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In the present study, the chemical composition, mineralogy, and mechanisms of alteration of a cementitious grout based on a CEM III/C with addition of smectite, hydrotalcite, and silica fume, are studied using a combination of chemical and physical methods. This material was designed in the context of geological repository of radioactive wastes, with a twofold aim: first, to fill the technical voids left by drilling operations at the interface between the geological formation and the disposal galleries. Second, to neutralize a potential acidic transient due to pyrite oxidation, and to create an environment that favors low corrosion rates of carbon steels. The grout is mainly composed of calcium silicate hydrates having a Ca/Si ratio of ~0.8, incorporating Al in the bridging site of the Si chains (C-A-S-H), and accounting for 29–36 wt.% of the sample. It also contains silica fume (38–48 wt.%), smectite with interlayer Na (11–17 wt.%), hydrotalcite with interlayer CO32− (3–4 wt.%), and lower amounts of portlandite, calcite, and possibly gibbsite and gypsum. Upon alteration by water in a flow-through reactor, the main modifications affecting the sample are calcite and gypsum dissolution, hence releasing aqueous Ca2+ that is adsorbed in smectite interlayer by replacing Na+, and stoichiometric C-A-S-H dissolution. The evolution of solution chemistry and of the solid phase composition are reproduced successfully using a thermokinetic model. [ABSTRACT FROM AUTHOR]

The aim of this research work is to develop a corrosion resistant fiber-reinforced concrete for radioactive waste disposal structures. In the case of precast concrete, the use of fibers is a solution to reduce the amount of steel reinforcement while maintaining high mechanical performance and durability. Concrete has a low strain capacity and a limited tensile strength. Generally, reinforcing bars are used to ensure tensile strength. A fiber reinforcement can also help to overcome such a mechanical weakness. For this purpose, an amorphous metallic fiber (AMF), corrosion-resistant and suitable for application in severe environment conditions are used. The fresh and hardened properties of the self-compacting fiber reinforced concrete (SCFRC) are studied with volume fractions of AMF of 0% and 0.28% and with three different aspect ratios (82, 114 and 123). Flexural tensile tests according to European standard EN 14651 are conducted to quantify the contribution of the fiber reinforcement on the residual flexural tensile strength. Since these fibers are electrically conductive, they are also tested to design a smart concrete. For this purpose, electrical resistance of specimens submitted to cyclic flexural loadings are monitored using a Wheatstone bridge.

In France, deep geological disposal is considered for the storage of high and intermediate‐level long‐lived radioactive wastes. For aluminium, the possibility to encapsulate the wastes in a cement‐based matrix is studied. However, cement being an alkaline environment, aluminium can lose its passivity, starts to corrode leading to hydrogen evolution in the infrastructures and generate a possible explosive hazard after decades of storage if hydrogen can accumulate somewhere in the facility. It is therefore necessary to study the corrosion behaviour of aluminium in the different cements considered for the encapsulation to estimate the possible amount of hydrogen that could be generated through corrosion and design the cement capsules accordingly. This work mainly focused on the reaction occurring at the aluminium‐cement interface. Raman spectroscopy did not highlight significant differences in the nature of the corrosion products forming at the cement/aluminium interface, leading to the conclusion that it is not the chemistry of the cement that is the key factor controlling the corrosion rate but rather the physical properties of the cement matrix. [ABSTRACT FROM AUTHOR]

Excavated soils and rocks are materials obtained in construction works that could represent an ecological issue if a durable and efficient reuse process is not set. The radioactive waste disposal planned by the French National Radioactive Waste Management Agency will generate large quantities of excavated soil (mainly as Callovo-Oxfordian argillite). The re-use of excavated soils is a recent question. There is a lack in the literature concerning the recycling of such materials. Therefore, this paper aims to investigate the possibility of using Callovo-Oxfordian argillite (COx argillite from the French URL) as a raw material for Portland cement clinker production. COx argillite was first characterized by X-ray diffraction (XRD) and X-ray fluorescence (XRF) then a Portland cement clinker was synthesized at laboratory scale. The produced clinker was characterized to verify the chemical and mineralogical composition. After adding gypsum, the reactivity of the resulting cement was assessed by setting time and isothermal calorimetry measurements. The compressive strength was assessed on standard mortar prisms at 1, 14 and 28 days. The results show that a Portland cement clinker containing 64% C3S, 14% C2S, 10% C4AF, 7% C3A and 1% CaO can be produced when 22.24% of raw meal was substituted by the COx argillite. The setting time and isothermal calorimetry results show that the produced cement shows an equivalent reactivity to conventional ordinary Portland cement. The compressive strength at 28 days is 56 MPa, showing that the produced cement can be considered as CEM I 52.5 N Portland cement. [ABSTRACT FROM AUTHOR]

