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

Concrete, a mixture formed by mixing cement, water, and fine and coarse mineral aggregates is used in the construction of nuclear power plants (NPPs), e.g., to construct the reactor cavity concrete that encases the reactor pressure vessel, etc. In such environments, concrete may be exposed to radiation (e.g., neutrons) emanating from the reactor core. Until recently, concrete has been assumed relatively 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. Specifically, while quartz undergoes disordering of its atomic structure resulting in a near complete lack of periodicity, i.e., similar to glassy silica, 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; i.e., an increase of around 3 orders of magnitude. Calcite however, shows little change in dissolution rates - although its density noted to reduce by around 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 (n$_c$) that are imposed on the atoms in the network. The outcomes are discussed within the context of the durability of concrete structural elements formed with calcitic/quartzitic aggregates in nuclear power plants

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

Restrained shrinkage cracking of cementitious composites containing soft PCM inclusions: A paste (matrix) controlled response

The addition of phase change materials (PCMs) has been proposed as a means to mitigate thermal cracking in cementitious materials. However, the addition of PCMs, i.e., soft inclusions, degrades the compressive strength of cementitious composites. From a strength-of-materials viewpoint, such reductions in strength are suspected to increase the tendency of cementitious materials containing PCMs to crack under load (e.g., volume instability-induced stresses resulting from thermal and/or hygral deformations). Based on detailed assessments of free and restrained shrinkage, elastic modulus, and tensile strength, this study shows that the addition of PCMs does not alter the cracking sensitivity of the material. In fact, the addition of PCMs (or other soft inclusions) enhances the cracking resistance as compared to a plain cement paste or composites containing equivalent dosages of (stiff) quartz inclusions. This is because composites containing soft inclusions demonstrate benefits resulting from crack blunting and deflection, and improved stress relaxation. As a result, although the tensile stress at failure remains similar, the time to failure (i.e., macroscopic cracking) of PCM-containing composites is considerably extended. More generally, the outcomes indicate that dosages of soft(er) inclusions, and the resulting decrease in compressive strength does not amplify the cracking risk of cementitious composites

Quantitative evaluation of carbonation in concrete using nonlinear ultrasound

A new nonlinear ultrasonic technique for nondestructive evaluation of concrete components is developed and implemented to characterize the effects of carbonation on concrete. The physical principle of this method is the second harmonic generation (SHG) in propagating Rayleigh surface waves which are detected by a non-contact air-coupled transducer. The nonlinearity parameter, as an indicator of material properties, is experimentally obtained from measured Rayleigh wave signals and is used to quantitatively evaluate the progress of carbonation under accelerated conditions. The experimental results show that there is a significant decrease in the measured nonlinearity parameter, most likely originated from the deposit of the carbonation product, CaCO3, in pre-existing voids and microcracks. The sensitivity of the nonlinearity parameter is also verified by comparing with the measured Rayleigh wave velocity. The results in this paper demonstrate that the SHG technique using Rayleigh surface waves can be used to monitor carbonation in concrete

Does a dissolution-precipitation mechanism explain 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 creep remains poorly understood, and controversial. Here, we propose that concrete creep at RH (relative humidity) > 50%, but fixed moisture-contents (i.e., basic creep), arises from a dissolution-precipitation mechanism, active at nanoscale grain contacts, as is often observed in a geological context, e.g., when rocks are exposed to sustained loads, in moist environments. Based on micro-indentation and vertical scanning interferometry experiments, and molecular dynamics simulations carried out on calcium-silicate-hydrates (C-S-H's), the major binding phase in concrete, of different compositions, we show that creep rates are well correlated to dissolution rates - an observation which supports the dissolution-precipitation mechanism as the origin of concrete creep. C-S-H compositions featuring high resistance to dissolution, and hence creep are identified - analysis of which, using topological constraint theory, indicates that these compositions present limited relaxation modes on account of their optimally connected (i.e., constrained) atomic networks

Apport de la simulation “matériau” à la maîtrise des propriétés d’usage des bétons

Le besoin d’estimer les propriétés d’usage des bétons en phase de prescription ou à des fins de maîtrise de la durée de fonctionnement des ouvrages de production en service a poussé EDF R&D à investiguer la piste de la simulation numérique afin de relier de manière théorique la formulation du matériau aux caractéristiques du matériau durci. La maturité des connaissances scientifiques actuelles en matière de théorie de l’homogénéisation et de chimie de l’hydratation des bétons, bien qu’il reste encore des travaux à accomplir sur ces deux sujets, a plaidé pour l’intégration de ces connaissances dans un outil unique baptisé Vi(CA)2T développé par EDF. Cet outil permet notamment d’estimer les propriétés d’élasticité au cours de l’hydratation et de fluage, caractéristiques qui sont de première importance pour le comportement structurel des ouvrages tels que les enceintes de confinement

Modélisation micro-macro du fluage propre du béton

On s'intéresse au fluage propre d'un béton. Les expériences de nano-indentation montrent que seuls les C-S-H présentent un fluage significatif. Ainsi, des changements d'échelle successifs sont réalisés par homogénéisation des milieux aléatoires pour passer de la particule de C-S-H (mécanisme couramment admis : glissement relatif des feuillets) au béton. Les fonctions de fluage obtenues sont comparées à des résultats expérimentaux sur plusieurs formules, et à des calculs sur microstructures 3D