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Cement and Concrete Research 49 (2013) 3847

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Cement and Concrete Research


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

Prediction of self-desiccation in low water-to-cement ratio pastes based


on pore structure evolution
Hui Chen a,, Mateusz Wyrzykowski b, c, Karen Scrivener a, Pietro Lura b, d
a
Laboratory of Construction Materials, cole Polytechnique Fdrale de Lausanne, Switzerland
b
Empa Swiss Federal Laboratories for Materials Science and Technology, Switzerland
c
Department of Building Physics and Building Materials, Lodz University of Technology, Poland
d
Institute for Building Materials, ETH-Zurich, Switzerland

a r t i c l e i n f o a b s t r a c t

Article history: High-performance concrete is sensitive to early-age cracking, mainly due to its rapidly-developing autogenous
Received 8 November 2012 shrinkage. Autogenous shrinkage and internal relative humidity (RH) decrease are direct consequences of the
Accepted 15 March 2013 emptying of capillary pores due to cement hydration in low water-to-cement ratio concretes. To predict
early-age cracking, it is desirable to model the evolution of the internal RH, and the accompanying autogenous
Keywords:
shrinkage, based on the microstructure evolution.
Cement (D)
Humidity (A)
In this paper, the pore size distribution of cement pastes measured by mercury intrusion porosimetry and the
Hydration (A) chemical shrinkage are used as input data for calculating the internal RH of Portland cement pastes with differ-
Mercury porosimetry (B) ent water-to-cement ratios (0.30, 0.35 and 0.40). The composition of the extracted pore solution is also taken
Microstructure (B) into account. The measured RH can be predicted with good accuracy (mostly within 12% RH). However, a
number of sources of error both in the experiments and in the analysis need to be identied and controlled.
2013 Elsevier Ltd. All rights reserved.

1. Introduction changes and thermal deformations, it may increase the risk of thermal
cracking as well. This is because the RH decrease leads to a considerable
As cement hydration proceeds in low water-to-cement ratio (w/c) increase of the coefcient of thermal expansion (CTE). For example, the
cement paste, the water becomes bound into hydration products and CTE increase caused exclusively by RH depression [6,7] in cementitious
adsorbed on their surfaces. Since hydration products have smaller materials with low w/c has been reported to reach about 30% [8] or
volume than the reactants, the total volume of a cement paste de- even 5060% [6,7,9].
creases during hydration [13]; this is known as chemical shrinkage. Finally, the decrease of the internal RH not only induces shrinkage
When a solid skeleton forms in the hardening paste, the overall sample of the porous medium, it also decreases the hydration rate and limits
can no longer follow the internal shrinkage. As water is consumed from the nal degree of hydration [10].
capillary pores, gas bubbles start to nucleate and grow in larger pores It has been observed [1,2], that autogenous development of RH is not
[4] and menisci are formed at the pore solutionvapour interfaces. only a result of the curvature of the uid/vapour menisci, but is inuenced
The capillary pores become progressively smaller with hydration, by the water activity of the pore solution as well. Ions dissolved in the
because the original spaces between cement grains become lled pore solution lead to a depression of water activity of the solution and
with hydration products. At the same time, the capillary pores are hence to the decrease of the internal RH. The internal RH observed in
progressively emptied by chemical shrinkage, which is accompanied the hydrating cement paste can thus be expressed as [11]:
by a continuous decrease of the internal RH, referred to as self-
desiccation [1,2]. The increasing curvature of the menisci leads to the RH RH S RHK 1
development of hydrostatic tensile stresses in the pore solution and
compressive stresses exerted on the solid skeleton, which lead to the where RHS is a term due to water activity depression caused by dissolved
bulk deformation of the cement paste, called autogenous shrinkage ions and is expressed as an absolute value. A solution of a certain activity
[1,2,5]. The driving mechanism of autogenous shrinkage is similar to stays in equilibrium with the ambient air of RH equal to the activity of the
the main driving mechanisms of drying shrinkage, except it originates solution [11]. For an ideal (diluted) solution, the equilibrium RH depends
from internally- and not externally-induced desiccation. only on the mole fraction of water present in the solution and can be
In addition, the decrease of internal RH leads not only to autogenous estimated e.g. using Raoult's law [2]:
shrinkage, but, if the concrete structure is exposed to temperature
nH 2 O
Corresponding author. RHS 2
E-mail address: hui.chen@ep.ch (H. Chen). nsolution