The Callovo-Oxfordian (COx) claystone is chosen as a potential geological barrier for the geological repository of radioactive waste in France, and high-performance concrete is used as a sealing plug and lining in repository facilities. In this study, the shear strength of the interface between the concrete and claystone is investigated in particular. Ultra-high-performance (UHP) concrete is directly cast and cured beside a COx claystone semi-cylinder to make a cylindrical specimen including an interface. First, a microscopic analysis of the interface surfaces using scanned electronic microscope images is presented. It is shown that the adhesion of the UHP concrete to the COx claystone is of good quality and there is almost no initial interface aperture between the two materials. By using a home-designed original device, a series of direct shear tests is performed on cylinder specimens with interface under different confining stresses. The interface deformation and shear strength are quantitatively analysed. It is found that the interface has a bonded cohesion and the shear strength can be approximated by a non-linear function of normal stress. In most cases, the shear deformation does not generate an opening but rather a closure of the interface. The morphology of the sheared interface is also analysed by optical microscopic scanning images. [ABSTRACT FROM AUTHOR]

Depending on the lifetime and level of radioactivity of radioactive wastes, different disposal facilities are considered. Though low‐ and intermediate‐level short‐lived waste can be disposed in surface disposal facilities, deep geological disposal is considered for high‐ and intermediate‐level long‐lived waste. In France and Belgium, long‐term disposal is studied in clay host rock media. For aluminum, the disposal concept is based on encapsulation of the waste in a cement‐based matrix. It is also well‐known that aluminum is prone to severe corrosion in sufficiently alkaline environments leading to possible hydrogen production. To ensure the safety of the disposal facilities and the integrity of the cement capsules, the amount of aluminum that is disposed in each waste package must be specified and is limited to mitigate the level of hydrogen production by aluminum corrosion. In the present study, the corrosion resistance of an aluminum alloy (grade EN‐AW‐5754/H111) in two different cement matrices was studied in different configurations at room temperature. In each case, the evolution of hydrogen production was monitored to address the corrosion rate variation versus time. [ABSTRACT FROM AUTHOR]

The current literature on ionic diffusion through porous media teaches that the diffusion coefficient is a complicated function depending on concentration, concentration gradient, and electrical potential gradient. This paper documents how natural diffusion tests and migration tests (electrically enhanced transport) lead to the measurement of a unique diffusion coefficient for a given ionic species and a given material. Natural diffusion tests for chloride and a ceramic of TiO2 were implemented at two different concentration levels. The experiments were designed to emphasize the impact of the membrane potential in the pore solution on the chloride flux. By accounting for the membrane potential it is shown that the chloride diffusion coefficient is unique for a given material. An iterative method based on a numerical model solving the continuity equations and the current law is proposed to determine the diffusion coefficient. The approach is applied with success to published results on a cement-based material. Migration tests were also performed with chloride in a cementitious material, where the chloride transport is enhanced by an external electrical field. The experimental results reveal the competition between diffusion and electrical effects in the case of noncontaminated porous materials. By varying the electrical potential difference it is shown that the flux of chloride varies linearly with the electrical field, meaning that the chloride diffusion coefficient does not depend on the electrical field. The main conclusion is that there is only one chloride diffusion coefficient for a given porous material. [ABSTRACT FROM AUTHOR]

