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Article history: The carbonation resistance of alkali-activated binders is often tested via accelerated test protocols designed
Received 23 December 2011 for Portland cements, without questioning whether the tests replicate the mechanisms observed in service.
Accepted 23 July 2012 Thus, validation of accelerated methods is required to enable realistic prediction of material performance.
Changes in pore solution equilibria cause the formation of sodium bicarbonates during accelerated carbon-
Keywords:
ation, compared with hydrous sodium carbonates in natural carbonation. This shifts the carbonation mecha-
Alkali-activated cement (D)
Durability (C)
nism to favour more rapid reaction progress, to give a higher apparent degree of acceleration (compared to
Carbonation (C) natural conditions) than in Portland cements. The pore solution pH under accelerated carbonation is signif-
Pore solution (B) icantly lower than at natural CO2 concentrations, leading to a falsely short predicted service life (time to
Thermodynamic calculations (B) expected corrosion of embedded steel), as natural CO2 concentrations appear not to reduce the pH below
10. Thus, accelerated carbonation testing is unduly aggressive towards alkali-activated binders, and test
results must be cautiously interpreted.
© 2012 Elsevier Ltd. All rights reserved.
1. Introduction a reliable method for predicting the service life of alkali-activated con-
crete under carbonating conditions is an important issue which needs
Carbonation of cement and concrete materials in service has been to be addressed.
identified as a critical problem in many parts of the world, particular- In all widely applied tests, acceleration of carbonation is achieved
ly where the environment is warm and relatively humid. In order to by increasing the concentration of CO2 in the atmosphere surround-
predict, in a short period of time, how a material will perform in ser- ing the specimens under a controlled relative humidity (RH). Howev-
vice when subjected to CO2 exposure, accelerated carbonation testing er, the testing methodologies have mostly not been validated in detail
of binders, mortars and concretes is widely applied to the study of by comparison to natural carbonation of comparable samples, and
materials based on both Portland cement [1–5] and alkali-activated there is still ongoing discussion regarding the most applicable testing
[6–12] binders. Carbonation of alkali-activated binders has been iden- methodologies and conditions [4], with no testing methodology or
tified from accelerated testing to be a potentially significant problem conditions being universally preferred. The work of Ho and Lewis
in some important applications, with laboratory tests often showing [2] provided a detailed study of Portland cement carbonation in ser-
relatively high carbonation rates [6–11]. However, alkali-activated con- vice, as well as direct comparisons with the results of accelerated test-
cretes removed from service after extended periods have not in general ing, which has given some validation for the accelerated carbonation
shown problems related to carbonation [8,13,14]. This indicates that the testing conditions used in that study (4% CO2, 50% RH, 23 °C) as ap-
outcome of the accelerated test is not as accurate a predictor of in- plied to the particular materials investigated. However, there are
service performance of alkali-activated materials as it is for Portland three key areas in which information is lacking with regard to the un-
cement-based systems. Establishing and validating durability testing derstanding of the carbonation of alkali-activated binders under ser-
methods for alkali-activated concretes remains the major obstacle to vice conditions:
their commercial adoption in demanding structural applications, and
– CO2 concentrations ranging from 1% to 100% CO2, relative humidities
ultimately their acceptance in national and international regulatory
from 50% to 90% and temperatures from 5 to 37 °C have been reported
standards for structural concrete [15,16]. Therefore, the availability of
as test conditions for accelerated carbonation of Portland cement
concrete [4]; it remains to be determined in which environments
⁎ Corresponding author. Tel.: +61 3 8344 8755; fax: +61 3 8344 4153. alkali-activated materials show carbonation mechanisms which accu-
E-mail address: jprovis@unimelb.edu.au (J.L. Provis). rately replicate natural carbonation mechanisms. Castellote et al. [17]
0008-8846/$ – see front matter © 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.cemconres.2012.07.002
1318 S.A. Bernal et al. / Cement and Concrete Research 42 (2012) 1317–1326
showed that CO2 concentrations exceeding 3% lead to changes in the the validity of accelerated carbonation testing procedures in analysing
mechanism of Portland cement carbonation when compared to natu- the durability of alkali-activated materials.
