Cement and Concrete Research 63 (2014) 7588

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Cement and Concrete Research

journal homepage: http://ees.elsevier.com/CEMCON/default.asp

A modied ASTM C1012 procedure for qualifying blended cements

containing limestone and SCMs for use in sulfate-rich environments
Laurent Barcelo a,b,, Ellis Gartner b, Rmi Barbarulo b, Ashlee Hossack c, Reza Ahani d, Michael Thomas c,
Doug Hooton d, Eric Brouard b, Anik Delagrave a,e, Bruce Blair e
a

Lafarge Canada Inc., 334 Avro, Pointe Claire, QC H9R 5W5, Canada
Lafarge Centre de Recherche, 95 rue du Montmurier, 38291 St Quentin Fallavier, France
University of New Brunswick, Fredericton, New Brunswick E3B 5A3, Canada
d
University of Toronto, 35 St. George Street, Toronto, Ontario M5S 1A4, Canada
e
Lafarge North-America, 12018 Sunrise Valley Drive, Suite 500, Reston, VA 20191, USA
b
c

a r t i c l e

i n f o

Article history:
Received 19 December 2013
Accepted 6 May 2014
Available online 6 June 2014
Keywords:
Sulfate attack (C)
Thaumasite
Durability (C)
Expansion (C)
Thermodynamic calculations (B)

a b s t r a c t
Blended Portland cements containing up to 15% limestone have recently been introduced into Canada and the
USA. These cements were initially not allowed for use in sulfate environments but this restriction has been lifted
in the Canadian cement specication, provided that the limestone cement includes sufcient SCM and that it
passes a modied version of the CSA A3004-C8 (equivalent to ASTM C1012) test procedure run at a low temperature (5 C). This new procedure is proposed as a means of predicting the risk of the thaumasite form of sulfate
attack in concretes containing limestone cements. The goal of the present study was to better understand how
this approach works both in practice and in theory. Results from three different laboratories utilizing the CSA
A3004-C8 test procedure are compared and analyzed, while also taking into account the results of thermodynamic
modeling and of thaumasite formation experiments conducted in dilute suspensions.
2014 Elsevier Ltd. All rights reserved.

1. Introduction
European standards for limestone-blended cements (up to 20%
limestone for CEM II/A-L and up to 35% for CEM II/B-L) have existed
for several decades, and such cements are widely used in Europe.
They were introduced more recently into North America, rst in
Canada in 2008 [1] and then in the USA in 2012 [2]. In Canada they
are called Portland limestone cements (PLCs) and there are only
slight differences between the CSA A3000 PLC and the European
CEM II-A/L specications [3]. There are similar quality criteria for
the limestone permitted (based on minimum total calcium carbonate and maximum total organic carbon contents as well as maximum
methylene blue values), but the maximum permitted limestone
content in North America is only 15%. The Canadian and US specications, as does EN 197, also provide for more complex blended hydraulic
cements, combining limestone with supplementary cementitious
materials (SCMs).

Corresponding author.
E-mail address: laurent.barcelo@lafarge.com (L. Barcelo).

http://dx.doi.org/10.1016/j.cemconres.2014.05.007
0008-8846/ 2014 Elsevier Ltd. All rights reserved.

In the Canadian specication for concrete [4], three sulfate exposure

categories are dened: S1 (very severe), S2 (severe) and S3 (moderate).1 Concrete exposed to S1 or S2 environments should be made
with highly sulfate-resistant (HS) cements, while moderately sulfateresistant (MS) cements are permitted for concretes subject to S3 environments. They can be either pure Portland cements (HS and MS) or
blended hydraulic cements (HSb and MSb). HS and MS cements have
specic chemical requirements (maximum C3A contents of 5% and 8%,
respectively) and must not exceed a specied 14-day expansion limit
when tested in standard mortars according to CSA A3004-C6 (equivalent to ASTM C452). HSb and MSb blended cements do not have different chemical requirements than other blended cements, but they
must meet stringent expansion limits (maximum expansion 0.10% at
6 months for MSb and 0.05% at 6 months or 0.10% at 12 months for
HSb2) when tested in mortar according to CSA A3004-C8 (equivalent
to ASTM C1012). The option of using blended cements in sulfate-rich
1
It should be noted that the minimum soluble sulfate concentration in groundwater for
the S1 class of exposure in Canada (10 g/l) is much higher than the maximum of the XA3
category in Europe (6 g/l). This reects the very high levels of sulfates found in the Prairie
provinces of Western Canada.
2
The 0.10% limit at 12 months is an option that can be used to qualify HSb cements if
the 6-month expansion exceeds 0.05%

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L. Barcelo et al. / Cement and Concrete Research 63 (2014) 7588

Table 1
Chemical analysis of cements and supplementary cementitious materials (SCMs) used by the different laboratories.
Cements chemical analysis (%)
Laboratory

Cement

SiO2

A12O3

Fe2O3

CaO

MgO

Na2O

K2O

SO3

LOI

% limest.

UNB

GU (OPC)
GUL #1 (PLC)
GUL#2(PLC)
GU #1 (OPC)
GU #2 (OPC)
GUL #1 (PLC)
GUL #2 (PLC)
GUL #3 (PLC)
GU (OPC)
GUL #1 (PLC)
GUL #2 (PLC)
GUL #3 (PLC)

19.9
18.1
16.8
20.6
19.7
18.9
18.5
17.4
20.2
18.8
19.1
18.2

4.9
3.8
4.2
5.5
5.4
5.1
5.0
4.6
4.3
4.0
4.5
4.3

3.1
2.2
2.6
2.2
2.1
2.0
2.0
1.9
2.7
2.4
2.6
2.5

63.2
61.5
59.6
63.4
62.7
61.9
61.3
59.8
61.5
61.2
60.2
61.2

1.9
1.9
1.8
2.4
2.4
2.3
2.4
2.3
4.5
4.3
2.5
2.8

0.23
0.21
0.23
0.23
0.24
0.21
0.22
0.20
0.22
0.19
0.12
0.27

0.90
0.91
0.90
1.22
1.18
1.15
1.12
1.07
0.60
0.57
0.74
0.89

3.5
3.5
3.4
4.2
4.7
4.3
4.4
4.1
2.8
2.7
3.8
3.4

NA
NA
NA
0.6
1.4
4.5
5.2
8.9
2.9
5.7
6.0
5.6

4
15
22
0
2.4
11
13
22
3.7a
10.5a
14.7
NA

UOT

Lafarge

SCMs chemical analysis (%)

Laboratory

SCMs

SiO2

Al2O3

Fe2O3

CaO

MgO

Na2O

K2O

SO3

LOI

UNB

Type F y ash
GGBFS
GGBFS
Type F y ash #1
Type F y ash #2
GGBFS

57.8
34.1
38.1
53.7
43.4
37.8

18.0
9.4
7.2
23.3
23.1
9.2

9.4
0.3
0.7
3.7
20.7
0.7

3.0
40.1
40.0
12.7
5.1
37.4

2.0
11.6
10.6
1.3
1.2
11.7

1.32
0.37
0.33
2.49
0.64
0.29

2.03
0.43
0.46
0.72
1.67
0.5

1.1
2.7
2.7
0.3
0.6
3.0

NA
NA
0.3
0.6
1.8
1.6b

UOT
Lafarge

a
b

Values refer to calcium carbonate content instead of limestone.

