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Abstract  

This paper reports an experimental study on the magnesium sulphate resistance of mortar specimens incorporating 0, 10 and 20% of metakaolin (MK). The evidence of the attack was evaluated through the content of calcium hydroxide (portlandite) and formation of magnesium hydroxide (brucite) by thermal analysis (thermogravimetric and derivative thermogravimetric analysis). The mechanical degradation of the mortar specimens was evaluated through splitting tensile tests after 200 days of exposition to the magnesium solution. The addition of metakaolin resulted in a reduction in the content of calcium hydroxide and in a smaller formation of brucite in comparison with reference mixture. A tensile strength loss of about 7% was observed for the metakaolin mortars submitted to the magnesium solution attack for 200 days.

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Abstract  

The thaumasite form of sulphate attack (TSA) concerns cements and concretes containing limestone and is attributed to the formation of thaumasite. This work deals with the confirmation of thaumasite formation in cement mortars. Three types of cement were examined: Portland cement and Portland limestone cement containing 15 and 30% mass/mass limestone. The specimens were cured at 5C, for 12 months, in a 1.8% MgSO4 solution. The formation of thaumasite was checked and confirmed by XRD, TG and SEM. It was concluded that mortars containing limestone suffer from TSA at low temperature. The combination of XRD, TG and SEM leads to the positive identification of thaumasite and resolves the well known problem of thaumasite and ettringite confusion.

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Calorimetric comparison of portland cements containing silica fume and metakaolin

Is silica fume, like metakaolin, characterized by pozzolanic activity that is more specific than generic?

Journal of Thermal Analysis and Calorimetry
Authors: R. Talero and V. Rahhal

Abstract  

This new study must be regarded to be a direct outcome of two previous studies published by these same authors, which were conducted to respond to interesting questions brought out about the effect of silica fume, SF and metakaolins, M and MQ, on the heat of hydration of portland cements, PC, with very different C3A and C3S contents. The answer to these so interesting questions has been the primary objective of the present research. For this purpose, the same PC, PC1 (14% C3A) and PC2 (≈0% C3A), metakaolins, silica fume and blended cements were once again used more 60/40 for sulphate attack, and the same analytical techniques (CC, pozzolanicity and XRD analysis) and parameters determined as well. In this new research, the sulphate attack was determined by two accelerated methods: Le Chatelier-Ansttet and ASTM C 452-68. The experimental results of sulphate attack mainly, have demonstrated definitively that the high, rapid and early pozzolanic activity exhibited by SF also is, as in the case of the two metakaolins, more specific than generic, for it indirectly stimulated greater C3A than C3S hydration, but only in the first 16 h monitored in this study. Thereafter it is the contrary, i.e., anti- or contra-specific for the same purpose. And the longer the hydration time, the more anti- or contra-specific it became, since, when exposed to sulphate attack, SF blended cements resisted or even prevented the aggressive attack against PC1 which, with a higher C3A content than PC2, was the more vulnerable of the two. By contrast, metakaolin MQ not only failed to hinder or prevent the attack, but heightened its effects, rendering it more intense, aggressive and rapid, leading to what could be called a rapid gypsum attack.

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] Santhanam M. , Cohen M. D. , Olek J. Sulfate attack research - whither now ? Cement and Concrete Research , Vol. 31 , 2001 , pp. 845 – 851 . [5] MSZ EN 12370

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Abstract  

Sulphate resistance and passivation ability of the mortars made from pozzolan cement of CEM IV/A (P) type according to European Standard EN 197-1 (zeolite blended cement with 60.82 mass% of PC clinker, 35.09 mass% of zeolite and 4.09 mass% of gypsum abbreviated as ZBC) and ordinary Portland cement (abbreviated as PC) are introduced. Resistance tests were performed in water and 5% sodium sulphate solution (both 20°C) for 720 days. The increased sulphate resistance of pozzolan cement relative to that of PC was found. The key quantitative insight into the hydrate phase behaviour is given by thermal analysis. This is due to pozzolanic reaction of zeolite with PC resulting in reduction of the formed Ca(OH)2 opposite to the reference PC. Ability of pozzolan cements with 15 to 50 mass% of zeolite to protect steel against corrosion was verified in 20°C/85% RH-wet air within 180-day cure. Steel was not corroded in the mortars made with pozzolan cement containing up to 35 mass% of zeolite. Pozzolan cement of CEM IV/A (P) type containing 35 mass% of zeolite is a suitable cementitious material for concrete structures exposed to sulphate attack. Steel is protected against corrosion by this pozzolan cement in the same measure as the reference PC.

