Journal of Cultural Heritage 4 (2003) 109–115

www.elsevier.com/locate/culher

Original article

Crystallization damage by sodium sulfate

Nicholas Tsui a, Robert J. Flatt b,*, George W. Scherer b
a
Materials Science and Engineering, 8-032, MIT, Massachusetts Avenue 77, Cambridge, MA 02139, USA
b
Department of Civil and Environmental Engineering, E-Quad, Princeton University, Princeton, NJ, USA
Received 20 May 2002; accepted 21 January 2003

Abstract

Experiments demonstrate that a stone containing thenardite suffers great damage when exposed to water below the temperature limit of
mirabilite stability. This is due to a transition between thenardite and mirabilite, and not to thenardite reprecipitation. Damage occurs whether
or not thenardite was produced previously by mirabilite decomposition. Together with recent results from the literature, these results indicate
that damage occurs because thenardite dissolution can produce solutions highly supersaturated with respect to mirabilite, so that precipitation
of this mineral can lead to large crystallization pressures. Finally, it appears that there is a salt content threshold beyond which damage
increases substantially.
© 2003 Éditions scientifiques et médicales Elsevier SAS. All rights reserved.

Keywords: Sodium sulfate; Mirabilite; Thenardite; Crystallization pressure; Salt; Deterioration; Durability

