Advances in Cement Research Advances in Cement Research

http://dx.doi.org/10.1680/adcr.14.00109
Pore structure of cement pastes through
NAD and MIP analysis
Zeng, Li, Fen-Chong and Dangla
Paper 1400109
Received 02/12/2014; revised 23/06/2015; accepted 23/06/2015
ICE Publishing: All rights reserved

Pore structure of cement pastes

through NAD and MIP analysis
Qiang Zeng Teddy Fen-Chong
Research Assistant, Civil Engineering Department, Tsinghua University, Senior Scientist, Navier Laboratory, UMR 8205 CNRS-IFSTTAR-ENPC,
Beijing, PR China Champs-sur-Marne, France
Kefei Li Patrick Dangla
Professor, Civil Engineering Department, Tsinghua University, Beijing, Senior Scientist, Navier Laboratory, UMR 8205 CNRS-IFSTTAR-ENPC,
PR China Champs-sur-Marne, France

Two cement pastes (water to cement ratio, w/c = 0·5, 0·3) were investigated through mercury intrusion porosimetry
(MIP) and nitrogen adsorption/desorption (NAD) methods at different hardening ages. The pore structure is
characterised by specific surface area, pore volume and pore size distribution. The results show that: (a) the pore
structure has strong scale dependence and NAD–MIP joint measurement helps to identify the different pore structure
patterns; (b) MIP total pore volume captures the global process of the hydrates filling process with curing age,
the mesopore (2–70 nm) volume is dominated by hydrates filling for w/c = 0·5 but countered by high-density
calcium-silicate-hydrate growth for w/c = 0·3; (c) specific surface area is sensitive to calcium-silicate-hydrate growth and
specific surface area values are likely to confirm that high w/c (0·5) favours low-density calcium-silicate-hydrate
growth whereas low w/c (0·3) facilitates high-density calcium-silicate-hydrate formation.

Introduction globules of 3 nm, composed of basic unit blocks of 1·1 nm,

Hardened cement pastes (HCPs) have a pore structure with a
broad distribution of pore sizes from nanometre to micrometre
(Mehta and Monteiro, 2006). The pore structure is formed by
the progressive filling of cement hydrates into the void space
initially occupied by mixing water. The connectivity among
the pores of different sizes seems to be complicated and ‘ink-
bottle’ pores are reported to exist extensively in the pore
network (Diamond, 2000). The multi-scale nature of HCP
pore structure has been proved crucial for predicting the
mechanical and durability properties, and different transport
processes dominate at different pore scales (Dridi, 2013;
Ghabezloo, 2010; Hall et al., 2013; Ma et al., 2014; Ulm
et al., 2004). Thus, understanding the pore structure of HCP
can help to optimise the performance of materials with respect
to transport processes.
Among the hydration products, calcium-silicate-hydrate and its
morphology have an important influence on the pore structure
of HCP (Jennings, 2008). The microstructure of calcium-
silicate-hydrate is the physical basis for HCP deformation,
such as shrinkage and creep, under different environmental
conditions and loadings (Vandamme et al., 2010). Calcium-
silicate-hydrate was first classified into inner products (IP) and
outer products (OP) by Taplin (1959); this was then confirmed
by observation through high-resolution transmission electron
microscopy (TEM) and electron microprobe analysis (EMPA)
(Richardson, 1999, 2000). Based on the specific surface areas
(SSAs) of HCPs, Jennings and coworkers (Jennings, 2008;
Tennis and Jennings, 2000) proposed a colloid model for the
calcium-silicate-hydrate microstructure: calcium-silicate-hydrate
constitute the high-density calcium-silicate-hydrate and low-
density calcium-silicate-hydrate following different packing
patterns (Constantinides and Ulm, 2007; Jennings, 2008;
Vandamme et al., 2010). This structure model from globules is
not fundamentally different from the calcium-silicate-hydrate
model proposed by Powers (1958). The repeating 3 nm globules
give a self-similar property to calcium-silicate-hydrate structure
for the size range 3–30 nm (Jennings, 2008). This statement
has been confirmed by Zeng et al. (2010), and the correspond-
ing fractal dimension was determined for HCP with different
binder types (Zeng et al., 2013a).
Nowadays, mercury intrusion porosimetry (MIP) and nitrogen
adsorption/desorption (NAD) measurements remain the pre-
ferred methods for pore structure characterisation of HCP.
MIP measurement provides a large range of pore size and easy
operation (Léony, 1998), and NAD shows good detection
capacity for pores smaller than 70 nm (Kaufmann et al., 2009).
According to Jennings (2008) and Tennis and Jennings (2000),
only the gel pores in low-density calcium-silicate-hydrate can be
penetrated by nitrogen. This provides a method to evaluate the
water removal quantity and microstructure alteration of HCP
subjected to different drying methods (Zeng et al., 2013b).
Actually the joint characterisation of pore structure with MIP
and NAD methods has been reported in literature (Kaufmann
et al., 2009; Kaufmann 2010; Zeng et al., 2012a).
The joint MIP/NAD method is used in this paper to investi-
gate the pore structure of two HCPs with water to cement
ratios, w/c = 0·5 and 0·3. The pore structure at three different

