Materials Science and Engineering A 443 (2007) 209–218

Mechanical behavior of nickel + aluminum powder-reinforced

epoxy composites
M. Martin a , S. Hanagud b , N.N. Thadhani a,∗
a School of Materials Science and Engineering, Georgia Institute of Technology, Atlanta, GA 30332, United States
b School of Aerospace Engineering, Georgia Institute of Technology, Atlanta, GA 30332, United States

Received 18 May 2006; received in revised form 9 August 2006; accepted 30 August 2006

Abstract
The mechanical behavior of composites containing micro-sized Ni particles and micro- or nano-sized Al particles, fabricated by casting/curing
with epoxy, were studied to investigate their mechanical behavior for potential application as structural energetic materials. Reverse Taylor anvil-
on-rod impact tests combined with high-speed digital photography provided information about the high-strain-rate transient deformation and failure
response. The nano Al-containing composite exhibited a higher elastic modulus and static and dynamic compressive strengths than pure epoxy and
micro Al-containing composite due to increased cross-link density, as revealed by dynamic mechanical analysis. Microstructural characterization
of the cast composites revealed that micro-sized Ni and Al remained homogeneously and intimately mixed within the epoxy matrix. In contrast, the
composites containing micro Ni and nano Al showed separation of the nano Al particles, effectively forming a nano Al + epoxy matrix surrounding
the Ni particles and consequently altering the physical response and enhancing the mechanical properties of the composite.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Nanocomposite; Cross-link density; Dynamic mechanical properties; Strain hardening

1. Introduction mixture (Hf < −2.0 MJ/kg) [3] reinforcements in an epoxy

Composite materials provide the opportunity to combine con-
flicting properties and design materials for applications requir-
ing multiple functionalities. A combination of structural and
energetic functions can be attained through use of reactive rein-
forcements in polymer-matrix composites, but the conflicting
requirements for reactivity and strength make design of such
materials a challenging task. Composites with polymeric matri-
ces and hard, non-dissipative fillers can possess high stiffness
and high damping, which is ideal for structural properties. Addi-
tion of polymers to Ni + Al intermetallic-forming mixtures [1]
and Al + Fe2 O3 thermite powder mixtures [2] has been shown
to significantly affect the energetics of the reaction between
the powders. Combination of these attributes can potentially
result in a material with desirable structural and energetic prop-
erties. The work presented in this paper is part of an effort
focused on design of multifunctional energetic structural materi-
als (MESMs) based on use of highly exothermic Ni + Al powder
∗ Corresponding author.
E-mail address: naresh.thadhani@mse.gatech.edu (N.N. Thadhani).
matrix which can provide the combination of properties of struc-
tural and energetic materials.
Understanding the mechanical properties of reinforced com-
posites under static and dynamic loading conditions is an
essential element in the design of MESMs. Static mechanical
properties can be obtained by conventional mechanical testing
approaches. Dynamic mechanical properties at strain rates of
102 to 105 s−1 can be measured using the Taylor rod-on-anvil
impact experiment [4] or its reverse configuration [5], in which a
rigid anvil mounted on a sabot is accelerated to impact a station-
ary rod-shaped sample. With either configuration, a measure
of average dynamic yield strength can be obtained by corre-
lating the areal expansion of the impact face [4], or length
change [6] of the specimen, with the impact velocity and density.
The Taylor impact test, which is more traditionally employed
for metallic samples, has also been applied to polymeric sys-
tems [7–9]. The dynamic mechanical behavior of composite
systems containing reactive powder mixtures has only recently
been investigated [1,10], although Taylor anvil impact tests have
been used to establish the deformation characteristics of plastic
bonded explosives (PBX) [1,11,12]. In these studies it has been
shown that there is a critical velocity below which no permanent

