Incorporation of antimony-bearing mining wastes into clinker Portland raw feed: The difficulty of Sb analysis in calcium silicates.

Within the global trend to valorise various mineral wastes as substituents in Portland cement clinker raw feed, mining wastes are promising candidates. However, they might still contain high levels of metallic elements. Their fate in the kiln is not always understood as well as their incorporation within the various clinker's phases. This is especially the case for antimony. Its in situ microanalysis by the means of energy-dispersive spectroscopy is tricky since several of its L lines (Lα1 = 3604,72 eV, Lα2 = 3595,32 eV) overlap with calcium lines (Kα1 = 3691,68 eV, Kα2 = 3688,09 eV). Hence, at low concentrations, it is not possible to visualise its characteristics peaks. Increasing the counting rate by increasing the acceleration current results in the generation of spurious sum peaks, rendering the analysis not viable. Wavelength dispersive spectroscopy (i.e. electron microprobe) allows a better spectral resolution and quantification of Sb in the clinker phases. In a Portland cement clinker doped with 1% of Sb-bearing mining waste, the Sb2O3 content in belite and alite is in the 0.2-0.4 wt.% range as well as for C3A; in C4AF the content is higher, from 1.4 wt.% to 2 wt.%. However, there are microstructural evidence that Sb forms blebs from less than 1 µm in diameter up to 10 µm, included in calcium silicates. Hence, its incorporation in the lattice of calcium silicates is dubious. However, for ferrites and aluminates there is no microstructural evidence for remaining Sb-bearing phases, suggesting a direct incorporation in crystal lattices.

Slags from roasting of antimony ore in the Brioude-Massiac (France) area used as aggregates: An early example of circular economy.

Towards the end of the 19th century and the early 20th century, France was the world's largest producer of antimony, especially due to the rich deposits in the Brioude-Massiac area. Even though all the mining and smelting activities are long gone, there are still some remains of those activities. The most original of those is the use of roasting slags as aggregates in former plant walls or industrial building. They are macroscopically characterised by a black or red colour with a vesicular aspect similar to natural pozzolanas. Common petrography and mineralogy tools have been used to characterise those slags: optical mineralogy, scanning electron microscopy coupled with energy dispersive spectroscopy (SEM-EDS) and X-ray diffraction (XRD). To gain an insight into their mineral complexity, a QEMSCAN map has been produced. The mineralogy is typical of high-temperature slags: cristobalite, quartz, mullite, fayalite-forsterite series and spinel. The antimony content is quite high, up to seven percent, under the form of various antimony oxides and native antimony.

Application of various microscopy techniques to study early-age and longer-term behaviour of super sulphated cement microstructure.

Super sulphated cement (SSC) is a very promising substitute for traditional construction materials (i.e. Portland cement), due to its enhanced durability and particularly low environmental impact. This paper explores the microstructure and certain properties of SSC, focusing on the particular complexities of its microstructure and the difficulties of microanalysis of its hydrates. To do so, SSC paste samples were first cast to identify hydration products using X-ray diffraction, then observed at early age using confocal laser scanning microscopy (CLSM) and at early and late age using scanning electron microscopy. In addition, concrete cores impregnated with fluorescein in order to highlight porosity, cracking and aggregates debonding were observed under UV light using optical microscopy (OM), showing a complete absence of cracking and aggregate debonding. Both microscopy techniques (CLSM and UV light OM) have been applied to this type of binder for the first time. The results show that SSC microstructure is characterised by a sophisticated intergrowth of various phases, including ettringite and amorphous calcium-(alumina)-silicate hydrate gels. Finally, Monte-Carlo simulation of electron-matter has been provided for a better understanding of EDS analysis.

First historical cements in France from Boulogne sur Mer: Investigations on 19th century's manufactured cement-based monuments.

The Boulogne-Sur-Mer area in the North of France is one of the cradles of the French cement industry (the other main one is Grenoble region due to Joseph Vicat's first cement works). From fast setting (Roman) to Portland, those cements were famous in France and have been used throughout the entire country. The main objective of this study is to give a preliminary insight of the type of binders used since there is currently few and scattered data on those specific structures and to assess the efficiency of traditional analytical techniques [X-ray diffraction (XRD), optical (OM) and scanning electron microscopy (SEM) observations, coupled with EDS analysis] used to differentiate natural and artificial cements.

