Mineral zircon: A novel thermoluminescence geochronometer

Mineral zircon contains trace amounts (typically 10-1000 v ppm) of the f -emitters uranium and thorium, which irradiate this mineral internally. This outstanding feature of zircon turns out to be extremely useful when this mineral is applied as a thermoluminescence (TL) dating medium, because the build-up of the age-dependent luminescence is dominated by the presence of well-defined internal radioactive sources and the contributions to the dose from external radiation sources are two orders of magnitude smaller. The results presented in this paper have led us to the conclusion that for zircon dating it is necessary to carefully select the best and homogeneous zircon grains of the highest optical quality. For successful dating experiments on very young and historically well-defined coastal dune sands, selection of the most stable luminescence component by means of narrow band interference filters is needed. Our results suggest that ultimately optical zircon dating will allow us to determine the age of extremely young samples ( e.g. 12 months!).     

Superlinear dose response of thermoluminescence (TL) and optically stimulated luminescence (OSL) signals in luminescence materials: An analytical approach

The phenomenon of superlinear dose response of thermoluminescence (TL) and optically stimulated luminescence (OSL) signals has been reported for several important dosimetric materials. We develop new analytical equations for the filling of traps and centers during irradiation and for the read-out stage of annealed luminescence materials, within the context of a two-trap and two-center model. The equations are applicable for both TL and OSL signals in annealed dosimetric materials, and are derived under the assumptions of low irradiation doses and dominant strong retrapping (weak recombination) processes. For low doses all traps and centers display linear dose response, which leads to quadratic dose response of the integrated TL/OSL signals. A new analytical expression is presented for this well-known quadratic dose dependence, in terms of the kinetic parameters in the model. The effect of elevated irradiation temperature on the integrated TL/OSL signals is also considered, and analytical expressions are obtained for this situation as well. A new type of dose-rate effect is reported based on the modeling results, which is due to irradiation during elevated temperatures. The accuracy of the analytical expressions is verified by comparing with the results of numerical simulations.     

TL and PTTL in natural fluorite previously irradiated with gamma rays and heavy ions

The effect of annealing temperature on the phototransfer thermoluminescence (PTTL) signal was studied to determine the appropriate annealing temperature for treating the natural powder before irradiation. The temperatures used to anneal virgin natural fluorite samples (only natural dose without giving the samples any artificial doses) were 150, 250, 350, 450, 550, 650 and 750°C for a duration of 1 h in each case. The results show that the PTTL response did not change for anneal temperatures up to 450°C, but at higher temperatures the signal decreased rapidly. The height of the 90°C peak decreased by two orders of magnitude as the anneal temperature increased from 450 to 750°C, whilst the height of the 180°C peak decreased by three orders of magnitude between the same two annealing temperatures. In order to investigate the effect of previous gamma rays and heavy ion irradiation on thermoluminescence (TL) and PTTL signals, powdered samples of natural fluorite from Cornwall, England, were annealed at 500°C and then irradiated (at GSI, Darmstadt, Germany) with ¹⁶¹Dy ions of energy 13 Mev/n; the range of fluences used was from 10⁴ to 10¹² ion cm⁻². Identical samples were given gamma doses in the range 1 Gy to 2.6 × 10⁴ Gy in order to compare the effects of gamma rays and heavy ions. The sensitivities of TL and PTTL were studied by giving the samples a gamma test dose of 1 Gy after annealing the samples at 500°C for 30 min in order to eliminate the TL resulting from previous gamma or heavy ion irradiation.     

Luminescence sensitivity changes of quartz by bleaching,annealing and UV exposure

The sensitivities of quartz luminescence signals to dose were studied after ionizing irradiation, ultraviolet (UV) exposure and different annealing conditions. The relationship between the 110 v °C thermoluminescence (TL) and optically stimulated luminescence (OSL) were studied on the same aliquot by looking at the ratio of both signals created by a test dose. It is suggested that the sensitivity changes of both signals are closely related, but not identical. Significant differences are observed when annealing to temperatures higher than 500 v °C. A modified model was proposed to interpret the observations. The similarity is interpreted as the same R hole centers are shared by both signals, whereas 110 v °C TL only uses additional R hole centers. Dramatic changes in luminescence sensitivity for quartz relate to the phase changes.     

