94
23 (2006) 94–100
Application of Mercury Porosimetry to Predict the Porosity and
Strength of Ceramic Catalyst Supports
Malcolm Yates*
(Received: 28 September 2005; accepted: 24 January 2006)
DOI: 10.1002/ppsc.200601015
Abstract
Ceramic based monolithic supports are used in many
catalytic reactions, especially in environmental remedia-
tion to avoid pressure drop limitations that may arise in
the treatment of large effluent gas volumes. In these sys-
tems, the active phases or their precursors can be incor-
porated into the paste prior to kneading, extrusion and
calcination, in order to achieve a uniform deposition
throughout the final structure. However, these types of
incorporated monolithic catalysts can suffer from diffu-
sion limitations that necessitate the inclusion of tempor-
Keywords: ceramic, porosity, strength
1 Introduction
Monolithic supports are normally used in catalytic reac-
tions to avoid pressure drop limitations that may arise in
the treatment of large gas volumes, especially in effluents
that may contain particulate matter or fly ash [1]. In these
systems the active phase or its precursor can be incorpo-
rated into the paste prior to kneading, extrusion and cal-
cination, in order to achieve a uniform deposition
throughout the final structure. However, these types of
incorporated ceramic monolithic catalysts can suffer
from diffusion limitations that reduce their catalytic
activity. To overcome or reduce these diffusion limita-
tions, temporary pore generating agents (PGAs) can be
included in the initial paste composition, which when re-
moved by thermal treatment, generate higher porosities
[2]. However, the increased porosity of the material re-
sulting from the incorporation and subsequent removal
* Dr. M. Yates,
Instituto de Catálisis y Petroleoquímica, C.S.I.C., c/Marie
Curie 2, 28049 Madrid (Spain).
E-mail: myates@icp.csic.es
http://www.ppsc-journal.com
Part. Part. Syst. Charact.
ary agents, which when removed by thermal treatments,
generate a higher porosity. This results in an increase in
the interconnectivity of the pore structure of the final
material. However, an upper limit is reached since an in-
creased porosity negatively affects the mechanical
strength of these ceramic materials. In this paper, the
mechanical strength and porosity of ceramic catalyst
supports are related to the primary particle size of the
raw materials, initial composition and final heat treat-
ment temperature.
of a PGA has a negative effect on development of the me-
chanical strength of the ceramic. Thus, there is a limit to
the maximum amount of PGA that can be added before
it leads to such a severe reduction in the final mechanical
strength that these catalysts cannot be used industrially.
In this work, three series of ceramic monoliths were pre-
pared from sepiolite, natural magnesium silicate clay of
high abundance and available at low cost in Spain,
sepiolite-titania and sepiolite-alumina with between
0 wt.-% and 20 wt.-% of starch added as the PGA. Starch
was chosen as the PGA since it acts as an agglomerating
agent during the extrusion process but subsequently may
easily be burnt out by heating in air to about 400 °C, lead-
ing to a highly interconnected porous structure.
2 Experimental
Three series of monoliths were prepared, based on a-se-
piolite, natural magnesium silicate, supplied by Tolsa SA
(Pansil 100), and two others with a 1:1 ratio by weight
with a clay binder and titania, D51 supplied by Millen-
nium, or alumina, Pural SB supplied by Sasol. Three sam-
ples were produced using the magnesium silicate (clay)
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
Part. Part. Syst. Charact. 23 (2006) 94–100
with 0, 10 or 20 wt.-% PGA incorporated. The other two
series were also produced with 0, 10 or 20 wt.-% of PGA,
in which the ratio of clay and either titania or alumina
was maintained at 1:1 by weight. In all of these prepara-
tions, the raw material powders were premixed in a dry
rotary mixer to ensure homogeneity. This powder mix-
ture was then added to a kneading machine where a paste
with adequate rheological properties was formed with
the addition of water. This dough was extruded as honey-
comb monolithic structures with parallel channels of
square section with a cell density of 8 cells cm–2 and a wall
thickness of 0.9 mm. The honeycomb monoliths were
dried at room temperature and then heated in air to
150 °C, 500 °C or 850 °C at a heating rate of 3 °C min–1
and maintained at this final temperature for 4 h. The
shrinkage of the materials with drying and calcining was
also determined. This shrinkage was designated as the
dimensional stability, in terms of the percentage change
relative to the original dimensions of the paste extruded
from the die, before drying and heat treatment.
Mercury intrusion porosimetry (MIP) analyses were em-
ployed to determine the pore size distribution and pore
volume over a range of ca. 100 lm down to 7.5 nm
diameter, utilizing CE Instruments Pascal 140/240 appa-
ratus, on samples previously dried overnight at 150 °C.
Approximately 0.2 g of sample was accurately weighed
into the sample holder, which was subsequently out-
gassed to a vacuum of < 10 Pa at room temperature for
five min, before filling with mercury and commencing
the analysis. The pressure/volume data were analyzed
by using the Washburn equation [3] assuming a cylindri-
cal nonintersecting pore model, taking the recom-
mended values for the mercury contact angle of 141°
and surface tension of 484 mN m–1 [4]. The primary par-
ticle sizes of the four raw materials were determined
from analysis of the intrusion curves in the interval
relating to the filling of the interparticulate pore space,
assuming spherical particle geometry [5]. For the mono-
lithic samples, a single-piece two channels in width and
ca. 1 cm in length was employed for the measurement.
The mechanical strength of the monolith was deter-
mined using a Chatillon LTCM Universal Tensile Com-
pression and Spring Tester with a test head of 1 mm
diameter. The test head was positioned over one of the
channel walls of the monolith composite, and the pres-
sure slowly increased until rupture of the wall occurred.
An average of ten measurements was taken to ensure
the precision of the result.
3 Results and Discussion
The natural magnesium silicate used in this study as an
agglomerating agent to aid in the formation and extru-
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
95
sion of the ceramic pastes, has a fibrous structure
ranging from 0.2 to 2 lm in length, and 0.1 to 0.3 lm in
diameter for the bundles of fibers [6]. In the composite
materials these fibers act as a matrix in which the alu-
mina or titania particles can be dispersed and stabilized
[7,8]. The phase changes that the silicate binder under-
goes with heat treatment have been thoroughly studied
[9,10]. Loosely physisorbed water is lost from 80–150 °C.
Between 300 °C and 350 °C the loss of zeolitic water and
water of crystallization associated with the collapse of
the internal structure by a rotation to produce anhy-
drous sepiolite occurs. At this point the structure can
still be rehydrated back to its original state. Heating be-
tween 400 °C and 500 °C causes the loss of constitutional
water and the material cannot be rehydrated. Further
weight losses between 600 °C and 700 °C are due to the
loss of water present as hydroxyl groups. A very well de-
fined exothermic peak observed at about 825 °C, is due
to the phase change to enstatite, although no further
weight losses are produced. The heat treatment tem-
peratures chosen in this work were 150 °C, 500 °C and
850 °C, respectively. The lower temperature leads to the
loss of any loosely bound physisorbed water, and while
it causes a significant shrinkage, it does not bring about
any significant improvement in the mechanical strength.
After treatment at 500 °C, the structure is stable when
exposed to water, and thus typical impregnation meth-
ods can be used to incorporate any active phases. After
heat treatment at 850 °C, with the formation of enstatite,
the structure undergoes further shrinkage, and a signifi-
cant enhancement occurs in the mechanical strength.
The MIP curves corresponding to the four starting mate-
rials used in this study are presented in Figure 1. It was
1.5
1.2
Pore Volume (cm3g-1)
0.9
0.6
0.3
0.0
1 10 100 1000 10000 100000
Pore Diameter (nm)
Fig. 1: Cumulative volume (filled symbols) and PSD (empty sym-
bols) curves of the four powder raw materials: Clay (䊉), Titania
(~), Alumina (䉬) and PGA (䊏).
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96 Part. Part. Syst. Charact. 23 (2006) 94–100

