Time-dependent diffusion coefficients in periodic porous materials

We derive an approximate solution for the Laplace transform of the time-dependent diffusion coefficient, D(t), of a molecule diffusing in a periodic porous material. In our model, the material is represented by a simple cubic lattice of identical cubic cavities filled with a solvent and connected by small circular apertures in otherwise reflecting cavity walls, the thickness of which can be neglected. The solution describes the decrease of D(t) from its initial value, D(0) = D, where D is the diffusion constant in the free solvent, to its asymptotic value, D(infinity) = D(eff), which is much smaller than D. A simple heuristic formula for the mean-squared displacement of the diffusing molecule is suggested. The theoretically predicted results are in good agreement with the data obtained from Brownian dynamics simulations.     

Radiochemical methods of measurements of fission products yields

Techniques used for the measurement of independent and cumulative fission yields are reviewed in this article.     

Beta-gamma counting system for Xe fission products

A beta-gamma coincidence counting system has been developed for automated analysis of Xe gas samples separated from air. The Xe gas samples are contained in a cylindrical plastic scintillator cell located between two NaI(T1) scintillation detectors. The X-ray and gamma spectra gated by coincident events in the plastic scintillator cell are recorded for each NaI(T1) crystal. The characteristic signatures of the^131mXe,^133gXe,^133mXe, and^135gXe isotopes of interest for nuclear test-ban verification as well as the procedures and results of absolute efficiency measurements are described. A NaI(T1) crystal with provision for 4 sample cells has been implemented for the system to be deployed in the field. Examples of data on ambient air samples in New York City obtained with the field prototype are presented.     

Advanced system for separation of rare-earth fission products

A microprocessor-controlled radiochemical separation system, which has been developed at the INEL, has been further advanced to separate individual rare-earth elements from mixed fission products in times of a few minutes. The system was composed of an automated chemistry system fed by two ∼300μg²⁵²Cf sources coupled directly by a He-jet to transport the fission products. Chemical separations were performed using two high performance liquid chromatography columns coupled in series. The first column separated the rare-earth group by extraction chromatography using dihexyldiethylcarbamoylmethylphosphonate (DHDECMP) adsorbed on Vydac C₈ resin. The second column isolated the individual rare-earth elements by cation exchange chromatography using Aminex A-9 resin with α-hydroxyisobutyric acid (α-HIBA) as the eluent. Significant results, which have been obtained to date with this advanced system, are the identification of several new neutron-rich rare-earth isotopes including¹⁵⁵Pm (T=48±4 s) and¹⁶³Gd (T=68±3 s). In addition a half-life of 41±4 s is reported for¹⁶⁰Eu. Work supported by the U.S. Department of Energy under DOE Contract No. De-ACO7-76IDO-1570.     

Kinetics of fission products accumulation on structural materials

The aim of the present work was to reveal the kinetics of the accumulation of some possible contaminant on the surfaces of structural materials (zirconium alloys and 08H18N10T stainless steel) in the primary circuit of Paks NPP. The kinetics of adsorption and desorption of iodide, caesium and cerium ions were investigated by quartz crystal microbalance (QCM) installed into a flow cell. The results on thin layers were confirmed by immersing experiments, using radiotracer technique and ??-spectrometry to detect the traced ions on the surfaces. Experiments were carried out in electrolyte solution which was similar to the cooling water. All measurements were carried out at room temperature. Both adsorption and desorption were found to be fast, taking only several seconds; time constants were also evaluated.     

Uptake studies of some fission products using ceramic materials

The uptake of Eu(III) and Zr(IV) was studied on ceramic materials of TiO₂, SiO₂ and Al₂O₃, prepared by the hydrolysis process. The uptake behavior of Eu(III) and Zr(IV) was investigated under different experimental conditions such as contact time, pH-value in the presence and in absence of complexing agent. X-ray fluorescence, powder morphology, specific surface area, X-ray diffraction analysis in addition to the DTA and TG were applied on the tested ceramic samples. The present study showed that the ceramic materials, prepared by an advanced technique are not only efficient for uptake of Eu(III) and Zr(IV), but also permitted the separation of these radioisotopes.     

Liquid-liquid microbatch extraction system for rapid mutual separation of fission products

The liquid-liquid microbatch extraction system (LMES) was developed for rapid separation of short-lived metal ions. The equipment is composed of three simple extraction cells for phase mixing, phase separation, and collection of a solvent. Metal separation can be completed in a single operation, lasting only a minute, from solvent extraction to preparation for gamma-ray spectrometry. As a demonstration of the rapid operation of the LMES, fission products were each separated into several categories after three stages of operation. The extractability in the LMES was comparable to that of traditional methods, and the developed method was feasible for rapid separation.     

