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CEMCON-05034; No of Pages 18

Cement and Concrete Research xxx (2015) xxxxxx

Contents lists available at ScienceDirect

Cement and Concrete Research


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

Investigation of the changes in microstructure and transport properties


of leached cement pastes accounting for mix composition
Quoc Tri Phung a,1,, Norbert Maes a,2, Diederik Jacques a,3, Geert De Schutter b,4, Guang Ye b,c,5
a
b
c

Institute for Environment, Health, and Safety, Belgian Nuclear Research Centre (SCKCEN), Boeretang 200, B2400 Mol, Belgium
Magnel Laboratory for Concrete Research, Department of Structural Engineering, Ghent University, B9052 Ghent, Belgium
Microlab, Faculty of Civil Engineering and Geosciences, Delft University of Technology, P.O. Box 5048, 2600 GA Delft, The Netherlands

a r t i c l e

i n f o

Article history:
Received 21 May 2015
Accepted 22 September 2015
Available online xxxx
Keywords:
B. Characterization
B. Microstructure
C. Transport properties
D. Cement paste
Leaching

a b s t r a c t
Ca-leaching of cement-based materials induces detrimental effects on properties related to long-term durability. A
better understanding of leaching degradation in terms of alterations in mineralogy, microstructure, and transport
properties is important for long-term assessments of concrete and reinforced concrete structures used in nuclear
waste disposal systems or in hydro structures. However, the decalcication process is not easy to study because
it is extremely slow. In this study, an ammonium nitrate (NH4NO3) solution of 6 mol/l was used to accelerate the
leaching kinetics. The experiments were performed on cement paste samples with different water/powder (w/p)
and limestone ller (LS) replacement ratios. Both the change of sample mass over time and the amount of calcium
ion leached out were monitored during the test. Different post-analysis techniques including SEM/SEM-EDX, XRD/
QXRD, MIP, ion chromatography, and N2-adsorption were used to characterize the microstructural and mineralogical changes. The effect of accelerated leaching on transport properties was studied by measuring the changes in
water permeability and diffusivity of dissolved gases. Results showed that the square-root-time law of degradation
was applicable under accelerated conditions. Both higher w/p ratios and LS replacements increased the rate of
leaching propagation; the former had a more signicant effect. The accelerated leaching signicantly altered the microstructure of the cement paste to a material with a higher specic surface area, increased total porosity and a shift
to larger pore sizes. Those changes led to a signicant increase in water permeability (one to two orders of magnitude) and diffusivity (less than one order) depending on degradation state.
2015 Elsevier Ltd. All rights reserved.

1. Introduction
Ca-leaching in cement matrices is a dissolutiondiffusion driven
process when the cement is in contact with a low pH or low alkaline solution. The typical pH of a cement pore water solution is about 12.513.
Therefore, in almost any environmental condition, surrounding waters
(e.g., rain water, soil water, and ground water) could be considered as
aggressive environments leading to Ca-leaching (e.g. [1]). Although an
extremely slow process under natural conditions (few mm leaching
front in a few hundreds of years [2]), Ca-leaching could be an important
degradation process for reinforced concrete structures if a long service
life is required (e.g. nuclear waste disposal system, or in hydro structures (dam, bridge, water tank)).
Corresponding author.
E-mail addresses: QPhung@skcen.be (Q.T. Phung), NMaes@sckcen.be (N. Maes),
DJacques@sckcen.be (D. Jacques), Geert.DeSchutter@ugent.be (G. De Schutter),
G.Ye@tudelft.nl (G. Ye).
1
Tel.: +32 14 333120; fax: +32 14 323553.
2
Tel.: +32 14 333235; fax: +32 14 323553.
3
Tel.: +32 14 333209; fax: +32 14 323553.
4
Tel.: +32 9 2645521; fax: +32 9 2645845.
5
Tel.: +31 15 2784001; fax: +31 15 2786383.

To study experimentally the long-term durability of concrete subjected to a slow degradation process, imposing accelerated leaching
conditions is a relevant approach to quantify the effects of leaching on
the alteration in microstructure and transport properties. A variety of
accelerated methods have been proposed such as applying an electrical
eld [3], using deionized water [4,5], using low pH solutions [6,7], applying ow-through conditions [8], or using high concentration ammonium nitrate (NH4NO3) solutions [9,10]. The latter is one of the most
popular methods. Leaching in a NH4NO3 solution leads to faster degradation compared to the other methods under diffusive-transport conditions while it gives the same end-products. For example, Carde et al. [9]
compared leaching of CEM I cement paste with a water/cement (w/c)
ratio of 0.5 using deionized water and ammonium nitrate solution. In
both setups, leaching leads to complete portlandite dissolution in the
degraded zone and to a progressive decalcication of C-S-H, but degradation rates are about two orders of magnitude faster with ammonium
nitrate. Importantly, porosity changes are identical at the same leaching
degree for both conditions. Besides being a low pH solution, NH4NO3 increases the solubility of the leachable phases in cementitious matrix
(e.g. portlandite, calcium silicate hydrate (C-S-H), monosulphate
(AFm), ettringite (AFt)) by forming the very soluble salt calcium nitrate
(Ca(NO3)2). Therefore, the concentration of Ca ions in pore solution is

http://dx.doi.org/10.1016/j.cemconres.2015.09.017
0008-8846/ 2015 Elsevier Ltd. All rights reserved.

Please cite this article as: Q.T. Phung, et al., Investigation of the changes in microstructure and transport properties of leached cement pastes
accounting for mix composition, Cem. Concr. Res. (2015), http://dx.doi.org/10.1016/j.cemconres.2015.09.017

Q.T. Phung et al. / Cement and Concrete Research xxx (2015) xxxxxx

much higher than in a portlandite-controlled system (e.g. 20 mM vs.


2730 mM [11]).
Most studies on Ca-leaching quantify the propagation of degraded
depth and the consequences for the mechanical behavior [12,13]. However, only a few studies discuss microstructural alterations after
leaching [14,15], typically leading to a material with coarser microstructure in case of accelerated leaching in ammonium nitrate solution, and
the effects of leaching on transport properties [16,17]. However, to
what extent the microstructure and transport properties are modied
is still questionable. Alterations depend, beside on cement type and
portlandite content, strongly on pozzolanic activity and other additives
which may eventually even lead to porosity decrease by secondary precipitation [1820]. Generally, additives such as y ash and blast furnace
slag or glass powder and silica fume [5] improve the resistance against
leaching. From a mineralogical point of view, Ca-leaching mainly affects
portlandite, but several studies show also important decalcication of
the C-S-H phases, especially in long-lasting leaching experiments [5,
21]. As llers in general, and also limestone llers, specically inuence
processes as carbonation [22], microstructure [23], hydration [24,25],
and mechanical properties [26,27], it is expected that they also have
an effect on Ca-leaching of cementitious materials. However, information is still missing in the literature.
A fundamental question raised in this study is how these microstructural and mineralogical changes during Ca-leaching alter effective transport properties as diffusivity and permeability. Alterations observed in
reported experiments are in most studies in line with the expectations,
which is an increase with increasing degradation [16,17,28], but the
link with the underlying micro-scale changes is mostly not studied. A
study of Bernard et al. [51] showed the importance of mineralogical
changes on the interpretation of measured HTO diffusivity on degraded
CEM I cement paste and mortar samples. The effective diffusivity increases from a 31-time increase, when only portlandite is completely dissolved, to a 118-time increase, when also hydrated aluminates and
sulfoaluminates are dissolved.
As cement additives and llers are expected to have consequences on
Ca-leaching, this study presents an in-depth investigation of mineralogical and microstructural alterations and changes in diffusivity and permeability after Ca-leaching of cement pastes with limestone ller within a
factorial design with limestone ller replacement and water/powder
ratio as experimental variables. The extensive experimental ow
chart consists of leaching cement pastes in aggressive environment
(NH4NO3), during which Ca-leaching was followed up by ion chromatography (IC), followed by a series of quantitative and qualitative analyses
(scanning electron microscopy (SEM) in combination with energy dispersive X-ray microanalysis (SEM-EDX), mercury intrusion porosimetry
(MIP), (quantitative) X-ray diffraction (XRD/QXRD), N2-adsorption, phenolphthalein spraying. Recent developed experimental setups were used
to measure water permeability [29] and diffusivity [30] of dissolved gases
in reference and leached samples.
2. Accelerated Ca-leaching in ammonium nitrate solution
2.1. Materials
Experiments were performed on cement pastes made from cement
Type I ordinary Portland cement (CEM I 52.5 N, Table 1), tap water,
and limestone ller. The limestone ller (Calcitec 2001S) has a Blaine
specic surface of 3500 cm2/g and a CaCO3 content of 98.30% (see
Table 1
Chemical properties (wt. %) of the cement (from manufacture fact sheet).
CaO
SiO2
Fe2O3
Al2O3
Sulphate SO3