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Advances in Cement Research Pore structure of cement pastes through
NAD and MIP analysis
Zeng, Li, Fen-Chong and Dangla

scales, that is the micropores (≤2 nm), mesopores (2–70 nm)
and capillary pores (≥70 nm), is analysed to characterise the
HCP pore structure.
Materials and experiments
Materials
The cement pastes were made from an ordinary Portland
cement, equivalent to CEM I type. Table 1 shows the chemical
composition and physical properties of the cement. The
mineral content of the cement was analysed using Bogue’s pro-
cedure: dicalcium silicate (C2S) (21·38%), tricalcium silicate
(C3S) (58·88%), tricalcium aluminate (C3A) (6·49%), tetracal-
cium alumino ferrite (C4AF) (8·77%), gypsum (0·75%) and
others (3·73%).
Samples preparation
Two cement pastes, paste I (w/c = 0·5) and paste II (w/c = 0·3),
were prepared. The mixing procedure observes the ACI stan-
dard (ACI, 1991). After mixing, cement pastes were cast into
cylinder tubes of 10 mm diameter and the hardened specimens
were de-moulded from the tubes at the age of 3 d, then
immersed in water. The volume ratio of samples to water was
kept roughly at 1:1 to avoid possible leaching. At the ages of 7,
28, 90 and 180 d, specimens were taken out of the water and
the middle parts of cylinder specimens were taken and crushed
into particles of size 1
2 mm for pore structure characteris-
ation. The particle samples were then vacuum-dried immedi-
ately to stop the hydration and stored in sealed containers to
limit possible carbonation. The freeze-drying was used to pre-
treat the particle samples for MIP and NAD tests. The
samples, together with the container, were first immersed in
liquid nitrogen (N2, −196°C) for 5 min, then transferred to the
freeze-dryer and vacuumed for 24 h before MIP/NAD tests.
The MIP and NAD measurements were then performed on
the freeze-dried particle samples.
Pore structure characterisation
Mercury intrusion porosimetry
The MIP measurement relies on the principle that the intru-
sion volume of mercury into a porous material depends on the
applied pressure. During the intrusion the applied pressure is
assumed to be in equilibrium with the surface tension of
mercury in pores. With the cylindrical assumption for pore
geometry the pore size (diameter) d can be related to the
applied pressure P by the Washburn equation: d = −4γcosθ/P,
where γ is the surface tension of mercury (0·485 N/m), θ is the
contact angle between mercury and the pore wall, and θ = 130°
is commonly adopted for cement-based materials (Zeng et al.,
2012a, 2012b). The pore size distribution (PSD) curve can
then be obtained by relating the intruded volume at a given
pressure to the pore size evaluated at the same pressure, see
Table 2. The SSA, S, can be calculated through the energy
conservation between the non-wetting internal surface exten-
sion and the external work for mercury penetrating (Rootare
and Prenzlow, 1967), that is, –γcosθdS = PdV; for details see
Table 2. The MIP measurement equipment used in this study
is of type Autopore IV 9510 with maximum and minimum
applied pressures of 414 MPa and 1·4 kPa, corresponding to a
minimum pore size of 3 nm and maximum pore size about
800 μm.
Nitrogen adsorption/desorption
The NAD experiment records the adsorbed nitrogen quantity
at different relative pressure of nitrogen P/P0 where P, P0 stand
for experimental and saturation pressures of nitrogen. The
NAD actually yields a nitrogen adsorption/desorption iso-
therm, needing further interpretation to characterise the pore
structure of HCP. As the gas (nitrogen) pressure is relatively
low it can be assumed that surface adsorption dominates. As
the relative pressure increases, further nitrogen condensation
occurs in the pores. The relation between relative pressure and
equilibrium pore size deq can be described through Kelvin
equation (Aligizaki, 2006)

