Heterogeneously structured conductive carbon ber composites

by using multi-scale silver particles

Shaokai Wang
a,
, David Haldane
a
, Peter Gallagher
a
, Teng Liu
a
, Richard Liang
a,
, Joseph H. Koo
b
a
High-Performance Materials Institute (HPMI), FAMU-FSU College of Engineering, Florida State University, Tallahassee, FL 32310, USA
b
KAI, LLC, Austin, TX 78739, USA
a r t i c l e i n f o
Article history:
Received 27 August 2013
Received in revised form 10 January 2014
Accepted 23 January 2014
Available online 31 January 2014
Keywords:
A. Polymermatrix composites (PMCs)
A. Laminates
A. Particle-reinforcement
B. Thermal properties
a b s t r a c t
This paper reports a new approach to enhance the through-thickness thermal conductivity of laminated
carbon fabric reinforced composites by using nanoscale and microscale silver particles in combination to
create heterogeneously structured continuous through-thickness thermal conducting paths. High
conductivity of 6.62 W/(m K) with a 5.1 v% silver volume fraction can be achieved by incorporating these
nanoscale and microscale silver particles in EWC-300X/Epon862 composite. Silver akes were distributed
within the inter-tow area, while nanoscale silver particles penetrated into the ber tows. The combina-
tion of different sizes of silver llers is able to effectively form continuous through-thickness conduction
paths penetrating ber tows and bridging the large inter-tow resin rich areas. Positive hybrid effects to
thermal conductivity were found in IM7/EWC300X/sliver particle hybrid composites. In addition, micro-
scale llers in resin rich areas showed less impact on tensile performance than nanoscale particles
applied directly on ber surface.
Published by Elsevier Ltd.
1. Introduction
Advanced composite materials have been widely used as struc-
tural materials for aerospace, military, and industrial applications
due to their high stiffness and strength to weight ratios. Currently,
low thermal conductivity of composites restricts their ability to re-
place metallic structures involving thermal management func-
tions; such as the leading edges of supersonic aircraft wings, the
inlet or exhaust areas of gas turbine engines, lightweight heat
exchangers, electronics packaging materials, hydraulic pump
enclosures and electromagnetic interference (EMI) enclosures [1].
In many cases, internal heat needs to be effectively dissipated from
these systems and high through-thickness thermal conductivity
(TTTC) is essential for using advanced composite materials in these
applications [24].
Carbon ber is widely used reinforcement in advanced polymer
composites due to its superior mechanical and physical perfor-
mances. Polyacrylonitrile (PAN)-based ber and pitch-based ber
are two of the types most commonly used. They have different
mechanical and thermal properties which directly impact the per-
formance of their composites [5]. PAN bers possess high strength
and relatively low modulus, while pitch-based bers have higher
modulus and lower tensile strength [6,7]. Pitch-based bers have
higher thermal conductivity than PAN-based bers due to their
higher degree of graphitization. Both types of carbon bers possess
higher thermal conductivity in its axial direction than the trans-
verse direction due to long and continuous crystal structures exist-
ing along ber axis direction to promote phonon transport. As a
result, laminated composites show a higher in-plane thermal con-
ductivity along ber axial direction than through-thickness direc-
tions transverse to the ber axis. The absence of bers in the
through-thickness direction and insulating resin rich areas be-
tween ber tows and layers further result in low through-thickness
thermal conductivity. Although Schuster et al. [8] and Sharp et al.
[9] achieved a noticeable increase in through-thickness or out-of-
plane thermal conductivity by using three-dimensional ber rein-
forcements, enhancing the through-thickness thermal conductivity
of widely used laminated composites is highly desired. Silver par-
ticles [10,11], copper particles [12], carbon black [13], carbon
nanotubes [1416], aluminum powder [17], aluminum nitride
[18] or combinations of different particles [19,20] have been tested
to improve the thermal conductivity of polymer materials, and
some have also been applied in the ber reinforced composite
materials as llers in matrix. The TTTCs of the composites pro-
duced with these llers were no more than 3.0 W/(m K) in thermal
conductivity. The interlaminar resin-rich layer has proven to be the
major reason for low through-thickness thermal conductivity. Han
http://dx.doi.org/10.1016/j.compositesb.2014.01.049
1359-8368/Published by Elsevier Ltd.