observed that the clay binder gave rise to a bimodal
pore size distribution. With diameters of greater than
about 300 nm, the porosity was due to the loose aggre-
gate structure of the powder; which was removed when
formed as a monolith due to the compaction of the sam-
ple during wet kneading and extrusion. Below 300 nm,
the porosity was due to the interparticulate and intrapar-
ticulate porosities. The bimodal porosity observed for
the titania was mainly due to interparticulate porosity in
pore diameters between 100 nm and 10 lm, and intra-
particulate porosity in diameters below 100 nm. For alu-
mina, the interparticulate porosity was located between
1–100 lm, while the intraparticulate porosity was very
low due to the nature of this sample, with mesoporosity
lying just below the detection limit of the porosimetry
technique, at ca. 6 to 7 nm [7]. For the starch sample, a
single distribution due to the interparticulate porosity
was observed between ca. 5 lm–100 lm. The primary
particle sizes of the raw materials estimated from ana-
lyses of these curves were 90% < 0.4 lm, 0.8 lm, 40.8 lm
and 76.6 lm for the clay, titania, alumina and PGA,
respectively.
The results for textural and mechanical strength ob-
tained with the nine monolith compositions are given in
Table 1. The changes in the porosity of the clay after
conformation as a monolith by drying at 150 °C, and
heat treatments at 500 °C and 850 °C, are shown in Fig-
ure 2. Conformation of the clay as a monolith elimi-
nated the porosity due to the loose aggregate structure
and that caused by the interparticulate porosity was
reduced and shifted to narrower pores due to the higher
degree of compaction during the wet kneading and ex-
trusion processes, and final shrinkage of the material
formed by drying at 150 °C. The PSD of this material