Composition/property Value 4γN VN

1: deq ¼   191 lnðP=P0 Þnm
RT lnðP=P0 Þ
Silica (SiO2): % 22·93
Alumina (Al2O3): % 4·29
where γN is the surface tension of liquid nitrogen (8·85  10−3
Iron oxide (Fe2O3): % 2·89
N/m), VN represents the molar volume of liquid nitrogen
Calcium oxide (CaO): % 66·23
(3·467  10−5 m3/mol), R is the ideal gas constant (8·314 J/K/
Magnesium oxide (MgO): % 1·92
mol), and T is the temperature of liquid nitrogen (77·3 K). To
Sulfur trioxide (SO3): % 0·35
evaluate the ‘real’ pore diameter, it is necessary to take into
Sodium oxide (Na2O) (eq): % 0·70
account the nitrogen sorption thickness on the pore wall t, that
Free calcium oxide (CaO(f)): % 0·64
is, d = deq + t.
Chloride (Cl−): % 0·006
Loss on ignition (LOI): % 1·70
The PSD and SSA can be evaluated by the Barrett–Joyner–
Density, ρ: g/ml 3·12
Halenda (BJH) interpretation (Barrett et al., 1951), see
Specific area, S: m2/kg 343
Table 2. In the BJH expression for PSD, the pore distribution
Table 1. Chemical composition and physical properties of cement is noted as pore volume Vn in terms of the pore diameter d,
δVexp is the measured gas adsorption volume, δVads represents

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Advances in Cement Research Pore structure of cement pastes through
NAD and MIP analysis
Zeng, Li, Fen-Chong and Dangla

Method Parameter Equation References

dV dV 4γ cos θ
MIP PSD: ml/g ¼ Aligizaki (2006)
dlnðdÞ dP d
ðV
1
SSA: m2/g S¼ PdV Rootare and Prenzlow (1967)
γ cos θ
0

2
d
NAD PSD: ml/g δV ¼ ðδVexp  δVads Þ Barrett et al. (1951)
deq
SSA: 106 m2/g S ¼ 435 Vm Aligizaki (2006)
P δV
SSA (BJH): m2/g S¼ Barrett et al. (1951)
d
V
SSA (t-plot): 10−4 m2/g S ¼ 1547 de Boer et al. (1966)
t
Table 2. PSD and SSA determined from MIP and NAD
measurements

the adsorbed volume on the exposed pores. For comparison, 25

the SSA evaluations by the Langmuir/Brunauer–Emmett–
Teller (BET) methods (Aligizaki, 2006) and the t-plot method 7d
20 28 d
(de Boer et al., 1965, 1966) are also given in Table 2. The
Adsorbed volume: ml/g

90 d
Langmuir/BET methods can give the SSA for relative pressure 180 d
in the range 0·05
0·35. The term Vm is the volume of 15
adsorbed gas when the entire pore surface is covered with a
mono-layer, evaluated from the classical BET expression
10
(Brunauer et al., 1938). For the t-plot method, the term V is
the total nitrogen sorption volume and the thickness of
adsorbed layer t is calculated from the Harkins and Jura’s 5
equation (Harkins and Jura, 1944). The NAD device used in
this study is of type ASAP2010 with the nitrogen pressure 0
range up to 126·66 kPa. 0 0·1 0·2 0·3 0·4 0·5 0·6 0·7 0·8
Statistical thickness: nm
Results analysis (a)
10 9·0
t-plot curves and specific surface area
The t-plot interpretation of NAD data on paste I and paste II 9 8·5

