Part. Part. Syst. Charact.
23 (2006) 919
Mercury Porosimetry: A General (Practical) Overview
Herbert Giesche*
(Received: 28 September 2005; accepted: 9 March 2006)
DOI: 10.1002/ppsc.200601009
Abstract
The paper describes general concepts of mercury porosi-
metry measurements and provides an overview on the
current status of pore-network analysis tools. Practical
Keywords: mercury porosimetry, overview, pore network
1 Introduction
Mercury porosimetry is an extremely useful characteri-
zation technique for porous materials. Pores between
about 500 lm and 3.5 nm can be investigated. A com-
plete analysis may take as little as half an hour of analy-
sis time. Mercury porosimetry provides a wide range of
information, e.g. the pore size distribution, the total
pore volume or porosity, the skeletal and apparent den-
sity, and the specific surface area of a sample. No other
porosity characterization technique can achieve this.
However, one should realize that mercury porosimetry
also has limitations. One of the most important limita-
tions is the fact that it measures the largest entrance to-
wards a pore (see Figure 1), but not the actual inner size
Fig. 1: Schematic representation of pores.
* Ass. Prof. Dr. H. Giesche, School of Engineering, Alfred Uni-
versity, 2 Pine Street, Alfred, NY 14802 (USA).
E-mail: giesche@alfred.edu
2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
9
aspects of the technique are described as well as empha-
sizing the need for testing of model pore structures and
the status on pore network modeling software.
of a pore. For obvious reasons it can also not be used to
analyze closed pores, since the mercury has no way of
entering that pore. Through various software techniques
an interpretation of the pore-network (cross-linking
structure between pores) can be achieved. However,
one should realize that numerous assumptions are made
in that process and the final results are somewhat arbi-
trary.
2 Theory and Key-parameters
A key assumption in mercury porosimetry is the pore
shape. Essentially all instruments assume a cylindrical
pore geometry using a modified Young-Laplace equa-
tion, which is most of the time referred to as the Wash-
burn equation.
 
