Kinetic analysis of the thermal decomposition of pristine and γ-irradiated zinc uranyl acetate

Thermal decomposition of pristine and γ-irradiated zinc uranyl acetate was investigated in air using isothermal and dynamic thermogravimetric techniques. The decomposition proceeded via one major process with the formation of triuranates ZnU₃O₁₀ as solid residues. Kinetic analysis of isothermal data, when compared with various solid-state reaction models, showed that the decomposition reaction is best fitted by the phase-boundary model. Kinetic analysis of the dynamic TG curves was discussed with reference to integral methods of modified Coats and Redfern equations. Kinetic and thermodynamic parameters were calculated and evaluated. IR spectroscopy and X-ray powder diffraction techniques were employed to follow the chemical composition of solid residue at different calcination temperatures. The results display that the triuranate ZnU₃O₁₀ starts forming by calcination of zinc uranyl acetate at temperatures?>?300 °C and undergoes decomposition at higher temperatures (>600 °C) with the formation of U₃O₈. The results were evaluated regarding the utilization of zinc uranyl acetate as an important source of diuranates and triuranates.     

Correlating the TL response of γ-irradiated natural quartz to aluminum and hydroxyl point defects

This paper investigates the relationship between Al- and OH-related point defects with the thermoluminescent (TL) response of natural quartz sensitized with high doses of γ radiation and heat-treatments. For this, specimens from a single crystal were progressively irradiated with doses of ⁶⁰Co from 2 to 50 kGy. After each step of sensitization, the absorption bands related to [AlO₄]⁰, [AlO₄/H]⁰, [H₄O₄]⁰ and Li-dependent OH point defects were measured by optical absorption and infrared (IR) spectroscopy. The sensitization of the 280 °C TL peak increased up to 15 kGy and then its intensity remained constant. The absorption intensity at 470 nm increased with γ doses suggesting a progressive creation of [AlO₄]⁰ acting as recombination centers for the sensitized peak. At the same time, the TL intensity of the 90 °C peak decreased with the accumulated dose. This effect was not related to the saturation in the number of recombination centers because both [H₄O₄]⁰ and [AlO₄]⁰ bands were increasing after 50 kGy. Compared to the as-received condition, it was found that IR bands associated with [AlO₄/H]⁰ and Li-dependent OH decreased with the effect of heat-treatments. The precursor for [AlO₄]⁰ is [AlO₄/Li]⁰ and the Li species dislodged from [AlO₄/Li]⁰ and Li-dependent OH centers play an important role in the sensitization process.     

ESR of γ-irradiated DI-, TRI- and poly-glycin

The effects of γ radiation on glycylglycine, triglycine, and polyglycine have been studied using ESR spectroscopy. The radiation exposures have been performed under vacuum at room temperature. All those irradiated substances show a doublet absorption signal often ascribed to a radical formed on the α carbon of the peptide chain. The magnetic susceptibility has been found to depend on temperature according to the Curie-Weiss law. The radio-sensitivity parameter G_r , the hyperfine splitting constant A_h and the spectroscopic factor g nave been determinated as well as θ which is the temperature corresponding to the Curie temperature of the irradiated substance. The results on C_r , θ and A_h for all peptides studied here agree with the assumption of radiation induced free radicals located at the α carbon of the peptide chain, leading to conclude that the degree of delocalization of the unpaired electron increases for increasing number of glycine units in the peptide. Finally, from negative θ values obtained, a conclusion has been reached on the antiferromagnetic nature of the interaction between unpaired spins.     

Kinetic studies for the non-isothermal decomposition of un-irradiated and γ-irradiated ruthenium(III) acetylacetonate

Kinetic studies for the non-isothermal decomposition of un-irradiated and γ-irradiated ruthenium(III) acetylacetonate in air were carried out. The results show that the decomposition proceeds in one major step in the temperature range of 150–250 °C with the formation of RuO₂ as a final solid residue for un-irradiated Ru(acac)₃. For γ -irradiated Ru(acac)₃ with 10² KGy total γ-ray dose, the decomposition goes eventually to completion with almost 100% decomposition and proceeds in one major step, which contains four overlapping decomposition stages in the temperature range of 200–320 °C. The kinetics is shown to be non-isothermal, using both model-fitting and model-free approaches. Infrared (IR) spectroscopy and X-ray powder diffraction techniques were employed to follow the chemical composition of the solid residue obtained at different temperatures.     