is illustrated in Figures 1(a) and 1(b). It can be seen that, 8 8·0

Adsorbed volume: ml/g

except for the curves at 7 d, the adsorption volume shows 7 7·5

linear dependence on the adsorbed thickness. The SSA value 6 7·0
can be determined by the slope of the t-plot, cf. Table 2. 0·60 0·65 0·70 0·75 0·80
5 7d
According to de Boer et al. (1965), some tiny pores, filled first
4 28 d
by multilayer adsorption, can make the t-plot curve drop 90 d
below the V–t straight line with thickness, for example the 3 180 d
t-plot curves of paste I and paste II at 7 d in Figure 1. 2
Moreover, it was stated that, as the capillary condensation
1
occurs in addition to multilayer adsorption, the t-plot curve
should deviate upward from the V–t straight line (de Boer 0
0 0·1 0·2 0·3 0·4 0·5 0·6 0·7 0·8
et al., 1965, 1966). This upward deviation is not observed in
Statistical thickness: nm
the results of the present study.
(b)

Table 3 summarises the NAD SSA values evaluated by Figure 1. t-plot for (a) paste I and (b) paste II at different curing
Langmuir, BET and BJH methods and MIP SSA values. The ages
principles of the methods can be found in Table 2. The SSA

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Advances in Cement Research Pore structure of cement pastes through
NAD and MIP analysis
Zeng, Li, Fen-Chong and Dangla

t-plot
Curing age BET Langmuir P/P0 = 0·2 BJH adsorption BJH desorption MIP

7d 26·69 (9·00) 36·46 (12·20) 26·45 (9·35) 21·17 (5·07) 32·03 (13·07) 35·53 (17·79)
28 d 36·62 (17·92) 50·38 (24·88) 35·92 (17·34) 33·61 (18·55) 56·44 (26·54) 64·43 (23·27)
90 d 40·42 (16·68) 56·11 (23·21) 39·11 (16·09) 42·98 (17·72) 58·51 (25·26) 58·82 (22·31)
180 d 44·66 (16·96) 61·85 (23·63) 43·12 (16·32) 48·44 (17·63) 61·94 (22·55) 55·32 (23·99)

Table 3. Specific surface area (m2/g) of paste I (II) by different

evaluation methods

values of paste II are much smaller than for paste I, for all
evaluation methods, indicating paste I has much larger internal
surface accessible to nitrogen and mercury than paste II.
Moreover, the SSA values show very different patterns in terms
of curing age for paste I and paste II. Note that SSA is con-
tributed mainly by pores in a size range < 100 nm. Accordingly
the SSA values are more related to the microstructure of the
calcium-silicate-hydrates. For paste I, all SSA values increase
with curing age except for MIP SSA, and the MIP SSA
values attain a maximum at 28 d. This reflects the differ-
ent accessibility of paste I to nitrogen and mercury: the
nitrogen can penetrate into very tiny pores of the calcium-
silicate-hydrate microstructure, whereas mercury can only
detect the large gel pores in the calcium-silicate-hydrate struc-
ture. Thus, NAD captures the calcium-silicate-hydrate growth
and evolution with curing age for paste I, but MIP fails to
trace the change of calcium-silicate-hydrate after the age of
28 d. For paste II, the SSA values reach a maximum at 28 d,
then remain stabilised with curing age regardless of the evalu-
ation methods (NAD/MIP), meaning that the accessibility
of paste II to nitrogen and mercury is somehow stabilised at
the age of 28 d. The same observation has been reached for
HCP with w/c = 0·33 in the literature (Hunt, 1966), and the
related mechanism is to be discussed later in the ‘Discussion’
Another important observation is that the NAD SSA of micro-
pores (< 2 nm) decreases with curing age for both paste I and
paste II, contrary to the total SSA values, cf. Figure 2.
Micropores with d < 2 nm are determined through the extrapol-
ation of the second straight line to P/P0 = 0 on the t-plot
(Aligizaki, 2006). Following Harkins and Jura (1944), this
interception at P/P0 = 0 on the t-plot can be interpreted as the
adsorption volume of nitrogen in the micropores (< 2 nm) with
an adsorption thickness of 0·354 nm. Recalling the t-plots in
Figure 1, a downward deviation from linearity at low P/P0 is
observed for both paste I and paste II at 7 d. Korpa and
Trettin (2006) suggested that some supermicropores and very
narrow mesopores of size 0·7–1·8 nm, presented in slit-shaped,
sheet-like nanostructures of calcium-silicate-hydrate, can be
filled in the low pressure range P/P0 = 0·01
0·4. Thus, this
downward deviation may indicate that micropores become
filled by multilayer adsorption at low relative pressure and
reduce the surface available for later adsorption (Aligizaki,
2006). With curing age this downward trend disappears, indi-
cating the micropores either decrease or become less accessible
20
SSA micropores: m2/g

