DC18C6.     

Surface Irradiation Damage of 316 Stainless Steel,Vanadium and Molybdenum by Helium Ion Bombardment

Molybdenum, V and 316 stainless steel were irradiated with 50~150 keV He ions at the temperatures between 413 and 1,298K for total doses ranging 1× 10²²~10ײ³ m^?2, and the characteristics of the surface damage were compared. Severe exfoliation was observed in all of these materials for the irradiation at 413±110 and 748±25K. The number of exfoliated skins was larger than that in literature, and increased nearly in proportion with the total dose. It increased in the order Mo<316SS<. When the dose was low, the amount of erosion increased rapidly with total dose, but tended to be saturated for higher doses than 3×10²² m^?2. It increased in the order Mo<V<316SS at 413±110K, while in the order 316SS<Mo<V at 748±25K. At higher temperatures than 923 K, blisters and porous surface were formed and the exfoliation of skins ceased. The amount of erosion increased with increasing incident ion energy in the energy range between 50 and 150 keV at 413±110K for a total dose of 1×10²² m^?2.     

Steady-state creep of zircaloy-4 fuel cladding from 940 to 1873 K

Steady-state creep rates of as-received zircaloy-4 fuel cladding have been determined from 940 to 1073 K in the α-Zr range, from 1140 to 1190 K in the mixed (α + β) phase region and from 1273 to 1873 K in the β-Zr phase region. Strain rates of between 10^?6 and 10^?2/s were determined under constant uniaxial load conditions. Assuming that creep rates can be described by a power law-Arrhenius equation, the creep rate for α-phase zircaloy-4 is given by: $\text{ge}{}_{\mathrm{ss}}\text{?}\text{= 2000 σ}{}^{5.32}\text{exp}\text{(?284 600/kT) s}{}^{\mathrm{?1}}$; for the β-phase zircaloy-4 by: $\text{ge}{}_{\mathrm{ss}}\text{?}\text{= 8.1 σ}{}^{3.79}\text{exp}\text{(?142 300/kT) s}{}^{\mathrm{?1}}$; and for the mixed (α + β) phase of zircaloy-4 (for creep rates ?3 × 10^?3 s^?1) by: $\text{ge}{}_{\mathrm{ss}}\text{?}\text{= 6.8 × 10}{}^{\mathrm{?3}}\text{σ}{}^{1.8}\text{exp}\text{(?56 600/kT) s}{}^{\mathrm{?1}}$. For the both the α and β phases, the activation energies for creep are in agreement with those of self-diffusion. For the mixed (α + β) phase region, the low creep rate range is controlled by grain boundary sliding at the α/(α + β) phase boundary.     

A Powerful Remote Source of O Atoms for the Removal of Hydrogenated Carbon Deposits

We describe a system to deliver a large flux of O atoms for the removal of hydrogenated carbon films from surfaces in remote areas of tokamaks with carbon divertors. The oxygen plasma is generated via electrode-less radiofrequency discharge in a discharge chamber connected to a remote chamber by a 2 m long complex-shaped glass tube 4 cm in diameter. The density of O atoms in the remote chamber was measured with a nickel catalytic probe and its variation with discharge power obtained. The density was close to the detection limit of the probe (around 1 × 10¹⁹ m^?3) as long as the vacuum system was pumped with a rotary pump at a nominal pumping speed of 80 m³ h^?1. The density increased well over 10²⁰ m^?3 when a Roots pump was added. The effective pumping speed at the current setup was up to 200 m³ h^?1. At such conditions, the maximal O-atom density at 2 m from the source was up to 3 × 10²⁰ m^?3. The density depended on the pressure as well as the discharge power. The behavior of O-atom density far away from the source was explained by gas phase and surface phenomena. The effective pumping speed was found to be of crucial importance. The setup was used for removal of model hydrogenated carbon films. Experiments were performed at sample temperatures up to 600 K and etching rates up to 50 nm/s were obtained. We found that the experimental setup is suitable for removal of hydrogenated atoms on a large scale.     

