Kinetics of Pu(IV) Reduction with Butanal Oxime

The reduction of Pu(IV) with butanal oxime in nitric acid solution in the presence of excess reductant follows the equation 4Pu^{4 +} + 2C₃H₇CHNOH + H₂O = 4Pu^{3 +} + 2C₃H₇CHO + N₂O + 4H⁺, and its rate is given by the equation -d[Pu(IV)]/dt = k[Pu(IV)]²[C₃H₇CHNOH]/{[Pu(III)][H⁺]}. The rate constant is k = 3.65±0.14 min^{- 1} at 20.2°C and the solution ionic strength = 2. The activation energy is E = 88.8±10.3 kJ mol^{- 1}. The probable reaction mechanism is discussed.     

Magnetic Resonance Studies of Impurity-Helium Solids Containing Hydrogen and Deuterium Impurities

Impurity-Helium Solids (Im-He) produced by injecting a mixed beam of helium and impurity gases into superfluid ⁴He have been investigated by electron spin resonance (ESR) and nuclear magnetic resonance (NMR) techniques. NMR signals from deuterium molecules in a D₂-He solid have been studied. Only samples prepared from gaseous mixtures containing high concentrations of D₂ molecules gave observable signals. The ESR experiments were performed on H and/or D atomic impurities in Im-He solids containing H, D, H₂, and D₂ in various combinations. The exchange tunneling reactions D+H₂HD+H and D+HDD₂+H were used to generate high concentrations of H atoms (10¹⁷/cm³) in Im-He samples.     

Hydrothermal Synthesis of Nanocrystalline SnO2 for Gas Sensors

Nanocrystalline SnO₂ is prepared by hydrothermal synthesis (130–250°C, 2–5 h) using three different precursors and is characterized by x-ray diffraction, transmission electron microscopy, and nitrogen BET measurements. The crystallite size of SnO₂ powders (d = 4–5 nm) prepared from amorphous stannic acid gels is found to vary very little with process temperature and duration. Air anneals at 500°C for 1–20 h demonstrate that the highest stability toward crystallite growth is offered by the samples prepared by oxidizing SnSO₄ with H₂O₂ (the crystallite size increases only slightly, from 4–5 to 5–7 nm), whereas the crystallite size of the samples prepared by high-temperature hydrolysis of SnCl₄ increases markedly, from 4–5 to 16–17 nm. Nanocrystalline NiO-doped SnO₂ is prepared by hydrothermal treatment, and its physicochemical properties are investigated. Both SnO₂ and SnO₂NiO exhibit gas sensitivity, as demonstrated by consecutively exposing the samples to different gaseous atmospheres: O₂ N₂ O₂ and O₂ N₂ + C₂H₅OH O₂.     

Rhombohedral Actinide Phosphates AIM2IV(PO4)3 (MIV = U,Np, Pu; AI = Na,K, Rb)

Double orthophosphates of actinides and alkali metals A^IM₂IV(PO₄)₃, where MIV = U, Np, or Pu; A^I = Na, K, or Rb, are studied by X-ray diffraction. Rhombohedral modifications (-forms) formed from the low-temperature monoclinic modifications (-forms) on heating in the range 600-1650°C are examined. The transition temperature depends on particular alkali metal and actinide. The crystallographic parameters of the complexes are tabulated. The trends in variation of the unit cell parameters in relation to the ionic radii of alkali metals and actinides are discussed.     

Sorption of Radioactive Iodine and Fluoride Ion on Hydroxyapatite from the Aqueous Phase

Sorption of the ¹³¹I^-, ¹³¹IO₃ ^-, and F^- ions on various samples of hydroxyapatite (HAP) from aqueous solutions was studied. The HAP samples were prepared by the following reactions: Ca(OH)₂ + H₃PO₄ HAP, CACl₂ + Na₃PO₄ + NaOH HAP, and Ca(NO₃)₂ + HAP seed + (NH₄)₂HPO₄ + NH₃ HAP. None of the HAP samples sorb ionic species of radioactive iodine from aqueous solutions. As for F^-, the best sorption properties are exhibited by the HAP sample prepared by the second reaction. The degree of recovery of fluoride ion with the HAP precipitate in 5 min, 4 h, and 5 days of the contact of the solid and liquid phases is 54, 66, and >95% of the initial F^- amount, respectively. The distribution factor K _d of the fluoride ion between the HAP solid phase and solution decreases with increasing V/m ratio and pH of the initial solution.     

