ACI MATERIALS JOURNAL
Title No. 111-M55
Volume Stability of Calcium-Silicate-Hydrate/Polyaniline
Nanocomposites in Aqueous Salt Solutions
by Rahil Khoshnazar, James J. Beaudoin, Laila Raki, and Rouhollah Alizadeh
The volume stability of phase pure calcium-silicate-hydrates
(C-S-H) and C-S-H/polyaniline nanocomposites prepared with two
CaO-SiO2 molar ratio (C/S) variations (0.8 and 1.2) was assessed
in MgSO4, MgCl2, LiCl, and NaCl aqueous solutions. The change in
the crystalline structure of the samples with the time of immersion
was also explored using X-ray diffraction, scanning electron micros-
copy, and thermal gravimetric analysis techniques. It was observed
that the modification of the C-S-H samples with polyaniline signifi-
cantly enhanced their volume stability and durability in all the salt
solutions. The beneficial effect of the polyaniline modification was
more pronounced in the C-S-H host with higher C/S (C/S = 1.2).
The longitudinal expansion of the C-S-H/polyaniline nanocompos-
ites with C/S = 1.2 in the salt solutions was about 30% of that of the
phase pure C-S-H with a similar C/S ratio. In addition, the polyani-
line modification of C-S-H samples reduced the rate of formation of
gypsum, brucite, and other reaction products in the samples.
Keywords: calcium-silicate-hydrate (C-S-H); durability; nanocomposites;
volume stability.
INTRODUCTION
The primary binding phases in cement-based materials
are the calcium-silicate-hydrates (C-S-H). The engineering
performance of mortars and concrete is inextricably linked to
the nature of the binder systems. Characterization of the nano-
structure of C-S-H has been the focus of numerous research
investigations in the past decade as it is considered funda-
mental to the ultimate resolution of problems associated with
the durability and sustainability of concrete infrastructure.1-3
The possibility of tailoring the nanostructure of C-S-H in
cement binders to improve mechanical behavior and resistance
to aggressive media is feasible and rapidly evolving. Exam-
ples include designing the CaO-SiO2 molar ratio (C/S) of
the C-S-H in cement paste through the use of C-S-H seeds
and the development of organo-C-S-H nanocomposites.4
The main ideas for the synthesis of nanocomposite
materials incorporating organic polymers were originally
developed in clay science.5 The nanocomposites in these
investigations were prepared by the interaction of a clay
mineral with a layered silicate structure such as montmoril-
lonite and a polymer matrix. The resulting nanocomposites
were reported to have superior characteristics compared to
the individual clay mineral or the polymer.6-8 However, it
should be noted that any physical mixture of a polymer and
a layered silicate material did not necessarily form a nano-
composite. When the polymer was unable to intercalate the
silicate sheets, a phase-separated composite was obtained
whose properties were in a similar range as those of tradi-
tional microcomposites.9,10
ACI Materials Journal/November-December 2014
TECHNICAL PAPER
The modification of C-S-H, which has a layered silicate
nanostructure,11 employing organic moieties was first intro-
duced by Matsuyama and Young in 1999.12,13 They showed
how intercalation of polymers in the C-S-H structure during its
precipitation from supersaturated solution was possible. The
influence of structural variations of C-S-H was also demon-
strated. Examples of the polymers investigated included
nonionic poly-vinyl alcohol (PVA), anionic poly-acrylic
acid (PAA), and cationic poly-diallyldimethylammonium
chloride (PDC). Evidence for intercalated species was
provided based on the changes in the X-ray diffraction 002
basal spacing (d002). Characterization was performed using
29
Si NMR, thermal analysis, carbon content determination,
and other methods. Omission of bridging silica tetrahedra
at C/S above 1.3 was considered as a possible source for
the creation of additional interlayer space that could accom-
modate extended linear PVA chains. Additional evidence for
the intercalation of PVA and PAA in the C-S-H host material
was also provided by Mojumdar and Raki14 and Mojumdar
et al.15 Merlin et al.,16 however, reported no clear signs of
intercalation of cationic, anionic, or neutral water-soluble
polymers in C-S-H. They argued that the polymer was
adsorbed in significant amounts on the surface or in the void
space left by lamellae stacks.