1 1 2 c cos h
DP c 1
r1 r2 rpore
It relates the pressure difference across the curved mer-
cury interface (r1 and r2 describe the curvature of that
interface) to the corresponding pore size (rpore) using
the surface tension of mercury (c) and the contact angle
(h) between the solid and mercury. The real pore shape
is however quite different and the cylinder pore assump-
tion can lead to major differences between the analysis
and reality.
As indicated in Eq. (1), we need to know surface tension
and contact angle for the given sample and then mea-
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10
sure pressure and the intruded volume in order to obtain
the pore size pore volume relation.
Pressure is one of the key measurement variables and
one has to realize that a wrong pressure reading will
automatically result in the wrong pore size. The mea-
surement spans 5 orders of magnitude. Consequently,
the pressure also changes over an equally wide range. It
would be very difficult to have a single transducer for
the entire measurement. Thus, for practical reasons
most instruments use several transducers. This set-up
then provides us with a better resolution within each
range, however, it can also cause artificial effects at the
switchover points between the various transducers.
When interpreting the analysis results one should always
be aware of those switchover points, e.g. between the
low and the high pressure run. Artificial effects at gles between mercury and various different or even very
that specific point are not only caused by the switch be-
tween different pressure transducer, but also because of
the different environment of the sample cell (air ver-
sus oil). It is difficult to detect problems with a pressure
transducer unless a transducer totally fails or if the
change is so severe that the results are obviously wrong.
Running standard samples, which have several (!) well
defined pore sizes, is one way to check the instrument.
However, even then, it is usually up to the instrument
manufacturer to correct for these problems. The instru-
ment operator has no way of changing or correcting the
pressure-transducer-readout. The operator can only re-
duce chances of a transducer failure by avoiding any
sudden pressure changes, over-pressure exposure and
major temperature swings.
The second key measurement parameter is the pore vo-
lume. Essentially all instruments use capacitance mea-
surement between a metal shield on the outside of a
glass capillary and the length of the mercury column in
the capillary. Obvious problems can arise if the inside or
outside of the glass capillary is not uniform or in case
there is any other external factor effecting the capaci-
tance. Bad electrical contacts are one of the most fre-
quent reasons for those problems. However, most of
these problems are easily detected, since they will cause
drastic spikes or other irregularities in the measurement.
The operator should primarily check that the capillary is
free of contaminations or obvious chips at the end of the
glass. Checking the volume calibration factor with a
known standard material is relative simple test and most
instruments allow for any necessary correction factor.
Nevertheless, one should contact the instrument manu-
facturer in case those deviations are detected, since it
could be a sign of failed electronic components as well.
The surface tension of mercury and the contact angle
between mercury and the sample surface are additional
factors, which have to be established.
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Part. Part. Syst. Charact. 23 (2006) 919
In general, the surface tension of mercury is not of any
great concern with respect to errors in the determination
of the pore size distribution. A value of 0.485 N m1 at
25 C is commonly accepted by most researchers. It is
advisable to use fresh (triple distilled) mercury for every
measurement. Although, using mercury, which was re-
claimed through a siphon technique, is sufficient in
many cases, it allows the possibility for a major and of-
ten undetected error. Reports by Allen [1] and Klobek
[2] describe the effect of temperature and pressure on
the surface tension value, but these corrections are not
used on a general basis.
The contact angle on the other hand is a parameter,
which clearly affects the analysis results and numerous
papers have demonstrated the wide range of contact an-
similar solid surfaces. For example, contact angles of 128
to 148 degree have been determined for identical sys-
tems of mercury on glass [3]. However, in most practical
situations and out of convenience users often apply a
fixed value irrespective of the specific sample material,
e.g. 130 or 140.
Several techniques are available to determine the con-
tact angle, such as: placing a drop of mercury on the flat
surface of the sample and either fitting the actual shape
of the drop or measuring the maximum height, hmax, as
the volume of mercury is increased. The contact angle
can then be estimated using Eq. (2).
r g h2max
cos h 1 2
2 cHg; air
with g, gravity acceleration, and q, density of the liquid.
Alternatively a powder compact can be pressed in such
a way that a well defined hole is created in a disk. Mer-
cury is now placed on top of this disk and the contact an-
gle can be calculated from the necessary pressure to
force the mercury through this cylindrical pore.
In addition, one should keep in mind possible errors due
to a surface contamination by impurities and effects of
microscopic surface roughness on the more macroscopic
contact angle measurements. Further details are de-