Corresponding authors. Tel.: +1 850 645 8998; fax: +1 850 645 9123.
E-mail addresses: swang5@fsu.edu (S. Wang), liang@eng.fsu.edu (R. Liang).
Composites: Part B 61 (2014) 172180
Contents lists available at ScienceDirect
Composites: Part B
j our nal homepage: www. el sevi er . com/ l ocat e/ composi t esb
et al. [3,13] enhanced TTTC by up to 60% by raising the curing pres-
sure and various interlaminar interface modications through the
incorporation of llers. Simon and Robitaille [21] suggested that
transverse thermal conductivity was also inuenced by the gap
thickness of the inter-tow area which played an important role
on composite conductivity prediction. A continuous through-thick-
ness thermal conduction path with good connection between ller
particles will improve TTTC of laminated composite effectively. Sil-
ver, aluminum, and copper all have high thermal conductivity.
Nanoscale aluminum and copper show extremely high reactive
activity and are explosive under certain circumstance. Silver was
chosen due to its high thermal conductivity, sintering phenomenon
and high security.
This research attempted to enhance the TTTC of laminated
carbon fabric reinforced composites by utilizing a size synergy
advantage of nanoscale and microscale silver particles. The goal
is to develop heterogeneously structured and continuous conduc-
tive paths of the silver particles along through-thickness direction
to effectively increase thermal conductivity as shown in Fig. 1. The
effects of silver particle size, concentration, and ber type on TTTC
values and tensile performance were investigated.
2. Experimental
2.1. Materials
Two kinds of the reinforcement fabric were used: IM7 GP-6k
plain weave fabric with an areal density of 190 g/m
2
produced by
Textile Products Inc., and pitch-based carbon fabric EWC-300X
with an areal density of 610 g/m
2
supplied by Cytec. Epon862 with
curing agent epicure-W was produced by Momentive Specialty
Chemicals Inc. Microscale and nanoscale silver particles were used
as llers. Silver akes and silver suspension with silver nanoparti-
cles were purchased from Alfa Aesar and Cabot Corporation,
respectively. Silver akes less than 20 lm and silver nanoparticles
smaller than 50 nm were used. Silver suspension contains approx-
imately 50 wt% nanoscale silver particles, ethylene glycol, polyvi-
nylpyrrolidone and water. The nanoscale silver particles could be
sintered at a temperature higher than 150 C to increase thermal
conductivity.
2.2. Sample design and preparation
The high conductivity composite samples were fabricated by
introducing silver particles in several methods to realize inter-
tow and intra-tow penetration in carbon fabrics. The silver suspen-
sion comprising of nanoscale particles and a solvent was sprayed
directly to dry carbon fabrics. The suspension inltrated the ber
tows by capillary force. After the fabric was impregnated with
the required amount silver suspension, the impregnated fabric
was further pressed to promote uniform distribution of nanoscale
silver particles. The solvent was volatilized at 150 C under a vac-
uum for 1 h. The nanoscale silver particles deposited on the surface
of each lament fully coating them; and the nanoparticles were
sintered at the volatilization temperature providing better connec-
tivity and conductivity.
Silver akes were evenly dispersed in the Epon862 resin sys-
tem, and then applied to impregnate the carbon fabric layer by
layer by hand lay-up process. The resin permeated into the ber
tows while microscale silver akes were blocked from impregna-
tion between the ber tows due to their larger size than the pores
between ber laments. The akes mainly distributed at the inter-
tow space. Three congurations of silver lled composites were
fabricated: microscale silver akes lled composite (ms-CFRP), sil-
ver nanoparticle lled composite (ns-CFRP) and a composite by
applying both nanoscale and microscale silver particles in combi-
nation (mns-CFRP) via the aforementioned methods. Fig. 2 illus-
trates the proposed microstructures of the different composite
designs. All samples were fabricated using a hot-press process.
The samples were cured at 190 C for 3 h.
2.3. Property characterization
Netzsch laser ash diffusivity tester (Netzsch LFA 457) was used
to measure the thermal diffusivity (a). The measurements followed
ASTM E1461 guidelines. The samples, measuring 10 10 mm
2
,
were coated with graphite. A graphite sample with known specic
heat and thermal diffusivity was used as a reference. The measured
specic heat by LFA457 had a systematic error of approximately
10%. Through-thickness thermal conductivity k can be calculated
by:
k a C
p
q 1
where C
p
is the specic heat and q is the specimen density [22,23].
Tensile property tests were conducted following ASTM D 3039,
by using a MTS Landmark machine with a non-contact video
extensometer for strain recording. The specimens were measured
at crosshead speed of 1 mm/min. E-glass ber reinforced epoxy
tabs were used.
Fig. 1. (a) Conventional homogeneously structured ller-enhanced CFRP; (b) heterogeneously structured continuous conductive paths to improve the through-thickness
thermal conductivity of structural composites.
S. Wang et al. / Composites: Part B 61 (2014) 172180 173
3. Results and discussion
3.1. TTTC of woven carbon fabric laminated composites
EWC300X graphite bers provide a high thermal conductivity of
250350 W/(m K) along the ber axial direction. The correspond-
ing EWC-300X/Epon862 control sample was measured to have a
thermal diffusivity of 0.97 0.09 mm
2
/s and a conductivity of
1.96 0.20 W/(m K) at 25 C along the samples through-thickness
direction. Fig. 3 shows the cross-section microstructures of the
EWC-300X/Epon862 composite sample (control) with a ber vol-
ume concentration of 58.1 v%. The morphology shows that the re-
sin well penetrated warp and weft ber tows in a laminated
structure. No noticeable contact among ber tows is observed,
leading to the absence of a continuous thermal conduction path
in the through-thickness direction. Instead, some resin rich areas
can be observed between ber tows and laminar layers. The resin
matrix possesses a low thermal conductivity (<0.2 W/(m K)). These
resin rich areas act as an insulation layer and cause a low TTTC of
laminated composites. These areas were mainly distributed at the
gap between adjacent parallel tows, interlaminar zones and inter-
section of warp and weft ber tows. The gap between parallel ber
tows appeared to be in rectangular shape. As an example, a typical
resin gap was approximately 204 lm 85 lm, as shown in
Fig. 3(a). Triangle shaped resin rich areas were formed at the warp
and weft ber tows intersection of the fabric weave structure. A
triangular area with the height of 390 lm and base of 80 lm can
be observed in Fig. 3(a and b). Some narrow resin rich areas were
present at the interlaminar areas, which were approximate 12 lm
wide as seen in Fig. 3 (a and c). The similar resin rich areas were
also observed in IM7/Epon862 composite, causing a lower diffusiv-
ity and conductivity of 0.34 0.03 mm
2
/s and 0.72 0.06 W/(m K),
respectively. IM7 ber has a much lower axial thermal conductiv-
ity of 5.40 W/(m K) [24] than ECW300X ber in the predicted range
of 250350 W/(m K), resulting in the difference between IM7 and
EWC300X composites.
3.2. Construction of heterogeneous through-thickness silver
conductive paths
3.2.1. Thermal diffusivity and conductivity
Nanoscale silver particle and microscale silver akes were used
to improve the TTTC of the carbon fabric reinforced composites.
Silver was chosen due to its high thermal conductivity and possible
ability to establish better continuous conduction paths through in-
ter-particle sintering at moderate temperatures. Three types of
EWC-300X/Epon862 composite samples were prepared utilizing
the nanoscale and microscale silver particles. These included ms-
Fig. 2. Composite sample designs of (a) control CFRP: carbon fabric composites without silver llers, (b) ms-CFRP: silver ake lled composites, (c) ns-CFRP: silver
nanoparticle coated ber fabrics composites, and (d) mns-CFRP: silver nanoparticle coated ber fabrics and silver ake lled composites.
Fig. 3. Morphologies of EWC-300X/Epon862 composite samples (control) with resin rich areas at (a) inter-tow, (b) intersection of warp and weft ber tows, and (c)
interlaminar areas.
174 S. Wang et al. / Composites: Part B 61 (2014) 172180
CFRP, ns-CFRP, and mns-CFRP samples. Fig. 4 shows the thermal
conductivities and diffusivities of different composite samples.
The thermal diffusivity decreases with the temperature increase,
while specic heat capacity showed an increase trend. The control
sample was measured to have a thermal diffusivity and conductiv-
ity of 0.97 0.09 mm
2
/s and 1.96 0.20 W/(m K) at 25 C, respec-
tively. Thermal diffusivity and conductivity noticeably increased
after applying about 5.0 v% volume fraction silver particles, as
shown in Fig. 4. The corresponding ns-CFRP and ms-CFRP samples
with silver concentrations of 5.2 v% and 4.7 v%, had densities of
2.21 g/cm
3
and 1.99 g/cm
3
, respectively. The ns-CFRP showed ther-
mal diffusivity and conductivity of 2.26 0.15 mm
2
/s and
4.33 0.35 W/(m K), while the ms-CFRP provided the similar ther-
mal performance of 1.86 0.14 mm
2
/s and 3.51 0.19 W/(m K).
