Strong ceramic foams from polyurethane

templates
J. Luyten1, I. Thijs1, W. Vandermeulen1, S. Mullens*1, B. Wallaeys2 and
R. Mortelmans2

Published by Maney Publishing (c) IOM Communications Ltd

The most conventional manufacturing route for ceramic foams with open cells consists of coating
reticulated polyurethane foams. The resulting material has well defined cell size, but suffers from
low mechanical strength owing to the presence of hollow struts. As a result, the performance and
utilisation of ceramic foams manufactured by this method are limited in certain applications. One
solution to overcoming this inherent disadvantage is to use a stronger ceramic coating material and
to ameliorate the wetting of the polyurethane template. Such a material is reaction bonded Al2O3
(RBAO), which has high mechanical strength as a result of its fine grain structure, with less or even
without glassy phases at the grain boundaries. The present work demonstrates the feasibility of
producing strong ceramic foams by using a reaction bonded modified replica technique starting
from polyurethane templates varying in both composition and cell size distribution.
Keywords: Cell size distribution, Ceramic slurry, Gas permeability, Reaction bonded alumina, Reticulated polyurethane foams, Wetting

Introduction
Ceramic foams are a special class of porous materials
comprised of large voids (cells), with linear dimensions
in the region of 10 mm to 5 mm and possessing a
geometry similar to that of a tetrakaidecahedron. Foams
can have open or closed cells, with cell edges (struts) and
cell windows.1,2 Owing to the combination of their
special geometry and resulting properties, they can be
used in a wide range of engineering applications.
Examples include molten metal, hot gas and diesel
exhaust filters, catalyst carriers, biomaterials, thermal
insulators for furnaces and aerospace applications, gas
combustion burners and lightweight materials.3
The most popular manufacturing route for ceramic
foams is the polyurethane (PU) foam replica technique.4
The first step in the manufacturing route involves
dipping a reticulated PU foam in a ceramic slurry, to
squeeze out the excess liquid and to dry the coated foam.
Next, the PU template is burnt out (at around 500uC)
and the structure is sintered at a temperature depending
on the ceramic material used. The main drawback of
ceramic foams produced by this route is their mechanical weakness due to the formation of hollow struts and
residual cracks during processing. This limits their
performance and their use in certain applications.
Efforts have already been made to improve material
strength, but without any substantial success.5,6
Nonetheless, recent research shows that higher strength
can be obtained when reaction bonded Al2O3 (RBAO)
powder is used instead of conventional Al2O3
1
2

Materials Technology, Vito, Boeretang 200, B-2400 Mol, Belgium

IDC Recticel, Damstraat 2, B-9230 Wetteren, Belgium

*Corresponding author, email steven.mullens@vito.be

materials.79 This beneficial effect is explained by the

finer grain sizes with less or even without glassy phases
at the grain boundaries. These materials were produced
by intensive milling of Al/Al2O3 powder mixtures, which
are oxidised after shaping. The oxidation of Al is one of
the critical steps in the preparation of the RBAO
material as the strong exothermic reaction can cause
cracks in the struts during heat treatment. The RBAO
material is then sintered and machined to the final
dimensions of the component.
The present paper describes research on the reaction
bonded modified replica technique. The main aim of the
study was to manufacture ceramic foams for application
as adequate soot filters. A series of PU templates varying
in composition, cell size distribution and hydrophobicity
was therefore tested. Conventional Al2O3 (as reference
material), reaction bonded Al2O3 and reaction bonded
mullite (RBM) were used. Special attention is given to
the wetting of PU by the ceramic slurry and to the
mechanical strength, microstructure and permeability of
the ceramic foams obtained.

Experimental procedure
Different PU reticulated foams were synthesised and
fully characterised. Table 1 summarises some important
properties of the tested PU materials.
To produce the reference foams, Al2O3 powder (CT
3000 SG Alcoa, Pittsburgh, PA, USA) was used. The
RBAO powder precursor consisted of a 40/60 by weight
mixture of Al powder (Baudier Poud. Met., France)
with a mean particle size of 8 mm and Al2O3 powder
(Amperit 740.0, H. C. Starck). The AlAl2O3 mix was
attritor milled for more than 6 h. After treatment with
stearic acid to prevent hydrolysis of the Al metal
fraction,10 stable ceramic aqueous slurries could be
2005 Institute of Materials, Minerals and Mining

Advances in Applied Ceramics

2005

VOL

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Published by Maney on behalf of the Institute

Received 1 July 2004; accepted 30 July 2004
DOI 10.1179/174367605225010990

Luyten et al.