ral carbonation, but no similar studies have been published for
alkali-activated binders. 2. Experimental program
– The relationship between accelerated carbonation rates and in-service
carbonation rates in alkali-activated concretes, which is essential in 2.1. Concrete samples
using the results of accelerated carbonation testing to calculate cover
depths required for a given service life, is unknown. Ho and Lewis A Colombian granulated blast furnace slag (GBFS 1) from the factory
[2] showed that, for a range of Portland cement concrete mixes, Acerías Paz del Río was used as the primary raw material for the produc-
1 week at 4% CO2, 50% RH and 23 °C gave a carbonation depth equiv- tion of concrete specimens. The basicity coefficient (Kb = CaO + MgO/
alent to 1 year indoors in ambient air in a laboratory environment, but SiO2 + Al2O3) and the quality coefficient (Kq = CaO + MgO + Al2O3/
also noted that exposure outdoors under uncontrolled conditions SiO2 + TiO2) based on the chemical composition (Table 1) were 1.01
gave as much as a factor of 3 difference (reduction) in natural carbon- and 1.92, respectively. Its specific gravity was 2900 kg/m3 and Blaine
ation rate. Carbonation rates are well known to be sensitive to wet/dry fineness was 399 m 2/kg. The particle size range, determined through
cycling, humidity, temperature and other exposure parameters laser granulometry, was 0.1–74 μm, with a d50 of 15 μm. The alkaline
[4,5,18], which means that a detailed mechanistic understanding of activating solution was formulated by blending a commercial sodium
the carbonation phenomenon itself is necessary for such predictions silicate solution with 31.7 wt.% SiO2, 12.32 wt.% Na2O and 56.9 wt.%
to be made with any confidence. H2O, and 50 wt.% NaOH solution, to reach a silicate modulus (Ms =
– During natural carbonation the binder structure is evolving over the SiO2/Na2O) of 1.3, and a concentration of activation of 4 wt.% Na2O
extended time periods (years) in contrast with accelerated tests with respect to the mass of slag.
which are generally conducted on relatively young concretes for The concretes were formulated with slag contents of 340 kg/m3,
short time periods (weeks). There is thus a need to incorporate an 412 kg/m3 and 512 kg/m3 and a water/(slag+anhydrous activator)
understanding of the influence of gel ageing into the analysis of nat- ratio of 0.48. Crushed gravel and river sand were used as coarse and
ural carbonation, but the structural changes taking place during fine aggregates in the manufacture of the concretes. The coarse aggregate
long-term ageing of alkali-activated binders remain incompletely was of 19 mm maximum size, with a specific gravity of 2790 kg/m3 and
understood on a mechanistic level. absorption of 1.23%. The specific gravity, absorption, and fineness mod-
ulus of the fine aggregate were 2450 kg/m3, 3.75% and 2.57, respectively.
The carbonation of Portland cement concrete proceeds predomi- Cylindrical specimens were produced, 76.2 mm in diameter and 152 mm
nantly by the reaction of atmospheric CO2 (via its dissolution in the in length, and the ends covered with an acrylic resin to give solely radial
water present in the pores) with the calcium in Ca(OH)2 and/or penetration of CO2. Samples were cured for 28 days at 25 °C and RH
Ca-rich C―S―H phases in the binder, to form calcium carbonate, >90% prior to the start of testing. Accelerated carbonation exposure
mainly as the calcite polymorph [17]. Alkali-activated binders are was carried out in a controlled environmental chamber at 25 °C, with
synthesised with lower calcium content (including systems with 7% CO2 and 65% RH. Natural carbonation exposure was carried out in a
no calcium), and thus show a binder structure based on gels laboratory in Cali, Colombia, with average daily conditions approximately
which are enriched in alkalis and aluminium and lower in Ca/Si 25±5 °C and 75% RH.