63.0%
20.0%
3.0%
5.0%
2.9%

Chromium(VI)
Cl
Na2O eq.
Loss on ignition
Insoluble residue

b2.104%
0.06%
0.85%
1.60%
0.50%

Table 2 for some other properties). Superplasticizer Glenium 27 was


added to the mix with content of 0.5% with respect to mass of cement.
Cement paste compositions were made on the basis of a factorial experimental design with 22 factorial points and 1 center point along the
experimental variables water/(limestone ller + cement) ratio (w/p)
and the cement replacement by limestone (ls/p = limestone ller/
(limestone ller + cement)). w/p ratio and ls/p ratio varied, respectively, from 0.325 to 0.425 and from 0 to 20% (Table 3). The material compositions used in this study simulate (but without coarse aggregates)
the composition for the Belgian Supercontainer in the new reference design for disposal of high-level waste and spent fuel [31], in which limestone has been used as ller and aggregates because it contains low
reactive constituents (silicon, aluminium, magnesium), which limits
the alkali-aggregate reaction resulting in expansion and cracking [32].
S1 to S5 and S1L to S5L are herein referred to the reference and leached
samples, respectively. The run order was randomly generated to eliminate bias. Note that in cement industry, Portland limestone cements
have been produced by inter-grinding clinker and limestone (and gypsum) in which different limestone/(limestone + clinker) ratios are initially chosen. Therefore, the water/cementitious material ratio for
Portland limestone cement is actually the water/powder ratio. For
consistency, w/p ratio rather than w/c ratio was chosen as one of the experimental variables. However, dilution effects due to limestone ller
addition can be easily obtained by converting w/p ratio to w/c ratio.

2.2. Experimental procedure and test setup


Cement pastes were poured and cured in a cylindrical PVC tube with
an inner diameter of 97.5 mm. The samples were then rotated during
24 hours to prevent segregation [29] and subsequently cured for
28 days under sealed conditions in a temperature-controlled room
(21 1 C). The cured cement pastes were sawn into 25 mm thick
slices. To impose only one-dimensional leaching at the bottom and top
of the slice, the PVC cover in the axial direction was not removed and
any gap between the PVC cover and cement paste was lled with
epoxy resin (Fig. 1a).
In order to avoid initial leaching, the cement slices were saturated in
a saturated lime solution following the procedure described in [29]. The
saturated cement slices were immersed in ammonium nitrate solution
6 M chambers. The water-contact surface area ratio was 8 cm3/cm2.
This factor ensured that the pH of the solution remained below 9.25 because this pH is critical to maintain leaching acceleration [33]. As such,
solution renewal was avoided which facilitated quantitative analysis
of the Ca-leached amounts.
A picture of the test setup is given in Fig. 1b. Nitrogen was bubbled
through the system to prevent carbonation during leaching and to remove the formed NH3 gas via the bubbler (water lock). The solution
was homogenized by a magnetic stirrer. There was an extraction line
to extract solution for further analysis and follow up the pH. The setup
consisted of three NH4NO3 chambers which allowed simultaneously
leaching of three samples. Reference samples were prepared from the
same batch of cement paste and kept under the same conditions except
for immersion in ammonium nitrate solution.

Table 2
Chemical and physical properties of limestone ller (from manufacture fact sheet).
Density
Blaine-specic surface
Particle size distribution:
Passing 2 mm
Passing 500 m
Passing 125 m
Passing 63 m
D50 (50% passing)

2.7 g/cm3
3500 cm2/g
100.0%
99.9%
97.0%
77.0%
10.1 m

CaCO3
MgO
SiO2
Al2O3
Fe2O3
Na2O eq.
pH

98.30%
0.36%
0.75%
0.25%
0.10%
0.05%
9.5

Please cite this article as: Q.T. Phung, et al., Investigation of the changes in microstructure and transport properties of leached cement pastes
accounting for mix composition, Cem. Concr. Res. (2015), http://dx.doi.org/10.1016/j.cemconres.2015.09.017

Q.T. Phung et al. / Cement and Concrete Research xxx (2015) xxxxxx
Table 3
Detail of factorial experiment design.
Run

Cement

LS

Powder

Water

w/c

w/p

ls/p

SP

order

kg

kg

kg

kg

1
2
3
4
5

450
360
450
405
360

0
90
0
45
90

450
450
450
450
450

146
191
191
169
146

0.325
0.531
0.425
0.417
0.406

0.325
0.425
0.425
0.375
0.325

0
20
0
10
20

2.3
1.8
2.3
2.0
1.8

Sample

S1
S2
S3
S4
S5

3. Characterization of mineralogical and microstructural alteration


3.1. Phenolphthalein spraying, ion chromatography, and mass loss
The leaching tests were stopped after 7, 14, 21, and 28 days to examine different leaching grades (sample S1 only after 7, 21, and 28 days).
The leached samples were cut into hemispherical parts and sprayed
by a phenolphthalein solution to determine the leached depth [35] by
a color difference between a zone above and below a pH of about 9
10. Note that the phenolphthalein indicator cannot detect exactly the
portlandite dissolution front as the portlandite dissolution front extends
beyond a pH zone of about 910 because of buffering by other cement
hydrates [36].
The amount of leached calcium was measured by ion chromatography (IC) in solutions extracted on a weekly basis from the setup. Prior to
the measurement, the solution was ltered through a 0.45 m syringe
lter, and then diluted with milli-Q water to a (1:1000) solution. The
IC analysis was performed using a Dionex CS12A column and a 20 mM
MSA isocratic elution. Detection was performed by a Dionex EC50
electro conductivity detector.
In addition, sample masses before and after leaching were determined under saturated condition by a precise balance (103 g). This is
a direct method to quantify the mass loss due to leaching.

