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A series of 22 figured Phoeno-Punic and Roman terra-cottas, of high relevant archaeological and patrimonial values, have been studied. The samples were recovered in the Roman Theatre of Malaga (Spain). A thorough analysis including stereomicroscopy, elemental analysis by WDXRF, mineralogical analysis by XRPD coupled with the Rietveld method, and SEM, has been carried out. Highly diluted fused glass beads probed to be enough for the X-ray fluorescence analyses, minimizing the damage to the samples. For selected samples, in addition to the classical use of the Rietveld method, the G-factor external-standard approach has been employed to get full quantitative crystalline and amorphous phase analysis. The analytical results allow proposing a local regional provenance for the main part of the samples, being a relevant data for several artifacts, not contextualized due to stratigraphic alterations in the site. In addition, some relevant samples, for instance a theatrical mask fragment (TRC005), are likely foreign. The overall amorphous is not negligible in phase quantification, accounting for up to 50 wt %. Technologically, all terra-cotta samples are similar, made of calcareous clays, fired at ~700-950 ºC.Se han estudiado 22 terracotas figuradas feno-púnicas y romanas, de alto valor arqueológico y patrimonial. Las muestras proceden de las excavaciones del Teatro romano de Málaga (España). El análisis realizado incluye estereomicroscopía, análisis elemental mediante WDXRF, análisis mineralógico cuantitativo mediante el método de Rietveld de los datos de XRPD y SEM. Para minimizar el daño realizado a las muestras, se prepararon perlas muy diluidas, que han demostrado ser suficientes para los análisis de fluorescencia de rayos-X. Para muestras selectas, además del análisis usual mediante el método de Rietveld, se ha utilizado el método del estándar externo mediante el factor-G para obtener análisis cuantitativos de fases cristalinas y amorfas. Los resultados analíticos permiten proponer una procedencia local/regional para la mayor parte de las muestras, siendo esta información de gran interés para algunas piezas descontextualizadas debido a alteraciones estratigráficas en el yacimiento. Adicionalmente, algunas piezas relevantes, como un fragmento de máscara teatral (TRC005) son posiblemente piezas de importación. La cuantificación de la fracción amorfa indica que la magnitud de ésta no puede ser despreciada en las cuantificaciones, llegando a ser cercana al 50 wt %. Tecnológicamente, todas las terracotas son muy similares, fabricándose en arcillas calcáreas cocidas entre unos 700 y 950 ºC.

Terra Sigillata was a Roman pottery, which was also produced in several workshops in Hispania. Two known workshops at Granada (Cartuja and Carmen de la Muralla, or Albayzin) are known to have produced both typical Terra Sigillata and low-gloss coating related pottery. Potsherds from these workshops have been thoroughly studied from an archaeological approach, but not by analytical chemistry techniques. Here, we report a full characterization of nine selected samples from these workshops and also a tenth sample, Terra Sigillata made in the Gaul, for comparison. The pastes characterization includes elemental analysis from XRF and quantitative mineralogical analysis by Rietveld analysis of XRPD data. Cluster analysis to both types of data has been carried out. SEM-EDX and GI-XRPD have been used to characterize the slips of the pottery. The elemental analysis results for the pastes suggest that terra sigillata potsherds from both workshops were likely made from the same clay, different to that used to make the low-gloss coating pottery. The firing temperatures have been estimated from the phase assemblages being about 900-950ºC for the Granada sigillata.La Terra Sigillata fue una cerámica romana, que se produjo también en varios talleres en Hispania. Los talleres ubicados en Granada (Cartuja y Carmen de la Muralla, o Albayzín) produjeron Terra Sigillata y cerámicas de barniz mate. Ambos talleres han sido ampliamente estudiados desde un punto de vista arqueológico, pero no mediante técnicas analíticas. En este trabajo, se estudian nueve muestras de estas producciones, y una décima de Terra Sigillata producida en la Galia, para su comparación. La caracterización de las pastas incluye análisis elemental por XRF, y análisis mineralógico cuantitativo mediante análisis de Rietveld de los datos de XRPD. Estos dos conjuntos de datos también se han evaluados mediante análisis de cluster. Los recubrimientos superficiales se han caracterizado mediante SEM-EDX y GI-XRPD. Los análisis sugieren que ambos talleres utilizaron probablemente la misma materia prima para la Terra Sigillata, y otra diferente en las cerámicas de barniz mate. Se ha estimado una temperatura de cocción para la Sigillata en el intervalo 900-950ºC.