Microstructure and properties of supersaturated ZA27 alloy during natural ageing

The decomposition of the supersaturated solid solution of ZA27 alloy at room temperature has been investigated by X-ray diffraction, TEM and mechanical properties testing. Based on the results obtained, both continuous precipitation and cellular reaction occur during the decomposition process. The continuous precipitation follows the sequence: ₁ + spherical GP zones ₂ + elliptical GP zones ₃ + R + . The cellular reaction can be written: + + . The properties of the alloy depend on the microstructure. After 1 month of ageing, a series of changes of microstructure have taken place. The properties of the alloy are: _b=500 MPa, =13%,H _v=148.     

Long term stability of H atoms in HD-D2-He solids

No Heading We employed en electron spin resonance (ESR) technique for investigating the long term behavior of hydrogen and deuterium atoms in the HD-D₂ impurity helium solids that were created by sending a gas mixture [H₂]:[D₂]:[He]= 1:4:100 through a radio-frequency electrical discharge into a volume of superfluid ⁴He at T = 1.5 K. H and D atoms were stabilized inside nanoclusters of impurity molecules. The exchange tunneling reactions D + H₂ HD + H and D + HDD₂ + H proceeded to eliminate D atoms and increase the concentration of H atoms in the HD-D₂ impurity-helium solids. Local concentrations of H atoms inside the molecular nanoclusters of order 10²⁰ cm^–3 were achieved. The high concentration of H atoms was stable during 40 hours storage of the sample at T = 1.35 K. These solids are possible candidates for collective quantum phenomena of atomic hydrogen if the Bose-Einstein degeneracy regime can be attained.PACS numbers: 61.46. +w, 67.40.Yv, 76.30.–v.     

A new formulation of Gor'kov's theory of clean type II superconductors

From Gor'kov's theory a functional for the free energy of the flux line lattice is derived which depends explicitly on the potentials andA. It may be interpreted as an extension of the Ginzburg-Landau functional to arbitrary temperatures. For periodic || ² andH=rotA, the functional is a rapidly converging series, of which often the main term (corresponding to the Brandt-Pesch-Tewordt approximation) plus a correction term depending on the lattice structure suffices. From the cutoff series all previously known results for the special casesT T _c ,B H _c2 ,orB 0 are reproduced by minimization with respect to || ² andH.     

Mullite formation from xerogels of (0.84–2.2) Al2O3·1SiO2

Xerogels of (0.84–2.2) Al₂O₃·1SiO₂ prepared by chemical coprecipitation of Al(NO₃)₃·9H₂O and Si(OC₂H₅)₄ experience three thermal reaction paths for mullite formation. Those with pseudoboehmite are found to form mullite via the paths of either Al-Si spinel mullite transformation or -Al₂O₃ -Al₂O₃ + amorphous SiO₂ mullite, depending upon the ratios of Al₂O₃/SiO₂. Higher SiO₂ content may prefer the former reaction. Xerogels composed of bayerite form mullite via the route -Al₂O₃ -Al₂O₃ + amorphous SiO₂ mullite. Mullite thus formed exhibits a different crystal size, being 20–25 nm for that obtained from pseudoboehmite and around 37 nm for bayerite. The highest yield of mullite formation may be achieved with xerogels of pseudoboehmite with the stoichiometric mullite compositions, 3Al₂O₃·SiO₂.     