3.2. Mercury intrusion porosimetry and N2-adsorption


The combination of mercury intrusion porosimetry and N2-adsorption
enables to characterize pore structural changes over a broad pore size
range where the former gives reasonable results for larger pore sizes,
while the later provides information on the smaller pores. The deformation of leached samples is very large at the high applied pressures of mercury during an MIP experiment which is not the case for an N2-adsorption
experiment. For this reason, combining MIP and nitrogen adsorption

measurements will give a better understanding of the pore structure of


cementitious materials, especially for leached paste.
Several leached paste pieces were taken within 3 mm from the reactive surface and referred as leached sample. The mass of each sample
was about 34 g. Freeze drying was chosen to prepare the samples for
MIP and nitrogen adsorption measurements. By freeze drying, water
crystals sublimate, which prevents micro crack formation because capillary stresses are created if drying passes through the liquid state [37].
This method also gives a dried sample in a relatively short period. Samples were directly immersed in liquid nitrogen until the escape of gas
bubbles stops. Subsequently, the samples were transferred to a vacuum
chamber where a vacuum pressure of 2.5 102 mbar was applied for
24 hours. Dried samples were kept in closed glass bottles until
examination.
MIP experiments were performed on the PASCAL 140/440
porosimeter. The pressurization was done in low and high pressure
parts. In the low pressure part, after evacuation and mercury lling, the
pressure was continuously increased up to 0.2 MPa then reduced to atmospheric pressure before moving to the high pressure part. Both the
sample volume and information on the larger pores were determined
from the low pressure part. In the high pressure part, the pressure of mercury was continuously increased up to a maximum pressure of 200 MPa
for reference samples and of 30 MPa for the leached material because of
its high ductility. The compression of the leached sample was also taken
into account in the pore structural calculations. Nitrogen adsorption measurements were done on a TriStar II 3020 Micromeritics. Dried samples
were weighed and degassed under vacuum at 35 C for 24 hours. The
amount of nitrogen adsorbed during the test was calculated by the volumetric method (based on gas laws). About 80 equilibrium points were
collected during adsorption and desorption. More data points were collected at the low relative pressure part in order to derive the micropore
volume.
3.3. Scanning electron microscope and energy dispersive X-ray microanalysis
Scanning electron microscope combined with energy dispersive Xray microanalysis (SEM-EDX) was used to identify the pore structure
and mineralogical changes. EDX was used to obtain atomic Ca/Si proles
and elemental mapping over the transition zone of leached materials.
Combination with backscattered electron (BSE) images allowed for better separation of the phases of reference/degraded cement pastes.
Polished sections are required for BSE images. The solvent replacement method was chosen to dry the samples. This method is found to
be a good technique to preserve the microstructure for SEM analysis
[38]. The samples were immersed in 2-propanol 99.5% for 2 weeks

Fig. 1. Preparation of cement paste slice (a) and accelerated leaching setup using NH4NO3 solution (b): 1magnetic stirrer; 2NH4NO3 vessel; 3nitrogen line; 4extraction line; 5bubbler
(adapted from [34]).

Please cite this article as: Q.T. Phung, et al., Investigation of the changes in microstructure and transport properties of leached cement pastes
accounting for mix composition, Cem. Concr. Res. (2015), http://dx.doi.org/10.1016/j.cemconres.2015.09.017

Q.T. Phung et al. / Cement and Concrete Research xxx (2015) xxxxxx

Fig. 2. Increase of phenolphthalein degraded depth (a) and normalized Ca-leached amount to cement over immersed time (b).

and then placed in a vacuum chamber under 2.5 10 2 mbar for


3 days. The dried samples were impregnated in a high strength and extremely low viscosity resin before grinding and polishing. Resin impregnation helps to ll the voids and pores, preserve the original
microstructure, enhance contrast between solid phases and pores, and
prevent cracking during grinding/polishing. The polished samples
were then coated by a thin gold layer (few m) to prevent charging during SEM examination. Even with gold coating, the samples might be
charged because of the non-conductive resin. Therefore, the top and
bottom of the sample were connected by a conductive copper tape.

SEM measurements of samples were done using a JEOL JSM 6610 scanning electron microscope. EDX analysis was carried out with the aid of
ESPRIT Software. ImageJ software was used for separation of pores
and solid phases.
3.4. Qualitative and quantitative X-ray diffraction
XRD was also used to identify mineralogical changes after leaching.
Powder was collected from reference and degraded samples by drilling
longitudinally in the samples. Drilling was halted every 3 mm to collect

Fig. 3. Main effects plot (a) and interaction plot (b) for degradation rate (top) and Ca-leached rate (bottom).

Please cite this article as: Q.T. Phung, et al., Investigation of the changes in microstructure and transport properties of leached cement pastes
accounting for mix composition, Cem. Concr. Res. (2015), http://dx.doi.org/10.1016/j.cemconres.2015.09.017

Q.T. Phung et al. / Cement and Concrete Research xxx (2015) xxxxxx

Fig. 4. Comparisons of mass loss of leached samples during leaching determined by weighing and ion chromatography methods with assumption of no C-S-H decalcication.

the dust. To prevent cross contamination, the hole was carefully cleaned
by compressed air before continuing the drilling. For the reference sample, the surface layer was removed before collecting the powder. Prior to
analysis, the samples were vacuum-dried. For samples on which a quantitative analysis was performed, 10% of ZnO internal standard material
was added to the mixture. The classical grinding procedure (by hand
with pestle and porcelain mortar) was used to reduce the size of the
grains. This method is time consuming compared to using micronizing
mill but avoids reaction of portlandite with alcohol (needed in the micronizing mill) forming a carbonate-like product (Ca(OCH3)2) [39].
Powder XRD measurements were done using a Philips X'Pert Pro Diffractometer. The samples were scanned over the 2 range of 570o
using CuK radiation at 45 kV and 40 mA.
The Rietveld method was used to rene the crystal structure model
of a material, allowing determination of the mass fraction at different
phases. A least squared error tting of the full prole tting was performed using the X'Pert Highscore Plus software. The crystal structure
database was downloaded from the American Mineralogist Crystal
Structure Database [40]. The following parameters were adjusted in a

Fig. 5. Adsorption/desorption isotherms of reference and 28-day leached sample S3L.

Please cite this article as: Q.T. Phung, et al., Investigation of the changes in microstructure and transport properties of leached cement pastes
accounting for mix composition, Cem. Concr. Res. (2015), http://dx.doi.org/10.1016/j.cemconres.2015.09.017

Q.T. Phung et al. / Cement and Concrete Research xxx (2015) xxxxxx

Table 4
Summary of N2-adsorption results of leached and reference samplesL denotes leached sample.
Sample
w/p
ls/p

S1
0.325
0

S1L
0.325
0

S2
0.425
0.2

S2L
0.425
0.2

S3
0.425
0

S3L
0.425
0

S4
0.375
0.1

S4L
0.375
0.1

S5
0.325
0.2

S5L
0.325
0.2

BET surface area, m2/g


Porosity (BJH), %
BJH adsorption average pore
diameter (4 V/A), nm

9.9
5.0
13.4

73.1
16.2
8.7

33.3
15.2
12.5

130.9
21.9
8.6

30.6
13.0
11.6

145.8
23.8
7.8

34.8
9.2
9.5

182.3
26.1
7.3

5.5
5.4
15.8

86.7
21.2
6.8

Table 5
Micropore information of leached and reference samples determined using DubininAstakhov model [45]L denotes leached sample.
Sample
w/p
ls/p

