Sorption of CH<Subscript>3</Subscript><Superscript>131</Superscript>I from water vapor-air medium on porous inorganic sorbents containing triethylenediamine and <Emphasis Type="Italic">d</Emphasis> element nitrates

Sorption of CH₃ ¹³¹I from a water vapor-air medium on porous inorganic sorbents based on silica gel of KSKG grade and containing triethylenediamine (CH₂-CH₂)₃N₂ and d element nitrates was studied. The sorbents prepared by impregnation with (CH₂-CH₂)₃N₂ and Zn, Ni, and Cu nitrates from aqueous solution recover CH₃ ¹³¹I from a water vapor-air flow poorly (degree of recovery <10%). Calcination of the sorbents at temperatures exceeding 250°C does not noticeably affect their sorption power. Heating of the complex Ag(NO₃)(OH)·(CH₂-CH₂)₃N₂H to 160°C causes its exothermic decomposition with a large heat release and formation of metallic silver. Thermal decomposition of the complex of Cu²⁺ with (CH₂-CH₂)₃N₂, synthesized from an aqueous solution at the molar ratio Cu(NO₃)₂: (CH₂-CH₂)₃N₂ = 1: 2, occurs similarly.     

Sorption of 131I2 and CH3 131I from gas-water vapor medium with porous inorganic sorbents containing d elements

Sorption of ¹³¹I₂ and CH₃ ¹³¹I from gas-water vapor medium on porous inorganic sorbents based on silica gel of the MSKG type, containing d elements, was studied. Sorbents containing Zn, Ni, Cu, and Co ammoniates show a low degree of recovery of ¹³¹I₂ and CH₃ ¹³¹I from the gas-water vapor flow (less than 30%); their calcination at a temperature above 250°C does not noticeably affect the sorption power of the sorbent. The sorbents containing Zn, Ni, and Cu nitrates, both unmodified and modified, show a low degree of recovery of CH₃ ¹³¹I from the gas-water vapor medium (less than 1%). At the same time, whereas for unmodified sorbents the degree of recovery of ¹³¹I₂ from the gas-water vapor phase does not exceed 70%, their modified analogs have higher degree of absorption of ¹³¹I₂ (more than 99%), comparable with the similar data for Ag-containing sorbents based on silica gel of the MSKG type.     

Sorbents for treatment of water vapor-air flows to remove volatile organic compounds of radioactive iodine

Sorption of CH₃ ¹³¹I from water vapor-air medium on Fizkhimin and Siloksid inorganic sorbents and on SKT-3I activated carbon was studied. The sorption power of Fizkhimin, Siloksid, and SKT-3I sorbents toward CH₃ ¹³¹I was examined (1) after their 20-h contract with water, followed by removal of the liquid phase and drying at 110°C; (2) after 4-h treatment with steam (95–98°C), followed by drying at 25°C; (3) after keeping for 9 months in 100% humid air at ambient temperature of 10 to 45°C; and (4) after treatment with a water vapor-air flow (95–98°C, 60–80 vol % water vapor) for 2 h. In most cases, Fizkhimin sorbent and SKT-3I activated carbon preserve high sorption efficiency toward CH₃ ¹³¹I from water vapor-air flow.     

Sorption of CH3 131I from a water vapor-air flow onto inorganic sorbents containing Ag and nonferrous metals (Cu,Ni, Zn)

Sorption of CH₃ ¹³¹I from a water vapor-air medium onto Fizkhimin inorganic sorbents containing Ag and nonferrous metals (Cu, Ni, Zn) was studied. Ag-free Fizkhimin inorganic sorbents exhibit poor ability to take up CH₃ ¹³¹I. No more than 51% of the initial 10-mg portion of CH₃ ¹³¹I is taken up by the sorbents heated to 350°C. The sorbents containing 1.4–2 wt % Ag and 5.6–8 wt % nonferrous metal (Cu, Ni, Zn) show high ability to take up CH₃ ¹³¹I (>99.8% uptake), with the performance of the Ni-containing sorbents remaining very high (>99.9%) with variation of various parameters of both the sorbents and the medium. The Cu- and Zn-containing analogs do not exhibit such properties.     

