Composites: Part A 33 (2002) 53±62

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Processing and characterization of aligned vapor grown carbon ®ber

reinforced polypropylene
Rex J. Kuriger a, M. Khairul Alam a,*, David P. Anderson b, Ronald L. Jacobsen c
a
Department of Mechanical Engineering, 251 Stocker Center, Ohio University, Athens, OH 45701-2979, USA
b
University of Dayton Research Institute, 300 College Park, Dayton, OH 45469, USA
c
Applied Sciences, Inc., 141 W. Xenia Avenue, Cedarville, OH 45314, USA
Received 25 August 2000; revised 26 February 2001; accepted 9 March 2001

Abstract
This investigation describes a method for aligning vapor grown carbon nano-®bers suspended in a polymer ¯ow during extrusion to
produce an improved thermoplastic composite. A twin-screw extruder was used to shear mix and extrude ®ber/polypropylene mixtures
through a converging-annular die that generates ®ber alignment along the ¯ow direction. The degree of ®ber alignment was quanti®ed by
using X-ray diffraction. It was shown that ®ber alignment could be improved by increasing the residence time in the die channel. Tensile
specimens were fabricated by molding the extruded strands and the strength properties of the aligned samples increased with ®ber content.
The tensile strength improved with greater ®ber orientation, however, more ®ber alignment had little affect on the modulus. The addition of
vapor grown carbon nano-®ber also increased the thermal conductivity and decreased the electrical resistivity. Published by Elsevier Science
Ltd.
Keywords: A. Discontinuous reinforcement; A. Polymer±matrix composites (PMCs); B. Anisotropy; E. Extrusion

