Polymer Nanocomposites for

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Aerospace Applications: Fabrication
By James Njuguna* and Krzysztof Pielichowski

Nanocomposite polymers have tremendous potential to enhance the performance of macromolecular

materials used for composite matrices. Effective utilization of carbon nanotubes in composite applica-
tions depends strongly on the ability to homogeneously disperse them throughout the matrix without
destroying their integrity. This work looks at the fabrication for montmorillonite, fullerenes and nano-
tubes polymer/nanocomposites tailored to fit aerospace needs. Further insight is also given on develop-
ments in nanofibers and nanotubes production for good load transfer on the composite systems.

1. Introduction host resin, if dispersed, and re-agglomerate soon thereafter

The term 'nanotechnology' was introduced in early 1970s
to give the distinction between engineering at the nanoscale
and microscale. Then, with presence of transmission electron-
ic microscopy, scanning tunneling microscopy and the atomic
force microscopy meant the scientists and engineers can
manipulate, take measurements, and see the atoms and ef-
fects on them as they go through various stages Ð culminat-
ing to the present status in materials science. Currently, the
evolution of science has taken a new era of which fullerenes
and carbon nanotubes (CNT) have emerged as key players in
the last decade or so.
Polymer nanocomposites (PNC), as we know them today,
comprise very small particles typically having diameters less
than 100 nm deposited on the surface of a support or within a
host matrix. Effective utilization of CNT in composite appli-
cations depends strongly on the ability to homogeneously
disperse them throughout the matrix without destroying
their integrity. It is hence appreciable that the conductivity,
strength, elasticity, toughness, and durability of formed com-
posites may all be substantially improved by the addition of
nanotubes. The carbon fibers are applied mainly as mechani-
cal and thermal improver of materials while the nanotubes
are employed for mechanical reinforcements and provisional
electronic applications. Good interfacial bonding is required
to achieve load transfer across the CNT-matrix interface, a
necessary prerequisite for improving the mechanical proper-
ties of the composite.[1]
The difficult to achieve polymer matrices with adequate
level of CNT is mainly due to the insolubility of the material
and the incompatibility with the host resin. It is known that
CNT[2] tends to agglomerate as bundles in solvents and the
due to electrostatic attraction. Table 1 demonstrates some of
the achievable material properties.
However, the mechanical properties (tensile modulus and
strength, and elongation) are still way much below those of
pure CNT reflecting on the improvements in debt as seen on
Table 1.[3] All in all, the polycarbonate and polybutylene tere-
phthalate nanocomposites displayed good conductivity and
dissipative qualities as a trade off.
There exist several techniques to produce nanotubes since
their discovery[2] more than a decade ago. The primary tech-
niques currently available can be classified into the vaporisa-
tion method (arc discharge and laser ablation) and the cata-
lytic decomposition of hydrocarbons over metal catalysts
alias the chemical vapour deposition method. Chemical
vapour deposition (CVD) has demonstrated the advantages
in controlling growth orientations and in producing massive
quantities of CNT. A majority of the techniques for direc-
tional growth of CNT can be found through the use of various
plasma-assisted CVD and vapour growth methods. Both the
arc-discharge and the laser-ablation techniques are limited in
±
[*] Dr. J. Njuguna+ and Prof. K. Pielichowski
Department of Chemistry and Technology of Polymers
Cracow University of Technology
Ul. Warszawska 24, 31-155 Krakow, Poland.
[+] on leave form City University, London, School of Engineering,
Northampton Square, EC1V 0HB, UK.
[**] This research has been supported by a Marie Curie Fellowship
of the European Community programme ªImproving the
Human Research Potential and the Socio-Economic Knowledge
Baseº under Contract No. HPMT-CT-2001-00379.

