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J Materials a n d Structures 38 (May 2005) 479-488

Mechanisms of salt scaling

J. J. Valenza II and G. W. Scherer

Dept. Civil & Env. Eng, Princeton University, Princeton, NJ 08544, U S A

Received: 16 February 2004; accepted." 20 May 2004

ABSTRACT
A great deal of information has been collected over the years about the phenomenology of salt scaling of concrete, and no single mechanism has
been identified that can account for all of the observations. We review the essential facts that any complete theory of scaling must explain, and
suggest two mechanisms that seem to be of primary importance. Experiments indicate that damage is worst when the water on the surface of the
concrete contains a small amount of solute, regardless of the type of solute. We argue that the role of solute is to create brine pockets in the ice that
act as mechanical flaws; when the weakened ice cracks, the crack runs to the surface of the concrete and does superficial damage. An analysis of
the stresses created in this way shows that they are more than sufficient to initiate cracks. A second phenomenon, which is present when chloride
salts are used, is expansion resulting from precipitation of Friedel's salt. The crystallization pressure from growth of these crystals causes significant
expansion of the paste, and results in high stresses on a local scale near the ice/paste boundary. This can substantially weaken the material and
facilitate scaling.
1359-5997 9 2004 RILEM. All rights reserved.

R/~SUMI~
Beaueoup d'informations ont Ot~ rassembldes au cours des dernikres annkes au sujet de la phknomOnologie d'Ocaillage du b~ton liOe aux sels,
mais aucun mOcanisme pouvant expliquer toutes ces observations n 'a Ot~ identifiO. Nous passons en revue les fairs essentiels que n 'importe quelle
thOorie complbte d'~eaillage doive expliquer, et suggkrons deux mOcanismes qui semblent ~tre d'importanee primaire. Les experiences indiquent
que les dommages sont les plus mauvais quand 1'eau sur la surface du bOton contient un peu de corps dissous, indOpendamment du type de corps
dissous. Nous arguons du fa# que le rrle du corps dissous est de erOer les poches de saumure dans la glaee qui agissent en tant que dOfauts
m~eaniques. Quand la glaee affaiblie fend, des dommages superficiels sont provoquOs par la propagation des fentes vers la surface du bOton. Une
analyse des pressions cr~Oes de cette faqon prouve qu 'elles sont au moins suffisantes pour initier des fissures. Un deuxiOme phOnombne, qui est
prOsent olz des sels de ehlorure sont employOs, est l 'expansion r~sultant de la precipitation du sel de Friedel. La pression de cristallisation de la
eroissance de ces cristaux cause l'expansion significative de la pdte, et provoque des pressions klevOes sur une ~chelle locale pros de l'interface
glaee/pdte. Ceci peut sensiblement affaiblir le matOriel et faciliter 1'~caillage.

1. INTRODUCTION
When a pool of liquid freezes on a concrete surface,
superficial damage called salt scaling (see Fig. 1) often occurs.
The phenomenon has been described in detail in several
excellent reviews [1-3]. The principal observations are as
follows:
i) the damage is worst when the water contains a moderate
amount (the so-called pessimum concentration) of solute
[3-5]
ii) the pessimum concentration is nearly independent of the
nature of the solute (e.g., salts, alcohol, and urea show
similar behavior) [5]
iii) the damage consists of small flakes of material removed
from the surface [6]
iv) no scaling occurs without free liquid on the surface o f the
sample (i.e., saturated surface-dry samples do not scale)
[5, 7]
v) damage is worse when the minimum temperature in the
cycle is lower [3, 7, 8]
vi) the salt concentration in the exterior liquid is more
important than that o f the pore liquid [1, 3]
vii) entrained air reduces the damage [1, 5]

Editorial Note
Prof. George W. Scherer is a RILEM Senior Member.

1359-5997 9 2004 RILEM. All rights reserved.