0921-5093/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.msea.2006.08.106
210 M. Martin et al. / Materials Science and Engineering A 443 (2007) 209–218

macroscopic deformation occurs. Above the critical velocity,
radial cracks originate on the outer edges and propagate toward
the center resulting in complete fracture of the material. Studies
of the dynamic properties of an epoxy matrix filled with Al or
Fe particles have revealed that the matrix becomes the principal
load-carrying element and metal powder filler provides a rein-
forcing effect due to restraint of the matrix [13]. This concept
can be exploited by using reactive powder filler to provide the
restraint on the matrix, thus achieving structural strength and
reactive capability.
In this paper, we report on the static and dynamic struc-
tural/mechanical properties of Ni + Al-reinforced epoxy com-
posites (20 wt.% epoxy) containing micro-sized Ni particles and
micro- or nano-sized Al. Pure epoxy is also examined for com-
parison.
2. Experimental setup
Equivolumetric (76.6 wt.% Ni, 23.4 wt.% Al) dry powder
mixtures of micro Ni (−325 mesh, Cerac) with micro Al
(−325 mesh, Cerac) or nano Al (average diameter 56.3 nm
with 2.1 nm oxide coating, Technanogy) were prepared by
mixing in a V-blender for 24 h. Particle size distributions for
both micro-sized Ni and Al particles are presented in Fig. 1(a)
and (b); the average Ni particle size is 21 ␮m and the average
Al particle size is 17 ␮m. Fig. 2(a) and (b) shows SEM images
revealing the morphology of the as-mixed particles. It can be
seen that while the micro-sized Ni and Al powders appear as
a homogeneous mixture of discrete particles (Fig. 2(a)), the
mixture of micro Ni with nano Al shows the obvious disparity
in respective particle sizes (Fig. 2(b)). Furthermore, the nano Al
particles form a dusting on the larger micro Ni powder particles,
which can be seen more clearly in the insert in Fig. 2(b).
Cylindrical samples of Ni + Al powder-reinforced compos-
ites were fabricated by casting/curing with epoxy (92.3 wt.%
Epon® Resin 826, Miller-Stephenson; 7.7 wt.% diethanolamine
hardener, Sigma–Aldrich). The composites were composed of
61.33% Ni, 18.67% Al and 20% epoxy by weight, or 22.15% Ni,
22.15% Al, and 55.7% epoxy by volume. Pure epoxy specimens
were also cast under similar conditions for use as a reference
material. To prepare these samples, the Ni + Al powder mix-
tures were first heated in an oven at 120 ◦ C for 2 h to eliminate
any moisture. Simultaneously, Epon® Resin 826 (92.3 wt.% of
epoxy) was heated at 120 ◦ C to decrease its viscosity. The desired

Fig. 1. Particle size distributions for the micro-sized Ni and Al particles. The average Ni particle size is 21 ␮m and the average Al particle size is 17 ␮m. (a) Ni
particle size distribution and (b) Al particle size distribution.

Fig. 2. SEM images revealing the morphology of as-mixed Ni and Al powder particles. (a) The mixture of micro Ni and micro Al powders shows discrete particles,
whereas (b) the mixture of micro Ni and nano Al shows obvious disparity in respective particle sizes resulting in the nano Al actually forming a dusting on the larger
micro Ni powder particles. The inset shows a closer view of the nano Al particle dusting on the surface of the larger Ni particles.
 M. Martin et al. / Materials Science and Engineering A 443 (2007) 209–218 211

Fig. 3. SEM micrographs showing the microstructure of the cast materials. (a) Micrograph of polished Ni + micro Al + epoxy section showing the geometry of the
particles, a homogeneous distribution with no clustering and evidence of three distinct phases: white Ni, dark Al and gray epoxy matrix. (b)–(d) Micrographs of static
fracture surfaces of the Ni + nano Al + epoxy composite. (b) A low magnification view of the composite with the light contrast being Ni particles and the remainder
a mixture of nano Al and epoxy. (c) A higher magnification view of the nano-containing composite which shows the nano Al has become dispersed in the epoxy. (d)
The surfaces of several Ni particles which are completely clean and free of the nano Al dusting observed before casting (Fig. 2(b)).