Strong ceramic foams from polyurethane templates

Published by Maney Publishing (c) IOM Communications Ltd

Table 1 Properties of PU templates

Template

Polyol type

Remarks

S-26-860
S-24-1230
S-27-1850
S-28-2820
S-28-580
S-28-2850
SB-34-460
SS-30
SS-60
T-20-1660
T-20-T
T-30-T
Felt-S-26-860
Felt-SS-30

Ester
Ester
Ester
Ester
Ester
Ester
Ester
Ester/ether
Ester/ether
Ether
Ether
Ether
Ester
Ester/ether

Accurate cell size

Accurate cell size
Accurate cell size
Accurate cell size
Accurate cell size
Accurate cell size
Accurate cell size
More hydrophilic
More hydrophilic
Accurate cell size
More hydrophilic
More hydrophilic
Felted ester
Felted hydrophilic

control
control
control
control
control
control
control

control

ester/ether

produced with Darvan C as dispersing agent (R. T.

Vanderbilt Co., Norwalk, CT, USA) and gelatin
(Cryogel 220/440, PB Gelatins, Vilvoorde, Belgium) as
binder. The ceramic slurries were optimised with
measurements of zeta potential (Delsa 440, Coulter
Corp., Miami, FL, USA) and viscosity (RS100, Haake,
Karlsruhe, Germany).
The wetting of the PU by the ceramic slurry was first
tested by contact angle measurements on felted PU
sheets but owing to their partial porosity, no accurate
measurements could be performed. Direct visual observation by optical microscopy of the PU struts after
infiltration with the ceramic slurry therefore proved to
be the most successful evaluation method.
Thermal treatments, involving calcination of the
polyurethane and other organics and different steps in
the oxidation reaction, were studied with simultaneous
TGA and DSC measurements (Netzsch STA 449C,
Munich, Germany). These experiments were performed
on PU material, on the pre-RBAO powder and on PU
coated with this powder. Because the experiments were
done on very small quantities of material, thermal
treatments on real components were also performed.
They were characterised by optical microscopic evaluation and by three point bending tests. The three point
bending tests were carried out on an Instron universal
testing machine using rectangular bars with standard
dimensions 60620615 mm.
Microstructures were analysed by image analysis
(KS400, Carl Zeiss, Oberkochen, Germany), field
emission scanning electron microscopy (6340F, Jeol,
Tokyo, Japan) and microcomputer assisted X-ray
tomography (m-CT). The latter was performed at the
University of Erlangen, Germany.
The permeability measurements were performed at
room temperature on a homemade installation in which
a cylindrical porous sample (diameter around 3.5 cm,
height 2.8 cm) is fixed in a tube into which pressurised
air is introduced. The pressure before and after the
sample is measured using a pitot tube.
Preliminary soot filter tests were performed on an
engine test bank using a Peugeot 1.9 L turbodiesel
engine. Particle concentration was measured before and
after filtering with two tapered element oscillating
microbalances. The filter element itself consisted of a
ceramic foam with a thickness of 3 cm and diameter of
6.3 cm.

Cell size, mm

Density, kg m23

860
1230
1850
2820
580
2850
460
600800
600400
1660

1000
200

25.5
24.4
26.5
26.7
28.0
28.0
34.2
28.0
58.0
20.5
19.0
29.0
80/120
80/120

Results and discussion

Wetting
Good wetting of the PU foam is one of the primary
requirements for obtaining defect free struts after heat
treatment. Evaluation of wetting by contact angle
measurements on felted sheets (i.e. PU foam pressed at
180200uC into a plate or sheet) failed, owing to the
residual porosity of the sheets. Instead, direct observation of the coating with stereomicroscopy was used. The
wetting behaviour of all ester PU templates in the
ceramic slurry was rather poor. Table 2 gives the wetting
behaviour of different ester/ether or ether based PUs
with Al2O3 slurry. From Table 2 it can be concluded
that only hydrophilic esters give improved wetting. The
ether based systems on the other hand were poorly
wetted by the Al2O3 slurries.
The addition of a wetting agent (denoted as WA) to
the slurry greatly improved the wetting of the ester
foams and of the SS-30 ester/ether foams. Poor wetting
was obtained for the SS-60 ester/ether foam. No
conclusive explanation has yet been found for this
result. The SS-30 and SS-60 ester/ether foams are of less
interest for soot filter applications, owing to less close
control of the cell size of the PU foam. The RBAO
precursor slurries show excellent wetting of ester foams.
Further research on the wetting mechanism and on the
reasons for good wetting behaviour is ongoing.
For soot filter applications, the pressure drop of the
filter should be as low as possible, requiring a relatively
open structure and low density. However, at the same
time sufficient mechanical strength is critical. For this
reason, the three point bend strength of Al2O3 foams
produced from different PU templates in the density
range 1020% of theoretical density (TD) was measured
(Fig. 1). Replacing the Alcoa powder CT 3000 SG with
Table 2 Wetting behaviour of ester/ether and ether PU
templates compared with ester PU
PU type