0008-8846/$ see front matter 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.cemconres.2013.03.013
H. Chen et al. / Cement and Concrete Research 49 (2013) 3847 39

where: nH2 O is the number of moles of water in the pore solution and from thin-lm interactions, especially when the lm is forming in
nsolution is the total number of moles in the solution (including solute). It pores that hinder the free development of its thickness, has a domi-
needs to be noted that the RHS depression due to ions in the pore solution nating contribution to the pressure drop across the vapourpore solu-
does not lead to any deformations, since it does not cause any increase tion interfaces. According to this approach [1921], the disjoining
of capillary pressures. However, it needs to be accounted for when pressure represents the main driving force for shrinkage or swelling,
interpreting the measured RH and when considering the coupling even in the high RH range. This approach is at odds with the assump-
between the measured RH and the deformations. tion that capillary pressure dominates the shrinkage response at high
The term RHK is due to curvature effects of the menisci at the pore RH [2,5,15,17]. Yet another approach is followed by Powers [22],
solutionvapour interfaces, which is expressed as an absolute quanti- according to whom the change in disjoining pressure is due to the
ty and can be described with the Kelvin equation [12]: appearance of tension in the adsorbed lm, and when capillary
  water is present [in the high RH range], hydrostatic tension appears
2 cosw Mw in the capillary water. In this paper, the capillary-pressure based
RHK exp w 3
rRTw approach is consistently followed; however, in the discussion of the
results, disjoining-pressure effects will be also addressed.
where R = 8.314 J/(molK) is the universal gas constant, T = As explained above, autogenous shrinkage originates from, and
293.15 K is the temperature expressed in the absolute scale, Mw can be predicted in terms of the internal RH evolution and of the cor-
[kg/mol] is the molar mass of pore solution, w [kg/m 3] is the density responding capillary pressure development. Internal RH and capillary
of pore solution, w [] is the contact angle that allows extending the pressure development are in turn dependent on the evolution of
Kelvin equation for the case of imperfect wetting, w [N/m] is the sur- the microstructure and on the emptying of the pores due to chemical
face tension of the pore solution and r [m] is the radius of the menisci, shrinkage. In order to predict autogenous shrinkage of cement-based
also known as Kelvin radius. materials, it is paramount to be able to predict the evolution of autog-
A renement of this approach takes into account the presence of enous phenomena directly based on the pore structure of the materi-
an adsorbed layer of thickness t [m] on the surface of the pore wall al. Following this kind of approach, Hua et al. [5] used mercury
[13], Fig. 1, and is referred to as KelvinCohan equation [14]: intrusion porosimetry (MIP) to determine the Kelvin radius and as a
  consequence the capillary pressure and shrinkage at different ages.
2 cosw Mw
RHK exp w : 4 In their model, Hua et al. assumed that the so-called access radius
rt RTw
for the mercury intrusion in the MIP measurements is equal to the
Kelvin radius, when the volume of intruded mercury is equal to the
At the same time, the capillary pressure pc [Pa], often used for
chemical shrinkage. This allows the actual Kelvin radius to be
shrinkage calculations, e.g. [2,5,15] is modelled using the Young
determined from a MIP curve, by assuming an intrusion volume
Laplace equation:
equal to the empty volume measured during the chemical shrinkage
2w cosw test. The main renement of the approach by Hua et al. in the present
pc : 5 paper regards accounting also for the thickness of the adsorbed layer,
rt
thus using Eq. (4) instead of Eq. (3).
One approach for predicting the shrinkage behaviour is based on In any case, if the autogenous shrinkage is to be predicted from the
calculating the capillary pressure from an internal state parameter microstructure, either experimentally [5] or via a 3D microstructural
of the hardening cement paste, such as the internal RH. Lura et al. model [23], a necessary intermediate validation of such scheme
[2], using the capillary pressure-based approach by Bentz et al. [16], entails comparison of the predicted capillary pressure or the corre-
showed that autogenous shrinkage can be modelled as a function of sponding RH with their measured evolutions. Comparison of capillary
capillary pressure based on the measured RH evolution. In their pressures is very difcult from an experimental viewpoint, while the
work, Lura et al. [2] also accounted for the RH drop due to the RH evolution can be measured on hydrating cement paste samples
dissolved ions in the calculation of the capillary pressure from the and provides an important validation step for establishing a reliable
measured internal RH. A similar approach, after accounting also for model of shrinkage.
the presence of creep strains accompanying autogenous shrinkage, In this paper, the chemical shrinkage and the pore size distribu-
was presented in [17]. In [17], the development of capillary pressure tion determined with MIP for cement pastes of w/c 0.30, 0.35 and
was described using a sorption isotherm-based approach, where the 0.40 are used together for the determination of the Kelvin radius
sorption isotherms were obtained based on RH and hydration evolution and, further, of the RHK. Further, the effects of the thickness of the
measurements, see also [18]. adsorbed water layer on the Kelvin radii are calculated, then the effect
It needs to be mentioned that some authors, e.g. Wittmann et al. of ions in the pore solution on the RH. Taking all these factors into
[1921], suggest that the so-called disjoining pressure, originating account, the RH predicted at different ages is compared with the
measured RH evolution. The assumptions underlying the modelling
scheme used, mainly the basic assumptions of MIP and chemical
shrinkage and the assumed parameters in the Kelvin equation, are
discussed in terms of their inuence on the predicted RH evolution.
In addition, the contribution of disjoining pressure to the pressure
drop across the vapourpore solution interface, and nally to the RH
evolution, is briey discussed.