Franceschini et al.17 described the production of organo-
C-S-H hybrids obtained by the reaction of copolymers of
polydimethylacrylamide and poly-butadiene-g-oxyethylene
silylated with T-silanes. Pellenq et al.18 discussed an
approach of grafting organic moieties on the mineral
lamellae by controlled hydrolysis of organo-silane precursor
mixtures or hydration of the anhydrous silicates in silanized
polymer solutions. An example was a layered hybrid calci-
um-silicate material incorporating organotriethoxysilane at the
end and at the middle of silicate chains of C-S-H. It would
appear that a modest amount of covalent hybridization of
the C-S-H with polymeric chains or organic groups had the
potential to generate a significant mechanical improvement of
these hydrates. Minet et al.19 described the synthesis of layered
calcium organosilicate hybrids that consisted of an inorganic
part analogous to that of smectites and a covalently linked
organic part of alkyl chains grafted to the Ca phyllosilicate part
through a Si-C bond organized in an all-trans conformation.
ACI Materials Journal, V. 111, No. 6, November-December 2014.
MS No. M-2012-379.R1, doi: 10.14359/51687127, received January 30, 2014, and
reviewed under Institute publication policies. Copyright 2014, American Concrete
Institute. All rights reserved, including the making of copies unless permission is
obtained from the copyright proprietors. Pertinent discussion including authors
closure, if any, will be published ten months from this journals date if the discussion
is received within four months of the papers print publication.
623
Fig. 1Schematic picture of aniline monomers (C6H7N) and polyaniline (C6H7N)n.
This study provides for the first time the assessment of
the durability of novel C-S-H/polyaniline nanocomposites
using original experimental evidence. The development of
new C-S-H-polyaniline nanocomposites has recently been
reported by the authors.20 The synthesis involved an in-place
polymerization technique that allows for an initial interaction
of monomers with the C-S-H followed by polymerization
using an external oxidant. The C-S-H/aniline and C-S-H/
polyaniline samples were characterized by the X-ray diffrac-
tion, 29Si NMR, thermal analysis, Fourier transform infrared
spectroscopy, and scanning electron microscopy techniques.
Evidence was obtained in support of the view that the aniline
and polyaniline were formed in two different locations of the
C-S-Hgrafted on the surface and partially intercalated in
the interlayer regions. It was also suggested that the poly-
aniline might be arranged between the C-S-H layers in a
way that the benzene ring was oriented parallel to the sheets.
The monomer molecules, however, had random positions in
various directions. A schematic picture of aniline monomer
(C6H7N) and polyaniline (C6H7N)n are presented in Fig. 1.
Key objectives inherent in the development of C-S-H
nanocomposites are the realization of enhanced engineering
properties and improvement in the durability characteris-
tics of cement-based materials. This study focuses on the
latter. The primary objective is to demonstrate that polymer
C-S-H nanocomposites can improve the volume stability
of cement-based materials in aggressive media. The results
of length-change and microstructural change of C-S-H/
polyaniline nanocomposites in aqueous salt solutions
(MgSO4, MgCl2, LiCl, and NaCl) typical of those central
to many durability issues are reported. An assessment of the
ability of the polymer to seal the C-S-H system from the
ingress of deleterious ionic species is presented.
RESEARCH SIGNIFICANCE
Volume stability and durability of concrete in aggressive
environments has long been a main concern of material
scientists and engineers. Hydrated cement phases are known
to contribute to most of the durability problems. Modifica-
tion of current hydrated cement phases and the development
of novel materials with enhanced durability is, therefore, a
primary objective for obtaining more durable concrete infra-
structure. It is suggested in this study that the interaction of
C-S-H, a primary hydrated cement phase, with organic poly-
mers can effectively improve volume stability and durability
of this phase in aggressive salt solutions.