Investigating permeation and transport of H isotopes in tungsten by first-principles

We have investigated permeation and transport of hydrogen (H) isotopes in tungsten (W) single crystal employing first-principles calculations in junction with Fick’ law. Permeability was approximately evaluated according to the solubility and diffusion coefficient of H. The solubility for H in bulk W from present calculation is consistent with the experimental results measured by Frauenfelder. The permeation fluxes of H isotopes are examined at the different thickness of W wall. The permeation fluxes of deuterium with the W thickness of 21 μm at the temperature of 770 K and with the W thickness of 50 μm at the temperature of 893 K were 0.68 × 10¹³ atom/m²s and 0.34 × 10¹⁴ atom/m²s, respectively. The dissociation coefficients of H isotopes are also evaluated. We believe that the present first-principles combined with Fick’ law method can be also generalized to investigate permeation and transport of H isotopes in most metals since such H isotopes behaviors in most metals are similar to those of H isotopes in W.     

Neutron Resonance Parameters of Silver-107 and Silver-109

Neutron transmission measurements were carried out on the separated isotopes of silver using the time-of-flight facility at the Japan Atomic Energy Research Institute electron linear accelerator. Neutrons were detected with the ⁶Li-glass detectors at 56 and 191 m. The samples used were metallic powder enriched to 98.2% for ¹⁰⁷Ag and 99.3% for ¹⁰⁹Ag. Transmission data were analyzed with the multi-level Breit-Wigner formula incorporated in a least squares fitting program. Resonance energies and neutron widths were determined for the large number of resolved resonances in the neutron energy region of 400 eV~7 keV. The s-wave strength functions and average level spacings were obtained to be; S₀= (0.43±0.05) × 10^?4, D₀ = 20±2 eV for ¹⁰⁷Ag and S₀= (0.45 ± 0.05) × 10^?4, D₀ = 20 ± 2eV for ¹⁰⁹Ag.     

Erosion of Pyrolytic Graphite and Ti-doped Graphite due to High Flux Irradiation

The erosion of pyrolytic graphite and titanium doped graphite RG-Ti above 1,780K was investigated by 5keV Ar beam irradiation with the flux from 4x10¹⁹ to 1x10²¹ m^?2·s^?1. The total erosion yields were significantly reduced with the flux. This reduction would be attributed to the reduction of RES (radiation enhanced sublimation) yield, which was observed in the case of isotropic graphite with the flux dependence of RES yield of φ^?0.26 (φ: flux) obtained in our previous work. The yield of pyrolytic graphite was roughly 30% higher than that of isotropic graphite below the flux of 10²⁰ m^?2·s^?1 whereas each yield approached to very close value at the highest flux of 1x10²¹ m^?2·s^?1. This result indicated that the effect of graphite structure on the RES yield, which was apparent in the low flux region, would disappear in the high flux region probably due to the disordering of crystal structure.

In the case of irradiation to RG-Ti at 1,780K, the surface undulations evolved with a mean height of about 3μm at 1.2×10²⁰ m^?2·s^?1, while at higher flux of 8.0×10²⁰ m^?2·s^?1 they were unrecognizable. These phenomena can be explained by the reduction of RES of graphite parts excluding Tic grains.     

Effect of Neutron Irradiation on Deformation Behavior of Zirconium

The effect of neutron irradiation on the tensile deformation behavior of zirconium was examined at room temperature at various strain rates ranging of 2.2×10^?4~2.2× 10^?2 sec^?1. The microstructure of the deformed specimens was observed by transmission electron microscopy. It was established that neutron irradiation diminishes the uniform elongation and the strain hardening rate, and hastens the onset of plastic instability. These phenomena are attributed to inhomogeneous deformation in the dislocation channels in the irradiated and deformed zirconium.

From the relation between strain rate and tensile properties (yield stress, ultimate tensile stress, uniform elongation and strain hardening rate), it was established that in unirradiated zirconium deformation is controlled by slip at strain rates below 6×10^?3 sec^?1, while above this threshold, twinning as well as slip contribute to deformation.

Neutron irradiation markedly inhibits deformation twinning in zirconium at room temperature. At 77 K, on the other hand, deformation by twinning is more prominent in irradiated specimens. The mechanism of twinning inhibition due to neutron irradiation is discussed.     

10Be annual fallout in rains in India

The ¹⁰Be concentrations of annual rainfall collections during 1979–1981, at eight stations in India, ranged from 0.43 × 10⁷ to 8.48 × 10⁷ atoms/l and the corresponding ¹⁰Be fallouts are in the range of 0.31 × 10 ⁶ to 2.73 × 10⁶ atoms cm^?2 a^?1. The estimated ¹⁰Be global fallout based on the presently available data is 1.55 × 10⁷ atoms^?2 a^?1 or 5 × 10^?2 atoms cm^?2 s^?1. Most of the measured rates of fallout and deep sea deposition of ¹⁰Be are a factor of 2–3 lower than the present estimate.     