amounts of the powder mixtures and the resin were then mixed longer form a dusting on the Ni particles as was observed after
for about 3 min using a mixing blade mounted on a drill, and powder mixing Fig. 2(b). It appears from these images that the
placed back into the 120 ◦ C oven for another 15 min to aid the composite containing nano Al effectively has only two compo-
mixing by further decreasing the viscosity of epoxy. After the nents: the Ni particles in a matrix of nano Al-containing epoxy.
resin and powders were fully mixed, the diethanolamine hard- The densities of the cast rods were measured via ASTM Stan-
ener (7.7 wt.% of epoxy) was added to the mixture and blended dard C 914-95: standard test method for bulk density and volume
using the home-made mixing device. The mixture was again of solid refractories by wax immersion. The densities of all three
placed in the oven for about 15 min. Next, the mixture was materials are reported in Table 1 and are based on an average of
degassed in a desiccator under vacuum for about 5 min (until multiple measurements performed on multiple specimens. The
a pressure of ∼1–2 Torr was achieved) to remove air bubbles, two composites have the same composition and vary only by par-
followed by reheating for an additional 30 min. Casting was ticle size, but the composite containing nano Al has a slightly
performed by pouring into Al molds (coated with grease on lower density. No obvious porosity was observed in the nano
the inside) of 0.6 in. diameter and 6 in. length, which were then Al-containing composites to account for the lower density of
placed in a 70–80 ◦ C oven for 48 h to allow complete curing. The this composite, which was consistently measured.
cured samples were removed from the molds and machined into Mechanical properties of the processed materials were eval-
various sized rods for testing. Microstructures of the cast com- uated using static compression tests and dynamic reverse
posite materials are shown in Fig. 3(a)–(d). Fig. 3(a) shows the
Ni + micro Al + epoxy composite, which has a relatively homo-
geneous and uniform distribution of both particle types. This Table 1
material clearly shows three distinct components; Ni is the light Experimentally measured mechanical properties of pure epoxy and Ni + Al
contrast phase, Al the dark contrast phase, and epoxy is the gray- powder-reinforced composites
ish contrast matrix. Fig. 3(b) shows the nano Al-containing com- Material Density Measured Measured
posite, which also exhibits homogeneous and uniform distribu- (g/cm3 ) E (GPa) σ y (MPa)
tion of the Ni particles in the epoxy matrix (the nano Al particles Epoxy 1.19 ± 0.00 3.0 ± 0.5 100.0 ± 4.1
cannot be discerned at that magnification). Higher magnification Micro Ni + micro Ni + epoxy 3.50 ± 0.13 7.5 ± 0.8 103.8 ± 12.2
images of the fracture surfaces of the Ni + nano Al + epoxy com- Micro Ni + nano Al + epoxy 3.26 ± 0.01 11.4 ± 1.3 156.8 ± 4.4
posite shown in Fig. 3(c) and (d) reveal that the nano Al particles Density was measured via Archimedes method and modulus and yield strength
have been dispersed in the epoxy matrix during casting and no were determined from the compressive stress–strain curves.
212 M. Martin et al. / Materials Science and Engineering A 443 (2007) 209–218

Fig. 4. (a) Schematic illustrating the reverse Taylor impact test setup showing the anvil-on-rod impact configuration, imaging with high-speed camera, and catch
tank for soft recovery of impacted sample. (b) Schematic illustrating the view down the impact axis of the rod-shaped sample epoxy mounted in an opening (with a
diameter greater than twice that of the specimen) in an acrylic ring.