EXPERIMENTAL PROCEDURE
Synthesis of phase pure and modified C-S-H
C-S-H with C/S of 0.8 and 1.2 were synthesized by mixing
the stoichiometric amounts of calcium oxide (CaO) and
624
silica (SiO2) in excess water (water/solid mass 10).13 The
CaO was freshly calcined from the reagent-grade calcium
carbonate at 900C (1650F). Reactive SiO2 was heated at
110C (230F) in order to remove any surface-adsorbed
water. De-ionized out-gassed water (75 mL [0.02 gal.])
was added to the solid mixture of CaO and SiO2 (2.24 g
[4.9 103 lb] of CaO and 3.00 g [6.6 103 lb] of SiO2 for
the sample with C/S = 0.8, and 3.37 g [7.4 103 lb] of CaO
and 3.00 g [6.6 103 lb] of SiO2 for the sample with C/S
= 1.2). C-S-H/aniline powder was also prepared in a method
similar to that used for the phase pure C-S-H, except that the
water contained aniline monomer (2 mL [5.3 104 gal.] of
aniline in 75 mL [0.02 gal.] of water). This solution was then
added to the dry mixture of the CaO and SiO2 in the high-
density polyethylene (HDPE) bottles to initiate the pozzo-
lanic reaction. All the bottles were mounted on a rotating rack
(speed = 16 rpm). The solution was filtered after 90 days. The
drying procedure of these samples included two steps: 4 days
of vacuum drying (5 mmHg), followed by conditioning in
desiccators at the relative humidity of 11%. Both steps were
performed at room temperature. The samples were considered
to be in equilibrium when they reached a constant mass.
Ammonium persulfate ((NH4)2S2O8 from Sigma-
Aldrich, 98% purity) was used as an external oxidant in order
to polymerize the aniline monomers. Dried C-S-H/aniline
powder (0.5g [1.1 103 lb]) was first mixed in 100 mL
(0.026 gal.) of water using a magnetic stirrer. Then 0.228g
(5 104 lb) of ammonium persulfate was added while stirring
the suspension solution. The stirring continued for 3days at
room temperature. The final material was filtered and washed
several times to remove the unreacted ions. It was then dried
under vacuum at room temperature for 4 days, and then equili-
brated at the relative humidity of 11%. It was estimated, based
on the thermal analysis, that the polyaniline content was about
3% in the C-S-H/polyaniline preparations.
Test solutions
The test solutions prepared for the dimensional stability
and durability assessments included MgSO4 (hepahydrate),
MgCl2 (decahydrate), LiCl and NaCl with the concentration
of 15 g/L (0.125 lb/gal.). All the salts were the reagent grade.
Experiments
The phase pure and modified C-S-H powders were
compacted into porous bodies in the form of circular discs
(32 mm [1.3 in.] in diameter by 1 mm [0.04 in.] thick).
The compaction pressure was adjusted to obtain a porosity
of 30% for all the samples. The porosity of the compacted
samples was determined using a Beckman helium pycnom-
eter.21,22 The use of compacts of hydrated portland cement
ACI Materials Journal/November-December 2014
Fig. 2Schematic picture of length change measurement setup: (a) whole setup; and (b) details of Tuckerman extensometer.
and synthetic C-S-H powders in the investigation of engi-
neering performance is well established.23-26
Prisms (5 x 25 x 1 mm [0.2 x 1 x 0.04 in.]) were cut from
the compacted discs and mounted on modified Tuckerman
extensometers with an accuracy of 1 microstrain. These
were then placed in small containers including the test solu-
tions so that the specimens were completely immersed. The
ratio of the solid to the solution was 1 g of solid per 50mL
(0.167 lb of solid per 1 gal.) of solution. The whole setup
was placed in sealed desiccators containing the same salt
solution as the test solution to avoid evaporation. The length
change of the samples in each solution was measured at least
for 7 days as almost all the samples exhibited a plateau in
the strain-time curves at this age. The schematic picture of
the set up for length-change measurements is presented in
Fig. 2. The length-change measurements were repeated two
times on two different samples.
In addition to the length-change measurements, several
samples of the C-S-H preparations were immersed in the test
solution for 2 hours, 8 hours, 1 day, 3 days, and 24 days to
investigate any change in the microstructure of the samples
during the time of immersion. The solid-solution ratio in
this case was exactly the same as that in the length change
measurements. The solution was filtered and the powder was
kept at the relative humidity of 11% for 48 hours to reach
equilibrium before starting the characterization by X-ray
diffraction (XRD), scanning electron microscopy (SEM),
and thermal gravimetric analysis (TGA).