Negative values: mass increase corresponding to oxidation of slag during LOI.

environments, provided that the blend is tested by CSA A3004-C8 or

ASTM C1012 and meets acceptance criteria is included in the Canadian
CSA A23.1 and US ACI 318 specications. Such blended cements have
been used industrially for decades without any indication of problems
(according to the scientic literature).
To the knowledge of the authors, the CSA A3004-C8 (or ASTM
C1012) test method for external sulfate attack does not have an equivalent in Europe, although country-specic test methods exist. As this
test method has a central role in this article, its principle is briey summarized here (see [5] for a detailed description). In the traditional version of the test, standard mortar is prepared by mixing 2.75 parts of
standard sand with 1 part of cement. The water/cementing material
ratio (W/CM) used for blended cements is 0.485 by mass.3 After mixing,
mortar bars of dimensions 25 mm 25 mm 285 mm are cast together
with companion mortar cubes for strength measurement. The samples
are cured in a water tank (the molds being watertight) at 35 3 C
for the rst day and are then demolded and stored in lime-saturated
water at 23 2 C until the strength of the mortar, measured on the
companion cubes, reaches 20 1 MPa. At that time, the initial length
of the mortar bars is recorded and the bars are immersed and stored
in a highly concentrated sodium sulfate solution (50 g/l of Na2SO4) at
23 2 C. The length change of the bars is measured periodically
and the sulfate solution is replaced at each measurement.
When PLC was rst introduced to the Canadian specications, in
2008 [1], due to insufcient data, it was not permitted for use in applications requiring traditional sulfate-resistant cements. But in 2010 [5],
the CSA A3001 cement specication was updated and two new cement
categories were created: HSLb and MSLb (for highly sulfate-resistant
and moderately sulfate-resistant Portland-limestone-based blended
hydraulic cements). These cements must comply with all the requirements of HSb and MSb cements, including the 6-month expansion
limit when tested in accordance with CSA A3004-C8, plus there are
also two additional requirements. Firstly, there are prescribed minimum
3
In case the blended cement is not made at the cement plant but is reproduced by
blending a PC or a PLC with SCM, the W/CM of 0.485 applies to a control mix done with
the corresponding PC or PLC. Then when the mix with SCM is produced, W/CM has to
be adjusted to the ow of the control mix 5%.

SCM contents. For blends containing a single SCM, they are 25% for type
F y ash, 40% for slag and 15% for metakaolin. There are also two different possible SCM combinations, i.e. N5% silica fume plus N25% slag, or
else N5% silica fume plus N 20% type F y ash. Secondly, the standard
mortars made with these cements must meet an 18-month expansion
limit of not more than 0.10% when tested according to a modied version of CSA A3004-C8 conducted at 5 C. Furthermore, if mortars expand
by more than 0.03% during the last 6 months (i.e. from 12 to 18 months)
the test must be continued to 24 months and the 0.10% limit must be
met at this later age. Concurrently, the CSA A3004-C8 test method was
also updated. The traditional procedure at 23 C (outlined above) was
renamed Procedure A and a Procedure B was introduced, involving
testing at 5 C. Procedures A and B are similar, with the only difference
being that when the 20-MPa strength is reached on the companion
cubes, the bars undergoing procedure B are stored in the same sodium
sulfate solution but at 5 2 C instead of 23 2 C. Procedure B
was created to determine resistance to the potential for the thaumasite
form of sulfate attack (TSA) [5], based on the knowledge that TSA
would be accelerated by the use of lower temperatures.
To summarize the rationale of the Canadian approach, there is a
gradation of requirements regarding CSA A3004-C84:
HS or MS Portland cements do not have to be tested in accordance
with this procedure. They are considered sulfate-resistant if their
C3A contents are below specied limits and the cement does not
exceed the 14 d expansion limit when tested in accordance with
CSA A3004-C6;
HSb or MSb blended hydraulic cements have to pass procedure A
(23 C) at 6 months (or 12 months) to demonstrate that the SCM
quantity is adequate to reduce the traditional form of external sulfate
attack to an acceptable level;
HSLb or MSLb blended hydraulic cements with a PLC base cement
have to meet a specied minimum SCM addition level and to pass procedure A (23 C) at 6 months (or 12 months) as well as procedure B
4
Note that, in CSA A3004-C2 (referenced by CSA A3004-C8), the requirements for
blended cements (HSb, MSb, HSLb, MSLb) apply for both pre-blended cements and for
combinations of cementing materials blended at the concrete plant (during mixing).

L. Barcelo et al. / Cement and Concrete Research 63 (2014) 7588

77

Fig. 1. Example of variation of W/CM ratio for different SCM combinations used in LG to obtain constant ow (A) and of variation of ow used in UOT at a xed W/CM of 0.485 (B).

(5 C) at 18 months (or 24 months) to demonstrate that the SCM

quantity is also adequate to reduce the thaumasite form of sulfate
attack to an acceptable level;
2. Testing and materials
2.1. CSA A3004-C8 procedure A testing (23 C) and procedure B testing
(5 C)
For this analysis, several mortar compositions were tested in university laboratories (University of New Brunswick, labeled UNB and University of Toronto, labeled UOT) as well as in two Lafarge laboratories.
Table 1 lists the chemical composition of the binders used by the laboratories. When blends of cements and SCMs have been done, there was no
modication of the SO3 content. All mixes were tested following CSA
A3004-C8 procedures A and B, however, small deviations from the testing protocol should be noted:
in the experiments from LG the binders were tested at different
water-to-binder ratio (W/CM): the W/CM ratio of the test mix with
SCM was adapted to match the ow of the control mix without SCM
when this control mix is tested at W/CM = 0.485. This is the

procedure specied when binder materials are blended at the concrete plant;
in the UNB and UOT laboratories, the mixes were tested at a constant
water-to-binder ratio (W/CM = 0.485). This is the procedure specied when the blended cement is made at the cement plant.
Typical differences in water-to-binder ratio (for LG) and ow (for
UOT) are provided in Fig. 1. It is apparent that following the procedure
specied when mixes are made at the concrete plant (constant ow
LG case) leads to signicant variations in the water-to-binder ratio.
2.2. Thermodynamic modeling
Thermodynamic calculations were run using the geochemical software CHESS [6] to calculate the evolution in the equilibrium phase assemblage of a fully hydrated cement paste as it reacts with an alkali
sulfate solution. The thermodynamic database was composed of the
standard CHESS database for minerals and aqueous ionic species, to
which data for the relevant cement-related minerals was added. The
formation equations and related solubility products (expressed as logK values) are given in Table 2, expressed in CHESS basis species. Phase
densities and data sources are also included.

