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The formation of ettringite (3CaOⴢAl2O3ⴢ3CaSO4ⴢ32H2O) extensively.5–9 The formation of these sulfoaluminates occurs
from monosulfate (3CaOⴢAl2O3ⴢCaSO4ⴢ12H2O) and gyp- during normal curing, but can also be caused by interaction
sum (CaSO4ⴢ2H2O) was investigated by isothermal calo- with a variety of environments, including intrusion of solutions
rimetry and X-ray diffraction (XRD) analyses. Hydration containing high concentrations of sulfate and/or other ionic
was carried out at constant temperatures from 30° to 80°C species. Thus the interaction of various ionic species and their
using deionized water and 0.2M, 0.5M, and 1.0M sodium effects on ettringite and monosulfate formation have also been
hydroxide (NaOH) solutions. Ettringite was found to be the studied extensively.10 Concrete is a hydrated, porous medium
dominant crystalline phase over the entire temperature and a certain amount of “free” water is usually present in the
range and at all sodium hydroxide concentrations. A so- pores. This porosity allows solutions to move through concrete
dium-substituted monosulfate phase was formed as a hy- and this may result in sulfoaluminate compound formation.
dration product in the 1.0M sodium hydroxide solution There is also evidence in the literature that the interaction of
regardless of temperature. XRD and calorimetry demon- ionic species (most notably alkali ions) initially present may
strate that hydration in increasing sodium hydroxide con- cause subsequent sulfoaluminate compound formation.11
centrations decreases the amount of ettringite formed and The presence of various ionic species can cause a conversion
retards the rate of reaction. The apparent activation energy of monosulfate into other AFm phases. One such phase is a
for the conversion of the monosulfate/gypsum mixture to sodium-substituted AFm phase referred to as the “U-phase.”
ettringite was observed to vary depending on the sodium Such a sodium-substituted AFm phase (4CaO⭈0.9Al2 O3 ⭈
hydroxide concentration. Ettringite formation was ob- 1.1SO3⭈0.5Na2O⭈16H2O) has been observed when C3A hydra-
served to depend upon the concentration of calcium in so- tion was carried out in high concentrations of sodium and
lution; thus the formation of calcium hydroxide and so- sulfate.12 Recent studies indicate that the U-phase also forms in
dium-substituted monosulfate phase competes with ordinary portland cement and its formation results in expan-
ettringite formation. sion, implying a deleterious effect in hardened concrete.4,13
Although much work has been done to study the formation
of ettringite from C3A followed by its conversion to monosul-
I. Introduction fate, we are unaware of any studies which have considered the
conversion of monosulfte to ettringite. Therefore, the mecha-
E TTRINGITE is a hydrated sulfoaluminate compound
(3CaO⭈Al2O3⭈3CaSO4⭈32H2O) and is commonly formed in
concrete during curing. Monosulfate (3CaO⭈Al2O3⭈CaSO4⭈
nism and kinetics of ettringite formation from monosulfate are
investigated in the present study. Deionized water and various
concentrations of sodium hydroxide solutions were used to
12H2O) is a related sulfoaluminate compound. In cement no- hydrate a monosulfate/gypsum mixture. Isothermal calorimetry
menclature ettringite is also referred to as AFt and monosulfate and X-ray diffraction (XRD) were used to characterize the rates
as AFm. Ettringite formation while the concrete is in a plastic of hydration and the crystalline phases formed. Analysis of the
state contributes to the initial “setting” of concrete. Alterna- results obtained by these methods provides insight into the
tively, ettringite formation after concrete has “set” into a rigid, kinetics of the hydration processes involved and the stability of
solid mass can be deleterious and can cause the loss of struc- the various phases formed.
tural integrity. The reason for this dual character is due to the
solid specific volume increase accorded to ettringite formation.
In the literature, expansion due to ettringite formation is attrib- II. Methods and Materials
uted to its needlelike structure.1 Monosulfate incorporates only
1 mol of sulfate and exhibits a platelike microstructural mor- (1) Monosulfate Synthesis
phology.2 The formation of monosulfate in hardened concrete The precursor monosulfate powder was prepared by mixing
is generally not considered deleterious, because its formation a slurry of tricalcium aluminate and gypsum under an inert gas
causes less expansion than does that of ettringite. There is, (nitrogen) using a modification of the method outlined by Tay-
however, evidence in the literature which indicates that mono- lor14 (CaCl2 or soda lime were not used for drying). The slurry
sulfate formation also causes expansion.3,4 was filtered and dried, again under nitrogen, and then mixed
The formation of ettringite and monosulfate from cement with gypsum powder at a molar ratio of 1:2.5.
phases (tricalcium aluminate and gypsum) has been studied
(2) Experimental Procedure
Isothermal calorimetry was performed using the experimen-
tal setup described by TenHuisen et al.15 Approximately 1.00
C. M. Jantzen—contributing editor g of the monosulfate/gypsum mixture and 3.0 mL of solution
were used for each sample run. Solutions used were deionized
water, and 0.2M, 0.5M, and 1.0M NaOH. The solid sample and
a syringe containing the solution were allowed to reach equi-
Manuscript No. 190392. Received February 9, 1998; approved April 24, 1998. librium at each experimental temperature before injection.