(anvil-on-rod) Taylor [4] impact tests. Static compression tests
were performed using a SATECTM Universal Materials Test-
ing Machine at a loading rate of 0.248 mm/s. These tests were
performed on five cylindrical samples (15 mm diameter, 30 mm
length) of each type of cast material according to ASTM Stan-
dard D 695-02a: standard test method for compressive properties
of rigid plastics.
Dynamic reverse Taylor anvil-on-rod impact tests were
performed using a helium-driven 80 mm barrel gas gun. A
schematic of the reverse Taylor impact test setup is shown in
Fig. 4(a). For each experiment, the projectile (80 mm diameter
6061 Al sabot with a ∼7 mm thick maraging steel rigid anvil flyer
plate secured to the front surface) was accelerated at a velocity
ranging from 88 to 152 m/s to impact a cylindrical rod (12.5 mm
diameter, 50 mm length) of cast material. It should be noted
that whereas the traditional Taylor test employs a rigid anvil of
infinite thickness, the reverse impact configuration used in this
study employed an anvil of finite thickness (∼7 mm), which was
kept consistent for all experiments. The rod-shaped sample was
secured into an opening (with a diameter greater than twice that
of the specimen) in the center of a 3 mm thick acrylic target
ring (Fig. 4(b)) using a brittle epoxy, such that about 1/4 of the
sample length was on the back side of the target ring, and the
remaining 3/4 was on the impact side. This sample mounting
configuration insured that the sample was almost free stand-
ing with no obvious interference of the acrylic mounting ring
or epoxy with the deformation of the specimen, at least within
the time interval before fracture, as revealed by digital imaging
of the impact-induced deformation process. The mounting ring
also does not interfere with specimen recovery since the open-
ing is much larger than the diameter of the specimen, allowing
even the deformed specimen to pass through without impacting
the mounting ring; specimens that do not fracture during impact
are recovered from the rag-packed catch tank. Prior to impact,
the sample assembly was aligned using a laser beam to ensure
a planar-parallel impact.
 M. Martin et al. / Materials Science and Engineering A 443 (2007) 209–218 213

Fig. 5. Example of 6 of 16 high-speed digital camera images revealing transient deformation profiles for experiment performed on pure epoxy sample at 152 m/s.
Images are backlit and show a side view of the specimen held by an acrylic mounting ring as the Al sabot and rigid steel plate are accelerated toward it (from the
left). The time in each frame is referenced to the time of impact, where t = 0 ␮s at impact.