scribed elsewhere [4].
3 Sample Preparation
The very first point in a good analysis is having a well-
defined unambiguous sample. One of the key para-
meters here is the sample weight. Porous materials are
prone to adsorb water or other chemicals, which should
be removed during the initial evacuation of the sample.
2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Part. Part. Syst. Charact. 23 (2006) 919
Mercury porosimetry has no direct way of noticing if
those impurities are removed and what the actual sam-
ple weight is. We can only indirectly judge from a low
vacuum pressure and the absence of any possible leak-
rates that the sample is in a clean and well defined
starting condition. Other external measures might be
needed to determine the clean sample weight.
Although advisable, it is usually not possible to apply
any heat treatment to the sample during the evacuation
process.
Another source of possible problems is the creation of
artificial pores due to packing of the sample inside the
penetrometer cell. The inter-particle voids between
(spray-dried) powder granules are an obvious example.
However, even the voids between sheets of a sample
(e.g. paper pieces) or the void between the sample and
the glass wall of the penetrometer are possible error
sources. Most of the time these errors will not be very
significant since the actual sample porosity is much lar-
ger, but in case of nearly non-porous samples, the rela-
tive error can be quite significant. These artificial pores
between sample pieces can be avoided by using a coarse
(e.g. 1 mm diameter) stainless steel wire to keep the
sample pieces separated.
On the opposite side, a sample can be sealed in a thin
walled rubber balloon, e.g. for determining the compres-
sibility of the sample. Being aware of possible compres-
sibility effects is especially important when analyzing
softer sol-gel type samples or porous polymers. Alter-
natively the sample can be partially encased in epoxy,
leaving only controlled areas of the sample free of
epoxy, which allows one to study a specific penetration
path into a sample.
4 Filling and Low Pressure System
Initially the sample is evacuated to remove air and resi-
dual moisture or other liquids from the pore system. A
complete evacuation is important in order to avoid pos-
sible air pockets and contamination issues. The sample
cell is then filled with mercury as the entire system is
still under reduced pressure. Slowly increasing the over-
all pressure then allows mercury to penetrate the largest
pores in the sample or any void spaces between sample
pieces. The first data point is usually taken at a pressure
of 3000 to 4000 Pa (0.5 psi) or higher. Lower pressure
readings are possible, but one has to understand that the
height of a 1 cm mercury column would already corre-
spond to a pressure of 1333 Pa. Thus, the top and bottom
of a 1 cm tall sample would experience a pressure differ-
ence of 1333 Pa solely due to the weight of the mercury
column. Each instrument uses different designs to keep
2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
11
this effect as small as possible. Nevertheless any re-
ported pore diameter of more than 500 lm is extremely
questionable due to the (head-pressure) effect as de-
scribed before.
Thereafter the pressure is increased up to several atmo-
spheres (limited by safety factors of the set-up), which
allows for a reasonable cross-over between the low and
the high pressure part of the analysis. At the end of this
low pressure-part of the analysis the weight of the pe-
netrometer, filled with mercury and the sample, is deter-
mined, which allows one to calculate the bulk density of
the sample (using corresponding blank-runs as a refer-
ence). The volume of intruded mercury is measured con-
tinuously through changes in the capacitance between
the column of mercury in the dilatometer stem (capil-
lary tube of know diameter connected to the sample
cell) and a coaxial metal sheet surrounding the stem. Al-
ternatively optical- and resistance- or contact-wire tech-
niques have been used in the past.
5 High Pressure System
Once transferred to the high-pressure system, the sam-
ple-cell is surrounded by hydraulic fluid and pressures
of up to 414 MPa (60,000 psi) are applied in an isostatic
way.
5.1 Equilibration
Most instruments can operate in a continuous or an in-
cremental mode.
The continuous mode offers the possibility to run an
analysis in a very short time, 5 to 10 min for an entire
analysis. However, this requires a careful consideration
of a variety of correction factors, which are primarily the
compressive heating effect and hindered flow of mer-
cury through small pore channels. On the other hand, it
allows for a large number of data points to be recorded
and even small differences between samples can be ob-
served, whereas those differences could occur between
two data point during the incremental mode. In contrast,
the incremental technique offers a better assurance that
true equilibrium is reached for each data point as long
as the equilibration time interval is chosen sufficiently
long and temperature effects can be avoided, which is
usually provided at equilibration times over 5 min. It is
important to notice that those effects are primarily im-
portant for the high pressure / small pore size range.
Volume readings taken before equilibrium has been
reached may result in shifting of the distribution toward
smaller pore sizes and smaller pore volumes during in-
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12 Part. Part. Syst. Charact. 23 (2006) 919