ratio than those which are observed in hydrated Portland cements As a reference material, Portland cement concretes were also pro-
[15,19,20]. This is expected to lead to differences in the carbonation duced, using a commercial Colombian Portland cement type I, which
mechanisms depending on the chemistry of the binder source ma- includes 25% limestone. Detailed information regarding the mix de-
terials, which will influence both the rate of natural carbonation signs, along with analysis of the engineering and durability properties
and the degree of acceleration of carbonation induced by a given of the concrete mixes assessed in this study, is reported elsewhere
CO2 concentration. [26].
The fact that the pore solution chemistry in alkali-activated binders
is dominated by alkali hydroxides [20–23] will lead to differences in the 2.2. Paste samples
CO2 uptake rates, as these solutions are well known to absorb CO2 from
gas streams or the air [24], to form alkali carbonates and/or bicarbon- To enable detailed analysis of binder mineralogy, paste samples were
ates. The low to zero Ca content and high degree of crosslinking of the synthesised from a different supply of granulated blast furnace slag
binder gel in alkali-activated binders is also likely to be relevant, as (GBFS 2), whose basicity coefficient Kb and quality coefficient Kq based
the degradation of gels by decalcification will be influenced by these on the chemical composition (Table 1) were 1.00 and 1.79 respectively.
parameters. The maturity of the alkali activated concrete is anticipated Its specific gravity was 2800 kg/m3 and Blaine fineness 450 m2/kg. In
to play a significant role in determining the accelerated carbonation order to regulate strength development, ordinary Portland cement
rates, considering the modification of both gel densification and the (OPC) type GP was incorporated in the binders as a minor admixture
structure of the pore network. These issues will be addressed in detail (4% of total binder). All raw materials were supplied by Zeobond Pty
in future studies, while the focus of this paper is specifically on the Ltd., Australia.
role of the pore solution chemistry in alkali-activated slags, containing
significant levels of Ca, but much lower than in Portland cement, in
Table 1
determining accelerated carbonation rates and mechanisms. As the Compositions of the GBFS supplies used, from X-ray fluorescence analysis. L.O.I. is loss
carbonation of Portland cement is to a large extent controlled by chem- on ignition at 1000 °C.
ical reactions involving the solid hydration products, the influence of
Component (mass % as oxide) GBFS 1 GBFS 2
the pore solution on the carbonation rate has rarely been analysed.
Most studies have taken the reverse approach, and instead focused on SiO2 31.08 33.80
Al2O3 13.98 13.68
the influence of carbonation on pore solution chemistry [18,25]. In
Fe2O3 3.09 0.40
this paper, we address the differences in carbonation rates induced by CaO 43.92 42.56
accelerated carbonation of alkali-activated binders when compared MgO 1.79 5.34
with Portland cement binders, and show that this is related to differ- SO3 0.66 0.83
Others 3.49 1.45
ences in alkali carbonate phase chemistry. The thermodynamic basis
L.O.I. 2.08 1.81
for these differences is discussed, and comments are provided regarding
S.A. Bernal et al. / Cement and Concrete Research 42 (2012) 1317–1326 1319
Fig. 2. X-ray diffractograms of (a) alkali-activated slag after 14 days of curing, and (b) the same sample after 3 years.
also identified as a reaction product, which is coherent with other studies of the activating solution and/or fresh paste before or during mixing of
[31–34] of the activation of slags containing åkermanite and significant the samples. In specimens with 3 years of curing, a small content of
contents of magnesium. vaterite is also identified. It is therefore likely that this is a metastable
An aluminosilicate with a zeolitic structure (gismondine, product formed in these systems indicating the very first stages of
CaAl2Si2O8∙ 4H2O, PDF #00-020-0452) is observed in specimens binder carbonation, consistent with recent data for Portland cements
after 14 days of curing, although the intensities of the peaks carbonated under supercritical conditions, where vaterite was in
assigned to this phase are reduced after 3 years. At this time, some cases observed as a rim ahead of the measured “carbonation
a (Ca,Na)-aluminosilicate product with a different zeolitic struc- zone” [38].