Adsorption of fission products onto soils using a fission multitracer

The adsorption behavior of fission products to various soils was studied using a multitracer. The multitracer was prepared by neutron irradiation of ²³⁵U. Distribution coefficients of fission products were obtained for seventeen kinds of Japanese soils. It was found that zirconium, niobium, and rare earth elements show high distribution coefficients for all soil samples, however, elements like alkali metals show varied values.     

Interpretation of diffusion coefficients in nanostructured materials from random walk numerical simulation

We make use of the numerical simulation random walk (RWNS) method to compute the "jump" diffusion coefficient of electrons in nanostructured materials via mean-square displacement. First, a summary of analytical results is given that relates the diffusion coefficient obtained from RWNS to those in the multiple-trapping (MT) and hopping models. Simulations are performed in a three-dimensional lattice of trap sites with energies distributed according to an exponential distribution and with a step-function distribution centered at the Fermi level. It is observed that once the stationary state is reached, the ensemble of particles follow Fermi-Dirac statistics with a well-defined Fermi level. In this stationary situation the diffusion coefficient obeys the theoretical predictions so that RWNS effectively reproduces the MT model. Mobilities can be also computed when an electrical bias is applied and they are observed to comply with the Einstein relation when compared with steady-state diffusion coefficients. The evolution of the system towards the stationary situation is also studied. When the diffusion coefficients are monitored along simulation time a transition from anomalous to trap-limited transport is observed. The nature of this transition is discussed in terms of the evolution of electron distribution and the Fermi level. All these results will facilitate the use of RW simulation and related methods to interpret steady-state as well as transient experimental techniques.     

Calibration system and analytical considerations for quantitative sesquiterpene measurements in air

Sesquiterpenes (C15H24, SQT) are semi-volatile organic compounds emitted from vegetation and are of interest for air quality considerations because of their suspected contribution to the formation of secondary aerosol. This article investigates the application of a capillary diffusion method for the generation of standard atmospheres of 16 SQT and four other related semi-volatile compounds. This instrument subsequently has been used in the testing of analytical materials, protocols and calibration of air sampling methods. SQT DB-1 retention indices, vapor pressures at 25 and 75 degrees C, and diffusion coefficients were determined. A quantitative, on-line GC method yielded improved results (median relative standard deviation of 5.0-6.1%) for the diffusion rate determination in comparison to a gravimetric approach (median relative standard deviation 18%). The GC method also allowed identifying errors in the gravimetric method stemming from residual solvent evaporation, impurities, and chemical analyte losses. Stainless steel, glass, nickel and PTFE tubing that were tested for transfer lines and a sampling loop had to be kept at temperatures in excess of approximately 110 degrees C in order to prevent significant analytical errors from the stickiness of SQT to these materials. In addition to SQT analysis, results from this research provide general guidelines for gas-phase analysis of related compounds in the C14-C16 volatility range.     

A gas-jet system for the study of short-lived,light fission products

A selective method for the solvent extraction and spectrophotometric determination of uranium(VI) is described. Uranium can be extracted into chloroform at pH 6.0 with N-m-chlorophenyl-2-theno-hydroxamic acid (N-m-CPTHA) and determined by spectrophotometry using 1-(2-pyridylazo)-2-naphthol (PAN). The molar absorptivity is 1.50·10⁴ 1·mol^–1·cm^–1 at 560 nm. The system obeys Beer's law within the range 0.95–20.00 ppm of uranium. Alternatively, a back-extraction procedure was also developed in which uranium is back-extracted by nitric acid and estimated spectrophotometrically using Arsenazo III. The molar absorptivity is 2.0·10⁴ 1·mol^–1·cm^–1 at 665 nm. The parameters concerning the optimum conditions for the analytical method are discussed. The proposed method is applied precisely for the determination of uranium in rock and sea water samples.     