An Imacon-200 high-speed digital camera was used to cap-
ture images of the transient deformation of the specimen upon
impact with the projectile. The camera recorded 16 frames at a
maximum rate of 200 million frames per second with each frame
having a resolution of 1280 × 1024 pixels. The timing between
the 16 frames was adjusted such that the images were captured as
follows—one immediately before impact, one at impact, and the
remaining 14 images separated by 5–10 ␮s intervals to capture
the transient profiles as the sample plastically deformed and sep-
arated from the acrylic holding ring. Fig. 5 shows an example of
the images revealing the transient deformation profiles captured
with the use of the high-speed digital camera for an experiment
performed on a pure epoxy specimen. The high-speed images
of the transient deformation allow for analysis throughout the
deformation path and also for analysis to be made in cases when
the specimen is not recovered due to fracture upon impact, as
was the case in this study.
For analysis of areal (diameter) and axial (length) strain vari-
ations throughout the deformation event, the specimen profile
was isolated from each individual frame using Adobe Photo-
shop software (Adobe; San Jose, CA). A filter was applied in
Photoshop to find the edges of the specimen; the edges could
then be measured to within three pixels of uncertainty. The tran-
sient areal expansion at the impact face and decrease in length
were then calculated by measuring these dimensions in pixels
and then calibrating pixels with a known dimension in the image.
Dynamic mechanical analysis (DMA) (TA Instruments;
New Castle, DE) was performed on the composites and pure
epoxy to determine the storage modulus of the various sam-
ples. The tests were performed at a frequency of 1 Hz on
15 mm × 3 mm × 1 mm samples using a three-point bend clamp
with a span of 10 mm. Load application was parallel to the 1 mm
thickness direction of the sample. After equilibrating at −25 ◦ C
and holding isothermally for 1 min, tests were performed from
−25 to 150 ◦ C at a heating rate of 5 ◦ C/min in a nitrogen atmo-
sphere. Multiple tests were performed on multiple specimens of
each type of composite to insure repeatability and that the results
were representative of the bulk.
3. Results and discussion
3.1. Static mechanical properties
Static compression tests were performed on five samples of
each type of composite as well as on plain epoxy. Examples
of typical engineering stress–strain curves are shown in Fig. 6.
These curves illustrate evidence of plastic deformation prior
to failure, which occurred in the case of all the samples. The
composites exhibited higher elastic moduli and yield strengths
than the pure epoxy samples, and only the nano Al-containing
composite exhibited significant strain hardening. Table 1 sum-
marizes the elastic modulus and yield strength values obtained
from the stress–strain curves for the composites and pure epoxy.
The results illustrate that the illustrate that the 20 wt.% epoxy
composite containing micro Ni + nano Al powders exhibits a
yield strength (156.80 ± 4.44 MPa) that is ∼157% higher than
214 M. Martin et al. / Materials Science and Engineering A 443 (2007) 209–218
Fig. 6. Engineering stress–strain curves generated from static compression tests.
that of the pure epoxy sample (99.96 ± 4.11 MPa), whereas the
yield strength of composite containing micro Ni and micro Al
powders (103.80 ± 12.15 MPa) is only slightly higher than that
of pure epoxy. The nano Al-containing composites also exhib-
ited an elastic modulus almost four times higher than that of pure
epoxy, whereas the micro Ni + micro Al-containing composite
exhibited a modulus slightly more than twice that of the pure
epoxy.
3.1.1. Dynamic mechanical properties
Dynamic mechanical properties of the cast composites were
measured by conducting reverse Taylor anvil-on-rod impact tests
as previously described. Experiments were performed on pure
epoxy samples at impact velocities of 85 and 152 m/s. Experi-
ments on the composite samples were performed at 89 m/s on
the micro Ni + micro Al + epoxy composite and at 100 m/s on the
micro Ni + nano Al + epoxy composite. Whereas the pure epoxy
cast rod impacted at 85 m/s survived without any observable
plastic deformation, all other samples fractured following defor-
mation. Hence, the classical Taylor [4] or Wilkins and Guinan
[6] analyses for determining the dynamic yield strength based
on area or length change, respectively, of the recovered impacted
specimen in comparison with the initial specimen could not
be applied. However, incremental areal and axial strain varia-
tions could be obtained using high-speed digital images obtained
during the experiments (Fig. 5). The profiles of the deformed
specimen were isolated from each image; Fig. 7(a)–(c) shows
representative profiles obtained following image processing for
the samples (two composites and pure epoxy) that exhibited clear
evidence of plastic deformation during impact. These transient
deformation profiles were then used to measure radial and length
changes using pixel calibration obtained from a known dimen-
sion in the images. Two strain definitions commonly used in
analysis of Taylor impact test specimens are areal engineering
strain [4] and longitudinal true strain [6], which are given in Eqs.
(1) and (2), respectively.
A0
εareal = 1 −
A by characterizing the fracture surfaces of samples recovered
 
