SCIENCE AND
TECHNOLOGY
Composites Science and Technology 66 (2006) 27092718
www.elsevier.com/locate/compscitech
Abstract
This article presents the mechanical behaviour of rigid polyurethane reinforced by mineral llers, for a density range (qf/qs) >
0.27. The inuence of the particle size on the foam microstructure and its mechanical behaviour has been studied using calcium
carbonate with two dierent sizes (with average diameter of 1 and 30 lm, respectively) and crystallised silica particles with an
intermediate size. The microstructural characterisation has been performed by electron microscopy. It has shown closed spherical
cells whose size is decreased when the llers are added. The results of mechanical characterisation by large and small deformation
(mechanical spectrometry) tests have been compared to dierent modelling approaches. It appeared that a correct description of
the viscoelastic properties and of the yield stress needs to take into account the ller size compared to the wall size. Two modelling hypothesis which consider the composite foam as either a ller dispersion in a foam or a void dispersion in a lled polymer
have been made. The rst one is adapted to the description of PU lled with the big carbonate llers, when the second one is
better to describe the PU lled with the small carbonate llers. The use of the crystallized silica particles gives composite foams
with properties in between that of the two calcium carbonate composites, showing that the ller size in the range studied is a key
parameter to take into account in the reinforcement level.
2006 Elsevier Ltd. All rights reserved.
Keywords: Polyurethane foam; A. Particle reinforced composites; B. Mechanical properties; B. Modelling
1. Introduction
Due to the presence of a skeleton made of cells (open or
closed) more or less regular [1,2] foams present very interesting mechanical properties such as a high capacity of
energy absorption, particularly useful for shock damping.
The mechanical response of these cellular materials depend
on the architecture and the intrinsic properties of the polymer constitutive of the cell walls [1]. The parameters of the
foam architecture are the wall width, the size distribution
and the shape of the cell.
For some years, their study have been extended to composite foams reinforced by the introduction of bres [3] or
*
Corresponding author.
E-mail address: laurent.chazeau@insa-lyon.fr (L. Chazeau).
0266-3538/$ - see front matter 2006 Elsevier Ltd. All rights reserved.
doi:10.1016/j.compscitech.2006.03.008
700
(mW/g)
600
f /s
0.63
0.27
500
0.1
400
Tan
2710
300
200
-10
10
30
50
70
90
Temperature (C)
110
0.01
130
Fig. 1. Tests by dierential scanning calorimetry (a) and by DMA (b) for
foams reinforced by calcium carbonate. (a) T = 10 at 130 C,
DT = 10 C/min. (b) f = 0.1 Hz, T = 10 at 130 C, DT = 1 C/min.
Table 1
Physico-chemical properties, elastic modulus and Poisson coecient of mineral llers used
Mineral llers
Density (g/cm3)
Specic
surfaces (m2/g)
d10 (lm)
d50 (lm)
d90 (lm)
Average
diameter (lm)
Modulus (GPa)
Poisson coecient
Calcium carbonate C1
Calcium carbonate C2
Crystallised silica
2.7
2.7
2.35
0.4
3.3
1
8.2
1.8
0.3
44
4.4
10.4
108.1
9.9
37.2
52
5.2
15
14
14
30.8
0.27
0.27
0.17
100 lm) and bimodal with two peaks at 0.3 and 30 lm. It
can be considered as an intermediate between the calcium
carbonate C1 and the calcium carbonate C2.
The foams are obtained by mixing the polyol matrix
with a polyisocyanate, diphenylmethanediisocyanate-4-4 0
(so-called MDI). Its reaction with the polyols products urethane bonds [12]. The water introduced with the polyol
reacts with the MDI to produce carbon dioxide at the origin of the foam expansion.
2.1.2. Processing
The initial water concentration being the main parameter regulating the nal foam density, its estimation and its
control are extremely important. The components of the
polyol matrix (polyols, surfactant, catalysts) are mixed at
600 rpm during 2 min with a mixer (Rayneri) with rotating
molecular sieve for
blades. Then this mix is dried on a 4 A
48 h to eliminate the residual water. The mineral llers are
kept in a drying oven during 24 h to eliminate water
adsorbed on the ller surface. For calcium carbonate the
temperature of drying is 200 C. This temperature is only
100 C for the silica to avoid any modication of its surface
chemistry by a degradation of the silanol groups. A volume
fraction /cc of calcium carbonate or of crystallised silica /s
is incorporated in the polyol matrix. This suspension is
mixed at 1500 rpm for 10 min. All these mixings are performed under a nitrogen gas ux to avoid the introduction
of water via the air humidity. The samples are then
degassed under vacuum during 24 h to eliminate air bubbles introduced in the resin during the mixing.