Table 2
Thermodynamic data used for the different minerals.
Mineral

Formation equation

log-K (temperature in C within brackets)

Density
(kg/m3)

Data source

Portlandite
CSH_16
CSH_08
Gypsum
Thaumasite
Ettringite
Calcite
Fe-monocarboaluminate
Strtlingite
Monocarboaluminate
Monosulfoaluminate

1 Ca[2+], 2 H[+], 2 H2O,

1.6 Ca[2+], 3.2 H[+], 2.18 H2O, 1 Si(OH)4(aq),
0.8 Ca[2+], 1.6 H[+], 0.34 H2O, 1 Si(OH)4(aq),
, 2 H2O
1 Ca[2+], 1 SO[2]
4
[+]
, 28 H2O, 2 Si(OH)4(aq), 2 SO[2]
6 Ca[2+], 2 HCO[]
3 , 6 H
4
[2+]
[3+]
6 Ca
, 2 Al
, 12 H[+], 38 H2O, 3 SO[2]
,
4
[+]
[2+]
[]
, 1 HCO3
1 H , 1 Ca
[+]
, 17 H2O, 2 Fe[3+],
4 Ca[2+], 1 HCO[]
3 , 13 H
2 Ca[2+], 2 Al[3+], 10 H[+], 11 H2O, 1 Si(OH)4(aq),
[+]
, 17 H2O,
4 Ca[2+], 2 Al[3+], 1 HCO[]
3 , 13 H
4 Ca[2+], 2 Al[3+], 12 H[+], 18 H2O, 1 SO4[2],

2240
1892
1630
2305.16
1768
1774
2709.89
2144
1768
2169
2014

Cemdata 07.2 [712]

[13]
[13]
[6]
Cemdata 07.2 [712]
Cemdata 07.2 [712]
[6]
Cemdata 07.2 [712]
Cemdata 07.2 [712]
Cemdata 07.2 [712]
Cemdata 07.2 [712]

Fe-monosulfoaluminate

4 Ca[2+], 12 H[+], 18 H2O, 1 SO4[2], 2 Fe[3+],

2118

Cemdata 07.2 [712]

C3AH6

3 Ca[2+], 2 Al[3+], 12 H[+], 12 H2O,

24.87(0) 22.81(25) 21.03(50)

29.74(0) 27.76(25) 25.99(50)
11.42(0) 10.8(25) 10.19(50)
4.5331(0) 4.4823(25) 4.6094(60)
17.94(0) 18.86(25) 18.34(50)
62.08(0) 56.85(25) 51.15(50)
2.2257(0) 1.8487(25) 1.333(60)
37.86(0) 33.36(25) 28.76(50)
55.97(0) 49.86(25) 44.37(50)
88.79(0) 80.61(25) 73.05(50)
80.76(0), 72.49(25), 64.85(50),
57.8(75), 51.34(100)
76.27(0), 67.63(25), 59.53(50),
51.99(75), 45.03(100)
90.42(0), 81.25(25), 73.11(50),
65.84(75), 59.35(100)

2521

Cemdata 07.2 [712]

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L. Barcelo et al. / Cement and Concrete Research 63 (2014) 7588

The system composition was dened as follows: a model OPC,

composed of:

C2.7S
C3A (1 to 9% wt. of OPC),
C4AF so that C3A + C4AF = 10% wt. of OPC
Gypsum (3% wt. of OPC).

The Ca/Si atomic ratio of 2.7 used here to represent the calcium
silicate phases is a typical value for standard OPC, simulating an OPC
with a C2S/C3S mass ratio of 0.42.
To this OPC was added various amounts of limestone (5, 15 and 20%
wt. of blend), treated as pure calcite. The impact of SCMs on the mineral
assemblage was estimated by adding pure reactive silica to the system
at 10% by mass of the total blend.
All the calculations were run at 5 C, in order to be representative
of CSA A3004-C8 procedure B. All phases present were allowed to
react completely so as to reach equilibrium. Thus, the initial system
state was calculated as the equilibrium state for a fully reacted
mixture of the OPC + limestone (+ silica fume) blend with water
at a water/solid ratio of 0.5, which corresponds to a fully-hydrated
cement paste.
Then this initial system was ushed 333 times with a sodium sulfate solution at 30 mmol/L. Every ushing step consists in removing
the totality of the interstitial solution (at equilibrium with the stable
mineral assemblage) and replacing it by an equivalent volume of sodium sulfate solution. This approach simulates, without taking into account the complex process of transport in the porous medium, what
may happen at equilibrium when a mineral assemblage is put in contact
with an aggressive medium, including leaching and ingress of external
ions.
The phase assemblages are expressed graphically as phase volumes
(in mL/100 g of binder) for minerals and porosity on the ordinate, as a
function of the number of ushing steps on the abscissa (333 steps on
the right hand side of the graphs).

2.3. Thaumasite growth rate experiments

Experiments were carried out in order to try to understand the factors inuencing the rate of growth of thaumasite, using dilute suspensions of synthetic C-S-H (with a Ca/Si ratio of 1) mixed with gypsum
and ultrane calcium carbonate in proportions corresponding to the
stoichiometry of thaumasite (a 1:1:1 molar mixture). During this
process, the addition of several potential catalysts was also tested.
The experimental procedure is detailed below.
Laboratory-grade chemicals (typically N99% pure) were used
throughout, and the water used was de-ionized water which had been
boiled to remove dissolved CO2. For each experiment, 1.25 mol (2.653
g) of Na2SiO35H2O were dissolved in 500 ml of water. To this was
added a solution of 1.25 mol (1.839 g) of CaCl22H2O in 500 ml of
water, and the mixture (which gave a massive precipitation of C-S-H
with a Ca/Si atom ratio very close to 1) was agitated for 30 min in a
closed polyethylene container. The slurry was vacuum-ltered on a
grade 42 lter and washed four successive times with 50 ml aliquots
of water. The wet C-S-H was then scraped off the lter (using a Teon
spatula) and placed into a ask, together with 1.25 mol (2.152 g) of
CaSO42H2O and 1.25 mol (1.251 g) of precipitated CaCO3. The ask
was then partially lled with additional water to give a water/initial
solid mass ratio of 20, and small amounts of additional reagents were
added if desired, (typically either readily water-soluble compounds or,
if poorly-soluble solids, then as nely-ground powders). The ask was
immersed in a temperature-controlled water bath and the mixture
(suspension) in the ask was agitated continually by means of a
Teon-coated magnetic stirrer. Experiments were run mostly at 20 C
and 8 C, but some were also run at 5 C. Small samples of the suspension were removed every week, ltered and dried with acetone and
ether, and subject to X-ray diffraction (XRD) analysis. Rough estimates
of the degree of advancement of the reaction were made by comparing
the peak heights of the strongest peak for thaumasite with the strongest
peaks for gypsum and calcite. In cases where gypsum disappeared
completely, the thaumasite formation reaction was assumed to be

Fig. 2. Evolution of expansion with time at 23 C (CSA A3004-C8 procedure A) for the different systems tested by the different laboratories.

