Speciation of actinide ions in aqueous solution by laser-induced pulsed photoacoustic spectroscopy

The oxidation-state specific detection of actinide ions, U(VI), Pu(IV), Pu(VI), and Am(III), was investigated by pulsed laser photoacoustic spectroscopy. With a single-beam differential technique, the solvent effect is compensated and thus the detection sensitivity substantially increased. The observed detection sensitivities are8×10^–7M/L for U(VI)7×10^–8M/L for Pu(IV)3×10^–8M/L for PU(VI)2×10^–8M/L for Am(III)The present method facilitates the study of complexation and polymerization of actinide ions in the submicromole concentration range.     

Spectrophotometric Study of Luminol in Dimethyl Sulfoxide–Potassium Hydroxide

The spectrophotometric study of luminol (LH₂) in dimethyl sulfoxide (DMSO), DMSO-water solutions, and alkaline DMSO and DMSO-water solutions has been done, focusing on the effect of the KOH additon on LH₂ absorption and fluorescence properties. The absorption spectra indicate an acid-base equilibrium, and the luminol dianion (L^2–) formation at 3 × 10^–4 – 2.4 × 10^–3 M KOH. The decrease of the fluorescence intensity and the variation of the excitation spectra of LH₂-DMSO-KOH solutions with KOH concentration have been similarly explained. The acid-base process is reversible. The addition of HCl to the solution with 3.0 × 10^–3 M KOH leads to an increase of the fluorescence intensity to its highest value, observed in pure DMSO. The addition of HCl to the LH₂-DMSO solution leads to the decrease of the fluorescence intensity as a result of the LH⁺ ₃ cation formation. In LH₂-DMSO-water, the fluorescence band is shifted from 405 nm to 424 nm and increased in the intensity. In the presence of KOH (in LH₂-DMSO-water-KOH solution) a new band appears, with the maximum at 485 nm and the band at 405 nm decreased. The changes in fluorescence lifetimes also evidence the different chemical species formed.     

Molecular Dynamics of Biological Probes by Fluorescence Correlation Microscopy with Two-Photon Excitation

We report on the application of fluorescence correlation microscopy under two-photon excitation of fluorophores of biological interest: FITC–dextran (MW, from 20 to 150 kDa), green fluorescent protein (MW, 27 kDa), and fluorescein (MW, 330 Da). Under these experimental conditions, the translational diffusion coefficients of these molecules in aqueous solutions derived from the fluorescence intensity autocorrelation function were determined for the first time and were found to be 24 × 10^–7, 8.2 × 10^–7, and 3 × 10^–7 cm² s^–1 for 150-kDa FITC–dextran, green fluorescent protein, and fluorescein, respectively. These results are discussed in connection with previously reported results obtained by different methods. The great sensibility of the system has been applied to single-molecule detection of the smaller fluorophore, fluorescein.     

Study of stress-strain characteristics of SBR and blended NR/SBR rubber

The effect of temperature and carbon black (CB) on the mechanical characteristics of styrene-butadine rubber (SBR) and natural rubber (NR) was studied at various temperatures. The relation obtained between true stress and true strain for both types of rubber showed three regions at room temperature and two regions at high temperature. The optimum CB concentration was found to be 95 phr for the unblended samples as it increases the stiffness of the SBR rubber materials at a maximum value. It was also found that the addition of NR to SBR increases the elasticity in the plastic region. The activation energy at the fracture of SBR samples decreased from about 2.7×10^–20 to 1.8×10^–20 J while for the blended samples NR/SBR it increased from 8×10^–20 to 10.1×10^–20 J with increasing CB concentration.     