The thermal conductivity of ns-CFRP and ms-CFRP samples in-
creased 121% and 79% compared with control sample, respectively.
By applying nanoscale and microscale silver particles in combina-
tion, the nal mns-CFRP with a silver concentration of 5.1 v% and a
density of 2.18 g/cm
3
exhibited the highest thermal diffusivity and
conductivity of 2.50 0.16 mm
2
/s and 6.62 0.51 W/(m K). The
resultant thermal conductivity increased 238% compared with
control sample.
The IM7/Epon862 composites showed similar thermal behavior
as shown in Fig. 5. The control sample with a ber volume fraction
of 55.3 v%, exhibited a thermal diffusivity of 0.34 0.03 mm
2
/s and
conductivity of 0.72 0.06 W/(m K) at 25 C. The mns-IM7/
Epon862 composite with a 5.5 v% silver showed improved thermal
diffusivity and conductivity of 1.23 0.08 mm
2
/s and 1.86
0.11 W/(m K) at 25 C, which was 158% increase compared with
the corresponding control sample. The TTTCs of both control and
mns-CFRP samples of IM7/Epon862 are much lower than those of
the EWC300X/Epon862 composites with similar laminated or het-
erogeneous silver structures. This was due to the large difference in
thermal conductivity between PAN-based and pitch-based carbon
ber. The thermal conductivity properties were related with the
microstructure of carbon ber. Fig. 6 shows the cross-sectional
morphologies of IM7 and EWC300X carbon ber. The IM7 PAN-
based carbon ber displayed a particulate cross-sectional morphol-
ogy. In contrast, EWC300X pitch ber showed dense packing of
long graphite sheets in its morphology, with basal planes radiating
from the bers center, forming radial transverse textures [25]. This
most likely contributed to a higher thermal conductivity in the
radial direction of the pitch ber.
3.2.2. Heterogeneous microstructures
Fig. 7 shows the morphologies of the resultant composite
samples. Nanoscale silver was able to penetrate the ber tows
and deposit on the surface of carbon bers, enhancing the thermal
conductivity within the ber tows. Fig. 7(b) shows the distribution
of nanoscale silver on the carbon ber. The bright circles surround-
ing carbon bers are silver depositions on the bers surfaces. The
nanoscale silver was not evenly distributed in the matrix among -
ber laments, but coated on the carbon ber surface to connect
adjacent laments, forming a continuous conductive path. Silver
nanoparticles were sintered to establish better connection causing
some particles to form larger agglomerates. Similar sintering phe-
nomenon of nanoscale silver was reported by Pashayi et al. [11].
Microscale silver ake was mainly distributed in the resin rich
areas between ber tows with only a small amount penetrating
the tows, as shown in Fig. 8. The size of inter-tow silver particles
was much larger than that of the pristine silver akes, indicating
silver agglomeration during the sample manufacturing process.
The resultant larger silver particles will be benecial to effectively
construct conductive paths across the large resin rich areas. The
distribution of silver particles was inuenced by the intra- and in-
ter-tow porosity.
Nanoscale or microscale silver particles alone were observed to
only improve the intra- or inter-tow conduction respectively, but
were not able to establish sufcient continuous paths crossing
the through-thickness direction. The combination of microscale
and nanoscale silver particles can effectively connect the conduc-
tion paths among intra- and inter-tow, resulting in greater thermal
conductivity of mns-CFRP under the similar density as shown in
Fig. 9.
3.2.3. Effect of silver concentration on TTTC
Fig. 10 shows the thermal diffusivity and conductivity results of
the EWC-300X/Epon862 composites with different silver concen-
trations. Thermal diffusivity and conductivity were enhanced by
increasing the silver concentration. The diffusivities of the EWC-
300X/Epon862 were approximately 2.5 and 3.6 mm
2
/s with
5.5 v% and 15.5 v% volume fraction silver, respectively. The corre-
sponding TTTCs were 6.62 0.51 and 10.63 0.81 W/(m K). The
side effect of increasing silver concentration should be pointed
out. Nanoscale silver increased the interface thickness between -
ber and resin matrix, weakening the load transfer capacity. Micro-
scale silver akes largely occupied inter-ply areas, causing less
resistance to delamination crack propagations.
3.3. Through-thickness thermal conductivity modeling
Through-thickness thermal conductivity can be simply modeled
by the Landau and Lifshitz models based on the material thermal
conductivities and their interactions [26,27].
20 40 60 80 100 120 140 160
0.0
0.5
1.0
1.5
2.0
2.5
T
h
e
r
m
a
l