7d 28 d 90 d 180 d
section. 15

The NAD SSA by the Langmuir method is systematically 10

larger than by the BET method because the former assumes a
5
mono-layer molecule adsorption and overestimates the Vm
value. It can be further found that the NAD SSA by the BET 0
method is very close to the t-plot SSA at P/P0 = 0·2. This Paste I Paste II
SSA micropores: m2/g

60
observation was confirmed by NAD measurement on HCP
blended with silica fume (Khalil, 1996). Table 3 shows that the 40
BJH (adsorp) SSA has a similar value to the BET SSA, and
the BJH (desorp) SSA has a similar value to the Langmuir
20
SSA. However, this must be a coincidence because the valid
range of the BET method (P/P0 = 0·05
0·35) is different from
0
that of the BJH method (P/P0 = 0·45
0·97) (Aligizaki, 2006).
It is worth noting that the BET method was originally devel- Figure 2. SSA of micropores (d ≤ 2 nm) (top) and mesopores
oped to measure the SSA of a flat, solid surface rather than (2nm ≤ d ≤ 70 nm) (bottom) determined by t-plot with curing age
porous materials and that cylindrical pore geometry is for paste I and paste II
assumed.

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Advances in Cement Research Pore structure of cement pastes through
NAD and MIP analysis
Zeng, Li, Fen-Chong and Dangla

to nitrogen. The SSA of mesopores (2–70 nm) increases with 200

BJH adsorption
curing age for paste I but reaches a maximum for paste II at 7d 28 d 90 d 180 d

volume: µl/g
150
age of 28 d, cf. Figure 2. The involved mechanism is to be dis-
cussed later. 100

50
Pore volume and pore size distribution
0
Figure 3 shows the micropore volume (d ≤ 2 nm) and total

BJH desorption volume: µl/g

Paste I Paste II
adsorbed pore volume (d ≤ 70 nm) with curing age for paste I 150
and paste II from NAD data. Like the micropore SSA the
micropore volume decreases with curing age monotonously for 100
both paste I and paste II in Figure 3. The reduction of micro-
pores is particularly important for paste II: the micropore 50
volume reduces from 4·141 μl/g to 0·219 μl/g for curing age
from 7 d to 180 d. The total pore volume increases with curing
0
age for paste I and shows a maximum for paste II at 28 d in
Figure 3. The pore volumes are evaluated using the BJH Figure 4. BJH adsorption pore volume (top) and BJH desorption
method from both nitrogen adsorption and desorption data pore volume (bottom) with curing age for paste I and paste II
and the results are presented in Figure 4. Again, a steady
increase is observed for BJH pore volume of paste I with
curing age, but a maximum at 28 d is observed for paste II.
MIP volume (total): µl/g MIP volume (3–70 nm): µl/g

200
The total volume measured by MIP decreases with curing age 7d 28 d 90 d 180 d
for both paste I and paste II in Figure 5. However, as the pore 150
size range is fixed to 3–70 nm, the MIP pore volume follows
the same pattern with curing age as in Figure 4: the pore
100
volume increases with curing age for paste I, whereas it
reaches a maximum at 28 d for paste II. Although different
in value, the MIP pore volume (3–70 nm) and BJH results in 50
Paste I Paste II
Figure 4 confirm the same pattern of mesopore evolution 250
in terms of curing age. The agreement between BJH and MIP
results was reported in literature for pore size range d ≤ 50 nm 200
(Kaufmann, 2009). Figure 6 shows the MIP PSD curves in the 150
pore size range of 1–1000 nm for paste I and paste II at
100

