Thermally stimulated luminescence and electron paramagnetic resonance studies of actinide doped calcium chloro phosphate

Electron paramagnetic resonance [EPR] and thermally stimulated luminescence [TSL] studies were conducted on self [α]-irradiated²³⁹Pu doped calcium chloro phosphate andγ-irradiated²³⁹Pu/²³⁸UO ₂ ²⁺ doped calcium chloro phosphate to elucidate the role of the electron/hole traps in thermally stimulated reactions and to obtain trap parameters from both TSL and EPR data. TSL glow peaks around 135 K (# peak 1), 190 K (# peak 2), 435 K (# peak 5) and 490 K (# peak 7) were observed and their spectral characteristics have shown that Pu³⁺ and UO ₆ ⁶⁻ act as luminescent centres in calcium chloro phosphate with respective dopants. EPR studies have shown the formation of the radical ions H⁰, PO ₄ ²⁻ , O⁻, O ₂ ⁻ and [ClO]²⁻ under different conditions. Whereas the [ClO]²⁻ radical being stable up to 700 K, was not found to have any role in TSL processes, the thermal destruction of other centres was found to be primarily responsible for the TSL peaks observed. The trap depth values were determined both by using the TSL data and also the temperature variation of EPR spectra of these centres.     

Thermally stimulated luminescence and electron paramagnetic resonance studies on uranium doped K2Ca2(SO4)3

Thermally stimulated luminescence (TSL) studies of gamma-irradiated uraniumdoped K₂Ca₂(SO₄)₃ revealed two glow peaks around 400 K and 435 K. Electron paramagnetic resonance (EPR) studies carried out on these samples have shown the formation of the radical ions SO ₄ ⁻ , SO ₃ ⁻ , SO ₂ ⁻ and O ₃ ⁻ . From the study of the thermal stabilities of these radical ions, it was found that the thermal destruction of SO ₂ ⁻ and SO ₄ ⁻ radical ions are associated with the glow peaks observed around 400 K and 435 K respectively. Uranate ion was identified as the luminescent centre for the observed TSL glow. The trap depth values for the glow peaks have been determined from TSL data.     

Radiation stabilization of U5+ in CaO matrix and its thermal stability: Electron paramagnetic resonance and thermally stimulated luminescence studies

Electron paramagnetic resonance (EPR) evidence is presented for the radiation stabilization of pentavalent uranium in CaO matrix. From the theoretical predictions ofg value for U⁵⁺ in axial symmetries, it was concluded that U⁵⁺ at Ca²⁺ site is associated with a second neighbour charge compensating Ca²⁺ vacancy. EPR measurements also revealed the presence of Mn²⁺, Mn⁴⁺ and Cu²⁺ impurities in the samples. The thermal stability of U⁵⁺ was investigated using EPR and thermally stimulated luminescence (TSL) techniques. The TSL and EPR studies on gamma irradiated uranium doped calcium oxide samples had shown that the intense glow peak at 540 K is associated with the reduction in the intensity of EPR signal of U⁵⁺ ion around this temperature. This peak is associated with the process U⁵⁺+hole→U^6+*→U⁶⁺+hv. The activation energy for this process was determined to be 1.4eV.     

Kinetics of thermally stimulated luminescence from alkaline earth borates

The kinetics of thermally stimulated emission (TSL) from XB₂O₄ (X= Ca, Sr, Ba) has been investigated employing both isothermal decay and peak shape analysis methods. For BaB₂O₄ the emission was observed to lie in the visible region and the kinetics of TSL emission could be determined without any ambiguity. However, the emission spectra of CaB₂O₄ and SrB₂O₄ were found to consist of two broad emissions: one in the UV and the other in the blue green regions. Consequent to the presence of two emission bands, the determination of TSL kinetics required collection of TSL data for the two components of emission separately. Otherwise, an unambiguous determination of the TSL kinetics just could not be possible. The kinetics of TSL emission for the three borates is found to be of second order.     