Distilled water and the polyisocyanate are then added to
the polyol matrix. The mix (suspension/polyisocyanate) is
then stirred at 1500 rpm for 20 s, and is poured into a cylindrical mould. The foam is obtained after free expansion in
this open mould. The expansion phase lasts about 3 min,
then the gelation phase begins (polymerisation and crosslinking). The foam is then unmoulded after 30 min.
The block obtained is then cut in three pieces, two with
45 20 30 mm dimensions and one with 80 30 40 mm
dimensions. The measurement of the apparent density (Dr)
is performed from the measurement of the volume and the
mass of this three blocks. Dr is dened as the ratio of the
foam density qf to that of the solid qs. This relative density
expresses the volume fraction of matter in the foam. It was
impossible to elaborate a material without bubbles and
therefore to measure qs. Indeed, the mixing of the suspension with polyisocyanate introduces bubbles which are
imprisoned during the polymerisation. qs has been estimated by calculation, considering the density of the dierent ingredients of the polyurethane foam, their quantity,
and a mixing law. Taking a volume fraction of calcium carbonate /cc equal to 21.6% (in the polymer) the calculated
density qs of the lled polyurethane is 1467 g l1. For the
polyurethane lled with 21.6 vol% of crystallised silica /s,
it is found qs = 1393 g l1. Then, the relative densities of
the dierent lled foams obtained can be calculated. They
vary from 0.27 up to 0.75.
2711
2.2. Experiments
2.2.1. Dierential scanning calorimetry (DSC)
The apparatus to characterise the glass transition temperature of the samples is a Pyris Diamond from Perkin
Elmer. To erase the thermal history of the samples, a rst
temperature ramp is applied with a heating rate of 10 C/
min from 10 up to 130 C. After cooling, a second ramp
is performed in the same conditions.
2.2.2. Electron microscopy
The characterisation of the cellular microstructure and
of the cell size of the polyurethane foam is performed with
a scanning electron microscope (SEM) JEOL 840 ALGS,
with a lament tension of 10 kV. First, the samples are broken in liquid nitrogen. Then the fracture surfaces are gold
coated to make them conducting. The micrographs
obtained are treated by image analysis with the software
Scion Image to quantify the size distribution of the voids
in the foam. The apparent pore diameters are then determined with the assumption of their sphericity. The Saltikov
method [13] enables the determination of the distribution
of the real diameter of the voids.
2.2.3. Mechanical tests
Preliminary tests on unlled foams have shown an eect
of physical ageing on their mechanical properties [9]. That
is why a thermal treatment has been performed to be sure
that the thermal history of each sample is the same. Before
any mechanical test, the samples are kept 10 min at 80 C
(rejuvenation above Tg) then 24 h at 25 C.
The elastic (G 0 ), and viscous (G00 ) moduli, and tan /
have been measured by dynamic mechanical analysis on
an apparatus Mecanalyser (Metravib S.A.) developed in
the laboratory [14]. It is an inverted torsion pendulum
working in forced harmonic regime, at low frequency,
from 105 up to 5 Hz, in a temperature range from 170
up to 400 C. The samples tested are parallelepipeds of
15 mm length, 5 mm width and 1.5 mm thickness. They
are submitted to sinusoidal torsion, with controlled deformation at a frequency f = 0.1 Hz. A temperature ramp is
performed during the test from 6 up to 130 C with a
heating rate of 1 C/min. Preliminary tests have shown
that humidity does not aect the mechanical properties
of the foams.
Uniaxial compression tests have been performed on a
tensile test machine Instron 8510. The compression plateaus are maintained parallel by a guidance device with ball
bearings. This machine possesses a thermo-regulated chamber to perform tests at temperature in between 90 and
230 C. The tested samples are cylinders with 10 mm diameter and 20 mm height (a compromise to avoid buckling
and barrel deformation) [15]. The samples are carefully
prepared so that their contact surfaces be strictly parallel.