Table 1: Composition and textural characterization of the ceramic monoliths.

Sample Original Heat Dimensional Mechanical Pore Interparticulate Interparticulate

Composition Treatment Stability Strength Volume Diameter Volume
(%) (°C) (%) (MPa) (cm3g–1) (nm) (cm3g–1)
150 84.8 22.7 0.41 20 0.283
Clay 100 500 84.5 24.8 0.50 25 0.329
850 81.8 48.8 0.43 39 0.203

150 85.3 21.5 0.49 340 0.373

Clay/PGA 90/10 500 84.9 22.8 0.56 350 0.400
850 81.8 37.6 0.54 385 0.332

150 85.2 12.2 0.54 793 0.425

Clay/PGA 80/20 500 85.4 18.1 0.68 853 0.505
850 81.3 37.2 0.64 905 0.431

150 89.2 13.4 0.53 121 0.417

Clay/Titania 50/50 500 88.8 21.1 0.64 125 0.455
850 83.6 29.3 0.48 154 0.352

150 89.7 11.0 0.56 115 0.446

Clay/Titania/PGA 45/45/10 500 88.6 19.7 0.72 125 0.536
850 83.3 28.5 0.53 148 0.408

150 90.2 10.2 0.75 133 0.617

Clay/Titania/PGA 40/40/20 500 89.0 16.7 0.83 139 0.650
850 83.2 25.6 0.63 165 0.512

150 90.9 8.5 0.40 3050 0.327

Clay/Alumina 50/50 500 90.5 5.8 0.59 3115 0.453
850 87.3 28.4 0.64 3820 0.327

150 91.4 6.8 0.54 4950 0.470

Clay/Alumina/PGA 45/45/10 500 90.8 6.0 0.69 5410 0.571
850 87.3 18.7 0.78 5570 0.482

150 91.8 6.0 0.62 5650 0.548

Clay/Alumina/PGA 40/40/20 500 91.4 3.9 0.94 6375 0.814
850 87.4 8.3 0.94 6760 0.653