Removal of volatile radioactive iodine compounds from water vapor–air medium

Sorption of CH₃ ¹³¹I and ¹³¹I₂ from water vapor–air medium onto SiO₂–C (2 wt %) composite material and a mixture of SKT-3I with SiO₂–Cu⁰ (10 wt %) was studied. SKT-3I shows high performance in sorption of ¹³¹I₂ and CH₃ ¹³¹I. The degree of localization of ¹³¹I₂ and CH₃ ¹³¹I exceeds 99.99% at ~60°С and gas phase–sorbent contact time τ of ~0.45 s. The degree of sorption of ¹³¹I₂ and CH₃ ¹³¹I onto the SiO₂–C (2 wt %) composite material under similar conditions does not exceed ~87 and ~8%, respectively. Experiments on ¹³¹I₂ and CH₃ ¹³¹I sorption onto mechanical mixtures of SiO₂–Cu⁰ and SKT-3I in the weight ratio varied from 1: 4 to 1: 1 showed that the degree of the ¹³¹I₂ and CH₃ ¹³¹I sorption at ~60°С and τ ~0.45 s exceeded 99.95 and 99.0%, respectively. The scheme of layer-by-layer arrangement of SiO₂–Cu⁰ and SKT-3I in the column was examined. It shows promise for use in AUI-1500VM filters in ventilation systems of nuclear power plants.     

Recovery of <Superscript>131</Superscript>I and <Superscript>137</Superscript>Cs from a solution simulating NPP trap waters

Sorption of ¹³¹I and ¹³⁷Cs from a solution simulating NPP trap waters on various inorganic and organic sorbents was studied. The highest degree of ¹³¹I recovery (>99%) can be attained with Fizkhimin granulated sorbents based on coarsely porous silica gel containing Ag and Ni in 1: 4 ratio, with K _d for ¹³¹I exceeding 10⁵ ml g⁻¹ at V/m = 10³ ml g⁻¹ and contract time of the solid and liquid phases of 120 min. Elevation of the solution temperature to 40°C does not affect the degree of ¹³¹I and ¹³⁷Cs recovery. The degree of ¹³⁷Cs recovery in all the experiments did not exceed 35%. The degree of ¹³¹I recovery by coprecipitation with AgCl and Ag₄[Fe(CN)₆] was about ∼96% and only 65%, respectively.     

Recovery of 137Cs, 90Sr, 90Y, and d-element ions from aqueous solutions with sorbents containing triethylenediamine

The possibility of using sorbents based on KSKG coarsely porous silica gel and containing triethylenediamine N(CH₂-CH₂)₃N (TEDA) for recovering ¹³⁷Cs, ⁹⁰Sr, ⁹⁰Y, and d-element ions (Cu²⁺, Ni²⁺) from aqueous solutions was examined. Both ⁹⁰Sr, ⁹⁰Y radionuclides and Cu²⁺, Ni²⁺ ions are sorbed on KSKG containing 0.01–6.72 wt % TEDA. However, on sorbents based on KSKG and containing complexes of Cu²⁺, Ni²⁺, and Zn²⁺ nitrates with TEDA, the ¹³⁷Cs, ⁹⁰Sr, and ⁹⁰Y radionuclides are not sorbed. The equilibrium in the systems with these sorbents is attained within 3 h. The sorption capacity for Cu²⁺ and Ni²⁺ strongly depends on the conditions of the sorbent synthesis. The capacity of the sorbents for Cu²⁺ varies from 63 to 320 mg of metal per gram of sorbent. For Ni²⁺, the sorption capacity is considerably lower (no more than 130 mg of Ni²⁺ per gram of sorbent). The distribution coefficients of ⁹⁰Sr and ⁹⁰Y are 300–700 ml g^?1 at the contact time of the solid and liquid phases of 96 h and V/m = 100 ml g^?1.     