1. Research aims commonly encountered, sodium sulfate is known to be the

The general aim of the research we are conducting on
crystallization is to develop a detailed understanding of the
mechanisms by which salts can damage building materials. It
is through the careful examination of the thermodynamics of
this problem that a novel solution to preventing salt damage
has emerged.
In the present study, we focus on the case of sodium
sulfate. A detailed examination of the magnitude of the
stresses involved has been presented elsewhere. In this paper,
we present simple experimental results that support the idea
that sodium sulfate is so damaging because of a process of
dissolution and precipitation rather than volume change as is
usually stated. As we explain in the conclusion section, this
finding has serious implication as to the relevance of crystal-
lization tests commonly used to judge the durability of build-
ing stone.
2. Introduction
Crystallization of salts in stones or concrete is an impor-
tant mode of decay of these materials [1,2]. Of all the salts
* Corresponding author. Present address: Sika AG, Corporate Research
and Analytics, Tüffenwies 16, 8048 Zurich, Switzerland.
E-mail address: flatt.robert@ch.sika.com (R.J. Flatt).
© 2003 Éditions scientifiques et médicales Elsevier SAS. All rights reserved.
DOI: 10.1016/S1296-2074(03)00022-0
worst, which is why it has become widely used in accelerated
durability testing [3]. There are two major ways in which
such tests are run. In the first, samples undergo cycles of
impregnation in a saline solution followed by drying. In the
second, samples are in permanent contact at their base with a
saline solution, while low humidity is imposed above to drive
continuous capillary rise compensating for water evapora-
tion.
Two main mechanisms are proposed to explain the exten-
sive damage caused by sodium sulfate: hydration pressure
and crystallization pressure. In fact, it has been shown that
the expression for hydration pressure accurately predicts the
upper bound of crystallization pressures [4]; nevertheless,
even though the predicted pressures are the same, it is impor-
tant to know which phenomenon is responsible for the ob-
served damage. Hydration results in a large volume expan-
sion (about 314%) as the anhydrous phase of sodium sulfate
(thenardite) converts to its decahydrate phase (mirabilite).
However, recent use of the environmental scanning electron
microscope (ESEM) demonstrated that this transition occurs
by dissolution and precipitation of mirabilite [5], ruling out
hydration pressure as a credible cause for the extensive dam-
age caused by sodium sulfate. It is important to point out that
this precipitation involves an overall expansion [6] that might
cause a destructive hydraulic pressure as in the case of freez-
110 N. Tsui et al. / Journal of Cultural Heritage 4 (2003) 109–115
Fig. 1. Phase diagram for sodium sulfate. The continuous lines indicate the
boundaries of the stable phases. Triangles and squares are experimental data
for mirabilite and thenardite, respectively [10]. The discontinuous line
corresponds to a solution in metastable equilibrium with respect to thenar-
dite and supersaturated with respect to mirabilite.
ing of water [7]. The magnitude of this pressure is likely to be
relatively small compared to ice because of the limited ex-
pansion involved and the probably low crystallization rates
[8]2.
On the other hand, sodium sulfate can develop particularly
large crystallization pressures. The first convincing argument
for this idea was presented by Chatterji and Jensen [9]. They
noted that the solubility of thenardite becomes increasingly
larger than that of mirabilite below 32 °C. Therefore, any
porous material containing thenardite that is exposed to wa-
ter or rising humidity will host both dissolution of thenardite
and precipitation of mirabilite. The key aspect is that the
thenardite dissolves until it reaches its equilibrium concen-
tration, which at ambient temperature is highly supersatu-
rated with respect to mirabilite as indicated in Fig. 1 (data are
from Kracek [10], construction of equilibrium lines is de-
tailed in [8]). Such situations are systematically repeated in
the durability test that involves cycles of impregnation and
drying. The expected tensile stresses are substantially larger
than the tensile strength of most stone and concrete, which
means that mirabilite precipitation alone is sufficient to dam-
age these materials during the rewetting [8].
These stresses originate from repulsive surface forces
between the pore walls of most inorganic building materials
and salt crystals [11,12] and each system has a maximum
2
Hydraulic pressure is created during freezing, because water is pushed
away from the site of growing ice crystals, owing to the expansion in volume
as ice forms [7]. As water is driven through the pores ahead of the advancing
crystals, frictional resistance between water and the pore walls produces a
back-pressure. The magnitude of this pressure increases with the rate of
growth of the crystals, so lower temperatures and faster cooling rates
increase the damage from hydraulic pressure during freezing. In the case of
mirabilite crystallization there is a volume increase, so water is displaced
during growth. However, the magnitude of the volume change is much
smaller (nine times at 20 °C) and the rate of growth of salt crystals is far
slower than that of ice, so the hydraulic pressure generated by mirabilite
crystallization is expected to be very small.
crystallization stress that is determined by the disjoining
forces of the salt/mineral interface. In the case of mirabilite,
it is conceivable that this maximum is higher than for other
salts [13], though we expect that stone and concrete are too
weak to resist crystal growth up to the maximum crystalliza-
tion pressures of most salts [11]. Therefore, as a general rule,
crystallization damage in these materials will depend on the
degree of supersaturation that can be achieved, the pore size
distribution and the tensile strength of these materials, rather
than on chemistry or mineralogy of the host [2,8,11].
Accepting that crystallization pressure is the source of
damage, Rodriguez-Navarro et al. [14] recently argued that
precipitation of thenardite rather than mirabilite may be the
culprit in damage from sodium sulfate, particularly in situa-
tions of constant capillary rise. These authors found that
under conditions of fast evaporation driven by low ambient
relative humidity, both mirabilite and thenardite could be
precipitated, instead of the precipitation of mirabilite and
subsequent dehydration expected from equilibrium thermo-
dynamics. With even lower relative humidities they were also
able to precipitate only thenardite. Since these authors also
observed that in experiments of constant capillary rise, dam-
age increased substantially with low relative humidities and
that the spallings of their samples contained thenardite of
similar morphology to the one produced in their experiments
described above, they inferred that thenardite crystallization
was probably responsible for the enhanced damage at low
relative humidity. On the other hand, the fact that in some
instances, both minerals form indicates that mirabilite is
precipitating under conditions of high supersaturation and
that the concentration in the solution must be at least satisfy-
ing thenardite saturation. Using thermodynamic data to ana-
lyze the conditions of this experiment, it was found that
mirabilite precipitation alone could generate stresses suffi-
cient to damage most stones and concrete [8]. This demon-
strates that contribution from thenardite crystallization pres-
sure is not a necessary condition, though it does not exclude
the possibility of its contribution.
Another observation of Rodriguez-Navarro et al. [14] is
that when thenardite that was formed by mirabilite dehydra-
tion is exposed to increasing humidity at ambient tempera-
ture, then precipitation of both phases can be observed (mira-
bilite appears and thenardite recrystallizes). In this case, the
formation of thenardite can be seen as an attempt to minimize
the surface energy of the sub-micron crystallites produced
during mirabilite decomposition, a process that leads to
pseudo-morphic substitution for mirabilite crystals. This ob-
servation again raises the question about which sodium sul-
fate phase causes most damage by precipitation. This time
however, the question applies to situations of cyclic impreg-
nation and drying rather than constant capillary rise.
In this paper, we present an approach similar to that of
Jensen and Chatterji [9], who subjected bricks to impregna-
tion cycles above 32 °C and then split these into two series for
further cycles. One series impregnated at 30 °C did not
undergo any damage, while the other series impregnated at
 N. Tsui et al. / Journal of Cultural Heritage 4 (2003) 109–115 111