Wetting behaviour

SS-30
SS-60
SB-20-1660
T-20-1660
T-30-T
T-20-T

Improved
Improved
Poor
Poor
Poor
Complete loss of shape after dipping in slurry

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Luyten et al.

Strong ceramic foams from polyurethane templates

1 Mechanical properties of Al2O3 foams with low relative

density

Published by Maney Publishing (c) IOM Communications Ltd

another powder (CS 400MS, Martins Werke) had less

influence on the results.
As mentioned above, changing the PU type or adding
a wetting agent improves wetting by the Al2O3 suspension, resulting in a slightly higher mechanical strength of
the ceramic foam. However, compared with the RBAO
foams, this effect is of only minor importance in the
range 1020% TD.

RBAO foams
The reticulated PU foam replica technique has to be
modified when using reaction bonded materials.
Figure 2 shows the flowchart for the adapted manufacturing route.
Intensive milling of the metalmetal oxide mixtures
was performed under acetone in a planetary ball mill.
This milling is very important because it produces a fine,
homogeneous distribution of Al metal and metal oxide.
To prevent reaction of the Al metal in aqueous
suspensions, long chain molecules are absorbed on its
surface.10 The further suspension preparation, involving
dipping, squeezing and drying, is similar to the conventional manufacturing route. The temperature range,

2 Adapted manufacturing route for RBAO foams

with a low heating rate (5 K h21) required to burn out

the PU without cracks, has to be extended to 600uC to
control the exothermic reaction caused by the oxidation
of the metal fraction. Sintering was done at 1700uC for
1 h.
Figure 3 shows the TGA/DSC curve for a RBAO
precursor mixture coated on PU as a function of
temperature. In a first stage of mass loss (up to around
400uC), the TGA/DSC curve indicates burnout of the
PU. An exothermic peak is observed at 519.2uC, owing
to the first strong oxidation. The melting point of the
residual Al metal is observed at 661.9uC. At higher
temperatures, further oxidation takes place. The
exothermic peak temperature can be shifted by controlling parameters such as heating rate, partial O2 pressure,
volume of Al present and so on.1113

Mechanical strength
Figure 4 shows the three point bend strength of Al2O3
foams as a function of relative density, calculated from
the model of Gibson and Ashby.14 The experimental

3 TGA/DSC curve for RBAO on PU as function of temperature: 2 K min21 heating rate, 50 mL min21 dry air flowrate,
alumina crucible

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Strong ceramic foams from polyurethane templates

Published by Maney Publishing (c) IOM Communications Ltd

4 Comparison of theoretical three point bend strength

values from Gibson and Ashby model with experimental values for RBAO and Al2O3

values for RBAO and Al2O3 foams with and without

wetting agent are compared. The equation of Gibson
and Ashby for three point bending of foams is s5doC(r/
ro)3/2, with s the three point bend strength of the foam,
do the three point bend strength of the dense material
(taken as 400 MPa for Al2O3) and C a constant (taken
as C50.18).15 This simple model supposes a defect free
strut structure. As such, the cell size is the maximum
crack length in the material. From Fig. 4 it is clear that
the best batches of RBAO material approximate the
theoretical values.