1. Introduction in cost. The high cost of producing carbon ®bers is the

There are currently many types of reinforcing ®bers used
in composite materials. Glass ®bers are the most common
reinforcing ®bers for polymer matrix composites due to
their low-cost and high strength, and are used in many
high-volume applications, particularly the automotive
industry. The disadvantages of glass ®bers are that they
have a relatively low modulus and poor abrasion resistance,
which decreases its potential strength, and poor adhesion to
polymer matrix resins, especially in the presence of moist-
ure. Other composites made from carbon, aramid, boron, or
other high modulus ®bers are used primarily for more exotic
aerospace and military applications where their higher costs
can be justi®ed by improved performance. Carbon ®bers are
currently the most widely used advanced ®bers and are
generally manufactured by the pyrolysis of a polyacryloni-
trile (PAN) or a pitch precursor. They also have the highest
speci®c strength and speci®c modulus of all reinforcing
®ber materials. When compared to glass ®bers, carbon ®bers
offer higher strength and modulus, lower density, outstand-
ing thermal and electrical conductivity, but are much higher
* Corresponding author. Tel.: 11-740-593-1558; fax: 11-740-593-0476.
E-mail address: alam@bobcat.ent.ohiou.edu (M.K. Alam).
1359-835X/02/$ - see front matter Published by Elsevier Science Ltd.
PII: S 1359-835 X(01)00 070-7
principle barrier prohibiting carbon ®ber reinforced compo-
sites from entering numerous commercial applications.
A method introduced by Tibbetts et al. [1] produces
carbon ®bers by a catalytic vapor deposition process from
hydrocarbons at signi®cantly lower costs. These nano-
®bers, known as vapor grown carbon ®bers (VGCF) are
highly graphitic with superior mechanical properties and
have good thermal and electrical conductivity. By being
more economically feasible, the low-cost VGCF has the
potential to override the cost barrier that has prevented
conventional carbon ®ber composites from entering into
cost-sensitive commercial markets. These composites
could ®nd their way into many new markets, particularly
the electronics, aerospace and automotive industries.
The bulk properties of composites are not only functions
of the ®ber and polymeric matrix materials, but also the state
of ®ber orientation. The greatest disadvantage of VGCF is
that the ®bers become aligned randomly and entangled
during production. Therefore, the most promising applica-
tions for this material would be in composites where the
reinforcement is oriented randomly in two or three dimen-
sions. Random orientation is not always undesirable, but
usually composites are designed to maximize performance
along a given direction. To achieve this objective, alignment
54 R.J. Kuriger et al. / Composites: Part A 33 (2002) 53±62
of the ®bers is necessary. This is an important issue with
regards to designing any short ®ber reinforced polymer
because numerous designs can utilize orientation to the
advantage of performance.
Much work has been done to control orientation of
discontinuous ®bers in composite materials. Die design for
an extrusion process can be altered to tailor the orientation
of the ®bers for particular applications. For instance, hollow
extrudates such as tubing products whose structures involve
stresses that require greater strength and stiffness in the
circumferential direction can be produced to withstand
such loading. Goettler et al. [2] developed an extrusion
process to obtain off axis orientation using a diverging die
channel so that the outlet area is at least two or more times
the inlet area of the die channel. This produced a substantial
improvement in physical properties in the hoop direction.
McPhee and Gray [3] developed an extruder head that
includes a doubled taper conical pin that orients ®bers of
an elastomer±®ber composite hose in the radial direction.
Jarrin et al. [4] also developed a die to improve burst
strength by orienting the ®bers in the circumferential
direction.
Numerous other ®ber-aligning techniques have been
developed for a broad range of products other than hollow
extrudates. For example, Morgan [5] reported an extrusion
apparatus having parallel top and bottom surfaces that
converges and has a diamond-shaped ¯ow bar for aligning
®bers during extrusion. Miani [6] used a two-component
extrusion head having a spinneret with high perforation
density and a distribution unit for introducing two reinfor-
cement components. An extrusion die for the extrusion of
continuous ®ber reinforced plastics was developed by El-
Sobky [7]. A twin-screw extruder was used by Michel [8] to
process a continuous carbon ®ber reinforced ¯uoropolymer
composite mixture, and by Sargent [9] to compound ther-
moplastic resin materials with randomly oriented ®bers. A
method to control the orientation of chopped ®bers by
subjecting the composite mixture to a drawing treatment
was introduced by Daimaru [10]. Finally, Tepic [11] utilized
sound waves and Knoblach [12] applied electric ®elds to
orient ®bers suspended in a matrix of a composite material.
Conventional chopped ®bers are generally straight and
have uniform diameters in excess of 5 mm and lengths
generally ranging from 0.1 to 13 cm. However, the end
product of procession VGCF is a discontinuous mass of
®bers with diameters of approximately 0.2 mm and typical
lengths ranging from 20 to 100 mm. The ®bers are entangled
in a loosely packed ®brous matrix giving them an extremely
low apparent bulk density (Fig. 1), thus making handling
and ®ber dispersion during composite processing a formid-
able challenge.
Since VGCF is generated in a different form than conven-
tional carbon ®bers, standard composite processing methods
may need to be modi®ed to accommodate VGCF compo-
sites. Dasch et al. [13] introduced a method to manufacture a
VGCF composite by combining the carbon ®bers with both
Fig. 1. Scanning electron micrograph of ¯oating catalyst VGCF.
polycarbonate and nylon resins. The mixtures were ®rst
vacuum dried at an elevated temperature and then mixed
in a Brabender mixing bowl at temperatures 10±208 above
the melting point of the resins. The material was then
compression molded into test specimens. A similar proce-
dure was used by Dasch and Alig [14]. The results showed
an increase in tensile and ¯exural strength from the matrix
strength for volume fractions below 30%. The tensile modu-