The mechanism of N-H bond decomposition in silicon nitride films

Thin dielectric films produced by the ammonolysis of monosilane in the temperature range 750–900 °C have 5–30% of their nitrogen atoms and 0.5–5% of their silicon atoms chemically bonded with hydrogen.We investigated the process of N-H bond decomposition under heat treatment at 900–1100 °C in vacuum and in different ambient gases by means of multiple internal reflection spectroscopy in the IR. It was found that in vacuum or in an inert gas ambient the activation energy of the process is 65 ± 2 kcal mol^?1, which is close to the N-H bond dissociation energy. When hydrogen or ammonia are added to the inert gas the activation energy of the process increases; pureammonia (P_NH3 = 1.01 × 10³ hPa) or hydrogen (P_h2 = 1.01 × 10³ hPa) suppress the decomposition entirely. The mechanism of the process and some features of the degradation of MNOS memory devices are discussed.     

Sorption of I2 and CH3 131I on ion-exchange materials from aqueous solutions at 20°C

Sorption of I₂ and CH₃ ¹³¹I from aqueous solutions at 20°C on the materials obtained by modification of KU-2 cation-exchange resin was studied. It was found that these materials are able to absorb I₂ both from distilled water and from a solution whose composition corresponds to the composition of aqueous coolant of the primary circuit of NPPs equipped with reactors of the WWER type, with the distribution coefficients K _d higher than 10³ ml g^?1 at the ratio V/m = 100 ml g^?1. Practically complete absorption of I₂ (>95%) is reached in 15 min. It was shown that AV-18 anion-exchange resin extracts CH₃ ¹³¹ I from aqueous solution with a distribution coefficient K _d exceeding 300 ml mg^?1 at the ratio V/m = 100 ml g^?1.     

Decomposition of uranyl nitrate in the silica gel matrix under the action of microwave radiation

Decomposition of aqueous solutions of uranyl nitrate in a matrix of granulated silica gel of KSKG grade under the action of microwave radiation (MWR) was studied. Microwave irradiation leads not only to formation of solid decomposition products UO₃, UO₂(OH)NO₃, and their hydrates in pores of KSKG granules, but also to accumulation of gaseous NO _x and H₂O. The presence of NO _x in KSKG pores leads to HNO₃ formation in the course of washing of sorbent granules with water. This prevents hydrolysis of uranyl nitrate and formation of UO₂(OH)₂·H₂O in KSKG pores. Washout of uranium with water and HClO₄ solutions from the KSKG fraction containing products of decomposition of 2 and 10 g of the initial UO₂(NO₃)₂·6H₂O under the action of MWR (hereinafter denoted as KSKG-P-I) was studied. Upon ∼7-day contact of the solid and liquid phases at the total ratio S : L = 1 : 20, from 5 to 14% of U passes into the aqueous phase from KSKG-P-I samples obtained in experiments with 10 and 2 g of UO₂(NO₃)₂·6H₂O, respectively. In the course of repeated treatments of KSKG-P-I with water, pH of the wash water increased from 3 to 6, owing to removal of NO _x from KSKG pores. Then an insoluble phase of uranyl hydroxide UO₂(OH)₂·H₂O, which can also be presented as hydroxylated uranium trioxide UO₃·2H₂O, is gradually formed from the solution obtained by treatment of KSKG-P-I with water. On treatment of KSKG-P-I with HClO₄ solutions (pH 1–2), virtually all uranium species formed by MWR treatment of aqueous uranyl nitrate solutions in KSKG matrix dissolve (at a contact time of the solid and liquid phases of ∼21 days, the amount of U that passed into HClO₄ solutions is ∼90%). The amount of the U form that is not extracted with HClO₄ solutions and remains in KSKG granules is ∼12% of its initial amount. X-ray phase analysis suggests that the uranium species remaining in KSKG are silicate compounds formed by sorbent saturation with a uranyl nitrate solution and subsequent MWR treatment.     

