Nilo F. Cano

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.

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.

Phase change and pyroelectricity in natural hemimorphite

The phase change of a natural hemimorphite sample from Minas Gerais (Brazil) was investigated by two X-ray diffraction (XRD) methods and by near-infrared reflectance spectroscopy. Applying successive thermal treatments, the crystal structure undergoes two orientation conversions. The first one occurs at about 550 °C, and it was revealed by the Laue method. Below 500 °C, the water molecules were partially expelled without changing the crystal structure. A fact that supports this statement is the sequential disappearance of the water bands at 1400 and 1900 nm by thermal treatment. The second conversion takes place below 939 °C. Moreover, at 972 °C a phase change to the willemite mineral (α-Zn2SiO4) has been observed. This last conversion was confirmed by the power XRD. In addition, natural hemimorphite displayed a high pyroelectricity, which is related both to the absence of inverse centre and to the presence of molecular water and hydroxyl groups in the crystal structure.

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.

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.

TL dating of pottery fragments from four archaeological sites in Taquari Valley, Brazil

Sixty-three pottery fragments from four archaeological sites, numbered RST110, RST101, RST114 and RST114, in the Taquari Valley, vicinity of the city of Lajeado, Rio Grande do Sul state, southern Brazil, have been dated by the thermoluminescence method. Some of them from RST110 and RST101 are as old as 1400–1200 years, whereas those from RST114 and RST107 are younger than 800 years. This result indicates that RST101 and RST110 were peopled earlier than RST114 and RST107. The recent dates found are 302, 295 and 146 years and they are possible, since the first German immigrants who arrived in this region encountered Tupi–Guarani Indians still living there. One interesting result refers to the glow curves of quartz grains RST110, RST101 and RST114 that differ from the glow curves of RST107 quartz grains.

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.

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.

Archaeometric studies of ceramics from the São Paulo II archaeological site

This paper aims at studying the elementary chemical composition of 70 ceramic fragments from the São Paulo II archaeological site by instrumental neutron activation analysis. The concentration data was studied next using multivariate statistical methods, such as cluster analysis, principal component analysis and discriminant analysis. The results showed three different chemical groups of samples regarding the similarity/dissimilarity between the samples. Ceramics from each group have been selected and dated using thermoluminescence. The firing temperature of the ceramics was determined by electron paramagnetic resonance.

Radiation effects on TL and EPR of sodalite and application to dosimetry

Sodalite, Na8Al6Si6O24Cl2, a natural silicate mineral, has been investigated concerning its thermoluminescence (TL) and electron paramagnetic resonance (EPR) properties. Samples, both natural and heat treated at 500°C for 30min, present an EPR signal at g=2.01132. The irradiation induces two signals at g=2.0008 and a group of 11 lines due to an O− ion in an intermediate position with respect to two adjacent Al nuclei, that are superimposed on the signal at g=2.0008. An annealing at 500 °C/30min produces a broad signal around g~2.0, probably due to Fe3+ magnetic dipole interactions. The samples were annealed at 500 °C/30min and then irradiated with gamma-ray doses varying from 1 Gy to 20 kGy. All the samples have shown TL peaks at 110, 230 and 270 °C. Similar results were obtained for natural samples. The accumulated dose (AD) was determined to be AD~2.5 kGy and the annual dose of (0.595±0.001) mGy/year was obtained from the concentration of U, Th, and K2O in the sample. Therefore, the age obtained for natural sodalite was (4.2±0.2)106 years.