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Abstract  

Thermal decomposition of thaumasite is a step-wise process strongly related to the hydrogen bond breaking. Description and classification of hydrogen bonds in this mineral is necessary for better understanding of steps of the decomposition reaction. A computer simulation of a structure is an effective tool for confirming or opposing indicated steps of decomposition reactions. Computer simulations were performed on the crystal structure of the mineral thaumasite. All atomic positions together with unit cell parameters were relaxed. Hydrogen bonds, representing the dominant feature of the structure, were analyzed. Four types of them were found: between i) water molecules and carbonate ions, ii) water molecules and sulfate ions, iii) Si(OH)6 2– and water molecules and iv) water molecules themselves. Obtained results contribute to the explanation of some uncertainties of X-ray experiments and of the complexity of the thermochemical process, particularly, of the stepwise thermal decomposition of thaumasite in the low-temperature region 100–300°C. Moreover, TG data of the 1st step sensitively and reliably enough detect thaumasite sulphate-attack and determine the content of thaumasite in attacked building constructions.

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Abstract  

Fly ashes from the combustion of coal thermal power stations are commonly incorporated into portland cements and/or concretes and mortars. The chemical and morphological composition of fly ashes, together with their particle size, make them suitable as pozzolanic(non-calcic) or pozzolanic/hydraulic(highly calcic) additions to manufacture such building materials. This work focuses on the incorporation of two different fly ashes (non-calcic but of very different Fe2O3(%) contents, fineness and morphology) to two ordinary portland cements (of very different mineralogical composition as well), to determine the effects those have and the interactions they produce in the hydration reactions of portland cement. The main techniques employed for this study have been: conduction calorimetry and Frattini test; secondary techniques applied have also been: determination of setting times and analysis by X-ray diffraction and SEM. Analysis of the results obtained permitted to find different effects of fly ash addition on the hydration reactions of portland cements. Thus, dilution and stimulation effects augment with the increased fly ash percentage. Delay and acceleration of the reactions depend mainly on the type of portland cement and are accentuated with increased fly ash contents. Their behaviour as concerns heat dissipation mainly, depends on the type of fly ash used and is more pronounced with increased cement replacement. On the other hand, the pozzolanic activity of these fly ashes has been revealed at 7 and 28 days, but not at 2 days. Finally, pozzolanic cements can be manufactured using different portland cements and/or types of fly ashes, in the appropriate proportions and compatible qualities, depending on the effect(s) one wish to enhance at a specific age, which is according to previous general conclusions drew out of sulphate attack and chloride attack researches.

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Abstract  

This paper analyzes the effect of fly ash chemical character on early Portland cement hydration and the possible adverse effects generated by the addition of gypsum. Behaviour was analyzed for pure Portland cements with varying mineralogical compositions and two types of fly ash, likewise differing in chemical composition, which were previously characterized under sulphate attack as: silicic-ferric-aluminic or aluminic-silicic ash in chemical character, irrespective if they are in nature, siliceous or siliceous and aluminous materials according to the ASTM C 618-94a. The experimental results showed that water demand for paste with a normal consistency increased with the replacement ratio in fly ash with a more aluminic than silicic chemical character, whereas it declined when silicic-ferric-aluminic ash was used. On the other hand, the differences between the total heat of hydration released at the first valley and the second peak also clearly differentiated the two types of ash. While the relative differences increased in the more aluminic than silicic ash, they declined in the more silicic than aluminic. In another vein, the findings indicate that within a comparable Blaine fineness range, the reactive alumina (Al2O3 r−) content in pozzolanic additions has a greater effect on mortar strength than the reactive silica (SiO2 r−) content, at least in early ages up to 28 days. Finally, the adverse effect generated in the presence of excess gypsum is due primarily to the chemical interaction between the gypsum and the C3A in the Portland cement and the reactive alumina (Al2O3 r−) in the fly ash.

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Skalny J., Marchand J., Odler I. Sulphate attack on concrete , Spon Press, London, 2002. Odler I. Sulphate attack on concrete

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. Aggregate expansivity due to sulfide oxidation, II, Physico-chemical modeling of sulfate attack , Cement and Concrete Research, Vol. 27 , No. 11 , 1997 , pp. 1627 – 1632 . [9

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