The XRD patterns were 6collected with a diffraction angle
range of 6 < 2 < 60 degrees using a step size of 0.08degrees
at a 5-second count interval. Intensities were then normal-
ized according to the mass of the samples. SEM images
were collected using a field emission scanning electron
microscope. Surface structure images were taken using a
beam current of 10 mA at 3.2 1016 J (2 kV). Images were
obtained at a working distance of 4 mm (0.157in.). TGA
was performed from room temperature to 1000C (1832F)
at a rate of 10C/min (18F/min) under the flow of nitrogen
gas (10 mL/min [0.3 fl oz/min]). The derivative mass loss
and heat flow were determined.
ACI Materials Journal/November-December 2014
RESULTS AND DISCUSSION
Length-change measurements
All the samples expanded following immersion in the
salt solutions. The amount of expansion, however, was
noticeably different for the phase pure C-S-H samples and
the nanocomposites. It is suggested based on the strain-
time curves plotted in Fig. 3 that the expansion of phase
pure C-S-H (C/S = 1.2) samples was quite significant in all
the solutions. The expansion of this sample in MgSO4, for
example, was approximately 3.4% after 7 days. The expan-
sion of modified C-S-H samples (C/S = 1.2) in all the test
solutions was considerably lower than that of the C-S-H
(C/S = 1.2) itself. The 7-day expansion of the C-S-H/aniline
samples (C/S=1.2) in different solutions was approxi-
mately 37 to 52% of that observed for the phase pure C-S-H
(C/S=1.2). The C-S-H/polyaniline samples with C/S = 1.2
were even more stable. The expansion of the C-S-H/polyani-
line samples (C/S = 1.2) after 7 days was approximately 20
to 30% of the expansion of phase pure C-S-H (C/S = 1.2).
It is suggested that dissolution and leaching of lime from
the structure is likely the main mechanism responsible for
the expansion of C-S-H preparations in the salt solutions.
The dissolution process of porous materials, which includes
break-down of the structure and leaching of the constit-
uent ions into the solution,27 was previously shown to be
an expansive process for porous glass samples immersed in
sodium hydroxide and cement paste samples treated with
acids.28,29 It was suggested that expansion accompanying
dissolution can be caused by changes to the surface-free
energy of the solid phase, gradients in the concentration of
dissolved species in the pore solution resulting in osmotic-
like pressures, disjoining pressure resulting from double
layer effects outside the surface generating repulsive forces,
and release of strain-energy stored in the sample.29 Beau-
doin et al.30,31 also suggested that samples of cement paste
or calcium hydroxide can expand in aggressive solutions
due to the dissolution process. Additional evidence on
the role of a dissolution mechanism on the length change
of cement-based phases was also obtained by Khoshnazar
et al.32 For example, the expansion of synthetic ettringite and
625
Fig. 3Strain of pure C-S-H, C-S-H/aniline, and C-S-H/polyaniline samples (C/S = 1.2) in aqueous solutions.
monosulfate samples in de-ionized water as well as in satu-
rated gypsum and lime solutions could only be explained by
the dissolution mechanism. The higher values of expansion
of monosulfate compared to those of ettringite were also in
conformity with the higher solubility of monosulfate than
that of ettringite in the aqueous solutions at 25C (77F).33
Intercalation of some water molecules into the layered
structure of C-S-H may be a source of expansion, although
at 11% relative humidity, many of the interlayer positions
are filled.34 Lime leaching, however, results in some defect
points in the structure of C-S-H which can facilitate the
entry of water molecules and ionic species into the interlayer
space. The entry of ionic species into the interlayer region of
the C-S-H structure can also cause expansion.35
Adsorption on hydrated silicate surfaces is generally
expansive. This is commonly known as the Bangham
effect which relates length change to change in surface-free
energy.34 It has, however, been previously shown that the
effect of surface adsorption on the expansion of hydrated
portland cement is less significant than the effect of lime
leaching and intercalation phenomena.26,34 Formation of
gypsum and brucite crystals on the samples immersed in the
sulfate and magnesium salt solutions may also be expansive.
There is not, however, a general agreement on the possibility
of expansion of C-S-H due to the formation of these crys-
tals.35-37 The formation of these crystalline products on the
samples will be discussed in greater detail later.
