Composites Science and Technology 59 (1999) 2087±2091

An analysis of the e€ect of the diameters of glass microspheres on

the mechanical behavior of glass-microsphere/epoxy-matrix
composites
J.R.M. d'Almeida
Materials Science and Metallurgy Department, PontifõÂcia Universidade CatoÂlica do Rio de Janeiro, Rua MarqueÃs de SaÄo Vicente, 225,
22453-900, Rio de Janeiro, RJ, Brazil

Received 17 November 1998; received in revised form 7 April 1999; accepted 15 April 1999

Abstract
The mechanical properties of epoxy-resin/glass-microsphere composites can be suitably tailored by using microspheres with dif-
ferent diameters. Under uniaxial compression the complex stress state generated by the contribution of di€erent events taking place,
such as the rupture of the microsphere-resin interface or rupture of the microspheres, could be represented as a single damage
parameter governed by the ratio between the wall thickness and the mean diameter of the microspheres. This ratio is, therefore, a
useful fabrication parameter. Volume-fraction dependent contour lines are constructed on a chart of speci®c properties and their
relative position is shown to be a function of the ratio of the glass microsphere wall thickness to its diameter. # 1999 Elsevier
Science Ltd. All rights reserved.
Keywords: A. Polymer-matrix composites; B. Mechanical properties; Performance indexes

1. Introduction tion of composites with higher volume fractions of

Since the end of the 1970s there has been a strong
increase in the use of composites consisting of hollow
glass microspheres in resin matrices in underwater
structures [1]. The main interest for this type of compo-
site material came from the very low densities, =500±
620 kg/m3, at which they can be fabricated. Initially
they were used in non-structural members for buoyancy
and mooring [1,2]. With the increasing research and
exploitation of o€-shore natural resources these com-
posites began to be used in more sophisticated struc-
tures such as pipelines and the hulls of mini-submarines
for deep underwater inspection [1,3].
Glass-microspheres/resin-matrix composites are also
commonly known as syntactic foams [4,5] and their
mechanical properties are, of course, dependent on the
volume fraction of the microspheres, V , and also on
their spatial distribution in the volume of the composite.
The common glass-microsphere composite are fabri-
cated by using microspheres with a large size distribu-
tion. For many instances, however, one can use
bigranulometric distributions, that enable the fabrica-
0266-3538/99/$ - see front matter # 1999 Elsevier Science Ltd. All rights reserved.
PII: S0266-3538(99)00066-4
microspheres [4].
The microsphere wall thickness is fairly constant,
ranging typically from 1 to 5 mm [4,6], irrespective of the
diameter of the microsphere. Therefore, the density, or
the wall thickness to diameter ratio, of the microspheres
will vary as a function of the microsphere size. For ¯y-
ash microspheres, it was shown that composites fabri-
cated with smaller microspheres, and hence with higher
wall thickness to diameter ratios, have a better crack
resistance [7]. All of these aspects mean that the
mechanical behavior of a syntactic foam could be var-
ied, and modeled, for a given constant volume fraction
of microspheres by just varying the size, i.e. the dia-
meter, of the microspheres to be used.
In this work, a study was undertaken to analyze the
variation of the mechanical properties of a glass-micro-
spheres/epoxy-matrix composite as a function of the
mean diameter size of the microspheres and to deter-
mine how one can take advantage of this dependence
during the fabrication of a syntactic foam. In order to
perform this analysis the composites were tested in uni-
axial compression.
2088 J.R.M. d'Almeida / Composites Science and Technology 59 (1999) 2087±2091

