Kinetic study of the annealing of fission tracks in a Fe2O3KPO3 glass containing 100 ppm of uranium

The kinetics of the annealing of fission tracks in an artificial glass were studied using an optical microscope. The annealing experiments were performed in an electric furnace at 160–230°C for 15–160 min. The measurement of the fission tracks through an optical microscope was carried out after etching the annealed tracks with 10 N NaOH aqueous solution at 40°C. All reactions were found to be of first order within the annealing temperatures. An activation energy of 0.66 eV for the annealing reaction was obtained from the Arrhenius plot of the rate constants determined at 160, 190, 210, and 230°C.     

Neutron damage of hexagonal boron nitride: h-BN

Hexagonal boron nitride (h-BN) was neutron damaged at an integral flux of 2.40 × 10¹² n cm⁻² s⁻¹ for 1, 2, 3 and 4 h. The h-BN samples undergo a transition from sp² to sp³ hybridization as a consequence of the neutron induced damage with the formation of cubic boron nitride (c-BN) spots, as suggested both by FT–IR and Raman spectroscopy. In addition to c-BN, also a certain degree of amorphization is achieved by h-BN already at the lowest neutron fluence of 8.64 × 10¹⁵ n cm⁻² as clearly evidenced by Raman spectroscopy. The Wigner or stored energy to the radiation-damaged h-BN samples was studied by DSC and also in this case there was a clear evidence that the neutron damage was partly irreversible and insensitive to the thermal annealing up to 630 °C. Electron spin resonance (ESR) was employed to further study the structural defects induced by the neutron bombardment of h-BN. Two kinds of paramagnetic defective structures centered on ¹¹B atoms were identified.

     

57Fe-Mössbauer study of electrically conductive alkaline iron vanadate glasses

A relationship between local structure, thermal stability and electrical conductivity (σ) of xR₂O·10Fe₂O₃·(90 ? x)V₂O₅ glasses (abbreviated as xRFV glasses, where R = Li, Na, K; x = 20 and 40 in mol %) was investigated by ⁵⁷Fe-Mössbauer spectroscopy, X-ray diffractometry, differential thermal analysis (DTA) and DC two- and four-probe method. From DTA study, thermal stability of 20RFV glasses is lower than that of 40RFV glasses by evaluating Hruby parameter (K _gl). Constant activation energy for crystallization (E _a) of 2.5 eV obtained from both 20RFV and 40RFV glasses indicate that the crystallization proceeds with the cleavage of Fe–O bond having the energy of 2.6 eV. Isochronally annealed 20RFV glass at 400–450 °C resulted in the increase in electrical conductivity (σ) from the order of 10^?3 to 10^?1 S cm^?1, whereas slight decrease in σ was observed for 20RFV glass annealed above 460 °C. A paramagnetic doublet with an identical isomer shift (δ) of 0.39 mm s^?1 was observed in the ⁵⁷Fe-Mössbauer spectra of 20RFV glass after isothermal annealing conducted at 400–450 °C for 100 min, which caused a decrease of quadruple splitting (Δ) from 0.67 to 0.52 mm s^?1 for 20LiFV glass and from 0.66 to 0.53 mm s^?1 for 20NaFV glass. On the other hand, three paramagnetic doublets with δ and Δ of 0.40 and 0.25, 0.38 and 0.60, and 0.31 and 1.11 mm s^?1 respectively were observed for 20RFV glass annealed at 460–550 °C, reflecting precipitation of semiconducting FeVO₄ phase having σ of 6.0 × 10^?7 S cm^?1. It can be concluded that isochronal annealing of 20RFV glass below 450 °C resulted in increase in σ due to the structural relaxation, while annealing above 500 °C resulted in the decrease of σ due to the precipitation of FeVO₄ phase.     