20 °C decayed rapidly. Results were used to infer the impor-

tance of mirabilite precipitation as the cause of damage.
However, in view of the above results they are insufficient to
discount the possibility that recrystallization of thenardite
could be the ultimate cause of damage during rewetting. The
slightly more complete experimental approach presented
here demonstrates clearly that it is indeed mirabilite that
causes damage in such situations. Furthermore, it is found
that the magnitude of damage greatly increases once enough
salt is present for mirabilite to fill all pores. This implies that
crystallization stresses will develop throughout the sample,
propagating strength limiting flaws. Durability classifica-
tions resulting from this test will, therefore, not necessarily
correlate with real exposure conditions in which stresses are
developed more locally by supersaturated solutions produced
by evaporation.

3. Experimental

3.1. Materials

Indiana limestone was cut into 2.5 cm cubes. The apparent

density of this stone was determined to be 2.31 g/cm3. The
skeletal density measured by helium pycnometry was found
to be 2.69 g/cm3. This gives a total porosity of 14%.
The sodium sulfate used was analytical grade obtained
from Merck and all water was demineralized.

3.2. Methods

Twenty-nine samples were subjected to cycles of impreg-

nation and drying. They were separated into three groups A,
B and C. All samples were initially dried to constant mass at
105 °C.
The 10 samples in group A were impregnated at ambient
temperature (20 °C) with mirabilite saturated solutions (16%
thenardite by mass). The 10 samples in group B were impreg-
nated at 50 °C with the same solutions. The nine samples of
group C were also impregnated at 50 °C but with solutions of
thenardite saturated at that temperature (31% thenardite by
mass).
Each sample was impregnated in its individual closed
screw-capped polypropylene flask (ID: 45 mm, h: 43 mm).
The mass of the polypropylene flask was measured. The
solution volume was chosen to be slightly greater than the
pore volume in the sample to limit loss of salt by diffusion out
of the stone. Prior to impregnation, samples were always left
to equilibrate thermally either in the dry oven at 50 °C or in a
closed container at room temperature. If the stones impreg-
nated at 50 °C were not preheated, precipitation at pore
entries would occur upon contact with the solution and the
amount of solution absorbed into the stone was much lower.
Impregnations lasted 6 h, a time found to be sufficient to
fully saturate these samples. The masses of the wet samples
and the mix of residue and solution remaining in the flask
were then measured. Samples impregnated at 50 °C were
taken individually out of the oven directly to be measured.
Fig. 2. Flow chart of experimental protocol.
The weighed samples were then placed on individual glass
Petri dishes previously weighed. They were placed into a
drying oven at 105 °C until constant mass was reached. At the
end of the drying step, the Petri dish and its contents were
weighed again to determine the mass of water lost. Decoher-
ing pieces were then scraped off the remaining sample. The
remaining sample and its residue were weighed separately.
This procedure was repeated six times for each group as
indicated in Fig. 2.
At the end of the sixth cycle, each group was split into two.
The first half was impregnated at 20 °C and the second at
50 °C.
4. Results
In Fig. 3, the average mass fraction lost per cycle during
both the impregnation and the drying steps is reported. In
each graph, the two sub-groups that received a different
treatment in the seventh cycle are plotted separately, along
with the error bar for the 95% confidence interval on the
average. It can be seen that in each case, both sub-groups are
indistinguishable before the seventh cycle. Any difference at
that point cannot, therefore, be attributed to a difference in
average properties of those sub-groups.
112 N. Tsui et al. / Journal of Cultural Heritage 4 (2003) 109–115

Fig. 3. Mass loss evolution during impregnation and drying cycles. Filled symbols indicate impregnation at 20 °C, open symbols 50 °C. Diamonds indicate
sub-groups with same impregnation temperature for all cycles. Squares indicate sub-groups that had a different impregnation temperature in cycle 7. Groups A
and B had solutions saturated at 20 °C, while group C had a solution saturated at 50 °C. Group A was run at 20 °C for cycles 1–6, while groups B and C were
run at 50 °C for those same cycles.