To decrease friction, they are polished and a lubricant is
used (molybdenum bisulphur). Tests have been performed
at 30 C with a constant crosshead speed corresponding to
2712
tion between the water and the isocyanate can then react
with the isocyanate to form ureas. However, though the
existence of this supplementary relaxation, the very good
modelling of the viscoelastic behaviour of the unlled foam
with the assumption of no modication of the matrix indicated that this slight modication is negligible. For lled
foams, this secondary relaxation is not observed. The introduction of llers enables a better absorption of the heat
released during the polymerisation reaction. This could
induce a decrease of the kinetic of formation of these byproducts which normally occur at temperature above
100 C. From these results we can conclude that the dierent foams processed have a similar polymer matrix.
3.2. Morphological characterisation
Fig. 2 presents an example of SEM micrographs
obtained for foams reinforced by both calcium carbonates
C1 and C2 and by the crystallised silica respectively. In the
density range studied (0.27 < q*/qs < 0.75), the cells basically appear spherical and closed. Whatever the ller type
and the foam densities, particles are correctly dispersed.
Fig. 2. SEM micrographs of foams reinforced by (a) calcium carbonate C1 (qf/qs = 0.31, 70), (b) calcium carbonate C1 (qf/qs = 0.51, 300), (c) calcium
carbonate C2 (qf/qs = 0.51, 1000), (d) crystallized silica. (qf/qs = 0.65, 300).
140
with C2
with C1
with silica
unfilled
120
100
80
60
40
20
0
0.3
G''
0 .4
0.5
0 .6
f / s
0.7
0 .8
0.9
106
105
G'
0.62
0.27
10
104
Assumption 1
30
50
70
90
Temperature (C)
103
130
110
108
1010
G' '
10
10
107
106
/
f
107
106
-10
0.75
0.35
10
105
G'' (MPa)
106
-10
G'' (MPa)
107
108
107
108
109
G' (MPa)
L A D B;
1010
G' (MPa)
2713
G'
104
Assumption 2
30
50
70
90
Temperature (C)
110
103
130
densities are presented on each one. The curves with dierent densities seem parallel and only shifted by a factor (in
logarithmic scale). The G 0 modulus measured at 30 C as
a function of the relative density is reported on the
Fig. 5. To evaluate the inuence of the ller addition,
experimental data obtained with the unlled foams [9] are
also reported. Whatever the ller type, one can observe a
decrease of the G 0 modulus with the decrease of the density.
For C1 lled foams with relative density below 0.5, the
addition of llers does not inuence the modulus value.
The increase of the modulus with the ller addition is only
visible for higher density, but this increase is relatively low.
Conversely, the C2 lled foams present G 0 values above
those of the unlled foams and the C1 lled foams, whatever the density. The silica lled foams with relative density
below 0.5 presents G 0 values in between those of the C1
lled foams and those of the C2 lled foams. For higher
density, their G 0 values tends toward those of the C2 lled
foams. These experimental results clearly show an eect of
the ller size on the elastic behaviour of the lled foams:
the modulus values increase when the average size of the
llers decreases.
Figs. 6a,b and 7 present the compression curves of PU
foams of dierent density lled with calcium carbonate
2714
(a) 1000
(a) 35
with C2
with C1
unfilled
with silica
30
with
= 1.03
25
with = 1.18
600
400
Stress (MPa)
G' (MPa)
800
with = 0.89
200
0.31
20
0.62
15
0.5
10
0.42
0
0.3
0.4
0.5
0.6
0.7
0.8
0
0
0.9
0.1
0.2
f / s
with C2
with C1
unfilled
with silica
0.7
0.52 0.42
0.35
25
Assumption
(2)
400
Assumption
(1)
200
0
0.3
0.6
30
Stress (MPa)
G' (MPa)
800
0.3 0.4
0.5
Nominal strain
0.75
(b) 35
(b) 1000
600
0.27
20
15
10
5
0.4
0.5
0.6
0.7
0.8
0.9
f / s
Fig. 5. Evolution of elastic modulus (G 0 ) as a function of relative density
obtained by DMA. Unlled and reinforced foams. (a) The lines represent
the predicted values with the Gibson and Ashby modelling [1]. (b) The
lines represents the predicted values with the 2 + 1 phase modelling [10].
f = 0.1 Hz, T = 30 C.