L. Barcelo et al. / Cement and Concrete Research 63 (2014) 7588

79

Fig. 3. Evolution of expansion with time in the CSA A3004-C8 test procedure B (5 C) for different SCM combinations. See legend. Specication limit for HS cement: 0.1% expansion at
18 months.

complete; but there was always some residual calcite present, most
probably due to atmospheric carbonation.
3. Results
3.1. Expansion testing
3.1.1. 23 C expansion results (CSA A3004-C8-procedure A)
The evolution of expansion with time at 23 C for the different
cementitious systems tested in the different laboratories is presented
in Fig. 2. Results are consistent with expectations. The mixtures without
SCM expand quite rapidly and eventually exceed the expansion limit of
0.05%. The addition of SCM (20% slag or higher and 15% Type F y ash or
higher) signicantly reduces the expansion and none of the systems
with SCM exceed the 0.05% expansion limit at 6 months or the alternative limit (for HSb or HSLb) of 0.10% at 12 months.
3.1.2. 5 C expansion results (CSA A3004-C8-procedure B)
Expansion results with time at 5 C (CSA A3004-C8-procedure B) are
presented in Fig. 3. Compared to the equivalent experiments at 23 C,
the levels of expansion reached are generally much larger, especially
in mixtures containing SCMs. When such large expansions occur, comparing expansion values to try to assess the performance of different
systems can be misleading as mortar bars gradually lose integrity,

Fig. 4. The 5 C failure index.

undergo warping, etc. Therefore, in order to better compare the different systems, a 5 C failure index is dened here for evaluating the
CSA A3004-C8-procedure B test data. It is dened as the time difference
(in days) between the moment when the mix reached 0.10% expansion
(estimated by linear interpolation of the data) and 18 months, which is
the duration of the test (see Fig. 4). Mixes that meet the expansion
criteria (b0.1% at 18 months) have a failure index of 0. Otherwise, the
sooner the 0.1% threshold is reached, the higher the failure index.
Note that this index is designed to compare the performance of mixes
in the context of this article and has not been correlated with any kind
of eld performance.
A plot of the 5 C failure index for the different mixes in the 3 different laboratories is shown in Fig. 5. As expected, mixes without any SCM
addition have the highest failure indexes as they reach the expansion
limit very rapidly.
Performance with SCM additions shows a much-contrasted picture
between the different laboratories:
For slag additions:
In UNB, 20% slag mixes failed and 40% slag mixes passed the 5 C test
(for both OPC and PLC)
In UOT, 30% slag mixes with OPC passed the 5 C test while with PLC
they did not (the PLC with the lowest amount of limestone did not
pass the 24 months limit, as the expansion between 12 and
18 months was larger than 0.030%). All mixes passed at 50% slag
addition;
In LG, all mixes (PLC or OPC) failed at 50% slag addition. At 65% slag
addition, the slag-PLC combination tested passed, while the slag
OPC combination failed to meet the expansion limit.
For y-ash:
In UNB, some mixes (both with OPC and PLC) met the 5 C expansion limit even for addition levels as low as 15%, while in more
recent test series (with a different clinker) mixes at 25% Type F y
ash addition failed (both with OPC and PLC).

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L. Barcelo et al. / Cement and Concrete Research 63 (2014) 7588

Fig. 5. 5 C failure index for the different mixes from the different laboratories. Color key is similar to Figs. 2 or 3.

For LG, mixes with 25% Type F y ash addition failed (both with OPC
and PLC). Some mixes at 35% addition met the expansion limit,
while others with different cements and y ashes failed even at
50% ash addition.

3.1.3. Expansion at 5 C vs. expansion at 23 C

Results from Figs. 2 and 3 suggest that much larger expansions are
reached at 5 C compared to 23 C. However, as shown in Fig. 6-A to F,
this does not appear to be true early on: at 56 days, 91 days and

Fig. 6. Expansions at 5 C vs. 23 C for different times. Red line corresponds to orthogonal regression line (variance ratio of 1) and the green line represents the equality line. A: 56 days, B:
91 days, C: 105d, D: 182 days, E: 182 days considering expansions below 0.1% only and F: 364 days considering expansions below 0.1% only.

L. Barcelo et al. / Cement and Concrete Research 63 (2014) 7588

81

Fig. 7. Matched Pairs t-test difference in the 6 month expansion at 23 C (%) vs. mean 6 month expansion at 23 C. Red line and dotted lines represent the average difference and its 95%
condence limit. A: All samples and B: combinations with expansions lower than 0.1%.

105 days, the levels of expansion at 5 C or 23 C are very similar. At

182 days and later expansions at 5 C start to become signicantly larger than expansions at 23 C, even when the data sets are restricted to
samples that expanded less than 0.1%.

3.1.4. Inuence of limestone addition (OPC vs. PLC)

In this section, a comparison is made between the performance of
OPC (with 2 to 4% limestone addition) with PLC having limestone
contents between 10 and 15%. Figs. 7 and 8 show the results of
matched-pair t-tests done on the 6 month expansion at 23 C and on
the 5 C failure index, respectively. At 23 C, when analyzing the data
globally (Fig. 7-A), the average matched-pair difference at 6 months is
0.017% with a slightly higher expansion for the mixes with PLC
compared to OPC. However, this difference is not statistically signicant
( = 0.05). It also seems that most of the difference can be attributed to
the mixes with high expansion values (i.e. exceeding the 0.1% failure
limit). Fig. 7-B, which represents expansions below 0.1%, conrms this
and shows a different picture: at low expansion values (i.e. mixes that
are sulfate resistant), mixes with PLC tend to expand slightly less than
their OPC counterpart.
At 5 C (cf. Fig. 8-A), the average difference in failure index is 16 days
(in favor of OPC) and this difference is not statistically signicant ( =
0.05). In Fig. 8-B only the higher failure indexes (mixes that reach the

expansion limit more rapidly) are considered and again, there is no

statistical difference between OPC and PLC.
3.2. Thermodynamic modeling
3.2.1. Typical chemical path when ushing a cement paste with a Na2SO4
solution at 5 C
The examples below refer to an OPC with 5% wt. C3A and 5% wt.
C4AF.
Without limestone (Cf. Fig. 9), the initial mineral assemblage at 5 C is
composed of C-S-H, portlandite, ettringite, C4AH19 and C4FH13. It should
be noted that from this modeling, monosulfate is not predicted as
C4AH19 appears to be more stable. However, the level of undersaturation
of monosulfate is very low and this phase could very well appear instead
of C4AH19 in reality.
Upon ushing with a 30 mmol/L sodium sulfate solution, the phase
assemblage is modied in the following way: formation of ettringite at
the expense of C4AH19 and portlandite, then formation of Fe-ettringite
at the expense of C4FH13 once C4AH19 is depleted, and nally formation
of gypsum when C4FH13 is depleted, inducing further consumption of
portlandite.
During this process, the solid volume increases by about 13%, of
which 10% is due to ettringite. However, this does not necessarily
imply that the paste will undergo bulk expansion (see discussion).

Fig. 8. Matched Pairs t-test difference in the 5 C failure index (d) vs. Mean 5 C failure index. Red line and dotted lines represent the average difference and its 95% condence limit. A:
All data and B: potential outlier removed.

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L. Barcelo et al. / Cement and Concrete Research 63 (2014) 7588

volume of solids (mL / 1 g of binder)

1.2

1.0

gypsum
0.8

Fe-ettringite

C4AH19
0.6

ettringite
portlandite

0.4

CSH_16
0.2

C4FH13
0.0
0

100

200

300

flushing steps
Fig. 9. Evolution of the mineral assemblage of an OPC cement paste when ushed 333
times with a 30 mmol/L sodium sulfate solution, at 5 C.

