Journal Paper

Title: Understanding the effect of thermal conductive nanomaterials on composite laminate selfhealing efficacy
Student Name: Stefano Gazzola
Student Email: s3379510@student.rmit.edu.au
First Supervisor Name: Dr. Everson Kandare
Second Supervisor Name: Dr. Shuying Wu

Abstract
In todays modern battlefield, the limiting factor in a soldiers defences is his amour
Traditional body armour/ballistic protection systems utilise Kevlar due to its relatively high
strength-to-weight ratio, its cost effectiveness and its non-brittle nature. While they do stop a small
portion of small arms fire, the often resultant broken ribs, winding (Solar Plexus Syndrome)
and, in some cases internal bleeding, raises the question of the effectiveness of the amour.
There is also the issue of repeatable usage as once the plate has been damaged the structural
integrity of the composite has been compromised. Self-healing polymers, along with
nanotechnology offers a promising future to help improve ballistic protection.

Keywords: Ballistic, Kevlar, self-healing, nanomaterials

1. Introduction
Aramid fibres such as Kevlar have
traditionally been used as the material of
choice for ballistic protection, as the fibres
are made of individual filaments, which
cause it to undergo fibril breakage during
impact. Along with this is the high
strength-to-weight ratio that Kevlar
exhibits, making it a cost effective choice
when compared to some of the other

alternatives, such as steel or titanium

plating.
However the problem with Kevlar is
that it is heavy and cumbersome. Along
with this is also the issue of repeatable
usage, as once the fibres are damaged it
can no longer transfer any loading
throughout the surrounding material, a
phenomena known as fibre bridging. This
reduces the effectiveness of the plate for
potential subsequent impacts or stresses.

(Seung-Chul Kim, 2011) (P.N.B. Reis, 2012).

This
is due to the fibres breaking in filaments,
rather than clean cracks such as carbon
fibre. This causes a weakening in the
Kevlar/epoxy interface, and the epoxy can
no longer act as a stress transfer
mechanism, which results in a lower
delamination strength then carbon/epoxy.
(Seung-Chul Kim, 2011) The fibre also has
problem bonding with polymer matrixes
due to its oriented chain structure and its
skin-core heterogeneity, and as a result its
interfacial strength is only approximately
half of glass or carbon fibres.
Interfacial strength is important
during ballistic impact due to the stresses
that both the fibre and the matrix have to
overcome. Damage during a high speed
impact consists of: compression, shear
plugging,
tensile
deformation,
delamination and matrix cracking.
Compression of the fibres occurs directly
beneath the impact region, also known as
region 1. These in-plane compression
waves travel throughout the throughthickness direction of the composite,
resulting in compression of the secondary
yarns, which is known as region 2. If the
force exerted by the projectile exceeds the
shear plug force the rear face of the plate
experiences conical deformation, and any
fibres that have not been damaged in shear
plugging, endure tensile loading/strain.
The matrix in region 1 and 2 fails due to
the load exerted exceeding the materials
upper limit, resulting in matrix cracking
which typically leads to delamination in
mode II. (Shaktivesh, 2013)
Therefore in order to remedy the
issue of fibre damage and its mechanisms,
carbon/epoxy will be used as it has higher

tensile and compressive strength and

Youngs modulus, being in the magnitude
of 1500MPa, 1200MPa, and 135GPa,
compared
to
Kevlar
which
is
approximately 1300MPa, 280MPa and
75GPa respectively for a unidirectional
laminate with a 60% fibre volume fraction
content. (Anon., 2009) While carbon-fibre
also undergoes fibre damage, it has higher
delamination strength then Kevlar; with
the max mode I load average for
carbon/epoxy and Kevlar/epoxy being
79.5N and 31.3N respectively (Seung-Chul
Kim, 2011). This, in theory will reduce the
damage that the round causes on both the
wearer and the plate itself, thus increasing
the number of rounds the vest can absorb.
The self-healing polymer is used to
increase the ballistic absorption by healing
over previous damage, much like human
skin.
The problem with Kevlar and
other fibre-reinforced laminates is that
they are susceptible to delamination
cracking, which is cracking or splitting
between the various plies or layers.
Therefore in order to combat this damage,
the mendable polymer EMAA (poly
(ethylene-co-methacrylic acid)), will be
used as the self-healing polymer because
of its ability to form strong adhesion with
the epoxy via hydrogen and covalent
bonding (T. Yang, 2012). It is considered a
mendable polymer due to its need of an
external stimuli to heal, typically in the
form of thermal energy, which is used to
reverse the damage used by reverse
covalent and/or non-covalent bonding in
order to rejoin the damaged layer.
However long term heat exposure can also
affect the self-healing ability of the
EMAA, resulting in lower adhesive
strength between it and epoxy. Studies

