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Volume Stability of Calcium Sulfoaluminate Phases PDF
Volume Stability of Calcium Sulfoaluminate Phases PDF
Journal
Volume Stability of Calcium Sulfoaluminate Phases
Rahil Khoshnazar,‡,† James J. Beaudoin,‡ Rouhollah Alizadeh,§ and Laila Raki‡
‡
National Research Council of Canada, Ottawa K1A 0R6, Ontario, Canada
§
Giatec Scientific Inc., Ottawa K1S 5R5, Ontario, Canada
The volume stability of calcium sulfoaluminate phases exposed There remains no general agreement on the theories of
to water, lime, and gypsum environments was investigated. The expansion of ettringite. In addition, very few investigations
length changes of compacted specimens of synthetic monosul- have been conducted on the volume stability of monosulfate
fate and ettringite were monitored in distilled water, lime-satu- itself. The published studies have focused mainly on the con-
rated water, gypsum-saturated water, and saturated water version of monosulfate to ettringite in the sulfate environ-
vapor. The X-ray diffraction analysis was also performed on ments6,13 although other mechanisms may also be associated
the samples to assess the changes in the crystalline structure of with the expansion of these phases. Dissolution of ettringite
each phase. Evidence was provided in support of the significant and monosulfate, for example, is a possible source of expan-
role of dissolution of monosulfate and ettringite, and the leach- sion that is not widely recognized.
ing of their constituent ions, on the expansion of these phases. The solid phase of porous materials can gradually break
down to release individual ions into the pores through a dis-
solution process.14 It has been suggested that dissolution of
I. Introduction porous materials and leaching out of ions into the liquid
phase is an expansive process. The results of previous investi-
E TTRINGITE (3CaO.Al2O3.3CaSO4.32H2O) and monosul-
fate (3CaO.Al2O3.CaSO4.12H2O) are the two common
forms of calcium sulfoaluminate phases present in the
gations by Litvan,15,16 Dent Glasser and Kataoka,17 and
Feldman and Sereda18 support this argument. Specifically,
hydrated cement paste. Ettringite is known to have a column Litvan15 investigated the volume stability of porous silica glass
and channel-like structure in which the columns have the specimens (1–8 mm thick) in NaOH solutions (0.1–6.4M) for an
empirical chemical formula of [Ca3Al(OH)6.12H2O]3+, and exposure period of about 24 h. The expansion of the samples
the SO42 anions and water molecules occupy the intervening was quite significant (e.g., 0.70% for a 1 mm thick glass sample
channels.1 The formation of ettringite is a key factor in the in the 0.4M NaOH solution). These length changes far exceed
setting process of the cement paste. Ettringite normally con- the length change of porous glass saturated with water
verts to monosulfate as the cement hydration continues.2 (~0.16%). In addition, Dent Glasser and Kataoka observed
Monosulfate has a lamellar crystalline structure. Its main lay- significant expansions of silica gel in NaOH solution. Feld-
ers are composed of [Ca2Al(OH)6]+, and the SO42 anions man and Sereda also reported a 0.19% expansion of porous
and water molecules are located between the layers.3 silica glass during alkali treatment.
The characteristics of ettringite and monosulfate are of Litvan15,16 further demonstrated that leaching of lime
significant importance, from the durability point of view, as from cement paste results in expansion as does the partial
these phases may exhibit considerable expansion due to the dissolution of cement paste by a 1 N aqueous solution of
environmental conditions. The expansions related to the HCl. He suggested that dimensional changes accompanying
calcium sulfoaluminate phases have long been studied by dissolution can possibly result for the following reasons:
cement chemists and researchers since the investigation of changes to the surface free energy of the solid phase; tran-
Michaelis in 1892.4 The mechanisms controlling these expan- sient length changes due to gradients in the concentration of
sions are, however, still under debate. dissolved species in the pore solution generating osmotic-like
The formation of ettringite in sulfate-rich environments pressures; disjoining pressure resulting from double layer
has been widely accepted as a main cause of expansion effects outside the surface generating repulsive forces; release
referred to as sulfate attack.5–8 The anisotropic growth of of strain-energy stored in the sample. Beaudoin et al.19 also
ettringite crystals, according to this theory, is an expansive suggested that cementitious materials can expand in aggres-
phenomenon, which can result in the deterioration of cement sive solutions due to the dissolution process.
