Journal of Colloid and Interface Science 246, 135–149 (2002)

doi:10.1006/jcis.2001.7962, available online at http://www.idealibrary.com on

Ink-Bottle Effect in Mercury Intrusion Porosimetry

of Cement-Based Materials
F. Moro1 and H. Böhni
Institute of Materials Chemistry and Corrosion, Swiss Federal Institute of Technology, CH-8093 Zürich, Switzerland

Received March 14, 2001; accepted September 3, 2001; published online December 21, 2001

where θ is the contact angle between the mercury and a sur-

Mercury intrusion porosimetry (MIP) is a widely used method face of the solid material tested and γ is the surface tension of
for studying porous materials, in particular, cement-based mate- mercury. There is good agreement as to the surface tension of
rials. The usual interpretation of such measurements is based on
mercury with accepted values ranging from 0.473 to 0.485 N/m
certain assumptions. One of these is that each pore is connected
to the sample surface directly or through larger pores. Pores not
(4). However, values for the contact angle of cementitious ma-
meeting this assumption are called ink-bottle pores. The effect that terials range from 117◦ to 141◦ , resulting in differences in pore
sample size has on the MIP characteristics of concrete samples, like radii by as much as a factor of two (4). These values are strongly
the ink-bottle effect and hysteresis, was studied by measuring ad- affected by the purity of the mercury.
ditional extrusion and intrusion cycles. In order to characterize the Porosimetry equipment can typically measure a maximum
extrusion and ink-bottle behavior, the amount of entrapped mer- pressure range between 0.004 and 400 MPa. This pressure range
cury χ(p) was estimated. Superimposition of extrusion and second corresponds to pore sizes from several hundreds of micrometers
intrusion curves is achieved if the contact angle θ is adjusted from θi , (low pressure) to a few nanometers (high pressure).
the intrusion contact angle, to θe , the extrusion contact angle. The The fraction of the porosity occupied by pores having radii
threshold radius is often assumed to be a dominant pore radius, in the interval (d; d + δd) is then deduced from the volume of
yet in this study the entrapped mercury content shows no evidence
mercury that intrudes within the pressure range (P; P + δ P)
for the presence of a dominant pore radius. Even if characteristic
properties of cement-based materials can be estimated with MIP,
corresponding to a pore radius range (r ; r + δr ) given by
comparison of results is rendered difficult by the significant effects
of sample preparation techniques and sample size and the ink-bottle d V = −DV (r )dr, [2]
effect due to randomly present air bubbles. °C 2002 Elsevier Science
Key Words: mercury porosimetry; cement-based materials; ink- where DV is the volume pore-size distribution function, defined
bottle effect. as the pore volume per unit interval of pore radius. Combining
Eqs. [1] and [2] gives
1. INTRODUCTION µ ¶
P dV
DV (r ) = . [3]
Many properties of concrete are directly or indirectly affected r dP
by its porosity. Characterization of concrete’s porosity is, there-
fore, often of great interest in order to explain differences be- Another useful function often used in place of the volume distri-
tween and give insights into these properties. Mercury intrusion bution function is the volume log radius distribution DV (log r ),
porosimetry (MIP) is a widely used method for studying porous which can be expressed as
materials, in particular cement-based materials. It provides a
function of cumulative pore volume versus applied pressure. dV
DV (log r ) = = r DV (r ). [4]
In order to interpret pressure values, they are usually con- d log r
verted into equivalent pore radii by applying the Washburn
equation (36), Combining the above Eq. [4] with Eq. [1], one obtains
µ ¶
2γ cos θ dV dV
r =− , [1] DV (log r ) = P = . [5]
p dP d log P