ture (thomsonite, NaCa2Al5Si5O20∙ 6H2O, PDF #00-046-1448) is To provide a point of comparison between the natural and acceler-
identified. Gismondine has been observed by high resolution X-ray dif- ated carbonation conditions, Fig. 3 shows the XRD data obtained for
fraction as a reaction product in low magnesium silicate-activated slag naturally carbonated alkali-activated slag, and specimens subjected
binders [9], and gismondine and thomsonite are known to be formed to accelerated carbonation at CO2 concentrations of 1%, 3% and 5%,
under very similar conditions via natural or laboratory hydrothermal pro- for 7 days. The naturally carbonated specimen displays a range of
cesses [35–37]. The two zeolites observed here have similar Si/Al ratios, carbonate phases: CaCO3 in three crystalline polymorphs (calcite, vaterite
and it appears that the gismondine has been partially converted to the and aragonite), most probably derived from the carbonation of the
more alkali-rich thomsonite during an extended period of exposure to C―S―H type products, the hydrous sodium carbonate phase natron
the alkali-rich pore solution environment. (Na2CO3∙10H2O, PDF #00-015-0800) attributed to the carbonation of
A small amount of calcite is present in the 14-day and 3-year the remnant alkali supplied by the activator and present in the pore solu-
uncarbonated specimens, associated with a slight degree of carbonation tion, and several carbonate double salts (pirssonite (Na2Ca(CO3)2∙2H2O),
Fig. 3. X-ray diffractograms of carbonated alkali-activated slag pastes: (a) carbonated under natural conditions for 3 years, and where accelerated carbonation was induced by ex-
posing the specimens to (b) 1% CO2, (c) 3% CO2 and (d) 5% CO2.
S.A. Bernal et al. / Cement and Concrete Research 42 (2012) 1317–1326 1321
PDF #00-022-0476), huntite (Mg3Ca(CO3)4; PDF #00-014-0409) and water from the naturally-carbonated samples, while the accelerated
dolomite (CaMg(CO3)2; PDF #01-083-1530), where the Mg-containing carbonation tests were conducted under a slightly higher (but con-
phases are consistent with the carbonation of hydrotalcite or other trolled) relative humidity, is likely to contribute to the carbonate
Mg-containing phases. Detailed discussion of the influence of natural and phase differences between the samples exposed to different conditions.
accelerated carbonation on the silicate and aluminosilicate binder phases The molar volume of pirssonite (102.58 cm3/mol) is lower than that of
will be presented in a subsequent publication [39]; the focus of this paper gaylussite (148.95 cm3/mol) [41], which may partially counteract the
is specifically on the carbonate phases. differences between natron and the less-hydrous bicarbonates as
The XRD results (Fig. 3) also reveal that the crystalline carbonation discussed above, but this difference is much less pronounced and so
products formed in specimens exposed to high concentrations of CO2 would only ever provide a partial compensation for the loss of natron
differ both in phase and in concentration from those which are as a pore-filling product.