D
i
f
f
u
s
i
v
i
t
y

(
m
m
2
/
s
)
Temperature (
o
C)
EWC300X/Epon862
ns-EWC300X/Epon862
ms-EWC300X/Epon862
mns-EWC300X/Epon862
(a)
20 40 60 80 100 120 140 160
0
1
2
3
4
5
6
7
EWC300X/Epon862
ns-EWC300X/Epon862
ms-EWC300X/Epon862
mns-EWC300X/Epon862
T
h
e
r
m
a
l

C
o
n
d
u
c
t
i
v
i
t
y

(
W
/
(
m
K
)
)
Temperature (
o
C)
(b)
Fig. 4. Comparison of (a) thermal diffusivity and (b) conductivity of the EWC300X/Epon862 ns-CFRP, ms-CRRP, mns-CFRP, and CFRP control samples with the densities of
2.21 g/cm
3
, 1.99 g/cm
3
, 2.18 g/cm
3
and 1.70 g/cm
3
, respectively.
S. Wang et al. / Composites: Part B 61 (2014) 172180 175
0.0
0.2
0.4
0.6
0.8
1.0
1.2
IM7/Epon862 (Control)
ms-IM7/Epon862
mns-IM7/Epon862
T
h
e
r
m
a
l

d
i
f
f
u
s
i
v
i
t
y

(
m
m
2
/
s
)
Temperature (
o
C)
(a)
20 40 60 80 100 20 40 60 80 100
0.0
0.5
1.0
1.5
2.0
T
h
e
r
m
a
l