lus and ¯exural modules also increased with ®ber content.
Caldeira et al. [15] and Carneiro et al. [16] also studied
polycarbonate composites reinforced with VGCF. Both of
their ®ndings showed that the tensile properties of the poly-
carbonate were improved marginally by the addition of
VGCF, and that the impact resistance decreased by the
addition of the ®bers.
VGCF composites with epoxy and poly(phenylene
sul®de) matrices was studied by Patton et al. [17]. This
work indicates that mixing is a very important variable in
determining the quality of VGCF composites. Increases in
stiffness and ¯exural strength demonstrated that the discon-
tinuous randomly oriented VGCF has great potential for
composite reinforcement. Yamanashi et al. [18] also
analyzed the properties of epoxy composites embedded
with VGCF. Their tests showed that the tensile shear
strength of VGCF reinforced epoxy composites are far
superior to conventional short-®ber carbon reinforcement.
Tibbetts and McHugh [19] showed that the mechanical
properties of VGCF reinforced thermoplastics could be
improved by ball-milling the ®bers before blending them
with the polymer matrix. This breaks down the ®ber clumps
and increases the in®ltration of the matrix material during
processing (injection molding). It was also shown that in®l-
tration of the ®bers could be improved by processing under
higher pressures. The addition of 11.5% by volume VGCF
approximately doubled the tensile strength and modules of
pure polypropylene. Van Hattum et al. [20] also used a
polypropylene matrix to investigate the properties the
composites reinforced with PAN ®bers and VGCF. The
 R.J. Kuriger et al. / Composites: Part A 33 (2002) 53±62
strength of the VGCF reinforced composites was similar to
those reinforced with the PAN ®bers, however, the stiffness
was marginally lower.
It can be concluded that it is possible to produce a viable
randomly oriented VGCF composite. However, the issue of
anisotropy due to ®ber orientation was not addressed. Dutta
et al. [21] attempted to extrude a polycarbonate sheet with
aligned VGCF. The composite blends were extruded
through a rectangular die by a single screw plasticating
extruder. Uniaxial alignment of the ®bers along the extru-
sion direction was produced by melt-drawing the ®lm as it
exits the die. The anisotropic ®lms could then be used as
prepegs to fabricate laminated composites. Their results
showed that it was dif®cult to disperse the VGCF because
the ®bers tend to agglomerate, especially as ®ber content
increases; thus inhibiting ®ber alignment. It was suggested
by Dutta et al. [21] that ®ber dispersion could be improved
by starting with a more homogeneous dry composite
mixture and melt blending the components in a mixer before
extrusion.
This paper introduces a method to produce an improved
anisotropic composite by alignment of VGCF suspended in
a polymer ¯ow during extrusion. The degree of ®ber align-
ment and the properties of the resultant composite products
are then evaluated.
2. Experimental
2.1. Materials
The VGCF used for this study was catalytically grown by
the vapor deposition process described by Tibbetts et al. [1].
The ®bers (Pyrografe III) had a diameter of about 0.2 mm
and lengths ranging from 20 to 80 mm [22], and were
supplied by Applied Sciences, Inc. (ASI, Cedarville, OH).
Two kinds of VGCF were used. The ®rst type, labeled PR-
21-PS was pyrolytically stripped to enhance interfacial
bonding and physical compatibility between ®bers and
matrix, thus providing high mechanical strength in compo-
sites. A second type labeled PR-19-HT was heat-treated at
30008C to improve the graphitic crystallite structure of the
®ber, thus increasing its conductive properties. Because of
these attributes, all of the tensile strength and modulus
measurements presented in this study were carried-out
using the PR-21-PS reinforced samples, whereas, the
PR-19-HT ®ber was used in samples tested for thermal
conductivity and electrical resistivity.
Both the PR-21-PS and the PR-19-HT ®bers have low
bulk densities of approximately 56 and 200 kg/m 3, respec-
tively [22]. The low apparent density of the ®bers is
attributed to the randomly entangled formation during
production (Fig. 1). The ®bers were dried in a vacuum
oven at approximately 3008C for 3 h to assure the removal
of moisture and volatiles. They were then thoroughly mixed
in a dual-shell dry blender with Pro-Fax 6301, a polypropy-
55
Fig. 2. Side view of extruder die.
lene homopolymer in powered form manufactured by
Montell U.S.A. Inc., until a homogeneous mixture is
formed.
2.2. Composite processing
After dry blending the ®ber/polymer mixture, a Leistritz
LSM 30.34 twin-screw laboratory extruder was used to
process the mixtures containing various ®ber volume
fractions. The composite mixtures were high shear mixed
by the intermeshing, counter-rotating extruder screws,
which helped disperse and in®ltrate the VGCF bundles. A
venting type screw con®guration was used. It consisted of a
feeding zone, a compression zone, a conveying zone, a
shearing zone, a venting zone, and a metering zone. A
vacuum pump was attached to the venting block. The
composite material was extruded with a melt temperature
of approximately 280±2908C and screw speed of 80 rpm.
A die with a 2 mm diameter opening was designed to
produce a continuous, uniform diameter composite strand
with the ®ber reinforcement aligned in the extruded direc-
tion (Fig. 2). The temperature of the die was set at 1808C.
This die con®guration generates a high degree of ¯ow-
induced ®ber alignment by taking advantage of two distinct
¯ow regimes that affects ®ber orientation. First, the die
inlet initiates a converging ¯ow pattern that aligns the ®bers
along the streamline direction (extrusion ration < 48). This
¯ow pattern is then transformed into shear ¯ow while
entering a 1.25 cm long annular portion of the die. The
shear ¯ow produces additional ®ber alignment due to the
differential shear rate along the boundary layer that orients
the ®bers in the direction of ¯ow.
The process is continuous and the composite strand is
collected and kept in constant tension (with minimal
reduction in the 2 mm strand diameter) by a pulling device
until the composite solidi®es due to air cooling. The strand
then passes through the puller mechanism and is collected
by a ®ber-winder. This process is shown in Fig. 3. The
56 R.J. Kuriger et al. / Composites: Part A 33 (2002) 53±62