In presence of 15% limestone (cf. Fig. 10), the initial assemblage at

5 C is composed of C-S-H, portlandite, ettringite, monocarboaluminate,
Fe-monocarboaluminate and calcite.
Upon ushing with 30 mmol/L sodium sulfate solution, the phase
assemblage is modied as follows: formation of ettringite at the
expense of monocarboaluminate and portlandite, then formation of
thaumasite at the expense of C-S-H, portlandite and calcite, and nally
formation of gypsum at the expense of portlandite when calcite is
depleted.
The solid volume increases by about 10% due to ettringite formation
and then a further 45% due to thaumasite formation. The possible implications of these volume changes will be discussed later.
An interesting aspect of the calculation results is that gypsum precipitates only once all possible thaumasite formation has occurred
(which in this case is limited by the exhaustion of calcite). This is in
1.2

volume of solids (mL / 1 g of binder)

gypsum
1.0

monocarboaluminate
0.8

thaumasite
calcite

0.6

contradiction with some experimental observations that detect gypsum

formation before thaumasite. We interpret this discrepancy as being
due to the slow kinetics of thaumasite formation in reality, as opposed
to the idealized instantaneous equilibrium of the calculations.
Fig. 11 gathers the results of the simulations for different limestone
(5, 15 and 20%) and C3A (1, 5 and 9%) contents. The sequences are the
same as for the example previously described: formation of ettringite
at the expense of monocarboaluminate and portlandite, then formation
of thaumasite at the expense of C-S-H and calcite, and nally formation
of gypsum when thaumasite formation is complete. The amount of
ettringite formed obviously increases with the C3A content of the binder, while the amount of thaumasite formed in these calculations increases with the limestone content because there is always an excess
of silica available from C-S-H and thus it is the amount of calcite
which is limiting.
3.2.2. Role of pozzolanic SCMs: evaluation using silica fume
The system considered here is an OPC with 5% C3A and 5% C4AF, used
in a blend containing 15% limestone. The role of pozzolanic SCMs on this
system was estimated by adding 10% silica fume to the initial blend. As
can be seen in Fig. 12, the nature of the minerals is unchanged in the
initial system: C-S-H, portlandite, ettringite, monocarboaluminate, Femonocarboaluminate and calcite. Of course the amounts of the minerals
have changed, essentially some portlandite has combined with silica to
form more C-S-H.
Upon ushing with a 30 mmol/L sodium sulfate solution, the mineral assemblage is modied in the following way: formation of ettringite
at the expense of monocarboaluminate and portlandite, then formation
of thaumasite at the expense of C-S-H and calcite until calcite is depleted. At the same time, some monocarboaluminate forms again at the expense of ettringite when portlandite is depleted. The calcium sulfate
released by this ettringite also goes into forming thaumasite. As lime
saturation is further reduced by the sodium sulfate solution there is
then formation of strtlingite and nally signicant decalcication of
C-S-H. Contrary to what was observed without silica fume, gypsum
does not appear, due to the lower calcium activity in this system.
Although the sequence of phase changes is subtly different from the
case without silica fume, it is believed that this difference cannot explain
why pozzolanic SCMs improve the sulfate resistance of OPClimestone
SCM systems. In both cases, similarly large volumes of ettringite and
thaumasite are predicted to form after about the same degree of reaction with the sulfate solution.
Simulations for different limestone (5, 15 and 20%) and C3A (1, 5 and
9%) contents have also been performed, in all cases with 10% silica fume.
Overall, the sequence of phase formation does not change, although the
amount of ettringite formed increases with increasing C3A content,
while the amount of thaumasite formed increases with increasing limestone content.
Based on these calculations, the following conclusions can be drawn
regarding the equilibrium phase assemblages produced by immersion
in alkali sulfate solutions:
during contact with a sodium sulfate solution for an OPC + limestone
binder:

portlandite

0.4

ettringite

CSH_16
0.2

Fe-monocarboaluminate
0.0
0

100

200

300

flushing steps
Fig. 10. Evolution of the mineral assemblage of an OPC + 15% limestone cement paste
when ushed 333 times with a 30 mmol/L sodium sulfate solution, at 5 C.

the amount of ettringite formed depends primarily on the C3A

content of the binder
the amount of thaumasite formed depends mainly on the amount
of limestone available
gypsum should not form before all thaumasite formation is
complete. The fact that gypsum is often observed to form before
thaumasite in real exposed concretes can be attributed to the low
rate of growth of thaumasite.
when additional reactive silica is brought in the system, as is the case
with pozzolanic SCMs: the sequence of ettringite and thaumasite
formation does not change signicantly. Therefore the positive effect
of pozzolanic SCMs on sulfate resistance is not likely to be the result

L. Barcelo et al. / Cement and Concrete Research 63 (2014) 7588

83

Fig. 11. Impact of the C3A and limestone contents on the evolution of the mineral assemblage of an OPC + limestone cement paste when ushed 333 times with a 30 mmol/L sodium
sulfate solution, at 5 C.

of a different equilibrium phase assemblage. It seems more reasonable

to propose that it may be the result of a lower rate of sulfate ingress
(due to the lower permeability of the cement paste), perhaps coupled
with enhanced paste strength. This point probably needs further
investigations as Kunther et al. [14] did not nd any impact of the
type of binder on the depth of sulfate ingress.
3.3. Thaumasite growth rate experiments
It was anticipated that some of the materials tested would act as catalysts for thaumasite formation in stirred C-S-H/gypsum/calcite suspensions. Small amounts (1% by mass of total solids) of nely divided solids
were tested as potential nucleating agents, including pure lab-grade
Mg(OH)2, Al(OH)3, Ca(OH)2, and also a sample of ettringite made by

agitating an aqueous suspension of lab-grade Ca(OH)2 and Al2(SO4)3

in a 6:1 molar ratio. Obtaining pure thaumasite for use as a nucleating
agent was initially not possible, so the impure source used for the preliminary experiments was simply a pulverized sample of paste taken
from a eld specimen of a severely TSA-degraded concrete containing
a fairly high fraction of thaumasite as shown by XRD. Some watersoluble compounds were also tested as potential catalysts, including
NaOH, triethanolamine and sucrose.
The principal results of these screening tests can be summarized as
follows:
1. At both 8 C and 20 C, no thaumasite formation could be detected in
the pure agitated suspensions after 12 weeks except for suspensions
to which 1% of either pure ettringite or impure thaumasite had

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L. Barcelo et al. / Cement and Concrete Research 63 (2014) 7588

volume of solids (mL / 1g of binder)

1.2

4. Discussion

1.0

0.8
calcite

thaumasite

0.6

0.4

ettringite

portlandite

CSH_08

monocarboaluminate
strtlingite

0.2

CSH_16
Fe-monocarboaluminate

0.0
0

100

200

300

flushing steps
Fig. 12. Evolution of the mineral assemblage of an OPC + 15% limestone + 10% silica fume
paste when ushed 333 times with a 30 mmol/L sodium sulfate solution, at 5 C.