C
o
n
d
u
c
t
i
v
i
t
y

(
W
/
(
m
K
)
)
Temperature (
o
C)
IM7/Epon862 (Control)
ms-IM7/Epon862
mns-IM7/Epon862
(b)
Fig. 5. Comparison of (a) thermal diffusivity and (b) conductivity of the IM7/Epon862 ms-CRRP, mns-CFRP, and CFRP control samples with the densities of 1.46 g/cm
3
, 2.01
g/cm
3
, and 2.11 g/cm
3
, respectively.
Fig. 6. Cross-sectional morphologies of (a) IM7 PAN-based and (b) EWC300 pitch-based carbon bers.
Fig. 7. Morphologies of (a) ber connection by silver nanoparticle coated on bers surfaces and (b) their distribution crossing the ber tow cross-section in the composites.
Fig. 8. Morphologies of silver ake lled composites: (a) continuous interply conduction path and (b) partly agglomerated silver akes.
176 S. Wang et al. / Composites: Part B 61 (2014) 172180
k
n
c
k
n
f
/
f
k
n
m
1 /
f
1 n 1 2
where k
c
, k
m
, and k
f
are the thermal conductivities of the composite,
matrix and ller. /
f
is volume fraction of ller. According to Eq. (2),
when n = 1, thermal conductivity k
c
of a two-phase mixture can be
written in parallel conduction model, which predicts the maximum
thermal conductivity:
k
c
k
f
/
f
k
m
1 /
f
3
When n approaches to zero, geometric mean model was given as
follows:
k
c
k
/
f
f
k
1/
f

m
4
For n = 1, a series conduction model can be yielded:
1
k
c

1 /
f

k
m

/
f
k
f
5
which provides the minimum thermal conductivity estimation. The
laminated composite structure can be treated as a simple series
conduction model with the unit of fabric ply. Individual ply parallel
conduction was established with the two units of ber tows and in-
ter-tow resin rich area. Along the through-thickness direction, there
was no continuous conductive path due to resin rich areas among
the ber tows and interlaminar resin gaps native to the construc-
tion of the composites. These resin rich areas supplied space for
highly conductive llers to construct effective through-thickness
conductive paths. Large size llers bridged the large resin rich areas
among ber tows and interlaminar areas, and smaller size llers
penetrated the ber tow.
The thermal conductivity of silver lled composites can be esti-
mated by Eqs. (3) and (4). Investigating the mns-EWC300/Epon862
composite with the density of 2.18 g/cm
3
for example, the volume
fraction of silver was calculated as 5.1 v% based on TGA analysis
and the respective densities of silver, ber and resin. The thermal
conductivity of ber and resin composition was equivalent to con-
trol sample: 1.96 W/(m K). Silver possesses a thermal conductivity
of 429 W/(m K). The thermal conductivity based on geometric
mean model assuming homogeneously distributed discontinuous
conductive llers was calculated as 2.56 W/(m K) for mns-CFRP
with the density of 2.18 g/cm
3
, which was much lower than the
experimental result of 6.62 W/(m K). However, the experimental
results were much lower than the estimated 23.2 W/(m K) calcu-
Fig. 9. Heterogeneous distribution of nanoscale and microscale silver in mns-CFRP.
0
1
2
3
4
T
h
e
r
m
a
l

D
i
f
f
u
i
v
i
t
y

(
m
m
2
/
s
)
Temperature (
o
C)
mns-EWC300X/Epon862 (5.5 v% Silver)
mns-EWC300X/Epon862(15.5 v% Silver)
20 40 60 80 100 120 20 40 60 80 100 120
0
3
6
9
12
15
mns-EWC300X/Epon862 (5.5 v% Silver)
mns-EWC300X/Epon862 (15.5 v% Silver)
T
h
e
r
m
a
l