obtained under natural carbonation conditions. The strong calcite
peak at 29.42° 2θ is much less evident under accelerated carbonation 3.3. Effect of carbonation on the pore solution of alkali-activated binders
conditions, and substantial increases in the intensities of peaks asso-
ciated with vaterite and aragonite are observed with increasing CO2 To understand the pore solution carbonation chemistry of alkali-
concentrations. This is most likely to be due to kinetic effects, as the activated binders, it is potentially instructive, as a first approximation, to
metastable CaCO3 polymorphs vaterite and aragonite will be the represent the solution as falling within the system Na+―OH−―CO32−
first to form, and will then convert to calcite as the reaction time ex- ―HCO3−―CO2―H2O. This neglects the contributions of Ca, Mg, Si, S and
tends, according to the Ostwald Step Rule [40]. This is consistent with Al, which are also identified in the pore solutions of alkali-activated
the presence of calcite as the primary CaCO3 phase in the carbonated binders, and discussion related to some of these elements will be
region (and vaterite in the “uncarbonated” region) of the sample presented later in this paper. There have been a number of published
exposed to natural carbonation conditions for 3 years, as discussed studies of phase equilibria in the sodium carbonate/bicarbonate system
above. In another study [9], calcite was the only CaCO3 polymorph in a wide variety of contexts, and probably the most relevant studies are
identified after accelerated carbonation of alkali-activated slag paste those which have been aimed at understanding phase equilibria in alka-
over 1000 h (a much longer timeframe than was used here), which line brine lakes and salt deposits in the Americas and Africa. Fig. 4 is
is consistent with this mechanism. adapted from one such study [46], and displays data for the system Na2-
The other important differences observed in Fig. 3 are the changes CO3―NaHCO3―H2O; i.e., without the addition of extra NaOH to the sys-
in the sodium-containing carbonate phases between the naturally tem. This diagram shows that the invariant point between natron, trona
carbonated samples and those subjected to accelerated carbonation.
No bicarbonates were observed in the samples exposed to natural
carbonation, while nahcolite (NaHCO3, PDF #00-015-0700) was nota-
ble at elevated CO2 concentrations. This change, coupled with the
presence of some thermonatrite rather than natron in the samples,
will have important consequences related to two important aspects
of concrete durability. The first of these consequences is that the dif-
ference in solid phases indicates a marked change in the dissolved
carbonate/bicarbonate equilibrium. This is important in determining
the pH of the carbonated pore solution, and therefore the potential
development of corrosion in the metallic reinforcement of structural
concrete. This issue will be explored in detail in the following sections
of this paper, with the aid of thermodynamic modelling tools.
The second important consequence of the change in phase prevalence
is that natron binds a very large quantity of water (5 water molecules per
Na+ cation), while thermonatrite has only 10% of this water content, and
nahcolite is anhydrous. This means that natron has a very large molar
volume (196.56 cm3/mol), while thermonatrite (54.96 cm3/mol) and
nahcolite (38.66 cm3/mol) [41] will fill much less space, and thus provide
a greatly reduced degree of pore blockage as they grow within the pore
space of an alkali-activated binder. Pore blockage is important in reducing
diffusion through all cementitious binders, and particularly in the case of
alkali-activated materials, where the binder phases are less space-filling
than in the case of Portland cement hydrates, and where reductions in
permeability (achieved either through reduced pore volume or increased
tortuosity) are essential in extending the time to corrosion of embedded
steel reinforcing elements [15,42].
It is also of interest that pirssonite (Na2Ca(CO3)2∙2H2O) is the Na―Ca
carbonate phase observed in the naturally-carbonated specimens,
where the more-hydrated gaylussite (Na2Ca(CO3)2∙5H2O) is instead ob-
served in the specimens subjected to accelerated carbonation. This is
likely to be related to the differences in water availability between the
sample sets; the relative prevalences of gaylussite and pirssonite are
known to be determined by aH2O and temperature [43–45]. As the sam-
ples were subjected to similar temperature regimes (23± 5 °C), falling
in the region in which gaylussite and pirssonite may both be formed in
Fig. 4. Phase diagram as a function of temperature and gas phase CO2 concentration for
a humid atmosphere, the former as a stable product and the latter meta- the Na2CO3―NaHCO3―CO2―H2O system in an air atmosphere at ambient pressure;
stable [43], it is unlikely that temperature is the determining parameter. after [46]. The dashed line represents a temperature of 23 °C, as used in the experi-
The fact that natron formation and atmospheric drying removed free mental work reported here.