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 Njuguna, Pielichowski/Polymer Nanocomposites for Aerospace Applications: Fabrication

Table 1. Polycarbonate (PC) and polybutylene terephthalate (PBT) nanocomposites and their properties that can be dinylenevinylene)- co- [(2,5-dioctyloxy-p-
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achieved using graphite nanotubes in comparison to the values for the base resin.
Property
Polymer [3] PBT PBT
Weight % CNT 3.5 5.0
2 1
Volume resistivity (ohm-cm) 10 10
7 3
Surface resitivity (ohm-square cm) 10 10
Static decay (seconds) <0.02 <0.02
Charge retention (volts, after 5 secs) 0 0
Tensile strength (kpsi) 9.5 9.5
Tensile Modulus (kpsi) 477 462
Elongationn (%) 10 7 300
Izod impact (un-notched, ftlb/in) 6.5 7.4
the volume of sample they can produce in relation to the size
of the carbon source (the anode in arc-discharge and the tar-
get in laser ablation). In addition, subsequent purification
steps are necessary to separate the tubes from undesirable
by-products. Having previously looked on the polymeric
materials for aerospace applications,[4] the fabrication meth-
ods for PNC are intrinsically discussed henceforth with
limitation to aerospace applicability.
2. Polymer/Single-walled Nanotubes (SWNT)
Composites
Published reports[1,5] showing the noncovalent fictionalisa-
tion of bundles of CNT with conducting polymers having the
capacity to form pseudorotaxanes represents the operation of
supramolecular forces at three different levels of superstruc-
ture; the aggregation of the nanotubes into bundles, the wrap-
ping of the bundles by the polymer, and finally the formation
through the sidearms. With such know-how, PmPV has been
used to develop nanocomposites for both multi-walled nano-
tubes (MWNT) and SWNT.[1,5,6]
Apparently, PmPV can be used as an organic filter for the
multi-walled system where the MWNT are indefinitely sus-
pended in the polymeric solution while the carbonaceous
material falls out of the solution. On a different approach,
micromechanics method[7] was utilised for the prediction of
bulk mechanical properties of SWNT/LaRC-SI and SWNT/
LaRC-CP2 composites, both SWNT/polymer composites[8]
having a PmPV interface, as a function of nanotube size, ori-
entation, and volume fraction. Following previous work,[5]
SWNT/PmPV complexes were formed[1] and accounted on
stabilizing noncovalent bonding interactions, presumably as
a result of d-d stacking and van der Waals interactions
between PmPV and the surfaces of the SWNT. The nature of
the interactions of PmPV, as well as that of poly {(2,6-pyri-
phenylene) vinylene]}(PpyPV) with
SWNT has been investigated and
Resin Resin compared to show that noncovalent fic-
PBT PC PC PC tionalisation of CNT can be achieved
0 3.5 5.0 0
without disrupting the primary structure
14
of the nanotubes themselves.
10 105 102 1017
Associated work to prepare alkoxysi-
12
10 106 106 ± lane/nanocomposite involved the use of
± <0.02 <0.02 ± oligomeric materials terminated with
± 0 0 ± reactive end groups.[9] Initial work using
this method involved the use of laser
8.0 8.7 8.9 10.0
ablation SWNT. On this experiment, the
390 364 399 ± researchers used a colourless polimide
24 30 125 prepared from stoichiometric amounts
± ± 26.5 ± of 4,4¢-perfluoroisopropylidiene dianhy-
dride and 1,3-bis(3-aminophenoxy)ben-
zene henceforth doped LaRC CP2. Tri-
methoxy silane end capped LaRC CP2
amide acid oligomers used to prepare high pressure carbon
monoxide (HiPCO) SWNT based nanocomposites prepared at
a stoichiometric offset of 2.5 %, which calculates to a Mn of ap-
proximately 27700 g/mol. The inherent viscosity of the oligo-
mer of 0.88 dL/g was recorded. Precursor nanocomposite solu-
tions were prepared by the addition of a sonicated suspension
of SWNT in N, N-dimethylacetamide to a stirred solution of
premade trimethoxy silane end capped LaRC CP2 amide
acid to afford solutions with a 0.03, 0.05, and 0.08 % by weight
concentration of SWNT. The solutions were stirred for around
16 h at ambient temperature prior to film casting. Once dried to
a tack-free state, the films were cured to 300 C in flowing air to
effect imidization and condensation. Due to the acidic nature of
the amide acid, no additional acid catalyst was required for the
hydrolysis and condensation of the alkoxysilane end groups.
Uniformly dispersed SWNT reinforced polyimide nano-
composites[10] were synthesized by insitu polymerisation of
monomers in the presence of sonication. The pure CP2 ±
colourless polyimide exhibited volume conductivity around
6 ” 10±18 S/cm, and incorporation of SWNT in the polyimide
increased the conductivity more than ten orders of magnitude
at very low SWNT loading. A sharp increase was observed
between 0.02 and 0.1 vol%, while the conductivity increased
moderately at loading levels in excess of 0.1 vol%. This beha-
viour indicates that a percolation threshold of the nanocom-
posites resides between 0.02 and 0.1 vol%. The resultant
nanocomposites exhibit a unique combination of properties,
including low colour in thin films, high optical transparency,
electrical conductivity sufficient to mitigate static charge
build-up, low solar absorptivity, high thermal emissivity,
high stiffness and strength, and high thermal stability.
Investigation on SWNT/epoxy composite displayed a
nearly constant value of Raman peak, which the authors[11,12]
blamed to tube sliding within the nanotube bundles resulting
in to poor interfacial load transfer between the nanotubes.
Another team of investigators prepared a composite speci-

