Etude de l'accélération des ciments à haute teneur en laitier de haut-fourneaux par du chlorure de calcium

Les laitiers de hauts fourneaux sont un coproduit de l'industrie métallurgique, utilisés dans les ciments composés (CEM II & III) en substitution partielle du clinker portland et reconnus notamment pour leurs avantages en termes d'abaissement de chaleur d'hydratation, d'augmentation des performances de durabilité et de réduction du bilan carbone des bétons. Bien qu'atteignant des performances mécaniques ultimes comparables voire supérieures au ciment portland (CEM I), les liants proposant de forts taux de laitier voient le développement de leur résistance mécanique fortement ralenti. Ce phénomène s'explique par une réactivité plus faible du laitier qui nécessite des conditions "d'activation" pour réagir correctement. Il existe divers additifs ayant pour effet d'accélérer le durcissement des ciments, parmi lesquels le chlorure de calcium montre les meilleures performances. Les effets du chlorure de calcium sont particulièrement importants durant les premiers jours de l'hydratation. Cependant, leur usage est fortement règlementé en raison de l'effet corrosif du chlore sur les aciers du béton armé. Les objectifs de la thèse visent à étudier les mécanismes d'action du chlorure de calcium sur les matrices ciment-laitier durant les premiers jours d'hydratation. Un panel de techniques expérimentales a été utilisé pour identifier spécifiquement l'action des chlorures sur le laitier et le ciment. Des couplages DRX-Analyse d'Images MEB et RMN montrent que le chlorure de calcium entraîne une précipitation accélérée de portlandite et d'ettringite, issus de l'augmentation du taux de réaction du clinker. Le démarrage de la réaction du laitier s'opère après environ 12 heures, et n'est pas impacté par le chlorure de calcium. En revanche, le taux de réaction du laitier augmente en présence de l'accélérateur. On observe la formation rapide, importante et exclusive de Sels de Friedel en présence de chlorure, en remplacement des AFm sulfatés et/ou carbonatés. L'augmentation du taux de réaction des phases anhydres entraîne la précipitation de C-S-H supplémentaire. Cette formation de Sels de Friedel et de C-S-H provoquent un remplissage plus rapide de la porosité et l'augmentation des performances mécaniques.Blast furnace slags are a co-product of the metallurgical industry, used in composite cements (CEM II & III) as a partial substitution for Portland clinker and recognized in particular for their advantages in terms of lowering the heat of hydration, increased durability performance and reduced carbon footprint of concrete. Although achieving ultimate mechanical performance comparable to or better than Portland cement (CEM I), binders offering high levels of slag see the development of their mechanical strength greatly slowed down. This phenomenon is explained by a lower reactivity of the slag which requires "activation" conditions to react properly. There are various additives that accelerate the hardening of cements, among which calcium chloride shows the best performance. The effects of calcium chloride are particularly important during the first days of hydration. However, their use is strongly regulated because of the corrosive effect of chlorine on steels of reinforced concrete. The objectives of the thesis are to study the mechanisms of action of calcium chloride on cement-slag binders during the first days of hydration. A panel of experimental techniques has been used to specifically identify the action of chlorides on slag and cement. Coupled results from XRD-NMR SEM experiments show that calcium chloride causes an accelerated precipitation of portlandite and ettringite, resulting from the increase in the reaction rate of clinker. The start of the slag reaction takes place after about 12 hours, and is not impacted by the calcium chloride. On the other hand, the reaction rate of the slag increases in the presence of the accelerator. The rapid, significant and exclusive formation of Friedel salts in the presence of chloride is observed, replacing sulphated and / or carbonated AFm. Increasing the reaction rate of the anhydrous phases results in the precipitation of additional C-S-H. This formation of Friedel salts and C-S-H causes a faster filling of the porosity and the increase of the mechanical performances

Molecular Interactions between Prions as Seeds and Recombinant Prion Proteins as Substrates Resemble the Biological Interspecies Barrier In Vitro

Prion diseases like Creutzfeldt-Jakob disease in humans, Scrapie in sheep or bovine spongiform encephalopathy are fatal neurodegenerative diseases, which can be of sporadic, genetic, or infectious origin. Prion diseases are transmissible between different species, however, with a variable species barrier. The key event of prion amplification is the conversion of the cellular isoform of the prion protein (PrPC) into the pathogenic isoform (PrPSc). We developed a sodiumdodecylsulfate-based PrP conversion system that induces amyloid fibril formation from soluble α-helical structured recombinant PrP (recPrP). This approach was extended applying pre-purified PrPSc as seeds which accelerate fibrillization of recPrP. In the present study we investigated the interspecies coherence of prion disease. Therefore we used PrPSc from different species like Syrian hamster, cattle, mouse and sheep and seeded fibrillization of recPrP from the same or other species to mimic in vitro the natural species barrier. We could show that the in vitro system of seeded fibrillization is in accordance with what is known from the naturally occurring species barriers