can then be calculated using

Fig. 3. Extrusion process for uniform diameter composite strand.
thermoplastic strands embedded with aligned ®bers can now
be reprocessed by any suitable means such as hot-pressing
and compression molding to form a functional composite
component with directional reinforcement.
2.3. Testing procedures
k ˆ aC c r c …1†
where Cp and r c is the speci®c heat and density of the
composite material, respectively. The density of the compo-
site material with a ®ber volume fraction Vf can be found by
simply using the rule of mixtures
rc ˆ Vf rf 1 …1 2 Vf †rm …2†
The ®ber density r f is known to be 2100 kg/m [23], 3
whereas the polypropylene has a density (r m) of 900 kg/
m 3 [24]. In a similar fashion, the heat capacity can be
found by

Test samples were prepared by cutting and placing the 1

Cc ˆ ‰V r C 1 …1 2 Vf †rm Cm Š …3†
strands in a unidirectional manner into a 10 £ 20 cm 2 mold rc f f f
with a temperature of approximately 2308C. The strands
In this expression, the speci®c heat of the ®ber (Cf) and the
were then slowly hot-pressed into a 2±3 mm thick sheet.
matrix (Cm) is 700 and 2100 J/kg K, respectively.
The mold was then submerged immediately into a cold-
To analyze the electrical conductivity of the cube speci-
water bath to help prevent crystallization during solidi®ca-
mens, they were ®rst machined square. As with the thermal
tion. Entrapment of air pockets or voids was a problem
conductivity measurements, the longitudinal (r L) and trans-
during initial trial runs, especially in the areas at the center
verse (r T) directions of the cubes were tested. The analysis
of the mold. The molding of specimens with higher ®ber
was performed by applying a uniform layer of Pelco
contents (.10% Vf) was challenging because the ®bers
Conductive Silver 415 (supplied by Ted Pella, Inc.) to the
increased the viscosity of the mixture, thus making it
opposing faces of the cube along the test direction. Electri-
more dif®cult for the air pockets to escape. In order to
cal leads were also bonded to the surfaces by coating them
alleviate this problem, the molding process was performed
with the conductive silver and holding them against the
in an evacuated chamber.
faces of the cube until the silver paint dried. This eliminates
Tensile test specimens were formulated with the PR-21-
contact resistance of the probes and allows for a two-point
PS ®ber containing volume fractions ranging from 1 to 11%.
measurement to be performed using a digital multimeter.
To prepare tensile test specimens, rectangular strips were
Since composite properties are directly affected by ®ber
then sawed from the composite sheets along the preferred
orientation, it would be helpful to quantify the amount of
direction. The strips were then machined in a router ®xture
alignment produced by the extrusion process, and to deter-
conforming to ASTM D638 Type II speci®cations. The
mine the ®ber misalignment caused by the molding process.
ultimate tensile strength and modulus was then measured
X-ray diffraction was employed for this purpose. Some of
and recorded by a Tinius Olsen bench-top testing machine
the X-ray diffraction data was collected at Beam line X27C
equipped with a Keithley data acquisition system with an
at the National Synchrotron Light Source, Brookhaven
extension rate of 4 mm/min.
National Laboratory. This Beam line used double crystal
To evaluate the thermal and electrical conductivity of the
monochromated synchrotron radiation at a wavelength of
aligned VGCF composites, the molded sheets containing 9±
0.1307 nm incident to the sample with ¯at-®lm Laue data
23% volume PR-19-HT ®bers were cut into 2.5 cm by
collected by an image plate. Other X-ray diffraction studies
3.8 cm rectangular pieces. These individual rectangular
were carried out using a Huber 4-circle X-ray diffractometer
composite pieces were then stacked into a 2.5 cm by
in symmetric transmission with an incident beam crystal
3.8 cm mold (typically 5±7 pieces) and hot-pressed again
monochromated CuKa radiation (wavelength ˆ 0.15418
using the same procedure performed on the sheets, thus
nm) from a Rigaku RU-200 rotating anode generator at a
producing an anisotropic composite cube.