doi: 10.1617/14345
480 J.J. Valenza, G.W. Scherer / Materials and Structures (2005) 479-488
Fig. 1 - Photo of sidewalk showing minor scaling (left) and
serious scaling (right).
Many theories have been offered to explain some of these
observations, but none of the proposed mechanisms is able to
account for all of them. For example, damage has been
attributed to crystallization just below the surface, where
saturation is made possible by the free water at the outer
surface [3]; however, testing shows damage after tens or
hundreds of freezing cycles, by which time the saturation
should extend well beyond the superficial zone [6]. Moreover,
the saturation should also be present when the pool contains
pure water, but that does not cause scaling [7]. Superficial
damage has been blamed on over-finishing or bleeding, which
alter the surface structure, and it has been demonstrated [9] that
the depth of scaling matches the depth of carbonation (in blast
furnace slag cement). These factors may account for the depth
of the damage, but do not explain what causes it. It has been
suggested that the damage results from precipitation of salt, but
solid sodium chloride does not form above -22~ which is
below the temperature range of most scaling tests. It has been
argued that increased saturation of the surface layer occurs
when salt is present in the pore liquid [3, 10], but that effect
would increase monotonically with salt concentration, not
show a pessimum. Finally, it has been proposed that osmotic
pressure drives water from the pores toward the free liquid
[11]; again, this effect would increase monotonically with salt
concentration, so it cannot account for the pessimum. We will
show that dilatation does occur when cement paste is exposed
to salt, but that swelling apparently results from crystallization
of Friedel's salt; there is no evidence of a significant osmotic
pressure.
To examine the stresses created during a scaling
experiment, we have developed a test in which a pool of
liquid is frozen on the surface of a thin plate of cement
paste or mortar. Stresses cause warping of the plate that is
easily detected. This type of experiment has revealed two
important mechanisms that have not been previously
analyzed: (1)mechanical bonding of the ice to surface
irregularities on the concrete that allows the ice to exert
stresses during cooling, owing to the huge mismatch in
thermal expansion coefficient between ice and concrete;
and (2) dilatation caused by exposure of paste to salt.
2. EXPERIMENTAL PROCEDURE
2.1 Cement paste
Plates of cement paste with dimensions 3 x 21 x 110 mm
were cast in polyvinyl chloride molds, as described in [12].
Type III Portland cement (Capitol Cement - Martinsburg,
WV) ~ and de-ionized water were mixed at a water/cement ratio
of w/c = 0.45 + 0.012. After curing overnight in the mold, the
floating bottom was carefully pushed out of the mold, mad the
sample was separated from the bottom. Upon removal, the
samples were placed in a calcium hydroxide (CH) saturated
bath, and allowed to cure for an additional 0-2 days. To ensure
saturation, the samples were submerged in a pressure vessel
containing a saturated CH solution, and placed under ~ 2 MPa
of pressure. After 24 hours, the samples were removed from
the pressure vessel and replaced in the saturated CH bath until
testing. The samples used in the warping experiments were
245-252 days old. The samples used in the swelling
experiments were 279-280 days old.
2.2 Porosity
Porosity samples -2 - 3 cm long were cut from the
plates. Their dimensions were measured with digital
calipers (+10 gin). The saturated surface dry weights were
measured with a Denver Instruments M-220D balance
(=~0.01 rng) and the samples were immediately placed in an
oven at 105~ The weight of the samples was measured
periodically until the weight loss stabilized.
2.3 Beam-bending procedure
The beam-bending method [13] was used to measure the
permeability and mechanical properties of the paste. The
beam-bending apparatus was shown and described in [14] and
[15]. The displacement of the specimen was measured with a
linear variable differential transformer (LVDT, MacroSensors)
with a range of 10 mm and a sensitivity of 0.01 ~tm. The load
on the sample was measured with a load cell (+250 g
SENSOTEC). The calibration of the load cell and
displacement were verified by bending metal beams of known
elastic modulus. The temperature was monitored with two
Type K thermocouples, one taped to the frame of the
apparatus, one placed in the bath. The apparatus was controlled
with a computer running DasyLab 5.0 software (IOTech Inc.).
The displacement, load, and temperature were logged through
a 16-bit A/D converter. Data were recorded logarithmically,
with an initial sampling rate of 50 Hz.
The sample span (L) was 100 mm. The supports consist of a
recessed steel ball (diameter = 6.34 mm) with 0.5 mm relief,
and a pivoting steel cylinder (diameter = 6.34 ram). The
purpose of this support configuration is to prevent torsion. The
end of the push rod that contacts the sample is a steel ball
(diameter = 6.3 mm). The supports sit in a stainless steel bath
filled with a saturated CH solution. Plexi-glass plates placed
over the bath, in contact with the liquid, suppress waves
caused by displacement of the pushrod. The entire apparatus,
including the data acquisition hardware, is inside a Forma-
 J.J. VaIenza, G. W. Scherer / Materials and Structures (2005) 479-488 481