2. Materials & methods

Rapid-hardening ordinary Portland cement (CEM I 52.5R) with


Blaine neness of 4025 cm 2/g was used. The XRD-Rietveld phase
composition by mass was: C3S 68.1%, C2S 9.2%, C4AF 8.7%, C3A 4.9%,
periclase 0.5%, gypsum 3.6%, hemihydrate 1.8%, anhydrite 0.7%, calcite
1%, quartz 0.4%, and arcanite 1.2%. The oxide composition is presented
Fig. 1. Schematic representation of menisci and adsorbed water layer in capillary pores. in Table 1.
40 H. Chen et al. / Cement and Concrete Research 49 (2013) 3847

For each specimen, 300 g of cement was mixed with demineralized Table 2
water in amounts corresponding to different w/c (0.30, 0.35 or 0.40) Setting times of the cement pastes with different w/c.

using an epicyclic Perrier mixer. The pastes were mixed at 60 rpm for w/c 0.30 w/c 0.35 w/c 0.40
1 min. After stopping for 20 s to scrape the bowl, another minute of
Initial set (min) 124 185 246
mixing followed at 120 rpm. Material storage, sample preparation Final set (min) 211 260 395
and all experiments were performed in controlled-climate rooms at
20 1 C.
Setting times were measured by automatic Vicat needle measure- the sizes are derived from a cylindrical pore model proposed by
ments. During the measurement, the sample was covered with plastic Washburn, hence the term equivalent.
wrap in order to limit the water evaporation, yet without hindering The MIP intrusion tests were carried out on the samples after stop-
the penetration of the needle. Two samples were measured for each ping hydration at the age of 8 h, 1 day, 3 days and 7 days. Directly
cement paste and the average results are presented in Table 2. after mixing the cement pastes were cast in sealed plastic containers
(diameter 3.5 mm, height 70 mm) and cured in a thermal bath at
2.1. Chemical shrinkage 20 1 C. At the chosen ages, disc samples with thickness 35 mm
were cut using a diamond saw with water as a lubricant and
Chemical shrinkage is the absolute volume reduction in a cement immersed in isopropanol for 7 days in order to stop hydration, then
paste, due to the fact that the volume occupied by the hydration dried in a desiccator over silica gel for 5 days. This method of stop-
products is lower than that of the reactants [1,2]. A procedure for ping hydration and drying is considered to be the least damaging
measuring chemical shrinkage according to ASTM C 1608-07 [24] to the microstructure [30].
was applied, which consisted of pouring the fresh cement paste into The porosimeter (Pascal 140 and 440 by Porotec) used was
transparent polystyrene vials (diameter 23 mm, height 59 mm) and equipped with two devices; the rst applies a low mercury pressure
carefully lling the remaining space in the vials with distilled water. up to 400 kPa to introduce the mercury into the sample and to mea-
The principle of the method is that the water above the sample is sure the macroporosity; the second applies a maximum pressure of
sucked into the paste to compensate for the chemical shrinkage; 400 MPa for the measurement of the micro- and nanoporosity. The
hence, by measuring the change of volume of the water plus the sam- discs were broken with pincers into pieces of about 35 mm size
ple, the chemical shrinkage is determined. The vials were tightly and about 1.5 g of these pieces was used for each measurement.
closed with rubber stoppers having capillary tubes passing through After closing the sample holder, and before the intrusion of mercury,
their centre. A syringe was used to inject red-coloured oil on the the samples were de-aired. For calculating the equivalent pore entry
top of the water in the capillary to facilitate visual detection of the radii, the Washburn model was applied, where the pores are viewed
water level change derived from chemical shrinkage. The uid level as cylindrical in shape. The Washburn equation allows calculation
was monitored by a webcam connected to a desktop computer, of the equivalent pore radii r based on the intrusion pressure of
which took an image every 20 min during the rst 7 days of hydra- mercury pHg:
tion. An image analysis software was used to automatically detect
the changes of uid level in the capillaries [25]. For each w/c, two 2Hg cosHg
r 6
samples were tested, with a relative difference in nal shrinkage pHg
between duplicate samples not exceeding 5% for w/c 0.30 and w/c
0.35 and about 12% for w/c 0.40. where the contact angle of the mercury on the solids Hg was assumed
as 140 and the surface tension of mercury Hg was assumed as
2.2. Mercury intrusion porosimetry 0.48 N/m [27].