1322 S.A. Bernal et al. / Cement and Concrete Research 42 (2012) 1317–1326
From Fig. 7, it is evident that the effect of carbonation on pore solution related to the natural carbonation of concrete specimens. JLP would also
pH in alkali-activated systems is highly dependent on the partial pressure like to thank E. Jagniecki (Binghampton State University) for useful dis-
of CO2; the pH does not drop below 10 under natural CO2 levels in the cussions regarding carbonate phase equilibria.
[Na+] range studied, while the pH induced by the elevated CO2 levels of
traditional accelerated-carbonation tests is almost two units lower. The Appendix A. Details of thermodynamic calculations
pH increases with NaOH concentration up to ~0.5 mol/kg, which is also
the point where Fig. 6 shows that the composition of the solution remains Table A1
approximately constant as solid alkali (bi)carbonates precipitate. Thermodynamic parameters for the phases and species simulated.
It is also important to note, from Fig. 7, that even if the NaOH concen-
Gas ΔHf0 (kJ/mol) S0 (J/mol∙K)
tration is reduced to 0.001 mol/kg, the calculated pH still remains above
Carbon dioxide CO2(g) −393.5 213.77
10. The loss of steel protection via alkali leaching from alkali-activated
Solid
binder systems thus appears to be a lesser concern with respect to car- Calcite CaCO3 −1206.9 92.90
bonation; alkali leaching may reduce the NaOH concentration, and thus Huntite CaMg3(CO3)4 −4529.6 299.53
the pH, but even when the majority of the alkalis have been removed, Magnesite MgCO3 −1095.8 65.70
the pH is not seen to drop into the region where steel depassivation Artinite Mg2(OH)2CO3∙ −2920.6 232.92
2H2O
would be expected. This is not to say that steel corrosion in alkali-
Natrite Na2CO3 −1130.8 138.78
activated binders will not ever be related to alkali leaching or carbon- Thermonatrite Na2CO3∙H2O −1432.0 168.10
ation—there may certainly be circumstances in which these phenomena Sodium carbonate Na2CO3∙7H2O −3192.7 422.20
are linked—but from these results, it is unlikely that carbonation in atmo- heptahydrate
Natron Na2CO3∙10H2O −4082.0 564.70
spheric conditions, even in combination with a significant degree of alkali
Trona Na3H(CO3)2∙ −2682.1 303.13
leaching, will reduce the pH to such an extent as to directly lead to steel 2H2O
corrosion. Conversely, under accelerated carbonation conditions and par- Nahcolite NaHCO3 −950.8 101.70
ticularly when the alkalis are leached from the material, the pore solution Aqueous
pH is certainly reduced to a level which could induce steel corrosion, and Carbonate ion CO32−(aq) −675.2 −50.00
2+
Calcium ion Ca (aq) −543.1 −56.48
it is therefore important to note that testing for steel corrosion in binders
Hydrogen ion H+(aq) 0 0
exposed to elevated CO2 environments will not give results which are Bicarbonate ion HCO3−(aq) −689.9 98.45
representative of in-service performance under atmospheric conditions. Magnesium ion Mg2+(aq) −466.0 −138.07
This is the key outcome of the work presented in this paper, which repre- Sodium ion Na+(aq) −240.3 58.41
Hydroxyl ion OH−(aq) −230.0 −10.71
sents the early stages of an extended work programme dedicated to anal-
Carbon dioxide CO2(aq) −413.84 117.61
ysis of the carbonation of alkali-activated binders under a variety of
formulation and testing conditions, aimed at providing a detailed scientif-
ic understanding of this process and how it may be tested and predicted. Table A1 presents the basic thermodynamic data used in the HSC
Chemistry 4.1 software [48] to describe the species modelled in this inves-
4. Conclusions tigation. This software package uses a Gibbs energy minimisation routine
to calculate stable phase assemblages, with the standard enthalpy of for-
Accelerated carbonation testing of alkali-activated binders has been mation and standard entropy of each component, and solution-phase
shown to provide results which are unlikely to represent the behaviour activity coefficients, as input parameters. The default database supplied
of the products under actual service conditions, due to changes in alkali with the HSC Chemistry 4.1 software was used for all thermodynamic
carbonate phase equilibria when the CO2 concentration is increased. parameters except the activity coefficients of dissolved species. All calcu-
The reaction products formed during natural and accelerated carbon- lations presented here were conducted at a temperature of 25 °C. The gas
ation testing of alkali activated slag binders are notably different, and phase also contained nitrogen and oxygen in a 79:21 ratio to simulate nat-
thermodynamic calculations support the experimental observations ural dry air, but these components were treated as inert.