5 a strut thickness distribution and b mean strut thickness and width of distribution for foams coated with
RBAO suspensions with low (20 vol.-%) and high (30
35 vol.-%) concentrations

Parameters influencing ceramic strut thickness

The strut thickness distributions of the different foams
obtained from ester PU were determined by X-ray
tomography. Figure 5a shows the influence of the cell
size of the PU templates and of the powder concentration of the ceramic slurry used to coat the PU foam on
strut thickness distribution for foams S-28-580 and S-271850. Figure 5b shows the mean strut thickness and the
width of the thickness distribution for foams produced
on PU templates S-28-580, S-26-860, S-24-1230 and S27-1850, coated with either a 20 or 3035 vol.-% RBAO
suspension.
From Fig. 5 it can be concluded that strut thickness
decreases with decreasing cell size of the PU template
and with decreasing solids loading. Reduction of strut
thickness has to be limited to the minimum thickness
which can just withstand the stresses caused by the
burnout step.

images and two-dimensional slices obtained by m-CT.

Assuming a relatively narrow distribution of spherical
pores, a stereological correction to convert the twodimensional data into the three-dimensions of the actual
pore space can be applied by dividing the twodimensional mean pore diameter by 0.785. Threedimensional characterisation of the pore architecture is
performed by m-CT, from which mean pore diameter is
derived.
The results obtained by the different techniques on the
original PU and on the sintered foams are shown in
Fig. 6. The data from visiocell measurement and image
analysis are in reasonable agreement when corrected
for the two-dimensional aspect of the latter technique.
This can be done either by selecting the largest

Cell size measurements

Cell size is one of the key parameters in the design of a
foam. For many applications, the performance of the
foam is directly influenced by the cell dimensions.
Efforts were therefore made to try to measure cell sizes
as accurately as possible.
Although resolving the structure of cellular foams has
been the subject of research for some time, no simple
standard experimental technique or procedure to determine some of the most common structural parameters
has so far been proposed. In the present case three
techniques were compared: the visiocell optical microscopic method optimised by Recitel,16 image analysis,
and microcomputer assisted X-ray tomography (m-CT).
Image analysis was performed on both microscopic

6 Comparison of cell size determined by different methods and on different templates

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Strong ceramic foams from polyurethane templates

Filter tests
Preliminary filter tests on a diesel engine outlet indicate a
filter efficiency of up to 90%. Further research will
therefore be conducted based on these positive results.

Conclusions

Published by Maney Publishing (c) IOM Communications Ltd

The benefits of a modified PU foam replica technique

are illustrated by comparing the properties of Al2O3
foams produced by the well known reticulated PU foam
replica technique and those from RBAO foams. The
mechanical strength of the RBAO foams is much higher
than for Al2O3 owing to better wetting behaviour and
because of the intrinsically stronger RBAO due to the
smaller grain size and the absence of glass phases at the
grain boundaries.
In view of their potential use as soot filters, cell size
and permeability of the foams were measured. It was
demonstrated that the pressure drop could be limited
when low density foams are used (around 15% TD).
Only RBAO foams with such low density can be
produced with sufficient mechanical strength for practical application as soot filters. Preliminary filter tests on
a diesel outlet gave filter efficiency values up to 90%.

Acknowledgements
7 Pressure drop as function of air velocity U for RBAO
foams with different cell sizes produced using a low
viscosity slurry and b viscous slurry

two-dimensional diameter (the d90 value) or by applying

stereological correction.
For almost all samples the mean pore diameters
measured by m-CT do not agree with the visiocell or
image analysis results. Part of the explanation probably
involves differences in threshold procedure, as the image
analysis on the m-CT slices does not completely match
the results on the microscopic value. The image analysis
results on the m-CT images are consistently lower than
the results on the microscopy images. In both methods,
the threshold procedure and possible deviations from
the actual pore boundary structure will have a significant influence on the actual measurement. Further
research into this matter is ongoing.

Gas permeability
To obtain a first indication of the pressure drop for
different gas velocities in the outlet of a diesel car, gas
permeability measurements were performed on different
foams produced from RBAO suspensions with respectively 20 and 35 vol.-% powder.1719 The results are
summarised in Fig. 7. It is found that even for foams
with rather fine cell sizes such as those produced using a
template such as S-28-580, the pressure drop is rather
low if a low viscosity suspension is used to coat the PU
template. As such, a nearly complete open foam
structure with low density (15% TD) can be obtained
by utilising suspensions with low solids loading. It is
clear that such low density foams with sufficient
mechanical strength are much more easily produced by
using the RBAO modified replica technique than with
the conventional one.

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The authors acknowledge Dr J. Zeschky and Dr M.

Scheffler (Glass and Ceramics Group, University of
Erlangen, Germany) for the microcomputer tomography images and reconstructions as well as the help of R.
Kemps (Vito) with the image analysis routine.

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