power of 45 kV and 70 mA.
Thermal conductivity measurements were made using a
Holometrix m Flash Thermal Properties Instrument. Disc-
shaped test samples (12.5 mm diameter ad 2 mm thick) 3. Theoretical modeling
were machined from the cubes to ®t the instrument's sample
holder. The thermal conductivity in both the longitudinal 3.1. Ultimate tensile strength and modulus
(kL) and transverse (kT) directions of the cubes was tested.
The results from several measurements were averaged to To verify experimental results, a theoretical model devel-
obtain the values of thermal diffusivity for composite oped by Baxter [25] was used to predict the ultimate tensile
material along each particular direction. By knowing the strength of the composite specimens. This method was used
thermal diffusivity value, the effective thermal conductivity by Tibbetts and McHugh [19] to predict the strength of
 R.J. Kuriger et al. / Composites: Part A 33 (2002) 53±62
ball-milled VGCF-reinforced nylon and polypropylene
composites. The model includes three failure mechanisms:
longitudinal ®ber failure, interfacial shear failure, and
matrix failure. These are incorporated into the Tsai-Hill
criteria for failure [26,27] to predict the composite strength
(s ) with ®bers randomly oriented in the plane as a function
of angle (u ) between the ®ber direction and the applied
stress. The strength is given by
" ! #21=2
cos 4 u 1 1 2 2 sin4 u
s…u† ˆ 1 1 2 sin ucos u 1
s L2 t2 sL s T2
…
In this expression, s T represents the transverse tensile
strength of the composite and is set equal to the matrix p
strength, whereas the shear strength t is taken as 1= 3
times the matrix strength which allows s to equal the matrix
strength at zero volume fraction. The longitudinal tensile
strength (s L) is found by using the rule of mixtures and
the shear lag model of Kelly and Tyson [28], which yields
l aligned ®bers (1-D), randomly oriented in the plane (2-D),
s L ˆ Vf s f 1 …1 2 Vf †s m …
2lc
where Vf is the ®ber volume fraction; lc the critical ®ber
length; l the average ®ber length; s f the ®ber strength;
and s m is the matrix strength. The longitudinal tensile
strength given by Eq. (5) is for a composite with ®bers of
an average length (l) less than the critical ®ber length (lc). It
is known that the critical ®ber length/®ber diameter (lc/d)
ratio is approximately equal to 100 [29], therefore the criti-
cal ®ber length, lc is 20 mm (d ˆ 0.2 mm).
The average length of the ®bers was found by performing
a transmission electron microscopy (TEM) analysis on each
of the composite samples. This was accomplished by
removing the polypropylene matrix from the samples by
heating them in an oven at approximately 4008C for 2 h in
argon. A small amount of ®bers was then dispersed in an
alcohol suspension and viewed on a 3000 mesh grid. From
the micrographs in the regions where the ®bers were
dispersed, the ®ber length distribution was found by deter-
mining the lengths of several ®bers from composite samples
from multiple experimental runs [30]. A typical distribution
curve is shown in Fig. 4, where the average ®ber length (l)
was found to be approximately 10.42 mm.
The issue of `appropriate values' for the strength and
modulus of Pyrograf IIIe is dif®cult to resolve since direct
measurement are not possible. Tibbetts and McHugh [19]
used a value of 2.92 and 240 GPa for the strength and modu-
lus of Pyrograf IIIe, respectively. However, a more recent
study [31] found that the strength of Pyrograf III e varied
from 2.0 to 4.5 GPa and the modulus varied from 200 to
240 GPa. Therefore, theoretical calculations were evaluated
with an average ultimate ®ber strength (sf) of 3.25 GPa and
modulus (Ef) of 220 GPa.
The strength of the polypropylene matrix (sm) was
measured by testing specimens processed under the same
57
4†
Fig. 4. Distribution of ®ber lengths after composite processing.
conditions as those used to produce the composite samples
and had an average value of 30 MPa. Average theoretical
strength calculations were made for composites with
5† and randomly oriented in three dimensions (3-D) by numeri-
cally integrating Eq. (4).
The stiffness for the composites was predicted using the
Cox [32] model in which
 