2. Experimental methods and materials Table 2

Glass microspheres can be made from several glass
compositions. As a common characteristic the available
commercial microspheres usually have a silica content
higher than 73% [4,6] and a large range of diameters.
Table 1 shows the typical granulometric distribution
found for the microspheres used in this work. To guar-
antee a large di€erence between the wall-thickness/dia-
meter ratio the composites were fabricated by using
only the material retained in 100±150, 200±270 and 325
mesh sieves. The composites fabricated with each of
these groups of microspheres will be referred to as 100,
200 and 325 materials.
The composites were fabricated with nominal V of
0.25, 0.45 and 0.55, by mixing together the appropriate
quantities of microspheres, resin and hardener in an
open container. After 5±10 min of continuous stirring
the mixture was cast into aluminum molds. A room-
temperature epoxy system, composed of a difunctional
liquid monomer, diglycidyl ether of bisphenol-A, and
the aliphatic triethylene tetramine hardener, was used as
matrix. The resin and the hardener were used in a mix
ratio of 13 parts, by weight, of hardener per 100 parts of
resin. The cure was achieved at room temperature,
25‹2 C, and, following the cure schedule proposed by
the resin manufacturer, a minimum of 7±15 days was
left between casting of the composites and machining of
the test specimens [8]. Table 2 summarizes the compo-
sites fabricated.
The tests were conducted on a mechanically driven
testing machine with a capacity of 100 kN. The test
velocity used was 1 mm/min and at least 5 specimens
were tested per composite. Cylindrical specimens with a
diameter of 10 mm and 20 mm in length were used.
Load axiallity was maintained during the tests by the
use of an alignment tool with a steel hardened ball joint,
as recommended by ASTM standard D-695M.
The actual volume fraction of the glass microspheres
was measured with the aid of quantitative analysis. The
method of analysis consists, brie¯y, in the digitisation of
the image of the microstructure, giving a dark gray
color to the microspheres and a white to pale gray color
Nominal volume fraction and microsphere sizes used to fabricate the
composites
V Mesh
0.25 100±150, 200±270, 325
0.45 100±150, 200±270
0.55 100±150, 200±270, 325
to the resin matrix, i.e. the pixels that form the image
were given values of 0 or 1. The volume fraction was
taken directly from the ratio between the `dark' pixels to
the total amount of pixels that form the image. Prior to
image analysis, the contrast between the glass micro-
spheres and the resin matrix was enhanced by covering
the polished specimens' surface with graphite powder.
The complete description of the method of preparation
of the specimens for the quantitative analysis is descri-
bed elsewhere [9].
3. Experimental results
The experimental results obtained are shown in Table
3, where c is the stress at rupture and Ec is the Young
modulus. Table 3 also shows the apparent density and
the actual measured volume fraction of the composites.
One can see from the results shown in Table 3 that the
properties obtained decrease as the volume fraction of
microspheres increases. In other words, the micro-
spheres act as pores inside the bulk resin matrix. At a
®xed volume fraction one can also see that the proper-
ties also vary, and both c and Ec are higher for the
composites fabricated with microspheres of smaller
diameters.
The apparent measured densities of the composites
also show how strong the e€ect of varying the mean
diameter of the microspheres can be. Once again, at a
®xed volume fraction, the composites fabricated with
smaller microspheres show higher values for the mea-
sured property, in this case the density.

Table 3
Experimental results
Table 1
Size distribution of commercial glass microspheres Material c (MPa) Ec (GPa)  (kg/m3) Microsphere
content, vol%
Mesh Maximum-minimum diameters (mm) %
25±100 57.8‹2.5 2.16‹0.09 887 32.6‹5.2
65 d>210 0.90 45±100 42.1‹1.7 1.86‹0.04 791 44.6‹4.5
65±100 210±149 15.50 55±100 30.7‹2.4 1.52‹0.06 593 53.1‹4.3
100±150 149±105 19.99 25±200 88.6‹0.8 2.74‹0.24 961 23.3‹2.5
150±200 105±74 20.45 45±200 51.2‹2.1 1.96‹0.05 724 47.3‹3.5
200±270 74±53 13.75 55±200 48.7‹1.9 1.95‹0.14 673 54.2‹2.6
270±325 53±45 7.59 25±325 77.5‹2.0 2.54‹0.21 920 29.0‹4.8
325 d<45 21.82 55±325 71.8‹1.8 2.56‹0.24 771 53.3
 J.R.M. d'Almeida / Composites Science and Technology 59 (1999) 2087±2091 2089

4. Discussion The large di€erence in the mechanical behavior of the

The mechanical behavior exhibited by the composites
can best be visualized by plotting the experimental
points on a chart of speci®c properties, i.e. speci®c stress
vs speci®c modulus (c = vs. Ec =). As one can see in
Fig. 1, all the data points fall along `volume-fraction
dependent' straight contour lines. From a design point
of view the results shown in Fig. 1 reveal that the per-
formance indices of a glass-microspheres composite can
be varied not only by changing the volume fraction, but,
also, by varying the mean diameter size of the micro-
spheres used to fabricate the composites. For example,
compare the points labeled as 1, 4 and 7 in Fig. 1.
This is considered to be an important result because
the higher a performance index is for a material, the
lower the mass of a component or part projected for a
given applied mechanical requirement [10,11]. In other
words, as shown in Fig. 1, the use of microspheres with
selected diameters, permits one to maximize the use of
these composites.
composites as a function of the variation of the mean
diameter of the microspheres can be associated with the
di€erent interactions of the microspheres to the exter-
nally applied stress state. A detailed analysis of the
stress state actually acting on the composite at the
microstructural level is very complex. In fact, the clas-
sical works dealing with the behavior of a material with
spherical inclusions, usually do not take into account
the interaction of the stress state due to neighboring
particles [12,13]. The local complex phenomena invol-
ving the rupture of particles during the event of loading
and rupture of a composite, or the rupture of the
microsphere-resin interface, are also usually considered
only from a macroscopic point of view and only the
average macroscopic behavior of a composite is mod-
eled [14]. Furthermore, the presence of resin rich areas
or, on the contrary, the presence of near touching
spheres, that can locally disturb the stress distribution
and that can cause strong deviations in the macroscopic
mechanical behavior, are also usually not taken into

