Ar-ion-milling-induced structural changes of Cu50Zr45Ti5 metallic glass

We have systematically studied Ar-ion-milling-induced microstructural evolution in Cu₅₀Zr₄₅Ti₅ metallic glass (MG) during specimen preparation for transmission electron microscopy (TEM). We have observed the formation of a Cu₁₀Zr₇ intermetallic phase in samples prepared using low energy ion milling (2 keV) but without evident crystallization. We also observed the formation of nanocrystalline Cu₁₀Zr₇ phase (with a possibility of being mixed with other minor phases) in samples prepared using high energy ion milling (?3 keV). In contrast, the MG samples remained in the glassy state without any microstructural changes when prepared by either electropolishing or low energy ion milling with liquid nitrogen cooling (2 keV). Further, our study suggests that chemical decomposition might be a necessary intermediate stage for crystallization. In situ TEM electron irradiation shows ion-milling-induced phase segregation and preferred nanocrystallization in the precipitated regions.     

DyF3: A promising new TL material for gamma dosimetry

This research describes preliminary investigation of some radiation dosimetry characteristics of commercial dysprosium fluoride powder. The as-received aliquot has strong thermoluminescence (TL) emission with one sharp peak at ∼234 °C. The TL characteristics have been examined under excitation of gamma (γ) doses in the range 1 Gy-50 kGy from a ⁶⁰Co gamma source. The dose response was linear up to 100 Gy and a sub-linear response was observed at higher doses. The TL signal is observed to remain stable for aliquots irradiated to γ-doses in the range 1-10 Gy over one month storage period in dark at ambient temperature and humidity conditions. This paper recommends using DyF₃ in doping of TL materials which may be promising for future dosimeter development.     

Thermoluminescence and photoluminescence of cerium doped CaSO4 nanosheets

Thermoluminescence (TL) and photoluminescence (PL) characteristics of CaSO₄:Ce nanocrystalline prepared by hydrothermal method has been studied. Its TL glow curve contains three overlapping glow peaks at around 490, 505 and 521 K. Emission spectra band at 303 and 324 nm were observed for the orthorhombic phase of nanosheets. TL response of the prepared nanocrystalline to β and γ radiation was studied and the sensitivity of the nanosheets was found much more than that of analogous microcrystalline and is around 10 times higher than the well known high sensitive TL dosimeter LiF:Mg, Cu, P (GR-200) hot-pressed chips. TL kinetic parameters of this nanocrystalline are also presented.     

A track structure model of optically stimulated luminescence from Al2O3:C irradiated with 10-60 MeV protons

We investigated the optically stimulated luminescence (OSL) signal from Al₂O₃:C irradiated with 10-60 MeV protons to estimate the potential use of this material as a proton dosimeter. After irradiation, OSL decay curves were read out and we used both the initial part and the total area of these curves as response signal. A precondition for optimal proton dosimetry is an LET-independent response and the experimental data showed such an independence at 0.3 Gy for the initial OSL signal.To understand the experimental results, we applied target and track structure theory. Here, the OSL signal is considered to be a result of target activation and the OSL proton signal is calculated from the OSL gamma signal and a radial dose distribution around the proton track. Although several simplifications were made to ease calculations, the classic track structure theory can qualitatively account for all the main features of the experimental data. We estimate a target radius to be between 30 and 150 nm and associate this radius with a charge migration distance in the crystal.The model calculations suggest that the dose and LET-dependency of the OSL signal is a result of an unique mixture of one- and two-hit targets. This implies that the initial OSL signal from Al₂O₃:C in general is not LET-independent at 0.3 Gy or lower doses. However, a mixture of the initial and total OSL signal could provide an LET-independent response in a given LET and dose interval.     