1 To whom correspondence should be addressed at Holcim Group Sup-

The usual interpretation of such measurements is based on
port Ltd., 5113 Holderbank, Switzerland, Fax: +41 (0)58 858 64 29. E-mail: certain assumptions. One of these is that each pore is connected
fabrizio.moro@holcim.com. to the sample surface directly or through larger pores, a criteria
135 0021-9797/02 $35.00
°
C 2002 Elsevier Science
All rights reserved.
136 MORO AND BÖHNI
which is not likely to be met by normal porous materials. In-
trusion into the wide inner body will not occur until sufficient
pressure is applied to force the mercury into the narrow open-
ings. It will, therefore, appear as if a large volume has intruded
into narrow pores. This is called the ink-bottle effect. The dis-
tribution curve should therefore be named the pore throat size
distribution.
The term intrusion curve is used to denote the volume change
that occurs with increasing pressure and extrusion curve to indi-
cate the volume change with decreasing pressure. The intrusion–
extrusion cycle does not close when the initial pressure is
reached, indicating that some mercury has been permanently
entrapped in the sample pore space. In fact, the path followed
by the extrusion curve is not the same as the intrusion path
(hysteresis). At any given pressure, the volume indicated on the
extrusion curve is greater than that on the intrusion curve and
for a given volume, the pressure indicated on the intrusion curve
is greater than that on the extrusion curve.
The pores in cement-based materials are classified accord-
ing to their origin as gel pores, capillary pores, and air bubbles
(25, 26). Gel pores are formed within the amorphous CSH phase,
the main hydration product. Capillary pores correspond to the
initially present interparticle space that is gradually filled with
hydration products and therefore this pore volume is reduced
with increasing hydration. Air bubbles derive from intention-
ally and unintentionally introduced air during the mixing of the
concrete. The size range of these pore classes differ in orders of
magnitude: the size of the gel pores are in the nanometer range,
capillary pores in the 0.01- to 1-µm range, and air bubbles in
the millimeter range. Additionally, cracks can form that may be
several micrometers in size. For concrete, typical total porosities
of a few percent up to 15–20% are found with the air content
ranging from around 1 to 6%. The air content, therefore, can
contribute up to 1/3 to the total porosity.
MIP measurements have been used to estimate total poros-
ity, to determine a characteristic pore size, and to investigate
the material’s characteristics (7, 23, 39). The equivalent pore
size corresponding to the steepest slope of the intrusion curve
is sometimes referred to as the threshold or critical pore size.
The shape of the curve provides an indication of the material’s
microstructure and can be used to distinguish between differ-
ent cement-based materials. The paste in concrete is found to
be more porous than plain paste and the difference increases
with increasing hydration (37). The additional porosity in con-
crete paste occurs mainly at equivalent pore sizes larger than the
plain paste’s threshold pore radius. These larger pores can be
assumed to be present only in the interfacial zones surrounding
each aggregate. This interfacial zone was studied and found to
exhibit percolation properties (38).
Although data from MIP experiments on cement paste have
been used to represent the pore-size distribution for many years,
there is still much debate about the validity of this method. For in-
stance, microstructural damage due to mercury porosimetry has
been reported (24, 28). In addition, sample drying was found to
have a major effect on the determined MIP characteristics (8, 22),
even affecting the contact angle (39). A recent review on mercury
intrusion porosimetry concludes that MIP measurements should
be abandoned as measures of the actual pores sizes present in
cement-based systems (6).
Knowing the inappropriateness of the assumptions, a proper
interpretation of such data was proposed using more sophis-
ticated models that were capable of describing the processes
of intrusion and extrusion, accounting for the phenomena of
capillary-pressure hysteresis and mercury entrapment. This ap-
proach provided quantitative information about the measured
pore structures (1, 2, 29, 30, 33). Unfortunately, simplified mod-
els are rarely realistic, and realistic models are likewise not sim-
ple and often unmanageable.
Sample size is often assumed to have no effect on the MIP
result and is therefore rarely reported. However, sample size
and shape influence surface area to volume ratios and there-
fore can affect the form of capillary pressure curves. Reducing
the sample size, the fraction of less accessible interior pores
should decrease and the intrinsic or “true” pore-size distribution
is approximated. Furthermore, increasing the network size of
network pore structure models is reported to increase hystere-
sis and mercury entrapment (1), simultaneously stating that in
almost every case, subsequent breakage of the materials indi-
cated the entrapped mercury to be uniformly distributed. The
pore-size distribution and interconnectedness of the pores have
a significant effect on the length scale below which sample size
significantly alters the MIP result. This is therefore a specific
property of the material tested. If the length scale is below the
minimum sample size, there will be no size effect on the MIP
result. Sample volume, ranging from 1 to 25 cc, is reported to
have no significant effect on the MIP measurements of Indiana
limestone, while the system does not behave as an infinite pore
system and, therefore, shows a size effect up to a minimum depth
of penetration of 1 mm (35). Larson et al. (13) studied the effect
of sample size on injection, withdrawal and reinjection capillary
pressure curves using percolation theory. They found that as the
sample thickness decreases the accessibility of the pore space
increases.
Precision and reproducibility of MIP-characteristics is an
often neglected question. In this work, a detailed study examing
the effect of sample size on the entrapment phenomena and on
the hysteresis of mercury porosimetry measurements of concrete
samples was conducted. These experiments enable for better
understanding of the mercury intrusion/extrusion process and
help to evaluate its potential, and limitations, for application to
cement-based materials.
2. MATERIALS AND METHODS
The different concrete mix designs investigated here are de-
scribed in Table 1. For a given sand/gravel size, the cement and
water amounts were chosen to create a constant cement-paste
volume in the concrete. This allowed for a direct comparison of
the results to be made as the porosity of the walls was directly
 MERCURY INTRUSION POROSIMETRY 137

TABLE 1
Mix Designs: Three Different Types of Portland-Cement, Types A and C Are CEM I 42.5, and Type B Is CEM I 42.5 HS; Three
Maximum Gravel Sizes and w/c Ratios and Two Mix Designs with the Addition of an Air-Entraining Agent

Cement Air entraining Air content Cement-paste

Mix type Cement (kg/m3 ) Gravel (mm) w/c-Ratio agent (%) content (%)

1 A 340 −16 0.5 No 2.6 27.81

2 A 300 −32 0.5 No 1.3 24.36
3 A 303 −16 0.6 No 2.3 27.80
4 A 387.5 −16 0.4 No 2.0 27.88
5 A 340 −16 0.5 Yes 6.0 27.41
6 A 387.5 −16 0.4 Yes 4.8 27.86
7 B 340 −16 0.5 No 3.0 27.62
8 B 303 −16 0.6 No 1.9 28.07
9 A 340 −16 0.5 No 3.5 27.52
10 C 340 −16 0.5 No 2.4 27.7
11 C 300 −32 0.5 No 1.4 24.15
12 C 370 −8 0.5 No 3.5 29.59

Note. Based on the measured properties of the fresh concrete, the volume content of the cement-paste is indicated (i.e., unreacted cement, hydration products,
and all kinds of pores present in the concrete including air bubbles). This corresponds to 100% volume content of aggregates.

