Identification of defect centers responsible for thermoluminescence emission in sol-gel synthesized calcium silicate phosphor.

The thermoluminescence (TL) of calcium silicate phosphor (CSO) prepared by the sol-gel method and sintered at 1200 °C were investigated. From Tm-Tstop curve, TL emission spectrum and computer deconvolution using electron traps with discrete and continuous distributions, the glow curves were found to be composed of four TL peaks (117, 190, 250 and 275 °C) with a single emission band centered at 370 nm. Electron paramagnetic resonance (EPR) investigation has been carried out to identify the defect centers formed in the CSO phosphor by γ-irradiation and find the centers related to the TL process in the phosphor. At room temperature, three defect centers were observed. The first center, characterized by the principal g-values of 2.014, 2.011, and 2.0080 was assigned to an O- ion. The second center with g-values 2.015, 2.013, and 2.010 is also attributed to an O- ion and is associated with the TL peak at 280 °C. The third center, with an isotropic g-value of 2.0011 was identified as the F+ center (singly ionized oxygen vacancy) and relates to the TL peak at 280 °C.

Chemical contamination in coastal areas alters shape, resistance and composition of carnivorous gastropod shells.

Morphological, structural and compositional alterations in shells of molluscs have been proposed as putative biomarkers of chemical contamination in coastal zones. Despite this, few studies were carried out using top predator gastropods which tend to be more susceptible to contamination exposure. Thus, the present study assessed disturbances on shells of Stramonita brasiliensis considering compression resistance and organic and mineralogical matrix composition, related to morphometric alterations. Results showed reductions in compression resistance and organic matrix content associated with higher contaminated sites. In addition, a predominance of calcite polymorphs was seen in shells obtained in polluted areas. Such outputs were consistent with local contamination levels which may have induced the observed alterations. Thus, changes in mollusc shells showed good performance as potential biomarkers of coastal contamination, being probably observed in other species of carnivorous gastropods around the world.

Identification of ESR centers and their role in the TL of natural salt from Lluta, Peru.

In this study, the thermoluminescence (TL) properties of natural NaCl from Lluta, Arequipa-Peru was investigated. The number of peaks and the kinetic parameters associated with the TL glow peaks of NaCl sample after gamma-irradiation were analyzed by initial rise and deconvolution method. Defect centers induced in pure salt by gamma irradiation have been studied by electron spin resonance (ESR) with a view to identify the centers associated with the TL process in the salt. Thermal annealing experiments indicate the presence of three defect centers. Center I characterized by the g-value 2.011 is identified as an O- ion and relates with the dominant TL peak at 220 °C. Center II with a g-value of 2.0058 is attributed to a F center and is found to correlate with the 128 °C TL peak. Center III has of g-value 2.014 and is also assigned to an O- ion.

Dating and determination of firing temperature of ancient potteries from Yumina archaeological site, Arequipa, Peru.

Pottery fragments from the Yumina archaeological site, Arequipa, Peru, were dated by means of thermoluminescence (TL) and optically stimulated luminescence (OSL). Electron paramagnetic resonance (EPR) technique was used to study the firing temperature using the iron signal (Fe3+) as a firing temperature reference. The ages of the samples were found to be between 1190 ±â€¯30 and 1240 ±â€¯80 years (777 ±â€¯80 and 827 ±â€¯30 A.D.) determined by both techniques. The firing temperature of ceramics was found to be around 550  ± 50 °C. Our study, based on the combination of TL and OSL techniques to study Yumina archaeological site pottery, will be helpful for archaeologists in Peru. With the results of this investigation, we can understand the chronology and determine the areas of dispersion and density of the archaeological occupation in the Arequipa Valley. In addition, the calculated ages are consistent with the occupation period of the Yumina archaeological site estimated by stratigraphic analysis of the potteries.

Dating of carbonate covering cave paintings at peruaçu, Brazil by TL and EPR methods.

In the present work, carbonate samples covering wall painting of four points in the same site found at Peruaçu National Park in the extreme northwest of the state of Minas Gerais, Brazil, has been investigated and dated by thermoluminescence (TL) and electron paramagnetic resonance (EPR) techniques. The EPR spectrum of the carbonate samples presented the typical six signals due to Mn2+ ion and signals around g~2.0 due to SO2- and CO2-. The thermal stability and dose response of the EPR signals were found to be suitable for an age determination using the center due to CO2-. The carbonate sample exhibits TL peaks at approximately 350 °C. TL and EPR dating of the carbonate samples that covered the cave paintings gave an age of 33.13 to 48.40 ka. This series of dating data indicate that in the region about 220-250 km from the coast and extending from the State of Piaui, Bahia to Minas Gerais people lived around 50000 years ago.

Synthesis, thermoluminescence, defect center and dosimetric characteristics of LiF:Mg,Cu,P,Si phosphor.

LiF:Mg,Cu,P,Si (MCPS), a new tissue equivalent phosphor, was synthesized by solid state method. Powder x-ray diffraction and scanning electron microscope were employed to determine the structural features. The dosimetric characteristics, electron spin resonance (ESR) and defect centers of this newly prepared phosphor were investigated. The MCPS phosphor is highly sensitive when compared with LiF:Mg,Ti and LiF:Mg,Cu,P (MCP), with the TL sensitivity being 35 times and 1.3 times higher respectively. The dosimetric peak occurs at 220°C with a well defined glow curve structure similar to MCP. MCPS phosphor shows a linear dose response till 10Gy. The minimum detectable dose has been found to be 8µGy. The thermal stability of the phosphor could be enhanced by 20°C from 240°C to 260°C when compared to MCP. Defect centers formed in the phosphor by gamma irradiation have been studied by ESR to identify the centers associated with the TL process in this phosphor. Thermal annealing experiments reveal the presence of several defect centers. Center I which shows an isotropic g factor of 2.0233 has been found to relate with the TL peaks at 160°C, 220°C and 265°C. Centers II and III are characterized by isotropic g values of 2.0096 and 2.0019 respectively and are attributed to F centers.