Localization of CH<Subscript>3</Subscript><Superscript>131</Superscript>I from Water vapor–Air flow on granulated sorbents containing nanoparticles of Ag and Ni compounds

Sorption of CH₃ ¹³¹I from the water vapor–air medium onto Fizkhimin inorganic sorbents containing nanoparticles of Ag and Ni compounds was studied. The developed solvents containing 2 wt % Ag and 4–10 wt % Ni exhibit high performance in CH₃ ¹³¹I sorption (>99.9% uptake). The sorption efficiency remains very high (>99.9%) as characteristics of the sorbents and the medium are varied.     

The chemical vapour deposition and characterization of ZrO2 films from organometallic compounds

ZrO₂ films were deposited on silicon substrates by oxygen-assisted decomposition of zirconium-β-diketonates at temperatures of 400–550°C. The deposits, fine-grained nearly stoichiometric monoclinic ZrO₂, were hard and showed strong adherence to the substrate. The films were characterized by transmission electron microscopy, X-ray diffraction and electron microprobe analysis and by measuring their dielectric and optical properties. The index of refraction was found to be 2.18, and the optical energy band gap was found to be 5.16 eV. The dielectric constant at 1 MHz was 17–18, and the dielectric strength varied between 1 × 10⁶ and 2.0 × 10⁶ V cm^?1. Capacitance-voltage measurements at 1 MHz indicated the presence of effective surface states with a concentration in the range (1.0?6.0) × 10¹¹cm^?2 for films deposited at temperatures above 500°C or for films deposited at 400–450°C and annealed at above 750°C. The flat-band voltages were between ?0.6 and + 0.2 V. The films showed satisfactory bias-temperature stability. The current-voltage characteristic followed an I ∝ V² dependence for negative bias and an I ∝ V^2.6 to I ∝ V^3.4 dependence for positive bias.     

In situ X-ray diffraction study of the effects of germanium and nickel concentrations on melting in gold-based contacts to gallium arsenide

Using X-ray diffraction in situ at 1 atm, the melting of the as-deposited film and the formation of the reaction product was investigated for gold, Au-Ge and Au-Ge-Ni contacts with various germanium and nickel concentrations. For the Au-Ge contact, the melting temperature of the as-deposited film was found to be 512±12 °C, 486±13 °C, 363±12 °C, and 363±12 °C with germanium concentrations of 0 wt.%, about 0.6 wt.%, 3 wt.% and 12 wt.% respectively. For the Au-Ge-Ni contacts, the melting temperature of the as-deposited film was 363±12 °C, 363±12 °C and 413±11 °C with germanium concentrations in the range 10–12 wt.% and nickel concentrations of 0 wt.%, 4 wt.% and 17 wt.% respectively. On subsequent cooling after the melting of the contact film, Au₇Ga₂ formed in Au-Ge contacts with 0–3 wt.% Ge and it melted on second heating at 405±5 °C, 387±18 °C and 337±12 °C for germanium concentrations of 0 wt.%, about 0.6 wt.% and 3 wt.% respectively. On subsequent cooling after the melting of the contact film, Au₂Ga formed in Au-Ge contacts with 12 wt.% Ge and Au-Ge-Ni contacts; Au₂Ga melted on second heating at 363±12 °C for Au-Ge-Ni contacts with 12 wt.% Ge and 4 wt.% Ni, and at 413±11 °C for Au-Ge-Ni contacts with 10 wt.% Ge and 17 wt.% Ni. Hence germanium decreased the melting temperatures of α-AuGa (gold-rich solid solution) and Au₇Ga₂ because of the presence of dissolved germanium in these phases. In addition, nickel increased the melting temperature of α-AuGa (gold-rich solid solution) and Au₂Ga owing to the presence of dissolved nickel in these phases.     