Considering first the cycles 1–6, it is seen that only group
A is damaged and that this occurs during the impregnation
and not the drying step. That group was impregnated at 20 °C
for cycles 1–6, while the other two were impregnated at
50 °C.
In the seventh cycle, each group was split into two sub-
groups. The first sub-group was impregnated at 20 °C and the
second one at 50 °C. Fig. 3 indicates that regardless of the
past history, degradation systematically occurs when impreg-
nation is done at 20 °C, and that no degradation occurs at
50 °C. Once again, no significant degradation occurs during
the drying.
Groups B and C are distinguished by the fact that the
concentrations of the impregnation solutions are respec-
tively, 16% and 31%. These concentrations, given as mass
fraction of thenardite, correspond to saturation of mirabilite
at 20 °C and of thenardite at 50 °C, which are respectively the
most stable phases at those temperatures. Degradation is
much greater in the second case because more salt has been
accumulated.
Appendix A shows how to determine the mass of stone
and salt within the sample at each cycle. Fig. 4 indicates that
in cycle 6, for group A, there is a simultaneous increase in the
mass loss accompanied by a decrease in the fraction of stone
within the sample. The salt content at that point of time
corresponds to about 4% of the stone mass. In this case, it is
the average of all samples of group A that has been plotted.
5. Discussion
All results indicate that damage occurs when the impreg-
nation is done at 20 °C. Results for groups B and C in the
 N. Tsui et al. / Journal of Cultural Heritage 4 (2003) 109–115
Fig. 4. Evolution of the mass the sample and the stone it contains (the
sample is the total of the remaining stone and the salt it contains). The
relative salt content (given with respect to the mass of stone in the sample) is
also reported. All data in this figure are for group A.
seventh cycle are particularly instructive since they show that
severe damage occurs at 20 °C, even though the thenardite
that is present in the samples would not have been produced
by mirabilite decomposition, since all prior impregnations
were performed at a temperature above the limit of stability
of this mineral (Fig. 1). On the other hand, the sub-group of
samples from group A that is impregnated at 50 °C in the
seventh cycle would undergo recrystallization of thenardite,
but no decay is observed. This demonstrates that, indepen-
dent of the way thenardite was obtained, damage occurs only
when mirabilite is allowed to crystallize.
We can, therefore, state that the conversion from thenard-
ite to mirabilite is the cause of damage. Such results could be
equally used in favor of hydration or crystallization pressure
as the source of damage. To satisfy the proposed mechanism
of hydration pressure, the crystals of thenardite would have
to undergo a continuous expansion by progressive integra-
tion of water into their lattice, eventually forming mirabilite.
Due to lattice mismatches, such a process is more than
unlikely. Furthermore, as mentioned earlier, the experimental
observation that this conversion takes place through dissolu-
tion and precipitation [5] establishes the validity of the crys-
tallization pressure view-point over the one of hydration
pressure. In addition, calculations show that if mirabilite
crystallizes from a solution at the saturation concentration of
thenardite, then mirabilite precipitation can generate tensile
stresses in excess of the tensile strength of most stones and
concrete [8].
An important factor in the crystallization inside porous
materials is that, whenever given the possibility, a crystal
would rather grow in directions where it does not encounter
resistance. One, therefore, expects damage to increase sub-
stantially once enough salt is present to fill the porous net-
work. For the stone we are dealing with, the porosity is 14%.
The molar volume of mirabilite being 220.7 cm3/mol and the
molar mass of thenardite being 144.0 g/mol, we would ex-
pect such an increase to occur once the salt contents reaches
3.9 wt.% of thenardite.
For the samples of group A, this condition is reached at
cycle 5 (Fig. 3) and there is indeed a clear increase in damage
113
during the next impregnation. Furthermore, the degree of
damage between the sub-groups of groups B and C impreg-
nated at 20 °C in cycle 7 is very different (5% vs. 30% weight
loss). The salt contents of those samples at the end of cycle 6
are respectively 3.2% and 7% salt mass with respect to the
stone. These values happen to be on each side of the critical
salt content estimated above, supporting the idea that exten-
sive damage occurs once the crystals no longer have the
possibility of growing in unrestrained directions. Having
pointed this out, a word of caution as to the exactitude of the
estimated salt contents of the samples must be made. Indeed,
the calculation described in Appendix A assumes that the dry
loss contains proportions of salt and stone equal to those
found in the bulk sample. In reality, particularly during the
first cycles the salt content will be higher due to efflores-
cence. As a result, salt contents are somewhat over-
estimated. However, the consequence should not be too large
since dry loss is small.
The substantial degree of damage reached in the ultimate
cycles of the testing procedure involving cycles of impregna-
tion and drying, therefore, seems intimately linked to the
inability of crystals to find possibilities for unrestrained
growth. Consequently stress fields develop over zones large
enough to propagate strength-limiting flaws, which explains
the large scale of damage observed. In real conditions of
exposure, it is unclear whether such a situation would occur.
In particular, for salts like sodium chloride, evaporation-
driven supersaturation only develops in a limited zone quite
close to the surface. In such a situation, durability would be
dictated by the smaller flaws, which require higher stresses to
be propagated. Damage would be expected to be more granu-
lar as is often observed in field exposure. In view of this, the
relevance of the durability test involving cycles of impregna-
tion in a sodium sulfate solution followed by drying must be
questioned.
6. Conclusions
The origin of the extensive damage that sodium sulfate
can cause in durability testing that involves cycles of impreg-
nation and drying is linked to mirabilite precipitation that
occurs during the wetting step. Damage is severe because
when water enters the thenardite-containing material, disso-
lution of this mineral creates a solution highly supersaturated
with respect to mirabilite. The concentration is high enough
for mirabilite precipitation to generate stresses in excess of
the tensile strength of most stones and concrete. This process
does not rely on thenardite having been obtained by mirabi-
lite dehydration, implying that thenardite recrystallization
does not contribute to damage in such situations.
Damage appears to increase abruptly as soon as enough
salt is present to prevent unrestrained precipitation of mira-
bilite during impregnation. This implies that stresses are
exerted over a large fraction of the sample’s volume, a situa-
tion that would lead to a different pattern of damage than in
field conditions for which the presence and amount of
114 N. Tsui et al. / Journal of Cultural Heritage 4 (2003) 109–115