Fabrication and characterization of an irradiation facility for large-sample geometry

An irradiation facility consisting of a modified beam port shielding plug has been designed, fabricated built and characterized for use in irradiating non-standard sample geometries. The shielding plug features a graphite moderator at the core end with a hole, or “well” drilled of sufficient diameter and depth to accommodate an eight ounce (227 gram) sample bottle. Added shielding behind the graphite consists of castable neutron- and -gamma-ray shielding. The modified shielding plug can be removed relatively quickly from its irradiation position to minimize personnel exposures. It is mounted in close proximity to the Ohio State University Research Reactor reactor core to allow performance of high-sensitivity neutron activation analysis studies. Using the SAND-II unfolding code, the energy-dependent neutron flux has been measured in the sample irradiation position. When operating at 100 % power, the total flux is 3.9 × 10¹² n/cm²/s. Of this, 55 % is thermal (<0.5 eV), 23 % is epithermal (>0.5 eV, <0.5 MeV), and 22 % is “fast” (>0.5 MeV). This makes the facility suitable for neutron activation studies. Recently it has been used for irradiation of filter papers collected in a study of particulate air pollution in the form of atmospheric particulate matter in an urban environment.     

Design calculation of a horizontal thermal neutronic beam for neutron radiography at the Syrian MNSR

The computer code MCNP4C and the ENDF/B-V cross-section library were used to design calculation of a horizontal thermal beam for neutron radiography (NR) at Syrian MNSR and to evaluate the safety of the reactor after installation of the NR facility (NRF). Thermal, epithermal and fast neutron energy ranges were selected as <0.30 eV, 0.30 eV–10.0 keV and >10.0 keV, respectively. To produce a good neutron beam in terms of intensity and quality, bismuth (Bi) and silicon (Si) were used as photon and neutron filters, respectively. The ratio of L/D of the NRF ranges between 90 and 125. The thermal neutron flux at the beam exit plane can be varied from 1.836 × 10⁵ to 3.057 × 10⁵ n/cm² s. If such thermal neutron beam would be built into the Syrian MNSR, many scientific applications of the NR would be available.     

Synthesis of highly pure nanocrystalline and mesoporous CaTiO3 by a particulate sol–gel route at the low temperature

The low temperature perovskite-type calcium titanate (CaTiO₃) thin films and powders with nanocrystalline and mesoporous structure were prepared by a straightforward particulate sol–gel route. The prepared sol had a narrow particle size distribution about 17 nm. X-ray diffraction and Fourier transform infrared spectroscopy revealed that, the synthesized powders had highly pure and crystallized CaTiO₃ structure with preferable orientation growth along (1 2 1) direction at 400–800 °C. The activation energy of crystal growth was calculated 5.73 kJ/mol. Furthermore, transmission electron microscope images showed that the average crystallite size of the powders annealed at 400 °C was around 3.5 nm. Field emission scanning electron microscope analysis and atomic force microscope images revealed that, the deposited thin films had uniform, mesoporous and nanocrystalline structure with the average grain size in the range 33–39 nm depending on annealing temperature. Based on Brunauer–Emmett–Teller (BET) analysis, the synthesized powders showed mesoporous structure with BET surface area in the range 51–21 m²/g at 400–800 °C. One of the smallest crystallite size and one of the highest surface areas reported in the literature is obtained which can be used in many applications, such as photocatalysts.     

Crystallite growth of rice husk ash silica

The effect of temperature of firing and time of annealing on crystallite size of silica obtained by burning boiled rice husk was studied by the X-ray broadening technique. The results showed that nuclei of disordered cristobalite were present in ash silica, and crystallite growth was governed by two processes, namely nucleation and growth taking place simultaneously with a rate varying with the temperature of treatment. The nucleation process manifested itself in the low temperature range of 800–900°C, while growth was more pronounced in the temperature range 1000–1100°C, occurring with different activation energies of 81.3 and 52.4 cal mole^?1, respectively. Both processes occurred with the same intensity at 964°C. A growth process and crystal perfection followed with an activation energy of 36.8 cal mole^?1.     

