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Journal ArticleDOI

Thermal analysis of hydrated calcium aluminates

01 Sep 1996-Journal of Thermal Analysis and Calorimetry (Kluwer Academic Publishers)-Vol. 47, Iss: 3, pp 765-774
TL;DR: Differential scanning calorimeter has been used to study the dehydration characteristics of hydrated calcium aluminates such as CA, CA2 and C12A7 where C and A stand for CaO and Al2O3 respectively.
Abstract: Differential scanning calorimeter (DSC) has been used to study the dehydration characteristics of hydrated calcium aluminates such as CA, CA2 and C12A7 where C and A stand for CaO and Al2O3 respectively. Dehydration of CAH10 and C2AH8 (whereH=H2O) occur ∼ at 160–180°C and 200–280°C respectively. These two phases are unstable and ultimately get transformed to AH3 and C3AH6. Dehydration of AH3 and C3AH6 occur between 290 and 350°C and overlap at lower scanning rate. The activation energy for dehydration of the stable AH3 and C2AH6 phases has been found to be 107.16 and 35.58 kJ mol−1 respectively. The compressive strength of the hydrated calcium aluminates has been determined. The result shows that in the case of CA, almost 90% of ultimate strength has been attained in 1 day whereas in CA2, ultimate strength has been attained in 14 days and in C12A7 in 1 day. DSC results have been correlated with the rate of strength developments.
Citations
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TL;DR: In this article, a structural model of a grafting process of the interlayer [Al(OH)4]− tetrahedron onto hydroxylated octahedrons of aluminum-oxide polyhedrons has been proposed in order to explain observed loss of one water molecule, shrinkage of interlayer spacing and qualitative changes of FT-IR spectra.
Abstract: Thermal dehydration of dicalcium aluminate hydrate, C2AH8, has been investigated by simultaneous differential thermal and thermo gravimetric analysis (DTA/TGA), powder X-ray diffraction (XRD), temperature-dependent infrared spectroscopy (FT-IR), and BET method of surface area measurement. The temperature-dependent infrared measurements were studied by two-dimensional infrared (2D-IR) correlation spectroscopy. The structure of aluminum-oxide polyhedron, characterized by 27Al solid state NMR spectrum method and FT-IR, shows tetrahedron and octahedron as the main forms of aluminum-oxide polyhedrons in C2AH8 sample. From the results obtained a variety of structural transformations observed are explained as a consequence of the removal of loosely held interlayer water molecules at lower temperatures, followed by grafting process of the interlayer [Al(OH)4]− anion. Structural model of a grafting process of the interlayer [Al(OH)4]− tetrahedron onto hydroxylated octahedrons of [Ca2Al(OH)6]+ layers has been proposed in order to explain observed loss of one water molecule, shrinkage of interlayer spacing and qualitative changes of FT-IR spectra. At higher temperatures the dehydroxylation of the lattice and decomposition of the interlayer species occurs, yielding amorphous material that crystallizes into C3A and C12A7 at 885 °C. Those findings provide improvement in the interpretation of thermo-analytical results of calcium aluminate cements (CAC) hydration products, and better understanding of CAC conversion process.

108 citations

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TL;DR: In this article, the system of different Ca/Si and Al/Si molar ratios were investigated and it was shown that incorporation of Al increases main basal spacing, amount of bounded water and decreases crystallinity of C-(A)-S-H (calcium (aluminium) silicate hydrate).
Abstract: Systems of different Ca/Si and Al/Si molar ratios were investigated. Incorporation of Al increases main basal spacing, amount of bounded water and decreases crystallinity of C-(A)-S-H (calcium (aluminium) silicate hydrate). Transmission electron microscope observations showed that aluminium results in formation of more compacted, foil-like microstructure. FTIR revealed the presence of rings within the structure of C-(A)-S-H. Low Ca/Si ratio promotes Al incorporation into C-(A)-S-H, while in case of high Ca/Si ratio aluminium is also incorporated into AFm. The results show, that Ca/Si ratio is of key significance deciding on Al incorporation into C-(A)-S-H in hydrating SCMs bearing blended systems.