initially been added. But the suspensions with ettringite or thaumasite

added showed signicant amounts of additional thaumasite formation
after as little as 2 weeks, and the amount of thaumasite continued
to increase rapidly with time after that. Moreover, in a test run
with the combined initial addition of 1% impure thaumasite and
1% portlandite, the suspension was apparently completely reacted
(i.e. no gypsum remained) after 13 weeks at 8 C.
2. None of the water-soluble chemical additives tested individually
resulted in any detectable thaumasite formation after 12 weeks.
But the use of a 0.16 molar NaOH solution coupled with a very high
(20%) aqueous concentration of sucrose was a very effective catalyst
despite including no solid nuclei. It resulted in the complete consumption of gypsum by 7 weeks at 5 C and by 12 weeks at 20 C.
This use of alkaline sucrose as a catalyst (already well known from
the literature) is interesting in that it appears to be capable of accelerating the nucleation process itself, and not just the growth of
thaumasite; but it is only really effective when very high sucrose concentrations are used, and does not represent a situation that is likely
to occur under any natural eld conditions.
These results show that the nucleation of thaumasite is very slow in
agitated mixtures of C-S-H, gypsum and precipitated (ultrane) calcite;
but that thaumasite, once nucleated, can grow at a signicant rate. It is
also important to note that pure ettringite was very effective at nucleating thaumasite growth, and this has important implications for better
understanding the sequence of events that may occur during the degradation of concrete under sulfate attack, where ettringite inevitably
forms before the conditions are right for thaumasite to form.
A few additional tests were conducted to determine the rate of reaction of hydrated Portland cement mortars with gypsum and limestone,
using a similar methodology. The mortars were crushed to completely
pass a 3-mm sieve, from which only the material passing a 200 m
sieve was taken, this being strongly enriched in cement paste. This
material was mixed with 11% gypsum and 7% nely ground limestone
(calculated to be more than sufcient quantities to convert the paste
into a mixture of ettringite and thaumasite) and stirred strongly in
excess water at room temperature (22 2 C) for two months. XRD
analyses of the products clearly showed the presence of ettringite but
were inconclusive for thaumasite. This supports the hypothesis that
ettringite forms before thaumasite during sulfate attack on Portland
cement pastes.

In the recent years, there has been a renewed interest among the
scientic community in the sulfate resistance of cements containing
limestone (see for instance [9,1534] for relevant research or reviews
in the last 10 years). A signicant portion of this recent work was focused on the conditions of thaumasite formation in the case of external
sulfate attack and was probably mainly fueled by the occurrence of a
few high-prole cases of TSA in the UK at the end of the 90s (in concretes made with limestone aggregates) and subsequently by the industrial development of limestone-based blended cements.
4.1. Thaumasite formation in the sequence of sulfate attack reactions
As shown in the thermodynamic modeling section, in equilibrated
cement pastes containing carbonates, it is clear that thaumasite formation follows ettringite formation as the content of sulfate is increased,
and can only occur after all of the AFm phases have been converted
into ettringite. As expected, thaumasite grows at the expense of C-S-H,
portlandite and calcium carbonates (the sulfate ions being supplied
externally). This indicates that thaumasite formation does not occur
concurrently with traditional sulfate attack but rather represents a
later stage of the process of concrete deterioration. This point is also in
very good agreement with the conclusions of the thermodynamic
modeling study of Schmidt et al. [9].
A growing number of microstructural analyses made on samples
that contain carbonates and are subject to sulfate attack also recognize
that ettringite appears rst and is followed by thaumasite formation
[9,18,32,34]. Based on the work of Gollop and Taylor [35], Irassar et al.
[18] summarize the sequence of the processes that occur in cement
pastes immersed in fairly concentrated alkali sulfate solutions:
1. Diffusion of sulfate ions and leaching of portlandite;
2.
3.
4.
5.

Ettringite formation;
Gypsum formation and depletion of portlandite;
Decalcication of C-S-H
Thaumasite formation.

According to this sequence of events, thaumasite formation should

only occur in already severely degraded portions of the sample. In the
CSA A3004-C8-procedure B testing, this corresponds well with observations made by Ramezanianpour and Hooton [32], who detected signicant amounts of thaumasite in the soft deteriorated pieces of spalled-off
surfaces but did not detect thaumasite in the solid mortar pieces.
The main difference between microstructural analyses and thermodynamic modeling lies in the apparition of gypsum [9,32]. While gypsum is predicted to precipitate only after all possible thaumasite has
formed (if limited by depletion of carbonates), it is frequently identied
in laboratory studies prior to the formation of thaumasite. This has been
attributed to the very high alkali sulfate concentrations used in the
standard laboratory experiments, coupled with the very slow rate of
thaumasite formation [9]. Schmidt et al. [34] and Yu et al. [36] also
state that this gypsum precipitation does not make an important contribution to the damage process, as it forms in pre-existing cracks at low
supersaturation levels. We believe that the relatively high mobility of
both calcium and sulfate ions in the systems in question also facilitates
gypsum formation in relatively unstressed locations where it creates
little if any damage. Note that precipitation of gypsum is directly
coupled with consumption of portlandite and ultimately also the decalcication of C-S-H. It only occurs if the sulfate solution used to attack the
specimen contains sulfate ions at a concentration high enough to form
gypsum by reaction with portlandite or C-S-H. This is generally the
case in accelerated lab tests using sodium sulfate solutions, but not
necessarily the case in all sulfate eld exposure conditions. However,
this consumption of calcium hydroxide per se is not required, thermodynamically, before thaumasite formation.

L. Barcelo et al. / Cement and Concrete Research 63 (2014) 7588

4.2. Mechanism of thaumasite formation

In classical sulfate attack, (for a description of the mechanism, see
[37]) crystallization pressure arising from the conversion of very ne
AFm crystals into ettringite is considered to be the source of the damage
[14,36]. This mechanism requires connement of the crystals in very
small pores (b0.1 m) and also requires the solution to be highly supersaturated with respect to ettringite. This mechanism also explains why,
although the increasing volume fraction of ettringite is the driving force
for the expansion, there is no good direct correlation between the
amount of ettringite formed and the observed expansion when comparing different systems [14].
In the thaumasite form of sulfate attack, the mechanism of degradation appears to be very different. While there is controversy regarding
whether or not there is any expansion uniquely associated with
thaumasite growth, the most damaging result appears to be related
to the disappearance of C-S-H and its replacement with a form of
thaumasite that appears to have no binding properties [27,31]. Thus,
the end product of the attack is a paste without cohesion that
has been widely described as a mush. Therefore, as the growth of
thaumasite is not clearly associated with expansion, but the CSA
A3004-C8-procedure B specication nevertheless involves length
change measurements, which are explicitly intended to determine
resistance to the potential for the thaumasite form of sulfate attack,
we can legitimately wonder if this procedure is appropriate and likely
to meet its objectives.
Several reaction pathways or mechanisms for thaumasite formation
have been proposed in the literature. Bensted [38] proposed two different
reaction pathways:
1. A direct route involving the reaction of C-S-H with gypsum and
calcite;
2. From ettringite, C-S-H and calcite via the woodfordite route,
woodfordite being the name sometimes used for a partial range of
solid solutions between ettringite and thaumasite: Bensted proposed
a reaction between ettringite, C-S-H and calcite to give thaumasite
(rst passing through woodfordite) plus (apparently) calcium and
aluminum hydroxides.
Crammond [15] proposed three possible mechanisms:
3. A through solution mechanism;
4. A topochemical replacement of ettringite by thaumasite;
5. A heterogeneous nucleation process, ettringite acting as a template
for thaumasite nucleation.
These ve propositions are not directly comparable because they are
not truly independent; some are mechanisms and others are pathways.
It is therefore necessary to clarify the main mechanistic issues in the
light of the data presented in this paper, which we choose to do by
posing three key questions:
1. Is there a direct reaction between C-S-H, gypsum and calcite?: This
pathway was clearly demonstrated in our own thaumasite growth
rate experiments as discussed above. Such a reaction also clearly involves the passage of many (if not all) of the component ions through
solution, because gypsum, calcite and C-S-H are all consumed during
the reaction, while no intermediate solid phases are observed to
form. One must therefore assume that at least two (and probably
all three) of the starting materials must fully dissolve and all of
their component ions must pass through solution to the site of
thaumasite formation. So one cannot avoid the conclusion that a
through solution mechanism must be involved in this simple direct
pathway.
2. Does ettringite act as a template for thaumasite nucleation?: Our
work clearly indicates that the direct reaction requires an initial
nucleation step, which is extremely slow in the presence of just
the normal starting materials plus some other common potential