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men by applying an epoxy-resin/nanotube mixture to the
surface of epoxy beam[11]. The investigations were made by
Raman spectroscopy that showed effective modulus of
SWNT dispersed in a composite could be over 1 TPa and that
of multi-walled nanotubes was about 0.3 TPa.
Yashino et al.[13] fabricated conducting polymer/C60 and a
C60 doped conducting polymer/C60 heterojunctions nano-
scale composite films by spin-coating or casting the solution
containing both organic polymers and fullerenes[14] on appro-
priate substrates. Multilayered structures were prepared by
spin-coating, molecular beam deposition, and also self-assem-
bly methods. Porous silicon and diamond were also used as
substrates for the junction formation. Nanoscale composites
were also prepared by infiltration of organic molecules into
porous inorganic materials such as synthetic opals, which are
fabricated by sedimentation of the suspension of monodis-
persed silica spheres of several hundred nm diameter. By
dipping the infiltrated opal in high frequency solution and
dissolving the SiO2 spheres, the free-standing polymer replica
was easily prepared.
A patented PNC[15] has been reported to effectively ab-
sorbs electromagnetic radiation in a range of 103 Hz±1017 Hz
and therefore making it a potential aerospace candidate. The
preparation involved pelletized polyethylene terephthalate
(PET) with 15 wt.% graphite nanotubes. This concentrate of
15 wt.% carbon fibers in unspecified extrusion grade PET
polyester resin was used as a master batch for let down (dilu-
tion) with neat Natural PET resin 0.85 IV Eastman natural
PET. Both resins dried four and a half hours at ~ 140 C and
kept in sealed glass bottles before use. The 1.5 % carbon resin
was a 9:1 blend of the concentrate and the neat resin by
weight. 2:1 blends of concentrate with natural PET were
made to reduce carbon content from 15 % to 10 % and again
from 10 % to 6.7 %. In doing so, varying concentrations of
nanotubes could be extruded for testing. The base PET was
easily extruded by a 3/4 inch Brabender single screw extru-
der with an engineering (higher compression) screw, running
at 110 to 115 rpm screw speed, with no evidence of moisture-
related bub. The master batch and a letdown thereof to the
plaque size required for EMI shielding testing were extruded
along with a neat PET control.
The same researchers later on produced another PNC
patent[16] claimed to be of high-use temperature, lightweight
polymer/inorganic nanocomposite materials, having en-
hanced thermal stability and performance characteristics.
These materials are made possible in part by the use of polar
organic phthalonitrile monomers and oligomers that can
exfoliate layered silicates, such as smectite clays, in percen-
tages greater than 10% inorganic by weight. This approach
offers a solvent-free direct melt intercalation technique that
greatly reduces the cost of processing nanocomposites with
thermal stability of the nanocomposite systems from 100±
150 C to over 450 C. Additionally, the use of unmodified
silicates overcomes temperature limitations of prior art,
which uses organically-modified layered silicates.