MIP is a standard method for determining the distribution of pore 2.3. Internal relative humidity
entry sizes in cementitious composites [26,27]. The method has been
criticised as suffering from artefacts, such as damage to the pore The internal RH development in the cement pastes was measured
structure by drying and other sample preparation steps, inadequacy with two AW-DIO water-activity probes by Rotronic, equipped with
of the assumed model (Washburn equation assuming cylindrical high-precision RH and temperature sensors with global nominal ac-
pores equally accessible from the surface) and damage to small curacy of 0.8% RH and 0.1 C. The temperature of the measuring
pores at high intrusion pressures [2628]. However the major prob- chambers was controlled by means of water circulating in the casings.
lem is the misinterpretation of the data as applying to pore sizes, rath- This allowed the temperature in the measuring chambers to be
er than to the volume accessible through pores of a given pore entry maintained at 20 0.07 C. Approximately 20 h after mixing, the
diameter (often called ink-bottle effect). If this is understood, MIP cement paste samples were broken into pieces of 510 mm sizes
is able to provide valuable information regarding the equivalent con- and then inserted into the sealed measuring chambers. The measure-
tinuous distribution of pore entry sizes [5,29]. ments were taken at 1 min intervals up to the age of 7 days. Before
In particular, MIP measurements on cement pastes generally show and after each measurement, the sensors were calibrated using satu-
very small intruded volumes down to a certain critical pore entry, rated salt solutions in the range 98 to 81%. During measurements, the
which corresponds to the maximum pore size for which there is a difference between duplicate measurements did not exceed 1% RH.
percolated path through the specimen. All pores larger than this crit-
ical size can only be intruded, once this critical radius is reached. In 2.4. Calorimetry in sealed and saturated conditions
view of these considerations, the determined size distributions refer
to the pore entries and not to the actual pores. At the same time, Because the chemical shrinkage measurement requires free access
to water (so-called open system), and the MIP samples were cured in
Table 1 sealed conditions (closed system), it can be expected that due to
Oxide composition of the cement tested. self-desiccation in the sealed samples, the degree of hydration of
the samples was different in the two cases [31]. Isothermal calorime-
Oxide CaO SiO2 SO3 K2O Na2O Fe2O3 Al2O3 MgO LOI
try was used to investigate the inuence of water availability on
Mass % 56.19 13.70 10.09 6.11 4.48 2.69 2.27 1.90 1.65 the hydration kinetics. The measurements were carried out in a TAM
Loss on ignition. Air calorimeter (Thermometrics) on samples with no additional water
H. Chen et al. / Cement and Concrete Research 49 (2013) 3847 41

(equivalent to sealed conditions) and samples for which a thin layer of


water (0.25 ml) was added on top of the paste (saturated conditions).
For each measurement, about 3 g of cement paste was poured into a
glass vial of 27-mm diameter and closed with a rubber stopper. The
thickness of the cement paste layer was about 4.5 mm, similar to the
chemical shrinkage measurements.

2.5. Pore solution extraction and analysis

In order to investigate the contribution of the salts dissolved in the


pore uid and the resulting depression of water activity on the overall
autogenous RH, the pore solution was extracted from the w/c 0.4 ce-
ment paste at different ages: 2 h, 1 day, 3 days, and 7 days. The w/c
0.40 cement paste was chosen due to the fact that it was impossible
to obtain sufcient amounts of pore uid from the pastes with
lower w/c, characterized by lower contents of free water and ner
pore structure. Fig. 2. Chemical shrinkage of cement paste with w/c 0.30 and different sample thick-
The extraction was performed using a compressed air ow at 2 h nesses. Each curve is a smoothed average from two samples.
and a hydraulic press at later ages. Directly after extraction, the pore
solution was ltered through a 0.45 m nylon lter. The extracted system and the curves started to diverge at about 1 day of hydration.
pore solutions were diluted 10 times with Milli-Q water to avoid any For the w/c 0.40 paste, this difference reduces to only about 3%, with
precipitation. no differences visible before 2 days of hydration.
The concentrations of Ca2+, Na+, K+ and SO42 ions were deter-
mined using inductively coupled plasma mass spectrometry (ICP-MS).
In order to determine OH concentrations, the pH values of the solu- 3.2. Mercury intrusion porosimetry
tions were measured. According to the ionic concentrations, synthetic
pore solutions were prepared and their equilibrium RH was measured All results are the average of duplicate MIP measurements. Fig. 5
using water activity probes (see section 2.3). shows an example of the results for duplicate specimens of the w/c
0.40 paste, where the relative difference between the specimens
3. Results was the highest. For lower w/c, the variability improves, especially
at later ages. The variability of the MIP results can originate both
3.1. Chemical shrinkage and isothermal calorimetry from the sample variability (existence of cracks and entrapped-air in-
clusions, size and shape of the specimens) and from the inaccuracy of
As hydration products are deposited in the originally water lled the test itself (errors in the measurements of the volume of entrained
space, continuous pore paths may become depercolated and this mercury and of the intrusion pressure). The variability of the data and
may occur at early ages in low w/c pastes [3234]. For the measure- its impact on the RH predictions are discussed in detail in Section 5.5.
ment of chemical shrinkage, it is of paramount importance that the The evolution of the equivalent pore entry size distribution mea-
water intended to compensate for chemical shrinkage can access sured by MIP as a function of age for cement pastes with different
emptying pores in the whole volume of the sample uniformly. In w/c is shown in Fig. 6. For decreasing w/c, the total porosity decreases
order to provide full saturation of the pores, very thin cement paste and the pore structure becomes ner. For all cement pastes, the most
samples should be used for this measurement [35]. In order to inves- signicant changes of the pore structure with time could be observed
tigate the impact of sample thickness on the measured chemical in the rst 3 days, while the differences between 3 and 7 days are
shrinkage of cement paste, samples of w/c 0.3 cement paste with rather minor. This is due to the rapid rate of hydration in the rst
thickness 2.5, 5, 10, and 20 mm were tested. The results presented 3 days, as can be also observed in the chemical shrinkage and calo-
in Fig. 2 show that all samples experience about the same evolution rimetry results (see Figs. 3 and 4).
of chemical shrinkage up to 20 h hydration. After about 20 h, the
curves diverge, with the thinnest samples reaching the highest chem-
ical shrinkage at seven days, about 0.06 ml/g of cement. On the other
hand, after 7 days the value for the thickest sample of 20 mm was
0.04 cm 3/g, thus only 66% of that for the 2.5 mm-thick sample. It
was also observed that the differences between 2.5 and 5 mm-thick
samples are minor. For this reason, the chemical shrinkage curves
for cement pastes of different w/c shown in Fig. 3 were measured
on 5 mm-thick samples. A thickness of 5 mm is a compromise be-
tween a sufciently small thickness in terms of water penetration
and sufciently large mass in terms of measurement accuracy. As
can be seen, the amount of chemical shrinkage increased with in-
creasing w/c. These pastes hydrate as open systems under saturated
conditions. Their degree of hydration and therefore their chemical
shrinkage are higher than for the same pastes hydrating under sealed
conditions.
The calorimetry results, shown in Fig. 4, conrm that access to
external water allows considerably higher degree of hydration (and
consequently also higher chemical shrinkage) in low w/c pastes. For
the w/c 0.30 paste, the amount of heat released after 7 days was Fig. 3. Chemical shrinkage of cement pastes of different w/c measured on samples with
about 19% higher in the saturated system compared to the sealed thickness of 5 mm. Each curve is a smoothed average of two samples.
42 H. Chen et al. / Cement and Concrete Research 49 (2013) 3847