S1
0.325
0

S1L
0.325
0

S2
0.425
0.2

S2L
0.425
0.2

S3
0.425
0

S3L
0.425
0

S4
0.375
0.1

S4L
0.375
0.1

S5
0.325
0.2

S5L
0.325
0.2

Micropore spec. surface, m2/g


Micropore volume, mm3/g
Meso/microvolume ratio

8.1
4.0
6.5

58.6
27.9
4.2

27.6
13.5
6.5

95.7
47.5
4.2

23.7
11.6
6.9

131.6
65.0
3.3

26.4
12.8
3.9

165.4
82.2
2.8

4.2
2.1
12.1

67.9
32.5
4.6

semi-automatic mode one-at-a-time: background, scale factor, zero


shift, lattice cell, Caglioti parameters (W, U, V), peak shape, asymmetry,
and preferred orientation.
4. Determination of the changes in transport properties
After the leaching tests, the samples were stored in water until the
water permeability and diffusivity were measured. This was to prevent
drying of the samples and migration of calcium nitro-aluminate (a reaction product of calcium nitrate and hydrated aluminates) to the dry surface which can generate micro cracks [9]. Prior to permeability/
diffusivity measurements, the samples were embedded in polycarbonate
rings by a resin under an atmosphere of 100% relative humidity. Water
permeability was determined using a controlled constant ow method
as described in [29]. The diffusivities of dissolved gases (He and Xe)
were determined using a through-diffusion methodology which allows
simultaneous determination of diffusivities of two dissolved gases as described in [30]. Permeability measurements were performed on all reference and leached samples after 28 days of leaching. Furthermore, the time
evolution of permeability was investigated by measuring the permeability of sample S3 after 1, 2, 4, and 8 weeks of immersion in an ammonium
nitrate solution. Diffusivity measurements were only performed on reference and leached samples S3 after 28 days of leaching.
5. Results and discussion
5.1. Effects of w/p ratio and limestone ller replacement on degraded depth
and Ca-leached amount
The degraded depth measured by phenolphthalein linearly increased with the square root of immersion (reaction) time in NH4NO3

(Fig. 2a), which indicates a diffusion-controlled process. Fig. 2b shows


the amount of calcium in the surrounding solution normalized to the cement content (limestone ller is not leached because of extremely low
solubility), which equals the amount of calcium leached. Again, a linear
relation of leached amount over square root of time was observed.
Degradation rates and Ca-leached rates estimated as the slope of degraded depths and Ca-leached amounts, respectively, versus t0.5 are
shown in Fig. 3. It is clear that the degradation and Ca-leached rates
strongly increase with the increase of w/p ratio. The degradation and
Ca-leached rates were increased by 70% and 50%, respectively, when w/
p ratio increased from 0.325 to 0.425. Adding LS also induced faster degradation and Ca-leached rates but had a smaller effect than the w/p ratio.
To improve the resistance to leaching, one should choose a mix design
with a low w/p ratio and low LS replacement. The regression equations
(rst-order) of degradation and Ca-leached rates are obtained as follows:
Ratedep 1:3970:538 ls=p 7:3 w=p3:5 ls=p  w=p

RateCa 0:715 0:168 ls=p 6:1 w=p 1:1 ls=p  w=p

where Ratedep [mm/day0.5] and RateCa [%/day0.5] are the degradation and
Ca-leached rates, respectively, ls/p is the ratio of limestone ller over
powder (cement + limestone ller), and w/p is the ratio of water over
powder. The correlation coefcients (r2) are 0.999 and 0.998 for Ratedep
and RateCa, repectively, indicating that the models t the experimental
data well.
The interaction plots (Fig. 3b) enable to visualize the interaction effects of w/p ratio and LS replacement on the degradation and Caleached rates. As the connected lines of factor levels are almost parallel
to each other, there might not be interaction present (or minor
contribution).

Fig. 6. Inuence of deformation of leached sample on MIP results: sample S1Lthe blue curves are the corrected curves.

Please cite this article as: Q.T. Phung, et al., Investigation of the changes in microstructure and transport properties of leached cement pastes
accounting for mix composition, Cem. Concr. Res. (2015), http://dx.doi.org/10.1016/j.cemconres.2015.09.017

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Fig. 7. Changes in pore structure due to leaching assessed by combining MIP and N2-adsorption: porosity vs. pore diameter (left) and differential pore size distribution (right) of leached
and reference samples.

5.2. Evidence of C-S-H leaching from mass loss


This section aims at giving indirect evidence that C-S-H decalcication contributes to the mass loss of the leached sample. When assuming

no C-S-H leaching, IC-measured Ca can be used to calculate the decrease


of the sample weight by making the assumption that the mass loss due
to the leaching of other ions (K+, Na+, and Mg++ ions) is negligible. IC
results of sample S1L (data not shown) with concentrations of Ca much

Please cite this article as: Q.T. Phung, et al., Investigation of the changes in microstructure and transport properties of leached cement pastes
accounting for mix composition, Cem. Concr. Res. (2015), http://dx.doi.org/10.1016/j.cemconres.2015.09.017

Q.T. Phung et al. / Cement and Concrete Research xxx (2015) xxxxxx

5.3. Changes in porosity and pore size distribution

Fig. 8. Comparison of porosity increases due to leaching of samples with different w/p ratios and limestone ller replacements.

larger than the concentrations of other ions conrmed this assumption.


The amount of dissolved portlandite is then obtained as:

CH CaV a

MCH
MCa

where CH is the dissolved portlandite content [g], [Ca] is Ca ion concentration determined by IC [g/l], Va is the volume of the NH4NO3 solution
[l], MCH is molar mass of Ca(OH)2, 74 [g/mol], and MCa is molar mass of
Ca, 40 [g/mol]. To link the change in portlandite content to the measured sample mass loss, it is further assumed that portlandite dissolution creates capillary pores which are quickly lled by water. The
change in porosity due to portlandite dissolution is
CH


MCH

V CH

Vs

100%;

where VCH is molar volume of Ca(OH)2, 0.033 [l/mol] and Vs is sample


volume [l]. Consequently, the decrease in sample mass is expressed as

CHCH


MCH

Ms

V CH w

100%;

where m is percentage of mass loss, [%], Ms is sample mass, [g] and w


is density of water, 1000 [g/l]. Fig. 4 shows a comparison between the
direct measured and the calculated mass loss during leaching. The sample masses linearly decreased as a function of square root of immersed
time. The mass loss obtained from direct measurements was smaller
than the mass loss obtained by the IC-calculated method. It is hypothesized here that the difference is attributed C-S-H leaching. Leaching of CS-H creates mainly gel pores and small capillary pores of which the former is hardly accessible by water under normal condition. By excluding
the possible not-relling of pores in the IC method, mass loss is potentially overestimated. The mass loss of sample S3L obtained by either
weighing or IC method was similar. This inconsistent observation is difcult to explain but should not be interpreted as no C-S-H leaching as
EDX results clearly indicated C-S-H dissolution (see Section 5.5.2).