salt
smaller flaws requiring higher stresses to be propagated We assume that moven is split between the dry residue and
would dictate the durability of these materials. Due to this, the sample in proportions equal to their masses, so the
salt
the ability of this durability test to produce a classification of amount of salt in the residue mresidue, dry is:

冉 冊
resistances that is relevant for in situ exposure must be given
S
further consideration. mdry, final
= 1−
salt salt
mresidue, dry moven P (A.7)
mdry, rest
Acknowledgements S
where mdry, final is the remaining dried sample, mdry, rest is the
P

dried residue mass.

N. Tsui was supported during the summer of 2000, by the
We can now determine the material lost during drying, not
NSF program Research Experience for Undergraduates.
including salt:
Support for R. Flatt was provided by a postdoctoral grant
from the Swiss National Science Foundation, and financial mlost, dry = mdry, rest − mresidue, dry
S P salt
(A.8)
support from Lafarge Co. and the National Center for Pres-
ervation Teaching and Training (Award No. MT-2210-9-NC- To get the amount of salt and stone in the remaining
21). sample, we assume that they are during impregnation in
identical proportions as found in the sample prior to that step:
salt
Appendix A. Calculations minitial
=
S S
mlost, wet mlost, wet S (A.9)
minitial
We determine the mass loss during impregnation and
drying cycles, as well as the mass of remaining stone (with- The amount of salt in the stone at the end of each cycle is
out salt content). For impregnation: given by:
mempty + madded + mdry, initial = mrest + mwet + mlost
F sol S F S W
(A.1) mfinal = minitial − mlost, wet + moven − mresidue, dry (A.10)
salt salt salt salt salt
F sol
where: mempty is the empty polypropylene flask mass, madded is
S
the solution mass, mdry, initial is the dry sample mass at the The mass of the stone remaining in the sample at the end
F of each cycle is then:
cycle start, mrest is flask and residue mass once the sample has
S
been removed after impregnation, mwet is the wet sample mfinal = minitial − mfinal
stone S salt
(A.11)
W
mass after impregnation, mlost is water lost probably because
of a badly closed flask.
F sol
The term mrest includes the remaining solution mflask and
S
the residue mlost, wet: References
= + +
F F sol S
mrest mempty mflask mlost, wet (A.2)
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(A.6)
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