trusion and larger pore sizes as well as a larger amount

of trapped mercury during the extrusion process.
The advancement of the mercury interfaces in horizon-
tal, cylindrical capillaries was computed and also veri-
fied experimentally by Wardlaw and McKellar [5].
For a horizontal cylindrical capillary mercury will enter
the capillary at the threshold pressure, as given by the
Laplace equation, but will not continue to advance. A fi-
nite rate of advance is dependent on an excess pressure
(DP) above the threshold pressure and the distance to
time relationship for the advancing mercury front is
then given by

l2 4 g
t 3
DP r2p

where t = time, l = distance, g = viscosity (1.536 centi-

poise), r = radius, and DP = pressure applied in excess of
the injection pressure.
The distance to time relationship for mercury in tubes of
five different sizes is shown in Figure 2. For example,
more than 100 seconds are needed to travel 3 cm in a
tube of 0.5 lm radius. In practice those limitations apply
primarily to large samples or to small (< 100 nm) pores.
Other side effects may require more attention, like the
heating or cooling effects due to compression or expan-
sion. A temperature increase of 10 to 15 C is not unu-
sual when the system is pressurized at a fast rate. Corre-
sponding negative temperature changes were observed
during a fast depressurization. Temperature swings cor- Fig. 2: Advancing mercury in cylindrical pores of different radii;
respond to volumetric expansion effects in the mercury applied pressure is 110% of injection pressure according to Eq. (3)
[5].
and/or the sample cell, which consequently present
themselves as artificial pore volume effects.
Pore size as well as pore volume can be greatly influ- the intrusion (b) and the extrusion (c) at specific pres-
enced by the intrusion rate settings as shown below. Five sure values. Prior to those individual tests, the sample
samples of an alumina extrudate were analyzed with a was measured under normal conditions (300 s equili-
Micromeritics Autopore 9420
using a so-called scanning mode
(equilibration by time for 0 sec-
onds), equilibration-interval set-
tings of 2, 10, and 30 seconds, and
an equilibration rate of 0.001 ll/g
sec. The cumulative intrusion
pore volume curves of the five ex-
periments are shown in Figure 3.
A difference of close to 10% in
pore volume and 40 to 50% in
pore size is noticeable between
the fastest and the slowest
analysis condition.
Another aspect of equilibration
time is shown in Figure 4. Here
the intrusion volume was fol-
lowed as a function of time for Fig. 3: Intrusion rate effects on pore size and pore volume [6].

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Part. Part. Syst. Charact. 23 (2006) 919 13

a) 0.60 data points at higher as well as lower pressure values

0.58 (pore size) compared to the intrusion data. Equilibra-
0.56 tion of the extrusion data points in that example took
CUMULATIVE INTRUSION (mL/g)

0.54
over 2 hours. It seems that other factors besides the flow
0.52
of mercury through the pore-network or temperature
0.50

0.48
effects are responsible for the delay in reaching equili-
0.46
brium.
0.44

0.42

0.40 5.2 Compressibility

0.38

0.36
Compressibility is another major effect, which has to be
0.34

0.32
considered. Ideally this would be corrected by a corre-
1 0.1 0.01
sponding blank-run using a non-porous sample of the
DIAMETER, (micrometers) same material. Unfortunately this is not always possible.
Compressibility, b, is defined as the fractional change in
b)
2 volume per unit pressure. The linear equivalent is the
2
Youngs Modulus. Most solids have a b-value of about
103 to 104 (Pa)1. Thus, a 1 cm3 sample will compress
1
by about 0.006 to 0.06 cm3 at the final pressure of
3 100 psi
(Dp = 70 nm) 1
400 MPa. Depending on the pore volume of the sample,
Pore Volume

1 100 psi 2 200 psi

this might be a minor effect. On the other hand, polymer
Pressure

(Dp = 100 nm) 1

or sol-gel materials usually have a substantially larger
1
compressibility and vice versa a much greater effect on
the analysis results. Compressibility effects can easily be
1
detected when plotting the cumulative pore volume on a
0 linear pressure scale. The combined compressibility ef-
fects have to be considered: mercury, sample cell as well
0

1060 1090 1120 1150 1180 as the sample itself. In case of highly non-compressible
Time /min. samples even a negative overall volume change might
1
be noticed. Compressibility is primarily important at
c)
smaller pore sizes or higher pressures. However, this is
1
also the region, which has the relative strongest effect
1 on surface area calculations. Thus, the latter values can
10 000 psi 2 000 psi
(Dp = 109 nm)
be significantly effected (increase as well as decrease)
1
by compressibility.
Pore Volume