tanh b
E c ˆ …1 2 Vf †Em 1 n 1 2 V f Ef …6†
b
where n ˆ 1/6 is for ®bers randomly oriented in three
dimensions, n ˆ 1/2 for ®bers randomly oriented in the
plane, and n ˆ 1 for aligned ®bers. The matrix stiffness
(Em) and was found to be 1.1 GPa. The factor b is taken as
s
1 Em
bˆ …7†
d …1 1 n†Ef ln…p=4Vf †
where l is the average ®ber length, d the ®ber diameter, and
Poisson's ratio (n ) equal to 0.38 [29].
4. Results and discussion
4.1. X-ray diffraction analysis
From X-ray diffraction, it is possible to measure the
graphene alignment, which is taken as the full-width of
the (00,2) graphitic plane azimuthal diffraction measured
at one-half the maximum intensity peak of the diffraction
pro®le de®ned by the Gaussian distribution equation. This
measurement is usually designated as `Z' and given in
degrees. This value characterizes the distribution function
of the ®ber orientation [33]. This value will also be used as a
measure of misalignment and should be thought of as a cone
angle since the alignment is in three dimensions. The value
should be halved if one wished to think of how far from the
preferred axis that most of the ®bers are aligned.
When this measurement is made on a composite
58 R.J. Kuriger et al. / Composites: Part A 33 (2002) 53±62

908 corresponds to the transverse direction of the composite

materials. If the ®bers are aligned, the intensity of the
diffraction pattern at high angles should be very low,
whereas the intensity in the preferred direction (08) should
be relatively high. The leveled intensity at ^908 is the back-
ground intensity. This can be seen in Fig. 5(a)±(c), where
the ®bers are oriented ^23.7, ^28.15 and ^30.08 along the
preferred direction for the 2.5, 7 and 11% specimens,
respectively.
From the ®gures it is seen that the degree of ®ber align-
ment tends to decrease as the ®ber content increases. As the
®ber/polymer mixture is extruded through the converging
annular die several factors affect the state of orientation of
®bers suspended in the polymer matrix. Fiber geometry,
®ber±®ber and ®ber±wall interactions, the suspending
¯uid rheology, and the ¯ow ®eld all have a direct effect
on ®ber orientation [34]. As the composite blend is
processed through the die, the ®bers suspended in a ¯owing
¯uid are subjected to local velocity gradients in the ¯uid.
These gradients cause a ¯uid element to stretch and rotate,
thus causing the ®ber to rotate in the preferred direction.
However, as the ®ber volume fraction was increased, the
amount of ®ber±®ber interaction and ®ber±wall interaction
also increased. This hinders the ®bers' ability to orient
themselves along the preferred direction in the ¯ow ®eld.
The amount of ®ber alignment along the preferred, extru-
sion direction can be improved by increasing the residence
time of the composite ¯ow through the die channel. The
strain ®eld is able to align the ®ber better with a larger
residence time. To demonstrate this effect, an extended
annular nozzle (length ˆ 5.25 cm) was attached to the
extruder die as shown in Fig. 6.
Composite specimens were extruded through this die
con®guration under the same conditions as those processed
by the die with no nozzle. This results in a composite
product with a higher degree of ®ber alignment along the
extrusion direction. This can be seen in Fig. 7, which gives
the diffraction pro®le for a 2.5% volume VGCF specimen.
Fig. 5. X-ray diffraction intensity versus azimuthal angle measured from the
preferred axis of polypropylene reinforced with various amounts of
partially aligned VGCF. (a) 2.5% ®ber volume fraction. (b) 7% ®ber
volume fraction. (c) 11% ®ber volume fraction.