ADVANCED ENGINEERING MATERIALS 2004, 6, No. 4 http://www.aem-journal.de
Cook et al.[17] developed methods and materials for
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fabrication of alumoxane polymers. Their invention described
as well as provided methods for the preparation of carboxyl-
ate-alumoxane/polymer composite and hybrid materials
through the reactions of amine, hydroxyl, acrylic and vinyl
substituted carboxylate-alumoxanes with low molecular
weight polymer precursors containing the appropriate
reactive functional groups, such as oxiranes, acid chlorides,
anhydrides, carboxylic acids, quinones, and olefins. These
reactions lead to incorporation of the carboxylate-alumoxanes
into the polymer matrix through chemical bonding between
the carboxylate-alumoxane and the polymer. In an alternative
embodiment, more than one type of substituted carboxylate-
alumoxane, with or without additional low molecular weight
polymer precursors may be employed, such that the different
reactive substituents on each of the substituted carboxylate-
alumoxanes react with each other, thus forming chemical
bonding between the different carboxylate-alumoxanes and
any polymer present. The self-reaction of the reactive substit-
uent on the carboxylate-alumoxane may also lead to an alu-
moxane-based polymer.
The above PNC highlights the various fabrication methods
in practice. Among other PNC of interest found in the literature
is CNT/poly(vinylalcohol) composite films,[18] spherical nano-
particle alumina filled polymethyl methacrylate (PMMA),[19]
epoxy/nano matrices,[20±24] nanofiber reinforced polycarbonate
composite,[25] CNT/polystyrene composites[26,27] and CNT/
PMMA composites[28] where the nanotubes were initiated by a
free radical initiator, 2,2 -azobisisobutyronitrile (AIBN) to open
their p-bonds.
3. Polymer/Multi-Walled Nanotubes (MWNT)
Composites
One-way of uniformly dispersing MWNT into solutions of
selected matrices is by using a high-energy ultrasonic
probe.[9,29] The low viscosity of the solution allows the CNT to
move freely through the matrix. This can be carried out in
two stages; by using a high-power ultrasonic probe to dis-
perse the MWNT in toluene or by dispersing suspension
mixed with a dilute solution (10 wt.%) of polystyrene (PS) in
toluene utilising an ultrasonic bath. This approach has been
used to minimize the risk of tube rupture during processing
and avoid disruption of the polymer structure by the power-
ful ultrasonic probe. The mixture was then cast on glass and
the solvent removed to yield MWNT-doped film.
The above described method is limited to matrices that
freely dissolve in common solvents as was noted by Park et al.
and Smith et al.[9,10] though their method involved initial soni-
cation of the SWNT in a polar aprotic solvent to adequately
suspend the SWNT. The diamine was then added to the sus-
pension followed by the addition of the dianhydride. The
mixture was allowed to stir under a nitrogen atmosphere at
ambient temperature to afford a visually viscous solution
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 Njuguna, Pielichowski/Polymer Nanocomposites for Aerospace Applications: Fabrication