Supported by the National Science Foundation under Grant No. CTS 93-09528 and
by the R. J. Lee Group, Inc. Sample runs were carried out at 30°, 40°, 50°, 60°, 70°, and
*Member, American Ceramic Society. 80°C.
2900
October 1999 Formation of Ettringite from Monosubstituted Calcium Sulfoaluminate Hydrate and Gypsum 2901
III. Results
Figures 1(a) and (b) show the rates of reaction and heat
output for reaction between monosulfate and gypsum hydrated
in deionized water between 30° and 80°C. In general, the rate
of hydration is observed to increase with increasing tempera-
ture in any given solution. The hydration reactions are, at all
temperatures, characterized by a single major peak. The dura-
tion of the peak is less than 1 h for every hydration tempera-
ture. The total heat evolved (Fig. 1(b)) reaches a maximum
value of approximately 140 kJ/(mol of Al2O3) at 70° and 80°C
and is indicative of complete hydration when ettringite is the
final product. The kinetics of reaction are apparent in Fig. 1(b)
and indicate only small differences with hydration temperature.
Specimens hydrated at 30° through 60°C evolve less total heat
than those at 70° and 80°C, evolving approximately 115 kJ/
(mol of Al2O3). Fig. 1. (a) Rates of heat evolved when monosulfate and gypsum are
Figures 2(a) and (b) also show rates of reaction and heat hydrated in deionized water. (b) Total heats evolved when monosulfate
output curves for specimens hydrated in 0.2M NaOH solutions and gypsum are hydrated in deionized water.
between 30° and 80°C. The rate curves (Fig. 2(a)) are again
characterized by single peaks which reach maxima before 1 h
for hydration temperatures greater than 50°C and at approxi- kJ/(mol of Al2O3) for samples hydrated between 30° and 60°C,
mately 2.5 h for hydration at 30° and 40°C. The reaction rates while 140 and 150 kJ/mol are evolved for samples hydrated at
are observed to increase as the temperature is increased. The 80° and 70°C, respectively.
total heat evolved reaches a maximum value of approximately Reaction rate curves for monosulfate and gypsum hydrated
120 kJ/(mol of Al2O3) for hydration at 80°C; these values are in 1.0M NaOH are very similar to those hydrated in 0.5M
approximately 110, 95, and 85 kJ/(mol of Al2O3) for hydration NaOH, shown in Fig. 4(a). The rate curves all show distinct
at 70°, 50°, and 60°, and 40° and 30°C, respectively. endothermic reactions, except for the sample hydrated at 80°C.
The rate curves shown in Fig. 3(a) for specimens hydrated in As with hydration in 0.5M NaOH solution, the rate curves are
0.5M NaOH are more complex than those observed for the very diffuse without apparent, distinct hydration peaks. The
deionized water and 0.2M solutions. There is still a single total heat evolved, shown in Fig. 4(b), reaches a maximum of
major peak observed for each specimen, but the peaks are not approximately 100 kJ/(mol of Al2O3) when hydration is carried
as distinct as those observed in less concentrated solutions. A out at 70°C.
distinct endothermic reaction is observed in specimens hy- Samples hydrated in deionized water generated approxi-
drated at 30°, 40°, and 50°C. The results of integrating the rate mately the same amounts of heat between 30° and 60°C, while
curves in Fig. 3(a) are shown in Fig. 3(b). The reaction rates more heat was liberated from samples hydrated at 70° and
are, as in the 0.2M solution, observed to increase with increas- 80°C. Because all of the experiments in deionized water were
ing temperature. The total heat evolved is approximately 80 carried out using approximately 1 g of mixed precursor, these
Fig. 2. (a) Rates of heat evolved when monosulfate and gypsum are Fig. 3. (a) Rates of heat evolved when monosulfate and gypsum are
hydrated in 0.2M NaOH. (b) Total heats evolved when monosulfate hydrated in 0.5M NaOH. (b) Total heats evolved when monosulfate
and gypsum are hydrated in 0.2M NaOH. and gypsum are hydrated in 0.5M NaOH.
