Interactions between hydrated cement paste and organic acids: Thermodynamic data and speciation modeling

International audienceInteractions of short-chain organic acids with hydrated cement phases affect structure durability in the agro-food and nuclear waste industries but can also be used to modify cement properties. Most previous studies have been experimental, performed at fixed concentrations and pH, without quantitatively discriminating among polyacidity effects, or complexation and salt precipitation processes. This paper addresses such issues by thermodynamic equilibrium calculations for acetic, citric, oxalic, succinic acids and a simplified hydrated CEM-I. The thermodynamic constants collected from the literature allow the speciation to be modelled over a wide range of pH and concentrations. Citric and oxalic had a stronger chelating effect than acetic acid, while succinic acid was intermediate. Similarly, Ca-citrate and Ca-oxalate salts were more insoluble than Ca-acetate and Ca-succinate salts. Regarding aluminium complexation, hydroxyls, sulphates, and acid competition was highlighted. The exploration of acid mixtures showed the preponderant effect of oxalate and citrate over acetate and succinate

Reactivity of nitrate and organic acids at the concrete–bitumen interface of a nuclear waste repository cell

This study investigates the fate of nitrate and organic acids at the bitumen–concrete interface within repository cell for long-lived, intermediate-level, radioactive wastes. The interface was simulated by a multiphase system in which cementitious matrices (CEM V cement paste specimens) were exposed to bitumen model leachates consisting of nitrates and acetic acid with and without oxalic acid, chemical compounds likely to be released by bitumen. Leaching experiments were conducted with daily renewal of the solutions in order to accelerate reactions. The concentrations of anions (acetate, oxalate, nitrate, and nitrite) and cations (calcium, potassium) and the pH were monitored over time. Mineralogical changes of the cementitious matrices were analysed by XRD. The results confirmed the stability of nitrates in the abiotic conditions of the experiments. The action of acetic acid on the cementitious matrix was similar to that of ordinary leaching in the absence of organic acids (i.e. carried out with water or strong acids); no specific interaction was detected between acetate and cementitious cations. The reaction of oxalic acid with the cementitious phases led to the precipitation of calcium oxalate salts in the outer layer of the matrix. The concentration of oxalate was reduced by 65% inside the leaching medium

Effect of Portland Cement on Mechanical and Durability Properties of Geopolymer Concrete at Ambient Temperature

Environmental concerns have prompted researchers to focus on the development of alternative building materials like geopolymer concrete. However, their implementation requires curing beyond 60°C, which limits their application on building sites. This study aims to design a geopolymer concrete at room temperature (30 ± 5°C) in a laboratory in Burkina Faso using a metakaolin-based geopolymer binder activated by an alkaline solution of NaOH and natural aggregates. Portland cement type CEM I 42.5 was used by mass substitution (0 to 25%) of metakaolin to promote curing at ambient temperature. The samples were cured for 7 to 28 days and characterized for physical, mechanical, and durability properties. The results showed that the incorporation of 0 to 20% cement significantly improved the compressive strength from 9.9 to 30.5 MPa and the tensile strength from 1.2 to 2.2 MPa. However, Portland cement has various effects on the durability of geopolymer concrete. It reduces the porosity accessible by water from 15 to 13% and decreases the resistance to acid attack by increasing the mass loss from 2 to 7%. This confirms that common concrete types C20/25 or C25/30 can be casted using geopolymer concrete on the sites in Burkina Faso once their durability is confirmed. Doi: 10.28991/CEJ-2023-09-07-04 Full Text: PD

Physico-chemical interactions at the concrete-bitumen interface of nuclear waste repositories

This study investigates the fate of nitrate and organic acids at the bitumenconcrete-steel interface within a repository storage cell for long-lived, intermediatelevel, radioactive wastes. The interface was simulated by a multiphase system in which cementitious matrices (CEM V paste specimens) were exposed to bitumen model leachates consisting of nitrates and acetic acid with and without oxalic acid, chemical compounds likely to be released by bitumen. Leaching experiments were conducted with daily renewal of the solutions in order to accelerate reactions. C-steel chips, simulating the presence of steel in the repository, were added in the systems for some experiments. The concentrations of anions (acetate, oxalate, nitrate, and nitrite) and cations (calcium, potassium, ammonium) and the pH were monitored over time. Mineralogical changes of the cementitious matrices were analysed by XRD. The results confirmed the stability of nitrates in the absence of steel, whereas, reduction of nitrates was observed in the presence of steel (production of NH4+). The action of acetic acid on the cementitious matrix was similar to that of ordinary leaching; no specific interaction was detected between acetate and cementitious cations. The reaction of oxalic acid with the cementitious phases led to the precipitation of calcium oxalate salts in the outer layer of the matrix. The concentration of oxalate was reduced by 65% inside the leaching medium

Functionalized styryl iridium(III) complexes as active second-order NLO chromophores and building blocks for SHG polymeric films

International audienceWe studied the second-order NLO properties in solution of various Ir(III) acetylacetonate complexes bearing a substituted cyclometallated 4-styryl-2-phenylpyridine (ppy-4-styryl-R, with R = NEt2, OMe, H, NO2) with the EFISH technique. The dipole moments were evaluated by Density Functional Theory (DFT) calculations. We have also investigated the Second Harmonic Generation (SHG) of composite films based on the various cyclometallated Ir(III) complexes dispersed and oriented in a polymethylmethacrylate (PMMA) matrix