96 citations

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TL;DR: The most widely identified degradation process suffered by calcium aluminate cement (CAC) is the so-called conversion of hexagonal calcine hydrate to cubic form, which is usually followed by an increase in porosity determined by the different densities of these hydrates and the subsequent loss of strength.
Abstract: The most widely identified degradation process suffered by calcium aluminate cement (CAC) is the so-called conversion of hexagonal calcium aluminate hydrate to cubic form. This conversion is usually followed by an increase in porosity determined by the different densities of these hydrates and the subsequent loss of strength. Mixes of calcium aluminate cement (CAC) and silica fume (SF) or fly ash (FA) represent an interesting alternative for the stabilization of CAC hydrates, which might be attributed to a microstructure based mainly on aluminosilicates. This paper deals with the microstructure of cement pastes fabricated with mixtures CAC-SF and CAC-FA and its evolution over time. Thermal analysis (DTA/TG), X-ray diffraction (XRD) and mid-infrared spectroscopy (FTIR) have been used to assess the microstructure of these formulations.

65 citations

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TL;DR: In this article, the influence of sodium sulfate on the hydration of CAC-fly ash-silica fume composites was investigated, and it was shown that Na2SO4 accelerated hydration reactions of calcium aluminate cement as well as the reactions of FA and SF with CAH10 and C2AH8 to form the stratlingite.
Abstract: The influence of sodium sulfate, as an activator, on the hydration of calcium aluminate cement (CAC)–fly ash (FA)–silica fume (SF) composites was investigated. Different mixes of CAC with 20% pozzolans (20% FA, 20% SF and 10% FA + 10% SF) were prepared and hydrated at 38 °C for up to 28 days. The hydration products were investigated by XRD, DSC and SEM. The results showed that sodium sulfate accelerated the hydration reactions of calcium aluminate cement as well as the reactions of FA and SF with CAH10 and C2AH8 to form the stratlingite (C2ASH8). The later reactions prevent the strength loss by preventing the conversion of CAH10 and C2AH8 to the cubic C3AH6 phase. The acceleration effect of Na2SO4 on the reactivity of fly ash was more pronounced than on the reactivity of silica fume with respect to reaction with CAH10 and C2AH8 phases.

53 citations

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TL;DR: The use of high alumina cement was used widely in the UK after World War I, expressing its higher content of aluminum oxide in comparison to Portland cement as mentioned in this paper, and the reason for looking into alternative cement materials was to develop cements with improved stability against sulfate corrosion.
Abstract: High alumina cement was used widely in the UK after World War I, expressing its higher content of aluminum oxide in comparison to Portland cement. Several descriptions of investigations on calcium aluminate cements appeared, starting around 1850, with a first patent field in 1888 (Scrivener and Capmas, in Hewlett 1998). More widely known is the work of Bied (1909, 1926) filing a patent in 1909 for the fabrication of cement using bauxite or some similar aluminum or iron-rich material, with low SiO2-contents and limestone. In 1918, the trade name Ciment Lafarge Fondue was used for the first time. Meanwhile in the USA, Spackman (1908, 1910a,b) developed cementitious material marketed under the name of Alca natural cements. Several patents were applied and granted (Bates 1921). A description of non-Portland cements was given by Muzhen et al. (1992). The reason for looking into alternative cement materials was to develop cements with improved stability against sulfate corrosion. Nowadays, calcium aluminate cements are used specifically for their distinct properties (Brown and Cassel 1977), some of which are presented in Table 1. Calcium aluminate cements do have special applications and are therefore widely used despite the fact that worldwide fabrication is by no means comparable to OPCs (Hohl et al. 1936; Garces et al. 1997; George 1976, 1980a,b, 1983, 1990, 1997; George and Montgomery 1992; George and Racher 1996; Gartner et al. 2002). Scrivener and Taylor (1990) and Scrivener et al. (1997a,b) described calcium aluminate cements and their use and microstructural developments. The use for experimental purposes was described by Auer et al. (1995). Thermal analyses for thermogravimetry of CAC-fraction and formation was discussed by Chudak et al. (1982, 1987). The …