proportional to the porosity of the cement-paste, with the excep-
tion of mix-designs having different gravel sizes. The samples
were taken from one of two 100 × 100 × 20-cm3 large walls
produced for each mix design. The sample cores investigated
here were drilled at an age of more than 3 years. From the
cores (d = 20 mm), parallel slices were cut in 1-, 2-, 5-, 10-,
and 20-mm thicknesses. All samples were saturated with water
and weighed and the volume was estimated by displacement of
water. This is an approved and widely used method measuring
the sample- and pore-volume of cement-based materials.
Finally, the samples were dried in an oven at 105◦ C at standard
atmosphere until constant weight was reached.
All MIP measurements were carried out with a Micromeritics
AutoPore II 9220. The samples were evacuated to 30 µm Hg =
0.03 Torr = 4 Pa. Equilibration time (the minimum time duration
for a stable mercury level before moving on to the next pressure
value) was chosen to be 50 s. The conversion from pressure to
pore size was done using the following constants: contact angle
θ = 130◦ , surface tension γ = 0.480 N/m.
The X-ray computed tomography (CT) images were mea-
sured on an industrial CT scanner made by Scientific Measure-
ment System, Inc. After applying an intrusion–extrusion cycle
up to the respective pressure, the samples were removed from
the porosimeter and CT images were taken at three different
heights (5, 15, and 25 mm).
3. X-RAY TOMOGRAPHY
Intrusion of mercury into cementitious material normally
takes place over a broad range of equivalent pore radii, start-
ing below 1 µm and occurring down to the lower bound on the
order of 1 nm. The idea of a threshold or critical pore size is
based on the assumption that an initial percolating network of
pores is formed, if pore radii equal to or larger than this critical
pore size are considered, and therefore mercury intrudes the in-
nermost part of the sample. As the equivalent pressure is reached,
most of the pores larger than the threshold radius should be in-
truded, the remaining intrusion presumably showing fewer char-
acteristics of the ink-bottle effect. The threshold radius should
be constant for samples of a certain minimal shape and size
representative of the material tested.
The combination of mercury porosimetry and X-ray com-
puterized tomography has been reported recently in the litera-
ture (11, 12, 21) and been used to determine mineral-specific
porosity distributions, inhomogeneous penetration of the mer-
cury and the nonuniform spatial variation of open porosity dur-
ing sintering of ceramic green bodies. Due to the high density of
mercury and, therefore, cross section of mercury for scattering
X-rays and the pronounced hysteresis between MIP intrusion
and extrusion curves of cement-based materials, mercury en-
trapment can be made visible by X-ray tomographic techniques
(Fig. 1). According to Li and Wardlaw (14), the amount of en-
trapped mercury in the pores of a network is comparable to
the pore volume of the sample. Filled air bubbles (containing
entrapped mercury after extrusion) indicate the sample volume
fraction where intrusion has occurred at the pressure noted. Due
to the very high amount of mercury present in the air bubbles,
the tomographic reconstruction used produces artifacts of rays
starting at these filled air bubbles. This is found to be a limiting
factor for using two-dimensional images to visualize the intru-
sion process into cement-based samples in the sub-micrometer
range and for calculating density distributions. Compared to the
observed changes in mercury intrusion, the movement of the
mercury menisci during the transfer between porosimeter and
X-ray CT are considered negligible.
Upon reaching a pressure of 13 MPa, air bubbles near the
sample surface have been filled, but no intrusion to the inner
volume has taken place. These air bubbles are noted as being
138 MORO AND BÖHNI

FIG. 1. X-ray tomographic cross sections of a mercury intruded sample (r = 10 mm). White dots correspond to pores filled with mercury. The sample was
measured (a) initially before intrusion and after intruding up to a pressure of (b)13 MPa and (c) 200 MPa. Cross-sections of the unfilled air bubbles appear as black
circles (a) that get filled with mercury with increasing intrusion pressure (b and c). The rays starting at the air bubbles are artifacts of the tomographic reconstruction.

ink-bottle pores with very narrow entrances compared to their were calculated. This function acts to scale the volume axes to
size. When a pressure of 200 MPa is applied, even the most values between 0 and 1, assigning 1 to the intrusion volume at
inner air bubbles become filled with mercury. The spatial distri- the highest pressure. In order to characterize the entrapment of
bution of the air bubbles, therefore, is shown to strongly affect mercury the parameter χ is defined as follows:
the MIP-characteristics of the material tested. Therefore, the
interpretation of the calculated pore-size distribution of cement- V t ( p)
0 ≤ χ ( p) = ≤ 1, [7]
based materials is not so simple, since the Washburn picture V i ( p)
is here quite far from truth. It also confirms, that mercury is
preferably retained in larger pores. where V t ( p) denotes the entrapped mercury volume after reach-
4. MULTICYCLE MIP AND ITS PARAMETERIZATION ing atmospheric pressure following an intrusion up to a pres-
sure p. χ is not defined for the range where no intrusion has
To more thoroughly study the effect of sample size on the ink- taken place, i.e., where V i ( p) = 0. χ corresponds to 1-WE /100,
bottle effect and hysteresis, additional extrusion and intrusion where WE is the withdrawal efficiency as defined by Wardlaw
cycles (34, 35) were measured after reaching pressures of 12.3, et al. (34, 35). χ is expected and reported to decrease with in-
25.6, 61.1, and 112.7 MPa. These values were chosen randomly, creasing saturation, i.e., pressure p, with throat to pore diame-
the only constraint being that they lie between the initial intru- ter and volume ratios, as homogeneity of throat and pore sizes
sion pressure and the final pressure. This method has been termed increases and as the number of connections (throats) per pore
elsewhere mercury porosimetry hysteresis loop scanning along increases.
the penetration line (MP-SHL-Pe) (3). It is assumed that mercury The shape of the curves is further characterized by the sin-
continuously intrudes more and more of the sample’s volume, gle threshold radius, estimated by the volume log radius dis-
that the relative amount of ink-bottle pore volume changes with tribution DV (log r ). The intrusion threshold radii θki and the
increasing pressure and that the filled pore domains increasingly extrusion threshold radii θke of the different respective cy-
percolate to possibly form a single domain at maximum pres- cles were found to coincide if they lay within the measured
sure. Thus, these MIP characteristics should vary to some extent pressure-range (Fig. 2). Only the threshold radius θ e of the fi-
with sample size. In (3), this method is called tomography, en- nal extrusion curve was found to be shifted to slightly larger
abling the detection of regions within the porous particle that radii.
show variations of the intrinsic particle-size distribution. A single measurement, therefore, generated a set of 20 num-
After an additional extrusion–intrusion cycle, the initial vol- bers:
ume was always reached to within a small error, indicating that 
 I maximum intrusion
no significant damage occurred to the sample during each re- 


 v (k = 1..4) relative intrusion
spective pressure increase (Fig. 2).  k
In order to parameterize the MIP data, the relative intrusion χ ( p) ink-bottle parameter


volumes, 
 ( p = 12, 26, 61, 113, and 400 MPa)

 i e i
V i ( p) Vi θ , θ , θk , and θke (k = 1..4) threshold radii.
vk = i = ki (k = 1, 2, 3, 4), [6]
V ( pmax ) V [8]
 MERCURY INTRUSION POROSIMETRY 139

present in the experimental run corresponding to the bulk vol-

ume of the sample BVsample and neglects the possible compres-
sion of the unintruded volume of the sample itself Vcs (5). A
form of the Tait equation can be used to calculate the volume of
mercury compression that corresponds to the additional blank
run component as follows:
µ ¶
00 p
VcHg = 0.175 · BVsample · log10 1+ . [9]
1820 MPa

