You are on page 1of 6

J. Am. Ceram. Soc.

, 95 [12] 3979–3984 (2012)

DOI: 10.1111/jace.12040
© 2012 The American Ceramic Society

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.
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 150°C for 4 d. The vessel was, then, removed from the oven,
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

which are not presented here, suggested that the expansion

of monosulfate sample in this solution, containing dissolved
ions of calcium, aluminum and sulfate, was ~1 9 10 3%
after 3 min. It was considerably lower than the expansion
observed for the monosulfate samples immersed in the other
solutions for a similar period of time (~1% after 3 min)
emphasizing that all three of these ions can have a role in
the volume stability of monosulfate depending on the
composition of the aqueous solution.
Dissolution of monosulfate also occurs, at a lower rate, in
the saturated water vapor (Fig. 1). The ions, especially those
that are near the surface, could gradually leach out, resulting
in the expansion.
The XRD patterns of monosulfate in distilled water are
presented in Fig. 3. The figure shows that the dissolution of
monosulfate resulted in the gradual growth of the ettringite
peak in the sample so that after 21 d the ettringite peak was
significantly more dominant than the monosulfate peak. The
appearance of ettringite due to the dissolution of monosul-
fate in distilled water was also reported by Atkins et al.26
The concentration of sulfate ion increases in both the pore
Fig. 2. Changes in pH with time of immersion of monosulfate solution and the bulk solution as a result of the leaching pro-
specimens of distilled water, lime-saturated water, and gypsum-
saturated water. cess tending toward an equilibrium concentration in a few
hours. The increased concentration of sulfate ions in the
sample pores, due to the dissolution of monosulfate, could
shown in Fig. 2 that the initial reduction of pH of the dis- result in the formation of ettringite which is more stable than
tilled water immediately after immersion of the monosulfate monosulfate in water at 25°C.26,27
sample is an indication of leaching of sulfate ions from the The growth of ettringite peaks occurred more slowly in
interlayer space of monosulfate structure into the distilled the lime-saturated water compared to that in the distilled
water. The pH, then, oscillated between 7.0 and 7.4 due to water (Figs. 3 and 4). It was also observed that the sulfate
the competing effects of leaching of both sulfate and lime. leached out of the monosulfate sample reacted with the cal-
The release of sulfate ions was, however, reduced after cium cations available in the lime-saturated solution and
~40 min, and the pH continued to increase due to the leach- formed gypsum crystals after 3 weeks. The formation of gyp-
ing of lime to the solution. sum crystals is an indication of some sulfate leaching from
The expansion of monosulfate in the gypsum-saturated the interlayer of the monosulfate sample even though the pH
water was significantly lower than that in distilled water. of the solution did not significantly change during the first
Sulfate ions and calcium ions were available in the gypsum 8 h (Fig. 2).
solution which possibly reduced the solubility of these ions The XRD pattern of the monosulfate samples immersed
due to the common-ion effect, and, consequently, decreased in the gypsum-saturated water is shown in Fig. 5. As
the expansion. It is also indicated from the results of Fig. 2 expected, the formation of ettringite was accelerated in the
that the pH of the gypsum-saturated solution did not presence of gypsum solution. However, in spite of the
decrease (during the first 40 min) after immersion of the higher rate of ettringite formation, the gypsum-saturated
monosulfate sample in it. In addition, the pH of the gypsum- water resulted in less expansion compared to the distilled
saturated solution exceeded that of the distilled water after water and the lime-saturated water [Fig. 1(a)]. In addition,
~1 h as the effect of lime leaching on the increase of the pH the sample did not disintegrate, and did not exhibit evi-
was not compensated for by that of the sulfate leaching dence of macro-cracking even though it exhibited more
occurring in the distilled water solution. than 7% expansion [Fig. 1(b)]. The higher resistance of the
The expansion of monosulfate in the lime-saturated water sample to disintegration in the gypsum-saturated water may
was very quick, and the sample disintegrated a couple of
minutes after the immersion [Fig. 1(a)]. The pH of lime-satu-
rated water did not significantly change after the immersion
of the monosulfate sample in it (Fig. 2). The leaching out of
lime from the monosulfate sample is minimized in the lime-
saturated water. Some sulfate ions likely leached out from
the sample, and resulted in a part of the expansion. The
amount of sulfate leaching, however, was not large enough
to change the pH of the solution; especially as the lime-satu-
rated water has a high alkaline buffer capacity which makes
it more resistant to change of the pH compared to the dis-
tilled water. Aluminum leaching possibly also played a role
in the expansion and the disintegration of the monosulfate
sample in the lime-saturated water. Aluminum can leach out
in the form of Al(OH) in the solutions with high values of
pH. As aluminum is a main component in the microstructure
of monosulfate layers, leaching of even a small amount of
aluminum can likely result in large expansions leading to the
disintegration of the sample.
The significant role of the dissolution of monosulfate in
the aqueous solutions as it pertains to volume stability was
also supported by the length-change measurements on a
monosulfate sample in a solution containing both aluminum Fig. 3. XRD patterns of monosulfate in distilled water–E:
sulfate hydrate (25 g/L) and gypsum (2.8 g/L). The results, Ettringite, M: Monosulfate.
3982 Journal of the American Ceramic Society—Khoshnazar et al. Vol. 95, No. 12