Sol–gel synthesis of Sm2InTaO7 and its photocatalytic activity on degradation of crystal violet dye and reduction of Cr(VI) ions

This paper reports the synthesis of Sm₂InTaO₇ and its photocatalytic activity on the degradation of crystal violet dye and reduction of Cr(VI) ions in aqueous solution. Sm₂InTaO₇ was prepared by sol–gel method at 1,200 °C. For comparison purposes, Sm₂InTaO₇ was prepared also by solid-state reaction at 1,400 °C. The evolution of the crystalline phases of the sol–gel sample with the annealing temperature was followed by X-ray diffraction. The cubic crystalline structure of Sm₂InTaO₇ was determined by Rietveld refinement method. Specific surface area was 5 m²g^?1 for sol–gel sample and 1 m²g^?1 for solid-state sample, whereas energy band gap was around 3.5 eV. Sm₂InTaO₇ prepared by sol–gel method showed better photocatalytic activity than Sm₂InTaO₇ prepared by solid-state reaction for the mineralization of crystal violet dye and reduction of Cr(VI) solution under UV-light irradiation.     

Synthesis and hydrogen absorption kinetics of V4Cr4Ti alloy

V₄Cr₄Ti alloy is synthesized by aluminothermy process followed by electron beam refining. Hydrogen absorption characteristics of the alloy have been evaluated by measuring the pressure composition isotherm (PCIT) at 57 °C temperature. Two plateau pressures are observed in the PCIT curve. Substantial decrease in the hydrogen absorption capacity of the alloy as compared to vanadium has been recorded. Hydrogen absorption kinetics of the alloy was investigated in the temperature range of 200–500 °C. Three-dimensional diffusion appears to be the rate controlling step of the hydrogen absorption. The apparent activation energy was calculated as 0.16 eV/atom-hydrogen.     

Growth Orientation of the Mechanosynthesized Fluorapatite-Based Composite Nanopowders: Influence of Subsequent Thermal Treatment

Growth orientation of fluorapatite–zirconia nanopowders was investigated after mechanical activation and thermal annealing process in the range of 600–1,300 °C for 1 h. Results revealed that during heating of the composite nanopowders the transition of the monoclinic zirconia to tetragonal form and its stabilization by calcium fluoride originating from the decomposition of fluorapatite as well as the formation of a solid solution of calcium fluoride in zirconia occurred. The influence of annealing on the growth orientation of fluorapatite–zirconia composite nanopowders indicated that the crystal growth of fluorapatite was preferentially accentuated on the (002) face in the direction of the crystallographic c-axis after heat treatment. Based on FE–SEM observations, the experimental outcome was composed of both agglomerates and fine particles (~33 nm) after 600 °C, while annealing of the sample at 1,300 °C demonstrated the occurrence of abnormal grain growth.     

Low-temperature synthesis of hexagonal barium ferrite (BaFe<Subscript>12</Subscript>O<Subscript>19</Subscript>) nanoparticles by annealing at 450 °C followed by quenching

Citrate precursor method has been used to obtain nanosized particles of barium hexaferrite at low temperatures. Samples were annealed at 450 °C for 3 and 5 h. Quenching of the third sample was done by taking the crucible out from the muffle furnace after annealing it for 5 h and putting it abruptly into an ice bath. The saturation magnetization has been found to be 4.36 and 0.04 emu g^?1 for the samples obtained upon annealing at 450 °C for 3 and 5 h, respectively, while that of the quenched sample has been found to be 4.61 emu g^?1. In case of the sample obtained after 5-h annealing, the squareness value was found to be maximum indicating significance in memory and switching applications. For the quenched and the 3-h annealing products, the magnetic data values are similar. Creation of spin disorders on the surface upon prolonged annealing, due to disappearance of oxygen ions and subsequent breakage of superexchange interactions between cations, has been undone upon quenching. The XRD and TEM data indicate that the particle size (9–17 nm) gets lower in case of the quenched samples. Photoluminescence study of the quenched sample furnished prominent peaks in UV, visible and near-IR regions under 200-nm excitation. The TG–DSC data were analysed for the kinetic parameters, activation energy (E), pre-exponential factor (A) using the Kissinger isoconversion and the Ozawa–Flynn–Wall methods for the first-step decomposition of the quenched sample.     