Comparison of 41Ca analysis on 0.5 MV and 5 MV-AMS systems

A comparative study was made between the compact AMS system at the PSI/ETH Laboratory of Ion Beam Physics in Zurich with 0.5 MV terminal voltage and the 5 MV-AMS system at the Scottish Universities Environmental Research Centre (SUERC), Glasgow. Overall 34 urinary samples with ⁴¹Ca/⁴⁰Ca ratios in the range from 4 × 10^?11 to 3 × 10^?10 were processed to CaF₂ and aliquots of the same material were measured on both instruments.Measurements on the compact AMS system were performed in charge state 3+ achieving a transmission of 4% at 1.7 MeV beam energy. Under these conditions a suppression of the interference ⁴¹K is virtually impossible. However, samples with an excess of potassium can be identified by a shift of the ⁴¹Ca/⁴¹K peak in the ΔE ? E histogram of the gas ionization detector employed and a criterion for data rejection can be defined. An overall precision of ～4% and a ⁴¹Ca/⁴⁰Ca background level of 5 × 10^?12 have been reached.For studies with higher demands on the detection limit AMS systems like the one at SUERC are attractive: in charge state 5+ and using a gas stripper beam energy of 27 MeV, a transmission of 5%, a ⁴¹K suppression factor of ～500 and a ⁴¹Ca/⁴⁰Ca background level of 3 × 10^?14 are achieved.We demonstrate that both systems are well suited for large-scale ⁴¹Ca biomedical applications.     

Sorption Behavior of Selenium(—II) on Rocks under Reducing Conditions

The sorption of radionuclides on rocks is an important factor for performance assessment of geologic disposal of radioactive wastes. Batch sorption experiments under reducing conditions were carried out to investigate the sorption behavior of selenium onto granodiorite, sandy mudstone, tuffaceous sandstone, and their major constituent minerals and accessory minerals. Rock cores and groundwater employed in the experiments were sampled with special care to avoid exposing the cores and groundwater to air to minimize their oxidation. Selenium was spiked as HSe^? and Se₄ ^2- in the experimental solutions, and reducing conditions were maintained throughout the sorption periods. Distribution coefficients, Kd (m³ kg^?1), were obtained in the ranges of 2.2 × 10^?4 to 4.0 × 10^?3 m³ kg^?1 for granodiorite, 3.3 × 10^?2 to 5.6 × 10^?2 m³ kg^?1 for sandy mudstone, and 2.9 × 10^?2 to 8.2 × 10^?2 m³ kg^?1 for tuffaceous sandstone at pHs 8.5 to 11.5. The dominant sorbent minerals for selenium over a neutral to alkaline pH range were determined to be biotite for the granodiorite samples and pyrite for the sandy mudstone and tuffaceous sandstone samples.     

Dissolution of Gaseous Methyl Iodide into Aqueous Sodium Hydroxide Solutions

Absorption process of gaseous methyl iodide by water or sodium hydroxide solutions was investigated using a semi-flow type experimental apparatus by measuring the concentration of all measurable chemical species in both the gas and the liquid phase. The experimental temperature ranged from 288 to 311 K and the gaseous methyl iodide and aqueous sodium hydroxide concentrations were approximately 0.6×10^?3 to 7×10^?3 and 0 to 0.2 mol/dm³, respectively. It is estimated that the dissolution of methyl iodide into the sodium hydroxide solution proceeds according to the following steps.

Step (1) Methyl iodide in air dissolves physically into the aqueous phase. Physical dissolution process obeys Henry's law.

Step (2) Methyl iodide dissolved into the aqueous phase is decomposed by a base catalytic hydrolysis and produces methyl alcohol and iodide ion.

The equilibrium constants of physical dissolution were obtained from the steady concentration in both the gas and the liquid phases in the semi-flow type experiment because the hydrolysis reaction rate of methyl iodide is very slow in comparison with the physical dissolution in this experimental conditions. The obtained value of the standard heat of solution of methyl iodide into water was 7.2kcal/mol.

Salting-out effect was observed when the concentration of sodium hydroxide in the absorbent was over 0.01 mol/dm³.