Modulating the luminescence of an iridium(III) complex incorporating a di(2-picolyl)anilino-appended bipyridine ligand with Zn2+ cations

International audienceA novel iridium complex incorporating a di(2-picolyl)anilino-appended bipyridine ligand was synthesized and its optical properties studied. The presence of Zn2+ ions specifically perturbs the excited state, giving rise to a blue-shifted absorption and emission, and a shorter luminescence lifetime

Catalyse biotique et abiotique de la réduction des nitrates en milieu alcalin dans le contexte du stockage profond des déchets radioactifs

Cette étude explore la réactivité des nitrates à l’interface bitume-béton dans une alvéole de stockage de déchets radioactifs de moyenne activité et à vie longue dans la perspective de déterminer les conditions redox qui s’y développeront. La première partie du travail visait à identifier, en conditions abiotiques (sans bactéries), les interactions entre deux composants du système : le béton (introduit sous forme de pâtes de ciment) et le bitume (simulé par des lixiviats modèles constitués de solutions d’acides organiques et de nitrates). La seconde partie de l’étude a été conduite en conditions biotiques avec deux espèces de bactéries hétérotrophes dénitrifiantes (Pseudomonas stutzeri – Ps et Halomonas desiderata – Hd) et avait pour but d’analyser la réaction de réduction des nitrates (cinétiques, sous-produits, rôle de la matière organique) en conditions de pH neutre à alcalin (caractéristiques de l’environnement chimique imposé par le béton). Les résultats ont montré que des interactions fortes se produisaient entre la matrice cimentaire et les acides organiques, acétique et oxalique, interactions susceptibles de réduire la biodisponibilité de cette matière organique (pour l’oxalate en particulier), et ont confirmé la stabilité des nitrates dans ces conditions. En conditions biotiques, les nitrates ont été réduits par Ps et Hd selon la voie métabolique de dénitrification anaérobie. Les cinétiques de réduction étaient plus élevées avec Ps mais les réactions étaient inhibées pour pH > 9. Hd était en revanche capable de réaliser la dénitrification jusqu’à pH 11 au moins

Variability of the mechanical properties of hemp concrete

International audienceThis study is focused on statistical analysis of hemp concrete properties. The main objective is to determine statistically the variability of the three main properties, which are: material density, compressive strength and Young’s modulus. The analysis is done with respect to four main parameters, namely: the testing laboratory equipment and procedure, the hemp shiv type, the batch elaboration and finally the specimen siz

Les ciments aux fillers calcaires : contribution a leur optimisation par l'etude des proprietes mecaniques et physiques des betons fillerises

SIGLECNRS T Bordereau / INIST-CNRS - Institut de l'Information Scientifique et TechniqueFRFranc

Durabilité des bétons auto-plaçants

Les bétons autoplaçants (BAP) sont des bétons très fluides dont la mise en place sans vibration présente plusieurs avantages tant au niveau environnemental, humain, technologique qu'économique qui intéressent de plus en plus les industriels. Cependant, une question reste souvent posée : à résistance mécanique égale, le béton autoplaçant est-il aussi durable que le béton vibré traditionnellement employé jusqu'alors ? L'objectif de ce projet de recherche a été de donner une réponse claire à ce problème. Pour cela, différents BAP et bétons vibrés (BV) de résistance mécanique équivalente ont été coulés avec les mêmes constituants, un squelette granulaire identique (à l'exception des bétons à hautes performances) et dans une gamme de résistance allant de 20 à 60 MPa. Les principales différences entre les deux types de béton sont le volume de pâte et le dosage en superplastifiant plus important pour les BAP et l'emploi éventuel d'un agent de viscosité dans ces derniers. Les résultats des essais expérimentaux menés sur ces formulations dans les domaines mécanique et physico-chimique ont montré qu'il y avait très peu de différences entre les deux types de béton. Le fluage des BAP semble légèrement supérieur à celui des BV, tandis que les autres propriétés mécaniques (module d'élasticité, retrait) et de transfert (perméabilité à l'oxygène, diffusion des ions chlore, absorption capillaire, carbonatation et lessivage au nitrate d'ammonium) peuvent être considérées comme équivalentes entre les BAP et les BV.The building industry is turning increasingly to the use of self-compacting concrete (SCC) in order to improve many aspects of building construction: SCC offers several advantages in technical, economic, environmental and human terms. However, there are still some problems with regard to its durability, in terms of physical and chemical properties. The purpose of this research project was to study various durability characteristics of self-compacting concrete compared with reference samples of vibrated concrete (VC) with similar compressive strength, from 20 to 60 MPa. For this purpose, SCC and VC mixes were prepared using the same ingredients in identical proportions (except for the high performances concrete), the only difference being that calcareous filler and more superplasticizer was used for the SCC mixes and the possible use of a viscosity agent. Tests carried out on these samples revealed that creep was slightly higher for SCC and that there was no significant difference in the other mechanical (elasticity modulus, shrinkage) and physico-chemical properties (oxygen permeability, chloride diffusion, water absorption, carbonation and leaching by ammonium nitrate) of the two types of concreteTOULOUSE-INSA (315552106) / SudocSudocFranceF