0
10
Total pore volume: µl/g

9 7d 28 d 90 d 180 d
8 Figure 5. MIP pore volume (3 nm ≤ d ≤ 70 nm) (top) and total MIP
7
6
pore volume (3 nm ≤ d ≤ 800 μm) (bottom) with curing age for
5 paste I and paste II
4
3
2
1
0 different curing ages. With curing age the critical pore size is
found to decrease significantly for paste I but is almost stable
Total pore volume: µl/g

Paste I Paste II
for paste II. The critical pore size corresponds to the inflection
100
point on the PSD curves, scaling the smallest pore size of per-
colated pores (Katz and Thompson, 1986). Note that this criti-
50 cal pore size is proposed in the context of mercury intrusion,
and the physical percolation of pores can assume different
sizes for the infiltration of other fluids or electrical currents
0
(Sant et al., 2011). This critical size has also been reported to
Figure 3. Micropore volume (d ≤ 2 nm) (top) and total adsorbed correlate strongly with the permeability and diffusivity of
pore volume (d ≤ 70 nm) (bottom) with curing age for paste I and cement-based porous materials (Halamickova et al., 1995). In
paste II terms of magnitude, the critical pore sizes of paste I are sys-
tematically larger than paste II, confirming the percolating

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Advances in Cement Research Pore structure of cement pastes through
NAD and MIP analysis
Zeng, Li, Fen-Chong and Dangla

0·25 0·025

7d
0·20 28 d 0·020 7d
90 d
28 d
180 d
dV/d(logd): ml/g

dV/dlog(d): ml/g
90 d
0·15 0·015 180 d

0·10 0·005

0·05 0·005

0
0
100 101 102 103
1 4 16 64
Pore diameter: nm Pore diameter: nm
(a) (a)
0·20
0·015

7d
0·15 28 d 7d
90 d 28 d
dV/d(logd): ml/g

180 d 90 d
0·010
dV/dlog(d): ml/g

180 d
0·10

0·05 0·005

0
100 101 102 103 0
Pore diameter: nm 1 4 16 64
(b) Pore diameter: nm
(b)
Figure 6. Differential PSD measured by MIP for (a) paste I
(w/c = 0·5) and (b) paste II (w/c = 0·3) at different curing ages Figure 7. Differential PSD for (a) paste I and (b) paste II at
different curing ages from BJH desorption data

nature of pores in paste I and the much less percolated state of

pores in paste II.
According to Jennings (2008) the size of large gel pores can
reach 10 nm. Two regions are thus classified in the PSD curves
in Figure 6: region I for pore size d = 3
10 nm and region II
for pore size d = 10
1000 nm. The MIP measurement in
region I can be assumed exempted from the ‘ink-bottle’ effect
so that the obtained PSD in this range is likely to approach
the real pore geometry. Note that the very high intrusion
pressure exerted on material for the pore size region I can
possibly induce pore collapse due to mechanical damage,
and this effect is not included in the interpretation. In region
II the percolation of pores is more complicated and the critical
pore size is actually the ‘throat’ size of ink-bottle pores
(Diamond, 2000). It can be further seen that the pore volume
in region I increases with curing age for both paste I and
paste II.
In Figure 7 the PSD curves evaluated from BJH desorption
data are presented for paste I and paste II at different curing
ages. The valid range of pore size for the BJH method is
argued to be less than 30 nm since the upper limit P/P0 is
about 0·97 (Aligizaki, 2006; Kaufmann et al., 2009). There is
no significant difference for these PSD curves with a peak
observed at pore size d = 3·5 nm. This pore size agrees well
with the interglobule pore size of calcium-silicate-hydrates, and
this peak is likely to reflect the nitrogen condensation in the
interglobule pores of the calcium-silicate-hydrate microstruc-
ture. The same conclusion is also reached by other authors in
the literature (Allen et al., 2007; Powers, 1958).
Discussion
The microstructure model of calcium-silicate-hydrate by
Jennings and coworkers (Jennings, 2008; Tennis and Jennings,
2000) is retained here to deepen the analysis of results in