Sensor Performance of Nanostructured TiO<Subscript>2</Subscript>–SnO<Subscript>2</Subscript> Films Prepared by an Aqueous Sol–Gel Process

Nanostructured TiO₂–SnO₂ thin films and powders were prepared by a facile aqueous particulate sol–gel route. The prepared sols showed a narrow particle size distribution with hydrodynamic diameter in the range 17.2–19.3 nm. Moreover, the sols were stable over 5 months, since the constant zeta potential was measured during this period. The effect of Sn:Ti molar ratio was studied on the crystallisation behaviour of the products. X-ray diffraction analysis revealed that the powders were crystallised at the low temperature of 400 °C containing anatase-TiO₂, rutile-TiO₂ and cassiterite-SnO₂ phases, depending on annealing temperature and Sn:Ti molar ratio. Furthermore, it was found that SnO₂ retarded the anatase to rutile transformation up to 800 °C. The activation energy of crystallite growth was calculated in the range 0.96–6.87 kJ/mol. Transmission electron microscope image showed that one of the smallest crystallite sizes was obtained for TiO₂–SnO₂ binary mixed oxide, being 3 nm at 600 °C. Field emission scanning electron microscope analysis revealed that the deposited thin films had nanostructured morphology with the average grain size in the range 20–40 nm at 600 °C. Thin films produced under optimized conditions showed excellent microstructural properties for gas sensing applications. They exhibited a remarkable response towards low concentrations of CO gas at low operating temperature of 200 °C, resulting in increased thermal stability of sensing films as well as a decrease in their power consumption.     

Studies on the thermal behavior and decomposition kinetic of drugs cetirizine and simvastatin

Understanding the response of drugs and their formulations to thermal stresses is an integral part of the development of stable medicinal products. In the present study, the thermal degradation of two drug samples (cetirizine and simvastatin) was determined by differential scanning calorimetery (DSC) and simultaneous thermogravimetery/differential thermal analysis (TG/DTA) techniques. The results of TG analysis revealed that the main thermal degradation for the cetirizine occurs during two temperature ranges of 165–227 and 247–402 °C. The TG/DTA analysis of simvastatin indicates that this drug melts (at about 143 °C) before it decomposes. The main thermal degradation for the simvastatin occurs during two endothermic behaviors in the temperature ranges of 238–308 and 308–414 °C. The influence of the heating rate (5, 10, 15, and 20 °C min^?1) on the DSC behavior of both the drug samples was verified. The results showed that as the heating rate was increased, decomposition temperatures of the compounds were increased. Also, the kinetic parameters such as activation energy and frequency factor for the compounds were obtained from the DSC data by non-isothermal methods proposed by ASTM E696 and Ozawa. Based on the values of activation energy obtained by ASTM E696 method, the values of activation energy for cetirizine and simvastatin were 120.8 and 170.9 kJ mol^?1, respectively. Finally, the values of ΔS ^#, ΔH ^#, and ΔG ^# of their decomposition reaction were calculated.     

Influence of annealing temperature on the electrochemical and surface properties of the 5-V spinel cathode material LiCr0.2Ni0.4Mn1.4O4 synthesized by a sol–gel technique

LiCr_0.2Ni_0.4Mn_1.4O₄ was synthesized by a sol–gel technique in which tartaric acid was used as oxide precursor. The synthesized powder was annealed at five different temperatures from 600 to 1,000 °C and tested as a 5-V cathode material in Li-ion batteries. The study shows that annealing at higher temperatures resulted in improved electrochemical performance, increased particle size, and a differentiated surface composition. Spinel powders synthesized at 900 °C had initial discharge capacities close to 130 mAh g^?1 at C and C/2 discharge rates. Powders synthesized at 1,000 °C showed capacity retention values higher than 85 % at C/2, C, and 2C rates at 25 °C after 50 cycles. Annealing at 600–800 °C resulted in formation of spinel particles smaller than 200 nm, while almost micron-sized particles were obtained at 900–1,000 °C. Chromium deficiency was detected at the surface of the active materials annealed at low temperatures. The XPS results indicate presence of Cr⁶⁺ impurity when the annealing temperature was not high enough. The study revealed that increased annealing temperature is beneficial for both improved electrochemical performance of LiCr_0.2Ni_0.4Mn_1.4O₄ and for avoiding formation of Cr⁶⁺ impurity on its surface.     