paste. Mehta,9–11 however, reported that the expansion of The intent of this study is to further investigate the details
ettringite does not necessarily occur in the presence of high of mechanisms responsible for the volume stability of cal-
sulfate concentrations. He attributed the expansion of cium sulfoaluminate phases. The experiments were designed
ettringite crystals of colloidal dimensions to the imbibition of to determine the length change of synthetic monosulfate and
liquid water. The observed expansion in this case could be ettringite in distilled water, and in presence of lime and gyp-
considerably greater than the expansions due to the ettringite sum solutions. The observed expansions were, then, com-
formation itself.9 Other proposed mechanisms include the pared with the changes of the pH of the solutions as well as
expansion of ettringite associated with the osmotic forces, the crystalline structure and the morphology of the specimens
similar to those responsible for the swelling of the clay in order to explore the possible origins of these expansions.
particles.12
II. Experimental Program
J. Biernacki—contributing editor (2) Preparation of Materials
Monosulfate was synthesized according to Kuzel.20 In this
method, stoichiometric amounts of tricalcium aluminate
(C3A) and gypsum (CaSO4.2H2O) were mixed in excess water
Manuscript No. 31600. Received June 12, 2012; approved September 19, 2012.
†
Author to whom correspondence should be addressed. e-mail: rahil.khoshnazar@
in a hydrothermal pressure vessel, and heated in an oven at
nrc-cnrc.gc.ca 150°C for 4 d. The vessel was, then, removed from the oven,
3979
3980 Journal of the American Ceramic Society—Khoshnazar et al. Vol. 95, No. 12
and the excess water was discharged after the temperature using a HitachiS-4800 Field Emission Scanning Electron
equilibrated with the room environment. The remaining solid Microscope (Hitachi High-Technologies Canada, Inc., ON,
was placed in a desiccator and dried over saturated lithium Canada). The surface structure images were acquired using
chloride, at 11% relative humidity, for 24 h. a beam current of 10 mA at 3.2 9 10 16 J (2 kV) at the
Ettringite was prepared by a method described by Struble working distance of 8 mm.
and Brown,21 which consisted of reacting stoichiometric All the tests were performed at room temperature (24°C–
amounts of aluminum sulfate (Al2(SO4)3) solution and cal- 26°C). The compacted samples were kept in desiccators at a
cium oxide (CaO) solution. The aluminum sulfate solution relative humidity of 11%. They were all examined using
was prepared in distilled water, and the calcium oxide solu- XRD, prior to immersing in the solutions, to verify that the
tion was prepared in a 10% sugar solution. The two solutions crystalline structures corresponded to those of 3CaO.Al2O3.
were, then, mixed for 60 h. The resulting solution was filtered 3CaSO4.30-32H2O24,25 and 3CaO.Al2O3.CaSO4.12H2O.24,25
and the filtrate was dried in a vacuum drying cell for 24 h. In the cases where a decrease of the main basal spacing of
the monosulfate samples was observed, the humidity of the
sample was adjusted to revert it to the 3CaO.Al2O3.
(2) Tests CaSO4.12H2O.
Porous solid bodies in the form of circular disks (32 mm in
diam 9 1 mm thick) were prepared by powder compaction.
III. Results and Discussion
The powders were ground to sizes smaller than 150 lm
before the compaction. The compaction pressure was The results are presented for the monosulfate and ettringite
adjusted to reach a porosity of 10% for the samples. Then, separately. In each part, the length change of the samples
prisms measuring 5 mm 9 25 mm 9 1 mm were cut from is discussed with reference to the changes in the pH of the
the compacted samples, and mounted on modified Tucker- solution, and the crystalline structure and morphology of the
man extensometer, which had an accuracy of 1 microstrain. samples detected using the XRD and SEM techniques. The
Details of this method are provided elsewhere.22 Compacts associated mechanisms of expansion are discussed.