Reactivity tests for supplementary cementitious materials: RILEM TC 267-TRM phase 1

A primary aim of RILEM TC 267-TRM: “Tests for Reactivity of Supplementary Cementitious Materials (SCMs)” is to compare and evaluate the performance of conventional and novel SCM reactivity test methods across a wide range of SCMs. To this purpose, a round robin campaign was organized to investigate 10 different tests for reactivity and 11 SCMs covering the main classes of materials in use, such as granulated blast furnace slag, fly ash, natural pozzolan and calcined clays. The methods were evaluated based on the correlation to the 28 days relative compressive strength of standard mortar bars containing 30% of SCM as cement replacement and the interlaboratory reproducibility of the test results. It was found that only a few test methods showed acceptable correlation to the 28 days relative strength over the whole range of SCMs. The methods that showed the best reproducibility and gave good correlations used the R3 model system of the SCM and Ca(OH)2, supplemented with alkali sulfate/carbonate. The use of this simplified model system isolates the reaction of the SCM and the reactivity can be easily quantified from the heat release or bound water content. Later age (90 days) strength results also correlated well with the results of the IS 1727 (Indian standard) reactivity test, an accelerated strength test using an SCM/Ca(OH)2-based model system. The current standardized tests did not show acceptable correlations across all SCMs, although they performed better when latently hydraulic materials (blast furnace slag) were excluded. However, the Frattini test, Chapelle and modified Chapelle test showed poor interlaboratory reproducibility, demonstrating experimental difficulties. The TC 267-TRM will pursue the development of test protocols based on the R3 model systems. Acceleration and improvement of the reproducibility of the IS 1727 test will be attempted as well

Hydration of cementitious binders containing high amounts of blast furnace slag accelerated by calcium chloride

Les laitiers de hauts fourneaux sont un coproduit de l'industrie métallurgique, utilisés dans les ciments composés (CEM II & III) en substitution partielle du clinker portland et reconnus notamment pour leurs avantages en termes d'abaissement de chaleur d'hydratation, d'augmentation des performances de durabilité et de réduction du bilan carbone des bétons. Bien qu'atteignant des performances mécaniques ultimes comparables voire supérieures au ciment portland (CEM I), les liants proposant de forts taux de laitier voient le développement de leur résistance mécanique fortement ralenti. Ce phénomène s'explique par une réactivité plus faible du laitier qui nécessite des conditions "d'activation" pour réagir correctement. Il existe divers additifs ayant pour effet d'accélérer le durcissement des ciments, parmi lesquels le chlorure de calcium montre les meilleures performances. Les effets du chlorure de calcium sont particulièrement importants durant les premiers jours de l'hydratation. Cependant, leur usage est fortement règlementé en raison de l'effet corrosif du chlore sur les aciers du béton armé. Les objectifs de la thèse visent à étudier les mécanismes d'action du chlorure de calcium sur les matrices ciment-laitier durant les premiers jours d'hydratation. Un panel de techniques expérimentales a été utilisé pour identifier spécifiquement l'action des chlorures sur le laitier et le ciment. Des couplages DRX-Analyse d'Images MEB et RMN montrent que le chlorure de calcium entraîne une précipitation accélérée de portlandite et d'ettringite, issus de l'augmentation du taux de réaction du clinker. Le démarrage de la réaction du laitier s'opère après environ 12 heures, et n'est pas impacté par le chlorure de calcium. En revanche, le taux de réaction du laitier augmente en présence de l'accélérateur. On observe la formation rapide, importante et exclusive de Sels de Friedel en présence de chlorure, en remplacement des AFm sulfatés et/ou carbonatés. L'augmentation du taux de réaction des phases anhydres entraîne la précipitation de C-S-H supplémentaire. Cette formation de Sels de Friedel et de C-S-H provoquent un remplissage plus rapide de la porosité et l'augmentation des performances mécaniques.Blast furnace slags are a co-product of the metallurgical industry, used in composite cements (CEM II & III) as a partial substitution for Portland clinker and recognized in particular for their advantages in terms of lowering the heat of hydration, increased durability performance and reduced carbon footprint of concrete. Although achieving ultimate mechanical performance comparable to or better than Portland cement (CEM I), binders offering high levels of slag see the development of their mechanical strength greatly slowed down. This phenomenon is explained by a lower reactivity of the slag which requires "activation" conditions to react properly. There are various additives that accelerate the hardening of cements, among which calcium chloride shows the best performance. The effects of calcium chloride are particularly important during the first days of hydration. However, their use is strongly regulated because of the corrosive effect of chlorine on steels of reinforced concrete. The objectives of the thesis are to study the mechanisms of action of calcium chloride on cement-slag binders during the first days of hydration. A panel of experimental techniques has been used to specifically identify the action of chlorides on slag and cement. Coupled results from XRD-NMR SEM experiments show that calcium chloride causes an accelerated precipitation of portlandite and ettringite, resulting from the increase in the reaction rate of clinker. The start of the slag reaction takes place after about 12 hours, and is not impacted by the calcium chloride. On the other hand, the reaction rate of the slag increases in the presence of the accelerator. The rapid, significant and exclusive formation of Friedel salts in the presence of chloride is observed, replacing sulphated and / or carbonated AFm. Increasing the reaction rate of the anhydrous phases results in the precipitation of additional C-S-H. This formation of Friedel salts and C-S-H causes a faster filling of the porosity and the increase of the mechanical performances