48 citations

References
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9,897 citations

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TL;DR: The chemistry of hydration of monocalcium aluminate, CA, has been studied at several temperatures using conduction calorimetry, X-ray diffraction and other techniques as discussed by the authors.
Abstract: The chemistry of hydration of monocalcium aluminate, CA, has been studied at several temperatures using conduction calorimetry, X-ray diffraction and other techniques. At 4 °C, hydration to the decahydrate CAH 10 occurs about 15 hours after mixing; this hydration time increases with increasing temperature up to 30 °C, and C 2 AH 8 appears as a hydration product. At 40 °C rapid hydration to C 2 AH 8 is followed over a period of weeks by the ‘conversion’ reaction producing C 3 AH 6 . The reaction of CA to form crystalline hydrates was monitored by X-ray diffraction analysis; the results indicate that hydration also produces significant amounts of noncrystalline material. The enthalpies of the reactions involved in hydration and ‘conversion’ were measured by conduction calorimetry.

55 citations

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TL;DR: In this article, the authors studied the hydration behavior of Secar 71 refractory aluminous cement using conduction calorimetry, X-ray diffraction and thermal analysis techniques.
Abstract: The hydration behaviour of Secar 71 refractory aluminous cement has been studied over a range of temperature using conduction calorimetry, X-ray diffraction and thermal analysis techniques. The first reaction is the hydration of monocalcium aluminate, CA, producing a sharp calorimeter peak within 12 hours of mixing. Following this reaction the other major component, calcium dialuminate (CA 2 ), undergoes slow hydration over a period of weeks. The enthalpies of these two reactions have been measured. The initial hydration products of both components are CAH 10 , or C 2 AH 8 with alumina gel. These can subsequently convert to C 3 AH 6 ; after one month significant conversion is observed even at room temperature. A method of estimating the degree of conversion based on X-ray measurement of C 3 AH 6 is proposed.

39 citations

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TL;DR: Differential scanning calorimetry (dsc) was used to investigate the freezing behaviour of hardened cement paste (hcp) subjected to nacl and cacl2 solutions containing up to 5.4 mol cl/l as mentioned in this paper.
Abstract: Differential scanning calorimetry (dsc) was used to investigate the freezing behaviour (-175 deg c to 20 deg C) of hardened cement paste (hcp) subjected to nacl and cacl2 solutions containing up to 5.4 mol cl/l. Thermograms were also recorded for samples dried to relative humidities (rh) between 61% and 96%. The low-temperature phase transition at -38 deg c exhibited the freezing behaviour of an aqueous solution in gel pores of approximately equal to 4 nm radius. Chloride ions strongly reduce the coupling forces between gel particles and structure the gel pore water. On desorption critical behaviour of the low-temperature transition energy was observed at 0.52 mol cl/l which is the concentration most damaging to hcp. Above 1.3 mol cl/l freezing of supercooled bulk water in macropores was observed at more than one temperature. (Author/TRRL)

27 citations

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TL;DR: In this paper, the hydration process of a high alumina cement was investigated through ultrasonic wave propagation techniques, and a correlation between wave amplitude and velocity and breaking strength of the cement was demonstrated.
Abstract: The hydration process of a high alumina cement was investigated through ultrasonic wave propagation techniques A correlation between wave amplitude and velocity and breaking strength of the cement is demonstrated The wave behaviour through hydrating cements was found to be a function of the cement-to-water ratio between values of 2 and 4 Changes in the temperature of the hydrating samples were found to exhibit a similar dependence

6 citations