Laser annealing of GaAs dual implanted with Si and P ions

Laser annealing of SI(100) GaAs:Cr implanted either with Si⁺ ions (150 keV, 6×10¹³-1×10¹⁵cm^–2) or dual implanted with Si⁺ ions (150 keV, 6×10¹⁴–1×10¹⁵cm^–2) and P⁺ ions (160 keV, 1×10¹⁴–1×10¹⁵cm^–2) has been examined using backscatteringchannelling technique and via electrical measurement of Hall effect. It has been found that at laser energy densities 0·8 J cm^–2 a full recovery of the sample surface occurs. In dual implanted samples (1×10¹⁵ Si⁺ cm^–2+1×10¹⁵P⁺cm^–2) up to 46% of Si atoms become electrically active after the laser annealing. Resultant Hall mobility of carriers is, however,lower than that obtained after common thermal annealing.The authors are pleased to take the opportunity of thanking Professor M. Kubát for his encouragement and continuous support. Accelerator staff is gratefully acknowledged for its assistance in the course of experiments.     

Parametrization of the radial distribution function and thermodynamic properties of the restricted primitive model of electrolyte solutions

Monte Carlo simulations for the restricted primitive model of 1-1 aqueous electrolyte solutions were performed on a minicomputer. The calculations covered the concentration range from 0·1 to 3 mol/dm³ and the ionic diameter varied from 2·0× ×10^–10 to 4·75×10^–10 m. On the basis of the Monte Carlo results a new analytical radial distribution function and excess internal energy parametrization were proposed for the restricted primitive model.     

ВЛИЯНИЕ ПЛАСТИЧЕСКОЙ ДЕФОРМАЦИИ НА ХАРАКТЕР ЭКСТИНКЦИИ И ОСТАТОЧНЫЕ ИСКАЖЕНИЯ РЕШЕТКИ ЧИСТОГО ПОРОШКОВОГО АЛЮМИНИЯ

The integrated intensities and widths of the X-ray diffraction lines of pure powder aluminium (99·99%) were measured after annealing above the recrystallization temperature and once more after the following plastic deformation at room temperature.An analysis of the values measured for the integrated intensities of the diffractions shows that, in the annealed state and in states after plastic deformation by grinding in an organic liquid medium, the primary extinction of this substance predominates. The corresponding magnitude of the mosaic blocks is 4×10^–4 cm and the minimum dislocation density calculated from it is 2×10⁷ cm^–2. On the other hand, an analysis of a sample of unannealed fillings from the same material shows that both kinds of extinction — primary and secondary — play equalroles.Measurement of the (420) diffraction line widths showed that plastic deformation at room temperature leads to a clear broadening of the diffractions in spite of the process of recovery intensively taking place. An interpretation of these broadenings by micro stresses in the region of individual grains led to values of the mean stress function of 7–8×10⁸ dyne cm^–2. This value is compared with the yield point and the corresponding values of the stored energy are calculated. The hypothesis is put forward that the maintenance of these stresses in the grains is due to the oxide envelope surrounding the grains.For plastically deformed samples the diffraction broadening led to maximum dislocation densities of the order of 2×10¹⁰–3×10¹⁰cm^–2 and thus to maximum stored energy values of the order of 1×10^–2 to 2×10^–2 cal/g.     

Thermodynamic studies of successive phase transitions in BaZnGeO4 and a new solid phase below 186.1 K

The successive phase transitions of BaZnGeO₄ have been studied on meltsolidified samples. A new solid phase (named phase VI) has been found below 186.1 K in samples of large particle size (diameter:D0.1 mm). The higher temperature crystalline phase V can be supercooled easily down to liquid helium temperature. On heating, however, it transforms into phase VI above 95 K in a slow exothermic process. Heat capacities have been measured by adiabatic calorimetry between 14 and 300 K. The enthalpy and entropy of the V–VI phase transition are 187.1 Jmol^–1 and 0.971 J K^–1 mol^–1, respectively. The corresponding data for the IV–V phase transition at 199.8 K are 229.3 J mol^–1 and 1.168 JK^–1 mol^–1. The phase VI does not appear in samples of smaller particle size (D0.1 mm).     

Low gas pressures obtained by means of sorbents

The paper describes the use of active charcoal and a 13X molecular sieve at 78°K to pump all-glass apparatuses with a small volume (up to 5000 cm³) from atmospheric pressure to a pressure region of 10^–2 mm Hg. At this pressure an outgassed second pumping stage (also sorbent) permits pressures from 10^–6 to 10^–7 mm Hg to be obtained. Active charcoal was also used as a two-stage fore pump (p=10^–6 mm Hg) for a one-stage mercury diffusion pump and in this system pressures of 5 to 10×10^–10 mm Hg were achieved.     