The French national radioactive waste management agency (Andra) is studying the building of a deep geological disposal for High and Intermediate Level radioactive waste. If accepted, the disposal will lead all along the operating period to the excavation of a large amount of host rock, mainly constituted by argillite. With the aim of using this by-product, alkali-activated materials have been prepared and studied, involving two different alkaline silicate sources (solution and powder). In order to increase the thermal resistance, the addition of sand, as filler, has been studied. A standard test and a thermal shock, both up to 800 °C, are used to study the physical stability of the samples under these thermal constraints. Analyses by XRD and SEM allow correlating the thermal resistance to the structural evolution occurring during the thermal tests. It was shown that the alkaline-silicate solution composition is the main parameter to control the reactions during the thermal treatment. The use of the powder-based solution, containing sodium, leads to the formation of more viscous flow and less crystalline phases, which reduces the thermal resistance and the mechanical properties. The addition of filler in the samples increases the resistance to thermal sudden increase, but is not sufficient to obtain a correct resistance to shock. The utilization of flash-calcined argillite, containing carbonate species, gives a better crystallization during the thermal treatment and leads to more cracks but an increase of the mechanical properties. Using, these different compositions, a value of 20 MPa can be reached after thermal treatment. [ABSTRACT FROM AUTHOR]

This research investigates the long-term shrinkage and Relative Mass Loss (RML) of mature Portland concretes (pure CEMI and blended CEMV/A), at temperatures of 20°C and 80°C. When placed at 80°C and at relative humidities (RH) below 50-60%, concrete shrinkage increases with very slow stabilization kinetics by several hundreds of μm/m, while RML remains of about 0.2%. The origins of this continued shrinkage, simultaneously with limited RML, are investigated through the changes in (i) the pore structure of the concretes (by Mercury Intrusion Porosimetry and nitrogen adsorption) and in (ii) their solid phases (by TGA/DTA, FTIR spectroscopy coupled to DVS, quantitative X-Ray Diffraction by Rietveld analysis, and 29Si and 27Al MAS NMR). While the pore structure coarsens during continued shrinkage, several phase transformations occur, namely ettringite decomposition and changes in the silicate chain length of the C-A-S-H. While these structural changes are documented, their relationship with shrinkage/RML and to the pore structure is novel. [ABSTRACT FROM AUTHOR]

An experimental campaign was carried out to study the passivity of steel embedded in blended cement paste. Mockup samples made of steel coupons (milled or pre-corroded) embedded in cement paste were tested under controlled relative humidity or in a solution simulating clay underground water and under aerated and de-aerated conditions, during up to 3 years. The results of gravimetric measurements show that the average corrosion rates determined on milled coupons are lower than 1 µm/year and vary from 0.2 to 2.7 µm/year for pre-corroded coupons. An apparent passive corrosion state is reached rapidly whatever the environmental conditions. Moreover, solid characterisations (Raman spectroscopy and SEM-EDS) point to a stable state in terms of the nature of the corrosion products and of the composition of the steel/cement paste interface. These results are similar to the ones previously obtained for steel coupons embedded in Portland cement mortar. This paper is part of a supplement on the 6th International Workshop on Long-Term Prediction of Corrosion Damage in Nuclear Waste Systems. [ABSTRACT FROM AUTHOR]

Abstract: This paper proposes to compare several experimental ways of obtaining the chloride diffusion coefficient through saturated porous materials. The first method is based on the application of the Nernst–Einstein equation for which the conductivity of the saturated sample is measured by impedance spectroscopy for two kinds of materials: inert samples of TiO2, and concretes based on type I and type V cements. The second method is a migration test in which the flux of chloride measured upstream allows calculating the diffusion coefficient by means of the Nernst–Planck equation. In the third case, the diffusion coefficient is calculated by current measurements in an equivalent configuration as the second method. It is shown that the formation factor does not vary neither with the ionic strength of the saturation solution, nor with the change in the pore solution constituents when the material is without mineral additions. The CEM-V concrete exhibits a specific behavior with a strong influence of the addition of chloride in its pore solution on the formation factor. The diffusion coefficients calculated with the three methods are in good agreement provided the metrology of the experiments is carefully controlled. [Copyright &y& Elsevier]

Abstract The impact of temperature on carbonation was investigated in laboratory conditions using a device developed for this purpose. Two hardened cement pastes (CEM I and CEM V/A) were tested between 20 °C and 80 °C at different levels of relative humidity (RH). The carbonation rate of the CEM I increased with temperature, whereas that of CEM V/A reached a maximum at around 50 °C. [ABSTRACT FROM AUTHOR]

