The use of mo and cu monochromatic radiations for quantitative phase analysis: study of the accuracy

Cement hydration is a very complex process in which crystalline phases are dissolving in water and after supersaturation hydrated crystalline and amorphous phases precipitate. Great efforts are being made to develop analytical tools to accurately quantify these processes and X-ray Powder Diffraction (XRPD) combined with Rietveld methodology is a suitable tool to quantify these complex mixtures and their time evolutions. However, some problems/drawbacks should be overcome to fully apply it to cement pastes characterization in order to get accurate phase analyses. In order to tackle this issue, a comparison of the Rietveld quantitative phase analyses (RQPA) obtained using Cu-Kα1, Mo-Kα1, and synchrotron strictly monochromatic radiations of three set of mixtures with increasing amounts of a given phase (spiking-method) is presented. The main aim is to test a simple hypothesis: high energy Mo-radiation, combined with high resolution laboratory X-ray powder diffraction optics, could yield more accurate RQPA, for challenging samples, than well-established Cu-radiation procedure(s). Firstly, a series of crystalline inorganic phase mixtures with increasing amounts of an analyte was studied in order to determine if Mo-Kα1 methodology is as robust as the well-established Cu-Kα1 one. Secondly, a series of crystalline organic phase mixtures with increasing amounts of an organic compound was analyzed. This type of mixture can result in transparency problems in reflection and inhomogeneous loading in narrow capillaries for transmission studies. Finally, a third series with variable amorphous content was studied. Limit of detection in Cu-patterns, ~0.2 wt%, are slightly lower than those derived from Mo-patterns, ~0.3 wt%, for similar recording times and limit of quantification for a well crystallized inorganic phase using laboratory powder diffraction was established ~0.10 wt%. From the obtained results it is inferred that RQPA from Mo-Kα1 radiation have slightly better accuracies than those obtained from Cu-Kα1. The results obtained in the previous comparison have been taken into account to obtain accurate RQPA, including the amorphous component with internal standard methodology, of hydrating cement pastes. The final goal of this second study was understanding the early-stage hydration mechanisms of a variety of cementing systems (Ordinary Portland Cement or Belite Alite Ye’elimite cement) as a function of water content, superplasticizer additives and type and content of sulfate source. In order to do so, X-ray powder diffraction data were taken in-situ with the humidity chamber coupled to the Mo-Kα1 powder diffractometer. Some results of this ongoing investigation will be reported and discussed.

In-situ Molibdenum X-ray powder diffraction study of the early hydration of cementitious systems on a humidity chamber

The durability of cement-based construction materials depends on the environmental conditions during their service life. A further factor is the microstructure of the cement bulk, established by formation of cement hydrates. The development of the phases and microstructure under given conditions is responsible of the high strength of cementitious materials. The investigation on the early hydration behavior of cements and cementing systems has been for a long time a very important area of research: understanding the chemical reactions that lead to hardening is fundamental for the prediction of performances and durability of the materials. The production of 1 ton of Ordinary Portland Cement, OPC, releases into the atmosphere ~0.97 tons of CO2. This implies that the overall CO2 emissions from the cement industry are 6% of all anthropogenic carbon dioxide. An alternative to reduce the CO2 footprint consists on the development of eco-cements composed by less calcite demanding phases, such as belite and ye'elimite. That is the case of Belite-Ye’elimite cements (BY). Since the reactivity of belite is not quick enough, these materials develop low mechanical strengths at intermediate hydration ages. A possible solution to this problem goes through the production of cements which jointly contain alite with the two previously mentioned phases, named as Belite-Alite-Ye’elimite (BAY) cements. The reaction of alite and ye'elimite with water will develop cements with high mechanical strengths at early ages, while belite will contribute to later values. The final goal is to understand the hydration mechanisms of a variety of cementing systems (OPC, BAY and pure phases) as a function of water content, superplasticizer additives and type and content of sulfate source. In order to do so, in-situ laboratory humidity chambers with Molybdenum X-ray Powder diffraction are employed. In the first 2h of hydration, reaction degree (α) of ye'elimite had been decreased for superplasticizer.

The influence of organic amendments on soil aggregate stability from semiarid sites

Restoring the native vegetation is the most effective way to regenerate soil health. Under these conditions, vegetation cover in areas having degraded soils may be better sustained if the soil is amended with an external source of organic matter. The addition of organic materials to soils also increases infiltration rates and reduces erosion rates; these factors contribute to an available water increment and a successful and sustainable land management. The goal of this study was to analyze the effect of various organic amendments on the aggregate stability of soils in afforested plots. An experimental paired-plot layout was established in southern of Spain (homogeneous slope gradient: 7.5%; aspect: N170). Five amendments were applied in an experimental set of plots: straw mulching; mulch with chipped branches of Aleppo Pine (Pinus halepensis L.); TerraCotten hydroabsobent polymers; sewage sludge; sheep manure and control. Plots were afforested following the same spatial pattern, and amendments were mixed with the soil at the rate 10 Mg ha-1. The vegetation was planted in a grid pattern with 0.5 m between plants in each plot. During the afforestation process the soil was tilled to 25 cm depth from the surface. Soil from the afforested plots was sampled in: i) 6 months post-afforestation; ii) 12 months post-afforestation; iii) 18 months post-afforestation; and iv) 24 months post-afforestation. The sampling strategy for each plot involved collection of 4 disturbed soil samples taken from the surface (0–10 cm depth). The stability of aggregates was measured by wet-sieving. Regarding to soil aggregate stability, the percentage of stable aggregates has increased slightly in all the treatments in relation to control. Specifically, the differences were recorded in the fraction of macroaggregates (≥ 0.250 mm). The largest increases have been associated with straw mulch, pinus mulch and sludge. Similar results have been registered for the soil organic carbon content. Independent of the soil management, after six months, no significant differences in microaggregates were found regarding to the control plots. These results showed an increase in the stability of the macroaggregates when soil is amended with sludge, pinus mulch and straw much. This fact has been due to an increase in the number cementing agents due to: (i) the application of pinus, straw and sludge had resulted in the release of carbohydrates to the soil; and thus (ii) it has favored the development of a protective vegetation cover, which has increased the number of roots in the soil and the organic contribution to it.