Reaction mechanism for the formation of intermetallic compounds from layered Sm/Fe powder obtained by mechanical milling

Solid-state reactions in layered Sm/Fe powder particles with an overall composition of Sm₁₂Fe₈₈, obtained by ball milling, have been investigated by X-ray diffraction. During annealing at 500C, one reaction, Sm+2FeSmFe₂ was observed in the time-range studied. However, during annealing at 800C, five reactions were observed: Sm+2FeSmFe₂, Sm +3FeSmFe₃, 2Sm+17FeSm₂Fe₁₇, 2SmFe₂+13FeSm₂Fe₁₇, and 2SmFe₃ +11FeSm₂Fe₁₇. It is proposed that such reactions occur by a nucleation and growth process. Reactions of samarium with iron can be governed by nucleation; Sm/Fe interfaces possessing a higher free energy per unit area can play an important role in the nucleation. The observed results are discussed.     

Synthesis and Luminescent Properties of ZnGa2S4:Eu,F and ZnGa2O4:Eu,F

ZnGa₂S₄:Eu,F and ZnGa₂O₄:Eu,F were synthesized and characterized by x-ray diffraction and photoluminescence (PL) measurements. ZnGa₂S₄:Eu,F has a tetragonal structure (sp. gr. ) with a= 5.272 Å and c= 10.451 Å, and ZnGa₂O₄:Eu,F has a cubic structure (sp. gr. Fd3m) with a= 8.32 Å. The PL spectrum of ZnGa₂S₄:Eu,F consists of a broad band (FWHM = 1.11 eV) at 565 nm due to the Eu²⁺ 5D ¹ 7F ² transition, and the spectrum of ZnGa₂O₄:Eu,F shows four emissions due to the Eu^{3+ 5} D ₀ ⁷ F ₄ (_max = 682 nm), ⁵ D ₀ ⁷ F ₂ (_max = 615 nm), ⁵ D ₀ ⁷ F ₁ (_max = 595 nm), and ⁵ D ₀ ⁷ F ₀ (_max = 584 nm) transitions.     

Amplifier based on a field-effect triode with negative current feedback

Conclusions A field-effect triode amplifier with series negative current feedback allows a voltage gain of the order of 200–300 to be obtained for a load resistance R_s1 M. The coefficient K_u begins to decrease noticeably only for a feedback resistance above 500 .The current gain reaches (8–10)·10³. Increasing the resistances R_s and R_L to hundreds of ohms has practically no effect on K_i. For a further increase of R_s and R_L the coefficient K_i decreases.The power gain reaches its maximum value (of the order of 10⁴ or more) for R_s100 and R_L=10–100 k. An increase in R_s leads to a reduction of K_pmax and to a shift of the extremum of the function K_p=f(R_L) into the range of higher values of R_L.A large input resistance of the amplifier (tens of megohms and higher) is obtained when R_s increases to 10–100 M. The maximum input resistance is obtained for R_L and R_s and may exceed values of from hundreds of megohms to several gigaohms. The minimum input resistance is hundreds of kilohms for R_L and R_s0.The minimum input resistance (5–10 k or less) is ensured for R_g and R_L0. An increase of the output resistance to hundreds of megohms or higher occurs for R_g and R_s.Translated from Izmeritel'naya Tekhnika, No. 9, pp. 67–70, September, 1971.     

X-ray diffraction and Ir-absorption characteristics of lanthanide orthophosphates obtained by crystallisation from phosphoric acid solution

Powders of LnPO₄ · H₂O (Ln = La, Ce, Pr, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb, Lu and Y) prepared by crystallisation from boiling phosphoric acid (2 M H₃PO₄/1) solution were characterised by X-ray diffraction and FTIR-spectroscopy. Hexagonal LnPO₄ · H₂O (La Tb), tetragonal (Ho Lu and Y) and orthorombic DyPO₄ · H₂O crystalline modifications were identified. Ir-spectra of the hydrated hexagonal, anhydrous tetragonal LnPO₄ · H₂O (Dy, Ho, Er, Tm, Yb, Lu and Y) and anhydrous monoclinic (La Tb) are consistent with those reported in the literature. However, the hydrated tetragonal LnPO₄ · H₂O (Ho, Er, Tm, Yb, Lu and Y) display a surplus band (625 cm^–1) in the region of ₄, which was not reported in the literature. The band disappears after ignition at 950°C, while the tetragonal structure is still maintained, which may imply that it is attributed to hydrogen bonding of H₂O molecules to the phosphate oxygen in hydrated salts. Some of the phosphates, after ignition at 950°C, display additional P₂O₇ ^4– band at 1265–1267 cm^–1. That may be resulted from HPO₄ ^2– for PO₄ ^3– substitution in the phosphates crystallised in acidic (2 M H₃PO₄/1) solution.     