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Part. Part. Syst. Charact. 23 (2006) 94–100
0.5
0.4
Pore Volume (cm3g-1)
0.3
0.2
0.1
0.0
1 10 100 1000
Pore Diameter (nm)
Fig. 2: Cumulative volume (filled symbols) and PSD (empty sym-
bols) curves of the Clay monolith treated at 150 °C (䊉), 500 °C
(~) and 850 °C (䉬).
was bimodal due to contributions from both intraparti-
culate and interparticulate porosities, which may be dis-
tinguished by the minima at 18 nm. Heat treatment at
500 °C caused a slight shift in the intraparticulate poros-
ity to wider pores, shown by the minima being located
to 23 nm. Although the measured pore volume was
greater after treatment at 500 °C, the mechanical
strength also rose. With heat treatment at 850 °C, the
differentiation between intraparticulate and interparti-
culate porosities became unclear due to further sinter-
ing, with only a single maximum at 39 nm. However, the
total porosity was reduced, partly due to further shrink-
age, doubling the mechanical strength. The variations in
the pore size distribution of the clay binder with drying
and heat treatment were important since they affect the
mechanical strength development in these materials,
and also in the monolith composites produced with tita-
nia and alumina.
The MIP curves for the clay series treated at 150 °C,
500 °C and 850 °C are presented in Figures 3a), 3b) and
3c), respectively. It is seen from Figure 3a) that for the
clay samples treated at 150 °C, the incorporation of 10
or 20 wt.-% PGA caused increases of pores greater than
200 nm, with corresponding reductions in the mechani-
cal strength. These increases in total pore volumes were
surprising since the soluble starch used as the PGA was
expected to fill the interparticulate pore space, and thus
cause a decrease in the total porosity.
From the curves presented in Figure 3b) it is observed
that decomposition of the starch by heat treatment at
500 °C led to well defined increases in the pore volumes
of about 19% and 36% in pores greater than 300 nm for
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
97
c
0.5
Pore Volume (cm g )
3 -1
0.0
b
0.5
0.0
a
0.5
0.0
10000
1 10 100 1000 10000
Pore Diameter (nm)
Fig. 3: Cumulative volume curves for Clay: (䊉), Clay/PGA 90/10
(~) and Clay/PGA 80/20 (䉬) monoliths treated at (a) 150 °C, (b)
500 °C, and (c) 850 °C.
the samples that had 10 wt.-% and 20 wt.-% PGA in
their original composition, compared to the sample pre-
pared without PGA, but had no effect on the porosity in
narrower pores. Similarly, for the samples treated at
850 °C, it is observed in Figure 3c) that the porosity in
pores of less than ca. 300 nm was equivalent for all
three, but increases of 25% and 50% in the pore vo-
lumes with respect to the clay monolith were produced
by elimination of 10 and 20 wt.-% PGA, respectively.
Similar results were obtained for the samples produced
by maintaining a clay/titania weight ratio of 1/1. The cor-
responding porosimetry curves obtained with this series
of samples, following treatment at 150 °C, 500 °C and
850 °C, are presented in Figures 4a), 4b) and 4c), respec-
tively. Thus, in Figure 4a) it is seen that after conforma-
tion and drying at 150 °C, pore volume increases of 6%
and 41% respectively, were observed for samples that
had 10 wt.-% and 20 wt.-% PGA in their compositions,
although the porosities of these three samples were
equivalent up to about 150 nm pore diameter. From the
porosimetry curves shown in Figure 4b) it is seen that
after heat treatment at 500 °C, the porosities of the ma-
terials in pores smaller than about 150 nm were equiva-
lent. Increases of the pore volumes in the larger pores of
13% and 30% for samples originally produced with
10 wt.-% and 20 wt.-% PGA, respectively, were ob-
served to the compared sample without PGA. Similarly,
with heat treatment at 850 °C, as shown in Figure 4c),
the porosities in pores of less than 150 nm remained
practically unchanged. The increased porosities in the
wider pores in comparison with the sample produced
without PGA were 11% and 31%, respectively.
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98 Part. Part. Syst. Charact. 23 (2006) 94–100

porosity of the samples in pores of less than 3 lm after

c
drying at 150 °C, but increased the pore volume by 33%
0.5 and 53% in the wider pores for the samples with
10 wt.-% and 20 wt.-% PGA, respectively. In Figure 5b)
Pore Volume (cm g )
3 -1

