Page 125 - Handbook of Thermal Analysis of Construction Materials
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108                           Chapter 3 - Formation and Hydration


                                     Ramachandran and Beaudoin [51]  followed the hydration of C AF
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                              containing 5–30% gypsum, prepared at w/s ratios of 0.08, 0.13, 0.5, and 1.0
                              and exposed to a temperature of 25°C or 80°C. Techniques such as DTA,
                              XRD, and conduction calorimetry were used. Compounds were identified
                              by their characteristic thermal effects as follows. Gypsum indicated two
                              peaks in the range 150–200°C representing the stepwise removal of water.
                              At low concentrations, gypsum gave a single peak at about 150–160°C. Free
                              water gave an endothermal effect at 100°C. The hexagonal phase exhibited
                              an endothermal peak at about 160–175°C, the cubic form at 300–325°C.
                              Ettringite was identified by an endothermal peak effect at 110–125°C and
                              the low sulfoaluminate by an endothermal peak at about 200–210°C.
                                     The relative amounts of unreacted gypsum and high sulfate alumi-
                              nate hydrate contained in samples cured for different times in a sample
                              hydrated at 25°C and a w/s ratio of 0.13 are given in Fig. 28. [53]  Calculations
                              suggest that within 1 hour relatively more gypsum has reacted to form
                              ettringite in mixes containing larger amounts of gypsum. Conduction
                              calorimetric investigation also indicates that in the first 30 minutes a larger
                              amount heat of heat is developed in samples containing greater amounts of
                              gypsum. Although almost all gypsum has reacted at 7 hours in samples
                              containing 5–20% gypsum, substantial amounts are still present in the
                              mixture prepared with 30% gypsum. All samples show a general decrease
                              in the amount of ettringite after 3–7 hours of hydration and an increase in
                              the amount of low sulfoaluminate phase. It is generally believed that
                              ettringite begins to convert to the low sulfate form after all gypsum has been
                              consumed. This may be valid at low gypsum contents. At a 30% gypsum
                              level, although there is a decrease in the amount of ettringite and an increase
                              in the amount of low sulfate form, there is still a large percentage of
                              unreacted gypsum at 7 hrs. It appears that after this length of time the
                              reaction between ettringite and ferrite phase to form low sulfoaluminate
                              progresses at a faster rate than the reaction between gypsum and C AF to
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                              form ettringite. Length measurements as a function of time in admixture
                              containing 30% gypsum show a higher expansion of 10.8% at 7 hrs
                              compared to only 2.9% for that containing 20% gypsum. A higher expan-
                              sion may result in a higher porosity and better availability of the C AF
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                              surface for the reaction. It was also found that at very low w/s ratios and a
                              higher temperature the low monosulfate phase need not result from the
                              conversion reaction involving ettringite.
                                     In Fig. 29, the thermal curves of C AF-CaSO •2H O mixes hy-
                                                                     4        4    2
                              drated at a w/s ratio of 0.5 or 1.0 are given. Most samples hydrated for 2 days
                              at 25°C contain mainly the low sulfoaluminate. [51]  The interconversions
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