The lower expansion of modified C-S-H samples
(C/S = 1.2) is possibly due to its higher level of silicate
polymerization, and the fewer defects in their structure due
to the shielding effect of organic materials adsorbed at the
defect locations on the surface of the C-S-H.20,38 The defects
626
can serve as the access points for the migration of water
molecules and ionic species into the layered structure of
C-S-H. The fewer the defects, the lower the rate of entry of
water molecules and ionic species into the interlayer space.
In addition, the rate of dissolution of lime from the C-S-H
structure would be slower as the entry of the interlayer water
occurs primarily at the end of the layers.26 Either of these
mechanisms can result in the reduction of the expansion.
The strain versus time of immersion in the salt solutions
for the phase pure and modified C-S-H samples with C/S of
0.8 is presented in Fig. 4. C-S-H/polyaniline nanocomposites
(C/S = 0.8) had a greater volume stability than the phase
pure C-S-H (C/S = 0.8). The expansion of C-S-H/polyaniline
nanocomposite samples (C/S = 0.8) after 7 days of immer-
sion in the salt solutions was approximately 40 to 50% of that
observed for the phase pure C-S-H samples depending on the
type of the salt solutions. The intercalation of aniline mono-
mers was not as effective as the polymers. The expansion of
C-S-H/aniline (C/S = 0.8) was approximately 80 to 95% of
that of phase pure C-S-H.
The influence of aniline and polyaniline intercalation in
the control of the expansion of C-S-H (C/S = 0.8) is also
likely due to its effect on increasing the silicate polymer-
ization level as described above for C/S = 1.2. It should
also be noted based on the comparison of Fig. 3 and 4 that
the expansion of phase pure and modified C-S-H samples
(C/S = 0.8) was generally lower than that of the samples with
C/S = 1.2. This was expected considering the higher silicate
chain length and the greater frequency of bridging tetrahedra
occurring in the structure of low-lime C-S-H (C/S = 0.8),38
which in turn makes its structure more resistant to the inter-
calation of water molecules and ionic species.
ACI Materials Journal/November-December 2014
Fig. 4Strain of pure C-S-H, C-S-H/aniline, and C-S-H/polyaniline samples (C/S = 0.8) in aqueous solutions.
Microstructural characterization of samples with
C/S = 1.2
Immersion in MgSO4 solutionThe microstructure of
phase pure C-S-H, C-S-H/aniline and C-S-H/polyaniline
samples was characterized by the XRD, TGA, and SEM after
2 hours, 8 hours, 1 day, 3 days, and 7 days of immersion in
the MgSO4 solution. Sharp peaks of gypsum crystals were
detected in the XRD pattern of phase pure C-S-H as early as
2 hours after immersion in the MgSO4 solution. No gypsum
peaks were detected in the XRD pattern of the samples with
aniline and polyaniline at this early immersion time. These
peaks with very low intensity, however, were detected in
the XRD patterns of C-S-H/aniline and C-S-H/polyaniline
samples after 8 hours, as shown in Fig. 5. In addition to
gypsum, brucite was also formed in the phase pure C-S-H
sample (C/S = 1.2), but not in the samples modified by aniline
or polyaniline after 8 hours of immersion in MgSO4 (Fig. 5).
The formation of gypsum and brucite crystals is an indica-
tion of lime leaching from the phase pure C-S-H sample. It is,
therefore, suggested that the lime leaching would be limited in
the C-S-H/aniline and C-S-H/polyaniline samples.
It was also suggested based on the XRD patterns of Fig.5
that the intensity of the peak at the basal spacing of 1.14 nm
(4.49 108 in.) of the phase pure C-S-H (C/S = 1.2) was
significantly reduced once the sample was immersed in the
MgSO4. This indicates the reduction of the crystallinity of Fig. 5XRD patterns of (a) control phase pure C-S-H,
the phase pure C-S-H sample after immersion in the MgSO4 C-S-H/aniline, and C-S-H/polyaniline samples (C/S = 1.2);
solution, which can be caused by leaching of lime from this and (b) samples immersed in MgSO4 solution for 8 hours.
sample. The intensity of the peak corresponding to the d002
basal spacing of the C-S-H/aniline and C-S-H/polyaniline

ACI Materials Journal/November-December 2014 627


Fig. 6SEM micrographs of (a) phase pure C-S-H; (b)
C-S-H/aniline; and (c) C-S-H/polyaniline samples (C/S = 1.2)
immersed in the MgSO4 solution for 8 hours.