0.0 it is observed that heat treatment at 500 °C led to well

b defined increases in the wider macropores of 18% and
0.5
0.0
a about 3 lm was practically the same for all three sam-
0.5
0.0
1 10 100
Pore Diameter (nm)
Fig. 4: Cumulative volume curves for: Clay/Titania 1/1 (䊉), Clay/
Titania/PGA 45/45/10 (~) and Clay/Titania/PGA 40/40/20 (䉬)
monoliths treated at (a) 150 °C, (b) 500 °C, and (c) 850 °C.
In the case of the 1/1 clay/alumina composites the ob-
served changes in porosity on drying at 150 °C and heat
treatment at 500 °C and 850 °C, were due to sintering
and phase changes in both the alumina and the clay.
Heat treatment at 500 °C produced c-alumina with the
loss of water, and d-alumina at 850 °C [7]. The increase
in the recorded mesoporosity due to the alumina com-
ponent was especially significant.
The MIP curves obtained for the clay/alumina monoliths
treated at 150 °C, 500 °C and 850 °C, are presented in
Figure 5a), 5b) and 5c), respectively. In Figure 5a) it is
observed that the addition of PGA had no effect on the
c
0.5
Pore Volume (cm g )
3 -1
59%, respectively for samples produced with 10 wt.-%
and 20 wt.-% PGA compared to the sample produced
from clay and alumina, although the porosity below
ples. Although there was a large increase in the meso-
porosity due to the sintering of the Alumina component
after heat treatment at 850 °C, it is observed in Fig-
ure 5c) that the three samples have identical porosities
1000 10000 in pores of less than about 3 lm. In larger pores the in-
crease in the pore volume caused by the elimination of
the PGA was 22% and 47% for the samples originally
formed with 10 wt.-% and 20 wt.-% PGA, respectively.
The additional pore volumes created on decomposition
of the PGA are difficult to predict since all of the sam-
ples underwent various degrees of shrinkage with drying
and heat treatment. From the results presented in
Table 1, it is observed that the shrinkage observed on
drying and heat treatment followed the order: clay >
clay/titania > clay/alumina. This also coincided with the
mechanical strength of these three series. With all of the
samples produced, there was a clear increase in the dia-
meter of the maxima observed for the wider pores, as
the amount of PGA employed in the original mixtures
was increased. This indicated that the starch must have
coated the wider primary particles, rather than entering
into the intraparticulate voids during monolith confor-
mation. However, there was no relationship established
between the mechanical strength and the width of these
largest pores.
The crushing strength of a brittle ceramic is usually
related to its total pore volume [11]. However, a better
understanding may be obtained when the pore volume
associated with the interparticulate porosity is consid-

0.0 ered [12,13], since fracture will occur due to the defect
b structure caused by the phase boundaries between the
0.5
compacted particles, rather than fracture of the indivi-
dual primary particles. When the clay used as the ag-
glomerating agent was dried and heat treated at 150 °C
0.0
a and 500 °C, it displayed bimodal distributions due to
contributions of both intraparticulate and interparticu-
0.5 late porosities that could be distinguished by the ob-
served minima in the PSD curves at 18 nm and 23 nm,
0.0 respectively. When this distinction between the two
1 10 100 1000 10000 100000 types of porosity disappeared following heat treatment
Pore Diameter (nm) at 850 °C, the limiting value was taken from the maxima
Fig. 5: Cumulative volume curves for: Clay/Alumina 50/50 (䊉), in the PSD curve at 39 nm. These three values were sub-
Clay/Alumina/PGA 45/45/10 (~) and Clay/Alumina/PGA 40/40/ sequently used to calculate the interparticulate poros-
20 monoliths (䉬) treated at (a) 150 °C, (b) 500 °C, and (c) 850 °C. ities of all the materials.