Scientific water-jacketed incubator. The temperature in the

incubator was held at 29 • 0.5~
Prior to performing the experiment it is necessary to find
the sample surface. The resolution of the stepper motor used
to translate the pushrod is 4-1 gm, which is two orders of
magnitude greater than the sensitivity of the LVDT
(0.01 gm). Therefore, the uncertainty in the position of the
probe relative to the sample surface is +1 gm. After
determining the position of the sample surface, the sample
was allowed to equilibrate for 1 h (-6 times the
hydrodynamic relaxation time, re). To ensure thermal
stability and equilibration of the sample, the load and
position of the pushrod were monitored throughout this time. Fig. 2a - Schematic design of warping apparatus. The optical probe
records vertical displacement of a foil reflector attached to the bottom
Five minutes of baseline data were taken at the end of the
surface of the sample.
equilibration period, then a sudden deflection (25 - 36 gin)
was imposed on the cement plate, and the load necessary to
sustain the deflection was measured; the displacement
stabilized in about 0.75 s. Experiments ran a minimum of
three times rR. After unloading the sample and prior to
terminating data acquisition, five minutes of baseline data
were logged to test for drift in the load cell reading.

2.4 Warping experiment

Fig. 2a shows a schematic of the apparatus used to detect
stresses when a pool of solution is frozen on the surface of
cement paste. The fiberboard outer box sits above an optical
probe (MTI Technologies - MTI 2000 Fotonic Sensor) on
six 1 cm Invar stilts; foam insulation is placed between the
box and the Invar support plate. Inside the outer box is a
copper box (125 x 35 x 35 mm) that contains the sample.
Foam insulation is placed in the front and back of the copper
box (Fig. 2b). At each end of the copper box is a 1 cm thick
copper block. A thermoelectric cooler (TEC) (Marlow
Industries - DT12-8-01LS) is sandwiched between the Fig. 2b - Photo of warping apparatus with sample in place, but with lid
and video camera removed. Aluminum blocks are penetrated by
copper block and a 1.5 cm aluminum block on each end of
channels for cooling water to remove heat from thermoelectric coolers
the apparatus. Heat is removed from the hot side of the TEC (TEC). A dam of vacuum grease around the perimeter of the sample
by a 50/50 - water/ethylene glycol mixture that is circulated contains a pool of solution on the top. The copper box and the
through the aluminum blocks by a refrigerated bath (Fisher surrounding insulation reduce temperature gradients to < 1~
Scientific - Isotemp 3006).
Inside the copper box the sample rests on Invar T- conductive tab (Ted Pella Inc. - 16084-1, normally used on
supports anchored to the havar plate. The optical probe passes SEM stubs). To prevent drying during the experiment, the
through three small holes drilled in the Invar plate, the bottom bottom and sides of the sample are covered with a light coating
of the outer box, and the bottom of the copper box. The of vacuum grease and then wrapped with plastic foil, with a
temperature inside the copper box and in the solution on the hole aligned over the aluminum reflector. A dam of vacuum
sample surface are monitored on both ends of the sample by grease is applied around the upper perimeter (Fig. 2b) and the
four type T thermocouples (TC) (OMEGA Engineering) sides of the plastic foil are wrapped around the edges of the
(Fig. 2b). The temperature of the optical probe and refrigerated sample.
bath are also monitored with type T TC. Two power supplies The typical thermal cycle during these experiments is
(Agilent Technologies - E3632A DC) provide power to the shown in Figs. 4 and 6. The temperature of the refrigerated
TECs. A borescope (Hawkeye Gradient Lens Corporation - bath and the power supplied to the TECs is controlled through
HH2700) connected to a closed-circuit camera (MicroImage a feedback control program written with DasyLAB V7.0
Video Systems - A206) is passed through a hole in the center software (IOTech). To insure temperature uniformity along
of the top of the copper box to permit video recording (-8 mm the sample length the power supplies axe individually
field of view) of the top of the sample. controlled. Data are logged every ten seconds through a 16-bit
The cement plate is rinsed with deionized water and the A/D converter.
dimensions are taken with Mitutoyo digital calipers (accuracy
0.01 mm). An aluminum reflector is attached to the center
of the sample's bottom (molded) surface using a carbon
482 J.J. Valenza, G.W. Scherer ~Materials and Structures (2005) 479-488

2.5 Salt swelling experiments

Salt swelling experiments were performed with a Perkin-
Elmer Dynamic Mechanical Analyzer (DMA) 7e. The
cement samples were cut to a height < 16 mm with a Buehler
ISOMET TM 1000 precision saw. A 50/50 water/ethylene
glycol mixture at 5~ was circulated through a heat
exchanger to keep the aluminum block that encompasses the
DMA furnace at a constant, low temperature (~ 10-11~
The salt solution was equilibrated in the DMA at room
temperature (~ 22.5~ Samples were measured, dried to a
saturated surface dry state, then placed in the sample holder.
The probe was lowered until it contacted the sample, then the
furnace assembly was raised, submerging the sample in the salt
solution. The sample temperature was held constant at room
temperature (22.5 + 0.5~ for the duration of the experiment.