The elusive ettringite under the high-vacuum SEM - a reflection based on natural samples, the use of Monte Carlo modelling of EDS analyses and an extension to the ettringite group minerals.

Ettringite, Ca6 Al2 (SO4 )3 (OH)12 .26H2 O, or C6 AS¯3 H32 as it is known in cement chemistry notation, is a major phase of interest in cement science as an hydration product and in polluted soil treatment since its structure can accommodate with many hazardous cations. Beyond those anthropogenic features, ettringite is first of all a naturally occurring mineral (although rare). An example of its behaviour under the scanning electron microscope and during energy dispersive spectroscopy (EDS) qualitative analysis is presented, based on the study of natural ettringite crystals from the N'Chwaning mine in South Africa. Monte Carlo modelling of the electron-matter interaction zone at various voltages is presented and confronted with actual, observed beam damage on crystals, which burst at the analysis spot. Finally, theoretical energy dispersive spectroscopy spectra for all the ettringite group minerals have been computed as well as Monte Carlo modelling of the electron-matter interaction zone. The knowledge of the estimation of the size of this zone may thus be helpful for the understanding of energy dispersive spectroscopy analysis in cement pastes or ettringite-remediated soils.

Characterization of fibrous mimetite.

Mimetite, Pb5(AsO4)3Cl, is a ubiquitous mineral that is of interest in various fields such as ore mineralogy, environmental studies, and minerals engineering. Mimetite generally forms hexagonal prisms and barrel-shaped crystals, but its fibrous form is quite an uncommon one. Here we attempt to present its worldwide occurrences on the basis of a literature review. We then present a study on fibrous mimetite from one of its historical locations based on the petrographic microscope, SEM-SE and EDX, and Raman spectroscopy.

The good, the bad and the ugly polishing: Effect of abrasive size on standardless EDS analysis of Portland cement clinker's calcium silicates.

Standardless Energy dispersive spectroscopy (EDS) on polished samples of Portland cement clinker is routinely performed both for unhydrated phases as well as in cement pastes. Typically, the calcium to silica ratio is investigated. EDS analyses are highly dependent on the polishing quality of the sample. It is thus worth studying the Ca/Si ratios of cement phases in a clinker since they can be used as a reference. Indeed, alite (Ca3SiO5 or C3S in cement chemistry notation) and belite (Ca2SiO4 or C2S) should have an atomic Ca/Si ratio of 3 and 2, respectively. EDS carried out under the scanning electron microscope (SEM) is routinely used on polished samples to assess the composition of such phases. In the present study, Ca/Si ratios are investigated on a commercial clinker polished at various steps (6, 3, 1 and 0.25 µm diamond pastes, 0.05 µm alumina). All along the polishing process, ratios are coherent with theoretical ones and with the reference ones obtained by electron probe microanalysis (EMPA) in the present study.

Use of hydraulic binders for reducing sulphate leaching: application to gypsiferous soil sampled in Ile-de-France region (France).

Polluted soils are a serious environmental risk worldwide and consist of millions of tons of mineral waste to be treated. In order to ensure their sustainable management, various remediation options must be considered. Hydraulic binder treatment is one option that may allow a stabilisation of pollution and thus offer a valorisation as secondary raw materials rather than considering them as waste. In this study, we focused on sulphate-polluted soil and tested the effectiveness of several experimental hydraulic binders. The aim was to transform gypsum into ettringite, a much less soluble sulphate, and therefore to restrict the potential for sulphate pollutant release. The environmental assessment of five formulations using hydraulic binders was compared to the gypsiferous soil before treatment (contaminated in sulphate). The approach was to combine leaching tests with mineralogical quantifications using among others thermogravimetric and XRD methods. In the original soil and in the five formulations, leaching tests indicate sulphate release above environmental standards. However, hydraulic binders promote ettringite formation, as well as a gypsum content reduction as observed by SEM. The stabilisation of sulphates is, however, insufficient, probably as a result of the very high content of gypsum in the unusual soil used. The mineralogical reactions highlighted during the hydration of hydraulic binders are promising; they could pave the way for the development of new industrial mixtures that would have a positive environmental impact by allowing reuse of soils that would otherwise be classified as waste.