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The mechanochemical process denoted as a mechanically induced self-sustaining reaction was successfully applied in obtaining Mn-doped ZnS samples with Mn content between 0 and 5 mol%. The process consists in milling Zn/Mn/S powder elemental mixtures with the appropriate stoichiometry, which promotes after approximately 80 min the induction of a combustion reaction. The doping level was properly adjusted by controlling the atomic ratio of the starting mixture. A complete characterization of samples was carried out, including X-ray diffraction, high-resolution transmission electron microscopy, selected area electron diffraction, energy-dispersive X-ray spectroscopy, Raman spectroscopy, diffuse reflectance UV–Vis spectroscopy and emission and excitation photoluminescence measurements. A wurtzite structure, in which Mn2+ replaces Zn2+, was obtained with a nanometric character. The photoluminescence of samples showed the characteristic Mn2+ 4T1–6A1 emission that was highly dependent on the doping level. The maximum luminescence efficiency through the ZnS excitation was found for a doping value of 1 mol%. The photoluminescence showed virtually no contribution from the host emission, which confirmed that samples were properly doped.

The identification of archaeological amber has been used in Iberian prehistory to evidence long-distance exchanges and engage Iberia in networks that connect western Europe with central and northern Europe, the emergence of social complexity, and the consolidation of trade networks. However, until now, no comprehensive analytical study of the Iberian amber has been produced to support any of the interpretive models currently in use. This paper approaches the analysis of Iberian Peninsula amber artefacts by considering their provenance (based on FTIR characterization), chronology, and spatial relationship with other exotica. Our work increases the number of analyzed artefacts to 156 (24%), out of the c. 647 currently known for the Iberian Peninsula. Based on these new data and a review of Murillo-Barroso and Martinón-Torres (2012), this overview outlines amber consumption patterns from the 6th to 2nd millennia BCE and demonstrates long-distance amber exchange connecting Iberia with the Mediterranean region from the Neolithic period onwards.

The low temperature of decomposition of some calcium carbonates and the bending of the TG curves of hydrated cement between 500 and 800°C suggested the presence of some complex compound(s), which needed complementary investigation (XRD, TG). Stepwise transformation of portlandite (and/or lime) into calcium carbonate, with intermediate steps of calcium carbonate hydroxide hydrates (CCH-1 to CCH-5), was indicated by the previous study of two OPC. This was checked here on four cements ground for t g=15, 20, 25 and 30 min and hydrated either in water vapour, successively at RH=1.0, 0.95 and 0.5 for 2 weeks each (WR1, WR2 and WR3, respectively) or as mortars in liquid water (1m), followed by WR as above. The d[001] spacing of portlandite was confirmed to vary: here between the lowest and the highest standard values. The diffractograms of n=32 different samples were analyzed for presence of standard CCH peaks, generally slightly displaced. These were: CCH-1 [Ca 3(CO3)2(OH)2]: N=11 peaks, of three different d[hkl] spacings, CCH-2 [Ca6(CO2.65) 2(OH657)7(H2O)2]: N=10 for two d[hkl], CCH-3 [Ca3(CO3)2(OH) 2•1.5H2O]: N=14 for five d[hkl], CCH-4, ikaite [CaCO3(H2O)6]: N=13 for six d[hkl], CCH-5[CaCO3(H2O)]: N=15 for five d[hkl]. Thus the most probable is the presence of the last three. The stepwise transformation of Ca(OH)2 into CaCO3 was confirmed: portlandite (varying d[001])→CCH-1→CCH-2→CCH-3→CCH-4→CCH-5→CaCO 3 The content of CCH was the highest at t gr=15 min, decreasing down to t gr=25 min and increasing slightly at 30 min, as inferred from the number of the peaks observed. After cement powder hydration at RH=1.0 (WR1) peak number increased gradually from CCH-1 to CCH-5, whereas in the hydrated mortar (1m) the peak number decreased from CCH-1 to CCH-5, indicating the respective progress of the carbonation reaction. © Springer-Verlag 2007.