Due to the large sample sizes used, differential mercury com-

pression correction could not be neglected here. Without dif-
ferential mercury compression correction, the initial extrusion
curve shows an increase in cumulative porosity with decreasing
pressure just after reaching maximum pressure (Fig. 3). From
the intrusion behavior displayed in the highest pressure region,
an additional intrusion at decreasing pressure due to nonequi-
librium can be excluded. The final extrusion curve still shows
evidence of need for additional correction, e.g., a sample com-
pression correction. The material tested was assumed to have a

FIG. 2. Typical MIP measurement and the values estimates in order to pa-
rameterize it (Eq. [8]). Threshold values are assigned to the radii where maxima
of the respective volume log radius distribution occurs. The volume log radius
distributions of the addition cycles are drawn upside-down.

5. CORRECTIONS TO VOLUME DATA

Where several smaller sample pieces were measured simulta-

neously, interparticle space was partially filled during the low-
pressure run. Since this volume is not of interest, this part of the
run was set to zero at the expense of neglecting intrusion into
pores with equivalent pore radii >3 µm. These are mainly air
bubbles lying at the surface of the sample. The total porosity of
smaller sample pieces was therefore underestimated compared
to the larger sample pieces. Furthermore, the sample volume es-
timated by comparing the penetrometer + sample + Hg-weight
with the weight of the penetrometer filled only with Hg gave
an inaccurate estimate of the sample’s volume. Therefore, the
sample volume was determined by displacement of water prior
to measurement.
Volume readings from a sample run are commonly corrected
by using volume readings from an experimental run performed
with an empty sample cell (blank run). This correction accounts
for expansion of the machine Vem and compression of the mer- FIG. 3. Effect of correction for mercury compression: (top) blank run cor-
cury in the empty sample cell VcHg . Although, this blank run rected; (bottom) additional differential mercury compression correction reduced
includes the compression of a volume of mercury that is not for the sample compression effect.
140 MORO AND BÖHNI
lower compressibility than the mercury and reasonable extrusion
characteristics were achieved for all samples measured by low-
ering the coefficient in Eq. [9] from 0.175 to 0.05–0.1. A value
of 0.08 was finally chosen.
6. MIP HYSTERESIS AND ENTRAPMENT
Various theories concerning the cause of MIP hysteresis and
entrapment have been proposed (31).
• Superimposition of the extrusion and second intrusion
curves can be achieved if the contact angle θ is adjusted from θi ,
the intrusion contact angle, to θe , the extrusion contact angle (15,
19). Thus, when depressurization starts, no extrusion occurs be-
tween the equivalent pore-radius r (cos θe / cos θi ) and r . The dif-
ference between intrusion and extrusion curves along the volume
axis reflects the quantity of entrapped mercury after completion
of an intrusion–extrusion cycle. Powell and Shields (16–18)
have postulated that in volume versus pressure plots, hystere-
sis is due to the influence of a pore potential.
• Intrusion–extrusion hysteresis and entrapment have been
attributed to ink-bottle-shaped pores. In pores of this type, in-
trusion cannot occur until sufficient pressure has been attained
to force mercury into the narrow neck whereupon the entire
pore will fill. However, upon depressurization, the wide pore
body cannot empty until a lower pressure is reached, leaving
entrapped mercury in the wide inner portion of the pore.
• Pore interconnectedness and constriction of the pore diam-
eter (1, 2, 30, 34) in combination with mercury snap-off are
being used to explain the hysteresis and entrapment of mer-
cury. According to this model, mercury withdraws in such a
sequence that two interfaces are formed at opposite ends of
a single segment, breaking the continuity of the mercury col-
umn. When this happens, mercury within the segment is iso-
lated and thereby becomes trapped. A so-called corrugated pore
structure model (CPSM) has been proposed to simulate mercury
porosimetry, in particular hysteresis and entrapment in mercury
porosimetry (1, 2, 30) .
Lowell and Shields (20) state that the ink-bottle model ignores
the following factors:
1. All porous samples exhibit hysteresis. This would require
that all porous materials contain pores which are ink-bottle in
shape.
2. Porosimetry curves exhibit various shapes. If hysteresis
were caused only by ink-bottle pores, one shape of hysteresis
curve should be observed.
3. Regardless of the maximum pressure attained, depressur-
ization always results in hysteresis. This implies that ink-bottle
pores are distributed over the entire range of pore sizes. There-
fore, pores with very wide entrances would have to possess even
wider inner cavities.
4. Intrusion into and extrusion out of the volume between
packed spheres, where the openings are wider than the interior,
show hysteresis.
FIG. 4. Cross section of a fcc lattice through the centers of the atoms.
5. The ink-bottle model ignores the question of the energy
required to break the mercury column in the pore in order for the
narrow entrance to empty while the inner cavity remains filled.
In the author’s opinion:
1. An ink-bottle-free porosity is a strong constraint and is
therefore unlikely to be found. Moreover, in the case of an ink-
bottle-free porosity, all the mercury is supposed to extrude fol-
lowing depressurization, resulting in a closed hysteresis loop.
This is normally not found in experiments.
2. Extrusion mechanisms cannot be assumed to produce the
same shape of hysteresis curve for all types of ink-bottle pores.
Far more important for the intrusion–extrusion behavior of
samples having ink-bottle pores is the connectivity of the pore
system, causing different shapes of the intrusion and extrusion
curves.
3. If intrusion occurs, hysteresis is encountered regardless
of the respective pore sizes.
4. In a face-centered cubic (fcc) packed sphere system,
openings are not wider than the interior. A cross-section of
a horizontal plane cut through the centers of three spheres is
shown in Fig. 4. As the cutting plane is moved upward, the
intersphere area increases.
Nevertheless, there is some doubt that the hysteresis observed
in MIP is due only to the ink-bottle effect. If a reference material
with a very narrow pore-entrance size distribution is measured
(Fig. 5), a considerable amount of mercury is entrapped and ex-
trusion takes place at equivalent pore radii four times larger than
the equivalent intrusion radii. Most likely, the equations govern-
ing the intrusion and extrusion processes, and/or the parameters
therein, differ. This is further supported by the fact that repeated
intrusions show hysteresis, which cannot be explained only by
the ink-bottle effect.
The threshold radii of single intrusion and extrusion cycles co-
incide respectively (Figs. 2 and 6). The extrusion threshold radii
are shifted to larger pores compared to the intrusion threshold
radii. This is in agreement with the assumption that two differ-
ent contact angles (or combination of contact angles and surface
tensions) exist for intrusion and extrusion, since a change in
 MERCURY INTRUSION POROSIMETRY
FIG. 5. MIP of a silica–alumina reference material.
FIG. 6. Graphs of cumulative volume (top) and volume log radius distri-
bution DV (log r ) (bottom). In addition to the original volume data, the (shifted)
extrusion curves calculated with an estimated extrusion angle are shown (shifted
curves). The volume log radius distributions of the additional cycles are drawn
upside-down.
141
FIG. 7. Box plots of the estimated extrusion contact angles θi corresponding
to the respective additional extrusion–intrusion cycles. An intrusion angle of
130◦ is assumed.
contact angle rescales the equivalent pore size by a factor of
sin(θe )/ sin(θi ), shifting the respective curve on a log-scale by
the logarithm of this value.
Assuming an intrusion contact angle of 130◦ , an extrusion
contact angle was estimated for the four additional extrusion–
reintrusion cycles such that adequate superimposition of the
extrusion curves and the following second intrusion curves is
achieved.
In general, very uniform values for the extrusion angle were
found (Fig. 7). Whereas for the first two cycles values of 102.5◦
were estimated, they are shifted to values of 104◦ for the last
two additional cycles. This difference is small and on the or-
der of the measurement error. This result strongly supports
the theory that different intrusion and extrusion contact angles
exist.
MIP hysteresis has been explained by a change in surface
area per unit volume of mercury and the respective change in
concentrations of surface impurities that cause in a continuous
change of contact angle/surface tension (35). A change in con-
tact angle from 130◦ to 104◦ corresponds to pi = 2.657 × pe .
Therefore, pi − pe = pi × (1 − 1/2.657), or the linear equation
on an exponential scale, log( pi − pe ) = log( pi ) − 0.21, which
perfectly fits the data in the paper of Wardlaw et al. (35). The
data of Wardlaw et al., therefore, support different values of
contact angles for intrusion and extrusion and not a continuous
change with increased amount of sample surface in contact with
mercury.
7. SAMPLE SIZE EFFECT ON MIP CHARACTERISTICS
The intrusion characteristics were parameterized with the
maximum intrusion volume I and the relative intrusion volumes
vk (Eq. [6]). Since the units of these respective parameters dif-
fer, the standardized form (based on the correlation matrix) of
the biplot (9, 10) was chosen to display the multivariate dataset
that rescales the original variables to unit variance using the
correlation matrix. The row metric preserving biplot is an ex-
cellent approximation of the inter-row comparisons, i.e., cases
142 MORO AND BÖHNI