The thick Pliocene clay beds located along the mouth of the Guadalhorce River in Malaga were used in the Roman era for amphorae production related to the ever-growing production of garum and salted fish. As a first step in their archaeometric characterization, a series of firing tests on the potential raw material have been carried out. The main aim of this work is to obtain a suitable tool for estimating the firing temperatures of those amphorae, as well as to make a comprehensive evaluation of the potential of an innovative external-standard method for measuring the amorphous content of a pottery sample, the G-factor method. The obtained results emphasize a highly amorphous content, over 50 wt% in some samples, which varies with the firing temperature. This shows the potential of this technique, which allows straightforward fully quantitative mineralogical analysis and a mineralogical comparison even between samples fired at very different temperatures. [ABSTRACT FROM AUTHOR]

Cement hydration is a very complex set of processes. The evolution of the crystalline phases during hydration can be accurately followed by X-ray powder diffraction data evaluated by the Rietveld method. However, accurate measurements of some microstructural features, including porosity and amorphous content developments, are more challenging. Here, we combine laboratory X-ray powder diffraction and computed microtomography (μCT) to better understand the results of the μCT analyses. Two pastes with different water-cement ratios, 0.45 and 0.65, filled within capillaries of two sizes, ϕ = 0.5 and 1.0 mm, were analysed at 50 days of hydration. It was shown that within the spatial resolution of the measured μCTs, ~2 μm, the water capillary porosity was segmented within the hydrated component fraction. The unhydrated part could be accurately quantified within 2 vol% error. This work is a first step to accurately determining selected hydration features like the hydration degree of amorphous phases of supplementary cementitious materials within cement blends.

Herein, we exploit the well-known swelling behaviour of metal-organic frameworks (MOFs) to create a self-folding polymer film. Namely, we show that incorporating crystals of the flexible MOF MIL-88A into a polyvinylidene difluoride (PVDF) matrix affords a polymer composite film that undergoes reversible shape transformations upon exposure to polar solvents and vapours. Since the self-folding properties of this film correlate directly with the swelling properties of the MIL-88A crystals, it selectively bends to certain solvents and its degree of folding can be controlled by controlling the relative humidity. Moreover, it shows a shape-memory effect at relative humidity values from 60 % to 90 %. As proof of concept, we demonstrate that these composite films can lift cargo and can be used to assemble 3D structures from 2D patterns. Our strategy is a straightforward method for designing autonomous soft materials with folding properties that can be tuned by judicious choice of the constituent flexible MOF., (© 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.)

We report the synthesis, structural characterization, and functionality (framework interconversions together with proton conductivity) of an open-framework hybrid that combines Ca(2+) ions and the rigid polyfunctional ligand 5-(dihydroxyphosphoryl)isophthalic acid (PiPhtA). Ca2[(HO3PC6H3COOH)2]2[(HO3PC6H3(COO)2H)(H2O)2]·5H2O (Ca-PiPhtA-I) is obtained by slow crystallization at ambient conditions from acidic (pH ≈ 3) aqueous solutions. It possesses a high water content (both Ca coordinated and in the lattice), and importantly, it exhibits water-filled 1D channels. At 75 °C, Ca-PiPhtA-I is partially dehydrated and exhibits a crystalline diffraction pattern that can be indexed in a monoclinic cell with parameters close to the pristine phase. Rietveld refinement was carried out for the sample heated at 75 °C, Ca-PiPhtA-II, using synchrotron powder X-ray diffraction data, which revealed the molecular formula Ca2[(HO3PC6H3COOH)2]2[(HO3PC6H3(COO)2H)(H2O)2]. All connectivity modes of the "parent" Ca-PiPhtA-I framework are retained in Ca-PiPhtA-II. Upon Ca-PiPhtA-I exposure to ammonia vapors (28% aqueous NH3) a new derivative is obtained (Ca-PiPhtA-NH3) containing 7 NH3 and 16 H2O molecules according to elemental and thermal analyses. Ca-PiPhtA-NH3 exhibits a complex X-ray diffraction pattern with peaks at 15.3 and 13.0 Å that suggest partial breaking and transformation of the parent pillared structure. Although detailed structural identification of Ca-PiPhtA-NH3 was not possible, due in part to nonequilibrium adsorption conditions and the lack of crystallinity, FT-IR spectra and DTA-TG analysis indicate profound structural changes compared to the pristine Ca-PiPhtA-I. At 98% RH and T = 24 °C, proton conductivity, σ, for Ca-PiPhtA-I is 5.7 × 10(-4) S·cm(-1). It increases to 1.3 × 10(-3) S·cm(-1) upon activation by preheating the sample at 40 °C for 2 h followed by water equilibration at room temperature under controlled conditions. Ca-PiPhtA-NH3 exhibits the highest proton conductivity, 6.6 × 10(-3) S·cm(-1), measured at 98% RH and T = 24 °C. Activation energies (Ea) for proton transfer in the above-mentioned frameworks range between 0.23 and 0.4 eV, typical of a Grothuss mechanism of proton conduction. These results underline the importance of internal H-bonding networks that, in turn, determine conductivity properties of hybrid materials. It is highlighted that new proton transfer pathways may be created by means of cavity "derivatization" with selected guest molecules resulting in improved proton conductivity.