Fig. 7TGA curves of (a) control phase pure C-S-H, C-S-H/
aniline, and C-S-H/polyaniline samples (C/S = 1.2); and (b)
the samples immersed in MgSO4 solution for 8 hours. (Note:
C = 5/9 F 32.)
(C/S = 1.2), however, was not noticeably changed by the
immersion in the MgSO4 solution.
The SEM micrographs for the samples immersed in
MgSO4 after 8 hours of immersion are presented in Fig. 6.
Gypsum crystals are detected in the phase pure C-S-H and
C-S-H/aniline samples (C/S = 1.2). No sign of the formation
of gypsum crystals was detected in the C-S-H/polyaniline
sample (C/S = 1.2) tested by the SEM.
The formation of new crystalline products due to the
immersion of the samples in MgSO4 solution was quanti-
tatively examined using the TGA technique (Fig. 7). The
percentages of gypsum and brucite formed on the samples
are provided in Table 1. It is known that gypsum decom-
poses at temperatures of about 130C (266F).39 Brucite
decomposes at a temperature of about 385C (725F).40 It is
possible to capture the formation of even a small percentage
of these crystals in the sample by the TGA. It is suggested that
about 7.3% of gypsum and 1.1% of brucite was formed in the
phase pure C-S-H (C/S = 1.2) after 8 hours of immersion in
MgSO4. These amounts were reduced to 1.1% gypsum and
628
Table 1Percentage of gypsum and brucite crystals
formed in C-S-H preparations (C/S = 1.2) after 8 hours
of immersion MgSO4, estimated by TGA technique
Amount of gypsum and brucite formed, % by mass
Sample Gypsum Brucite
C-S-H 7.3 1.1
C-S-H/aniline 1.1 0.58
C-S-H/polyaniline 0.9
0.58% brucite for the sample with aniline, and 0.90% gypsum
in the sample with polyaniline. No brucite was detected by the
TGA in the C-S-H/polyaniline (C/S = 1.2).
Immersion in MgCl2 solutionThe XRD patterns of phase
pure and modified C-S-H (C/S = 1.2) immersed in MgCl2 for
7 days are presented in Fig. 8. The intensity of the d002 basal
spacing of the high-lime phase pure C-S-H sample was signifi-
cantly reduced due to the immersion in the MgCl2 solution which
is an indication of significant lime leaching and collapse of the
microstructure of this sample. In addition, peaks corresponding
to brucite were detected on this sample. The d002 basal spacing of
the C-S-H/aniline sample (C/S = 1.2) was also reduced in inten-
sity due to the immersion in MgCl2 due to the lime leaching.
No brucite, however, was detected in this sample by the XRD.
The d002 basal spacing of the C-S-H/polyaniline sample with
C/S = 1.2 was unchanged by the immersion in the MgCl2 solu-
tion. Brucite peaks were not detected in this sample either. This
is in conformity with the length change results suggesting the
significant enhancement of volume stability of C-S-H/polyani-
line samples with C/S = 1.2 compared with that of the C-S-H/
aniline and the phase pure C-S-H samples with similar C/S.
Additional peaks were observed in the XRD patterns of the
samples immersed in MgCl2, especially in the XRD patterns
of C-S-H and C-S-H/aniline. These peaks correspond to
calcium carbonate crystals which were formed due to the
reaction of calcium leached out of the sample and carbonate
in the air during the preparation of the samples for the test.