samples’ aggregate volume content, and therefore the samples’

cement paste volume content in concrete MIP samples taken
from the same concrete, varies strongly, since the normal sample
size is much too small to be representative. The aggregate con-
tent, therefore, has a significant effect on the measured porosity.
In order to achieve a characteristic porosity value, an average
porosity value should be derived from values estimated on differ-
ent samples taken from the same concrete piece. The relative in-
trusion values on the other hand, are characteristic of the shape of
the curve. Due to the normalization of the relative intrusion val-
ues with respect to the total porosity, these are only indirectly
affected and, therefore, less influenced by the sample’s aggregate
content.
Relative intrusion values have been found to generally in-
crease with sample size. The larger the measured sample, the
lower the pressure needed to reach a certain relative amount of
intruded volume. Considering the percolation process of mer-
cury intrusion, the larger the sample, the higher the pressure that
is needed to force mercury into the sample. Hence, a contrary
sample size effect would be expected, as reported in (13). But, the
smaller the sample, the more air bubbles that are directly acces-
sible at the surface and thus do not contribute to the intrusion vol-
ume, since the low-pressure run was not considered in this study
(section 5). Intrusion therefore starts at lower pressures when
larger samples are measured. Furthermore, damage due to drying
may cause less damage to small samples than to large samples
resulting in higher relative porosities for the latter (8, 22).
The shape of intrusion–extrusion curves is further character-
ized by the various threshold values (Eq. [8] and Fig. 2). Only
FIG. 8. MIP: standardized RMS biplot (correlation matrix) of the total the threshold values of the main cycle and the last two addi-
porosities I and relative porosities v i . tional cycles, which lie in the higher pressure range, are shown
in Fig. 9. Due to the fact that the parameters under consideration
comparisons. With the first two principal components, 92.7% of have identical units, the centered form of the biplot was chosen
the variance can be explained (statistical summary [7.1]). to display the multivariate dataset that is based on the covariance
matrix. The length of the vectors, therefore, represent the stan-
STATISTICAL SUMMARY 7.1. Principal component analysis dard deviations. With the first two principal components, 98.6%
based on the correlation matrix of the total and relative intrusion of the variance can be explained (statistical summary [7.2]).
values (Eq. [8] and Fig. 8).
Importance of components: STATISTICAL SUMMARY 7.2. Principal component analysis
Comp.1 Comp.2 Comp.3 Comp.4 Comp.5 based on the covariance of the intrusion and extrusion thresh-
Standard deviation 1.953 0.906 0.5183 0.2495 0.18588 old radii of the main and the third and fourth additional cycles
Proportion of variance 0.763 0.164 0.0537 0.0125 0.00691 (Eq. [6] and Fig. 9).
Cumulative proportion 0.763 0.927 0.9806 0.9931 1.00000 Importance of components:
Whereas the maximum intrusion volume I of samples of iden- Comp.1 Comp.2 Comp.3
tical size and shape varied mostly in relation to the mix design, Standard deviation 0.0532 0.0125 0.00503
relative intrusion volumes vk changed most significantly with Proportion of variance 0.9343 0.0518 0.00834
sample size (Fig. 8). Maximum intrusion volume is known to Cumulative proportion 0.9343 0.9860 0.99437
change mainly by varying the w/c ratio of the mix. For mix de- Comp.4 Comp.5 Comp.6
signs 4 and 6, which were designed with w/c = 0.4, maximum Standard deviation 0.00334 0.00208 0.001254
intrusion values at the lower end of the range were estimated, Proportion of variance 0.00368 0.00143 0.000519
whereas for mix-designs 3 and 8 with w/c = 0.6, values at the Cumulative proportion 0.99805 0.99948 1.000000
higher end were estimated.
Concrete is composed of two phases with marked varying All intrusion (peaks number 1 and 4 in Fig. 2, at an equiv-
porosity: nonporous aggregates and porous cement paste. The alent pore radius of 0.035 µm) and extrusion threshold radii
 MERCURY INTRUSION POROSIMETRY
FIG. 9. MIP: centered RMS biplot (covariance matrix) of the intrusion and
extrusion threshold radii of the main and the third and fourth additional cycles.
Except for the axis of the extrusion threshold value of the main cycles, all other
axes are superimposed.
(peak numbers 2 and 5 in Fig. 2. at an equivalent pore ra-
dius of 0.09 µm) were, respectively, constant, only the extrusion
threshold radii of the main cycle (peak number 3 in Fig. 2, at
an equivalent pore radius of 0.15 µm) were generally shifted
to slightly larger pore radii. If the threshold radius of the main
cycles did not lie in the measured pressure range of the first
two additional cycles (lower pressure), threshold radii one order
of magnitude larger were estimated for these cycles. For this
reason, the threshold radii of the first two additional extrusion–
reintrusion cycles were not considered in Fig. 9. Reinjection
curves are reported to be shifted toward higher pressures/smaller
pore sizes, if all but one surface are coated (Figs. 5 and 16 in
(35)). The measurement of uncoated samples exhibit a knee.
This is reflected by the peak number 2 of the intrusion curve,
whose position corresponds to the threshold radii of the extru-
sion curves of the additional cycles.
Since the values shown in Fig. 9 are centered over the respec-
tive mean values, the shift of the extrusion compared to intru-
sion values (section 6) is not shown on the biplot. This biplot
displays the effect that mix design and sample size have on the
143
threshold radii. With the exception of the extrusion threshold
value of the main cycles, the threshold values are highly corre-
lated. With increasing sample size, larger threshold values were
estimated. Dividing a sample into different pieces, accessibility
of the pore volume is increased and the contrary behavior would
be expected. The threshold radius therefore most likely corre-
sponds to the filling of air bubbles. Furthermore, drying may
cause less damage to small samples than to large samples, re-
sulting in larger threshold radii for the latter.
Chloride permeability was reported (15) to correlate more
closely with the reversible subdistribution (in this paper the ad-
ditional cycles), i.e., its intrusion threshold radius, than with
either the total (in this paper the main cycle) or the irreversible
distribution. In contrast, constant intrusion threshold radii for
the main and all additional cycles were found for all samples in
these study.
8. MERCURY ENTRAPMENT IN MIP
OF CONCRETE SAMPLES
For each measurement, a characteristic ink-bottle func-
tion χ (r ) was calculated (Eq. [7] and Fig. 10). If extrusion and
reintrusion at any saturation are reversible processes, this func-
tion can also be calculated from the initial intrusion, the final ex-
trusion and a final reintrusion curve. Mercury entrapment varies
within wide limits, i.e., 30–90% of the total amount of Hg pene-
trated the pore structure of the respective volume fraction. Both
sample size and the intruded volume fraction have a significant
effect on the amount of entrapped mercury, which is therefore
not uniformly distributed within the sample.
All curves show the same characteristics. The ink-bottle func-
tion χ decreases approximately linearly with decreasing radius
on a logarithmic scale, randomly fluctuating at equivalent pore
radii where intrusion starts (r = 0.05 µm). These fluctuations in
χ at r = 0.05 µm were found mainly for the small samples and
could therefore not be attributed to randomly present air bubbles.
Overall, curves with similar slopes were found that vary only
with respect to their intercept. Generally lower values were es-
timated for smaller samples. A sharp bend in the curve could be
an indication of the threshold radius, but this was not found.
The mix-design of the concrete, e.g., neither w/c-ratio nor the
addition of an air-entraining agent, had a significant effect on
the curve.
This reduction in relative entrapment of mercury with de-
creasing sample size has been theoretically predicted (13) using
percolation theory. There, sample size mainly affects residual
saturations, i.e., χ and the initial intrusion, the surface saturation
being negligible for large samples with low surface/volume-
ratios and significant for small samples with high surface/
volume-ratios. The changes in the initial saturation (knee) would
result in slightly lower threshold pressures and higher relative
porosities v k for smaller samples than for larger samples,
mainly with respect to the first additional cycles. As already
stated in section 7, the opposite is found in this study (Figs. 8
144
FIG. 10. Entrapped mercury content χ of five different sample sizes calculated for five different equivalent pore radii evaluated with 12 different mix designs.
and 9). The sample thickness effect reported in (13) vanishes
for samples of thickness greater than about 70 pore-throat
diameters, corresponding in the case of cement-based binders
to sample sizes thicker than approximately 0.1 mm, indicating
that the sample-size effect is, therefore, not relevant for the
samples normally studied. Accordingly, measuring samples of
thickness ≈1 mm provides a unique characterization of the
cement-based material, since the effect of the air bubbles is
then canceled and no size effect is present. Due to the reasons
mentioned, this cannot be confirmed in this study.
MORO AND BÖHNI
Similar results are found if the withdrawal efficiency WE
vs initial saturation Vki /V i are plotted according to (34, 35)
(Fig. 11), since χ = Vkt /Vki = 1 − WE /100. Withdrawal effi-
ciency increases considerably as initial saturation increases,
much more than reported for different carbonate rocks (34, 35).
Another method to trace pore structure inhomogeneity is
shown in Fig. 12 (3). The amount of entrapped mercury relative
to the final ( final pressure) amount of entrapped mercury (spe-
cific mercury entrapment) versus the amount of maximum cycle
specific saturation does not lie on the diagonal and therefore
 MERCURY INTRUSION POROSIMETRY 145