related to differences in carbonate/bicarbonate equilibria and in the
nature of the carbonation products. In particular, bicarbonates favoured In the thermodynamic calculations, dolomite formation is suppressed,
over carbonates at high CO2 partial pressures. This gives a significantly as this phase is known to be kinetically very slow to precipitate [52].
greater decrease in pH upon carbonation than would be observed in Calcite is predicted to be the stable form of calcium carbonate under all
natural CO2 environments, rendering the pore solution environment conditions simulated in this paper. The relative stabilities of magnesite
in an accelerated test far more damaging to embedded steel reinforcing (MgCO3) and nesquehonite (MgCO3∙3H2O) are calculated to be very sim-
than is the case in actual service conditions. In fact, natural CO2 concen- ilar, but only the former has been observed in the XRD analyses of
trations appear unlikely to reduce the pore solution pH below 10, even alkali-activated binders conducted in our laboratory, and so this is the
when combined with alkali leaching effects, while the bicarbonate- phase considered in the calculation. Solid alkali or alkaline earth hydrox-
dominated pore solutions present at high pCO2 have a much lower ides (NaOH, brucite or portlandite) were not calculated to be stable under
pH, giving a falsely early predicted likelihood of corrosion initiation. the conditions simulated. Some of the carbonate minerals listed, such as
Accelerated carbonation testing of alkali-activated binders at elevated artinite and thermonatrite, were also not predicted to be stable under
CO2 partial pressures is a far more aggressive test when compared any of the conditions discussed in this study, but do appear in the phase
with the exposure of Portland cement to the same conditions, and assemblages under other specific sets of conditions, and so are retained
may provide outcomes which show apparent degradation much more in the computations for completeness. Following the discussion pres-
rapid and extensive than would actually be experienced in service. ented by Reardon [53] for Portland cement pore solutions, the formation
of aqueous complex ions or neutral complexes (e.g. NaCO3−(aq), CaOH+
Acknowledgements (aq), CaCO30(aq) and others) is not considered explicitly, as the effect of
the formation of these species on the solution-phase activity coefficients
This work has been funded by the Australian Research Council, is encapsulated in the fitting of the activity coefficient model parameters
through a Linkage Project co-sponsored by Zeobond Pty Ltd, and also for the dissociated ions.
including partial funding through the Particulate Fluids Processing The solution-phase activity coefficients utilised in the model were
Centre. SAB thanks E.D. Rodríguez and Professor R. Mejía de Gutierrez calculated using the Pitzer model [54]. This is a widely used semi-
(Universidad del Valle) for collaboration and support in the test program empirical correlation model for osmotic and activity coefficients,
S.A. Bernal et al. / Cement and Concrete Research 42 (2012) 1317–1326 1325
ions and anions respectively. The equations given are for mixed electro- x 1 2 x −y
lyte systems, generally following the widely-used notation of Harvie Ω0 ðxÞ ¼ −1 þ ∫ y 1− exp − e dy ð12Þ
4 x0 y
and Weare [55] where possible, but including the β(2) term for ion asso-
ciation in 2–2 electrolytes following Pitzer & Mayorga [56].