The rapid formation of calcium carbonate crystals in the
samples is also a result of lime leaching. The rate of forma-
tion of calcium carbonate crystals is also affected by the
specific surface area of the samples. The nitrogen Brunauer-
Emmett-Teller (BET) surface area of C-S-H/aniline
(C/S = 1.2) was 107.6 m2/g (75.8 106 in.2/lb), which
was considerably higher than that for phase pure C-S-H
(41.4m2/g [29.1 106 in.2/lb]) and C-S-H/polyaniline
(54.3m2/g [38.3 106 in.2/lb]) with similar C/S. No signifi-
cant change could be detected by the SEM in the morphology
of these samples after the immersion except the formation
of some calcium carbonate crystals on the surface of the
samples (Fig. 9). Calcium carbonate crystals were mainly
formed in the form of calcite and aragonite on the phase pure
C-S-H and C-S-H/polyaniline samples, respectively. Both of
these crystals were, however, detected on the C-S-H/aniline
sample. This might be due to the changes in the surface area
of the samples, the concentration of lime leached out of
the samples, as well as the pH in different solutions, which
could favor the formation of one crystal rather than the other.
Results obtained using the TGA technique for the C-S-H
preparations (C/S = 1.2) immersed in MgCl2 were also in
ACI Materials Journal/November-December 2014

Fig. 8XRD patterns of (a) control phase pure C-S-H,
C-S-H/aniline, and C-S-H/polyaniline samples (C/S = 1.2);
and (b) samples immersed in MgCl2 solution for 7 days.
Peaks correspond to calcium carbonate crystals.
conformity with those of the other techniques, suggesting the
greater resistance of C-S-H/aniline and especially C-S-H/
polyaniline samples to the formation of new crystalline
products compared to that of phase pure C-S-H (Fig.10).
The amount of brucite based on the TGA was estimated as
1.7% for the phase pure C-S-H (C/S = 1.2) and 0.28% for
the C-S-H/aniline (C/S = 1.2). No brucite was detected in the
sample with polyaniline.
Immersion in LiCl and NaCl solutionsThe XRD patterns
of the C-S-H samples (C/S = 1.2) immersed in the LiCl and
NaCl solutions after 7 days did not show any significant
change in the crystalline structure except the formation of
some calcium carbonate peaks which had a considerably
lower intensity in the C-S-H/polyaniline compared to that
in phase pure C-S-H and C-S-H/aniline (C/S = 1.2). The
XRD patterns of these samples immersed in LiCl solution
for 7days are presented in Fig. 11. Less damage to the
crystalline structure of the samples immersed in LiCl and
NaCl solutions compared to those in MgSO4 and MgCl2
solutions is in conformity of the length-change measure-
ments suggesting the greater volume stability of the samples
immersed in the two former solutions.
The results of SEM and TGA techniques for the C-S-H-
based samples (C/S = 1.2) immersed in LiCl and NaCl
solutions did not show any significant change in the micro-
structure of the samples except the formation of calcium
carbonate crystals. The quick formation of these crystals is
an indication of lime leaching of the samples. The results
ACI Materials Journal/November-December 2014
Fig. 9SEM micrographs of (a) phase pure C-S-H; (b)
C-S-H/aniline; and (c) C-S-H/polyaniline samples (C/S = 1.2)
immersed in MgCl2 solution for 7 days.
Fig. 10TGA curves of (a) control phase pure C-S-H,
C-S-H/aniline, and C-S-H/polyaniline samples (C/S = 1.2);
and (b) samples immersed in MgCl2 solution for 7 days.
(Note: C = 5/9 F 32.)
of these two techniques also support the argument that the
amount of calcium carbonates formed on the C-S-H/poly-
aniline (C/S = 1.2) was considerably less that that formed
in phase pure C-S-H and C-S-H/aniline sample (C/S = 1.2).
Microstructural characterization of samples with
C/S = 0.8
Characterization by the XRD, SEM and TGA was
also performed on the C-S-H preparations with C/S = 0.8
immersed in various aggressive solutions for different time
intervals (2 hours to 7 days). No evidence of the formation
of new products was detected by the XRD technique for the
C-S-H samples (C/S = 0.8) after 8 hours of immersion in
MgSO4. The XRD patterns showed that gypsum crystals
were formed on the phase pure C-S-H sample (C/S = 0.8)
after 1 day of immersion. The gypsum formation, however,
was delayed to approximately 3 days for the C-S-H/aniline
sample and to approximately 7 days for the C-S-H/poly-
aniline samples (C/S = 0.8). The XRD patterns of phase
pure and modified C-S-H samples (C/S = 0.8) immersed in
629

Fig. 11XRD patterns of (a) control pure C-S-H, C-S-H/
aniline, and C-S-H/polyaniline samples (C/S = 1.2); and
(b) samples immersed in LiCl solution for 7 days. Peaks
correspond to calcium carbonate crystals.