Radiation effects in KMgF 3 crystals

Effects of x, g and UV irradiation on Tb 3+ and Eu 2+ doped KMgF 3 crystals were studied. Thermoluminescence (TL) excited by VUV radiation was compared to that induced by x and g rays. TL excitation spectra showed maxima at 125, 140, 155 and 180 v nm. The main TL peaks appeared after VUV irradiation at about the same temperatures and with the same thermal activation energies as after x or g irradiation, indicating that these peaks are due to the same trapping levels. In samples, which had previously been exposed to ionizing radiation, TL could also be excited with longer wavelengths that could not excite any TL in un-irradiated crystals; this is attributed to a process of phototransfer (PTTL). The x and UV excited luminescence was measured at LNT and RT and showed essentially the same main emission bands that appeared in the TL and PTTL peaks of these crystals. The dose dependence of the 730 v K TL peak in of KMgF 3 :Eu 2+ was linear up to about 2000 v Gy. The TL sensitivity of KMgF 3 :Eu 2+ was by an order of magnitude higher than that of KMgF 3 :Tb 3+ , which was by a factor of two greater than that of the known TLD-l00 phosphor.     

锆英石的抗γ射线辐照能力和Rietveld结构精修

为研究放射性核素固化介质备选矿物锆英石的抗γ射线辐照结构稳定性,以澳大利亚锆英石为研究对象,通过⁶⁰Co源γ射线辐照装置对样品施以1728 kGy的γ射线辐照.利用X射线荧光光谱仪、扫描电子显微镜和X射线衍射仪对样品的元素含量、γ射线辐照前后的微观形貌及物相变化进行表征,同时利用Rietveld方法对γ射线辐照前后的样品进行了结构精修.结果表明:澳大利亚锆英石经1728 kGy剂量的γ射线辐照后未发生物相变化,射线辐照前后样品的晶胞参数仅发生了10^-4 量级的变 关键词： 锆英石 γ射线 辐照 Rietveld结构精修     

Relative response of TL and component-resolved OSL to alpha and beta radiations in annealed sedimentary quartz

Knowledge of the relative luminescence response to alpha and beta radiation is very important in TL and OSL dating. In the present study the relative alpha to beta response is studied in a sedimentary quartz sample, previously fired at 900 °C for 1 h, in the dose region between 1 and 128 Gy, for both thermoluminescence (TL) and linearly modulated optically stimulated luminescence (LM – OSL). The LM – OSL measurements were performed at room temperature and at 125 °C. All OSL signals were deconvolved into their individual components. Comparison of OSL curves after alpha and beta irradiation strongly supports that quartz OSL components follow first order kinetics in both cases. In the case of TL, the relative alpha to beta response is found to be very different for each TL glow-peak, but it does not depend strongly on irradiation dose. In the case of LM – OSL measurements, it is found that the relative behaviour of the alpha to beta response is different for three distinct regions, namely the fast OSL component, the region of medium OSL component originating from the TL glow-peak at 110 °C when stimulation takes place at room temperature and finally the region of slow OSL component. Following stimulation at ambient temperature, the relative alpha to beta response of all components was not observed to depend significantly on dose, with the value of ratio being 0.03 and a tendency to decrease with increasing dose. However, in the case of measurements performed at 125 °C, the relative response of the fast components is much enhanced, and for the remaining components it increases with increasing dose. Special care must be taken to examine the relative alpha to beta response of the fast component at 125 °C which contrasts the relative response of the TL peak at ca. 325 °C. The implications for the dating of annealed quartz are also briefly discussed.     

Comparison of ‘blue’ and ‘infrared’ emission bands in thermoluminescence of alkali feldspars

Dating quaternary sediments by thermoluminescence (TL) or optically stimulated luminescence (OSL) calls for a detailed knowledge of the luminescence of feldspars. TL of the various alkali feldspars ((K, Na) Si₃AlO₈) display many common features, and some of these cause great difficulties for dating. After long storage following ionizing irradiation, the TL of most alkali feldspars is known to fade away by “anomalous fading”, which is incompatible with dating. This effect had been attributed to tunnel recombination. Following irradiation, a very intense tunnelling afterglow is observed at temperatures down to liquid nitrogen, in accordance with the observed rate of fading. This emission has a Gaussian spectrum entirely in the infrared (IR) with a maximum at 1.7 eV. It displays an important thermal quenching from 77 to 300 K. Its intensity is related with the ‘disorder’ of the crystal lattice. At higher temperatures, in TL proper, two emission bands can be separated. One is the well-studied complex visible emission, distributed over the spectral region from UV to orange, but mostly ‘blue’. The other is the ‘infrared’ band already observed at lower temperatures, which is attributed to Fe³⁺ ions. These two bands are clearly separated, with the spectral maxima, respectively, below and above 600 nm. They have also different kinetics, the glow peaks temperatures are different. But these two different bands are also coupled in many ways, they have parallel growth and fading. With ‘disordered’ feldspars, the ‘blue’ emission displays anomalous fading, which is stronger than that of the ‘infrared’. The infrared emission is more stable, which may be interesting for the purpose of dating.     