results indicate the extent of hydration to be affected by a The primary calcium hydroxide peak also increases with tem-
change in ettringite morphology and/or an unidentified change perature above 40°C, in the 1.0M solution. Small XRD peaks
in the hydration reaction. observed in samples hydrated at 50°, 60°, and 70°C are also
The total heat evolved varies as a function of temperature for attributable to calcium hydroxide, but their intensities are only
hydration in a given sodium hydroxide concentration; in gen- slightly above those observed in samples hydrated in 0.2M
eral the introduction of higher sodium hydroxide concentra- sodium hydroxide.
tions causes the rate of the reaction to be retarded and the total Again, in general, the amount of gypsum detected by XRD
heat evolved to be reduced. decreases as the sodium hydroxide solution concentration in-
Analyses of the XRD patterns shown in Figs. 5, 6, 7, and 8 creases. Gypsum detected in the XRD patterns is due to an
indicate that ettringite, gypsum (CaSO4⭈2H2O), calcium hy- excess of gypsum present in the precursor mix. As the sodium
droxide (Ca(OH)2), and a sodium calcium aluminum sulfate hydroxide concentration and temperature increase, more of
hydrate phase (3CaO⭈Al2O3⭈CaSO4⭈0.5Na2SO4⭈15H2O, desig- gypsum is observed to go into solution. In the 0.2M solution
nated “U-phase”) are the crystalline phases observed. The gypsum is observed to substantially decrease in samples hy-
amounts of these phases vary with hydration temperature and drated between 60° and 80°C (indicating a reaction occurring
hydration solution. No residual monosulfate was observed in at approximately 50°C). In the 0.5M solution gypsum is ob-
any of the samples. served in samples hydrated at 40° and 50°C, but is not present
In general, in each sodium hydroxide concentration, the in samples hydrated between 60° and 80°C (again indicating a
amount of ettringite is observed (by XRD) to increase with reaction is occurring at 40° to 50°C). Small amounts of gypsum
increasing temperature. However, the extent to which increased are observed in the sample hydrated in 1.0M sodium hydroxide,
ettringite formation is observed decreases as the concentration and at 30°C, none of the other samples hydrated in 1.0M so-
of sodium hydroxide is increased. Ettringite and gypsum are lution show any indication of gypsum.
the only crystalline phases observed, over the entire tempera- The conditions under which gypsum was not completely
ture range, in samples hydrated in deionized water, and 0.2M consumed or where Ca(OH)2 precipitated were calculated us-
and 0.5M sodium hydroxide solutions. Ettringite, the U-phase, ing the aqueous geochemical code PhreeqC.16 These calcula-
and calcium hydroxide are observed, over the entire tempera- tions were carried out as a function of temperature (30°, 50°, or
ture range, in samples hydrated in 1.0M sodium hydroxide. The 70°C) and NaOH concentration (H2O, 0.2M NaOH, and 1.0M
primary U-phase XRD peak is also observed to increase with NaOH). Table II summarizes the output from the calculation
temperature and substantially at 80°C, in the 1.0M solution. reporting the pH, the saturation indices for calcium hydroxide
October 1999 Formation of Ettringite from Monosubstituted Calcium Sulfoaluminate Hydrate and Gypsum 2903
Fig. 4. (a) Rates of heat evolved when monosulfate and gypsum are
Fig. 7. XRD patterns obtained when monosulfate and gypsum are
hydrated in 1.0M NaOH. (b) Total heats evolved when monosulfate
hydrated in 0.5M NaOH at various temperatures.
and gypsum are hydrated in 1.0M NaOH.
Fig. 5. XRD patterns obtained when monosulfate and gypsum are Fig. 8. XRD patterns obtained when monosulfate and gypsum are
hydrated in deionized water at various temperatures. hydrated in 1.0M NaOH at various temperatures.
(CH) and gypsum (a value of zero indicates saturation), and the tion. Increasing the sodium hydroxide concentration increases
moles of solid (gypsum or CH). These calculated results are the extent of gypsum dissolution via the double decomposition
consistent with the XRD analyses. reaction:
IV. Discussion CaSO4⭈2H2O(s) + NaOH(aq) ⳱ Ca(OH)2(s) + Na2SO4(aq)
The first observation to be discerned from a review of the Thus sodium hydroxide promotes gypsum dissolution and the
data concerns the amount of gypsum dissolved into each solu- formation of calcium hydroxide. Our studies have shown the
2904 Journal of the American Ceramic Society—Clark and Brown Vol. 82, No. 10