conducted by, show that 5minutes at

150C provided the maximum adhesive
strength between EMAA and epoxy.
EMAA works by forming small
bubbles that occur post curing of the resin.
During damage such as impact, the
bubbles will burst during crack expansion,
to create a surface that is resin and EMAA
rich. The EMAA, which melts at the high
temperatures, then flows into the crack
plane via microscopic bubbles that swell
during post-curing, and rebind the
opposing sides of the fractured epoxy
surfaces. The long term efficacy of the
healing ability is dependent on the amount
of volatiles (chemical groups which make
the EMAA) remaining encapsulated within
the thermoplastic, as these provide the
pressure required to propel the EMAA into
the
crack.
Should
the
volatiles
escape/diffuse out of the thermoplastic;
this will result in lower pressure and
reduce the efficacy of the self-healing.
An interesting feature of EMAA is
that during high speed (ballistic) impact,
the transfer of kinetic energy and friction
can actually provide enough thermal
energy to repair the polymer in real time
(Ming Qiu Zhang, 2011). This occurs by the
hydrogen (polar groups), which require
low energy to reform. Once the hole has
been created, it begins to seal over, the
remaining strength of the polymer is
dependent on continuing inter-diffusion
processes, crystallisation as well as longterm relaxation of polymer chains. The
elastic response the polymer enables it to
recoil and the viscosity of the polymer
induces final sealing (Diana Dhler, 2013).

Figure 1-1: Chemical structure of EMAA

{Image courtesy from
http://www.sigmaaldrich.com/catalog/pr
oduct/aldrich/426628?
lang=en&region=AU}

(CH2CH2)x[CH2C(CH3)(CO2H)]Y
Figure 1-2: Chemical structure of
E.M.M.A

The use of carbon nanofibres (CNF) in

the experiment is used to increase thermal
conductivity in between the various plies and
the epoxy and EMAA matrixes. This is due to
the insulating properties of thermosetting
polymers such as epoxy, which is why during
the curing phase of composite materials such
as carbon-fibre there is such a long dwell time
in an autoclave. Long term exposure to heat
can cause oxidation to the epoxy matrix,
reducing the mechanical properties of the fibre
reinforce polymer composite. (POLYTEC
GmbH,

n.d.).

CNF which are essentially graphene plates,

that are stacked on top of each other, have a
high in-plane thermal conductivity, along with
high tensile strength .Studies have shown that
CNFs can improve the in-plane and throughthickness thermal conductivity in carbon fibre
reinforced
composites
(CFRP)
by
approximately 33%. Research has shown that
embedding CNFs into SHP such as poly (ecaprolactone) (PCL) can improve mechanical
performance without sacrificing the SHP
healing efficacy. The optimum blend was 9010%wt of epoxy to PCL and containing
0.2%wt CNFs which gave almost double the
flexural strength and toughness, while
preserving 78% of the self healing efficiency.
(Zhang

et

al.,

2012)

Figure 1-3: Flexural and Toughness

increase VS. CNF content. (Zhang et t
al., 2012)

Figure 1-4: Tensile strength and

Hardness VS. CNF content (Zhang et t
al., 2012).

2. METHODS
The aim of the project will be to
test the mechanical properties such as
stiffness and strength in both tensile and
compressive loading. However the main
emphasis will be on testing the impact
performance of carbon-fibre prepreg with
carbon nanofibres that will be embedded in
a self-healing polymer. The mixture will
then be layered on the carbon-fibre prepreg
in a mesh pattern, and repeated for each
ply. In order to assess the improvement of
using self-healing polymers and carbon
nanofibre, three specimens will be
fabricated; a carbon-fibre prepreg without
SHPs and CNF, a carbon-fibre prepreg
with SHP but no CNFs and lastly a carbonfibre prepreg with both SHPs and CNFs.
This will show whether or not the SHPs
improve mechanical performance of
carbon prepregs, and also if using CNFs
will decrease the regeneration time of selfhealing materials by increasing thermal
conductivity, which will also decrease the
chances of thermal damage to the
composite.

2.1.
Manufacturing
and Testing
In the manufacturing phase, neither
the carbon nanofibres nor the self-healing
polymer will need to be created as these
will be purchased. However the CNF will
need to be embedded into the self-healing
polymers and made sure that they are
evenly dispersed and are oriented in the
same direction.
The material will be tested for
different percentages by volume for the
carbon nanofibres. These will be between
0.1 to 2 percent CNF per unit volume, and
then tested for their mechanical properties.
At each of these percentages, two batches
of samples will need to be manufactured to
satisfy ASTM standards for both tests. The
standards for the DCB tests and impact
tests are (ASTM International, 2012) (ASTM
International, 2013)

Once the samples have been

created, they will be tested using two
methods will be used the first being the
Double Cantilever Beam (DCB) test. The
DCB test involves inducing a split in the
laminate by inserting a non-adhesive
material such as Teflon which must not
exceed 13m in thickness (ASTM
International, 2013), then using piano

hinges to pry open the material, the length

of the crack propagates along the material.
The stronger the bonds in the material, the
higher the force needed to pry open the
material.
The second method of testing will
be a low speed impact test, to test the
polymers ability to heal during ballistic
events. This involves the test specimen
being held in a set of jaws while a weight
is dropt vertically. (ASTM International,
2012)

3. Results
No testing has been started however
the DCB testing for the controlled
carbon/epoxy specimen will commence on the
12th of June.
The process for making the
carbon/epoxy laminate is as follows: four plies
of unidirectional carbon fibre epoxy prepreg
were laid up together at 0 before being
debulked. This process was repeated 3 more
times to create 4, 4 ply laminates. These were
then laid up to form a 16 layer laminated
before being debulked for a final time. The
laminate was then cured in an autoclave at
150C.

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