2.6 X-Ray diffraction

X-Ray powder diffraction was performed with a gigaku
diffractometer. Patterns were collected at ambient Fig. 3 - Relaxation in applied force, W, as function of elapsed
temperature using CuK radiation in the 20 range 4 ~ - 60 ~ time, t, during beam-bending of a cement plate identical to
those used in the warping experiments. The relaxation results
with a 0.04 ~ step size. Samples were prepared by smearing
from equilibration of the pore pressure (represented by the
a thin layer of vacuum grease on a glass microscope slide, curve, Hydrodynamic) and from viscoelastic stress relaxation
and sprinkling a thick coating of finely ground cement paste in the solid phase (corresponding to the curve, Viscoelastic).
over the width of the vacuum grease (~1 cm.) To reduce
undulations in the sample topography the sample was then
compressed between the host slide and a second slide.

3. RESULTS

3.1 Properties of cement paste

The porosity, qb, of cement paste decreased from a mean
value of 45.26 + 0.41% at early ages (22-40 days), to 42.6%
at 496 days. The mean of these two values: r = 44%, is
used in the analysis of our experiments.
Fig. 3 shows the force relaxation curve for a beam-
bending experiment on a plate of cement paste of the same
type used in the warping experiments. The force, W,
required to sustain a fixed deflection of 36 gm on a span of
10 cm decreases as the pore pressure equilibrates, and as
the solid phase undergoes viscoelastic stress relaxation.
Each contribution is evaluated and their product yields the
total relaxation; the fit is nearly invisible under the data Fig. 4 - Deflection of plate of cement paste (2.9 mm thick) by a
points. The characteristic time for relaxation of the pressure layer of pure ice (3.1 mm thick). Temperature decreases in
gradient in the pore liquid is found to be rR -- 555 s. steps down to about-2~ where nucleation occurs. The
temperature of the lower surface drops while the upper
temperature is held at 0~ by heat of fusion as the water
3.2 Warping with pure water/ice freezes. When freezing is complete, the temperature drops
Fig. 4 shows the deflection of a plate of cement paste rapidly, resulting in a sudden deflection of about 50 ~tm.
Thereafter, the deflection shows oscillations corresponding to
2.9 mm thick when a pool of pure water freezes on its
the temperature cycles (see Fig. 5).
surface, creating a layer of ice 3.1 mm thick. Initially the
temperature is reduced stepwise from ambient to about
-2~ where nucleation of ice occurs. Following each solid phase, so it tends to retreat into the pores. On the
decrease in temperature, the sample deflects upward lower surface, this results in formation of liquid/vapor
(concave down) by -15 ~tm, then relaxes back flat. This is a menisci, so negative pressure develops in the pores; on the
result of the contraction of the pore liquid: as the top surface, the pool o f free liquid prevents menisci, so the
temperature drops, the liquid contracts much more than the pore liquid remains at atmospheric pressure.
 J.J. Valenza, G. W. Scherer / Materials and Structures (2005) 479-488 483

Consequently, a pressure gradient forms in the pores 3.3 Warping with NaCI brine
each time the temperature drops, and the suction in the
pores near the lower surface causes that side to contract and Fig. 6 shows the deflection of a plate of cement paste
produce an upward deflection of the plate. The pore suction similar to that used in Fig. 4, except that the liquid contains
draws liquid into the plate from the pool, so the gradient 7~ NaC1. Nucleation occurs at about 4~ but there is no
gradually decreases and the plate becomes flat. The time oscillation of the deflection as there was when pure ice formed.
required for the relaxation is about 15 minutes, which is in We attribute this to the weakness of the ice, which contains a
good agreement with the hydraulic relaxation time found on large proportion of unfrozen brine. As shown in Fig. 7, even at
the same sample using the beam-bending method. the lowest temperature of this experiment (-10~ there is still
After nucleation of ice occurs, the temperature of the --45 vol% unfrozen brine in the layer on top of the cement
water (Top thermocouple) remains at 0~ because of the paste [21], so the layer does not have enough stiffness to
release of heat of fusion, as freezing progress; meanwhile, deflect the plate. However there is a continuously increasing
the temperature of the box (Bottom thermocouple)
decreases. By the time that freezing is complete, the
temperature of the surrounding box is about -5~ so the
sample coots quickly, resulting in a deflection (concave
upward) o f - 5 0 / a m . This deflection results from the
thermal contraction of the ice, whose linear thermal
expansion coefficient is eq = 5.1 x 10S~ -1 [16, p. 114],
whereas that of the cement paste is ~q ~ 1.0 x 105~ -1 [17].
The radius of curvature, R, of a bimaterial plate by thermal
expansion mismatch was analyzed by Timoshenko [18].
The result can be written as [19]