不同退火温度的Al_2O_3:C薄膜热释光和光释光性能

α-Al_2O_3:C晶体的热释光和光释光性能优越,但其制备要求高,需高温和高还原气氛.与α-Al_2O_3:C晶体性能接近的α-Al_2O_3:C陶瓷,热释光峰不单一.本文采用两次阳极氧化法在0.5 mol/L的草酸溶液中5℃恒温制备高度均匀有序的多孔Al_2O_3:C薄膜,主要研究不同退火温度对其热释光和光释光特性的影响.结果表明,经不同温度退火后的Al_2O_3:C薄膜均为非晶结构;不同退火温度的Al_2O_3:C薄膜热释光的主发光峰约在310℃左右,符合通用级动力学模型.600℃退火后的Al_2O_3:C薄膜热释光灵敏度最强,其热释光剂量曲线在1-10 Gy范围内具有很好的线性响应,在剂量10-120 Gy范围内出现超线性响应;在相同的辐照剂量下,随着退火温度的升高(≤600℃)光释光的初始发光强度逐渐增强.不同退火温度的Al_2O_3:C薄膜光释光衰减曲线都呈典型的指数衰减且快衰减速率相比α-Al_2O_3:C晶体显著加快.600℃退火后的Al_2O_3:C薄膜光释光灵敏度最强,其光释光剂量响应曲线在1-200 Gy整体上都具有很好的剂量线性关系.与热释光相比,Al_2O_3:C薄膜的光释光具有更宽的线性剂量响应范围.此研究为Al_2O_3:C薄膜作为光释光辐射剂量材料做出了有益的探索.     

Spectral information from minerals relevant for luminescence dating

The paper reviews basic spectral features of luminescence from minerals used in dating and allied research. Luminescence production is a result of multiple interactions within the imperfect crystal lattice and spectral information is not limited to the emission of light. Results of spectral investigations of luminescence emission during thermal stimulation (TL) or optical stimulation (OSL) form the main part of the paper. However, information on luminescence excitation and light absorption spectroscopy is also presented and possible links between luminescence production in minerals and particular lattice defects are considered. Quartz and feldspars, the most commonly used minerals, receive special attention, but the review includes other materials such as polymineral fine-grained fractions from sediments, zircon, calcite and other salts (halite, sulfate), meteorites, flint, volcanic materials (obsidian, tephra), ceramics and metallurgical slags. Although a wide range of different luminescence emission wavebands occur, it can be shown that certain emissions dominate in particular materials. Basic dosimetric properties are often known just for single emission wavebands of a particular mineral, and are listed in this case. The paper also aims to provide a starting point and inspiration for the study of other TL and OSL emissions, with particular regard to their potential and suitability for dating and related dosimetry tasks. These investigations, involving palaeodose determination based on an emission waveband with known characteristics, need careful separation of the particular emission peak, which may be influenced by its behaviour during the dating procedure (sample preparation, irradiation, preheat treatments, luminescence measurements, etc.). Spectral information available in this context and some technical remarks on the experimental conditions will be given to pave the way for conventional TL or OSL measurements in luminescence dating and dosimetry using natural or semi-natural materials.     