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Advances in Cement Research Pore structure of cement pastes through
NAD and MIP analysis
Zeng, Li, Fen-Chong and Dangla

previous section. According to this model, the globules of 1·0

Low-density calcium-silicate-hydrate
calcium-silicate-hydrate sheet of size 3 nm pack together and High-density calcium-silicate-hydrate
constitute the calcium-silicate-hydrate microstructure Total calcium-silicate-hydrate
0·8
(Jennings, 2008). The micropores (<2 nm) refer to the space
between the globules and interlayer pores (intragranular

Volume fraction
pores), cf. Figure 8 (left). Through different packing density 0·6
the globules constitute low-density calcium-silicate-hydrate or
high-density calcium-silicate-hydrate. The low-density calcium- 0·4
silicate-hydrate structure has larger intergranular pores,
whereas high-density calcium-silicate-hydrate has smaller ones.
The mesopores (2–70 nm) refer to the intergranular pores in 0·2
low-density/high-density calcium-silicate-hydrate structure as
well as some small capillary pores among low-density/high- 0
density calcium-silicate-hydrate groups, cf. Figure 8(middle). 0·25 0·30 0·35 0·40 0·45 0·50
At much larger scale, the pore space that can be percolated by Water to cement ratio
free water is identified as capillary pores, cf. Figure 8(right).
The fraction of low-density calcium-silicate-hydrate in total Figure 9. Volume fraction of low-density calcium-silicate-hydrate
calcium-silicate-hydrate amount in HCP, fLD, can be estimated (circles), high-density calcium-silicate-hydrate (rectangles) and the
from the w/c ratio and hydration degree α as (Tennis and total calcium-silicate-hydrate (diamonds) in terms of w/c ratio for
Jennings, 2000) completely hydrated cement pastes using Jennings’ model (Tennis
and Jennings, 2000) and cement composition data in Table 1
2: fLD ¼ ½3017ðw=cÞ  1347α þ 0538

(b) the total pore volume (MIP), and the micropore volume
(NAD) decrease for both paste I and paste II, and the meso-
pore volumes (NAD/BJH/MIP) increase for paste I but reach a
Figure 9 shows the volume fraction of low-density/high-density
maximum at 28 d for paste II. These observations are closely
calcium-silicate-hydrate and total calcium-silicate-hydrate of
related to the hydration process of HCP, especially the hydrates
totally hydrated HCP with different w/c ratios. The calculation
filling and calcium-silicate-hydrate growth processes. In fact,
is performed following the stoichiometry presented in Taylor
the pore volume is more sensitive to the hydrates filling process
(1997) and the chemical composition data of cement clinkers
and the SSA is more pertinent to calcium-silicate-hydrate
in Table 1 are used. It can be found that, as w/c increases, the
growth, considering the main contribution of SSA comes from
amount of low-density calcium-silicate-hydrate increases but
gel pores. The last important point is the attainable pore size
high-density calcium-silicate-hydrate decreases.
of NAD in this study. Zeng et al. (2013b) confirmed that for
paste I and paste II freeze-drying pre-treatment can only reach
Focusing now on the main observations in the previous section
partially the low-density calcium-silicate-hydrate structure and
on pore characterisation in terms of curing age: (a) the total
cannot reach the high-density calcium-silicate-hydrate struc-
SSA increases with curing age for paste I but is stabilised for
ture. Quantitative interpretation of the NAD data by the same
paste II after the age of 28 d, and the SSA of micropores
authors (Zeng et al., 2013b) indicated that the low-density
decreases constantly for paste I and paste II with curing age;
calcium-silicate-hydrate volume of paste II even decreases as
curing age increases, see Figure 10.