Spin-polarization effect on electron attachment to atomic hydrogen on liquid helium surface

No Heading Reaction rates of electron attachment to atomic hydrogen are measured as a function of magnetic field. The reaction takes place in a two-dimensional mixture of hydrogen atoms and electrons on liquid helium surface. Surface electron density, measured by using vibrating capacitor electrometer technique, decreases when H atoms are introduced. Applied high magnetic field suppresses electron attachment, H + e^– H^–, as well as hydrogen recombination, H + H H₂. Since the electronic state of negative hydrogen, H^–, is spin singlet, electron attachment is suppressed by spin-polarization. Possible microscopic mechanisms to explain the measured magnetic field dependence of the reaction kinetics are discussed.PACS numbers: 67.65.+z, 68.     

Interface reaction between oxide glasses and Fe-Al-Si magnetic alloy

The interface reactions between oxide glasses and magnetic alloy, Fe-Al-Si (so-called Sendust), were analysed. The oxide glasses used were SiO₂-PbO, SiO₂-Na₂O, SiO₂-Li₂O and B₂O₃-Na₂O binary glasses. It was observed that the lattice constant of the alloy decreases and the saturation magnetic-flux density of the alloy increases on reaction with the glasses. It was found that the aluminium atoms in the alloy diffuse to the interface and dissolve into the glass melt as Al³⁺ ions, leading to the iron-rich composition of the alloy. On the other hand, Pb²⁺, Na⁺ and H⁺ ions in the molten glasses were reduced at the interface. Metallic lead particles about 20 m in diameter were found to be dispersed in the SiO₂-PbO melt. Reduced sodium was thought to evaporate from the SiO₂-Na₂O melt, and H₂ gas bubbles were observed at the interface between B₂O₃-Na₂O melt and the alloy. These reactions were analysed based on the standard free energy diagrams of oxidation-reduction reaction, and expressed as 3Pb _glass ²⁺ +2Al_alloy 3Pb+2Al _glass ³⁺ 3Na _glass ⁺ +Al_alloy 3Na+Al _glass ³⁺ 6H _glass ⁺ +2Al_alloy 3H₂+2Al _glass ³⁺     

Influence of Stefan Flow and Convection on the Kinetics of Chemical Reactions and Heat and Mass Exchange of Carbon Particles with Gases

The problem of the heat and mass transfer and the kinetics of chemical transformation of a carbon particle (C + O₂ CO₂ (I), 2C + O₂ 2CO (II), C + CO₂ 2CO (III)) is solved within the framework of the model of a reduced film with account for the Stefan flow and natural and forced convection. Analytical expressions are obtained for the velocity of the Stefan flow, the rates of chemical reactions, the concentrations of gaseous components, the densities of the heat and mass fluxes, and the density of chemical heat release on the surface of the carbon particle.     

Photoreaction of a ZnO gel film chemically modified with β-diketones

Chelate formation is confirmed by a red shift of the n * absorption peak of benzoylacetone (BzAcH) from 309 to 336 nm with its addition to a sol containing Zn²⁺ ions. The chelate bonds between Zn²⁺ and BzAc^– are mostly maintained in the gel film prepared from the sol. Irradiation of the gel film by a Xe lamp with a cut filter (_ex > 300 nm) in the presence of H₂O leads to decomposition of the chelate ring. As a result of the photolysis, ZnO–H groups, CH₃CHO and other carbonyl compounds are generated with the lost of CH₃ groups of the BzAc^– ligand and H₂O involved in the film. INDO/S calculations on a model complex (Zn(BzAc)(OEt)) assign the n * absorption to the electronic transition from a non-bonding molecular orbital (MO) distributed mainly at the phenyl group to an anti-bonding MO localized at the CO bonds. On the basis of these results, a photo-induced hydrolysis mechanism was presented to explain the formation of positive-type patterned ZnO films.     