Pressure

700 psi
1 Using an encapsulated sample, e.g. a sample sealed in a
(Dp = 310 nm)
1
thin rubber balloon, is one way of evaluating compressi-
200 psi bility. However, one has to be aware that the compressi-
(Dp = 1090 nm)
0
bility of a porous sample, as measured when encapsu-
0
lated, is not the same as the compressibility of the solid
without porosity. Thus, the encapsulated sample simu-
1500 1560 1620 1680 1740
0

1800
lates the sample behavior before any mercury has
Time /min. entered the pore space, whereas the solid-compressibil-
ity is describing effects after mercury has filled the pore
Fig. 4: How fast does the system (data points) equilibrate? space and is now compressing the pore walls.
The original data points collected are shown in a); graph b) shows
the time-volume curves for intrusion {steps between the intrusion
data points shown in a)}; and c) shows the time-volume curves for
the blue extrusion data points. 6 Data Interpretation and Analysis

bration time; Figure 4a)). Interestingly reaching the 6.1 Pore Size and Pore Volume
equilibrium during intrusion (Figure 4b)) was achieved
much faster than during extrusion (Figure 4c)) even so it Intrusion pressure values are directly converted into the
was the same sample and the extrusion tests covered corresponding pore size by using the Washburn equa-

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14
tion. This is a straightforward calculation. However, one
should be aware that mercury porosimetry does not
actually measures the internal pore size, but it rather de-
termines the largest connection (throat or pore channel)
from the sample surface towards that pore. Thus, mer-
cury porosimetry results will always show smaller pore
sizes compared with Scanning Electron Microscopy
(SEM) or optical micrographs.
6.2 Density
A simple pycnometry type calculation allows measuring
the sample density. Especially for samples like spray
dried granules density determination at the point when
mercury has filled all the inter granular pores is of inter-
est, since it will then describe the internal density of the
granules. However, the precision of those measurements
is rather rough (2 to 5% error) unless special care is
taken with respect to temperature control.
6.3 Surface Area
Rootare and Prenzlow [7] derived the following equa-
tion:
ZV
1
A PdV 4
cHg cos h
0
which allows converting the pore volume data into the
corresponding surface area under the assumption of a
reversible intrusion process. Even so, an interconnected
pore network does not strictly follow this rule; many
publications [7,8] have reported good correlations be-
tween surface areas determined by mercury porosime-
try and nitrogen adsorption measurements. Irrespective
of this, one should be aware that minor measurement
errors especially in the high pressure or small pore size
range can effect the calculated surface area to a very
large degree and one has to be especially careful with
respect to good data points in that part of the analy-
sis.
6.4 Particle Size
Data from mercury porosimetry can also be used to esti-
mate the particle size of a powder material. Two possi-
ble methods are available for this purpose. On the one
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Part. Part. Syst. Charact. 23 (2006) 919
hand, the surface area as determined during the analysis
can be converted into the equivalent sphere diameter
(particle size) by assuming a specific density, q, of the
material.
3m
r 5
rA
On the other hand, the pore size can be used to estimate
the corresponding particle size by assuming a particular
packing structure of the powder particles.
The surface area technique calculates too small of a par-
ticle size if surface roughness, pores inside the particles,
or a larger quantity of very small particles exists.
The pore size conversion method on the other hand may
lead to wrong results if the particle shape is not
spherical or when the degree of compaction changes,
e.g. due to moisture acting as a lubricant between parti-
cles. On a rough scale the particle size is approximately
2 to 4 times larger compared with the measured pore
size. In all of these situations the assumed packing struc-
ture is critical. One might use the measured pore vo-
lume as an indicator for the actual packing structure,
but this can only be used as a vague approximation.
Further details are described in a classical paper by
Mayer and Stowe [9,10] and later publications by Smith
and Stermer [11].
6.5 Multi-modal Pore Size Distributions
Often analysis data show groups of pore sizes, which can
either be attributed to the intentional structure of the
materials or they could be caused by artificial measure-
ment effects. For example, larger pores are frequently
associated with the packing structure of powder parti-
cles or between sample pieces. In order to control the
spacing between sample pieces one can prepare a stain-
less steel wire cage around individual sample pieces, e.g.
membrane or filter plates, to create a minimum spacing
(or pore space) between those pieces, which then shifts
the size range of these artificial pores to larger sizes and
thus, allows to distinguish porosity of the sample from
artificial pores.
Figure 5 shows an example of a multi-modal pore size
distribution. The first step at 20 to 30 lm describes the
inter granular porosity between spray-dried granules of
about 60 to 100 lm in size. The second and third step
(slope change below 0.07 lm) are part of the internal
pore structure, which is caused by the various primary
particles present within the granules.
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Part. Part. Syst. Charact. 23 (2006) 919 15