Modifying transparent electrode with conjugated organic semiconductor hole transport material as interface for enhancing performance of organic solar cell

Indium tin oxide (ITO) is used as a substrate was covered with 4-[4-(4-methoxy-N-naphthalen-2-ylanilino) phenyl] benzoic acid (MNA) as a self-assembled monolayer (SAM). Poly(3-hexylthiophene) (P3HT) and 1-(3-methoxycarbonyl)-propyl-1-phenyl-(6,6) C₆₁ (PCBM) were mixed and used as a donor–acceptor in organic solar cell (OSC). The MNA (SAM) layer is used as an interface instead of poly(3,4-ethylenedioxythiophene) polystyrene sulfonate (PEDOT: PSS) for hole injection. The HOMO-LUMO energy level of MNA-SAM molecule and the electronic charge distribution were calculated theoretically using Chemissian software. The HOMO-LUMO energy level of the MNA is calculated as E_HOMO = ?5.10 eV and E_LUMO = ?1.60 eV. The OSC modified with MNA showed an efficient performance in the absence of PEDOT: PSS as hole transport layer. The annealing of the ITO/SAM/P3HT: PCBM films at different temperatures are also investigated to study the effect of reducing defects. The interface structures of the organic semiconductor layer on ITO were characterized by Atomic Force Microcopy (AFM). In addition, Kelvin Probe Microscopy (KPM) is used to understand how the annealing changes the surface potential energy of the ITO/SAM substrate. Using the KPM method, which measures the surface potential energy of the films, the energy bands of the ITO were increased to maximum 5.09 eV. The ITO/SAM/P3HT: PCBM film's surface potential was determined to be 0.18 eV after being annealed at 80 °C. The surface potential of the modified films was discovered to be 0.33 V and 0.39 V when the annealing temperature was raised from 80 °C to 120 °C and 160 °C. The maximum device efficiency was demonstrated by the ITO/SAM/P3HT: PCBM film after an hour of annealing at 160 °C.     

Effect of the catalyst MCM-41 on the kinetic of the thermal decomposition of poly(ethylene terephthalate)

The aim of this work is to determine the activation energy for the thermal decomposition of poly(ethylene terephthalate)—PET, in the presence of a MCM-41 mesoporous catalyst. This material was synthesized by the hydrothermal method, using cetyltrimethylammonium as template. The PET sample has been submitted to thermal degradation alone and in presence of MCM-41 catalyst at a concentration of 25% in mass (MCM-41/PET). The degradation process was evaluated by thermogravimetry, at temperature range from 350 to 500 °C, under nitrogen atmosphere, with heating rates of 5, 10 and 25 °C min^?1. From TG, the activation energy, determined using the Flynn–Wall kinetic method, decreased from 231 kJ mol^?1, for the pure polymer (PET), to 195 kJ mol^?1, in the presence of the material (MCM-41/PET), showing the catalyst efficiency for the polymer decomposition process.     

Carbonization and graphitization of pitch applied for anode materials of high power lithium ion batteries

The artificial graphite materials were prepared by carbonizing coal tar pitch using two methods, namely, one- and two-step processes, and all sintered samples were graphitized at 2800 °C. Effects of different heat treatments on the performance of the samples were characterized by scanning electron microscopy, transmission electron microscopy (TEM), X-ray diffraction, Brunauer–Emmett–Teller, electrochemical impedance spectroscopy (EIS), particle size analysis, polarized light microscopy, and charge–discharge measurements. All samples show a typical graphite crystalline structure; moreover, the degree of graphitization (g factor) and crystallite size along the c-axis (L _c ) were calculated from (002) peak. The polarized light microscopy indicates that the coke with carbonization at 700 °C has an obvious wide domain (D) optical structure, while that with two-step sintering at 400 and 700 °C has a mixed optical structures of wide D, flow domains, and mosaics. TEM analysis revealed a number of irregular graphene layer images which are caused by the defects of graphite. EIS shows that the sample carbonized by two-step has a larger diffusion coefficient than the sample carbonized at 700 °C by one step. Higher carbonization temperature leads to better cycle performance as the temperature increasing from 500 to 700 °C in the one-step route. Specifically, the charge (Li⁺ extraction) capacity at the 50th cycle increases from 318 mA?h?g^?1 to 357 mA?h?g^?1. The results show that the rate performance of the artificial graphite is improved with the addition of the presintering at 400 °C.     