Lanthanum samarium oxalate — its growth and structural characterization

Lanthanum samarium oxalate (LSO) single crystals are grown in silica gels by the diffusion of a mixture of aqueous solutions of lanthanum nitrate and samarium nitrate into the test tube having the set gel impregnated with oxalic acid. Tabular crystals of LSO having well defined hexagonal basal planes are observed at different depths inside the gel. LSO crystals grown by this method are colourless and transparent. Laue transmission X-ray diffraction pattern of LSO reveals well defined spots with two-fold symmetry along the horizontal axis. Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) support that LSO loses water around 120°C, and CO and CO₂ around 350–450°C. The infrared (IR) absorption spectrum of LSO establishes the presence of oxalate (C₂ O₄)²⁻ ions. Energy dispersive X-ray analysis (EDAX) confirms the presence of La and Sm in the sample. X-ray photoelectron spectroscopic (XPS) studies of LSO confirm the presence of La and Sm in their respective oxide states. An empirical structure for LSO has been proposed on the basis of these findings.     

Silica‐Templated Synthesis of Ordered Mesoporous Tungsten Carbide/Graphitic Carbon Composites with Nanocrystalline Walls and High Surface Areas via a Temperature‐Programmed Carburization Route

Ordered mesostructured tungsten carbide and graphitic carbon composites (WC/C) with nanocrystalline walls are fabricated for the first time by a temperature‐programmed carburization approach with phosphotungstic acid (PTA) as a precursor and mesoporous silica materials as hard templates. The mesostructure, crystal phase, and amount of deposited graphitic carbon can be conveniently tuned by controlling the silica template (SBA‐15 or KIT‐6), carburizing temperature (700–1000 °C), the PTA‐loading amount, and the carburizing atmosphere (CH₄ or a CH₄/H₂ mixture). A high level of deposited carbon is favorable for connecting and stabilizing the WC nanocrystallites to achieve high mesostructural regularity, as well as promoting the carburization reaction. Meanwhile, large pore sizes and high mesoporosity of the silica templates can promote WC‐phase formation. These novel, ordered, mesoporous WC/C nanocomposites with high surface areas (74–169 m² g^?1), large pore volumes (0.14–0.17 cm³ g^?1), narrow pore‐size distributions (centered at about 3 nm), and very good oxidation resistance (up to 750°C) have potential applications in fuel‐cell catalysts and nanodevices.     

Spark plasma sintering and decomposition of the Y<Subscript>3</Subscript>NbO<Subscript>7</Subscript>:Eu phase

The spark plasma sintering (SPS) of Eu³⁺-doped Y₃NbO₇ niobate phase was investigated to obtain dense ceramics. Although SPS allowed obtaining high-density ceramics, decomposition of the niobate phase occurred at high temperature and was promoted by the SPS process, which limited its use as an optical material. The niobate phase has been prepared by two synthesis methods: a solid-state route and a sol–gel method. The purity, density and microstructure of the dense ceramics were analyzed after spark plasma sintering. Translucent ceramics were only obtained from sol–gel powders after SPS at 1600 °C during 20 min with a heating rate of 5 °C/min. The sintering study of the pure niobate phase showed that during SPS process and especially in the presence of the high electrical field the Y₃NbO₇ phase is metastable at 1600 °C. A decomposition of the niobate compound is clearly demonstrated by luminescence measurements when high heating rates were used.     

Recovery of iodine and cesium radionuclides localized on granulated sorbent Fizkhimin from air-vapor phase

A procedure for recovery of ¹³¹I and ¹³⁷Cs radionuclides from Fizkhimin sorbent containing ¹³⁷Cs¹³¹I and ¹³⁷CsOH radioaerosols and also of Ag¹³¹I formed in the sorbent matrix during chemisorption of gaseous ¹³¹I₂ and CH₃ ¹³¹I was developed. Sequential treatment of the sorbent with 6.0 M HNO₃ and then 10.0 M N₂H₄·nH₂O allows practically complete (more than 99%) removal of ¹³⁷Cs and noticeable decrease of the ¹³¹I content in the sorbent matrix (in some cases, by a factor of more than 10).     