0.8 6.6.1 Contact Angle Hysteresis

0.7
Cum. Pore Volume /ml/g

Differences in advancing and receding contact angles

0.6
are frequently observed, but the idea is somewhat ques-
0.5
tionable from a thermodynamic point of view. The sur-
0.4
face roughness or impurities on the mercury or solid sur-
0.3
face could certainly change the value of the contact
0.2
angle. However, some observations cannot be explained
0.1
by the contact angle hysteresis (see Figure 7). Such as:
0
0.001 0.01 0.1 1 10 100 1000
a) Contact angle hysteresis cant explain why some mer-
Pore Diameter /m
cury remains trapped in the pore system after com-
plete depressurization.
Fig. 5: Multimodal pore size distribution of a spray dried catalyst b) Re-intrusion and extrusion curves should have a simi-
sample. lar shape when plotted on a logarithmic pressure or
pore size scale. However, literature data frequently
show only a marginal fit between these curves.
6.6 Hysteresis, Trapped Mercury, c) No volume changes should be observed, when scan-
and Pore-connectivity ning between the hysteresis branches (extrusion and
intrusion curve). Yet, frequently those scans within
Hysteresis between the intrusion (increasing pressure) the hysteresis-range arent constant with respect to
and extrusion (decreasing pressure) is observed in es- pore volume.
sentially all samples during mercury porosimetry mea- d) Chemical changes on the sample surface (with no
surements. change in the pore structure) can lead to drastic
Several explanations have been proposed. Primarily changes in the extrusion curve, whereas the intrusion
those are: contact angle hysteresis, the ink bottle theory, curve is frequently unaffected. A fact, which can not
and the percolation-connectivity model. be explained by contact angle hysteresis.
A typical example is given in Figure 6, which shows For further information on contact angle effects, the
results for a sample made from monodispersed silica reader is referred to the publications by Lowell et al.
spheres. The sample is of special interest, since the or- [12] and Salmas et al. [13].
dered arrangement of the spheres allows one to com-
pare measured with predicted pore sizes. Understanding
the behavior in these model structures then allows one
to gain further insight into the general aspects of intru-
sion and extrusion.

0.25

Extrusion
0.2
2nd extrusion run; Fig. 7: Schematic drawing of theoretical (left) and experimental
0.15
partially
2nd filled run
intrusion (right) observations with respect to contact angle hysteresis.
with mercury
partially )
filled ((D)

0.1

6.6.2 Ink Bottle Theory

0.05
It is obvious that pores rarely are of uniform shape. The
Intrusion throat or entrance opening to a pore is smaller than
0

Silica sample 1000 C 31 h the actual cavity. So, mercury will enter the pore cavity
-0.05 at a pressure determined by the entrance size and not
0.01 0.1 1 10
the actual cavity size.
Pore diameter /m
During extrusion the mercury network would then
Fig. 6: Scanning within the mercury porosimetry hysteresis of silica break at all the throats (narrower connections) between
samples calcined at 1000 C for 31 hours [20]. pores, leaving a large amount of mercury trapped inside

2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim http://www.ppsc-journal.com