Simultaneous determination of binary diffusion coefficients from multiple response curves by chromatographic measurements

A validated two-dimensional HPLC method for the comprehensive analysis of small quantities of branched aliphatic D-amino acids in the presence of large amounts of their L-congeners in mammalian tissues and physiological fluids is described. The quantitative analysis of these aliphatic amino acids (Val, allo-Ile, Ile, and Leu) is important for the diagnosis of various inherent metabolic disorders of amino acids, and the D-enantiomers are expected to be of particular interest from a pharmacological point of view. Target analytes were determined as their fluorescent derivatives, pre-column labeled with 4-fluoro-7-nitro-2,1,3-benzoxadiazole (NBD-F), using an automated two-dimensional column-switching high-performance liquid chromatographic system combining a narrow bore reversed-phase column and an enantioselective column connected with an integrated multi-loop peak fraction storage device. The described two-dimensional analysis concept proved to be successful for the given task in biological samples taken from mammals. Total analysis time for the reversed-phase separation of the four target NBD-amino acids is 60 min, and the integrated enantiomer separation of each of the four analytes is completed in approximately 5 min. In the rat, significant amounts of D-Leu were found in all tissues and physiological fluids tested (trace-1.3 nmol/g tissue), and in the urine, the presence of high amounts of D-allo-Ile (D-isomer of a non-proteinogenic amino acid, 22.2 nmol/ml) was demonstrated. D-allo-Ile was also found in the urine of dog and mouse, which indicates the ubiquitous presence of this unusual D-amino acid and the potential need to clarify its unique metabolism in mammals.     

Experimental measurements of short-lived fission products from uranium,neptunium, plutonium and americium

Fission yields are especially well characterized for long-lived fission products. Modeling techniques incorporate numerous assumptions and can be used to deduce information about the distribution of short-lived fission products. This work is an attempt to gather experimental (model-independent) data on short-lived fission products. Fissile isotopes of uranium, neptunium, plutonium and americium were irradiated under pulse conditions at the Washington State University 1 MW TRIGA reactor to achieve ~10⁸ fissions. The samples were placed on an HPGe (high purity germanium) detector to initiate counting in less than 3 min post irradiation. The data was analyzed to determine which radionuclides could be quantified and compared to the published fission yield data.     

Measurement of diffusion coefficients for diffusion-controlled reactions

The Taylor dispersion technique has been used to measure the diffusion coefficients of nine compounds in dilute solution in isopropanol at 300 K. These compounds correspond, by the difference of a single hydrogen atom, to nine free radicals, for which the rate constants for bimolecular (termination) reactions have been previously measured under the same conditions by e.s.r. Comparison of the two sets of results show the termination reactions to be essentially diffusion-controlled, and, assuming no activation-energy effect, interaction parameters for the termination reactions are calculated and discussed.     

Relaxation times,diffusion coefficients and high frequency NMR measurements of methane dissolved in MBBA

The measurements of proton T₁, T₂ and diffusion coefficients of CH₄ and deuterium T₁ in CD₄, dissolved in MBBA are reported as a function of the temperature in the nematic and solid phases. Also reported are cw measurements of CH₄ in MBBA at 250 MHz which definitely prove that it is oriented. The results are discussed in terms of their relation to previously published cw NMR measurements on these systems.     

Interaction between lactose and cadmium chloride in aqueous solutions as seen by diffusion coefficients measurements

Diffusion coefficients of an aqueous system containing cadmium chloride 0.100 mol · dm⁻³ and lactose at different concentrations at 25 °C have been measured, using a conductimetric cell and an automatic apparatus to follow diffusion. The cell relies on an open-ended capillary method and a conductimetric technique is used to follow the diffusion process by measuring the resistance of a solution inside the capillaries, at recorded times. From these results and by ab initio calculations, it was possible to obtain a better understanding of the effect of lactose on transport of cadmium chloride in aqueous solutions.     

Isomeric yield ratios of fission products in proton-induced fission of232Th

Isomeric yield ratios of 11 fission products were measured in the system of 13 MeV proton-induced fission of²³²Th by an on-line ion-guide isotope separator. It was found that the closed shell structures of primary fragments and their complementary fragments affect the isomeric yield ratios. Isomeric yield ratios of¹²¹Cd (11/2⁻, 3/2⁺) and¹³⁵Xe (11/2⁻, 3/2⁺) were measured precisely in the proton energy range of 13 to 26 MeV to investigate their energy dependence. It was found that the isomeric yield ratios increased slightly with proton energy. The results were discussed in connection with the deformation of fission fragments and fission modes.     

A transportable gamma spectroscopy system applied to the measurement of fission products

Normally, gamma-ray spectroscopy is performed by equipment positioned in the SLOWPOKE-2 Facility at the Royal Military College; however, there have occasionally been requirements for analyses externally. A transportable gamma spectroscopy system was thus assembled by acquiring a commercially available multichannel analyzer, analysis program and detector, and by designing and constructing a transportable shielding castle. It was then used to take measurements of fission product concentrations at several research reactors.