Isabella Pignatelli

A dissolution-precipitation mechanism is at the origin of concrete creep in moist environments

Long-term creep (i.e., deformation under sustained load) is a significant material response that needs to be accounted for in concrete structural design. However, the nature and origin of concrete creep remain poorly understood and controversial. Here, we propose that concrete creep at relative humidity ≥ 50%, but fixed moisture content (i.e., basic creep), arises from a dissolution-precipitation mechanism, active at nanoscale grain contacts, as has been extensively observed in a geological context, e.g., when rocks are exposed to sustained loads, in liquid-bearing environments. Based on micro-indentation and vertical scanning interferometry data and molecular dynamics simulations carried out on calcium-silicate-hydrate (C-S-H), the major binding phase in concrete, of different compositions, we show that creep rates are correlated with dissolution rates-an observation which suggests a dissolution-precipitation mechanism as being at the origin of concrete creep. C-S-H compositions featuring high resistance to dissolution, and, hence, creep are identified. Analyses of the atomic networks of such C-S-H compositions using topological constraint theory indicate that these compositions present limited relaxation modes on account of their optimally connected (i.e., constrained) atomic networks.

A MULTI-TECHNIQUE CHARACTERIZATION OF CRONSTEDTITE SYNTHESIZED BY IRON–CLAY INTERACTION IN A STEP-BY-STEP COOLING PROCEDURE

The cooling of steel containers in radioactive-waste storage was simulated in a step-by-step experiment from 90 to 40ºC. Among newly formed clay minerals observed in run products, cronstedtite was identified by a number of analytical techniques (powder X-ray diffraction, transmission electron microscopy, and scanning electron microscopy). Cronstedtite has not previously been recognized to be so abundant and so well crystallized in an iron—clay interaction experiment. The supersaturation of experimental solutions with respect to cronstedtite was due to the availability of Fe and Si in solution, as a result of the dissolution of iron metal powder, quartz, and minor amounts of other silicates. Cronstedtite crystals are characterized by various morphologies: pyramidal (truncated or not) with a triangular base and conical with a rounded or hexagonal cross-section. The pyramidal crystals occur more frequently and their polytypes (2M1, 1M, 3T) were identified by selected area electron diffraction patterns and by automated diffraction tomography. Cronstedtite is stable within the 90-60ºC temperature range. At temperatures of ⩽ 50ºC, the cronstedite crystals showed evidence of alteration.

Topological Control on Silicates’ Dissolution Kinetics

Like many others, silicate solids dissolve when placed in contact with water. In a given aqueous environment, the dissolution rate depends on the composition and the structure of the solid and can span several orders of magnitude. Although the kinetics of dissolution depends on the complexities of both the dissolving solid and the solvent, a clear understanding of which structural descriptors of the solid control its dissolution rate is lacking. By pioneering dissolution experiments and atomistic simulations, we correlate the dissolution rates-ranging over 4 orders of magnitude-of a selection of silicate glasses and crystals to the number of chemical topological constraints acting between the atoms of the dissolving solid. The number of such constraints serves as an indicator of the effective activation energy, which arises from steric effects, and prevents the network from reorganizing locally to accommodate intermediate units forming over the course of the dissolution.

A multi-technique, micrometer- to atomic-scale description of a synthetic analogue of chukanovite, Fe2(CO3)(OH)2

A synthetic analogue of chukanovite Fe 2 (CO 3 )(OH) 2 is formed during experimental work on iron–clay interactions simulating the cooling of containers in radioactive waste repositories. Despite its small size and the mixture with other minerals it is undoubtedly identified by X-Ray Diffraction, Fourier Transform Infrared Spectroscopy, Scanning Electron Microscopy and Transmission Electron Microscopy. For the first time, the structural characterisation of a synthetic chukanovite is carried out thanks to the combination of Automated Diffraction Tomography and Precession Electron Diffraction. Refinement results and comparison with literature data show that the structure of this synthetic chukanovite is consistent with that proposed for natural chukanovite found in Dronino meteorite.