C1, calcium carbonate C2 and crystallised silica respectively. They are typical of that of a PU foam, with an elastic domain, followed by a densication plateau, a
hardening domain and a nal rupture. It is noticeable that
the plateau occurs at constant strain level around 0.4. The
C2 lled foam appeared to be more brittle, as shown by
instabilities on the curve (Fig. 6b). All the curves show,
at a given strain level, a decrease of the stress value with
the decrease of density. Compression elastic modulus
of the dierent samples can be deduced from the slope at
the origin of their compression curve. However, due to
the foam nature of the material, the error made to estimate
it is large. In fact this leads to an underestimation of the
real value. The important result is that they show the same
trend as the results with G 0 and lead to the same comment
on the inuence of the ller size. The yield stress (rf) of the
dierent lled foams can be more precisely estimated. Their
values are plotted as a function of the density for the dierent llers on Fig. 8. They increase with the density. For
density below 0.6, the addition of C1 ller does not induce
any signicant change of the yield stress value. However,
0
0
0.1
0.2
0.3 0.4
0.5
Nominal strain
0.6
0.7
(a) 35
0.55
0.43 0.36
30
Stress (MPa)
25
20
15
10
5
0
0
(b)
0.1
0.2
0.3 0.4
0.5
Nominal strain
0.65
35
0.55
0.6
0.7
0.43 0.36
30
Stress (MPa)
25
20
15
10
5
0
0
0.1
0.2
0.3 0.4
0.5
Nominal strain
0.6
0.7
35
with C2
30
with C1
25
with silica
PU matrix
Step 1
f (MPa)
unfilled
20
15
2715
Assumption
(2)
Void
Homogeneous medium
Assumption
(2)
PU matrix
Filler
Homogeneous medium
10
Assumption
(1)
PU foam
Step 2
0
0.3
0.4
0.5
0.6
0.7
f / s
0.8
0.9
Fig. 8. Evolution of the stress value at the beginning of the plateau (rf) as
a function of relative density obtained by compression tests. Unlled and
reinforced foams. The line represents the predicted values with the 2 + 1
phases modelling [10]. Initial strain rate = 103 s1, T = 30 C.
Filler
Homogeneous medium
Filler dispersion in a
foam
Filled PU
Void
Homogeneous medium
Void dispersion in
a filled polymer
"
e
p
31 D
#
13 p
3
1 AD B.
2
The calculated cell wall as a function of the density is presented in Fig. 10 for the dierent ller types. This can be
compared to the experimental average particle size of the
dierent llers. As expected, in the density range studied,
the C1 llers are in average much bigger then the cell wall
thickness of the C1 lled foams. Conversely, the cell wall
thickness of the C2 lled foams are in the same range than
the calculated cell wall thickness. This explains why one
can observe for the modulus value of these foams the
beginning of the transition from a value predicted with
assumption 2 to one predicted with assumption 1. Concerning the crystallised silica, the calculation is less convincing since the average particle size is above that of the
calculated wall thickness. However, one must notice that
the silica size distribution present two peaks, whose one
is below 1 lm, i.e. well below the calculated wall thickness.
This probably explains the modulus evolution of the silica
lled foam as function of the density, which is always in between the predictions with the two dierent assumptions.
The modelling has been extended to the viscoelastic
behaviour. Fig. 4 compares experimental data and theoretical curves and shows that the previous modelling, suitable
in the glassy domain does not correctly predict the G 0
(Fig. 4a) and G00 (Fig. 4b) values at temperature above
Tg. It largely underestimates the moduli in the rubbery
domain. However, it was previously shown [9] that this
modelling correctly predicts the G 0 modulus of the unlled
foams in the whole density range and in the whole temperature range studied (from 10 up to 130 C). One assumption to explain the underestimation observed in the case of
lled foams is that the introduction of ller leads to an
increase of the resin crosslink density: an inuence of the
ller in the foam processing is already evidenced by the
change of size distribution of the bubbles, as discussed previously. Moreover, CaCO3 ller surface is highly hydrophilic and probably absorbs a large part of the water
added in the formulation. This might modify the complex
14
Calculated
average cell width (m)
2716
12
10
8
6
4
2
0
0.3
0.4
0.5
0.6
0.7
f / s
0. 8
0.9
Fig. 10. Calculated width of the cell walls as a function of the density, for
the C1 lled foams (- - -), the C2 lled foams ( - -), and the silica lled
foams ().
2717
2718
4. Conclusion
The authors acknowledge S. Youssef for his contribution to the experimental work and G. Vigier for fruitfull
discussions.
Acknowledgements
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