Internal irradiation effects in239Pu doped K2Ca2(SO4)3): EPR,TSL and PAS investigations

The electron/hole trapped centres created during internal irradiation in²³⁹Pu doped K₂Ca₂(SO₄)₃ were investigated using electron paramagnetic resonance (EPR), thermally stimulated luminescence (TSL) and photoacoustic spectroscopic studies (PAS). These techniques were used to identify the defects and characterize the thermally induced relaxation processes. TSL studies of self (α)/γ-irradiated²³⁹Pu doped K₂Ca₂(SO₄)₃ revealed two glow peaks around 400 and 433K. Plutonium introduced as Pu⁴⁺ was partly reduced to Pu³⁺ due to self irradiation. This was ascertained from PAS studies. EPR studies carried out on these samples showed the formation of radical ions SO ₄ ⁻ , SO ₃ ⁻ , O ₃ ⁻ , etc. The thermal destruction of SO ₄ ⁻ ion was found to be associated with the prominent glow peak around 433K. Pu³⁺ was found to act as luminescent centre for the observed TSL glow. The trap depth for the glow peak at 433K has been determined from TSL and EPR data.     

Decay kinetics and thermally stimulated luminescence of Mn4+ in SrTiO3

Abstract

Decay kinetics of Mn⁴⁺ luminescence in SrTiO₃ and thermal stimulation of this luminescence (TSL) after low-temperature irradiation with light from the 355—520 nm region, have been investigated in the temperature range of 4.2—150K and 12—110K, respectively, for the first time. It is concluded that TSL glow peaks are associated with thermal release of carriers from shallow traps followed by Mn⁵⁺→Mn⁴⁺(²E) and/or Mn³⁺→Mn⁴⁺ (²E) charge transfer decay kinetics has been explained by considering trap energy levels taking part in the TSL process.     

Test for quasi-equilibrium in thermally stimulated luminescence and conductivity

The uncertainty about the existence of quasi-equilibrium (QE) condition during the readout of thermoluminescence and thermally stimulated conductivity glow peaks in real materials causes doubts about the validity of applying the QE-based analytical expressions to analyse these glow peaks. In this paper a simple method is given to verify the QE condition during the readout of these glow peaks in real materials. The method is based on changes in the glow peak shapes caused by changing the heating rate in non-QE cases. It is illustrated by using synthetic glow peaks derived from two different physically meaningful models.     

Correlation of optically and thermally stimulated luminescence of natural fluorite pellets

Natural fluorite (CaF₂), a dosimetric material of large usage, presents Thermoluminescence (TL) and Optically Stimulated Luminescence (OSL). This study examined the behavior of TL and OSL (stimulated with Blue LEDs) signals from the Brazilian natural fluorite pellets with NaCl as binding agent, as well as their correlations, in order to study and optimize the dosimetric process with this material. A series of experiments were conducted, basically with thermal treatments before OSL acquisition, and optical bleaching before TL readout. The role of NaCl in the TL and OSL emission was investigated. It was observed that natural CaF₂ TL signal is still ample to be used in dosimetric applications, as dose re-assessment in personal dosimetry after an OSL measurement. Also it was verified that the fluorite OSL signal is extinguished by a 350 °C heating and that NaCl has no contribution to the stable part of the OSL signal.     

Optically stimulated luminescence of dosimetric anion-defective corundum crystals

The relationship between the characteristics of optically stimulated luminescence (OSL) and thermally stimulated luminescence (TSL) of dosimetric crystals based on nominally pure single-crystal, ion-defective corundum is considered. It is established that the TSL and OSL characteristics of these crystals are closely interrelated and are caused by the same active traps. It is shown that the OSL of deep traps has a form difficult to interpret, which can be due to the effect of both more shallow and deeper traps.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 1, pp. 140–142, January–February, 2005.     

Optically stimulated luminescence in Ag doped Li2B4O7 single crystal and its sensitivity to neutron detection and dosimetry in OSL mode

Optically stimulated luminescence (OSL) measurements have been carried out on single crystals of Ag doped Li₂B₄O₇ (LTB:Ag) after exposure to various nuclear radiations. The time integrated OSL intensity is found to be linear in the range from 0.1 Gy to 500 Gy. Fading of the OSL signal was found to be around 36% in 48 h. The presence of ⁶Li and ¹⁰B has been gainfully utilized to measure doses of thermal neutrons. Further, the large difference between the wavelength of the stimulation source (∼460 nm) and emission from the LTB:Ag at 270 nm has enhanced the signal-to-noise ratio in a simple OSL set-up with suitable filters. The high sensitivity of the LTB:Ag to thermal neutrons will be useful in variety of applications including personal dosimetry in mixed-fields and imaging devices for neutron radiography.     