Fig. 6. XRD patterns of monosulfate in saturated water vapor– E:

Ettringite, M: Monosulfate.

Fig. 4. XRD patterns of monosulfate in lime-saturated water–E:

Ettringite, M: Monosulfate, G: Gypsum.

Fig. 5. XRD patterns of monosulfate in gypsum-saturated water–E:

Ettringite, M: Monosulfate.

be related to the limited amount of ions leached out of the

sample. The XRD patterns of Fig. 5 together with the
expansion curve of Fig. 1(b) suggest that the monosulfate
Fig. 7. SEM micrographs of monosulfate specimens immersed in
sample in the saturated-gypsum solution exhibited about distilled water, lime-saturated water, gypsum-saturated water, and
6% longitudinal expansion before its complete conversion saturated water vapor for 24 h.
to ettringite. About half of this expansion occurred in the
first day of the experiments, although a significant growth
of ettringite crystals occurred after this period. This also water. It can also be seen that the particles exhibiting plate-
suggests that the dissolution of the sample is a main source like morphology for the monosulfate sample immersed in the
of expansion. In addition, the length change curve of the lime-saturated water are smaller than those in the other test
ettringite formed through the dissolution process of the solutions. The alterations to the surface of the monosulfate
monosulfate sample is concave up [Fig. 1(b)] corresponding sample in the water vapor were lesser than those in the other
to the length change curves of the synthetic ettringite solutions as was expected.
presented in the following section.
The XRD patterns of the sample in the saturated water
vapor show that the expansive behavior of monosulfate in (2) Expansion of Ettringite
the water vapor is very similar to that in the distilled water, Ettringite also exhibited a significant expansion when it
but the expansion occurs at a lower rate (Figs. 3 and 6). was exposed to the distilled water (Fig. 8). The expansion
The SEM micrographs of the monosulfate samples after of ettringite in the lime-saturated water was very similar to
24 h immersion in the distilled water, lime-saturated water, that in the distilled water. The samples, in both solutions,
gypsum-saturated water, and water vapor are shown in disintegrated after ~40 min. The expansion of ettringite in
Fig. 7. It was observed that the surface texture and the hex- the gypsum-saturated water was lower than that in distilled
agonal morphology of the monosulfate plates were altered water and lime-saturated water. In addition, the sample had a
following immersion in the test solutions for 24 h. The ettringite higher resistance to the disintegration in the gypsum-saturated
crystals are likely formed on the surface of the samples, water, and it did not disintegrate for a period of up to
especially on the one immersed in the gypsum-saturated ~100 min. The ettringite sample also expanded in the water
December 2012 Volume Stability of Calcium Sulfoaluminate Phases 3983

Fig. 10. XRD patterns of ettringite specimens after 21 d immersion

in distilled water, lime-saturated water, gypsum-saturated water, and
saturated water vapor.

Fig. 8. Length change of ettringite specimens in distilled water,

lime-saturated water, gypsum-saturated water, and saturated water

Fig. 9. Changes in pH with time of immersion of ettringite

specimens of distilled water, lime-saturated water, and gypsum-
saturated water.