C
o
n
d
u
c
t
i
v
i
t
y

(
W
/
(
m
K
)
)
Temperature (
o
C)
Fig. 10. Thermal diffusivity and conductivity of EWC-300X/Epon862 with silver fractions of 5.5 v% and 15.5 v%.
S. Wang et al. / Composites: Part B 61 (2014) 172180 177
lated from the parallel conduction model, which is based on full
continuous silver conductance path assumption. This result
indicated some through-thickness continuous conduction paths
were established by the silver materials, forming heterogeneous
structure in the composites, which is in agreement with the estab-
lishment of heterogeneously conductive paths in the composites as
shown in Fig. 9.
3.4. Hybridization to tailor thermal conductivity and mechanical
properties
3.4.1. TTTC of IM7/EWC300X fabric hybrid composite
In order to obtain the synergy of high mechanical performance
of IM7 composites and high conductivity property of EWC300X
composites, a hybrid IM7/EWC300X composite was explored.
Fig. 11 compared the thermal conductivity of IM7/Epon862 and
EWC300/Epon862 composites, as well as their hybrid compos-
ites-IM7/EWC300/Epon862. The hybrid composite was prepared
following the ply stacking sequence [IM7
2
/EWC300X]
S
. These sam-
ples were lled with both nanoscale and microscale silver particles
or mns-type according to our sample design. The density was
2.17 g/cm
3
and silver fraction is 5.7 v%. We can see that the hybrid
composite showed a thermal conductivity of 4.27 0.39 W/(m K),
which is in between 1.96 W/(m K) of IM7/Epon862 composite
and 6.62 W/(m K) of EWC300X/Epon862 with 5.5 v% silver load.
The thermal conductivity results illustrate that it is effective to
improve IM7 composite conductivity through the hybridization
approach. The volume fraction ratio of EWC300X to IM7 was
approximate 3:2. According to Eq. (5) the calculated thermal
conductivity was 3.39 W/(m K) lower than experimental result,
suggesting a positive hybrid effect.
3.4.2. Tensile property characterization
Fig. 12 shows typical tensile stressstrain curves of the silver
lled IM7/Epon862 and control composites. The densities of IM7/
Epon862 control, ms-CFRP, ns-CFRP and mns-CFRP composites
were 1.46, 2.01, 1.99, and 2.11 g/cm
3
, respectively. The tensile
stress was almost linearly proportional to the strain until failure
for all four kinds of specimens. Table 1 shows the resultant tensile
strength and modulus properties. The control sample had a tensile
strength of 730.2 MPa and a modulus of 60.1 GPa. The ms-CFRP
exhibited a similar strength of 724.9 MPa and modulus of
55.3 GPa. This was due to the silver akes mainly distributed in
resin rich area, which did not affect the load bearing capability of
carbon bers. With the application of nanoscale silver, an audible
cracking sound could be heard during the tests in the linear phase
of the stressstrain curves. The tensile strength and modulus of
ns-CFRP and mns-CFRP decreased to 621.2 MPa and 639.1 MPa,
respectively. Nanoscale silver coating reduced the interface bond-
ing with the resin matrix and decreased load transfer within the
sample. Compared with the control sample, tensile strength and
modulus of the mns-CFRP samples decreased about 12.5% and
13.6%, respectively.
Fig. 13 shows the tensile stressstrain curves of the IM7/
Epon862, EWC300X/Epon862 and IM7/EWC300X/Epon862 com-
posites and their heterogeneously lled counterparts. The resul-
tant EWC300/Epon862 composite showed a lower strength of
324.1 MPa and higher modulus of 91.2 GPa than the IM7/Epon862
composite. Both IM7 and EWC300X composites experienced a
brittle failure mode. After applying silver materials, the tensile per-
formance of the nms-EWC300X/Epon862 and mns-IM7/Epon862
composite noticeably decreased. The IM7/EWC300X/Epon862
hybrid composite with a lay-up of [IM7
2
/EWC300X]
S
showed a
stage-wise stressstrain curve. The modulus of the hybrid compos-
ites was between the mns-IM7 and EWC300X composites in the
0 20 40 60 80 100
0
2
4
6
8
10
T
h
e
r
m
a
l

C
o
n
d
u
c
t
i
v
i
t
y

(
W
/
(
m
K
)
)
Temperature (
o
C)
mns-IM7/Epon862
mns-IM7/EWC300X/Epon862
mns-EWC300X/Epon862
Fig. 11. Comparison of IM7/Epon862 and EWC300X/Epon862 composites, and IM7/
EWC300X/Epon862 hybrid composite with approximate 5 v% nanoscale and
microscale silver llers.
0.0 0.4 0.8 1.2
0
200
400
600
800
S
t
r
e
s
s