FIG. 11. Withdrawal efficiency versus initial saturation (34, 35) of five different sample sizes calculated for five different equivalent pore radii evaluated with
12 different mix designs. Minimum unsaturated pore volume (Umin ) was set to zero.

shows structural inhomogeneities. Points on the diagonal cor-
respond to intrusion experiments in which the amount of
entrapped mercury increases equally with the saturation, the ra-
tio Vkt /Vki being constant for all saturation levels. In contrast to
Figs. 10 and 11, these characteristics seem to be independent of
the sample size. Since this graph is drawn with relative parame-
ters, the differences found in Figs. 11 and 10 for different sample
sizes mostly cancel out. The reduction of specific mercury en-
trapment with increasing saturation is equal for all sample sizes,
but the absolute mercury entrapment increases with sample size.
The 1-D corrugated random pore model is assumed to be
best suited for the simulation of the mercury porosimetry op-
erations associated with partially saturated pore structures (30).
In this model and the modified version (2), the positions of the
intrusion and extrusion curves are determined by the number of
segments per pore and the intrinsic pore-size distribution. For
146 MORO AND BÖHNI

FIG. 12. Comparison of the specific mercury entrapment (residual saturation) V t ( pk )/V t ( pmax ) vs maximum cycle specific saturation V i ( pk )/V ( pmax ) for
the general kth scanning cycle of five different sample sizes evaluated with 12 different mix designs (3). The line indicates the position of equality.