Gamma irradiation effects on ZnO-based scintillating glasses containing CeO2 and/or TiO2

Irradiation resistance of as-studied scintillating glass samples were tested under the ⁶⁰Co γ-ray radiation at doses between 60 and 700 Gy. Photoluminescence properties of glasses with and without cerium ions were investigated to show the effect of cerium (III) on the luminescence of ZnO. Ultraviolet and visible optical transmittance spectra were compared before and after irradiation treatment. The so-called radiation-induced absorption coefficient (RIAC) was introduced to compare more effectively the radiation damage on glass samples. The much reduced transmittance change and decreased RIAC value in UV-Vis region indicate that the density of electron centers and hole centers caused by radiation decreased, which helps to confirm that the reduction and oxidation reaction of cerium ions took place in radiation process. From RIAC curves, it can be seen that TiO₂ enhances the irradiation resistance of sample in UV region. However, high TiO₂ content has negative effect on visible transmittance of glasses after the higher dose irradiation (700 Gy).     

Gamma-ray shielding and structural properties of PbO-SiO2 glasses

Gamma-ray attenuation coefficients have been determined experimentally using a narrow beam transmission method for the xPbO(1−x)SiO₂ (x = 0.45-0.70) glass system at 662, 1173 and 1332 keV photon energies. These values have also been obtained theoretically using the ‘mixture rule’ and the ‘XCOM’ computer software. The results have been used to calculate half value layer parameters. Gamma-ray shielding properties of PbO-SiO₂ glass samples have been compared with standard radiation shielding concretes. The molar volume, FTIR and acoustic investigations have been used to study the structural properties of the prepared glass system.     

Ge nanocrystals embedded in SiO2 in MOS based radiation sensors

In this work, the effects of gamma radiation on the Raman spectra of Ge nanocrystals embedded in SiO₂ have been investigated. SiO₂ films containing nanoparticles of Ge were grown using the r.f.-magnetron sputtering technique. Formation of Ge nanocrystals was observed after high temperature annealing in an inert atmosphere and confirmed by Raman measurements. The intensity of the Raman signal originating from Ge nanocrystals was found to decrease with increasing gamma radiation. The study also includes the gamma radiation effects on MOS structure with Ge nanocrystals embedded in SiO₂. The gamma radiation effects from 500 up to 4000 Gray were investigated. Capacitance-voltage measurements were performed and analyzed. Oxide traps and interface trap charges were calculated. Results show that MOS structure with Ge nanocrystals embedded in SiO₂ is a good candidate to be used in radiation sensors, especially at high radiation doses.     

Radiation effects on PbO-Al2O3-B2O3-SiO2 glasses by FTIR spectroscopy

The infrared absorption spectra of PbO-Al₂O₃-B₂O₃-SiO₂ glasses have been measured in the spectral range 600-4000 cm⁻¹ before and after absorbed dose of 50 Gy, 4 kGy and 50 kGy to investigate the structural change due to irradiation. The structural change due to composition has also been discussed. The experimental results clearly indicate that after irradiation, a significant change in structure of lead alumino borosilicate glass network is observed. It was shown that BO₄ groups decreases and BO₃ groups increases with the increase of Al₂O_3.     

Use of Al2O3 layer as a dielectric in MOS based radiation sensors fabricated on a Si substrate

The use of Al₂O₃ dielectric in MOS based radiation sensors has been investigated. Their response has been compared with conventional MOS capacitors with a SiO₂ dielectric. The study includes gamma radiation effects with dose up to 4 Gy. The effect of radiation has been determined from the valance band shift in C-V curves. The amount of charge induced by the radiation has been calculated and compared with the response of MOS capacitors with SiO₂ with the same and different thicknesses. Fading properties have been studied and compared. Results show that MOS capacitors with Al₂O₃ dielectric exhibit sensitivity greater than that obtained from MOS capacitors with SiO₂. This higher sensitivity is attributed to higher trapping efficiency in the Al₂O₃ layer.     