(
M
P
a
)
Strain (%)
IM7/Epon862 (Control)
ms-IM7/Epon862
ns-IM7/Epon862
mns-IM7/Epon862
Fig. 12. Typical stressstrain curves of the silver lled and control IM7/Epon862
composite.
Table 1
Tensile performances and through-thickness thermal conductivities of IM 7/862, EWC300/862 and their hybrid composites.
Density (g/cm
3
) Silver fraction (v%) Thermal conductivity (W/(m K)) Tensile strength (MPa) Tensile modulus (GPa)
IM7/Epon862 1.46 0 0.72 0.06 730.2 25.4 60.1 2.1
ms-IM7/Epon862 2.01 5.3 1.21 0.09 724.9 20.3 55.3 2.9
ns-IM7/Epon862 1.99 5.2 1.17 0.08 621.2 18.4 44.0 3.1
mns-IM7/Epon862 2.11 5.5 1.86 0.11 639.1 10.5 51.9 5.1
EWC300X/Epon862 1.70 0 1.96 0.20 324.1 19.6 91.2 5.2
mns-EWC300X/Epon862 2.18 5.1 6.62 0.51 222.5 17.9 82.2 4.7
IM7/EWC300X/Epon862 1.60 0 1.28 0.08 373.2 19.4 74.1 4.3
mns-IM7/EWC300X/Epon862 2.17 5.7 4.27 0.39 309.3 12.8 61.2 5.4
178 S. Wang et al. / Composites: Part B 61 (2014) 172180
initial stage. EWC300X layer rst failed due to its smaller ber
elongation, while the IM7 bers with higher strength held the
tensile load until the sample nal fracture. This phenomenon
was similar with the IM600 carbon/K13D pitch-based ber hybrid
composite reported by Naito [28]. The silver lled hybrid compos-
ites exhibited a similar tendency, but with much lower perfor-
mance. The resultant tensile and thermal conductivity are
summarized in Table 1. Both tensile and thermal conductivity
performance of IM7/EWC300X hybrid composite were in between
IM7 and EWC300X composite. The results indicated that hybrid
composite inherited the excellent tensile performance of IM7 com-
posite and superior thermal conductivity of EWC300X composite.
4. Conclusions
This research attempted to enhance the through-thickness ther-
mal conductivity of laminated graphite ber fabric reinforced com-
posites by applying nanoscale and microscale silver particles to
construct heterogeneous thermally conductive paths along the
composites through-thickness direction. By separately applying
5.0 v% microscale silver akes and nanoscale silver particles, the
TTTC of EWC300X/Epon862 composite increased from 1.96 W/
(m K) of the control sample to 3.51 and 4.33 W/(m K), respectively.
The corresponding morphology indicated that microscale silver
akes were distributed within the inter-tow area, while nanoscale
silver particles penetrated into the ber tows and formed a coating
layer on the ber surfaces through sintering. Neither ller alone
can form continuous conductive paths due to their size limitations.
A higher conductivity of 6.62 W/(m K) of EWC300X/Epon862 com-
posites under a similar total silver volume fraction of approxi-
mately 5.0 v% can be achieved from the formation of continuous
through-thickness conduction paths by jointly applying nanoscale
and microscale silver particles and sintering them partly. The TTTC
increased with increasing silver volume fraction, and a TTTC of
10.61 W/(m K) was achieved with the silver volume fraction of
15.0 v% in EWC300X/Epon862 composite. The mns-IM7/Epon862
composite with 5.5 v% silver exhibited lower thermal conductivity
of 1.86 W/(m K) than the EWC300X pitch-based ber composites
due to the low thermal conductivity of IM7 ber. Hybrid IM7/
EWC300X composites were explored to seek the synergy of IM7
composites higher mechanical properties and EWC300X compos-
ites attractive thermal conductivity. The hybrid composites with
a silver volume fraction of 5.7 v% demonstrated promising thermal
conductivity of 4.27 W/(m K) and only approximately 17% reduc-
tion of tensile performances compared with control sample. Fur-
ther study to optimize the heterogeneous microstructure and
improve interfacial bonding between the silver llers and resin
matrix in the hybrid composites could lead to attractive structural
carbon ber composites with thermal management
multifunctionality.
Acknowledgements
This effort was performed under contract AFOSR STTR#
FA9550-11-C-0081. We would like to thank the management and
guidance provided by Mr. Roger Gerzeski from AFRL/RX and Dr.
Joycelyn Harrison from AFOSR.
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