Optical bistability in fluorescein dyes

Optical bistability has been observed in highly concentrated fluorescein dye solutions and in thin (1 m) doped polymeric films. At concentrations larger than 10^–5 mole/l dye dimers are formed. For fluorescein dye, the dimer-monomer equilibrium constant is 10⁵ l/mole so that most of the dye species are in the dimer form. At 480 nm the dimer absorption cross section is 10^–18 cm²/molecule, while that for the dye monomer molecule is 7.6×10^–17 cm²/molecule. Upon laser excitation dimers dissociate to form monomers thus providing a highly nonlinear laser induced absorption. This high nonlinear absorption coefficient can be utilized for optically bistable response of the dye system.Optical bistability was observed by placing dye solutions or dye thin films inside a Fabry-Perot resonator and exciting it with 480 nm dye laser pulses of 10 ns duration. The effect is more pronounced in 10^–4 mole/l fluorescein than in 10^–6 mole/l fluorescein in which dimer formation is not that efficient.In disodium fluorescein no significant dimer formation is observed even at 10^–3 mole/l dye concentration. The observed bistability both in solution and in thin films can be explained in terms of recent models for optical bistability in nonlinearly absorbing molecular systems.     

Studies of divacancy in Si using positron lifetime measurement

The charge state dependence of positron lifetime and trapping at divacancy (V₂) in Si doped with phosphorus or boron has been studied after 15 McV electron irradiation up to a fluence of 8.0×10¹⁷ e/cm². The positron trapping cross sections for V ₂ ^2– , V ₂ ^– and V ₂ ⁰ at 300 K were about 6×10^–14, 3×10^–14 and 0.1–3×10^–14 cm², respectively. For V ₂ ⁺ , however, no positron trapping was observed. The marked difference in the cross sections comes from Coulomb interaction between the positron and the charged divacancy. The trapping rates for V ₂ ⁰ and V ₂ ^2– have been found to increase with decreasing temperature in the temperature range of 10–300 K. These results are well interpreted by a two-stage trapping model having shallow levels with energy of 9 meV (V ₂ ⁰ ) and 21 meV (V ₂ ^2– ). The appearance of a shallow level for V ₂ ⁰ can not be explained by a conventional Rydberg state model. The lifetime (290–300 ps) in V ₂ ⁰ is nearly constant in the temperature range from 10 to 300 K, while that in V ₂ ^2– increases from 260 ps at 10 K to 320 ps at 300 K. The lifetime (260 ps) in V ₂ ^2– is shorter than that in V ₂ ⁰ at low temperature, which is due to the excess electron density in V ₂ ^2– . At high temperature, however, the longer lifetime of V ₂ ^2– than that of V ₂ ⁰ is attributed to lattice relaxation around V ₂ ^2– .     

On search and identification of tracks due to short-lived SHE nuclei in extraterrestrial crystals

The unique approach for search and unambiguous identification of short-lived (T_1/2=10³–10⁷ years) superheavy nuclei in cosmic-ray products of the recent nucleosynthesis in our Galaxy are discussed.It is based on: (a) the ability of non-conducting crystals to register and to store for many million years the tracks due to fast nuclei with atomic number Z20 (“fossil” tracks);(b) calibrations of the said crystals with accelerated heavy ions (20Z92) and on revealing the volume etchable track length (VETL) of the fast nuclei coming to rest inside crystals—both of fossil and “fresh” tracks—to determine the charge distribution of cosmic-ray nuclei tracks and(c) the so-called “four-zone” model of tracks in crystals (and also glasses) which provides not only the VETL track length dependence for 20Z92 nuclei but also demonstrates the regular annealing behavior of VETL of 20Z92 nuclei in a broad temperature interval.This approach was first applied in the early 1980s to investigate the “fossil” tracks due to 22Z92 cosmic-ray nuclei in olivine crystals from meteorites-pallasite Marjalahti and Eagle Station.The discovery of Th–U cosmic-ray nuclei tracks in 1980 was unambiguously confirmed by calibrations of the same crystals with ²³⁸U, ¹⁹⁷Au and ²⁰⁸Pb accelerated ions in the late 1980s. More than 1600 tracks due to cosmic-ray actinide nuclei were measured during the last two decades of the 20th century.Also, 11 anomalously long tracks (track length exceeds by a factor (1.6±0.1) the track length due to Th–U nuclei were measured. The detailed analysis shows that at least 5 of these tracks could not be attributed to the Th–U nuclei. It means that now we have a preliminary proof on the existence Z110 nuclei in cosmic-rays. The abundance is Z110/Th–U=(1–3)×10⁻³ in Z110 freshly formed cosmic-rays (time interval 10³–10⁷ years).The method proposed can provide the necessary and sufficient conditions for the discovery of Z110 nuclei in nature.     