Nanoparticles of Al2O3:Cr as a sensitive thermoluminescent material for high exposures of gamma rays irradiations

Aluminum Oxide (Al₂O₃) doped with proper activators is a highly sensitive phosphor commonly used for radiation dosimetry using thermoluminescence (TL) technique. Nanoparticles of this material activated with Chromium (Cr) have been synthesized using the propellant chemical combustion technique and studied for their TL response. They were characterized by X-ray diffraction and scanning electron microscope. The synthesized material has spherical nanoparticles with grain size around 25 nm. These nanoparticles were exposed to heavy doses from γ-rays of ¹³⁷Cs. The TL glow curves show a prominent peak at around 474 K. This peak is found to be sensitive for high exposures of γ-rays and has linear response in the range of 100 Gy-20 kGy without showing saturation. This remarkable result suggests that Al₂O₃:Cr nanoparticles might be used for the dosimetry of food and seed irradiations.     

Decomposition and multiphase reactions in the system UO2(NO3)2·6H2O-Ni(NO3)2·6H2O at elevated temperatures

Solid state reactions between uranyl nitrate hexahydrate and nickel nitrate hexahydrate in mixtures of various ratios have been studied at elevated temperatures. The binary system of uranyl nitrate hexahydrate and nickel nitrate hexahydrate was found to form a eutectic of composition 53 mol% uranyl nitrate hexahydrate and 47 mol% nickel nitrate hexahydrate at 40 °C. The overlap of evolution of nitric oxide (NO) and water vapour above 230 °C confirmed the presence of hydroxynitrates of uranium and nickel as intermediate products. These hydroxynitrates began to react above 280 °C to form nickel uranate, NiU₃O₁₀, in the case of mixtures containing 75 mol% uranyl nitrate hexahydrate. When the proportion of uranyl nitrate hexahydrate in the mixture was higher than 75 mol%, U₃O₈ formed along with nickel uranate. For the mixtures containing uranyl nitrate hexahydrate lower than 75 mol%, NiO was observed to form along with NiU₃O₁₀.     

Structural studies of Ge nanocrystals embedded in SiO2 matrix

Germanium nanoparticles embedded in SiO₂ matrix were prepared by atom beam sputtering on a p-type Si substrate. The as-deposited films were annealed at temperatures of 973 and 1073 K under Ar + H₂ atmosphere. The as-deposited and annealed films were characterized by Raman, X-ray diffraction and Fourier transform infrared spectroscopy (FTIR). Rutherford backscattering spectrometry was used to quantify the concentration of Ge in the SiO₂ matrix of the composite thin films. The formation of Ge nanoparticles were observed from the enhanced intensity of the Ge mode in the Raman spectra as a function of annealing, the appearance of Ge(3 1 1) peaks in the X-ray diffraction data and the Ge vibrational mode in the FTIR spectra. We have irradiated the films using 100 MeV Au⁸⁺ ions with a fluence of 1 × 10¹³ ions/cm² and subsequently studied them by Raman and FTIR. The results are compared with the ones obtained by annealing.     

Study on TL and OSL characteristics of indigenously developed CaF2:Mn phosphor

CaF₂:Mn phosphor is known for its high thermoluminescent sensitivity and dose linearity up to few kGy. In the present study CaF₂ phosphor with different concentration of Mn dopant was prepared and was characterized through different techniques. The phosphor was prepared through chemical root using CaCO₃, HF acid and MnCl₂ as raw materials following co-precipitation method. TL sensitivity of the prepared phosphor was compared with other well established phosphors used for radiation dosimetry. It was found that the TL sensitivity is higher by a factor of 10 with respect to LiF:Mg, Ti, TLD-100 and half to that of CaSO₄:Dy (0.05 mol%) phosphor. X-ray diffraction, TL emission spectrum and ESR spectrum taken of the prepared phosphor confirms the crystal structure, Mn²⁺ emission and incorporation Mn in the crystal, respectively. No significant fading of the dosimetric peak was observed of the prepared phosphor for a storage period of 45 days. The dose linearity of the phosphor was found to be in the range of 50 Gy-3 kGy within an uncertainty of about 10%. An attempt was made to determine the kinetic parameters of TL glow curve and the parameters related to optically stimulated luminescence. In view of its long range of dose linearity, it can be used for the dosimetry of commercial irradiator generally used for the irradiation of food and grains in our country.     