85

concrete impurities. The results indicate that C-S-H, gypsum and calcite, as well as portlandite, brucite and gibbsite, do not act as good
nucleation sites for thaumasite. When thaumasite is added, however,
the nucleation problem is overcome; and the use of ettringite appears to be similarly effective. It is concluded, therefore, that nucleation of thaumasite can be a rate-determining step in the reaction,
and that ettringite surfaces can denitely act as a site for thaumasite
nucleation.
3. Is topochemical replacement of ettringite by thaumasite possible
under TSA conditions?: Isomorphic replacement reactions are well
known in geology, but tend to be very slow. Crammond suggests the
possibility of such a replacement mechanism during TSA but did not
give a very plausible pathway. But we can consider the woodfordite
route proposed by Bensted to be a pathway involving replacement
of ettringite by thaumasite, so this pathway, if it is thermodynamically
permitted, could be a mechanism for the topochemical process. However, our thermodynamic analysis shows that it cannot occur in
the way described by Bensted (i.e. as a reaction between ettringite,
C-S-H and calcite to give thaumasite plus gypsum, portlandite and
gibbsite). So, under what conditions might a topochemical replacement reaction actually occur? In order to help answer this question,
it is helpful to treat the reaction as the simplest conceivable exchange
of ions or dissolved neutral species with the solution; for example:
n







^
CD
15Hg 2 AlOH SO :
C3 A
3CD
32H 2 SiOH4 2HCO3 2 CS
CC
4
3

The above equation5 shows clearly that sources of silica and carbon
dioxide are needed for the reaction to progress, and that the reaction itself produces alumina and sulfate in addition to thaumasite. The fact
that this reaction actually releases sulfate ions clearly shows that it is
unlikely to be important in sulfate attack, because increasing sulfate
concentrations will tend to drive the reaction in reverse. On the other
hand, the fact that this reaction consumes carbon dioxide suggests
that it might occur, for instance, in concretes subject to attack by highly
carbonated waters. Matschei and Glasser [32] showed clearly that
thaumasite should form at the expense of ettringite (and that their
solid solution should form rst) during concrete carbonation, provided
that the relative humidity remains high enough. So it is now clear that
the woodfordite route should not occur during simple sulfate attack
conditions, although it is theoretically possible under carbonation
conditions.
As further evidence for our own mechanistic conclusions, we can
also cite the extensive study of the conditions of thaumasite nucleation
in cement pastes and dilute cement suspensions by Kohler et al. [19].
They tested different sulfate carriers (sodium sulfate or gypsum), different temperatures (5 C and 10 C), different base cement compositions (pure C3S, alite, mixtures of alite and C3A, mixtures or alite and
C4AF), different seeding conditions (no seeding, seeding with ettringite)
and the addition (or not) of very ne silica. They concluded that:
Woodfordite was rarely observed and there was no evidence to support the idea of it being an intermediate step in the reaction to form
thaumasite. Mixtures containing ettringite and calcite but no additional source of sulfate did not form thaumasite.
Thaumasite was almost never observed in mixes containing no alumina, even if the stoichiometric conditions for its formation were met.
Without prior formation of ettringite, the formation of thaumasite in
cement pastes is extremely slow.
The heterogeneous nucleation mechanism involving ettringite is the
most likely, with thaumasite growing as an epitaxial overgrowth on
the surface of ettringite.
The observations of our own study are certainly consistent with the
conclusions of Kohler et al. [19].
5

$ represents SO3 and represents CO2

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L. Barcelo et al. / Cement and Concrete Research 63 (2014) 7588

4.3. Kinetics of thaumasite formation

4.4. Relevance of CSA A3004-C8 procedure B

Although the thermodynamic analysis shows clearly that ettringite

formation should precede thaumasite formation in the normal sequence of sulfate attack reactions on Portland cement pastes, the question remains as to why thaumasite formation, when it does occur, is so
much slower than ettringite formation. This is clearly the case in the
laboratory and also appears to be true in the eld. While some have proposed the unusual silicon in 6-coordination with hydroxyl as a potential
explanation for the low formation rate [38], we here propose an alternative explanation based on our own observations.
Ettringite can be made easily and rapidly in the laboratory by the
method used here, involving the reaction between two relatively soluble precursor phases: portlandite (moderately soluble) and aluminum
sulfate (highly soluble), via the overall reaction shown below (in an
excess of water):

Regarding the relevance of the CSA A3004-C8 procedure B to determining resistance to the potential for the thaumasite form of sulfate
attack, we rst summarize its main features as follows:

AD3 H18 6CHC3 A
3CD
32H:

Because of the relatively high solubility of both initial reactants, the
initial supersaturation can locally reach very high values, which leads
to rapid nucleation. And, for similar reasons, diffusion of ions through
solution is unlikely to be rate limiting at least until the degree of reaction
is quite high.
In the more practically relevant case of sulfate attack on hardened
concrete, ettringite typically forms by the reaction of one very poorly
soluble phase (e.g. monosulfoaluminate-AFm) with one moderately soluble phase (e.g. gypsum) in the presence of excess water, as shown
below:
C3 A
CD
12H 2CDH2 C3 A
3CD
32H:
In this case, the calcium and sulfate ions can diffuse quite rapidly toward the poorly soluble precursor AFm phase, which means that the
ettringite formed is likely to occur very close to the site of the AFm
phase, rather than close to the source(s) of calcium and sulfate. In the
case where sulfate ions are provided by an alkali sulfate solution their
concentrations can be even higher. The calcium in that case will usually
come from portlandite or C-S-H in the surrounding cement paste
matrix, at moderate concentrations. But, either way, there is no need
for ions to diffuse long distances under very low concentrations gradients, so rates of reaction can still be fairly rapid.
On the other hand, there are no such easy routes to thaumasite formation, because in all practical cases the reaction involves at least three
separate precursor phases, of which at least two (e.g. C-S-H and calcite)
have extremely low solubilities. The reaction (in excess water) occurs as
shown below:
^
CD
15H:
^ CDH CS
CC
CSH CC
2
Since there is no known stable intermediate phase containing
both silicate and carbonate ions, the reaction must involve counterdiffusion of carbonate and silicate ions under conditions where both
are present at extremely low source concentrations. Thus, it is unlikely
that a high degree of supersaturation will occur initially (which explains
the very low nucleation rates observed) and the rate of growth even
after nucleation is also likely to be severely limited by the low average
concentrations of silicate and carbonate ions (which also implies low
concentration gradients). Additional support for this conclusion comes
from qualitative observations that (a) strong agitation of the suspensions signicantly enhances the reaction rate, and (b) the use of ground
limestone as the source of calcite, instead of the ultrane precipitated
calcite used in most of our suspension experiments, results in a much
lower reaction rate.