Fig. 1. Variation of the speci®c properties of glass microsphere-epoxy composites as a function of the volume fraction and glass microsphere size.
Mesh 100±150: points 1, 2, 3, mesh 200±270: points 4, 5, 6, mesh 325: points 7, 8.
2090 J.R.M. d'Almeida / Composites Science and Technology 59 (1999) 2087±2091
account [13,14]. Although each of the above considera-
tions are important to model the mechanical behavior
of the composites here analyzed, their e€ects are dicult
to separate from each other and the actual stress state
developed at the microstructural level is beyond the
scope of this work.
Nevertheless, the behavior of a material can also be
modeled from its macroscopic properties. Therefore, the
e€ect of the variation of the microspheres' diameter and
volume fraction can be interpreted from the experi-
mental results obtained. From the values shown in
Table 3 it is clear that the smaller the microsphere is, the
better is its resistance to crack propagation. In other
words, there is a direct in¯uence of the wall thickness to
diameter ratio of the spheres on the mechanical beha-
vior of these composites.
The stress at rupture of the composites analyzed is
lower than that for the neat resin (r =257‹2,1 MPa
[15]). Therefore, it can be considered that under an
externally imposed uniaxial compression stress state the
glass microspheres act as sources for crack initiation. In
fact, the properties obtained are an average answer of
the material to the many microscopic events that occur
during the test. Each one of these events reduce the
strain energy stored in the composite and, therefore, are
damage events [16].
To understand the e€ect of the wall thickness to the
microsphere diameter ratio on the macroscopic behavior
of the composites the following equation was used [17]:
m :Vm
c ˆ …
scf
where m and Vm are the stress at rupture and the
volume fraction of the resin matrix, respectively, and scf
is a `stress concentration factor'. It should be clear,
however, that this parameter is to be understood as
representative of the summation of all damage events
that a€ect the behavior of the composites. The scf
values obtained are, therefore, average measures of the
in¯uence of local events occurring at the microscopic
level on the macroscopic mechanical behavior of the
composites. It is proposed here that the scf factor is, in
fact, to be understood as an indirect measure of a
damage parameter, that depends on the microspheres'
properties and on their interaction with the resin matrix
and with the externally imposed stress state.
The mean scf values obtained are listed in Table 4. It
can be seen that regardless of the volume fraction, the
composites fabricated with microspheres with the same
diameter size have the same scf value. The values shown
in Table 4 are, therefore, a direct indication that micro-
spheres with di€erent diameters interact in a very dif-
ferent way with the overall imposed stress state and with
a running crack. One can also see that, the smaller the
microspheres are the lesser is the their detrimental e€ect
Table 4
Stress concentration factor
Mesh scf
325 2.0‹0.4
200-270 2.4‹0.2
100-150 3.4‹0.5
upon the overall mechanical behavior of the composite.
Therefore, microspheres with smaller wall thickness to
diameter ratio are more resistant to crack propagation
and this ratio is a controlling parameter that can be
used to advantage in the design of glass microspheres
composites.
5. Conclusions
The mechanical behavior of glass-microsphere/epoxy
composites can be modeled by using microspheres with
di€erent diameters. As the wall thickness of the com-
mon microspheres is almost independent of their mean
size, the use of a select diameter range establishes an
optimum wall thickness to diameter ratio as another
important processing parameter of these composites.
The behavior of the composites as a function of the
volume fraction and the wall thickness to diameter ratio
could be plotted on straight contour lines on a chart of
speci®c properties. Therefore, di€erent performance
indexes could be correlated to each set of composites
and the performance of the material can be designed not
1†
only as a function of the volume fraction but also as a
function of the microsphere size. The dependence of the
measured properties with the mean diameter of the
microspheres is related to the level of the microspheres
properties and microsphere±resin interaction by an
overall damage factor, that can be determined from a
proper interpretation of a `stress concentration factor'
obtained from a commonly used equation derived from
the micromechanic approach of composite materials.
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