ai+ac 6(m+lymn(ai-ac)(T-Tf) (1)

R -m4n 2+4m3n+6m2n+4mn+1

where a; and ac are the thicknesses of the ice and cement

paste layers, respectively, m = ai/ac; Young's moduli of the
layers are Ei and Ec, and n = EJE~; T=-temperature and Tf is
the freezing point. If the plate rests on supports separated
by a distance L, the deflection, A, of the top surface is Fig. 5 - The symbols are the measured deflection, A, of the
plate from Fig. 4 as temperature oscillates around -5.5~ The
C2 curve is calculated using Timosbenko's theory for a bimaterial
k = -- (2)
8R plate, Equation (1), using the known properties of the ice and
cement paste, and the measured temperature of the ice (Top T).
Fig. 5 shows the oscillations of the deflection as the
controller causes the temperature to cycle near -7.5~ There
is an upward drift in the baseline of about 7 gin/hour that
results from creep of the ice from the cement paste [20];
superimposed on that drift is the cycling resulting from the
bimaterial expansion mismatch. Using Equations (1) and (2),
the deflection expected from the measured temperature
variation can be calculated; the result is shown in Fig. 5. This
is an a priori calculation, not a fit to the data, as it was
obtained using the measured properties (G = 10 GPa [16, p.
108] and Ec = 16 GPa) and dimensions of the sample. The
calculated peak heights are slightly too high, largely as a
result of the creep of the ice that produces the upward drift in
the measured deflection. The deflection from expansion
mismatch is predicted to be 9.1 I,tm/~ which agrees with all
the rapid movements, where creep is not a factor, including
the large deflection (viz., 46 btm following a drop by 4.8~
occurring at N225 minutes in Fig. 4, and with each of the
other deflections following temperature drops (near 360, 430, Fig. 6 - Deflection of plate of cement paste (2.9 mm thick) by a
510, 560 minutes). water layer containing 7 wt% NaC1. In contrast to the pure ice
in Fig. 4, there is no oscillation of the deflection after freezing
occurs. Instead, there is a continuous upward deflection that
becomes steeper as the temperature decreases.
484 J.J. Valenza, G.W. Scherer / Materials and Structures (2005) 479-488

Fig. 7 - Volume fraction of ice formed in aqueous solution of

NaCI at the indicated concentration; data from [21].