Nearest neighbor effect on capture cross sections measured in IR phototransients on Si:In

The extrinsic photoconductive decay at T=20–100 K is analyzed in FZ-grown Si: In material after pulsed irradiation by a PbSSe infrared laser (=4 m). Trapping time constants (=10 ns-100 s) are resolved for the prevalent In acceptor (N _In=10¹⁶–10¹⁷ cm^–3) and for additional shallow acceptors B, Al, and the X(In)-center present at low concentrations (N=10¹²–10¹⁴ cm^–3). Hole capture cross sections determined for the acceptor levels show a large scatter over up to 4 orders of magnitude. It is shown that the capture cross section is dependent on all the dopant concentrations present in the sample due to nearest neighbor interaction. Due to the formation of donor-acceptor dipoles, the capture cross section assumes low values. A model calculation of the interaction based on only fundamental parameters of Si is in accordance with the experimental data within the experimental error. The hole capture cross sections for isolated acceptors are _p=1×10^–12, 1×10^–14, 1×10^–13, 2.5×10^–13 cm² for indium, X-center, aluminum, and boron at the temperatures T=95 K, 100 K, 70 K, 45 K, respectively.     

Mismatch and electron mobility in MBE GaxIn1−xas epitaxial layers on InP substrates

Composition inhomogeneity in nearly matched epilayers of the ternary semiconductor alloy Ga_xIn_1–xAs (x close to 0.47), grown by molecular beam epitaxy (MBE) on (001) InP substrates is correlated to variation of the lattice mismatch by x-ray imaging and local diffractometry. Misfit dislocations are shown to develop in areas of large misfit (above 2 × 10^–3) and are at the origin of a severe degradation of the electron mobility: an increase by a factor of about 4 in the intrinsic misfit (2.3 × 10^–3 compared to 0.6 × 10^–3) results in a 35 % reduction of the 77 K electron mobility.Part of this work has been done while this author was with Thomson-CSF Central Research Laboratory, Orsay, France     

A Sensitive Fluorimetric Method for the Determination of Epinephrine

A sensitive fluorimetric method for the determination of epinephrine (E) is described in this paper. The experiments indicate that epinephrine can react with formaldehyde (HCHO) in an acid medium to form a condensation product, which can be oxidized by potassium hexacyanoferrate(III) (K₃[Fe(CN)₆]) in borax buffer (pH = 9.5). The reaction product can emit strong fluorescence. Ascorbic acid (AA) is used in order to consume excess potassium hexacyanoferrate and stabilize the fluorescent product. Under optimum conditions, a linear relationship has been obtained between the fluorescence intensity and the concentration of epinephrine in the range of 1.4×10^–9–2.1×10^–6 mol/l, and the detection limit is 2.4×10^–10 mol/l (4.3×10^–11 g/ml, S/N = 3). The method is applied for the determination of E in both actual sample and the synthetic sample with E and norepinephrine (NE) by using the coupling technique of synchronous fluorimetry and H-point standard addition method, and the results obtained are satisfactory.     