Direct Experimental Evidence for Differing Reactivity Alterations of Minerals following Irradiation: The Case of Calcite and Quartz

Concrete, used in the construction of nuclear power plants (NPPs), may be exposed to radiation emanating from the reactor core. Until recently, concrete has been assumed immune to radiation exposure. Direct evidence acquired on Ar+-ion irradiated calcite and quartz indicates, on the contrary, that, such minerals, which constitute aggregates in concrete, may be significantly altered by irradiation. More specifically, while quartz undergoes disordering of its atomic structure resulting in a near complete lack of periodicity, calcite only experiences random rotations, and distortions of its carbonate groups. As a result, irradiated quartz shows a reduction in density of around 15%, and an increase in chemical reactivity, described by its dissolution rate, similar to a glassy silica. Calcite however, shows little change in dissolution rate - although its density noted to reduce by ≈9%. These differences are correlated with the nature of bonds in these minerals, i.e., being dominantly ionic or covalent, and the rigidity of the mineral’s atomic network that is characterized by the number of topological constraints (nc) that are imposed on the atoms in the network. The outcomes have major implications on the durability of concrete structural elements formed with calcite or quartz bearing aggregates in nuclear power plants.

Colombian Trapiche Emeralds: Recent Advances in Understanding Their Formation

Colombia is the traditional source of the world’s finest emeralds, including the famed trapiche crystals, with their distinctive texture resembling a wheel with six spokes. This gemological curiosity, found exclusively in the black shales of the country’s western emerald zone, is linked to the peculiar structural geology of the deposits. The study presents a review and update on Colombian trapiche emeralds, followed by a three-dimensional examination of the crystals combined with spectroscopic and chemical analyses. The proposed formation model incorporates the structural geology of the deposits with the formation of trapiche and non-trapiche emeralds. The fluid accumulation at the faults’ tip in the black shales leads to maximum fluid overpressure and sudden decompression and formation of the emerald-bearing vein system. The authors show that trapiche emerald growth starts at the beginning of the decompression that is responsible for local supersaturation of the fluid. The hydrothermal fluid comes in contact with the black shale matrix, favoring the formation of emerald seed crystals. During the growth of these seeds, textural sector zoning occurs, sometimes associated with chemical sector zoning, along with displacement of the matrix. Displacement growth occurs because the emeralds continue their growth, pushing the matrix material away from the growing faces. An overgrowth, generally of gem quality, can form after decompression, surrounding the core, the arms, and the dendrites, restoring the emeralds’ euhedral habit.

Vertical scanning interferometry: A new method to quantify re-/de-mineralization dynamics of dental enamel

OBJECTIVE Remineralization and demineralization are processes that compete in the oral environment. At this time, numerous therapeutic agents are being developed to promote remineralization (precipitation) or suppress demineralization (dissolution). To evaluate the relative efficacy of such treatments, there is a need for non-invasive, real-time, high-resolution quantifications of topographical changes occurring during demineralization and remineralization. METHODS Vertical scanning interferometry (VSI) is demonstrated to be a quantitative method to assess reactions, and topographical changes occurring on enamel surfaces following exposure to demineralizing, and remineralizing liquids. RESULTS First, the dissolution rate of enamel was compared to that of synthetic hydroxyapatite (HAP) under acidic conditions (pH=4). Second, VSI was used to compare the remineralization effects of F(-)-based and CCP-ACP agents. The former produced a remineralization rate of ≈349nm/h, similar to simulated body fluid (SBF; concentration 4.6×) while the latter produced a remineralization rate of ≈55nm/h, corresponding to 1.7× SBF. However, the precipitates formed by the CCP-ACP agent are found to demineralize 2.7× slower than that produced by its F(-)-counterpart. SIGNIFICANCE Based on this new VSI-based data, a remineralization factor (RF) and demineralization (DF) factor benchmarked, respectively, to 1× SBF and the demineralization rate of human enamel are suggested as figures of merit of therapeutic performance of dental treatments. Taken together, the outcomes offer new insights that can inform clinicians and researchers on the selection of remineralization strategies.