Fig. 4. Heat of hydration of w/c 0.30 and 0.40 pastes measured on samples cured in
saturated and sealed conditions. The sample thickness was 4.5 mm.

3.3. Internal relative humidity

The development of internal RH in the cement pastes with different


w/c is shown in Fig. 7 for duplicate samples. As expected, the highest
RH drop was observed for the w/c 0.30 paste, followed by the w/c 0.35
paste. The w/c 0.40 paste desiccated to a RH of about 90% after one
week, while for the w/c 0.30 paste the RH at the same age was about
86%. Duplicate specimens showed a very good repeatability of the
measurements, see Fig. 7.

4. Modeling

4.1. Modeling of RH

To calculate the radius of the largest capillary pore lled with


water, the chemical shrinkage and the MIP results can be combined
according to the method of Hua et al. discussed earlier [5]. The
scheme of the calculation is presented in Fig. 8.
The presence of an adsorbed water lm of thickness t can be taken
into account by using the KelvinCohan equation, which leads to re-
placing r in Eq. (3) with (rt). The thickness t depends on the RH
and can be described with an empirical relationship according to
Badmann et al. [36]:

t K 1 K 2 lnlnRH 7

Fig. 6. Size distribution of pore entries measured with MIP for different hydration times
for a) w/c 0.30, b) w/c 0.35, and c) w/c 0.40.

where: the thickness t is expressed in nm and the coefcients K1 =


0.385 and K2 = 0.189 were determined based on adsorption mea-
surements of water on hardened cement pastes.
As the thickness t is dependent on RH, r cannot be found directly
and an iterative procedure needs to be applied. At each iteration
step i, the RHi is calculated based on the adsorbed water thickness
ti1 from the previous step. The whole procedure is repeated until
the thickness t converges; in practice, only a couple of iterations are
Fig. 5. MIP of w/c 0.40 paste at 8 h, 1 day, and 7 days showing results for duplicate needed. The resulting thickness of the adsorbed water layer varies
specimens. from 1.61.4 nm at early ages to 0.90.8 nm at 7 days.
H. Chen et al. / Cement and Concrete Research 49 (2013) 3847 43