Spectrochemical studies on charge transfer bands due to d0, d5 and d10 ions in a sodium silicate glass

Titanium, vanadium and copper are normally present in glasses in their variable valency states but only Ti⁴⁺ (3d⁰), V⁵⁺ (3d⁰) and Cu⁺ (3d¹⁰) ions were found to exhibit charge transfer bands in glasses in the ultra-violet region of light. The molar extinction coefficients of these ions were calculated at their wavelength maxima in a 30Na₂O·70SiO₂ glass using Beer's-Bouger's equation and the intensities of their bands were found to lie of the order of around 10³ gm mol lit^–1cm^–1. The values of the molar extinction coefficients for these ions were compared with those of Ce⁴⁺ (5d⁰), Cr⁶⁺ (3d⁰) and Fe³⁺ (3d⁵) ions calculated earlier in 30Na₂O·70SiO₂ glass at their wavelength maxima in UV-region. The mechanism of electronic transition was suggested as L M, M L and M L M charge transfer available till date as a result of absorption of high energy UV-radiation extensively for d⁰, d⁵ and d¹⁰ ions respectively in glass depending upon the glass melting conditions. The low energy tail, of the UV-bands due to all these ions were found to obey Urbach's Rule in the present sodium silicate glass. The intensities of the charge transfer bands due to these ions are expected to depend upon their nature and symmetries, electronic configurations and wavelength of maximum absorption in the glass.     

Absorption and Circular Dichroism Spectra of Bi12SiO20<Nd> Crystals

The absorption and circular dichroism spectra of Nd-doped Bi₁₂SiO₂₀ crystals were measured in the range 10000 to 20000 cm^–1. The spectra showed electronic transitions related to only one type of Nd-related center: Nd substituting for Bi in position with symmetry C ₁. The bands due to the transitions from the first Stark component of the ground state to Stark components of excites states (⁴ I _9/2 ⁴ G _5/2, ⁴ I _9/2 ² G _7/2, and ⁴ I _9/2 ⁴ G _7/2) were analyzed in detail. The dipole strength D _0k , rotatory power R _0k , and anisotropy factor G _0k of these transitions were calculated. The intensities of transitions to Stark components were shown to vary by more than one order of magnitude within an excited-state multiplet. The anisotropy factors of the ⁴ I _9/2 ² G _7/2 and ⁴ I _9/2 ⁴ G _7/2 transitions, allowed in the magnetic dipole approximation, are, on the average, larger than that of the ⁴ I _9/2 ⁴ G _5/2 transition, which points to a significant contribution of the magnetic moment (<>²) to the total intensity of the transition.     

The effect of a Cr2O3-addition on the phase transformation and catalytic properties of γ-Al2O3 in treatment of lean-burn exhausts

The solid-state thermal behaviour of -Al₂O₃ doped with 10 mol% Cr (oxide) was studied with respect to phase-transition behaviour and the co-ordination of the dopant Cr cations. A series of transformations: -Al₂O₃ -Al₂O₃ -Al₂O₃ -Al₂O₃ was observed for Cr₂O₃-doped alumina samples between 500 °C and 1100 °C. Rapid grain growth occurred at temperatures close to 1100 °C. The electron spin resonance (ESR) spectra for the sample heat-treated at 500 °C corresponded to the resonance of -Cr³⁺ in an amorphous Cr oxide impregnated onto the - and -alumina support. The change of ESR spectrum indicated the existence of Cr³⁺, suggesting the formation of a solid solution with the same structures as -Al₂O₃ and/or -Al₂O₃ at 800–1000 °C. The evaluation of catalytic activities for model exhaust was performed under lean-burn (an excess of oxygen) condition of air/fuel ratio A/F = 18 and space velocity SV = 100 000 h^–1 . The modified Al₂O₃ catalyst heat-treated at 1000 °C in air showed removal conversion of 100% for hydrocarbon (C₃H₆), 92% for CO and 5% for NO at 550 °C. Present results suggest that Cr-modification to Al₂O₃ leads to catalytic improvement with good thermal durability.