5.3.1. Nitrogen gas adsorption results


Fig. 5 compares the nitrogen adsorption/desorption isotherms of
leached and reference samples. The shape and size of the hysteresis
loop of the leached sample are characteristic for large ink-bottle-shaped
pores, whereas the hysteresis loop of the reference sample is more characteristic for a slit-shaped or plate-like pore system [41]. Such a platelike pore system corresponds to C-S-H gel which consists of very thin
sheets [42]. The alteration toward ink-bottle-shaped pores might indicate that part of the C-S-H has been dissolved during leaching. The specic surface areas (SSA) determined by the BET method of the leached
samples signicantly increased (Table 4). The SSA of samples with
high w/p ratio (S2L, S3L, S4L) increased 45 times after 28-day of
leaching in ammonium nitrate solution. For the samples with a low
w/p ratio, the SSA increased up to 7 and 15 times for S1L and S5L, respectively. Such an increase cannot only be attributed to portlandite
dissolution but also to C-S-H dissolution. The gel pores of C-S-H which
have a higher SSA compared to micro-/mesopores are more easily accessible by nitrogen after leaching as also observed by Thomas et al.
[43] and Trapote-Barreira et al. [44].
Leaching seriously increased the porosity in the mesopore region in
all leached samples as shown in Table 4. The largest increase in porosity
was for sample S4L which showed the largest porosity increase with a
factor of almost three. The samples with 20% limestone ller replacement (S2L, S5L) had similar porosity after leaching despite different initial porosities. Interestingly, the average pore diameter determined by
BJH method decreased after leaching for all compositions. Rather than
a renement of the pore structure of the leached materials (a renement is inconsistent with the MIP results, see further), this reduction
is an additional indication of opening of initially inaccessible gel pores.
Sample S1L and S5L (low w/p ratio) exhibited the largest decrease in average pore diameter, which could be the reason for obtaining the
highest SSA increase (relative values) after leaching.
Table 5 presents the change in micropore structure of the leached
materials. The micropores of all leached samples were strongly affected
by leaching in ammonium nitrate solution; among them, the highest alteration was again from the samples S1L and S5L. Both micropore surface area and micropore volume were signicantly increased during
accelerated leaching. The meso/micro volume ratio was reduced after
leaching which can serve as an evidence for C-S-H decalcication
which resulted in higher accessibility of gel pores.

5.3.2. Combined MIP and N2-adsorption results


MIP with leached samples is a delicate measurement because
leaching decreases elasticity and increases ductility. The leaching reduces the Ca/Si ratio of C-S-H (see Section 5.5.2), which decreases the
stiffness of C-S-H evidenced by nanoindentation [46]. Furthermore,
portlandite leaching leads to a more homogeneous matrix with less
stress resulting in a lower brittleness of the cement matrix [47]. The deformation at failure of leached samples can increase with a factor of in
tension and 2 in uniaxial compression [47]. As a sample is under isotropic compression during MIP, deformation must be higher than that reported in [47]. No samples were broken after the MIP, but the
compression effect must still be taken into account in the interpretation

Table 6
Changes in porosity, critical and threshold pore diameters and bulk density due to leaching determined by N2-adsorption and MIP combinationL denotes leached sample.
Sample
w/p
ls/p

S1
0.325
0

S1L
0.325
0

S2
0.425
0.2

S2L
0.425
0.2

S3
0.425
0

S3L
0.425
0

S4
0.375
0.1

S4L
0.375
0.1

S5
0.325
0.2

S5L
0.325
0.2

Accessible porosity, %
Critical pore diameter, nm
Threshold pore diameter, nm
Bulk density, g/cm3

11.2
25.7
60
1.89

27.8
180
800
1.39

26.7
49.9
300
1.72

44.8
150
2000
1.10

19.7
32.0
1000
1.78

38.4
110
900
1.11

16.8
36.4
200
1.85

40.5
170
800
1.14

13.8
29.0
300
2.06

35.8
180
450
1.43

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Fig. 9. XRD patterns of reference and leached samples taken in the rst 3 mm from the reactive surface.

because the porosimeter interprets sample compression as occurrence


of pores (applied correction method is described in Appendix 1).
An example of the correction procedure in (Fig. 6) shows the cumulative intrusion curves and differential pore size distributions (PSD) of
leached sample S1L before and after correcting for the compression effect. It can be seen that the pore volume is compressed by 33% which
cannot be disregarded. However, even with compression correction,
the MIP corrected results cannot be considered as the complete pore
structure of the tested sample because the pore volume of the sample
is always higher than the mercury intruded volume due to pore volume
compression under pressure. The difference is larger when the pressure
increases. In the context of this study, the corrected and uncorrected
curves started diverging more and more at pressure larger than approximately 30 MPa (corresponding to a pore diameter of 0.05 m).

Furthermore, N2-adsorption enables to measure the pores up to


0.07 m. For these reasons, the combination of MIP and gas adsorption
measurements will give a better understanding of the pore structure
of cementitious materials, especially for leached pastes. The MIP gives
reasonable results for pore size larger than 0.05 m, while N2adsorption provides information on the smaller pores. In this way,
pore structure information is obtained in a broader pore size range
and compression effect is reduced. For reference samples, the pores
with diameter larger than 0.007 m was determined by MIP and smaller
pores was determined by N2-adsorption. Note that the pore information
obtained by MIP and N2-adsorption is not identical because different
methods/models are applied to calculate the porosity and PSD. The porosity calculated by N2-adsorption was shifted at the combined pore diameter (i.e. 0.05 m) in order to obtain a continuous curve.

Please cite this article as: Q.T. Phung, et al., Investigation of the changes in microstructure and transport properties of leached cement pastes
accounting for mix composition, Cem. Concr. Res. (2015), http://dx.doi.org/10.1016/j.cemconres.2015.09.017

0.5
0.9
1.1
2.8
2.2
0.4
0.3
0.6
3.1
1.5
0.1
0.2
0.2
0.5
0.7
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.0
0.1
0.2
0.0
0.0
0.0
0.0
0.0
0.2
0.2
0.3
0.1
0.3
0.2
0.2
0.5
0.1
0.3
0.2
0.2
0.1
0.2
0.1
0.9
1.3
1.2
0.9
0.8
1.4
0.7
1.2
0.9
1.0
0.1
0.9
0.7
1.3
1.5
0.1
0.1
0.2
0.1
0.2
0.1
0.1
0.1
0.0
0.2
0.2
0.1
0.1
0.2
0.1
0.8
0.5
0.3
0.4
0.7
1.2
0.0
0.2
1.3
1.1
0.0
0.7
0.2
0.7
0.7
0.4
0.5
0.3
0.3
1.5
0.4
0.4
0.2
0.2
0.3
1.0
0.5
0.2
1.2
0.8
0.0
0.0
0.0
0.0
0.0
0.4
0.0
0.0
0.0
0.0
0.0
0.1
0.0
0.0
0.0
1.4
1.2
1.2
2.3
1.5
1.4
1.2
1.4
2.7
3.1
1.0
1.1
0.6
2.3
3.4
0.0
0.6
0.8
2.0
0.9
0.0
0.0
0.5
0.0
0.5
0.2
0.8
0.4
0.4
0.0
0.2
0.5
0.8
0.6
0.5
0.3
0.7
1.0
0.6
0.5
0.5
0.6
0.7
0.5
0.8
2.4
5.0
2.6
1.9
1.4
6.7
17.1
13.4
11.0
8.2
13.1
21.8
19.9
15.6
12.2
S5
S5L

S4
S4L

Ref.
03
36
69
912
Ref.
03
36
69
912
Ref.
03
36
69
912
S3
S3L

16.7
0.0
0.0
0.6
12.3
17.7
0.0
0.0
1.0
9.9
15.3
0.0
0.0
4.7
13.8

Thaumasite
Stratlingite
Jennite
Clinotobermorite
Tobermorite
Calcium
monocarboaluminate
Brownmillerite
Tricalcium
aluminate
Alite
Belite
Ettringite
Calcite
Portlandite
Depth interval, mm