Kinetics and reaction mechanism of isothermal oxidation of Iranian ilmenite concentrate powder

Thermal oxidation of commercial ilmenite concentrate from Kahnouj titanium mines, Iran, at 500–950 °C was investigated for the first time. Fractional conversion was calculated from mass change of the samples during oxidation. Maximum FeO to Fe₂O₃ conversion of 98.63 % occurred at 900 °C after 120 min. Curve fit trials together with SEM line scan results indicated constant-size shrinking core model as the closest kinetic mechanism of the oxidation process. Below 750 °C, chemical reaction with activation energy of 80.65 kJ mol^?1 and between 775 and 950 °C, ash diffusion with activation energy of 53.50 kJ mol^?1 were the prevailing mechanisms. X-ray diffraction patterns approved presence of pseudobrookite, rutile, hematite, and Fe₂O₃·2TiO₂ phases after oxidation of ilmenite concentrate at 950 °C.     

Reed straw derived active carbon/graphene hybrids as sustainable high-performance electrodes for advanced supercapacitors

Reed straw-derived active carbon@graphene (AC@GR) hybrids were prepared by one-step carbonization/activation process using a mixture of reed straw and graphene oxide (GO) as raw materials and ZnCl₂ as activation agent. The as-prepared hybrids exhibit high specific surface area in a range of 1971–2497 m² g^?1, abundant porosity, as well as excellent energy storage capability. The symmetric C//C supercapacitor using the hybrid obtained at 700 °C as electrodes demonstrates superior cycling durability, ca. 90 % retention after 6000 cycles at 2 A g^?1, and a high energy density of 6.12 Wh kg^?1 at a power density of up to 4660 W kg^?1 in 6 M KOH aqueous electrolyte. The excellent capacitive performance is attributed to the synergistic effect of AC and GR.     

Application of k 0-based internal monostandard NAA for large sample analysis of clay pottery: as a part of inter comparison exercise

As a part of inter comparison exercise of an IAEA Coordinated Research Project on large sample neutron activation analysis, a large size and non standard geometry size pottery replica (obtained from Peru) was analyzed by k ₀-based internal monostandard neutron activation analysis (IM-NAA). Two large size sub samples (0.40 and 0.25 kg) were irradiated at graphite reflector position of AHWR Critical Facility in BARC, Trombay, Mumbai, India. Small samples (100–200 mg) were also analyzed by IM-NAA for comparison purpose. Radioactive assay was carried out using a 40 % relative efficiency HPGe detector. To examine homogeneity of the sample, counting was also carried out using X–Z rotary scanning unit. In situ relative detection efficiency was evaluated using gamma rays of the activation products in the irradiated sample in the energy range of 122–2,754 keV. Elemental concentration ratios with respect to Na of small size (100 mg mass) as well as large size (15 and 400 g) samples were used to check the homogeneity of the samples. Concentration ratios of 18 elements such as K, Sc, Cr, Mn, Fe, Co, Zn, As, Rb, Cs, La, Ce, Sm, Eu, Yb, Lu, Hf and Th with respect to Na (internal mono standard) were calculated using IM-NAA. Absolute concentrations were arrived at for both large and small samples using Na concentration, obtained from relative method of NAA. The percentage combined uncertainties at ±1 s confidence limit on the determined values were in the range of 3–9 %. Two IAEA reference materials SL-1 and SL-3 were analyzed by IM-NAA to evaluate accuracy of the method.