MgSO4 for 7days are compared in Fig. 12. It is suggested,
based on the data in the figure, that the modified C-S-H
with C/S = 0.8 performed better than the phase pure C-S-H
(C/S = 0.8) in the MgSO4 solution. The gypsum peaks
formed after 7 days in the C-S-H/aniline sample (C/S = 0.8)
were significantly less intense than those formed in the phase
pure C-S-H sample (C/S = 0.8). These peaks were almost
negligible for the C-S-H/polyaniline sample (C/S = 0.8) after
7days of immersion. No brucite peaks were detected on any
of the samples even after 7 days. These results were also
confirmed by the SEM and TGA.
The microstructure of the samples (the phase pure or
the modified C-S-H sample) with C/S = 0.8 was almost
unchanged up to 7 days of immersion in other solutions.
The improvement of the durability of the C-S-H (C/S = 0.8)
samples by the aniline or polyaniline modification was not,
therefore, readily discernible although the length-change
curves provide clear evidence that modified systems are
superior. It is suggested that the damage to the microstruc-
ture of the samples with C/S=0.8 was generally less than
that of the samples with C/S=1.2 samples. It confirms the
results of the length-change measurements, and is because
of the higher degree of polymerization in the samples with
lower C/S.
CONCLUSIONS
The length change of phase pure C-S-H and C-S-H
modified with aniline and polyaniline due to immersion
in the MgSO4, MgCl2, LiCl, and NaCl aqueous solutions
was assessed. The formation of crystalline products on the
630
Fig. 12XRD patterns of (a) control phase pure C-S-H,
C-S-H/aniline, and C-S-H/polyaniline samples (C/S = 0.8);
and (b) samples immersed in MgSO4 solution for 7 days.
samples was also explored by the XRD, SEM and TGA tech-
niques. Two different C/S (0.8 and 1.2) were considered. The
main conclusions are as follows:
1. Lime leaching from the structure of C-S-H samples, espe-
cially from the high-lime samples, is likely to be the main mech-
anism underlying their expansion in the salt solutions studied.
2. The formation of new products such as gypsum and
brucite, the generation of pressure due to crystal growth, or
swelling pressure due to intercalation phenomena are possible
additional mechanisms that may contribute to expansion.
3. The expansion of C-S-H nanocomposites in the test solu-
tions was considerably lower than that of the phase pure C-S-H.
4. The formation of crystalline productsfor example,
gypsum and brucitewas limited in the C-S-H/aniline and
C-S-H/polyaniline samples.
5. Modification of C-S-H with aniline and polyaniline is
more effective in improving the volume stability when the
host C-S-H has a higher C/S.
6. Intercalation of polyaniline within the C-S-H layers
(for both C/S) had a greater effect on the volume and micro-
structural stability of the C-S-H samples compared to that of
aniline monomers.
AUTHOR BIOS
ACI member Rahil Khoshnazar is a Doctoral Student in civil engineering
at the University of Ottawa, Ottawa, ON, Canada. Her research inter-
ests include the nanostructure and durability of hydrated cement phases,
cement-based nanocomposites, and volume stability of sulfoaluminate
phases in cement paste.
ACI member James J. Beaudoin is a Researcher Emeritus at the National
Research Council of Canada, Windsor, ON, Canada. He received the ACI
Wason Medal for Materials Research in 1999. His research interests include
ACI Materials Journal/November-December 2014
the relationship between the nanostructure of hydrated cement phases and their
engineering properties.
ACI member Laila Raki is a Senior Research Officer at the Nation Research
Council of Canada. She is a member of ACI Committee 236, Material
Science of Concrete. Her research interests include the nanostructure of
hydrated cement phases and polymer nanocomposite technologies.
ACI member Rouhollah Alizadeh is the CEO of Giatec Scientific Inc., Canada,
and an adjunct professor in the Department of Civil Engineering at the Univer-
sity of Ottawa. He is a member of ACI Committee 236, Material Science of
Concrete. His research interests include the nanostructure of hydrated cement
phases, durability of concrete, and infrastructure sustainability.
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