Photoinduced oxygen-vacancy related centers in PbWO 4 : Electron spin resonance and thermally stimulated luminescence study

Using electron spin resonance (ESR) and thermally stimulated luminescence (TSL) three different electron traps based on regular W sites perturbed by oxygen vacancies have been identified in PbWO 4 . Analysis of ESR spectra parameters ( g -factor values and principal axes orientations) has shown that revealed centers are (WO 3 ) m vacancy containing complex anions associated with a defect in Pb sublattice: (WO 3 ) m m A Pb complexes. One of the centers (W 1 ) is thermally stable up to 350-370 v K, while the other two (W 2 and W 3 ) only to 270-290 v K. Above these temperatures trapped electrons become free and recombine with localized holes, giving rise to TSL glow peaks at T\approx 323\,\hbox{K} and 365\,\hbox{K} . Using the initial rise method the 323\,\hbox{K} TSL peak-shape was fitted allowing the first order recombination kinetic that gives trap parameters E = 0.88\,\hbox{eV} and s\simeq 5\ast 10^{12}1/\hbox{s} .     

Cryostat for low temperature x-irradiation and electron paramagnetic resonance

A cryostat for x-irradiation of solid samples at liquid air temperature is described. The design of the sample mount in the cryostat enables quick transfer of the sample after x-irradiation into EPR cavity to facilitate EPR study without warming the sample.     

Electron paramagnetic resonance of Cr3+ ions in ferroelastic CsLiSO4

The X-band EPR studies of Cr³⁺-doped LCS have been performed. The values of the spin-Hamiltonian parameters for Cr³⁺ ions have been estimated at room temperature. The effect of crystal twinning on the EPR spectra has also been described. The temperature behaviour of EPR lines originated from two structurally different chromium complexes has been studied close to the ferroelastic phase transition. From the temperature dependence of positions of the split resonance lines a value of the critical exponent β of the order parameter was found to be β = 0.25.     

Thermoluminescence and optically stimulated luminescence characteristics of Al2O3 doped with Tb

In the present work policrystals of α − Al₂O₃ doped with terbium were synthesized using the solvent evaporation method. The samples were prepared using Al(NO₃)₃·9H₂O and Tb(NO₃)₃·5H₂O reagents, with Tb concentrations between 1 and 5 mol% and thermally treated at high temperature above ∼1400 °C. X-ray diffraction measurements showed the α-phase formation of samples. TL glow curve presented an intense peak at ∼190 °C and two other with low intensity at 290 and 350 °C after gamma irradiation. The best doping concentration which presented high luminescence was the sample doped with 3 mol% of Tb. TL spectra and fluorescence measurements showed similar luminescence spectra with lines attribute to Tb³⁺ ions. A linear behavior to gamma dose between 1 and 20 Gy was observed in TL, using 190 °C peak as well as in OSL signal, this last carried out using 532 nm wavelength stimulation.     

Thermally stimulated luminescence of polycrystalline CdWO4 at low temperatures

CdWO₄ scintillator powders were produced via solid state reaction and investigated by thermally stimulated luminescence technique after UV irradiation. Under a heating rate of 0.1 K/s, the glow curve presented a superposition of peaks at low temperatures. Four peaks were identified below 80 K by partial heating method and their kinetic parameters were evaluated from the initial rise analysis. Measurements were also performed for heating rates of 0.05 and 0.2 K/s and allowed the kinetic study by peak position method. Surface effects due to the polycrystalline feature of the sample were investigated by comparing the results with those reported for CdWO₄ single crystals.     

Thermally stimulated luminescence studies of undoped,Cu- and Mn-doped CaSO4 compounds

Thermally stimulated luminescence (TSL) of undoped and doped CaSO₄ with activators such as Cu and Mn has been investigated. The polycrystalline samples of undoped and doped CaSO₄ are prepared by the melting method. The formation of CaSO₄ compound is confirmed by X-ray diffraction and Fourier transform infrared studies. Scanning electron microscopic studies of CaSO₄ are also carried out.

The TSL glow curves of undoped CaSO₄, Cu- and Mn-doped CaSO₄ are studied. Comparison of the thermoluminescence (TL) intensity of the most intensive glow peak of Cu-doped CaSO₄ compound with that of undoped CaSO₄ shows that addition of Cu impurity in CaSO₄ compound enhances the TL intensity by about four times. However, the addition of Mn impurity to undoped CaSO₄ increases the TL intensity by about three times when compared with that of undoped CaSO₄. The TL-dose dependence of all three samples was studied and was observed to be almost linear in the studied range of irradiation time. Among the samples studied, namely undoped CaSO₄ and Cu- and Mn-doped CaSO₄, Cu-doped CaSO₄ is found to be the most sensitive. The trap parameters, namely order of kinetics (b), activation energy (E) and frequency factor (s) associated with the most intensive glow peaks of CaSO₄:Mn, CaSO₄:Cu and CaSO₄ phosphors were determined using the glow curve shape (Chen's) method.     