Phonon density of states in γ-, β-, and α-AgCuS

The ternary superionic conductor AgCuS was studied by means of inelastic neutron scattering at temperatures of 150 to 398 K. The experimental time-of-flight spectra were recalculated into the generalized phonon density of states G(ɛ) in an incoherent approximation. It is shown that G(ɛ) of AgCuS has a nontrivial temperature dependence over the low-energy range. The relation between the temperature dependence of G(ɛ) and the existence of a low-energy mode in AgCuS is discussed. The text was submitted by the authors in English.     

Enhanced luminescent properties and optical absorption of γ-irradiated KI: Ce, Tb crystals

This paper reports that KI doped with Ce³⁺ or double doped with Tb³⁺ and Ce³⁺ were prepared by the Bridgman-Stockbarger method and characterized by optical absorption photoluminescence (PL), thermoluminescence (TL), photostimulated emission (PSL) and TL emission. The optical absorption measurement indicates that F and V₁, V₂ centers are formed in the crystals during the γ irradiation process. It was attempted to incorporate a broad band of Ce³⁺ activator into the narrow band emission of Tb³⁺ in the KI host without the reduction of emission intensity. Ce³⁺-co-doped KI and Tb crystals showed a broad band emission due to the d-f transition of Ce³⁺ and a reduction in the intensity of emission peaks due to the ⁵D₃-⁷F_j (j=3,4,5,6) transition of Tb³⁺, when they were excited at 240 nm.These results supported that an effective energy transfer occurs from Tb³⁺ to Ce³⁺ in the KI host. Co-doping Ce³⁺ ions greatly intensified the excitation peak at 260 nm for the emission at 393 nm of Tb³⁺, which means that more lattice defects, involved in the energy absorption and transfer to Tb³⁺, are formed by the Ce³⁺ co-doping. The integrated light intensity is an order of magnitude higher as compared to the undoped samples for similar doses of irradiation and heating rates. The defects generated by irradiation were monitored by optical absorption and TSL Trap parameters for the TL process are calculated and presented.     

The TL and room temperature OSL properties of the glow peak at 110 °C in natural milky quartz: A case study

The LM–OSL signal of quartz, while measured at room temperature, is dominated by an intermediate, broad and intense OSL component, so that its contribution and general characteristics are derived very accurately. Through a series of dose–response, bleaching and thermal decay at room temperature experiments, in conjunction with curve fitting studies, a component resolved analysis is carried out studying the correlation between this specific component, termed as LM–OSL component C₂ and the 110 °C TL glow peak in quartz. The dose–response of these two luminescence components behaves exactly similar being linear at low doses and saturating at almost 100 Gy. Both signals decay exponentially under illumination, providing identical optical detrapping cross-section values. Residual of both luminescence signals after thermal decay at room temperature follows an exponential law, yielding similar mean half-lives. All previous luminescence features provide strong evidence for the electron trap being the same for both the 110 °C TL trap and the LM–OSL component C₂. The results of the present work are very promising and clearly support the possibility of extrapolating the TL pre-dose methodology to the OSL pre-dose effect using only the LM–OSL component C₂.     

Combined measurement of dose and α/γ radiation-field-components using the shape of composite peak 5 in the glow curve of LiF:Mg,Ti

The shape of composite peak 5 in the glow curve of LiF:Mg,Ti (TLD-100), specifically, the ratio of the intensity of peak 5a to peak 5, is employed to separately estimate the gamma and alpha particle components in a mixed radiation field. A blind test demonstrates the reasonable accuracy of the technique which yields results between 3.8% and 30%.     