Fig. 9 presents the XRD patterns for leached and reference samples.
Note that leached sample refers to a subsample taken from the
leached zone (pH b 9) of the sample. Portlandite was completely dissolved in all leached samples as the two intense peaks at 2 = 17.9
and 34.2o for the reference samples were absent in the leached samples.
On the other hand, the most visible phases in the XRD patterns of the
leached samples are calcite, ettringite, and unhydrated cement, which
indicate that they are hardly degraded by the NH4NO3 solution. Note
that the intense peaks for calcite in reference and leached samples
S2L, S4L, and S5L are due to the limestone ller addition. Similar to
leaching in deionized water [49,50], no new crystalline phases were observed. This underpins the statement that leaching in ammonium nitrate results in same end-products (solid phases), as obtained for
natural leaching processes.
The quantitative XRD results of 28-day leached and reference samples S3, S4, and S5 are shown in Table 7. Among 15 quantied phases,
portlandite and calcite were the most occurring phases in the mixtures.
The results showed that unhydrated phases, mainly alite, were still
present in both leached and intact materials. There was no portlandite
detected within 6 mm depth from the reactive surface, which is consistent with the degraded depth determined by phenolphthalein spraying.
The quantitative XRD analysis (Fig. 10) also shows a gradual portlandite
leaching front beyond the phenolphthalein degraded depth (at 9.25,
7.5, and 5.9 mm for S3L, S4L, and S5L, respectively).
Although it is expected that the absolute amount of calcite should
remain constant (or slightly decreased) because calcite leaching is negligible, the relative amount increased toward the exposed surface in
Fig. 10 as leaching decreased the bulk density. The relative amount of
calcite provides information to calculate the relative change in bulk
density along the sample as described in Appendix 2. Fig. 11 presents
the changes in bulk density with depth in samples S4L and S5L. The calcite amount in sample S3 (without limestone llers) was too small to
allow for reliable estimations of bulk density. The estimated reductions
in bulk density in the 03 mm interval (43% and 30% for samples S4L

Table 7
Quantitative XRD results of leached and reference samples S3, S4, and S510% internal standard ZnO was added to the mixtures.

5.4. Phase changes via XRD/QXRD

Anhydrite

Fig. 7 compares the porosity and PSD of leached and reference samples determined by the combined MIP and N2-adsorption method. In
the range of 0.003100 m, the porosity of leached samples increased
from 68% up to 159% compared to the porosity of reference samples.
Such a porosity increase is larger than the initial volume of portlandite
which has a maximum value of about 12.8% for sample S1 [48]. After
leaching, sample S1L had the smallest porosity, while sample S2L had
the largest porosity. This may be attributed to different initial porosities
because of different w/p ratio and LS replacements. However, samples
S3L, S4L, and S5L exhibited a similar nal porosity after leaching despite
their differences in w/p ratio and LS replacement (Fig. 8).
Despite the difference in w/p ratios in composition (with/without
limestone llers), the cumulative pore volume curves of all leached
samples exhibit two stages of signicant porosity increase. This is also
indicated in the differential PSD plots (Fig. 7, right) with two
(S1L, S5L) or three (S2L, S3L, S4L) peaks. The rst stage was in the
range of about 60500 nm pore sizes, which corresponds to portlandite
dissolution. The second stage was for pore sizes smaller than 10 nm
which corresponds to C-S-H (and other phases) dissolution. In contrast,
the reference samples exhibited only one signicant pore volume increase stage. The critical pore size (which was determined from the average of two peaks with large pore sizes for S2L, S3L, and S4L; while the
peak with large pore size for S1L and S5L) was signicantly shifted to
bigger pore size range. The threshold pore diameter tended to increase
in most leached samples, except for S3L and S5L of which the threshold
pore diameters remained almost unchanged. In most cases, the bulk
densities of the leached samples largely decreased after leaching
(Table 6). Sample S4L had the largest decrease in bulk density caused
by the largest Ca removal as shown in Table 6.

0.1
0.1
0.2
0.7
0.5
0.0
0.0
0.0
0.0
0.4
0.0
0.4
0.1
0.1
0.0

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Sample

10

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Fig. 10. Portlandite (CH) and calcite (CC) proles in the leached samples S3L, S4L, and S5L after 28 days of leaching in ammonium nitrate solution.

and S5L, respectively) were similar to the MIP estimations (38% and 31%
for S4L and S5L, respectively). The bulk density gradually increased over
the depth of the sample. Beyond the phenolphthalein degraded depth
the bulk density of S5L still decreased 5%, while S4L exhibited a larger
reduction (13%).

5.5. SEM results


5.5.1. Microstructural alterations
SEM images (Fig. 12) show, similar to the MIP and N2-adsorption
measurements, an increase in pore sizes and porosity after leaching.
Some big pores with diameter up to about 10 m were observed in
most of the leached samples which can be attributed to the portlandite
dissolution. The dissolution of C-S-H mainly contributes to the increase
of pore volume in the micropore to low mesopore range which is difcult
to detect by SEM. Micro cracks were observed in all leached samples,
especially around the limestone llers (S2L, S4L, S5L) and unhydrated cement particles. Decalcication of C-S-H induces polymerization shrinkage,
especially when the Ca/Si ratio is lower than 1.2 [10]. In addition, leaching
induces a signicant loss of mechanical properties. As a consequence, decalcication shrinkage could generate tensile stresses around rigid particles (e.g. limestone llers, unhydrated cements) which results in
cracking. The decalcication shrinkage even can generate differential
stresses in the region where a gradient of Ca/Si ratio exists [10].
A third element in the microstructural changes after leaching is an
increased connectivity in the XY direction (examined on 2-D SEM

images). Creating connected pathways during leaching of Ca and other


leachable elements can increase the percolation of the pore system
and, consequently, transport properties.

5.5.2. Modication in atomic Ca/Si ratio


An EDX measurement crossing the transition zone of leached sample
S1L as indicated by the red arrow in Fig. 13 (top-left) quantied the Ca
and Si amount. The atomic Ca/Si ratio was obtained from the normalized
mass percentage of Si and Ca. It was found that the average Ca/Si ratio
was approximately double in the intact area compared to the degraded
area. The sudden jump in Ca/Si ratio at distance of about 220 m was
due to scanning through a Ca-rich region.
Fig. 13 (top-right) shows the spatial distribution of Ca, while Fig. 13
(bottom-right) shows the combined spatial distribution of four main elements (Si, Ca, Al, and Fe) in the transition zone. The intact area clearly
had a higher amount of Ca indicated by the more intense green color.
Other elements (Si, Al, Fe) seemed to be equally distributed, which indicates that those elements did not undergo signicant leaching. Micro
cracking was also observed in the degraded part in both SEM image
(top-left) and mapping picture (bottom-right). A similar change in element distribution was also found for S4 and S5 (results not shown).
Detailed proles of the Ca/Si ratio were obtained from element line
scans on 28-day leached samples with scan intervals of 9.9, 6.1, and
0.5 m for S3L, S4L, and S5L, respectively. Smaller scan interval gave noisier results as seen in Fig. 14. However, the scan results may be better with
low scan interval, especially in the transition zones. It is conrmed that C-

Fig. 11. Changes in bulk density over the depth of leached samples S4L and S5L after 28 days of leaching in ammonium nitrate solution.