Synthesis and Study of Fe-Doped Bi2S3 Semimagnetic Nanocrystals Embedded in a Glass Matrix.

Iron-doped bismuth sulphide (Bi2-xFexS3) nanocrystals have been successfully synthesized in a glass matrix using the fusion method. Transmission electron microscopy images and energy dispersive spectroscopy data clearly show that nanocrystals are formed with an average diameter of 7-9 nm, depending on the thermic treatment time, and contain Fe in their chemical composition. Magnetic force microscopy measurements show magnetic phase contrast patterns, providing further evidence of Fe incorporation in the nanocrystal structure. The electron paramagnetic resonance spectra displayed Fe3+ typical characteristics, with spin of 5/2 in the 3d5 electronic state, thereby confirming the expected trivalent state of Fe ions in the Bi2S3 host structure. Results from the spin polarized density functional theory simulations, for the bulk Fe-doped Bi2S3 counterpart, corroborate the experimental fact that the volume of the unit cell decreases with Fe substitutionally doping at Bi1 and Bi2 sites. The Bader charge analysis indicated a pseudo valency charge of 1.322|e| on FeBi1 and 1.306|e| on FeBi2 ions, and a spin contribution for the magnetic moment of 5.0 µB per unit cell containing one Fe atom. Electronic band structures showed that the (indirect) band gap changes from 1.17 eV for Bi2S3 bulk to 0.71 eV (0.74 eV) for Bi2S3:FeBi1 (Bi2S3:FeBi2). These results are compatible with the 3d5 high-spin state of Fe3+, and are in agreement with the experimental results, within the density functional theory accuracy.

Dating stalagmite from Caverna do Diabo (Devil´S Cave) by TL and EPR techniques.

A cylindrical fragment of stalagmite from Caverna do Diabo, State of São Paulo, Brazil, has been studied and dated by thermoluminescence and electron paramagnetic resonance techniques. The thermoluminescence glow curves of stalagmite samples and subsequently gamma irradiated, have shown rise of three peaks at 135, 180 and 265 °C. From electron paramagnetic resonance spectra of stalagmite was possible to clearly identify three paramagnetic centers in the g = 2.0 region: Centers I, II and III are due to , and , respectively. The additive method was applied to calculate the accumulated dose using thermoluminescence peak at 265 °C and the electron paramagnetic resonance signal at g = 1.9973 of CO- 2 radical. The ages of the different slices of stalagmite were determined from the Dac- values and Dan- value, obtaining an average of 86410 for central slice, 53421 for second slice, 31490 for third slice and 46390 years B.P. for the central region of upper end.

Radiation dosimetry using decreasing TL intensity in a few variety of silicate crystals.

This study shows that there are some ionic crystals which after irradiation with high gamma dose Dm and subsequent irradiation with low doses ranging up to 500Gy present a decreasing TL intensity as dose increases. This interesting feature can be used as a calibration curve in radiation dosimetry. Such behavior can be found in green quartz, three varieties of beryl and pink tourmaline. In all these silicate crystals it can be shown that irradiation with increasing γ-dose there is a dose Dm for which the TL intensity is maximum. Of course, Dm varies depending on the crystal and irradiated crystal with the dose Dm is stable. If one of these crystals is taken and irradiated with doses from low values up to 400-500Gy, a curve of decreasing TL intensity is obtained; such a curve can be used as a calibration curve.

Study of luminescence, color and paramagnetic centers properties of albite.

A sample of natural albite, NaAlSi3O8, from the state of Minas Gerais, Brazil, has been investigated. The mineral is a solid solution of K-feldspar (4600 ppm--K) and Ca-feldspar (1100 ppm--Ca). The TL spectra of natural and the pre-annealed at high temperature albite presented a very intense band around 275 nm and weaker bands around 400 and 560 nm. Other TL properties have been investigated through monochromatic (275 nm and 400 nm) glow curves. The EPR spectrum measured at low temperature (77K) shows the typical 11 lines signal due to Al-O(-)-Al center superposed on Fe(3+) signal around g=2.0. The EPR spectra above 260 K show only g=2.0 signal due to Fe(3+) ions.

Effect of Fe2O3 concentration on the structure of the SiO2-Na2O-Al2O3-B2O3 glass system.

The structural properties of the glass matrix 40SiO(2)·30Na(2)O·1Al(2)O(3)·(29-x)B(2)O(3)·xFe(2)O(3) (mol%), 0.0≤x≤29.0 were studied by X-ray diffraction (XRD), differential thermal analysis (DTA) and Raman and infrared spectroscopy (FT-IR). XRD demonstrated Fe(3)O(4) crystal formation for Fe(2)O(3) concentrations of 29.0 mol%. DTA showed that glass transition and crystallization temperatures changed as a function of Fe(2)O(3) concentration and that these alterations were related to structural change in the glass system. Interesting aspects of Raman and FT-IR spectra were found, and this gives information about of the structure changes in Si-O-Si units of these glasses as a function of Fe(2)O(3) concentration.