Thermal expansion studies on UMoO5, UMoO6, Na2U(MoO4)3 and Na4U(MoO4)4

In the present work, thermal expansion behavior of lower valent sodium uranium molybdates, i.e., Na₂U(MoO₄)₃ and Na₄U(MoO₄)₄ were studied under vacuum in the temperature range of 298-873 K using high temperature X-ray diffractometry (HTXRD). Expansion behaviors of UMoO₅ and UMoO₆ were also studied in vacuum from 298 to 873 K and 773 K, respectively. UMoO₅ was synthesized by reacting UO₂ with MoO₃ in equi-molar proportion in evacuated sealed quartz ampoule at 1173 K for 14 h. Na₂U(MoO₄)₃ and Na₄U(MoO₄)₄ were prepared by reacting UMoO₅ and MoO₃ with 1 and 2 moles of Na₂MoO₄, respectively, at 873 K in evacuated sealed quartz ampoule. XRD data of UMoO₅ and UMoO₆ were indexed on orthorhombic and monoclinic systems, respectively, whereas, the data of Na₂U(MoO₄)₃ and Na₄U(MoO₄)₄ were indexed on tetragonal system. The lattice parameters and cell volume of all the four compounds, fit into polynomial expression with respect to temperature, showed positive thermal expansion (PTE) up to 873 K.     

D2 gas-filled blisters on deuterium-bombarded tungsten

Most of spherical blisters formed by deuterium (D) bombardment (38 eV/D) up to 3 × 10²⁴ D/m² at 300 K on polycrystalline tungsten are fully elastic deformations. This has been proven by opening individual blisters with a focused ion beam and in situ observation of their complete relaxation by scanning electron microscopy. The D₂ gas filling is confirmed by observing simultaneously the D₂ puff. The gas pressure is causal for the stability of such spherical blisters after implantation and the gas release leads to sudden relaxation. The dilatation of the blister cap by trapped D can be excluded as cause for the blisters.     

Effects of MeV Si ions bombardment on the thermoelectric generator from SiO2/SiO2 + Cu and SiO2/SiO2 + Au nanolayered multilayer films

The defects and disorder in the thin films caused by MeV ions bombardment and the grain boundaries of these nanoscale clusters increase phonon scattering and increase the chance of an inelastic interaction and phonon annihilation. We prepared the thermoelectric generator devices from 100 alternating layers of SiO₂/SiO₂ + Cu multi-nano layered superlattice films at the total thickness of 382 nm and 50 alternating layers of SiO₂/SiO₂ + Au multi-nano layered superlattice films at the total thickness of 147 nm using the physical vapor deposition (PVD). Rutherford Backscattering Spectrometry (RBS) and RUMP simulation have been used to determine the stoichiometry of the elements of SiO₂, Cu and Au in the multilayer films and the thickness of the grown multi-layer films. The 5 MeV Si ions bombardments have been performed using the AAMU-Center for Irradiation of Materials (CIM) Pelletron ion beam accelerator to make quantum (nano) dots and/or quantum (quantum) clusters in the multilayered superlattice thin films to decrease the cross plane thermal conductivity, increase the cross plane Seebeck coefficient and cross plane electrical conductivity. To characterize the thermoelectric generator devices before and after Si ion bombardments we have measured Seebeck coefficient, cross-plane electrical conductivity, and thermal conductivity in the cross-plane geometry for different fluences.     

Enthalpy measurements of La2Te3O9 and La2Te4O11

Enthalpy increment measurements on La₂Te₃O₉(s) and La₂Te₄O₁₁(s) were carried out using a Calvet micro-calorimeter. The enthalpy values were analyzed using the non-linear curve fitting method. The dependence of enthalpy increments with temperature was given as: H°(T) − H°(298.15 K) (J mol⁻¹) = 360.70T + 0.00409T² + 133.568 × 10⁵/T − 149 923 (373 ? T (K) ? 936) for La₂Te₃O₉ and H°(T) − H°(298.15 K) (J mol⁻¹) = 331.927T + 0.0549T² + 29.3623 × 10⁵/T − 114 587 (373 ? T (K) ? 936) for La₂Te₄O₁₁.     