all assumed pore-size distributions, an increase in the number
of segments per pore results in a shift of the extrusion curves
toward larger pores/smaller pressures and of the (initial) intru-
sion curves toward smaller pores/larger pressures. The concrete
type, the sample size and increasing the partial saturation by
going from the first additional cycle to the last additional cy-
cle (i.e., increasing the intruded sample volume and relevant
range of pore sizes) change the entrapment behavior of mercury
porosimetry considerably (section 8). Though, according to the
results found in this study, this has no effect on the distance (in a
log-scale) between the pressure range where intrusion and where
extrusion takes place. In the corrugated random pore model the
amount of entrapped mercury on the other hand, is determined
by the critical pore constriction ratio λc and the intrinsic pore-
size distribution. The difference in size- and spatial-distribution
of the air bubbles could account for this change in entrapment
behavior. It is nevertheless less obvious that, due to the constant
relative hysteresis positions found in this study for all degrees of
 MERCURY INTRUSION POROSIMETRY
partial saturation, for all sample sizes and for all concrete mix
designs, the number of segments per pore in combination with
the relevant intrinsic pore-size distributions have an identical
effect on the hysteresis.
In a recent paper (27), low-temperature nitrogen sorption
porosimetry and mercury porosimetry experiments were per-
formed on samples of an anodic aluminum membrane and the
results were interpreted in terms of the corrugated pore struc-
ture model. These samples are regarded as being free of any
pore structure networking effect and the mercury porosime-
try hysteresis, therefore, is concluded to be a pure mercury
porosimetry contact angle hysteresis. Using the CPSM and al-
lowing for different contact angles for intrusion and extrusion the
(first) intrusion and (first) extrusion curve were modeled, giving,
among other characteristics, the appropriate pair of contact an-
gles. For these controlled pore structure materials contact angles
(θi = 143◦ , θe = 100.5–107.5◦ ) are reported. This is equivalent
to the following pair of contact angles: (θi = 130◦ , θe = 98.4–
104.0◦ ), the values being slightly lower than the ones found in
this study for cement-based materials. The pore structure of the
concrete samples studied here exhibit a networking effect that
varies for the different sample sizes and probably also for the dif-
ferent concrete types. Nevertheless, a constant pair of contact an-
gles has been determined using extrusion and reintrusion curves.
9. SUMMARY
The effect of mix design and sample size on the MIP mea-
surements of concrete samples was studied. X-ray tomographic
cross sections indicate the presence of a significant ink-bottle
effect when measuring concrete samples. In order to better
study this effect and the intrusion–extrusion behavior, additional
extrusion–intrusion cycles have been measured. Superimposi-
tion of extrusion and second intrusion curves of concrete sam-
ples can be achieved, when assuming an intrusion contact angle
of 130◦ , an extrusion contact angle of 104◦ is used to calculate
the equivalent pore radius. This strongly supports a difference
between the governing equations in the intrusion and the ex-
trusion processes and/or the parameters therein. The amount of
entrapped mercury χ was estimated as a function of the applied
pressure or the equivalent pore radius. This function shows no
evidence for the presence of a dominant pore radius, but varies
mostly due to the sample size. Generally, the effect of mix de-
sign on the MIP characteristics was found to be obscured to
some extent by the effect of sample size, drying behavior, and
randomly present content of air bubbles in the sample selected.
Even if characteristic properties of the material tested can be es-
timated with MIP, comparison of results is rendered difficult by
the significant sample size and ink-bottle effects due to randomly
present air bubbles. Normally, samples as variant in size as used
in this study are not chosen and using a defined and constant
sample size is recommended. In order to cancel out the effect of
randomly present air bubbles, repeated measurements should be
made. Nevertheless, they will always contribute considerably to
147
the MIP measurement and its ink-bottle effect. Proper interpre-
tation of the results requires measurements and an appropriate
model that are able to distinguish the ink-bottle air bubbles from
the rest of the pore system. To the author’s knowledge, there is,
as of yet, no way to achieve this experimental discrimination.
APPENDIX: MULTIVARIATE ANALYSIS
Multivariate analysis is concerned with datasets that have
more than one response variable for each observational or ex-
perimental unit (9, 10, 32). The datasets can be summarized by
data matrices X with n rows and p columns, the rows represent-
ing the observations or cases and the columns the variables. The
matrix can be viewed either way, depending on whether the main
interest is in the relationships between the cases or between the
variables.
Linear methods are the heart of classical multivariate analysis,
and depend on seeking linear combinations of the variables with
desirable properties. Principal component analysis seeks linear
combinations of the columns of X with maximal (or minimal)
variance. Additionally, these linear combinations are uncorre-
lated with each other.
Another point of view is to seek new variables y j which are
rotations of the old variables to best explain the variation in the
dataset. These new variables should be taken to be the princi-