Lf
ε long
= ln (2)
L0
Incremental strains of both types were calculated according to
Eqs. (1) and (2) by using the areal expansion at the impact face
and the length change of the specimen for each transient frame
captured in which the entire specimen was present and fracture
had not begun.
The reverse Taylor anvil-on-rod experiments were performed
on the various types of composite samples of different density
(ρ) and impact velocity (U). Hence, to eliminate any variabil-
ity in strain caused by effects of specimen density or impact
velocity, the values of areal engineering strain and longitudinal
true strain measured for each frame were normalized by ρU2 .
The normalized areal and longitudinal strain values plotted as
a function of the time after impact (time when each frame was
captured) are shown in Figs. 8 and 9, respectively. Both plots
demonstrate increasing strain with time after impact. The pure
epoxy sample and the composite containing micro Ni and micro
Al exhibit greater areal and longitudinal strains than the com-
posite containing micro Ni and nano Al. Since dynamic yield
strength has been shown to be proportional to sample density and
the square of impact velocity, according to the definitions by both
Taylor [4] and Wilkins and Guinan [6], the strains normalized
by density and impact velocity provide a qualitative inference of
the strength of the various samples. Hence, based on the plots in
Figs. 8 and 9, it can be inferred from the lower overall strain of
the nano Al-containing composite that its dynamic flow strength
is higher than the pure epoxy and the Ni + micro Al-containing
powder composite. This is in agreement with the higher static
strength exhibited by the nano Al-containing composite as com-
pared to the pure epoxy and the micro Al-containing composite.
It should be noted that the pure epoxy sample impacted at 85 m/s
showed no plastic deformation and it is therefore believed that
this impact took place below the aforementioned critical veloc-
ity for this material [11,12], so this experiment was not included
in Figs. 8 and 9. While lack of plastic deformation of the pure
epoxy rod impacted at a similar velocity to those of the com-
posite rods may imply higher yield strength of the pure epoxy
sample, its perfectly plastic behavior leads to significant plastic
deformation upon impact at 152 m/s and lower overall dynamic
flow strength than the nano Al-containing composite.
3.1.2. Analysis of mechanical behavior
As revealed by the above-mentioned experiments, the
addition of Ni and Al particles to epoxy produces a powder-
reinforced composite and increases both its static and dynamic
strengths, particularly in the case of the composite reinforced
with micro Ni and nano Al powders. The results suggest
inherent strengthening of the epoxy matrix caused by the
addition of nano-sized Al powders. It is unknown whether this
difference in behavior is due to the presence of an oxide coating
on the nanoparticles, the interaction of the nanoparticles with
epoxy, or solely a particle size effect. The dissimilar composite
responses observed as a function of the variations in Al particle
size (micro versus nano) were therefore further investigated
(1)
 M. Martin et al. / Materials Science and Engineering A 443 (2007) 209–218 215

Fig. 7. Representative deformation profiles obtained following image processing for the samples that exhibited clear evidence of plastic deformation during impact.
(a) Pure epoxy impacted at 152 m/s, (b) micro Ni + micro Al + 20 wt.% epoxy composite impacted at 89 m/s, and (c) micro Ni + nano Al + 20 wt.% epoxy composite
impacted at 100 m/s.

following the anvil-on-rod impact experiments. The micro Ni
and micro Al-containing composite revealed a glassy fracture of
the epoxy matrix surrounding the particles, as seen in Fig. 10(a)
and (b). Also noticeable in these figures is particle pullout from
the epoxy matrix and the practically undeformed Ni and Al
particles, which indicates that the epoxy matrix was the primary
load bearer. The micro Ni and nano Al-containing composite
(Fig. 10(c) and (d)) showed very different fracture behavior with
a rougher fracture surface due to the nano Al particles providing
sufficient reinforcement to increase the cohesive strength of the
epoxy, which consequently reduced the glassy or brittle fracture.
Additionally, the nano Al particles may provide obstacles to
cracks formed in the epoxy matrix, resulting in less convenient
crack path and therefore more difficult fracture. The nano Al
particles which were observed to form a dusting on the micro Ni
particles during powder mixing (as revealed in Fig. 2(b)) appear
to have detached from the Ni particles and dispersed in the epoxy
matrix during casting. Fracture surfaces reveal the clean surfaces
of the micro Ni particles with no dusting of nano Al (Fig. 10(d)),
and again there is no obvious deformation of the Ni particles. It
is possible that the dispersion of nano Al in the epoxy is creating
a structurally different matrix phase, and therefore providing
a new strengthening mechanism and altering its mechanical
response.
Several explanations were explored for the difference in
behavior caused by use of nano Al particles. Use of nano Al
particles led to strain hardening, as evidenced by the static
stress–strain curves (Fig. 6), whereas the pure epoxy and the
composite containing micro Ni and micro Al exhibited a typi-
cal perfectly plastic response, suggesting a particle size effect.
One explanation for this behavior is that the epoxy matrix of
the Ni + micro Al composite absorbs the load and dominates
the deformation response, whereas the load is transferred from
the nano Al-dispersed epoxy to the micro Ni particles in the
nano Al-containing composite. According to this explanation,
the deformation response of the micro Ni particles would then
216 M. Martin et al. / Materials Science and Engineering A 443 (2007) 209–218