upward deflection that becomes steeper as the temperature

decreases. At about 570 minutes in Fig. 6, the sample cracks; it
is held together by the ice layer until the temperature rises, Fig. 8 - Deflection of a plate of cement paste 2.9 mm thick
when a 4.6 molar solution is placed on its surface at room
then the sample falls onto the optical probe at -640 minutes.
temperature. The expansion caused by sodium nitrate (NaNO3)
When the box was opened, the sample was in three pieces. We is -35% as great as for sodium chloride (NaC1); neither
will show that this deflection results from swelling of the paste expansion is reversible. The deflection is positive (i.e., the
in contact with the salty liquid. plate is concave down), because the upper surface swells first;
as the salt diffuses into the plate and the interior begins to
3.4 Swelling in NaCl brine swell, the curvature decreases toward zero. The peak occurs in
about 700 minutes for the NaCI solution, corresponding to a
If a salt solution is placed onto the plate o f cement paste at diffusion coefficient o f - 5 x 10-11 mZ/s.
room temperature and held isothermally, the plate begins to
warp upward (becoming concave down); the amount o f
deflection increases with the concentration of salt [22]. As
shown in Fig. 8, the deflection is about 35% as great for a
solution of NaNO3 as for NaC1 at the same molarity (4.6 M).
The direction of warping indicates that the upper surface o f the
plate is expanding. As the salt diffuses into the plate and the
interior of the plate begins to dilate, the curvature decreases,
and will become flat again when the entire plate is uniformly
expanded. Assuming that the peak o f the deflection
corresponds to the time when the salt has diffused half way
through the plate, we can estimate the effective diffusion
coefficient as D ~ x2/t; given x ~ 1.5 mm and t ~ 700 min, we
f m d D ~ 5 x 10H m2/s.
To get a direct measurement of the amount o f swelling
caused by contact with the brine, a piece of a plate o f cement
paste (-3 x 14.5 x 21.4 mm) was immersed in aqueous NaC1 at
room temperature in a DMA. The swelling results in a strain o f
-5.5 x 10-4 after - 4 8 hours o f exposure, as shown in Fig. 9.
This is not an osmotic effect. If it were, one would expect
water to diffuse out of the sample to dilute the concentrated Fig. 9 - Linear strain of cement paste (-3 x 14.5 x 21.4 mm)
brine, resulting in negative pore pressure and contraction - not exposed to an aqueous solution of 17 wt% NaC1. The strain
expansion - o f the sample. Moreover, the suction in the pores approaches a constant value after -48 hours. Two experiments
would draw a flow of water from the unfrozen pool, and it on different samples are shown to be in excellent agreement.
would take only a matter of minutes to equilibrate the pressure,
since we have seen that the hydrodynamic relaxation time for 21% NaC1, no contraction was observed, so the expansion
this material is short. Based on the rapid viscoelastic stress seems to be entirely irreversible.
relaxation shown in Fig. 3, we estimate (see Appendix) that It has been observed previously that various types o f
25-30% of the strain in Fig. 9 can be attributed to creep. When cement expand upon exposure to salts [23]. Alkali adsorb
samples were re-exposed to limewater after equilibration in reversibly on C-S-H, apparently binding to deprotonated
 J.J. Valenza, G. W. Scherer / Materials and Structures (2005) 479-488 485

silanols [24, 25]; chloride adsorbs, largely irreversibly [26],
and simulations indicate that the primary adsorption site is
the surface of calcium hydroxide crystals [27]. After
equilibration o f a 3 mm-thick plate of paste in 21 wt% NaC1
for 24 h, we dried it and performed X-ray powder
diffraction (XRD). Comparing the pattern to a sample that
had not been exposed to the salt reveals that the only
differences are peaks corresponding to Friedel's salt [28],
as shown in Fig. 10. This suggests that part of the expansion
may result from crystallization pressure upon precipitation
of Friedel's salt, which results from reaction of chloride
with calcium aluminates. The expansion observed in
NaNO3 indicates that sodium adsorption also contributes to
the strain, since XRD performed on that sample indicated
no new phases.
is suggested by the observation that cements containing
higher C3A contents are more susceptible to scaling [1].
To see whether noticeable damage results from salt
exposure, we performed a beam-bending measurement on a
3 mm plate of paste, then soaked it in 21 wt% NaC1
solution for - 4 0 h, and repeated the measurement with the
sample immersed in the salt solution. As shown in Fig. 11
(Sample B), Young's modulus dropped by - 1 6 % (from
E = 17.1 to 14.6 GPa) and the permeability rose by - 2 5 %
(from 1.6 x 10 "21 m 2 to 2.0 x 10 -2~ m2). The sample was then
placed in limewater (i.e., water saturated with calcium
hydroxide) for 5 days and remeasured while immersed in
limewater; the properties showed a small additional
deterioration: E = 14.0 GPa and D = 2.1 x 10 21 m 2. These

4. DISCUSSION

The expansion of paste on exposure to salt solutions may

contribute to scaling damage. As an NaC1 solution freezes,
the remaining liquid becomes highly concentrated in salt;
regardless of the initial concentration of salt (as long as it is
> 0), when the temperature reaches -20~ the remaining
brine will contain the eutectic concentration o f - 2 1 wt%
NaC1. We can estimate the effective stress resulting from
that exposure. The linear strain reaches ex ~ 5.5 x 10 -4 in
Fig. 9; attributing - 3 5 % of this to the swelling of C-S-H by
adsorbed Na ions, and - 2 5 % to creep, the remaining strain
is -2.2 x 10 -4. The measured elastic modulus (from the
experiment in Fig. 3) is E = 16.6GPa; if we assume
Poisson's ratio for the paste to be v ~ 0.2, then the bulk
elastic modulus of the paste is K = E/[3(1-2v)] = 9.2 GPa.
The hydrostatic tensile stress that would be required to
produce this strain is ~x = 3 K ex ~ 6 MPa, which is
considerably larger than the tensile strength of the paste. If
that stress resulted from crystallization pressure exerted by
Friedel's salt, the sample should be damaged. A connection
between scaling damage and precipitation of Friedel's salt