Thermal quenching of far-red Fe3+ thermoluminescence of volcanic K-feldspars

Strong thermal quenching is observed from 77 to 550 K in the far-red luminescence of K-feldspars. This far-red emission, next to the emission in the UV-to-blue spectrum recorded for thermoluminescence (TL), is reported in most alkaline feldspars with a characteristic peak centered on 710 nm with a width of 100 nm. This emission was observed by cathodoluminescence (CL) at room temperature (RT) for more than 30 K-feldspars, ranging from volcanic sanidines to granitic microclines and sediments and it is attributed to an Fe³⁺ impurity. Contrary to ‘blue’ emission in volcanic feldspars, the far-red emission displays very low anomalous fading (AF). This makes it attractive for dating purposes; however, it has weak natural TL intensity, even at saturation, which competes with the black-body emission of the heater plate. This is in contrast to an intense tunneling afterglow at liquid nitrogen temperature (LNT). Further observations show that the disadvantage of weak TL can be overcome. Photoluminescence (PL) under UV shows a very strong thermal quenching effect of the far-red emission from 77 to 550 K, which accounts for the above contrast. Near the LNT, the far-red Fe³⁺ photoluminescence is at a maximum and is dominant over other emissions in the spectrum. However, as the temperature increases, the efficiency decreases, falling to well below one percent, whereas the ‘blue’ emissions remain stable. This thermal quenching effect in photoluminescence is paralleled in TL. After irradiation and during storage at RT, whereas the ‘blue’ emission in volcanic feldspars is affected by ‘fast’ anomalous fading, charge trapped at Fe³⁺ centers as latent far-red emission is almost stable. As the TL evolves and the extant ‘blue’ emission is emitted, more and more of the trapped charge associated with far-red emission recombines non-radiatively, resulting in an efficiency for emission in natural TL that is less than one percent. A modified band model, which calls for 'hopping' conductivity during the storage, accounts for the anomalous fading. Trap emptying at lower temperatures should lead to better use of the stable latent far-red stored charge for the dating of volcanic deposits.     

Thermoluminescence of natural and synthetic diopside

Diopside, a natural silicate mineral of formula CaMgSi₂O₆, has been investigated concerning its thermoluminescence (TL) and electron paramagnetic resonance (EPR) properties. Glow curves and TL vs. γ-dose were obtained irradiating natural samples to additional dose varying from 50 to 10,000 Gy. Except for a 410 °C peak found in the Al-doped artificial diopside, all the other peaks grow linearly with radiation dose, but saturate beyond 1 kGy. To investigate high-temperature effect before irradiation, measurements of TL intensity in samples annealed at 500–900 °C and then irradiated to 1 kGy γ-dose were carried out. Also the TL emission spectrum has been obtained. To compare with natural diopside, a synthetic pure polycrystal was produced and further those doped with iron, aluminum and manganese were also produced.     

Investigation of thermoluminescence of natural zircon relevant to dating application

The thermoluminescence (TL) characteristics of natural zircons from Vietnam were studied for potential application to TL dating. All the glow curves of samples irradiated by gamma radiation or UV light showed a complex structure that consisted of a low temperature part (LTP) and a high temperature part (HTP). The TL emission spectra and monochromatic glow curves indicate that the two main impurities governing the TL emission are Dy³⁺ (LTP) and Tb³⁺ (HTP). The anomalous fading of the TL signal was assigned to the emission associated with Dy³⁺ whereas the 545 nm emission associated with Tb3⁺, exhibits significantly lower fading and consequently more suitable for TL dating.     

Dating archeological ceramics from the Valley of Vitor,Arequipa by the TL method

The age of some ancient pottery from the Valley of Vitor in the region of Arequipa, Peru, is determined by the thermoluminescence (TL) method. For dating, a 325 °C TL peak was used and irradiation with γ-dose from 5 to 50 Gy was carried out for the additive method, and from 0.4 to 5 Gy for the regeneration method. For these dose values, the TL intensity is observed to grow linearly, obtaining an accumulated dose of 1.62±0.09 Gy and 1.36±0.03 Gy for the additive and regeneration methods, respectively. The age (A) of the sample was calculated by the two methods, being A=867±195 years after Christ (AC) for the additive method and A=1050±157 years AC for the regeneration method. Both results are within 800–1200 years AC, which is the period of the Wari culture.     

