Chemical process to separate iron oxides particles in pottery sample for EPR dating

Ancient potteries usually are made of the local clay material, which contains relatively high concentration of iron. The powdered samples are usually quite black, due to magnetite, and, although they can be used for thermoluminescene (TL) dating, it is easiest to obtain better TL reading when clearest natural or pre-treated sample is used. For electron paramagnetic resonance (EPR) measurements, the huge signal due to iron spin-spin interaction, promotes an intense interference overlapping any other signal in this range. Sample dating is obtained by dividing the radiation dose, determined by the concentration of paramagnetic species generated by irradiation, by the natural dose so as a consequence, EPR dating cannot be used, since iron signal do not depend on radiation dose. In some cases, the density separation method using hydrated solution of sodium polytungstate [Na(G)(H(2)W(12)O(40))center dot H(2)O] becomes useful. However, the sodium polytungstate is very expensive in Brazil: hence an alternative method for eliminating this interference is proposed. A chemical process to eliminate about 90% of magnetite was developed. A sample of powdered ancient pottery was treated in a mixture (3:1:1) of HCI, HNO(3) and H(2)O(2) for 4 h. After that, it was washed several times in distilled water to remove all acid matrixes. The original black sample becomes somewhat clearer. The resulting material was analyzed by plasma mass spectrometry (ICP-MS), with the result that the iron content is reduced by a factor of about 9. In EPR measurements a non-treated natural ceramic sample shows a broad spin-spin interaction signal, the chemically treated sample presents a narrow signal in g= 2.00 region, possibly due to a radical of (SiO(3))(3-), mixed with signal of remaining iron [M. lkeya, New Applications of Electron Spin Resonance, World Scientific, Singapore, 1993, p. 285]. This signal increases in intensity under -gamma-irradiation. However, still due to iron influence, the additive method yielded too old age-value. Since annealing at 300 degrees C, Toyoda and Ikeya IS. Toyoda, M. Ikeya, Geochem. J. 25 (1991) 427-445] states that E `(1)-signal with maximum intensity is obtained, while annealing at 400 degrees C E`(1)-signal is completely eliminated, the subtraction of the second one from 300 degrees C heat-treated sample isolate E`(1)-like signal. Since this is radiation dose-dependent, we show that now EPR dating becomes possible. (C) 2008 Elsevier B.V. All rights reserved.

Formation Mechanism via a Heterocoagulation Approach of FePt Nanoparticles Using the Modified Polyol Process

Herein, we report a new approach of an FePt nanoparticle formation mechanism studying the evolution of particle size and composition during the synthesis using the modified polyol process. One of the factors limiting their application in ultra-high-density magnetic storage media is the particle-to-particle composition, which affects the A1-to-L1(0) transformation as well as their magnetic properties. There are many controversies in the literature concerning the mechanism of the FePt formation, which seems to be the key to understanding the compositional chemical distribution. Our results convincingly show that, initially, Pt nuclei are formed due to reduction of Pt(acac)(2) by the diol, followed by heterocoagulation of Fe cluster species formed from Fe(acac)(3) thermal decomposition onto the Pt nuclei. Complete reduction of heterocoagulated iron species seems to involve a CO-spillover process, in which the Pt nuclei surface acts as a heterogeneous catalyst, leading to the improvement of the single-particle composition control and allowing a much narrower compositional distribution. Our results show significant decreases in the particle-to-particle composition range, improving the A1-to-L1(0) phase transformation and, consequently, the magnetic properties when compared with other reported methods.