16
the sample. Figure 8 demonstrates this for a glass model
sample with a carefully arranged pore structure. It is in-
teresting to notice that more mercury is remaining in
the structure as the ratio of inner pore-size and throat-
size increases. The ink-bottle theory can, thus, easily
explain trapped mercury, but it does not necessarily ex-
plain the pore size shift between intrusion and extru-
sion.
Fig. 8: Glass model of an artificial pore system. Trapped mercury
is visible in black in the bottom picture after release of pressure
[5].
6.6.3 Connectivity Model
The connectivity model uses a network of pores. It is
kind of an extension of the ink-bottle theory. Yet it has
an added component in terms of considering the connec-
tion effects between the pores. In order for a pore to be-
come filled with mercury it must be equal to or larger
than the corresponding pore size at the applied pres-
sure, but it also requires a continuous path of mercury
leading to that pore. Large internal voids, which are sur-
rounded by smaller pores, will not be filled unless the
pressure is sufficient to fill a pathway towards that pore.
During the extrusion process, the reverse process occurs,
and certain pores or islands of pores will remain filled
with (trapped) mercury, once they no longer have a con-
tinuous mercury path towards the sample surface. Var-
ious studies [5,1320] have taken this idea and studied
the effects in model pore structures as described in the
following section.
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Part. Part. Syst. Charact. 23 (2006) 919
6.6.3.1 Energy Barrier or Snap-off Factor,
and Pore Geometry
Ideally intrusion into and extrusion out of uniformly
sized pores of cylindrical shape should happen at the
same pressure. However, in most real samples we do not
have that type of ideal pore geometry. During the extru-
sion process new mercury interfaces have to be created
as the mercury retracts from the pore system. This pro-
cess requires additional energy, thus, an energy-bar-
rier is to be expected. Alternatively the energy barrier
can be expressed as a snap-off factor; describing to
what degree the extrusion pressure (an additional pull)
has to be lowered relative to the corresponding intrusion
pressure until the mercury network breaks apart and
mercury can retreat from a specific pore. Several simu-
lated ideas have been presented trying to calculate this
snap-off factor for different pore geometries. For exam-
ple, the snap-off factor for long cylindrical pores of uni-
form diameter is relative small. However, the factor be-
comes larger as the pore length is decreased (see
Figure 9). In a similar way the snap-off factor is affected
by the opening angle of conical cylinder pores (as shown
in Figure 10) or the contact angle between mercury and
the solid. Moreover, Tsakiroglou and Payatakes [17]
simulated the snap-off factor for lenticular throats. The
authors then combined their calculations with model
pore structures etched in glass slides and compared the
simulated and experimental intrusion and extrusion
curves. It is interesting to notice that a pore will empty
not only according to their own size and the size of the
connecting throats, but the specific geometric arrange-
ment of the throats, which are still filled with mercury, is
important as well. For example a pore, which is con-
Cylindrical Pore
1 m diameter; = 140; = 0.48 N/m
Length Intrusion Extrusion PI/PE
m MPa MPa
100 0.735 0.726 1.01
10 0.735 0.650 1.13
5 0.735 0.566 1.31
2 0.735 0.309 2.78
1.5 0.735 0.166 7.58
1.4 0.735 0.050 14.66
Fig. 9: Calculation of Energy-Barriers (snap-off factors) in
cylindrical pores of different aspect ratios [19,20].
2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Part. Part. Syst. Charact. 23 (2006) 919
Fig. 10: Calculation of Energy-Barriers (snap-off factors) in
conical cylinder pores [19,20].
nected to the mercury network by only one filled throat
(and 3 empty throats), is drained at a higher pressure
(earlier) during extrusion compared to a pore, which is
connected via 2 or 3 filled throats.
Similar effects were observed in an ordered packed
sphere structure as demonstrated in Figure 6. On partial
intrusion (as compared to a complete 100% intrusion)
the mercury network contained numerous breakage-
points. Thus, extrusion from the smaller tetrahedral
pores could be observed separately from the octahedral
pores during the extrusion, in case they were connected
to empty channels or throats. On the other hand the
completely filled pore network did not have those exist-