Fig. 8. Areal strain normalized by specimen density and the square of impact
velocity plotted as a function of time after impact for dynamic reverse Taylor
impact tests performed on pure epoxy, micro Ni + micro Al + 20 wt.% epoxy
composite and micro Ni + nano Al + 20 wt.% epoxy composite. The plot shows
that the nano Al-containing composite exhibits the least amount of total areal
strain throughout the deformation process. Error bars correspond to a three-pixel
uncertainty on each edge of the specimen when measuring incremental strain
from the images.
Fig. 9. Longitudinal (axial) strain normalized by specimen density and the
square of impact velocity, plotted as a function of time after impact for
dynamic reverse Taylor impact tests performed on pure epoxy, micro Ni + micro
Al + 20 wt.% epoxy composite and micro Ni + nano Al + 20 wt.% epoxy com-
posite. The plot shows that the nano Al-containing composite exhibits the least
amount of total axial (longitudinal) strain throughout the deformation process.
Error bars correspond to a three-pixel uncertainty on each edge of the specimen
when measuring incremental strain from the images.

be expected to dominate the stress–strain behavior of the nano
Al-containing composite, and hence, give rise to strain harden-
ing, as seen in Fig. 6. However, SEM images of the fracture
surfaces of these specimens showed brittle fracture of the nano
Al-containing epoxy and pullout of the Ni particles to be the pri-
mary fracture mechanisms (Fig. 10(c)), with no deformation of
the micro Ni particles (Fig. 10(d)). Hence, the strain hardening
observed in this sample is not believed to be due to the micro
Ni particles dominating the response, but rather due to the nano
Al-containing epoxy matrix.