Fig. 11 - Change in properties of cement paste after exposure to salt

Fig. 10 - X-ray powder diffraction for cement paste before and after
exposure to a solution containing 21 wt% NaC1. The ovals indicate the
main peaks of Friedel's salt, which appear after exposure to the
solution.
solutions: (a) permeability, D, and (b) Young's modulus, E. Sample
B was measured in limewater (CH), then soaked in 21 wt% NaC1 for
-40 h (NaC1 lSt), then -5 days in CH (NaC1 + CH), then soaked
again in NaC1 (NaC12nd). Sample A received the same treatment, but
the measurement was repeated after each treatment, to demonstrate
the excellent reproducibility of the results.
486 J.J. Valenza, G. W. Scherer / Materials and Structures (2005) 479-488
changes are modest, but they are well outside the typical
sample-to-sample variation for our bending measurements
(standard deviation ~ 10% of the mean [12]), where the
maximum stress on the sample is -0.8 MPa. This point is
demonstrated by Sample A in Fig. 11, where the
measurement was repeated after each change of pore fluid.
From the evident change in properties, we conclude that
some microcracking has resulted from the salt exposure.
However, it does not appear that a single exposure to a
concentrated salt solution causes extensive microcracking
of cement paste, so the stress from crystallization pressure
must be much less than the 6 MPa estimated above. The
damage might be worse for mortar, however, because the
paste will expand away from the aggregate, possibly
resulting in high local stresses.
The freezing experiments revealed another effect that may
be the most important factor in scaling damage: a layer of pure
ice causes severe warping of the sample owing to the
mismatch in thermal expansion in the bimaterial composite of
ice and paste. The stress produced from this mechanism can
amount to a few MPa, and increases as the temperature
decreases. Damage could result from shearing of asperities
from the surface at points where the ice and cement paste are
interlocked. However, a more likely mechanism is that the
frozen layer cracks, and the crack continues a short distance
into the concrete, resulting in superficial damage. A
mechanism of this kind is used to produce a decorative surface
on glass [29]: a layer of epoxy is spread on a plate of glass,
which is then cooled until the thermal expansion mismatch
causes the epoxy to crack; the cracks penetrate into the glass
and remove a thin layer, resulting in a scalloped surface. The
lower the temperature to which the body is cooled, the greater
the probability that the layer will crack, so this mechanism is
consistent with experiments which indicate that scaling
damage is worse when the minimum temperature of cooling is
lower [3, 30].
A layer of pure ice does not crack, even when held at -
18~ for several hours. This may explain why scaling is not
serious when pure water is used in the surface layer.
However, when any amount of salt is present, then the ice
contains pockets or channels of brine that constitute
mechanical flaws, and encourage fracture of the layer. This
could account for the pessimum: pure ice does not crack in
the temperature range used in scaling tests (typically down
to -20~ and high salt concentrations yield ice with so
much brine that they cannot impose significant stress at -
20~ however, intermediate salt contents permit
development of substantial stresses and contain flaws that
will promote cracking when the stress becomes high. This
will lead to damage from low to moderate salt
concentrations, but less damage at high concentrations.
The occurrence of cracking in a layer of ice made from a
3% solution of NaC1 is demonstrated by the photos that
were obtained by introducing a video camera lens through
the top of the box, as indicated in Fig. 2. The first cracks are
observed [22] when the temperature reaches -7.5~
weakening of the ice by the cracks results in upward
deflection because of the salt-induced swelling. Numerous
cracks are observed in the ice at the end of the experiment.
The bimaterial effect seems to account for most of the
phenomenology of scaling. Damage is seen only when there
is free liquid on top, because a certain thickness of ice is
needed to generate the stress. The pessimum results from
the mechanical properties of brine: pure ice is too strong to
break, but impure water freezes into ice containing brine
pockets that constitute mechanical flaws. This explains why
damage diminishes at high solute levels, where the ice is
too weak to exert appreciable stress, and why the nature of
the solute does not matter. Cracking of the ice creates
tensile stresses where the ice joins the surface of the paste
[29], and damage may therefore result from fatigue after
many cycles. On the other hand, salt-induced swelling
causes cycles of stress that create some microcracking,
thereby weakening the surface, and may cause buckling of
thin layers of paste over aggregate particles.
The beneficial effect of air entrainment is more difficult
to explain on the basis of either of these mechanisms. It
may be that air entrainment, by reducing bleeding, leads to
greater strength in the superficial layer of paste and thereby
reduces damage. It is also possible that the air voids provide
a site where crystals of Friedel's salt precipitated upon
exposure to NaC1 can grow without generating stress.
However, this remains to be proven, so the effectiveness of
air entrainment presents an important challenge to the
bimaterial or salt-swelling mechanism.
5. CONCLUSIONS
The warping experiment introduced in this study reveals
two important mechanisms that contribute to stress during
freezing of saline solutions on the surface of cement paste.
First, there is a large mismatch in the thermal expansion
coefficients of the materials, so that the frozen layer
develops high tension during cooling. We find that pure
water ice does not crack when cooled to -18~ on the
surface of cement paste. However, when the water contains
solute, the unfrozen liquid creates brine pockets that
weaken the ice and promote cracking; as in the glue-spall
process, the crack is expected to intersect the surface of the
paste and cause damage. This mechanism accounts for most
of the phenomenology of salt scaling: (i) the pessimum
occurs because pure ice doesn't crack and high solute
concentrations make the ice too weak to exert stress on the
paste; (ii) the pessimum is independent of the type of
solute, because any solute creates brine pockets in ice; (iii)
damage is in the form of flakes, as expected from the glue-
spall mechanism; (iv) damage requires free liquid, because
cracks can only form when a layer of ice is present; (v)
damage is worse when the minimum temperature is lower,
because the stress in the ice increases and more cracks
develop from smaller and smaller flaws; (vi) the exterior
salt concentration is more important than the composition
of the pore liquid, because the role of the solute is to create
brine pockets in the external ice layer.
The solute may play an additional role by contributing to
weakening of the surface of the paste. As the saline solution
freezes, it produces pure water ice plus a brine whose
 J.J. Valenza, G. W. Scherer / Materials and Structures (2005) 479-488
concentration increases as temperature decreases; for NaC1
solutions, the brine approaches the eutectic concentration o f
21 wt% at -21~ Exposure to sodium chloride solutions
causes expansion o f cement paste, and some microcracking
seems to result. One indication that other solutes, such as
alcohol, can damage the surface is the observation [15] that
immersion in pure isopropanol causes a hundred-fold
increase in the permeability o f cement paste. We are
currently examining the effect o f exposure to other solutes
on the properties o f cement paste.
ACKNOWLEDGEMENTS
This work was supported by National Science
Foundation Grant CMS-0200440.
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488 J.J. Valenza, G.W. Scherer / Materials and Structures (2005) 479-488