Reconstruction of all-electron orbitals from one-electron pseudowave functions and calculations of the intensities of Si X-ray emission spectra of Si, β-SiC,stishovite, and β-cristobalite crystals

The intensities of Si X-ray emission spectra of Si, β-SiC, stishovite, and β-cristobalite crystals are calculated. The wave functions of the initial and final states are obtained in the framework of the density-functional theory with the use of the norm-conserving and ultrasoft pseudopotentials. The all-electron crystal orbitals are reconstructed from the one-electron pseudowave functions. The probabilities of X-ray emission transitions are calculated by reconstructing the all-electron orbitals in two different gauges, namely, the length and velocity gauges. The calculated intensities are compared with the experimental spectra and the partial densities of states.     

FTIR spectra and rovibrational analysis of parallel bands involving the ν1, ν2, and ν3 levels of natural and monoisotopic FClO3

Fourier Transform infrared spectra of gaseous natural FClO₃ and monoisotopic F³⁵ClO₃ have been recorded at 293 and 225 K with a resolution of 0.04 cm⁻¹. Rotational J structure and, in part, K structure were resolved for the parallel fundamentals, combination bands, and overtones ν₁, ν₂, ν₃, ν₁ + ν₂, ν₁ + ν₃, ν₂ + ν₃, 2ν₁, 2ν₂, and 2ν₃. Band origins ν₀, anharmonicity constants χ_ij, and vibration-rotation interaction constants α_i^A and α_i^B have been determined. For F³⁵ClO₃, ν₀ values are ν₁ = 1063.238(6), ν₂ = 716.814(6), and ν₃ = 549.877(3) cm⁻¹. No perturbation was found at the present level of accuracy.     

Phase stability of α-, γ-, and ε-Ce: DFT+DMFT study

We present the total energy calculation of α-, γ-, and ε-Ce phases in the frame of GGA, GGA+U, and DFT+DMFT methods. It has been shown that taken into account of Coulomb correlations in the frame of dynamical mean-field theory allows reproducing the phase diagram of Ce in correct way. Equilibrium volume calculated within the DFT+DMFT method for face-centered cubic (fcc) structure agrees with experimental Ce-γ cell volume. With temperature decrease energy minimum shifts toward α cell volume. Moreover, the DFT+DMFT total energy for body-centered tetragonal (bct) structure becomes smaller than for fcc one with increase in pressure in agreement with experimental phase diagram. Importance of accounting of Coulomb correlation in the frame of DMFT is discussed.     

The reaction 36S(α, γ)40Ar: Yield curve,excitation energies and decay of 40Ar resonance levels

The 8 to 10 MeV levels in ⁴⁰Ar have been studied for the first time through the reaction ³⁶S(α, γ)⁴⁰Ar (Q-value 6.80 MeV). Energy and strength of 51 resonances have been determined in the bombarding energy range E_α = 2.3 to 3.55 MeV. The decay schemes have been studied for 13 resonances.     

Dielectric behaviour of α-cyclodextrin,heptakis (2,3,6-tri-Omethyl)-β-cyclodextrin,randomly methylated β-cyclodextrin and low frequency Raman spectra of α- and β-cyclodextrins