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

The data presented in Fig. 8 indicate that no significant Acknowledgments

change was observed in the XRD patterns of ettringite
The authors would like to acknowledge the technical assistance of Dr. Taijiro
samples in the test solutions up to 21 d. The comparison Sato, Mr. Gordon Chan and Miss Dan-Tam Nguyen. They would also like to
of Figs. 8 and 10 indicates that the dissolution of ettringite, thank Dr. Sahar Soleimani and Dr. Pouria Ghods for providing the equipment
and especially the leaching of sulfate ions located between for the pH measurements.
the columns of the ettringite structure, plays an important
role in the expansion of ettringite in the test solutions. References
Leaching of sulfate ions did not affect the general nature 1
of the channelled structure of ettringite. It, however, A. W. Moore and H. F. W. Taylor, “Crystal Structure of Ettringite,” Acta
Crystallogr. B Struct. Sci., 26, 386–93 (1970).
resulted in considerable expansion that could contribute to 2
S. N. Ghosh, Advances in Cement Technology: Chemistry,Manufacture
cracking and the disintegration of the ettringite sample. In and Testing, Second Edition. Tech Books International, New Delhi, India,
addition, leaching of aluminum is likely to be very expan- 2002.
sive and may result in the disintegration of the ettringite
R. Allmann, “Refinement of the Hybrid layer Structure [Ca2Al(OH)6]+[1/
2SO43H2O] ,” Neues Jahrbuch fur Mineralogie Monatsheft, 3, 136–44 (1977).
sample. Defects in the crystalline structure of ettringite due 4
W. Michaelis, “Cement Bacillus,” Tonindustrie Zeitung, 16, 105–6 (1892).
to the leaching of aluminum cannot be necessarily detected 5
W. C. Hansen, “Attack on Portland Cement Concrete by Alkali Soils and
by the XRD technique as it may affect only a small per- Waters-A Critical Review,” Highway Res. Rec., 113, 1–32 (1966).
centage of the ettringite crystals. Ghorab et al.28 also sug- I. Odler and M. Gasser, “Mechanism of Sulfate Expansion in Hydrated
Portland Cement,” J. Am. Ceram. Soc., 71, 1015–20 (1988).
gested that no significant change in the XRD patterns of 7
B. Mather, “A Discussion of the Paper ‘Mechanism of Expansion-Associ-
the ettringite samples immersed in the distilled water does ated Ettringite Formation’ by P.K. Mehta,” Cem. Concr. Res., 3, 651–2
not guarantee that there is no damage to the structure of (1973).
the ettringite crystal. W. C. Hansen, “A Discussion of the Paper ‘Scanning Electron Microscopic
Studies of Ettringite Formation’ by P.K. Mehta,” Cem. Concr. Res., 6, 595–6
The SEM micrographs of ettringite samples immersed in the (1976).
distilled water, lime-saturated water, gypsum-saturated water, 9
P. K. Mehta, “Mechanism of Expansion Associated with Ettringite Forma-
and water vapor for 24 h are presented in Fig. 11. The size of tion,” Cem. Concr. Res., 3, 1–6 (1973).
the ettringite crystals resulting from exposure to the test solu- P. K. Mehta and F. Hu, “Further Evidence for Expansion of Ettringite by
Water Adsorption,” J. Am. Ceram. Soc., 61, 179–81 (1978).
tions is smaller than that in the control sample. In addition, 11
P. K. Mehta and S. Wang, “Expansion of Ettringite by Water Adsorp-
gypsum crystals formed near the surface of the ettringite crys- tion,” Cem. Concr. Res., 12, 121–2 (1982).
tals exposed to the water vapor. This is an indication of sulfate T. Thorvaldson, “Chemical Aspects of the Durability of Cement Prod-
and calcium leaching from the ettringite sample. ucts”; pp. 436-84 in Proceedings of the 3rd Int. Symp. Chem. of Cem., Cement
and Concrete Association, London, 1952.
The comparison of Figs. 1 and 8 indicates that the expan- 13
M. Collepardi, “Ettringite Formation and Sulfate Attack on Concrete”;
sion of ettringite in distilled water is considerably lower than pp. 25–42 in supplementary papers, Proc. 5th CANMET/ACI Int. Conf. on
monosulfate, which is also in conformity of the previously Durability of Concrete, Edited by V. M. Malhotra. American Concrete Insti-
published investigations on the lower solubility of ettringite tute, Barcelona, Spain, 2000.