APPENDIX.
E X T R A P O L A T I O N OF CREEP CURVE

For a linearly viscoelastic material, the creep function can 1.3oi ........................................
be calculated from the stress relaxation function, so the data
from the beam-bending experiment can be used to predict the
creep rate of the paste. Of course, the calculation is accurate
only over the time scale over which the measurements were
made, but the logarithmic nature of the function permits a 1_0.9
relatively long extrapolation without serious error. The
mathematical details are discussed in [31]. The stress x

relaxation function, ~. is related to the creep function, r

through the Laplace transform: 9~ 0.85
1.10 ~ 9
L [~]= 1/(s 2 L [g/I) (3)
~ 0.8
1.05 ~ ~ ~ ~ ~
where s is the transform parameter [32] and L indicates the
transform with respect to time. The function ~ obtained by
beam-bending was used to generate a set of numerical values 1.00 . . . . . I 0.75
at logarithmic time intervals from 0.1 to 106 seconds, then o 5 lO' 1 lo' 1.5 lO' z 1r
those data were used to find L [ ~/] by numerically integrating t (s)

Fig. 12 - The right ordinate shows the stress relaxation function

LIt//]= j~e-st I//(t)dt (4)
Equation (3) was inverted numerically using Mathematica |
[33] to obtain ~b,with the result shown in Fig. 12. At the end of
two days of creep, comparable to the time scale in Fig. 9, the
creep strain is ~28%; that is, the total strain is ~1.28 times the
instantaneous elastic strain.
extrapolated to 48 hours; this is an extrapolation o f the data in
Fig. 3 from 4 x 103 to 2 x 105 s. The left ordinate shows the creep
function calculated from the stress relaxation data, as explained
in the Appendix. The result indicates that a sustained stress will
cause creep strain N1.28 times larger than the instantaneous
elastic strain.