the concentration of dissolved ions (see Table 3), it was possible to de-
termine the average molar mass of the solution at different ages:
0.01814 kg/mol at 1 day and 0.01809 kg/mol at 7 days. No data was
found on the surface tension of pore solutions with similar composition.
However, the surface tension of KOH, NaOH, MgSO4 and Na2SO4
saturated water solutions are 0.073 N/m, 0.074 N/m, 0.073 N/m, and
0.073 N/m, respectively [38]. Thus, a negligible difference in surface ten-
sion between pore solution and pure water is expected; consequently,
the surface tension of the pore solution is taken as the one of pure
water in this paper. In cement pastes containing water reducing agents
or superplasticizer, the surface tension of the pore solution might be
different. For this reason, the cement pastes examined in this study
contained only water and cement.
The contact angle of pore uid on the surface of the pores, w, is usu-
ally assumed as 0 [2,5]. Different angles can be applied, e.g. Bentz [39]
measured a contact angle of 28 for distilled water on hydrated cement
Fig. 7. Internal RH development at 20 C presented for duplicate cement paste paste surfaces. Fig. 9 shows the RH evolution in a w/c 0.40 cement
specimens.
paste calculated with the KelvinCohan equation for pure water
and contact angle of 0 and pore solution with contact angle assumed
As shown in Eq. (4), besides the pore radius, other quantities also as 0 or 28. The most pronounced inuence is due to the contact
need to be known when estimating the RH depression due to menisci angle of the pore uid. In the absence of more reliable data, perfect
formation, namely the molar mass, the density, the surface tension wetting with the contact angle equal to 0 is assumed in all calcula-
and the contact angle of the solution. These parameters are usually as- tions (including Fig. 11).
sumed as for pure water in calculations, i.e., Mw = 0.01802 kg/mol, A parameter of equal importance for the Kelvin radius and RH pre-
w = 1000 kg/m 3, and w = 0.073 N/m [2,5,37]. In this paper, an at- dictions is the contact angle for mercury, Hg, as it is used for calculat-
tempt is made to assess the inuence of the pore solution composition ing the radii based on mercury intrusion pressure data according to
on these properties. Eq. (6). Again, different values of this parameter have been assumed
The density of the synthetic pore solution corresponding to w/c 0.40 in the literature [5,27,37]. Shi and Winslow [40] intruded mercury
cement paste (see Section 2.5), measured on duplicate samples with at known pressures into cylindrical holes of known diameter (150
calibrated 5 ml volumetric asks at 20 C, was 1023 7 kg/m3 at 2 h, 1000 m) drilled in hardened cement paste samples and determined
1029 5 kg/m3 at 1 day, 1033 1 kg/m3 at 3 days and 1034 values of 121139. A similar procedure was used by Cook and Hover
1 kg/m3 at 7 days. Further, knowing the density of the solution and [41], who determined values of 139152 and also suggested that the
contact angle decreases for decreasing sizes of pores. Thus, such
values may not be relevant for much smaller pore sizes and the sur-
faces of the pore walls articially created due to drilling and their
roughness are certainly different than those of natural pores. Adolphs
et al. [42], using direct microscopical observation of the contact angle
of a mercury droplet on a cement paste surface, determined values of
about 142 after correction for effects of surface porosity.
An increasing value of contact angle implies the intrusion of larger
pores at a certain pressure in MIP. This results in the prediction of
higher values of RH for increasing contact angle. In Fig. 9 the effect
of the assumed contact angle for mercury is presented for the case
of 130 compared to 140 [27]. The value of 140 is used in all other
calculations presented in this paper.

4.2. RH depression due to dissolved ions

The pore solution composition at different ages was determined


for the w/c 0.40 paste, Table 3. It is expected that the ionic concentra-
tions and hence the ionic strength are higher for the pastes with less
free water (lower w/c), which would result in a higher RH depression
due to dissolved ions; the composition of the pore uid of the w/c
0.30 paste up to the age of one day is presented in Table 4. However,

Table 3
Composition of pore solution extracted from w/c 0.40 cement paste.

Time Ca2+ K+ Na+ SO42 OH


Fig. 8. Schematic illustration of the procedure for determination of r from chemical (mmol/l) (mmol/l) (mmol/l) (mmol/l) (mmol/l)
shrinkage and MIP curves (after [5]) (see also Fig. 12). It is assumed that the volume
2 h 0.344 376 53.1 137 156
of pores emptied by chemical shrinkage corresponds to the radius at which the same
1 day 5.24 575 91.8 130 420
volume of mercury is intruded during MIP (a). Based on this assumption, knowing
3 days 2.05 629 97.4 31.5 669
the volume of chemical shrinkage at certain age, the Kelvin radius can be determined
7 days 1.02 711 115 20.7 788
from the MIP curve obtained at the same age (b).
44 H. Chen et al. / Cement and Concrete Research 49 (2013) 3847

Fig. 9. Comparison of the RH calculated for the w/c 0.30 paste with the KelvinCohan Fig. 10. Comparison of the equilibrium RH measured on synthetic pore solution and
equation assuming different properties of the pore uid and different contact angles simulated with Raoult's law based on the pore solution composition presented in
of mercury. The thick line represents the chosen parameters used in all the calculations Table 3.
in this paper (w = 0, Hg = 140).