S. Békri, J. F. Thovert, and P. M. Adler, “Dissolution of Porous Media,”
(at 25°C) compared to that of monosulfate.26 Chem. Eng. Sci., 50 2765–91 (1995).
G. G. Litvan, “Volume Instability of Porous Solids: Part 2. Dissolution of
Porous Silica Glass in Sodium Hydroxide,” J. Mater. Sci., 19, 2473–80 (1984).
IV. Conclusions G. G. Litvan, “Volume Instability of Porous Solids: Part 1”; pp. 46–50 in
7th Int Congress on the Chem. of Cem. VII, Vol. III. Edited by General Secre-
In this study, mechanisms of expansion of monosulfate and tariat. Editions Septima, Paris, 1980.
ettringite in distilled water and in presence of lime and L. S. Dent Glasser and N. Kataoka, “The Chemistry of Alkali-Aggregate
gypsum solutions were investigated. The main conclusions Reaction,” Cem. Concr. Res., 11, 1–9 (1981).
R. F. Feldman and P. J. Sereda, “Characteristics of Sorption and Expan-
are as follows: sion Isotherms of Reactive Limestone Aggregate,” J. Am. Concr. Inst., 58 [2]
203–14 (1961).
1. Dissolution of ettringite and monosulfate phases in the 19
J. J. Beaudoin, S. Catinaud, J. Marchand, and T. Sato, “Volume Stability
aqueous solutions results in significant expansion. of Hydrated Portland Cement Exposed Aggressive Solutions,” Industria Itali-
2. A dissolution mechanism may be also a significant ana del Cemento, 72, 954–67 (2002).
source of expansion in cement paste. H. J. Kuzel, “Synthesis and X-Ray Study of the Crystalline Composition
3CaO.Al2O3. CaSO4. 12H2O,” Neues Jahrb. Mineral. Monatsh., 7, 193–7
3. Expansion of monosulfate and ettringite can occur in (1965).
aqueous solutions containing no sulfate ions. 21
L. J. Struble and P. W. Brown, An Evaluation of Ettringite and Related
4. Monosulfate exhibited larger expansion than ettringite Compounds for Use in the Solar Energy Storage, 11pp. NBSIR 82-253. US
in the test solutions, which may be related to the Dept. of Commerce, 1982.
P. J. Sereda and R. F. Feldman, “Compact of Powdered Materials as Por-
higher solubility of monosulfate. ous Bodies for Use in Sorption Studies,” J. Appl. Chem., 13, 150–8 (1963).
5. Leaching of the sulfate ions which occurred immedi- 23
I. Soroka and P. J. Sereda, “The Structure of Cement-Stone and the Use
ately after the exposure to all the test solutions of Compacts as Structural Models”; Proceedings of the 5th Int. Symp. Chem.
resulted in a significant expansion. The effect was not of Cem., Vol. III, 67-73 Cement Association of Japan, Tokyo, 1968.
H. F. W. Taylor, The Chemistry of Cements. Academic Press, London and
detected in the XRD patterns as these ions leached out New York, 1964.
of the interlayer of monosulfate structure or channels 25
L. Zhang and F. P. Glasser, “Critical Examination of Drying Damage to
of the ettringite structure. Cement Pastes.,” Adv. Cem. Res., 12, 79–88 (2000).
6. Leaching of aluminum and calcium ions from the M. Atkins, F. P. Glasser, and A. Kindness, “Cement Hydrate Phases: Sol-
ubility at 25°C,” Cem. Concr. Res., 22, 241–6 (1992).
structure of monosulfate and ettringite cannot be 27
M. Atkins, D. Macphee, A. Kindness, and F. P. Glasser, “Solubility Prop-
detected using the XRD technique when it affects only erties of Ternary and Quaternary Compounds in the CaO-Al2O3-SO3-H2O
a small percentage of the crystals. The leaching of System,” Cem. Concr. Res., 21, 991–8 (1991).
these ions, especially aluminum, however, likely results H. Y. Ghorab and E. A. Kishar, “Studies on the Stability of the Calcium
Sulfoaluminate Hydrates. Part I: Effect of Temperature on the Stability of
in a significant expansion. Ettringite in Pure Water,” Cem. Concr. Res., 15, 93–9 (1985).
7. Monosulfate and ettringite also expanded when they 29
H. Y. Ghorab, E. A. Kishar, and S. H. Abou Elfetouh, “Studies on
were exposed to the saturated water vapor. The mecha- the Stability of the Calcium Sulfoaluminate Hydrates. Part II: Effect of Al-
nism of expansion is similar to that of exposure in lite, Lime and Monocarboaluminate Hydrate,” Cem. Concr. Res., 28, 53–61
distilled water, but the expansion occurs at a lower rate. (1998). h