The preparation and characterization of dense,highly conductive Na5GdSi4O12 nasicon (NGS)

Na₅GdSi₄O₁₂ has been prepared via conventional ball-milling technique and through spray-freezing/freeze-drying. The ball-milled materials were calcined at 700°C or 925°C and sintered at 1050°C/3.5h to 89% dense multiphase ceramics. Spray-frozen/freeze-dried powders were calcined at 530°C and sintered at 1050°C/25 min to 99 ± 1% theoretical density. The latter material was single-phase NGS nasicon with a 300°C resistivity of 3.8 Ω·cm, an activation energy for Na⁺-conduction of 4.4 kcal/mol, a flexural strength of 105 MPa, a duplex grain structure with average sizes 0.4 μm and 3 μm and a unique linear thermal expansion coefficient (25–540°C; α = 12.6 × 10^?6/°C±4%).     

Chemical vapor deposition and characterization of HfO2 films from organo-hafnium compounds

HfO₂ films were deposited on silicon substrates by the oxygen-assisted decomposition of hafnium β-diketonates at temperatures in the range 400–550 °C. These films were characterized by using transmission electron microscopy, X-ray diffraction, electron microprobe analysis and measurements of dielectric and optical properties. It was found that the films were fine-grained (approximately 325 Å) nearly stoichiometric monoclinic HfO₂. The films showed high resistance to most aqueous acids and bases. The deposits had a refractive index of 2.1 and an optical energy gap of 5.68 eV. The dielectric constant at 1 MHz was 22–25, and the dielectric strenght of the HfO₂ films varied between 2 × 10⁶ and 4.5 × 10⁶ V cm^?1. C-V measurements at 1 MHz indicated the presence of effective surface states which varied between 1.0 × 10¹¹ and 6 × 10¹¹ cm^t?2 for films that were deposited at temperatures higher than 500 °C or that were annealed at above 750 °C if deposited at 400–450 °C. The V_FB values were between ?0.6 and 0 V. The annealed films or films grown above 500 °C showed good bias-temperature stability. When positive bias and elevated temperatures were applied, the original C-V curve moved towards higher positive field values (0.2-0.5 V). After applying negative bias at elevated temperatures the C-V curved moved back in the direction of the original C-V curve. Measurements of the dependence of the current I on the electric field showed a dependence of I ∝ V² over a wide range.     

A novel route for the preparation of CoCr<Subscript>2</Subscript>O<Subscript>4</Subscript>/SiO<Subscript>2</Subscript> nanocomposite starting from Co(II)–Cr(III) carboxylate complex combinations

This study reports the preparation and characterization of the spinel CoCr₂O₄. In order to obtain 20% CoCr₂O₄/80% SiO₂ and 50% CoCr₂O₄/50% SiO₂ (mol%) nanocomposites, we have used a versatile pathway based on the thermal decomposition of some particular precursors, Co(II) and Co(III) carboxylate-type complex combinations, inside the SiO₂ matrix. The ligands of these coordination compounds result in the redox reaction between Co(II) and Cr(III) nitrates and 1,3-propylene glycol by heating at 150 °C of the gels (tetraethylorthosilicate–metal nitrates–1,3-propylene glycol). The as-obtained precursors, embedded in silica gels, were characterized by FT-IR spectrometry and thermal analysis. Both precursors decompose up to 350 °C, leading to the corresponding metal oxides inside the silica matrix. X-ray diffraction of the powders annealed at different temperatures has evidenced the formation of CoCr₂O₄ starting with 400 °C for 20% CoCr₂O₄/SiO₂ and 300 °C for 50% CoCr₂O₄/SiO₂. This behaviour can be explained by the fact that, by thermal decomposition of the chromium carboxylates, a nonstoichiometric chromium oxide Cr₂O_3+x is formed. At ~ 400 °C, Cr₂O_3+x turns to α-Cr₂O₃, which interacts with CoO leading to cobalt chromite nuclei inside the pores of the silica matrix. CoCr₂O₄ has been obtained as nanocrystallites homogenously dispersed within the silica matrix as resulted from XRD, TEM and EDX mapping, with mean particle size in the range 5–20 nm.