only the highest w/c of 0.40 is discussed in the following, since it was 4.3. Inuence of the experimental scatter
impossible to extract sufcient amounts of pore uid from pastes of
w/c lower than 0.40 at ages older than about 1 day. In calculations presented in the previous section, in each set of
The RH drop due to dissolved salts in a w/c 0.40 paste was calcu- data the average values obtained from 2 to 3 measurements were
lated using Raoult's law (Eq. (2)), assuming that the ions are used. This section discusses the inuence of the experimental scatter
completely dissociated, and is shown in Fig. 10 compared with the on the predicted RH. For this purpose, the extreme values of chemical
RH measured over a synthetic pore solution prepared according to shrinkage and MIP pore size distribution are considered in the calcu-
the composition in Table 3. It can be seen that the application of lation of the Kelvin radius. The radius is calculated for the two ex-
Raoult's law may lead to an overestimation of the prediction of the treme cases: (1) the lower boundary for the chemical shrinkage is
RH depression. However, the RH measurements at such high RH combined with the upper boundary for the MIP pore size distribution
have low accuracy. On the other hand, if the ions in the solution are to provide the upper boundary for the Kelvin radius, and (2) the
not completely dissociated, this will lead to higher RH than for com- upper boundary for the chemical shrinkage is combined with the
plete dissociation. As indicated in Table 3, with the consumption of lower boundary for the MIP pore size distribution to provide the
water due to hydration, the concentration of ions in the pore uid in- lower boundary for the Kelvin radius, see Fig. 12. The results, showing
creases, which leads to decreasing water activity over time, Fig. 10. the inuence of experimental scatter on the predictions using the
The effect of a decrease in w/c can be estimated in a simplied KelvinCohan and Raoult equations, are compared with the experi-
way by taking into account the difference in water content based on mental data in Fig. 13. As shown, the uncertainty of the MIP and the
the initial differences in mixture composition and the measured evo- chemical shrinkage measurements can have a very pronounced effect
lution of the hydration degree and assuming that the concentration is on the predicted RH evolution, even up to 1.7% RH depending on
inversely proportional to the water content. According to this rough the cement paste and age of testing.
estimation, the ionic concentration in a w/c 0.30 paste may be about
40% higher and about 9% in a w/c 0.35 paste at later stages of hydra- 5. Discussion
tion with respect to the w/c 0.40 paste. This estimation neglects the
effects of possible differences in the amount of ions bound in the hy- Considering the possible sources of error, the calculated and the
dration products at different ages or precipitated out of solution. measured RH evolution agree very well, especially after approximate-
Comparing Tables 3 and 4, one can see that the decrease in initial ly 3 days of age. There is some overestimation of the RH depression in
water available for dissolution leads to an increase in ion concentration the initial stages (around 1 day), where the predicted RH is a couple
only for some of the ions. In any case, the calculations of RH depression of % lower than the measured one. It appears that following the ap-
using Raoult's law are performed based on the experimentally-obtained proach originally suggested by Hua et al. [5], once the inuence of
pore solution composition for w/c 0.40, which is likely to underestimate water activity of the pore solution is also taken into account [2], it is
the actual RH depression due to salts in the lower w/c pastes. This possible to simulate the development of self-desiccation in Portland
approximation means that in Fig. 11 a and b, the curves Kelvin cement pastes with good accuracy. On the other hand, the additional
Cohan + Raoult would be slightly lower if the actual RH depression correction of the Kelvin equation by taking into account the thickness
due to salts in the w/c 0.30 and 0.35 pastes could be calculated based of the adsorbed water layer (KelvinCohan equation) does not inu-
on their pore solution composition. ence the results substantially in this RH range (10086%), though it
would become signicant at lower RH.

5.1. Mechanisms leading to autogenous shrinkage


Table 4
Composition of pore solution extracted from w/c 0.30 cement paste. The capillary pressure has been claimed by some authors, e.g. [1921]
to have only a minor inuence on the deformations of hydrating cement
Time Ca2+ K+ Na+ SO42 OH
paste even at high RH. According to these authors, the main driving
(mmol/l) (mmol/l) (mmol/l) (mmol/l) (mmol/l)
mechanism is the disjoining pressure. The lack of experimental data on
1h 1.40 271 69.6 174 156 which to base quantitative values for the disjoining pressure makes it
1 day 4.84 519 114 237 420
difcult to estimate its impact.
H. Chen et al. / Cement and Concrete Research 49 (2013) 3847 45

Fig. 12. Scheme illustrating the inuence of experimental scatter in MIP and chemical
shrinkage experiments on the variability of RH calculations.

is according to a number of authors [2,5,1518,37,39,44] the domi-


nant mechanism of both autogenous shrinkage and drying shrinkage
in the high RH range. The results demonstrate that this is perfectly
adequate to predict the RH evolution with good accuracy. At lower RH
it is possible that the effects of increasing disjoining pressure may
dominate with respect to capillary pressure.

5.2. Water activity of pore solution

The ions dissolved in the pore uid, especially the alkali, sulphate
and hydroxyl ions, reduce the activity of the water and hence the in-
ternal RH [37]. Raoult's law is strictly valid for an ideal solution and it
can be only used in the case of low-concentration solutions. In the
case of pore solution extracted from the w/c 0.40 cement paste, it
seems that those assumptions are reasonable and the agreement of
predicted and measured RH evolution is satisfactory. With increasing
concentrations (for lower w/c), Raoult's law would be expected to
underestimate the RH depression [45]. An alternative approach to
Raoult's law would be to employ the ion interaction model by Pitzer,
which is expected to yield more precise activity estimations for con-
centrate solutions [46]. Grasley and Leung [47] compared Pitzer's
equations and Raoult's law for one pore solution as the water was
removed by drying, nding a good agreement in the high water satu-
ration range.

5.3. Contact angles of water and mercury

The contact angles for water and mercury are of substantially


Fig. 11. Comparison of the average measured RH and RH calculated based on Kelvin ra- higher importance relative to all other parameters in the Kelvin and
dius only (Kelvin), after accounting for the adsorbed layer (KelvinCohan), and Washburn equations. The assumption of perfect wetting of water
after accounting for dissolved ions with Raoult's equation (KelvinCohan + Raoult)
(0 contact angle), which is almost invariably applied in the literature
for a) w/c 0.30, b) w/c 0.35, and c) w/c 0.40 pastes.
(e.g. [2,5,37]) and also here, gives the lowest estimation of RH. If the
real contact angle is larger the RH will be higher. However, the as-
Combining Eqs. (4) and (5), and considering that the disjoining sumption of perfect wetting (contact angle 0) seems realistic, since
pressure acts together with the capillary pressure, one obtains the receding pore uid is actually not in contact with the solid surface
[21,43]: of the pore wall, but with the adsorbed uid lm. The assumed
  contact angle for mercury is of equivalent importance. Considering a
p M w realistic uncertainty for these values, differences of about 45% RH
RH exp c 8
RTw at lower RH levels can be found in the predicted RH evolution, see
Fig. 9.
If a constant value of 1 MPa [21] is assumed in Eq. (8), a decrease
in RH by 0.7% at most is observed. The opinion of the authors is that at 5.4. Calculation of Kelvin radius from MIP and chemical shrinkage
this moment there is insufcient information available for a quantita-
tive model based on the disjoining pressure approach. In this paper, A further possible source of error in the predictions originates
the approach based on capillary pressure has been followed, which from the assumptions implicit in the approach used. When pores
46 H. Chen et al. / Cement and Concrete Research 49 (2013) 3847