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S-H is dissolved in part of the samples as its Ca/Si ratios are below the Ca/
Si ratio in initial C-S-H (roughly 1.7dotted line in Fig. 14). In front of the
phenolphthalein-identied degraded depth, the atomic Ca/Si ratios
slightly increased over the depth with lowest average atomic Ca/Si ratio
of about 1, 1.1, and 1.2 for S3L, S4L, and S5L, respectively, close to the reactive surface. These Ca/Si ratios dropped in the range where high decalcication shrinkage occurs. As a result, micro cracking was observed in
SEM images. In the transition zones of about 1 mm, Ca/Si ratios rapidly increased toward the intact area. Beyond the transition zones, the Ca/Si
ratio still increases slightly which is in line with the quantitative XRD results which showed a portlandite decrease beyond the degraded zone.

5.6. Change in water permeability


The permeability of sample S3L increased as a function of immersion
time in ammonium nitrate solution (Fig. 15). The permeability increased with proceeding leaching time, hence progressing leaching
depth. After 1 week of NH4NO3 immersion, the permeability coefcient
increased 6 times, from 2.3 1020 to 1.4 1019 m2. It continued increasing up to 3.2 1019 m2 and 1.4 1018 m2 after 2 weeks and
8 weeks NH4NO3 immersion, respectively.
It is important to note that the decalcication of the sample was not
uniform with depth, and thus, the permeability represents a composite

Fig. 12. SEM backscattered electrons images of reference (top-left) and leached (top-right) samples; and increases in porosity (in black), pore size, and percolation due to leaching
(bottom)eld width of 128 m.

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Fig. 12 (continued).

permeability of different permeabilities in series corresponding to different degrees of degradation. The intrinsic permeability of samples
leached during 28 days increased one to two orders of magnitude depending on w/p ratio and composition (Table 8). Sample S1L with the
lowest w/c ratio (0.325) exhibited an increase in permeability by a factor of 6, while sample S2L with the highest w/c ratio (0.531) increased
by a factor of 235. The extent of permeability increase is correlated
with the porosity and PSD after leaching. As seen in Fig. 8, the porosity
is the largest and the PSD is the coarsest for sample S2L and vice versa
for sample S1L. Because the samples S3L, S4L, and S5L differed in degraded depth rather than in nal porosity and PSD, the differences in

permeability increase were due to the former. An increase with a factor


of 8, 18, 25 was obtained after 28 days of leaching for samples S5L, S4L,
and S3L, respectively, with respective degraded depths of 5.9, 7.5, and
9.25 mm. For a full leached sample (S5L after 142 days of leaching),
the permeability increased by a factor of 592.
The permeability change is not limited to the zone where the pH is
larger than 9 (phenolphthalein indicator). A model with two permeabilities in series (unknown permeability in degraded zone and known permeability in intact zone) estimated a negative value for the intrinsic
permeability of the leached zone. Therefore, it is assumed that there exists a relatively thick transition zone over which the permeability

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Fig. 12 (continued).

increased from a value representative for fully leached material to a


value representative for intact hardened cement paste. Because the
Ca/Si ratio still decreases beyond the degraded depth (Fig. 14), microstructure and thereby permeability are still expected to be altered in
that zone. However, a numerical model is needed to conrm this assumption and to quantify the depth of the transition zone [48].
In general, mass transport properties are mainly affected by capillary
and large pores [16]. As such, an increase in permeability after leaching
is linked to an increase in capillary pores (see MIP results and SEM images) resulting from portlandite dissolution. In addition, it is

hypothesised here that C-S-H decalcication under accelerated leaching


conditions is also an important factor because it increases the connectivity of different types of pores (gel, micro- and mesopores). Furthermore,
the decalcication shrinkage originating from a polymerization of C-S-H
due to lower Ca/Si ratio induces micro cracks as seen in SEM images. The
study of Agostini et al. [28] also conrmed the contribution of C-S-H
leaching to permeability increase. When the sample is completely degraded (complete dissolution of portlandite) and further immersed in
NH4NO3 solution (for an extra 8 days), the intrinsic permeability slightly
increases.

Fig. 13. SEM BSE image of transition zone of leached sample S1L: CH = portlandite, CSH = C-S-H phase, C = residual cement clinkers (top-left); Ca/Si ratio along the red arrow (bottomleft); spatial distribution of Ca (right-top) and element (Si, Ca, Al, Fe) mapping generated by x-ray imagingeld width of 500 m.

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15

Fig. 14. Decrease in atomic Ca/Si ratio of sample: (a) S3L due to leachingscan interval was 9.9 m; (b) S4L due to leachingscan interval was 6.1 m; and (c) S5L due to leachingscan
interval was 0.5 m; the dotted line denotes the Ca/Si ratio in initial C-S-H.

5.7. Change in diffusivity


The diffusion experiments were performed on a 28-day leached
sample S3L. A 1-D diffusive transport model was used to interpret the
experimental data [30]. Like permeability, the effective diffusion coefcient of the leached sample should be treated as the composite (overall)
effective diffusion coefcient. The porosity of the leached sample, which
is one of inputs of the transport model, is not constant over the sample
length. The average porosity of the leached sample was calculated by
weighted average method as follows:
a

l dl re f ddl
d

where a, l, and ref [] denote the average porosity of the leached


sample, the porosity of the leached zone, and the porosities of the reference sample, respectively; dl and d [m] denote the thicknesses of
leached zone and the sample, respectively, as determined by phenolphthalein. Slow hydration processes which may decrease porosity during long-time experiments were not taken into account in the
calculation. Fig. 16 shows the tted and measured partial pressure proles of He and Xe at the outlet for sample S3L. The experimental diffusion proles were well described by the diffusion model. The He
effective diffusion coefcient of S3L was 9.48 1011 m2/s, which is
4.1 times higher than the effective diffusion coefcient of the reference
sample S3. Compared to the increase of permeability, the increase in diffusion due to leaching is much lower because permeability is much

Fig. 15. Change in intrinsic permeability of leached sample S3L due to leaching in 6 mol/l
NH4NO3 as a function of immersed time.

more sensitive to porosity change and the development of percolated


pore networks, and also to cracking compared to diffusivity.
The Xe effective diffusion coefcient of the leached sample S3L was
8.58 1012 m2/s, which is much smaller than the one of He. The effective diffusion coefcient of Xe for S3L is almost double compared to the
estimated effective diffusivity [48] of intact material (the measured effective Xe diffusivity for the reference sample S3 was not obtained due
to very long time experiment). It is important to note that the change
in He diffusivity is different of that of Xe. One possible explanation for
this observation is the difference in molecular size of He (0.26 nm)
and Xe (0.46 nm). Leaching modied the microstructure of cement
paste from micrometer scale down to subnanometer scale as observed
by MIP and N2-adsorption experiments. Therefore, the change of pores
with smaller diameter likely affects the diffusion of He (with smaller
molecular size) more than the diffusion of Xe.