ing breakage points and a much lower pressure was re-
quired to create these breakage points. The additional
pull for the breakage point then resulted in an extrusion
pressure, which was too low to distinguish octahedral
and tetrahedral pores (as visible in the extrusion of the
partially filled sample in Figure 6). The hysteresis fine-
structure was no longer detectable.
G. Mason et al. [2126] published simulations on the in-
trusion/extrusion process as related to different pore
geometries. They studied rods of equal or different dia-
meters, rods in contact with a flat plate and so on. He
also performed detailed calculations of the exact surface
curvature and energy minimization and calculated the
influence between adjacent pores with respect to drai-
nage and extrusion.
6.6.3.2 Network Simulation Software
Another approach was taken by P. Matthews and his co-
workers [2729]. They simulated the pore system by a
2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
17
10 10 10 array of cubes (pores) joined by a network
of cylinders (throats) in the 3-D network. The software
program, commercially distributed as Pore-Cor, uses
a similar snap-off as well as a connectivity (pore
blocking) factor to optimize the fit between simulated
and experimental data. The model is somewhat crude by
using only a 10 10 10 pore matrix, but it is a very in-
teresting approach to extract and simulate pore network
information from the mercury porosimetry measure-
ments and to use that information thereafter to calculate
and predict permeability or tortuosity of a sample.
Similar network simulations, which are not specifically
mentioned here, have been published by S. Rigby
[3033].
7 Conclusions
Pore size distribution data generated by mercury porosi-
metry are primarily useful in comparative studies of
similar materials. This is true because the absolute accu-
racy of the data depends on various assumption and ex-
perimental factors. Some of these factors cancel out for
the relative comparisons of similar materials and thus, it
is not quite as critical to have perfectly correct values in
these cases. In general, pore size and pore volume are
repeatable to better than 1% standard deviation, but the
results are also limited a priori in three ways:
Mercury porosimetry determines the largest en-
trance to a pore, but not the actual pore size.
The smallest pore size, which can be filled with mer-
cury, is limited by the maximum pressure, which can
be achieved by the instrument, e.g. 3.5 nm diameter
at 400 MPa assuming a contact angle of 140.
The largest measurable pore size is limited by the
height of the sample, which determines a minimum
head-pressure, e.g. a 1cm sample height is approxi-
mately equivalent to a pore of 1 mm diameter.
In addition properties of the sample may affect the re-
producibility and create difficulties in giving an unam-
biguous interpretation of the result:
A loosely packed powder might become further
compacted due to the pressure exerted on the sam-
ple before the mercury actually penetrates the pore
spaces. Erroneously the compaction effect then
might be interpreted as porosity.
Likewise elastic or permanent structural changes can
occur in highly porous or soft materials due to the
applied pressure. A second intrusion run can only
partially reveal those changes.
The concept of a connected pore network and the exis-
tence of a snap-off factor, during the extrusion process,
has been studied and demonstrated by different re-
http://www.ppsc-journal.com
18
search groups. These concepts provide the most power-
ful explanation at the moment for hysteresis effects and
the fact that mercury remains trapped inside the sample
after depressurization. However, these concepts are still
in their early stages and more detailed studies of model-
pore-structures are needed to fully understand the ef-
fects of individual factors in those models. Ordered
packed-sphere structures are a very useful model sys-
tem, since they have very well defined pore sizes and
connections between the pores. Additional studies
should include the theoretical calculations combined
with experimental intrusion/extrusion data of samples of
etched channels in glass, which will further enhance our
understanding of these network effects.
Despite all these limitations mercury porosimetry still is
an extremely useful analysis technique. It provides ex-
ceedingly important information about the porosity of
samples, not at least due to the fact that it covers pore
sizes over a range of 5 orders of magnitude from 0.4 mm
to less than 4 nm.
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