specimen, a measure of the alignment of the ®bers can be

obtained from the graphene alignment within the composite.
Some of the spread in the azimuthal intensity is from misa-
lignment of the graphene planes but the remainder is from
the misalignment of the ®bers within the strand. Therefore, a
relative amount of alignment can be inferred from this
measurement. Fig. 5(a)±(c) show the X-ray diffraction
pro®les of composite samples containing 2.5, 7 and 11%
VGCF by volume.
The intensity of the X-ray diffraction at different angles
indicates the distribution of ®ber orientation in the compo-
sites. The specimens were tested so the 08 azimuthal angle
corresponds to the preferred (longitudinal) direction, and Fig. 6. Side view of extruder die with an extended nozzle.
 R.J. Kuriger et al. / Composites: Part A 33 (2002) 53±62
Fig. 7. X-ray diffraction intensity versus azimuthal angle measured from the
preferred axis of a 2.5% volume VGCF-reinforced specimen extruded
through an extended nozzle.
It can be seen from Fig. 7 that the ®bers are oriented
within ^15.08 along the preferred direction when the resi-
dence time is increased by extruding through the die with a
5.25 cm long nozzle. This is a 58% increase in the alignment
when compared with the specimens extruded without the
nozzle, which aligned the ®bers ^23.78 along the preferred
axis.
Table 1 shows the degree of ®ber orientation for strands,
sheets, and cubes produced by the extrusion and molding
process. The deformation of the composite strands when
consolidated by the molding procedure can cause a certain
degree of misalignment. This was seen to be the case by
performing X-diffraction analysis on the products, and the
results are shown in Table 1.
4.2. Mechanical properties
The dependence of the tensile strength and modulus on
®ber content for the composites reinforced with the partially
aligned PR-21-PS ®ber are shown in Figs. 8 and 9. The
results are given with values from injection molded samples
reported by Van Hattum et al. [20] and Tibbetts and
McHugh [19]. The experimental data from Tibbetts and
McHugh is for `ball-milled CO2 etched' samples that are
very similar to PR-21-PS used for this study [22]. Both the
tensile strength and modulus for the samples reinforced with
partially aligned ®bers increased with ®ber volume fraction.
The tensile strength increases as the ®bers become more
aligned by extruding through the 5.25 cm nozzle attach-
ment. With 11% ®ber volume content, there was a 20%
increase in strength when compared to the specimens
Table 1
Fiber orientation along the preferred axis of the composite materials
Fiber fraction
2.5% 7% 9% 11% 17% 23%
Strand (degrees) ^22.6 ^26.3 ^28.3 ^30.0 ^30.6 ^34.7
Sheet (degrees) ^26.5 ^29.0 ± ± ± ±
Cube (degrees) ± ± ^36.5 ± ^38.7 ^50.1
59
Table 2
Void content in the composite samples after processing
Fiber volume fraction
5% 9% 17% 23%
Void content (%) 0.92 1.03 1.72 2.23
extruded without the nozzle attachment, and more than
double the strength of the polypropylene. As the ®ber
content is increased, the strength of the samples diverges
from the 1-D theoretical model. This occurs because the
degree of ®ber alignment decreases as the ®ber loading
increases (Table 1); this may also be due to an increase in
stress concentrations and void content [35]. In order to
determine void content in the samples, the ASTM D2734
Method A guideline was used and the results are shown in
Table 2. The void content is not excessive because the twin-
screw extruder provides high shear and high extrusion
pressures.
The maximum variation of the experimental strength data
given in Fig. 8 was ^5.1% from the average for the 5.25 cm
nozzle, and ^6.1% for the 1.25 cm nozzle. In Fig. 9, the
maximum variation of the experimental modulus data was
^5.8% from the average for the 5.25 cm nozzle and ^6.8%
for the 1.25 cm nozzle.
The strength of the aligned ®ber composites was greater
than that predicted by the two and three-dimensional
randomly oriented models, as well as the experimental
results of Van Hattum et al. [20] and Tibbetts and McHugh
[19]. From Fig. 9 it is seen that there were generally no large
differences between the stiffness of the aligned samples
when compared with the results of randomly oriented ®ber
composites from the other studies, and the samples extruded
through the nozzle attachment. The stiffness increased with
®ber volume fraction; the addition of 11% by volume VGCF
approximately tripled the tensile modulus of pure polypro-
pylene. However, at higher ®ber loading the modulus is
closer to the theoretical value for 3-random ®ber orientation.
Such behavior was also reported by Tibbetts and McHugh
[19]. Previous studies [30] have shown that there is inade-
quate wetting of the ®bers as well as an increase in void
concentration at higher ®ber loading.
4.3. Thermal conductivity and electrical resistivity
Many theories have been developed for predicting the
thermal conductivity of composite materials [36,37] with
continuous ®bers or isotropic reinforcements. Since VGCF
is composed of an annular geometry parallel to the ®ber
axis, the conductive properties along the ®ber axis are
very different from the transverse direction (up to
2000 W/m K in the axial direction versus 10±110 W/m K
in the transverse direction). This makes it dif®cult to apply
the existing models to VGCF composites. Most of the
simple models for calculation of thermal conductivity of
60 R.J. Kuriger et al. / Composites: Part A 33 (2002) 53±62

Fig. 8. Ultimate tensile strength of polypropylene composites reinforced with partially aligned and randomly oriented VGCF at various ®ber volume fractions.