∞
2 x 1 2 x −y x −y
lnγM ¼ zM F þ ∑ ma ð2BMa þ ZC Ma Þ þ ∑ mc 2ΦMc þ ∑ ma ψMca Ω1 ðxÞ ¼ − ∫ y 1− 1 þ e exp − e dy ð13Þ
a c a 4 x y y
ð1Þ 0
þ∑ ∑ma ma0 ψaa0 M þ jzM j∑ ∑ mc ma C ca
aba0 c a
All Pitzer model parameters used in this work have been obtained
lnγX ¼ z2X F þ ∑ mc ð2BcX þ ZC cX Þ þ ∑ ma 2ΦXa þ ∑ mc ψXac from the literature, as outlined in Table A2. The full multicomponent
c a c
ð2Þ Pitzer model was implemented using Microsoft Excel 2007, and the
þ∑ ∑mc mc0 ψcc0 X þ jzX j∑ ∑ mc ma C ca activity coefficients for all dissolved species were then transferred nu-
cbc0 c a
merically to the HSC Chemistry software for computation of phase
M and X refer to the cationic and anionic species of interest respective- equilibria.
ly, while c and a are dummy summation indexes used to indicate sums The parameters β(0), β(1), β(2), CMX and θ are fitted for each pair of
over cations or anions. I is the ionic strength, Aϕ is the Debye–Hückel pa- ions—β and CMX parameters for interactions between oppositely-
rameter (0.392 for aqueous solutions at 25 °C), and b is an empirical pa- charged ions from single-electrolyte data, and θ and ψijk for interactions
rameter set to 1.2 kg1/2.mol−1/2 following the discussion of Pitzer [54]. between like-charged species and three-species combinations, from
F is a collection of terms that depend only on ionic strength, as mixed-electrolyte data. β(2) is set to zero for interactions involving uni-
given by Eq. (3): valent species, with α1 = 2.0. For interactions of type 2–2 (i.e., between
alkali metal cations and CO32−here), α1 =1.4 and α2 = 12 are used [54].
" pffiffi #
2
I pffiffi 0
Reliable θ and ψijk parameter values are scarce in the literature, and
ϕ
F ¼ −A pffiffi þ ln 1 þ b I þ ∑ ∑ mc ma Bca these parameters are set to zero unless shown otherwise in Table A2.
1þb I b c a
0 0
þ ∑ ∑mc mc0 Φcc0 þ ∑ ∑ma ma0 Φaa0 ð3Þ
0 0
cbc aba
Table A2
The B and Φ terms in Eqs. (1)–(3) represent measurable combina- Pitzer ion interaction parameters used in the model, and literature sources. Where pa-
rameters are not listed, zero values are used.
tions of second virial coefficients for interactions between pairs of
unlike- and like-charged species respectively. The B terms are defined Ions Single-electrolyte parameters Reference
by Eqs. (4)–(7): β(0) β(1) β(2) CMX
pffiffi pffiffi Na+―OH− 0.09226 0.2424 – 0.003343 [57]
ð0 Þ ð1Þ ð2Þ
BMX ¼ βMX þ βMX g α 1 I þ βMX g α 2 I ð4Þ Na+―HCO3− − 0.5535 – 0.008285 [57]
0.05876
pffiffi pffiffi Na+―CO32− 0.04625 1.264 – 0.002943 [57]
0 0
0
ð1 Þ
g α1 I ð2Þ
g α2 I Ca2+―OH− −0.1421 −0.3727 – − [58]a
BMX ¼ βMX þ βMX ð5Þ 0.00092
I I
Ca2+―HCO3− 0.39975 2.9775 – – [54]
Ca2+―CO32− 0.16 2.38 −69 – [59]
where:
Mg2+―OH− – – – – b