of hydrated cement have been successfully used as models
for cement paste.23
The prepared samples were placed in the test solutions, (1) Expansion of Monosulfate
and the length changes were measured continuously. Distilled Monosulfate specimens exhibited a significant expansion
water, lime-saturated water, gypsum-saturated water and sat- immediately after immersion in distilled water (Fig. 1). The
urated water vapor were used as the test solutions. For the rate of expansion was significantly reduced ~20 min after the
liquid solutions, the ratio of solid sample to the solution was immersion. The amount of expansion, however, was quite
1 g of solid per 50 mL of the solution. The whole setup was large as the total expansion of monosulfate was 2.7% after
placed in desiccators containing the test solution to avoid 8 h. The observed expansion was possibly due to the dissolu-
evaporation. The pH of the test solutions were monitored tion of monosulfate, and the release of its ions to the distilled
using a VWR-SP90M5 pH meter (VWR International Ltd, water. The rate of the dissolution decreases as the dissolution
Leighton Buzzard, UK) for the first 24 h after immersion of continues, due to the increased ion concentrations in the
the samples in the test solutions. solution, likely resulting in a decrease of the rate of expan-
Parallel to the length change and pH measurements, sam- sion. Expansion due to the change in the surface energy of
ples of the solid compacts were immersed in the solution for the samples (due primarily to sorption phenomena) seems to
XRD analysis at various times. The solid/solution ratio in be insignificant as the samples were conditioned at the rela-
this case was exactly the same as the one in the length tive humidity of 11% before starting the tests. The surface of
change measurements. The sample was removed from the the samples was, consequently, covered with water molecules
solution, and ground to obtain the powder 10 min before prior to immersion in the distilled water. Length change of
starting the XRD measurements. The X-ray diffraction mea- porous bodies, due to flattening of menisci that occurs on
surements were performed using a Scintag XDS 2000 diffractom- adsorption of water vapor at a partial pressure generally
eter (Scintag Inc., Cupertino, CA) using CuKa radiation. The greater than 0.45 is also minimized when a sample is directly
spectra were obtained in the range 6° < 2h < 60° using a step immersed in liquid water.16
size of 0.08° at 5 s intervals. They were, then, normalized The data for the change in the pH with time of immersion
according to the mass of the samples. in distilled water also support the role of dissolution of
Changes to the morphology of the samples were observed monosulfate and the leaching out of the ions associated with
using the SEM techniques. SEM images were collected the observed expansion. It is suggested based on the results
(a) (b)
Fig. 1. Length change of monosulfate specimens in distilled water, lime-saturated water, gypsum-saturated water, and saturated water vapor–(a)
up to 8 h, (b) up to 21 d.
December 2012 Volume Stability of Calcium Sulfoaluminate Phases 3981
vapor at a lower rate compared to those in the other solu- Fig. 11. SEM micrographs of ettringite specimens immersed in
distilled water, lime-saturated water, gypsum-saturated water, and
tions. The expansion of ettringite sample, however, was still saturated water vapor for 24 h.
significant so that the total length change of ettringite in the
saturated water vapor was ~1.3% after 8 h.
It is suggested that the expansion of ettringite in the et al.29 also suggested that the concentration of sulfate ions
aqueous solutions is also associated with the dissolution was lower in the presence of lime solution. The 1:1 ettringite-
process. Data from the pH versus time of immersion curves lime water solution, however, contained ~0.045 g/L sulfate
in Fig. 9 support this argument. It is suggested that the ions. It is possible that aluminum leaching in the form of
reduction in pH of the distilled water, from 7.0 to 6.7, Al(OH) , which is probably accelerated in the alkaline solu-
40 min after immersion of the ettringite sample is due to tions was also responsible for some expansion and especially
the leaching of sulfate ions from the intercolumnar space of for the disintegration of the ettringite sample. Aluminum has
the ettringite structure. Ghorab et al.28,29 reported that a a critical location in the structure of ettringite columns. Only
total of ~0.2 g/L of sulfate ions are available in an equili- a small amount of aluminum leaching is probably required
brated ettringite-water solution at 30°C. The pH, then, to result in the significant expansion, and loss of integrity of
gradually increased to 9.14 after 8 h due to the leaching of the ettringite sample.
lime into the solution. The pH of gypsum-saturated water did not decrease after
The pH of lime-saturated water did not significantly the immersion of ettringite as expected. It only gradually
change after the immersion of ettringite. Lime leaching from increased due to the lime leaching. These results are in good
the ettringite sample is minimized in the lime-saturated conformity with the length-change curves of Fig. 8. A lower
water. The sulfate leaching is also lower in the lime-saturated expansion and higher resistance to the disintegration of the
water. Some sulfate, however, likely leached from the ettring- ettringite sample in the gypsum-saturated water compared to
ite sample and resulted in some expansion although it did that in the distilled water and lime-saturated water are
not noticeably decrease the pH of the solution. Ghorab shown.
3984 Journal of the American Ceramic Society—Khoshnazar et al. Vol. 95, No. 12