Diffusion of Al in ion-implanted Pd and Pt

The diffusion coefficients of aluminium have been measured in polycrystalline fcc Pd and Pt. The Al-implanted palladium and platinum samples were annealed at 400°–800 °C and 450°–900 °C, respectively. The aluminium profiles were probed using the nuclear resonance broadening (NRB) technique. Values of (1.41±0.09) and (1.38±0.09) eV for the activation energy and (1.5 _–1.0 ⁺⁵ )×10^–6 and (4 _–3 ⁺¹⁰ )×10^–7cm²/s for the frequency factor were obtained for Al in Pd and Pt, respectively. These anomalous results, compared to the normal impurity diffusion, were checked using also Al-evaporated samples.     

Dislocation structure of kcl crystals grown with vibration of the melt

Summary The amplitude at all frequencies was 0.04 mm. Three crystals were grown at each frequency, with seeds of dislocation density D = 6 × 10⁴ cm^–2. Figure 1 shows the frequency dependence of the final D. Each point in Figs. 1 and 2 is the mean from 50 measurements (50 fields of view). At all frequencies except 180 Hz, D was 2–4 times less than that without vibration, while at 100 and 160 Hz it was less by nearly an order of magnitude.The effects of amplitude (0.02 to 0.2 mm) were examined at 100 Hz, the minimum D occurring at 0.1 mm (Fig. 2). At 0.04–0.08 mm, D was less by a factor 3–4 than for crystals grown without vibration, while at 0.1 mm it was less by an order of magnitude, being 2 × 10^–4 cm^–2. The size of the etch pits on crystals grown at amplitudes up to 0.1 mm did not differ from that for crystals grown at rest, but above 0.1 mm the size increased, by more than a factor 3 at 0.2 mm. Figure 3 illustrates these effects.Optimal vibration reduces D by improving the growth conditions (reduction of temperature gradients by mixing, more uniform impurity distribution).     

Practical separation of silicon isotopes by IRMPD of Si2F6

Large-scale silicon isotope separation based on the IRMPD of natural Si₂F₆ has been carried out using a commercially available high power CO₂ TEA laser and a flow reaction system. The decomposition product SiF₄ containing 19–33% of ³⁰Si was obtained at a production rate of 1.5×10^–2–2.6×10^–2 mol·h^–1, depending on experimental parameters such as laser wavelength, laser fluence, pressure, and flow rate. SiF₄ containing 12% of ²⁹Si was obtained under slightly different conditions, i.e., at a shorter wavelength than that for ³⁰Si. When 39% of Si₂F₆ was decomposed at a slow flow rate, residual Si₂F₆ was found to have 99.7% of ²⁸Si. The production rate was 4.2×10^–2 mol·h^–1.     

Diffusion of nitrogen in ion-implanted chromium and tungsten

The diffusion of N in the group VI B metals Cr and W has been studied in the previously uninvestigated temperature ranges 300°–550 °C (Cr) and 600°–800 °C (W) using ion-beam techniques. Diffusion couples were created by ion-implantation. The timedependent diffusion profiles were monitored by the use of the Nuclear Resonance Broadening (NRB) technique. The linear Arrhenius plots extracted from the measured diffusivities indicate that the diffusivity of implanted N in Cr and W can be described by the activation energyQ=1.39±0.06 eV and 2.32±0.16 eV and the pre-exponential factorD ₀=(7.0±7.2)×10^–4cm^2/s and 4.3±8.3cm^2/s, respectively. The solubilities of N in Cr and W from the implanted distributions were found to deviate from those obtained using conventional metallographical methods.     

Use of radar methods in increasing sensitivity in emission spectral analysis. Part I. Use of correlation

Special scanning methods applied to line and continuous background cause these to build up according to different laws; a line of unvarying intensity is transformed to a train of video pulses (frequency 50 kc), while the background fluctuations remain purely random. Some characteristics are derived for the autocorrelation function; these enable one to use it to reduce the limit of detection in spectral analysis. The autocorrelation function is reported for the arc determination of Cr at concentrations of 5×10^–3, 5×10^–4, 5×10^–5, and 5×10^–6%. Calibration curves are given for these concentrations as determined by photographic and autocorrelation methods. The limit of detection by the photographic method is found to be about two orders of magnitude larger than that for the autocorrelation one.I am indebted to Professor N. A. Prilezhaeva and senior scientist N. G. Preobrazhenskii for valuable advice and discussions, and also to student V. I. Donin for assistance.