The consequences of accelerated carbonation at 3% CO 2 were compared with those of natural carbonation (0.04%). Cement pastes (CEM I and CEM V/A) as well as the three major constitutive phases (C-S-H of different C/S ratios, portlandite and ettringite) were used and changes in the mineralogy, microstructure, water retention and cracking were investigated. The main conclusion was that accelerated carbonation at 3% CO 2 was representative of natural carbonation although it promoted the precipitation of metastable calcium carbonate (aragonite and vaterite) in place of calcite. The results also showed that the presence of aragonite and vaterite were characteristic of the carbonation of ettringite and C-S-H respectively. [ABSTRACT FROM AUTHOR]

The aim of this study is to determine the Representative Volume Element (RVE) size related to the desorption isotherm on concrete. Slices of three thicknesses taken from cast cylinders of an OPC concrete were desorbed from fully saturated condition to the dry state. The slice thickness had no clear influence on the water content once mass stabilization was reached. A method is being proposed to determine the RVE based on a statistical analysis of the water contents (or water saturation degrees) of the slices. The results show that a sample with the volume 7 d 3 may be considered as the RVE of an OPC concrete ( d is the maximum aggregate size). [ABSTRACT FROM AUTHOR]

In unsaturated conditions, the durability of concrete structures is strongly dependent on the evolution of the amount of free water within concrete porosity. Reliable durability assessment of concrete structures in relation to their environment thus requires accurate unsaturated water transport description as well as reliable input data. The effect of carbonation on water transport remains poorly studied and data are lacking. It was then the purpose of this article to acquire all the data needed to describe unsaturated water transport in carbonated cementitious materials (porosity, water retention and unsaturated permeability). Four hardened pastes made with four different binders were carbonated at 3% CO 2 to ensure representativeness with natural carbonation. Beyond the modification of the water retention curve and porosity clogging, significant microcracking due to carbonation shrinkage was observed. The consequence on permeability highlighted a competition between porosity clogging and microcracking that was dependent on the initial mineralogical composition. [ABSTRACT FROM AUTHOR]

Abstract: Relative permeabilities and water vapor diffusion reduction factor coefficients are essential data regarding the modeling of moisture transport and hence the prediction of structure lifetimes. The dependency of these parameters on the humidity history and the chemical evolutions of the material limits their experimental measurement since tests are long to carry out. For cement-based materials, the most usual approach for the calculation of relative permeabilities is the one developed for soils by Van Genuchten, requiring calibration on experimental water retention curves. Moreover, the model involves a pore network connectivity factor, the value of which varies from one author to another. The water vapor diffusion reduction factor is often calculated via Millington's semi-empirical model. This paper presents new methods for calculating transport factors based on physical and statistical considerations associated with a pore network model developed for the prediction of water sorption isotherms. [Copyright &y& Elsevier]

Abstract: The healing of cracks plays an important role with regard to the air- and water-tightness of concrete structures and the durability of cement based materials in general. This paper aims at further characterization and better comprehension of the healing phenomenon induced by the precipitation of calcite in localized cracks. The experimental program consisted in generating a localized crack in a cement paste or concrete specimen and healing the crack created by percolation tests with carbonated water or gas (CO2-air mixture). For tests with liquid, results show that the healing process depends on physical parameters like crack width, pressure gradient and carbonate content in the percolating fluid. For tests with gas, the supply of the crack with Ca2+ ions to form calcite depends on the moisture transport mode on the crack edges, conditioned by the relative humidity of the percolating gas mixture. A simplified model of the leakage rate evolution is proposed. It provides indications concerning the effect of each test parameter on the healing process and allows the experimental results to be reproduced. Application of the model to other tests from the literature shows its limits and gives guidance for future investigations. [Copyright &y& Elsevier]

Abstract: This experimental study aims at identifying the water retention properties of two industrial concretes to be used for long term underground nuclear waste storage structures. Together with water retention, gas transfer properties are identified at varying water saturation level, i.e. relative gas permeability is assessed directly as a function of water saturation level Sw. The influence of the initial de-sorption path and of the subsequent re-saturation are analysed both in terms of water retention and gas transfer properties. Also, the influence of concrete microstructure upon water retention and relative gas permeability is assessed, using porosity measurements, analysis of the BET theory from water retention properties, and MIP. Finally, a single relative gas permeability curve is proposed for each concrete, based on Van Genuchten–Mualem''s statistical model, to be used for continuous modelling approaches of concrete structures, both during drying and imbibition. [Copyright &y& Elsevier]