High-density calcium-silicate-hydrate Capillary pore As hydration starts the capillary space occupied initially by
Small gel pore
free water is progressively filled by hydrates, thus the percolated
capillary pore volume and the critical pore size decreases with
curing age for both paste I and paste II in Figure 5. This capil-
lary filling process is globally captured by the MIP total pore
volume for paste I and paste II. Figures 11(a) and 11(b) show
the microstructure observed by scanning electric microscopy
Interlayer pore
Cement paste (SEM) for paste I and paste II at 90 d, confirming the micro-
Calcium-silicate-hydrate Large gel pore
sheets with bound water Low-density calcium-silicate-hydrate structure of paste I is more porous than paste II. With curing
age the calcium-silicate-hydrate grows in a more percolated
Figure 8. Schematic illustration of the scale-dependent pore network in paste I and the formation of low-density
microstructure of HCP (after Jennings, 2008) calcium-silicate-hydrate is favoured, but in paste II the
calcium-silicate-hydrate forms in a much less percolated

7
Advances in Cement Research Pore structure of cement pastes through
NAD and MIP analysis
Zeng, Li, Fen-Chong and Dangla

0·40 Paste I: Paste II:

Low-density Low-density
calcium-silicate-hydrate calcium-silicate-hydrate
High-density High-density
Gel volume: ml/g cement

calcium-silicate-hydrate calcium-silicate-hydrate
0·30

0·20

0·10

0
0 20 40 60 80 100 120 140 160 180
Curing age: d
5·0 µm
Figure 10. Calculated gel volume of pastes I and II at different
curing ages, data from Zeng et al. (2013b) (a)

context, thus high-density calcium-silicate-hydrate formation is

favoured, cf. Figure 9 and Figure 10. Since high-density
calcium-silicate-hydrate is less likely to be detected by NAD
after freeze-drying (Zeng et al., 2013b), only the exposed low-
density calcium-silicate-hydrate after drying can be interpreted
from NAD data. Accordingly the NAD SSA captures the
growth of low-density calcium-silicate-hydrate in paste I as a
steady increase, but remains stabilised after 28 d due to less for-
mation of low-density calcium-silicate-hydrate and a less perco-
lated pore network in paste II. According to Figure 9, paste II
has only about 6%–15% low-density calcium-silicate-hydrate,
one-third of the low-density calcium-silicate-hydrate fraction
for paste I. This result agrees roughly with the SSA data pre-
sented in Table 3. 5·0 µm

The SSA of micropores should have captured the growth of
high-density calcium-silicate-hydrate but fails due to the freeze-
drying treatment. The same reason leads to the micropore
volume decreases with curing age for paste I and paste II in
Figure 3. The range of mesopores (2–70 nm) is actually subject
to a combined effect of calcium-silicate-hydrate growth, provid-
ing mesopores up to 10 nm according to Jennings (2008), and
pore refinement by hydrates filling. The constant increase of
mesopores for paste I in Figure 4 and Figure 5 may indicate
that the hydrates filling dominates, whereas in paste II this
filling is countered by (high-density) calcium-silicate-hydrate
growth, which can no longer be detected by MIP–NAD in this
study, after the age of 28 d.
Conclusion
(a) The pore structure for two hardened cement pastes
(paste I and paste II) with w/c = 0·5, 0·3 were investigated
through a joint MIP–NAD measurement. Several
methods were used to evaluate the SSA and PSD of
(b)
Figure 11. SEM images for (a) paste I (w/c = 0·5) and (b) paste II
(w/c = 0·3) after 90 d curing
cement pastes with curing age from 7 d to 180 d. The
pore characterisation through joint MIP–NAD methods
can provide insight into the pore structure evolution with
respect to the hydrates filling and calcium-silicate-hydrate
growth processes.
(b) The hydrates filling process can be best captured by total
MIP pore volume and the SSA values are more related to
calcium-silicate-hydrate growth. Owing to pretreatment
by freeze-drying the MIP–NAD measurement can only
reach partially the low-density calcium-silicate-hydrate.
The SSA values with curing age are likely to confirm that
high w/c ratio favours low-density calcium-silicate-
hydrate, whereas low w/c ratio favours the high-density
calcium-silicate-hydrate. With high w/c ratio the hydrates

8
Advances in Cement Research
filling dominates in mesopore contribution, but this
filling effect is countered by high-density calcium-silicate-
hydrate growth under low w/c ratio.
Acknowledgements
The research is supported by NSFC grant no. 51378295 and
Tsinghua University grant no. 2014Z01004.
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