6. Conclusions and remarks


In this study, an ammonium nitrate solution of 6 M was used to accelerate the decalcication kinetics of hardened cement paste samples. A variety of techniques including IC, XRD and quantitative XRD, SEM/SEMEDX, MIP, and N2-adsorption were used to characterize the microstructural and mineralogical changes of cement pastes with different mixtures
after leaching. The effect of accelerated leaching on transport behavior
was studied by measuring changes in the water permeability and diffusivity of dissolved gases.
Results showed that NH4NO3 solution was a reactive agent which
can be used to accelerate leaching kinetics while still keeping the nature of the leaching process. The mineralogical changes under leaching
in ammonium nitrate solution were quite similar to leaching in pure
water as no new phase was formed during leaching in ammonium nitrate solution. In this way, we can imitate long-term naturally degraded
cementitious materials by accelerated leaching using ammonium nitrate solution. However, deeper investigations in the changes of mineralogy are still needed especially when Ca/Si is lower than 1. The squareroot-time law of propagation of the leaching front and leached Ca
amount was applicable under accelerated conditions indicating diffusive transport conditions. Cement mixture had a signicant impact on
leaching; a higher w/p ratio or limestone ller replacement gave a larger
rate of leaching propagation (degraded depth). The effects of w/p ratio
were more signicant than limestone ller replacement. The comparison of mass change calculated from IC results and direct measurements
(weighing) proved that C-S-H leaching contributes to the mass loss of
the sample.

Please cite this article as: Q.T. Phung, et al., Investigation of the changes in microstructure and transport properties of leached cement pastes
accounting for mix composition, Cem. Concr. Res. (2015), http://dx.doi.org/10.1016/j.cemconres.2015.09.017

16

Q.T. Phung et al. / Cement and Concrete Research xxx (2015) xxxxxx

Table 8
Intrinsic permeability of cement pastes before and after leachingsample S5L-full was measured after 142-day leaching when the sample was fully decalcied (determined by phenolphthalein), the others were measured after 28-day leaching.
Sample
Permeability, m2
Sample
Permeability, m2

S1
1.5 1021
S4
1.4 1020

S1L
9.1 1021
S4L
2.5 1019

S2
1.1 1019
S5
2.0 1020

A combination of MIPnitrogen adsorption analysis was used to obtain information on the porosity and pore size distribution changes. The
accelerated leaching highly altered the microstructure of the cement
paste to a more porous material which is evidenced by the increases
of specic surface area and total porosity and by the creation of a coarser
pore size. The total accessible porosity of the leached samples highly
depended on w/c ratio. Beside the increase in meso volumes, it is interesting to observe that the micropore volume was altered much more
than the mesopore volume. Probably, the leaching of C-S-H with a larger
volume fraction than portlandite results in a signicant modication of
the micropore structure. The bulk density was signicantly reduced due
to Ca removal (up to 42%). It was not uniform but increased over the
depth of leached zone, which indicates a gradual alteration in mineralogy. Quantitative XRD indicates that portlandite was completely degraded in the leached zone while C-S-H was partially dissolved as
evidenced from microstructural analysis. Beyond the leached front,
part of the portlandite was also dissolved as conrmed by quantitative
XRD and SEM-EDX.
SEM image analysis showed a signicant increase in porosity and
pore size for the leached materials. Some big pores (up to 10 m)
were observed. The decalcication shrinkage resulted in formation of
micro cracks. More micro cracks were observed in samples with limestone ller. The Ca-leaching created connected pathways resulting in
an increase of the percolation of the pore system. In the leached zone,
the atomic Ca/Si ratio was gradually increased toward the degraded
front with a jump in Ca/Si ratio indicative for the transition zone.
The changes in microstructures and mineralogy led to a signicant
increase in transport properties. The permeability increased by one to
two orders of magnitude depending on the immersion time in
NH4NO3 and w/c ratio. For similar w/c ratio (S3, S4), the addition of
limestone helps to reduce the permeability alteration. The extent of permeability increase is correlated to the porosity and pore size distribution after leaching. The permeability of the non-invasion zone
(determined by phenolphthalein) was probably altered as the Ca/Si
ratio still decreased beyond the degraded depth. The diffusivity also signicantly increased after leaching, but with smaller magnitude

S2L
2.6 1017
S5L
1.6 1019

S3
2.3 1020
S5L-full
1.2 1017

S3L
5.7 1019

compared to the change in permeability (e.g. factor of 24 for water permeability compared to factor 4 for He diffusivity of sample S3L).
Acknowledgements
The nancial support by Belgian Nuclear Research Centre (SCKCEN)
is gratefully acknowledged.
Appendix 1. Correction procedure for compression effect during MIP
measurements.
In order to account for the deformation of the sample, the measurement needs to be corrected by subtracting the volume of sample compression as:

vc vi

1
1

b a


7

where vc is specic compression volume [m3/kg], vi is specic intruded


volume [m3/kg], b is bulk density [kg/m3], and a is the apparent density which is dened as unit weight of sample at the end of the lling
process [kg/m3]:
a

ms
V b V cor
i

where ms is sample mass [kg], Vb is sample volume (including pores)


[m3], Vcor
is corrected intruded volume [m3] and can be calculated as
i
follows:
vi vc ms
V cor
i

Appendix 2. Change in bulk density due to leaching


The following derivations enable to understand the variation of bulk
density of leached sample over the depth. The mass fractions of calcite

Fig. 16. Comparison of the He (a) and Xe (b) partial pressure at the outlet obtained from experiment and model for carbonated sample S3L after 28 days of leaching in ammonium nitrate
solution.

Please cite this article as: Q.T. Phung, et al., Investigation of the changes in microstructure and transport properties of leached cement pastes
accounting for mix composition, Cem. Concr. Res. (2015), http://dx.doi.org/10.1016/j.cemconres.2015.09.017

Q.T. Phung et al. / Cement and Concrete Research xxx (2015) xxxxxx

in reference, CCref [], and in leached, CCl [], materials are expressed
as in Eqs. (10) and (11):
CC re f

CC l

mCC
msolid
mare f
re f

10

mCC
msolid
mal
l

11

solid
where mCC is the absolute mass of calcite [kg]; msolid
are the
ref and ml
total mass of solid phases in reference and leached materials, respectively [kg]; and maref and mal are the mass of amorphous phases in reference and leached materials, respectively [kg]. Note that XRD only
detects crystalline phases; therefore, the denominators of Eqs. (10)
and (11) are the mass of crystalline phases instead of the total mass of
solid phases. With the assumption that there is no shrinkage during
leaching, the total volumes of material before and after leaching are
identical. Thus, the ratio between the mass fractions of calcite in reference and leached materials is related to the bulk densities and amorphous fractions of the reference and leached materials as expressed in
Eq. (12):

CC re f
msolid
mal
l
solid

CC l
mre f mare f
CC re f
CC l

mal
msolid
msolid
l
 lsolid
mare f
m

re f
1 solid
mre f


l  V solid
V pore
l
1Al
1Al

l




 l
1Are f  V solid V pore
1Are f re f
re f
re f
re f

12

where Al and Aref are the mass fractions of amorphous phases in leached
solid
and reference materials, respectively []; Vref
and Vlsolid are the volumes of solid phases in reference and leached materials, respectively
pore
[m3]; Vref
and Vlpore are the pore volumes in reference and leached materials, respectively [m3]; and ref and l are the bulk densities of reference and leached materials, respectively [kg/m3]. The reduction in
bulk density due to leaching can be written as follows:

re f l
100%
re f



CC re f 1Are f
100%
1
CC l 1Al

13

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accounting for mix composition, Cem. Concr. Res. (2015), http://dx.doi.org/10.1016/j.cemconres.2015.09.017