composites used by other investigators [13,17] tend to over
predict the thermal conductivity of VGCF composites. If
Cox's model [13] or the simple rule-of-mixtures [17] is
applied to this non-isotropic ®ber composite, the theoretical
value for thermal conductivity would be much higher than
the experimental results. The results presented in the study
were best predicted by the semi-theoretical Lewis and Niel-
sen model for uniaxially oriented ®bers [38]. However, it
can be seen from Fig. 10 that there are signi®cant differ-
ences between theory and experiment, particularly in the
transverse direction. This occurs because of the anisotropic
characteristics of VGCF, and the fact that the ®bers are not
perfectly aligned in the longitudinal direction. Therefore, a
more comprehensive model for thermal conductivity must
be developed for anisotropic, partially aligned, discontinu-
ous ®ber composites.
The thermal conductivity results shown in Fig. 10 are also
compared with VGCF composites found from other studies.
It can be seen that the current thermal conductivity values
are considerably higher than those obtained by Dasch et al.
[13] and Patton et al. [17]. This extreme difference occurs
because the VGCF used in the current study has been heat-
treated to improve the conductivity.
The thermal conductivity and electrical resistivity in both
the longitudinal and transverse direction of the polypropy-
lene (PP) samples reinforced with partially aligned PR-19-
HT ®bers are given in Table 3. It can be seen from Table 3
that the electrical resistivity increases from the strand to the
sheet and to the cube. This is due to the additional misalign-
ment of ®bers (Table 1) that occurs during processing of the
composite. As expected, the resistivity decreases with ®ber
volume fraction. This is characteristic of the electrical

Fig. 9. Tensile modulus of polypropylene composites reinforced with partially aligned and randomly oriented VGCF at various ®ber volume fractions.
 R.J. Kuriger et al. / Composites: Part A 33 (2002) 53±62 61

Fig. 10. Thermal conductivity of polypropylene reinforced with partially aligned heat-treated VGCF compared with randomly oriented VGCF composites
from other studies.

conductivity of composites which is governed by percola-
tion and quantum mechanical tunneling between the ®bers.
It should be noted that the electrical resistivity is much
lower than glass ®ber reinforced polymers. For example,
PET reinforced with glass (15±45% Vf) has a resistivity
value of 10 15 V cm [39].
5. Conclusions
This investigation demonstrated a method in which
VGCF can be oriented in a polymer matrix during extrusion
to produce an improved composite with preferred strength
characteristics. A converging-annular die was used to
produce ¯ow-induced alignment of the VGCF. The degree
of ®ber alignment was quanti®ed by using X-ray diffraction.
It was determined that the amount of orientation along the
preferred axis decreases as the ®ber content increases.
It was also shown that degree of ®ber alignment along the
preferred direction could be improved by increasing the
residence time of the composite ¯ow through the die
channel. This was demonstrated by attaching an extended
annular nozzle to the die. The increase in ®ber alignment also
increases the strength properties of the composite materials.
The tensile strength increases with ®ber volume fraction
and was observed to be intermediate between a uniaxial (1-
D) model and a 2-D model. This indicates that the ®ber
alignment by extrusion produces higher mechanical
strength. However, the tensile modulus value does not
increase beyond the 2-D model. The increase at high ®ber
loading is intermediate between the 2-D and 3-D (random
orientation) model.
Acknowledgements
The authors like to thank Dr Gary Tibbetts of General
Motors Research and Development Center, and Jerry
Glasgow of ASI for their helpful suggestions and discus-
sions. This work was supported in part by NSF Grant No.
DMI-9960480 and the Ohio University Of®ce of Research.
This work was also partially supported by the U.S. Air Force
under Contract number F33615-95-D-5029 and Air Force
CRDA #95-WL-004-01 with ASI.

Table 3
Longitudinal (kL, r L) and transverse (kT, r T) thermal conductivity and electrical resistivity of partially aligned VGCF (PR-19-HT) composites

Direction Fiber volume fraction

9% 17% 23%

Thermal conductivity (W/m K) Cube kL 2.09 2.75 5.38

kT 2.42 2.47 2.49
Electrical resistivity (V cm) Strand rL 3.3 0.23 0.10
Sheet rL 3.6 0.26 0.17
rT 5.62 1.35 0.98
Cube rL 12.63 2.87 0.56
rT 23.3 3.21 2.31
62 R.J. Kuriger et al. / Composites: Part A 33 (2002) 53±62
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