Electron paramagnetic resonance, optical and electrical properties of vanadyl doped alkali germanoborate glasses

Glasses with composition xGeO₂.(0.30−x)M₂O.0.70B₂O₃ (M=Li, K) containing 2.0 mol% of V₂O₅ have been prepared in the range 0.00≤x≤0.15 by normal melt quenching method. Electron paramagnetic resonance (EPR), optical transmission and absorption spectra and dc conductivity of these glasses have been studied. Spin Hamiltonian parameters (SHPs) of VO²⁺ ions, dipolar hyperfine coupling parameter, P, Fermi contact interaction parameter, K and molecular orbital coefficients (α² and γ²) have been calculated. In GeO₂·Li₂O·B₂O₃ glasses there is no change in the tetragonality of the V⁴⁺O₆ complex and the size of 3d_xy orbit also remains unchanged with increase in GeO₂ content. In GeO₂·K₂O·B₂O₃ glasses, there is an increase in the tetragonality of the V⁴⁺O₆ complex and the 3d_xy orbit expands with increase in GeO₂ content. Values of the theoretical optical basicity, Λ_th, have also been reported. Optical band gap decreases with increase in GeO₂ content. The dc conductivity of these glasses decreases and the activation energy increases with increase in GeO₂:M₂O ratio.     

Electron paramagnetic resonance and luminescence of chromium in calcium germanate crystals

The luminescence of Ca₂GeO₄: Cr⁴⁺ single crystals at wavelengths in the range of 1.3 μm upon excitation with a 1-μ m semiconductor laser is investigated in the temperature range up to 573 K. At T<110 K, the Ca₂GeO₄: Cr⁴⁺ crystals are characterized by the electron paramagnetic resonance, which is attributed to the Cr⁴⁺ ions substituted for Ge⁴⁺ ions. The components of the g tensor and its principal axes are determined. It is revealed that the Cr⁴⁺ impurity centers in calcium germanate affect the crystal symmetry to a lesser degree compared to Cr⁴⁺ ions in forsterite. The observed deviation of the temperature dependence of the electron paramagnetic resonance from the Curie law is explained by the transition to the excited state with a low activation energy, as is the case in impurity 3d ions in diamond-like semiconductors. The inference is made that the giant effective degeneracy multiplicity of the excited state is associated with the initiation of soft phonon modes in the crystal upon excitation of the defect.     

Thermally stimulated luminescence of urine salts

We investigated thermally stimulated luminescence (TSL) of urine salts in the normal state and with oxalate, urate, and phosphate salts. We found that the presence of pathological salts leads to a decrease of TSL intensity and to the appearance of additional TLS bands with maxima at 118 and 205 K in addition to the characteristic bands at 173 and 260 K. The TLS bands are related to the urine components. The TSL intensities of urine salts of different chemical composition are compared. The thermal activation energy of the strongest TSL bands is determined. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 4, pp. 548–551, July–August, 2007.     

Behavioural studies of stimulated luminescence from feldspars

Since the work of Mejdahl in the mid-1980s feldspars have been used widely for palaeodosimetry. They have proved particularly popular because of the technical ease with which an optically stimulated luminescence signal can be obtained, and the potential for their use in dating over a wider time range than quartz. However, while the use of infrared stimulated lminescence has been a great success, the realisation of the potential for dating over a wide time range has been hampered by a series of behavioural problems, in particular concerned with the stability of the luminescence signal. This paper surveys the current state of knowledge of a range of aspects of the stimulated luminescence behaviour of feldspar. Particular attention is paid to the thermal and optical properties of the thermoluminescence (TL) and optically stimulated luminescence (OSL) signals from feldspars since these are of greatest relevance to their use as palaeodosimeters. Results obtained from well-characterised museum specimens demonstrate the variety of responses that are seen from different types of feldspar, particularly in their TL behaviour. Less variation is seen in their OSL response. In contrast, the response of potassium-rich feldspars separated from Quaternary sediments tends to be very consistent when many grains are analysed simultaneously, suggesting that averaging of the signal simplifies the behaviour of the system.