The frequency and temperature dependence of the real (?′) and imaginary (?″)parts of the dielectric constant of α-cyclodrextrin (form 1; α-CD. 5.9H₂O) and α-cyclodextrin (form III; α-CD.7.6H₂O) and of the corresponding dried forms (α-CD.1.1H₂O, α-CD.2.9H₂O, respectively) has been investigated over the frequency range 0–100 k Hz and temperature range 130–350 K. In addition the dielectric behaviour has been investigated of heptakis-(2,3,6-tri-O-methyl)-β-cyclodextrin (β-CD.TRIME. 0.3H₂O) and randomly methylated β-cyclodextrin (β-CD.RAME.0.8H₂O). The dielectric behaviour is described well by Debyetype relaxation (α-disperson). All α-CD systems exhibit an additional ω-dispersion at low frequencies, which is attributed to proton transport. The fact that the ?′ values of α-CD form III are larger than those of α-CD form I is attributed to the different numbers and different strengths of the intramolecular hydrogen bonds. Form III has a stable conformation which is shown by the constant values of ?′ in the temperature range 125–250 K. By contrast, in form I the ?′ values increased linearly with temperature, indicating that the system passed through succesive conformations. The temperature dependence of ?″ and phase shift ∞ in all the specimens of α-CD (forms I, III) and fully methylated β-CD do not reveal any orderdisorder transition, because the developed hydrogen bonds ae not of the flip-flop type according to their crystal structures. The partially methylated β-CD reveals the characteristics of the order-disorder transition, which was observed before in the systems dried β-CD.2H₂O and non-dried β-CD.9.8H₂O. There is a direct relation between the hydroxyl groups of β-CD and the order-disorder transition. The order-disorder transition could also be shown in dried β-CD.2.4H₂O and non-dried β-CD.9.8H₂O samples but not in dried α-CD.1.1H₂O and non-dried a-CD.5.9H₂O samples, by low frequency Raman spectroscopy (< 180 cm^?1). The step-like temperature dependence of the band at 33.7cm^?1 reveals a transition at about 223K for both β-CD samples. In the case of α-CD samples the almost linear temperature dependence of the band at 49.1 cm^?1 does not reveal any transition.     

Crystal growth,optical and thermal studies of nonlinear optical γ-glycine single crystal grown from lithium nitrate

Single crystals of the nonlinear material γ-glycine have been grown in the presence of lithium nitrate by slow-evaporation method. Structural characterization of the grown crystals was carried out by powder and single crystal X-ray diffraction (XRD) methods and it is observed that the samples crystallize in hexagonal system with non-centrosymmetric space groups. The modes of vibrations of different molecular groups present in glycine have been identified by spectral analyses. UV–visible transmittance study was performed to analyze optical transparency of γ-glycine crystals and found that the crystal was transparent in the entire visible-NIR region. Second harmonic generation (SHG) conversion efficiency has been estimated as 62 mV and the output power by the crystal was 1.72 times that of potassium dihydrogen phosphate (KDP) crystal. The thermal stability and decomposition of the sample have been studied by thermal analysis and it is observed that the γ-glycine crystal have good thermal stability.     

On the significant relativistic heavy atom effect on 13C NMR chemical shifts of β- and γ-carbons in seleno- and telluroketones

Unexpectedly large ‘Heavy Atom on Light Atom’ (HALA) effects have been found in ¹³C NMR (Nuclear Magnetic Resonance) chemical shifts of β- and γ-carbons of seleno- and telluroketones established by means of the high-accuracy calculations of ¹³C NMR chemical shifts in three representative real-life compounds, 2,2,5,5-tetramethyl-3-cyclopentene-1-selone, selenofenchone and 1,1,3,3-tetramethyl-1,3-dihydro-2H-indene-2-tellurone. The proposed computational scheme consists of the combination of accurately correlated coupled-cluster singles and doubles model approach for the non-relativistic calculations of shielding constants taking into account the solvent, vibrational and relativistic corrections, the latter obtained within the 4-component fully relativistic gauge-including atomic orbitals KT2 approach resulting in a very good agreement of the performed calculations with the experiment. The stereochemical dependence of the ‘long-range’ γ-HALA effect on the dihedral angle has been established in the model seleno- and telluroketones providing the largest shielding effect in the orthogonal orientation of the X=C_α–C_β–C_γ (X=Se, Te) moiety.     

Measurement of photon energy and approach angle from an analysis of the tracks of the (e+e−) pair in a multilayer γ-telescope spark chamber

An investigation is made of the problems involved in measuring the characteristics of a photon in the energy range 5–200 MeV with a -telescope whose main recording element is a multilayer spark chamber with an inhomogeneous structure.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 6, pp. 55–58, June, 1979.