Fig. 10. SEM micrographs of fracture surfaces of micro Ni + micro/nano Al + epoxy composites after reverse Taylor dynamic impact. (a) and (b) Ni + micro Al + epoxy
fracture surfaces showing brittle, glassy fracture in the epoxy matrix and little deformation in both the Ni and Al particles. There are also signs of pullout of the
particles from the epoxy. (c) and (d) Ni + nano Al + epoxy fracture surfaces showing a very different fracture behavior due to the dispersion of the nano Al particles
in the epoxy matrix. This nano-scale reinforcement appears to have changed the fracture mechanism and a more flaky fracture surface can be seen in addition to
particle pullout. The Ni particles remain undeformed, as with the previous case, and most deformation is absorbed by the nano Al + epoxy matrix.
 M. Martin et al. / Materials Science and Engineering A 443 (2007) 209–218
Table 2
DMA data including storage modulus, E , at 140 ◦ C and cross-link density, N, calculated based on Fig. 11 and Eq. (3)
Material E at 140 ◦ C (MPa)
Epoxy 11.69 ± 1.69
Ni + Al + 20% epoxy 146.13 ± 20.75
Ni + nano Al + 20% epoxy 233.25 ± 93.22
This data shows a ∼100% increase in cross-link density resulting from a reduction in Al particle size from micro to nano-scale.
The dispersion of nano Al particles in epoxy can also alter
the molecular structure of epoxy and thus change its deforma-
tion and strain hardening response. Van Melick et al. [14] have
found that strain hardening in polymers is proportional to net-
work density, regardless of whether the density is caused by
chemical cross-links or physical entanglements. The dispersion
of the nano Al particles throughout the epoxy matrix can provide
physical entanglements since nanoparticle/matrix interactions
lead to a loss in mobility of the chain segments [15]. Nanopar-
ticles have a very large surface area, and due to their increased
contacts with the epoxy, the cohesive strength of the epoxy can
increase and lead to a higher mechanical strength of the inter-
faces [16]. This is partially due to the mechanical interlocking
resulting from the extensive contact between the epoxy and the
nano-sized filler particles [16,17]. Increases in strength have also
been seen with increasing cross-linking density in many studies
[18–20]. The increase in strength and strain hardening seen in
the nano Al-containing composite in this study seems likely to
be induced by the entanglements and interlocking caused by the
dispersion of nano Al particles in the epoxy matrix.
Dynamic mechanical analysis was utilized to further inves-
tigate the effects of the Ni and Al particles on the behavior of
the epoxy and to verify the mechanism by which the particles
are altering the mechanical response of the epoxy. Fig. 11 is a
plot of storage modulus measured as a function of temperature
for the pure epoxy and the two composite samples. These traces
show the storage modulus in the glassy region, during the glass
transition, and in the rubbery region. The storage modulus in the
rubbery region is related to cross-link density according to the
Fig. 11. Typical curves of storage modulus plotted as a function of temperature
based on measurements performed using DMA. The modulus in the rubbery
region, i.e., following the glass transition, is related to the cross-link density of
the material.
217
Cross-link density, N (nm−3 ) Cross-link spacing (nm)
0.68 ± 0.10 1.14 ± 0.06
8.54 ± 1.21 0.49 ± 0.02
13.64 ± 5.45 0.43 ± 0.05
following relationship [21]:
E
N= (3)
3kT
where N is the cross-link density, E the value of the elastic
modulus in the rubbery plateau, K Boltzmann’s constant, and
T is the temperature (well above Tg ) at which E is measured.
Values of cross-link density at 140 ◦ C are reported in Table 2.
Also reported are values of the average cross-link spacing, which
is calculated by assuming a uniform three-dimensional cross-
link distribution [21]; cross-link spacing is the inverse cube root
of the cross-link density and merely provides a more intuitive
means for comparison of cross-link density. The results illustrate
that the nano Al-containing composite indeed has a much higher
cross-link density, or smaller distance between cross-links, than
both the micro Al-containing composite and the pure epoxy sam-
ple. Although this increase in cross-link density is physical and
not chemical in nature, it nevertheless explains the reason for
higher strength and different hardening response of the nano
Al-containing composite as compared to the other samples. It
should be noted that the increase in cross-link density is not the
only factor affecting the strengthening of the composites since
the micro-scale composite also shows a significant (but lesser)
increase in cross-link density. Other factors causing a greater
degree of inhibition of chain mobility in the nano-containing
composite than in the micro-containing composite are also pos-
sible and need to be explored. The observed results provide the
rationale for further exploiting this effect to alter the mechanical
behavior of epoxies via use of nano-sized particles by influenc-
ing their inherent physical structure.
4. Summary and conclusions
The structural behavior of Ni + Al + epoxy composites was
evaluated using static compression tests and dynamic reverse
Taylor anvil-on-rod impact tests performed using a gas gun
with high-speed digital photography. The material with 20 wt.%
epoxy and nano-sized Al powder showed the most superior
mechanical properties with an elastic modulus of 11.4 GPa, a
static compressive yield strength of 156 MPa and the highest
dynamic compressive strength based on comparison of incre-
mental areal and longitudinal strain values. Composites contain-
ing nano Al powder also exhibit strain hardening in addition to
increased strength. The superior mechanical properties and the
strain hardening exhibited by the nano Al-containing compos-
ite can be explained by the increased polymer network density
caused by physical entanglements from the dispersion of nano
Al particles in the epoxy matrix.
218 M. Martin et al. / Materials Science and Engineering A 443 (2007) 209–218

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[10] L. Ferranti, N.N. Thadhani, Dynamic impact characterization of
Funding for this research was provided by AFOSR/MURI
Al + Fe2 O3 + 30% epoxy composites using time-synchronized high-speed
Grant no. F49620-02-1-0382 and a Boeing Graduate Fellowship. camera and VISAR measurements, in: N.N. Thadhani, R.W. Armstrong,
The authors would like to thank Harpreet Singh for help with A.E. Gash, W.H. Wilson (Eds.), Multifunctional Energetic Materials, MRS
the particle size distribution measurements and Professor Ken Symp. Proc., vol. 896, 2006, pp. 197–202.
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