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 Part. Part. Syst. Charact. 23 (2006) 94–100
The relationships between the interparticulate porosity
and mechanical strength are presented in Figures 6a),
6b) and 6c) for the clay, clay/titania and clay/alumina
series, respectively. As the heat treatment temperature
was increased for the clay and clay/titania systems, the
mechanical strengths also rose, especially after treat-
ment at 850 °C. This development of mechanical
strength was mainly due to phase transformations of the
magnesium silicate binder. These changes caused a
slight increase in the mechanical strength coupled with
an increase in the interparticulate pore volume, follow-
ing treatment at 500 °C, and a reduction in the interpar-
ticulate pore volume accompanied by a significant in-
crease in mechanical strength, after treatment at 850 °C.
25
Mechanical Strength (MPa)
0
25
0
25
0
0.0 0.1 0.2 0.3 0.4 0.5
Interparticulate Pore Volume (cm g )
Fig. 6: Mechanical Strength versus Interparticulate Pore Volume
for: (a) Clay (䊉), Clay/PGA 90/10 (~) and Clay/PGA 80/20 (䉬),
(b) Clay/Titania 50/50 (䊉), Clay/Titania/PGA 45/45/10 (~) and
Clay/Titania/PGA 40/40/20 (䉬), and (c) Clay/Alumina (䊉), Clay/
Alumina/PGA 45/45/10 (~) and Clay/Alumina/PGA 40/40/20 (䉬)
treated at 150 °C (solid lines), 500 °C (dashed lines) and 850 °C
(dotted lines).
The mechanical strengths were much lower for the clay/
alumina composites, probably due to the size of the alu-
mina particles that inhibited the ability of the fibrous-
clay agglomerating agent to bind them effectively. From
the results presented in Figure 6c), it may be observed
that decomposition of the PGA with heat treatment at
500 °C increased the interparticulate pore volume but
led to further reductions in the mechanical strengths.
Heat treatment at 850 °C led to improvements in the
mechanical strength of these materials, probably due to
a combination of the phase changes in both the clay and
alumina and further shrinkage of the monolith, which
led to a reduction in the interparticulate pore volume.
These results show that the mechanical strength devel-
opment in these three series may be predicted from
© 2006 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
99
their interparticulate porosities. However, the relation-
ships were different for each system and each heat treat-
ment since the mechanical strength development in
these composites is dependent on the size and bonding
between the individual primary particles, the interparti-
culate porosity, and temperature of the final heat treat-
ment. However, these curves are useful for estimating
the expected mechanical strength for an unknown com-
position which falls within the measured range and pre-
dicting the maximum amount of PGA that could reason-
ably be added to any of the formulations without
causing too great a reduction in the final mechanical
strength of the heat treated monolith, for its industrial
use as a catalyst support.
c 4 Conclusions
Incorporated monolithic catalysts have found use
mainly in environmental remediation such as the selec-
b tive catalytic reduction of nitrogen oxides from the ef-
fluent gases of adipic acid and nitric acid production
plants or fossil fuel fired power stations. The open chan-
nel structure of these systems avoids any problems asso-
a ciated with pressure drop across the catalytic bed. How-
ever, the maximum catalytic activity is not always
achieved due to diffusion limitations. These problems
can be reduced by increasing the pore volume and con-
0.6 0.7 0.8
3 -1
nectivity of these ceramic bodies through the incorpora-
tion of PGAs, which are subsequently eliminated by
thermal treatment. However, the loss in mechanical
strength of these systems as the amount of PGA is in-
creased must be taken into account, especially in
systems that operate in dusty environments, where the
mechanical strength and abrasion resistance can be ser-
iously reduced, if the porosity of these incorporated
ceramic catalysts is too high.
In this study, it has been shown that the mechanical
strengths of these ceramic systems are governed by a
combination of interparticulate porosity, raw material
particle size distributions and the final heat treatment.
Although the relationship between the mechanical
strength and porosity is different for each system, it has
been shown that MIP is a valuable tool in predicting the
expected mechanical strength development of these
types of systems.
5 Nomenclature
MIP mercury intrusion porosimetry
PGA pore generating agent
PSD pore size distribution
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100 Part. Part. Syst. Charact. 23 (2006) 94–100

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