Etude de l'accélération des ciments à haute teneur en laitier de haut-fourneaux par du chlorure de calcium

Blast furnace slags are a co-product of the metallurgical industry, used in composite cements (CEM II & III) as a partial substitution for Portland clinker and recognized in particular for their advantages in terms of lowering the heat of hydration, increased durability performance and reduced carbon footprint of concrete. Although achieving ultimate mechanical performance comparable to or better than Portland cement (CEM I), binders offering high levels of slag see the development of their mechanical strength greatly slowed down. This phenomenon is explained by a lower reactivity of the slag which requires "activation" conditions to react properly. There are various additives that accelerate the hardening of cements, among which calcium chloride shows the best performance. The effects of calcium chloride are particularly important during the first days of hydration. However, their use is strongly regulated because of the corrosive effect of chlorine on steels of reinforced concrete. The objectives of the thesis are to study the mechanisms of action of calcium chloride on cement-slag binders during the first days of hydration. A panel of experimental techniques has been used to specifically identify the action of chlorides on slag and cement. Coupled results from XRD-NMR SEM experiments show that calcium chloride causes an accelerated precipitation of portlandite and ettringite, resulting from the increase in the reaction rate of clinker. The start of the slag reaction takes place after about 12 hours, and is not impacted by the calcium chloride. On the other hand, the reaction rate of the slag increases in the presence of the accelerator. The rapid, significant and exclusive formation of Friedel salts in the presence of chloride is observed, replacing sulphated and / or carbonated AFm. Increasing the reaction rate of the anhydrous phases results in the precipitation of additional C-S-H. This formation of Friedel salts and C-S-H causes a faster filling of the porosity and the increase of the mechanical performances.Les laitiers de hauts fourneaux sont un coproduit de l'industrie métallurgique, utilisés dans les ciments composés (CEM II & III) en substitution partielle du clinker portland et reconnus notamment pour leurs avantages en termes d'abaissement de chaleur d'hydratation, d'augmentation des performances de durabilité et de réduction du bilan carbone des bétons. Bien qu'atteignant des performances mécaniques ultimes comparables voire supérieures au ciment portland (CEM I), les liants proposant de forts taux de laitier voient le développement de leur résistance mécanique fortement ralenti. Ce phénomène s'explique par une réactivité plus faible du laitier qui nécessite des conditions "d'activation" pour réagir correctement. Il existe divers additifs ayant pour effet d'accélérer le durcissement des ciments, parmi lesquels le chlorure de calcium montre les meilleures performances. Les effets du chlorure de calcium sont particulièrement importants durant les premiers jours de l'hydratation. Cependant, leur usage est fortement règlementé en raison de l'effet corrosif du chlore sur les aciers du béton armé. Les objectifs de la thèse visent à étudier les mécanismes d'action du chlorure de calcium sur les matrices ciment-laitier durant les premiers jours d'hydratation. Un panel de techniques expérimentales a été utilisé pour identifier spécifiquement l'action des chlorures sur le laitier et le ciment. Des couplages DRX-Analyse d'Images MEB et RMN montrent que le chlorure de calcium entraîne une précipitation accélérée de portlandite et d'ettringite, issus de l'augmentation du taux de réaction du clinker. Le démarrage de la réaction du laitier s'opère après environ 12 heures, et n'est pas impacté par le chlorure de calcium. En revanche, le taux de réaction du laitier augmente en présence de l'accélérateur. On observe la formation rapide, importante et exclusive de Sels de Friedel en présence de chlorure, en remplacement des AFm sulfatés et/ou carbonatés. L'augmentation du taux de réaction des phases anhydres entraîne la précipitation de C-S-H supplémentaire. Cette formation de Sels de Friedel et de C-S-H provoquent un remplissage plus rapide de la porosité et l'augmentation des performances mécaniques