1. Like procedure A designed for assessing resistance to traditional sulfate attack, procedure B is a length-change measurement procedure;
2. Samples are kept immersed in a highly concentrated sulfate solution
at low temperature (5 C);
3. Immersion starts when samples have reached a compressive
strength of 20 1 MPa.
4.4.1. The relevance of length-change measurement
Since both thermodynamic analysis and microstructural examinations have shown that thaumasite formation can occur only after all potential ettringite formation is nished; and since it has also been shown
that, even once it becomes thermodynamically stable, thaumasite
nucleation is very slow when ettringite is absent, it is reasonable to
use a method that is sensitive to the formation of ettringite to evaluate
the potential for thaumasite formation. Moreover, direct evaluation of
thaumasite formation using the currently available methods (XRD for
instance) would be difcult and impractical in the context of an
industrial quality control procedure. Length change measurement
appears adequate to fulll this objective. An alternative approach
using surface-sensitive leaky Rayleigh waves was examined recently
[34], but the conclusion of the study was that this technique did not
bring any advantage in terms of sensitivity compared to a length change
measurement. However, a qualitative rating of the surface/edge damage
of the test specimens could be added to the current procedure at little
cost.
One might reasonably still ask whether or not there might be a
pessimum scenario, (e.g. for low C3A cements), where the amount of
ettringite formed would be small enough to generate only modest
expansions but yet still high enough to initiate subsequent thaumasite
formation that might severely weaken the samples without necessarily
giving much linear expansion. However, although this risk cannot be
completely discounted, it now appears quite unlikely, because the evidence shows that, if the microstructure is not opened-up by cracking,
thaumasite formation tends to remain purely a surface phenomenon.
As Irassar concludes in his review article [27]: Regardless of limestone
ller content, in pastes, mortars and concretes made with low-C3A
cements (b 5%) and using a low effective w/c ratio (b0.50), which
complies with the ACI 201 recommendation for moderate sulfate
environments, no early damage at low temperatures resulted. In this
case, thaumasite is also found on the specimen surface on long time
exposure, but it lacks relevance in the damage process.
4.4.2. Comments on the use of low temperature and the 20 MPa strength
criterion
As shown in this article, longer-term expansions are generally greater at 5 C than at 20 C, independently of the presence or absence of
limestone. This is due to an earlier take-off of the expansion (the
rate during the initial slow expansion phase being apparently independent of temperature). This take off is generally attributed to the percolation of the crack network in the sample [36]. Thaumasite formation is
also generally reported to be thermodynamically favored by lower
temperatures.
The reason for the more rapid expansions observed at 5 C is difcult
to elucidate from the research conducted for this study. From the thermodynamic model of Schmidt et al. [9] it does not seem that this temperature change should have a signicant impact on the driving force
for ettringite formation. One hypothesis is related to the fact that,
when the mortar is put in the sodium sulfate solution it has a fairly
low degree of hydration (noting that 20 MPa is well below its ultimate
fully-cured strength). A low temperature (5 C) applied at this early

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stage will then signicantly decrease the subsequent hydration rate

compared to the use of 20 C curing, so the maturity of the sample at
any subsequent time is likely to be lower in the 5 C test than in the
20 C test, and its permeability is therefore likely to be higher. Therefore, sulfate ingress is likely to be faster in the test run at lower temperatures, resulting in the same or higher crystallization pressures applied
to a weaker microstructure. This hypothesis can also explain why the
tendency for greater and more rapid expansions at low temperatures
is not seen in other studies like the one of Schmidt et al. [34] where
the samples are allowed to cure for 28 days at 20 C before immersion
in the sulfate solution at low temperature.
Similarly, this maturity hypothesis can explain the unexpected failure of some mixes containing Type F y ash or slag. Because the reactions of these SCMs are especially temperature-sensitive, the effect of
reduced sample maturity at the lower curing temperature is likely to
be more severe with mixes containing such SCMs. This puts the mixes
with slag or y ash at a signicant disadvantage, whereas in most real
concrete structures they would have much more time to hydrate before
being subject to signicant sulfate exposure. This hypothesis is further
reinforced by the fact that additional results have shown that silica
fume additions are much more effective than the other SCMs in reducing the expansion at 5 C, presumably because of its ability to reduce
the permeability of the sample much more rapidly. As a result, we believe that further research should be conducted to evaluate alternative
curing procedures for use (in a modied test procedure) prior to sulfate
exposure at 5 C.

5. Conclusions
The purpose of this article was to investigate the test method CSA
A3004-C8 procedure B and its relevance to assess the risk of thaumasite
form of sulfate attack. Through comparisons of results obtained in
different laboratories on different cementitious systems as well as thermodynamic modeling and kinetic experiments, we can draw the following conclusions:
The length change measurement procedure proposed in CSA A3004-C8
appears to be relevant as an indirect evaluation of the risk of the
thaumasite form of sulfate attack:
1. Thermodynamic modeling conrms that the thaumasite form of sulfate attack is the nal step of the sulfate attack and happens after the
regular form of sulfate attack;
2. Kinetic experiments conrm that thaumasite formation is always extremely slow compared to ettringite formation (and gypsum formation) but can nevertheless be catalyzed to some extent by prior
formation of ettringite;
3. Alternative, usually more complex, techniques investigated by other
authors have not shown any benet compared to the standard simple
length change measurement;
4. Visual qualitative rating of corners and edges of the sample could be
added to the test procedure at little cost and could provide additional
useful information.
The testing condition of 5 C coupled with a high concentration of
Na2SO4 (50 g/l) also appear to be relevant.
1. The temperature is representative of the temperature in soils in
Canada;
2. High sodium sulfate concentrations have been questioned but they
are representative of sulfate concentrations in certain soils in North
America;
3. This high sodium sulfate concentration has been used in CSA A3004C8 procedure A for a long time and cementitious systems that have

87

been qualied by this procedure seem to have performed satisfactorily in the eld.
In its current version, the CSA A3004 procedure B appears overly
severe:
1. Many SCM combinations fail the test, independently of the presence
of limestone. This includes some SCM combinations that have a good
history of eld use in sulfate environments;
2. Mixes with limestone do not clearly appear to perform worse than
mixes without limestone, although this should be investigated further
as some datasets are conicting. The fact that PLCs in North America
are ground so as to give equivalent performance to Portland cements
in terms of strength development may explain the observation.
3. The severity of the test is probably due to the low maturity of the
samples when they are put in the solution at 5 C. At low temperatures, hydration rates, in particular for SCM, are expected to be
much slower, and sulfate ingress is expected to be faster.
4. We suggest modifying CSA A3004-C8 procedure B to ensure sufcient hydration maturity before the samples are subjected to sulfate
attack at low temperatures.
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