This effect will be most pronounced when the Kelvin radius is greater
than the critical breakthrough radius of the MIP measurements. As
the Kelvin radius decreases at later ages, the degree of overestimation
decreases. The ink-bottle effect, leading to a difference between the
actual pore size distribution and the size distribution of pores entries,
cannot be exactly quantied. In fact, only the amount of ink-bottle
pores related to their entrances can be determined using MIP [27],
but not their actual size distribution. Nevertheless, the comparison
of experimental and simulated RH in this study appears to show a
decreasing importance of the ink-bottle effect with the progress of
porosity renement, as the simulated values are signicantly lower
than the experimental ones at early ages (up to 3 days), while the
difference is smaller at later ages.
Further, part of the chemical shrinkage occurring before setting
leads to an external volume change of the pastes rather than empty-
ing the porosity [35]. This effect could be simply taken into account by
zeroing the chemical shrinkage curves at the time of setting. Further
research would however be needed to determine if the curves are
best to be zeroed at initial or nal set or at any intermediate point.
For the extreme case of w/c 0.40, zeroing the chemical shrinkage at
the time of initial set would result in an increase of the calculated
RH at 7 days of 0.6% and 0.9% for zeroing at nal set. For the lower
w/c pastes, this effect is even smaller.
On the other hand air voids would have an opposite effect. Since
entrapped air voids do not contain water, their volume should be
subtracted from the total porosity determined with MIP, as they do
not contribute to menisci-related pressure. The effect of entrapped
air can however be neglected in a rst approximation, since 1% of
entrapped air porosity corresponds to only about 5 mm 3/g of pore
volume (compare with the total porosity shown in Fig. 6).

5.5. Effect of experimental uncertainties

As shown in Section 4.3, experimental scatter plays an important


role in the RH calculations. The scatter of both chemical shrinkage
and MIP lead to possible errors quantied here as 1.7% RH for the
extreme case.
A further source of uncertainty regards the measurement of chem-
ical shrinkage. Chemical shrinkage was measured on saturated sam-
ples, while the RH was measured on sealed, self-desiccating samples,
for which lower values of hydration might be expected. Applying
values from chemical shrinkage overestimates the volume of empty
pores from which the Kelvin radius is then calculated. As a result,
smaller Kelvin radii and lower RH values are calculated. Based on the
comparison of the heat of hydration evolution curves for the saturated
and sealed systems, Fig. 4, the overestimation of the degree of hydra-
tion is at most 19% for the w/c 0.30 cement paste. This leads to a
maximum overestimation of the RH depression by about 1.35% RH
for the w/c 0.3 cement paste at 7 days.
Fig. 13. Inuence of the experimental scatter of chemical shrinkage and MIP on the RH
predictions obtained using the combined KelvinCohan and Raoult equations for a) w/c 6. Conclusions
0.30, b) w/c 0.35 and c) w/c 0.40 pastes. The continuous lines refer to the simulations
based on average MIP and chemical shrinkage, while the dotted lines refer to the RH
The results presented here show that the evolution of RH in
calculated with extreme values (see Fig. 12). The experimental results are presented
with dashed lines. self-desiccating samples can be well estimated from an approach
based on the formation of menisci in capillary pores. It is important
to take into account the inuence of the pore solution composition
empty during hydration due to chemical shrinkage, there are large on RH.
pores from which water can be consumed without raising the capil- The various sources of error have been discussed. The most signif-
lary pressure substantially; however, in the MIP measurements, icant are the values taken for the contact angles of water and mercury.
these pores can only be accessed from narrower entrances, an artefact Experimental variability accounts for errors in the range of 12% RH.
that is commonly referred to as the ink-bottle effect [26]. In conse- The thickness of the adsorbed water layer assumed has only a very
quence, the real pore size distribution will be shifted to the right slight effect on the calculation of RH values.
(toward larger radii) with respect to the curve representing the size The connectivity of the pore structure and the way this differently
distribution of pore entries determined with MIP. In view of this arte- affects self-desiccation compared to MIP leads to an overestimation of
fact, the predictions of the Kelvin radius are minimum values and lead the RH depression at early ages when the Kelvin radius is greater than
to an estimation of the RH depression greater than the actual one. the critical breakthrough diameter in MIP. After 3 days the predicted
H. Chen et al. / Cement and Concrete Research 49 (2013) 3847 47

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