Experimental evidence for the acceleration of slag hydration in blended cements by the addition of CaCl2

International audienceCements with high substitution rates of ground granulated blast furnace slags (GGBS) have the potential to significantly lower CO 2 emissions of concrete, but their early age strength is often below those of traditional OPC cements. One way of mitigating this drawback is to use accelerating admixtures. In this study, the effect of CaCl 2 additions on the hydration of blended cements was investigated by measuring compressive strength, porosity, heat release and propagation of ultrasound in blends containing 70 wt.% of GGBS. The onset of formation of aluminate phases was monitored using in-situ XRD. The effect of CaCl 2 on slag hydration was isolated by replacing GGBS by an inert quartz filler. Results showed that compressive strength values at one, two and seven days were increased by 50% by the CaCl 2 addition. The increases in compressive strength corresponded to a reduction in pore space. GGBS hydration contributed to the heat development, structuration and compressive strength of the blended cements from 15 hours. The addition of CaCl 2 led to an earlier onset of the GGBS reaction, at around 10 hours, and increased the rate of GGBS hydration during the first seven days. The time of onset of the GGBS contribution was also the moment when AFm precipitation started. In CaCl 2-containing blends, Cl was incorporated in AFm

Ability of the R3 test to evaluate differences in early age reactivity of 16 industrial ground granulated blast furnace slags (GGBS)

International audienceGround granulated blast furnace slag (GGBS) is a glassy by-product of pig iron production and is commonly used in concrete industry to replace cement and thereby lower the carbon footprint of the material. Large variations in reactivity exist depending on the GGBS physical and chemical features. Here we investigate the ability of three rapid calorimetric methods to evaluate the reactivity of GGBS. On a set of 16 industrial GGBS, we show that 24 h heat release, using the R3-protocol, correlates well with 2d compressive strength of standard mortars using 75 wt% GGBS. The correlation of R3-test results (R2 = 0.87) is better than for traditional reactivity indices calculated from chemical composition. Furthermore, we present data on the repeatability of the test protocol and show that the R3-protocol is very sensitive to sample fineness. Finally, XRD patterns show that slight differences in phase assemblage exist between the most and least reactive GGBS

Synchrotron X-ray micro-tomography investigation of the early hydration of blended cements: A case study on CaCl2-accelerated slag-based blended cements

International audienceIn situ X-ray Micro-Tomography (XMT) analyses with a pixel size of 0.325 µm were conducted on slag-based blended cements containing 75% of Ground-Granulated Blast-Furnace Slags (GGBS) and 25% of Ordinary Portland Cement (OPC), with or without CaCl2 acceleration. Results show the identification of the main cementitious phases and the need to perform data repeatability tests in order to allow their quantification. Investigation of the early hydration during the first 31 h of hydration by image subtraction showed (i) the dissolution of OPC/GGBS, (ii) the precipitation of hydrates including C-S-H, (iii) the accelerating effect of CaCl2, and (iv) phase-identification based on their specific grey level

Effect of TiO2 and 11 minor elements on the reactivity of ground‐granulated blast‐furnace slag in blended cements

International audienceGround granulated blast furnace slags (GGBS) are glasses (>99%) of the CaO-Al 2 O 3-SiO 2 compositional system and are widely used as supplementary cementitious materials. Differences in reactivity of GGBS were screened by modifying the content of 11 minor elements (namely Ba, Ce, Cs, Cr, Mn, P, Sn, Sr, Ti, V, Zr). SEM observations showed that most elements entered the silicate glass matrix, only Sn was reduced to its metallic form and P accumulated in minor minerals. Mortar strength tests showed that 2d-compressive strength was reduced by > 50% for a TiO 2 content of 2.5 wt.% in the slag. At 28 days the loss in compressive strength was still > 40%. Calorimetric tests on other element additions showed that network modifiers (Ba, Cs and Sr) and GGBS reactivity are positively correlated, whereas Ce, Cr, V and Zr significantly decreased reactivity. It is shown that these effects can be well estimated by the weighted field strength of the added element