Reactivity of hydrogen peroxide towards Fe3O4, Fe2CoO4 and Fe2NiO4

The kinetics of CRUD oxidation by H₂O₂ has been studied using aqueous suspensions of metal oxide powder. Fe₃O₄, Fe₂CoO₄ and Fe₂NiO₄ were used as model compounds for CRUD. In addition, the activation energies for the reaction between H₂O₂ and the three CRUD models were determined. The rate constants at room temperature were determined to 6.6 (±0.4) × 10⁻⁹, 3.4 (±0.4) × 10⁻⁸ and 1.6 × 10⁻¹⁰ m min⁻¹ for Fe₃O₄, Fe₂CoO₄ and Fe₂NiO₄, respectively. The corresponding activation energies are 52 ± 4, 44 ± 5 and 57 ± 7 kJ mol⁻¹, respectively. The mechanism of the reaction is briefly discussed indicating that the final solid product in all three cases is Fe₂O₃. In addition to the experimental studies, the theoretical grounds for kinetics of reactions in particle suspensions are discussed. The theoretical discussion is also used to explain the somewhat unexpected trends in reactivity observed experimentally.     

Radiation damage effects in layered thin film MgO/HfO2 structures

In this report, we present a study of a thin film tri-layer structure, HfO₂/MgO/HfO₂, irradiated at room temperature with 10 MeV Au ions over a wide fluence range from 5 × 10¹³ to 3.7 × 10¹⁶ Au/cm². The tri-layer structure is a model representation for the microstructure in a composite dispersion nuclear fuel or waste form. Microstructural and chemical composition changes were examined by transmission and scanning transmission electron microscopy (TEM & STEM) combined with energy dispersive X-ray spectroscopy (EDXS), grazing incidence X-ray diffraction (GIXRD) and Rutherford backscattering spectroscopy (RBS) techniques. The microstructural evolution in the HfO₂/MgO/HfO₂ trilayer was similar to the radiation damage behavior of the individual HfO₂ and MgO constituents. For instance, we observed an absence of amorphization in both the MgO and HfO₂ layers and a phase transformation of HfO₂ from the monoclinic to the tetragonal HfO₂ polymorph. In addition, we observed the formation of void-type defects at one of the MgO/HfO₂ interfaces. Such voids are not characteristic to either bulk material (MgO or HfO₂) exposed to ion irradiation.     

Synthesis of KNaSO4:Tb and MgSO4:Dy phosphors for lyoluminescence dosimetry

KNaSO₄:Tb³⁺ phosphors were synthesized by melt technique with different concentration of Tb³⁺ ions and MgSO₄:Dy³⁺ phosphor is prepared by solid state diffusion method. Lyoluminescence and photoluminescence characterization of KNaSO₄:Tb and MgSO₄:Dy³⁺ phosphors are reported in this paper. Only one sharp peak is observed in the lyoluminescence (LL) glow curve and KNaSO₄:Tb(0.05 mol%) phosphor shows maximum efficiency. The LL intensity increases linearly with gamma ray dose. LL emission occurs in the blue and yellow region of the spectrum. Photoluminescence (PL) characterization of KNaSO₄:Tb(0.05 mol%) phosphor shows PL emission at 486 and 546 nm. These PL emissions from KNaSO₄:Tb³⁺ are due to ⁵D₄ → ⁷F₆ and ⁵D₄ → ⁷F₅ transitions of Tb³⁺ ion respectively. Lyoluminescence of MgSO₄:Dy³⁺ phosphor shows the high sensitivity to γ-ray exposure and LL emission observed at 486 and 572 nm in the blue and yellow emission of the spectrum is due to Dy³⁺ ion. Experimental results obtained in the present investigation show that KNaSO₄:Tb³⁺ and MgSO₄:Dy³⁺ phosphors are suitable as a lyoluminescence dosimetry phosphor for ionizing radiations.