pal components, in order. Suppose we use the first k principal
components. Then the subspace they span contains the “best”
k-dimensional view of the data. It has both a maximal covariance
matrix (both in trace and determinant) and best approximates the
original points in the sense of minimizing the sum of squared
distance from the points to their projections. The first few prin-
cipal components are often useful to reveal structure in the data.
The principal components depend on the scaling of the orig-
inal variables, and this will be undesirable except if they are in
comparable units. (Even in this case, correlations would often
be used.) Otherwise it is conventional to take the principal com-
ponents of the correlation matrix, implicitly rescaling all the
variables to have unit sample variance.
The most well-known diagram representing information on
samples and variables is the ordinary scatterplot of two vari-
ables. Points in such scatterplots represent the samples, and the
two axes represent the two variables concerned. When more than
two variables are involved, however, things become more diffi-
cult. Biplots are the multivariate analog of scatter plots (9, 10).
They approximate the multivariate distribution of a sample in
a few dimensions, typically two, and they superimpose on this
display representations of the variables on which the samples are
measured. In this way, the relationships between the individual
sample points can be easily seen.
X is assumed to have been centered to remove column means.
The biplot represents X by two sets of vectors of dimensions n
(cases, points in the diagram) and p (variables, vectors in the
diagram), producing a rank-2 approximation to X:
X ≈ X̃ = ABT . [A.1]
148 MORO AND BÖHNI
The biplot then consists of plotting the n + p two-dimensional
vectors that form the rows of A and B. The interpretation is based
on inner products between vectors from the two sets, which give
the elements of X̃. The single value xik is approximated by the
inner product hai , bk i of the ith case and kth variable. Geomet-
rically, the inner product of vectors a and b can be visualized
by multiplying the length of a by the component of b along a
or equivalently by multiplying the length of b by the coordinate
of a along b. This is intuitively done, if a two-dimensional scat-
terplot is studied, by considering the projection of the vectors
belonging to the cases onto the variable-axes.
A biplot is not unique. What Gabriel (9) calls the RMP biplot
is an excellent approximation of inter-row distances of X and,
therefore, of the cases.
The most popular choice is what Gabriel (9) calls the CMP
(column metric preserving) biplot, which is an excellent approxi-
mation of intercolumn variability and, therefore, of the variables.
The lengths of the vectors represent the standard deviations and
the angle between the vectors approximate the correlation be-
tween them.
The closeness of the two-dimensional approximation of the
multidimensional data is measured by the goodness-of-fit coef-
ficient. At 100%, the goodness-of-fit corresponds to the sum of
squares of the differences between the biplot fits and the data
(deviation in the column means) of the sum of squares of the
data themselves (again as deviations from the means).
Taking Fig. 9 as an example, the following can be deduced
from the biplot:
• The six variables are very closely approximated in the biplot
plane (cumulative proportion, 98.6%).
• All vectors representing the variables, except the thresh-
old radii of the main extrusion cycle θe , are overlapping and
therefore are highly correlated. If one of these threshold radii is
found to increase from one measurement to the other, all other
threshold radii also are increasing. Actually, if Figs. 2 and 6
are considered, all respective intrusion threshold radii and all
respective extrusion threshold radii of a measurement coincide
(which cannot be seen in a biplot, since the values are centered
over the respective mean values there). The 90◦ angle between
the θe vector and all other variables’ vectors indicate that the
threshold radii of the main extrusion cycles do not at all cor-
relate with the other threshold radii. Since this is an RMS bi-
plot, the cases are well approximated, but not the variables and
the correlation between them, so a better approximation of the
variables and its correlations would be found if the CMS bi-
plot is used. In the CMS biplot (not shown in this paper), the
previously collinear parameter vectors (RMS biplot) are inter-
secting with angles of around 1◦ , still reflecting a high corre-
lation between them, and the variable vector θe intersects at
an angle of around 30◦ with the other variable vectors reflect-
ing a far lower degree of correlation with the other threshold
radii.
• Since this is a centered biplot, the length of the variables’
vectors approximate the variance of the respective variable. The
standard deviation of the extrusion threshold radii has to be larger
than the standard deviation of the intrusion threshold radii.
• With increasing sample size, larger threshold values were
estimated. The cases corresponding to 1-mm samples are po-
sitioned to the left, the 5-mm samples in the middle, and the
20-mm samples to the right. Projecting the vectors of the cor-
responding cases vertically on the variable axes θi , θi1 , θi2 , θe1 ,
and θe2 , the largest values (further in the direction of the vari-
able axes) are found for the larger samples, and similarly, for the
projections onto the variable axes θe .
ACKNOWLEDGMENTS
This research was supported by the Swiss National Science Foundation.
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