双极集成电路低剂量率辐射损伤增强效应的高温辐照加速实验

选择了四种典型双极集成电路,在两种不同剂量率下,开展了不同温度的高温辐照加速实验,测量了典型双极集成电路的辐射敏感参数在不同高温辐照下的变化规律。实验结果表明:高温辐照能够给出空间低剂量率辐射损伤增强效应的保守估计,且存在最佳辐照温度,最佳辐照温度随总剂量的增加向低温区漂移,随剂量率的增大向高温区漂移,在相同剂量率和总剂量下,输入级为NPN晶体管的双极集成电路比输入级为PNP晶体管的最佳辐照温度低。     

Effects of 60Co gamma-ray irradiation on the optical properties of natural and synthetic quartz from 85 to 300 K

Optical absorption and luminescence measurements have been made between 85 and 300 K on natural and synthetic quartz during and after ⁶⁰Co gamma-ray irradiation. Absorption vs. dose curves can be resolved into the sum of a saturating exponential and a linear component. At 85 K the slope of the linear component is small, while at 300 K the linear term dominates the growth curves. The coloring induced by irradiation at 85 K decreased in a complex manner during anneal at a linear rate to 300 K. During this annealing process multiple-peak thermoluminescent (TL) glow curves were observed and recorded. The TL emission spectra are described accurately by single Gaussian-shaped bands, whereas the gamma-ray induced luminescence is comprised of several poorly resolved bands. All recorded TL glow curves are characterized by a set of four first order glow peaks between 150 and 220 K. The temperature dependence of radioluminescence intensity is described by a classical model in which a temperature-independent radiative transition competes with a thermally activated non-radiative process.     

New scheme for dual readout of dose in polycrystalline Li2B4O7 irradiated with synchrotron X-rays from Indus-2

A new thermoluminescent (TL) dosimeter readout scheme was developed which allows for the measurement of both the single incident dose and the accumulated dose from multiple irradiations, through a novel dual readout procedure. Undoped, Mn doped and Cu doped polycrystalline Li₂B₄O₇ pallets were irradiated by synchrotron X-rays from Indus-2 with different dose. Thermoluminescence glow curves were taken at various heating rates. Two glow peaks were observed in each sample. TL intensities of different samples were compared and it was found that TL counts are more in Cu doped Li₂B₄O₇ sample. TL counts under each peak were calculated and a fixed ratio for two peaks was obtained. A new method of reading out the two peaks separately was formalized, allowing for greater flexibility in the use of TL based personnel dose monitoring devices.     

Investigation of the optical absorption characteristics of slow-cooled LiF:Mg,Ti (TLD-100)

The optical absorption (OA) spectrum of LiF:Mg,Ti has been studied as a function of dose at two different cooling rates following the 400 °C pre-irradiation anneal in order to further investigate the role of cooling rate in the thermoluminescence (TL) mechanisms of this material. “Slow-cooling” following the pre-irradiation 400 °C anneal substantially decreases the OA bands at 3.25 eV and 4.0 eV, in agreement with the overall loss in TL peaks 2–5 intensity using slow-cooling routines. Slow-cooling appears to shift the maximum intensity of peak 5 to lower temperatures (a behaviour which has been attributed to an enhanced intensity of peak 5a), however, no difference in the shape of the 4.0 eV OA band is detected following “slow-cooling”. Apparently the OA band related to peak 5a is too close in energy to the peak 5 OA band to be observed due to lack of sufficient resolution and spectral deconvolution process or it is not present at room temperature (RT) and formed during heating of the sample. The intensity of the 4.0 eV OA band does not change if the sample (prior to irradiation to a standard dose of 200 Gy) is irradiated to 4 kGy followed by a 500 °C/1 h post-irradiation anneal. This result demonstrates that the loss of intensity at high levels of dose (so-called radiation damage) of TL glow peak 5 results from alteration of the LCs or to the creation of additional competitive centers and is not correlated with the dose behaviour of the TCs.     

Effect of ion irradiation on the thermoluminescence properties of K2Ca2(SO4)3 phosphor

This paper presents the thermoluminescence (TL) studies of ion-irradiated potassium–calcium mixed sulfate phosphor. The sample was prepared by the solid-state diffusion method. The X-ray diffraction study of the prepared sample suggests an orthorhombic structure with an average particle size of 0.16 μ m. The samples were irradiated with 1.2 MeV argon ions at fluences varying between 10¹¹ and 10¹⁵ ions/cm². The argon ions penetrate to a depth of 1.93 μ m and lose their energy mainly via electronic stopping. Due to ion irradiation, a large number of defects such as oxygen vacancies, radicals and color centers are formed in the sample. TL glow curves were recorded for each of the ion fluences. A linear increase in the intensity of TL glow peaks was found with an increase in the ion dose from 72 kGy to 720 MGy. The kinetic parameters associated with the prominent glow peaks were calculated using glow curve deconvolution, different glow curve shapes and sample heating rate methods.