and subsequently chemically imidized to the corresponding

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imide. Solutions with a 0.1 and 0.2 % by weight concentration

of SWNT were attained. The polyimide/SWNT mixtures
were isolated and redissolved in dimethylformamide prior to
casting films. Films cast from the neat poly (amide acid) were
darker in colour and more brittle; presumably due to low
molecular weight. Unoriented thin films were cast from the
imide/SWNT compositions and air-dried to 225 C.
A more practical method of producing MWNT/polymer
composites[1,20] involves shear mixing[30,31] followed by extru-
sion or injection moulding to fabricate artefacts in the
required form. The dispersion of CNT in a range of polymers
including high-impact polystyrene, acrylonitrile-butadiene-
styrene, and polypropylene has been investigated using a
Haake Polylab high shear mixer.[32] Tests were performed to
determine the operating conditions required to disperse
MWNT; variables investigated included temperature, mixing
time, rotor speed, and MWNT concentration. By this method,
thin films have been prepared from the polymer/MWNT
composite materials using a hydraulic press fitted with
heated platens.[32]
Through the shear mixing followed by extrusion or injec- Fig. 1. Schematic diagrams of the possible layered silicate based nanocomposite struc-
tion moulding to fabrication procedure, a small sample of the ture [33].

crushed composite was loaded into a polytetrafluoroethylene

vacuum bag.[32] Metal shims were inserted between the pla-
tens to set a uniform separation. With the envelope evacu-
ated, and once the sample has reached the required tempera-
ture, the sample was compressed into a film by applying a
static load. Temperature, time, hydraulic pressure, and eva-
cuation of the envelope were used to control film thickness
and uniformity. Fibers were produced from the crushed com-
posite materials by extrusion. The polymer/MWNT compos-
ite samples were transferred to a bench-scale extruder fitted
with a 6.2 mm diameter screw and 0.3 mm diameter by
1 mm capillary die operating at 200 C. The extruded thread
was attached to a wind-up drum rotating at speeds of up to
1800 rpm to draw filament in the range 20±75 lm. The shear
fields generated during spinning produced composite fibers
with the MWNT aligned with the axis of the fiber.
4. Montmorillonite Nanocomposites
The reported performance improvements in polymers
modified with low loadings of organo mica-type silicates
offer promise of economically improving the performance of
the fiber reinforced composite. In general, polymer±clay
nanocomposites have been prepared by four techniques;
either though exfoliation-adsorption, in situ intercalative
polymerisation, melt intercalation or template synthesis as
the one illustrated in Figure 1.
A literature review reveals Nylon-6/montmorillonite
nanocomposite as the first polymer/clay composite to be
reported back in 1993.[34] The organo clay, [H3N (CH2)11
COOH]+, was synthesized by ion-exchanging the cations of
the parent clay with more hydrophobic organic onium ions;
resulting in a commercialised product with enhanced ther-
mo-mechanical properties. Since then polymer clay has suc-
cessfully extended to other polymer systems such as PS,[35]
poly (e-caprolactone),[36,37] polystyrene-polyisoprene (PS-PI)
block copolymers[38±40] and polypropylene (PP),[41,42] offering
significant thermal, mechanical, barrier and flame-retardant
properties to the polymers.[43] It must be appreciated that
epoxides undergo facile self-polymerisation in the presence
of acidic smectite clays to form nano-structured polyther-clay
composites.
Zhua et al. prepared polystyrene-clay nanocomposites[44]
and later PMMA-clay nanocomposites[45] on a similar fabrica-
tion process. The PMMA-clay nanocomposites was prepared
by mixing 3 g of organically modified clay and 100 g of
monomeric methyl methacrylate plus 1 g AIBN as radical
initiator. This mixture was then stirred at room temperature
under flowing nitrogen gas until it was homogeneous, then it
was heated to 80 C for a few minutes to prepolymerize. After
cooling to room temperature, the sample was polymerized at
60 C for 24 h, then at 80 C for another 24 h under nitrogen
atmosphere. The nanocomposite was finally dried under
vacuum for 6 h at 100 C.
Researchers interested on exploiting the unique polymeric
materials of polyurethane such as non±toxicity, non-air pollu-
ter and flame-retardant, developed polyurethane/clay nano-
composite.[46] Aqueous emulsion of polyurethane ionomers,
based on poly (tetramethylene glycol) or poly (butylene adi-
pate) as soft segment, isophorone diisocyanate as diisocya-
nate, 1,4-butandiol as chain extender, dimethyl propionic acid
as potential ionic center, triethylene tetramine as crosslinker,
and triethyl amine as neutralizer, were reinforced with orga-
noclay to give nanocomposites. The reported performance

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improvements in polymers modified with low loadings of
organo mica-type silicates offer promise of economically
improving the performance of the fiber reinforced composite.
Mass transport studies of polyimide±clay nanocomposites
by Yano et al.[47] revealed a several-fold reduction in the
permeability of small gases, e.g., O2, H2O, He, CO2, and the
organic vapour ethyl acetate with the presence of only small
fraction of organoclay. The authors noted permeability de-
crease with increasing aspect ratio while thermal expansion
coefficient decreased for an identical loading with increasing
nanolayer aspect ratio hectorite 50, saponite 170, montmoril-
lonite 220 and synthetic mica 1230. The synthesis of this poly-
imide-clay nanocomposite is illustrated in Figure 2.
Triantafillidis et al.[48] prepared montmorillonite and fluo-
rohectorite clays from diprotonated forms of polyoxy-
propylene diamines of the type a,x[NH3CHCH3CH2
(OCH2CHCH3) xNH3]2 with x = 2.6, 5.6, and 33.1 for the for-
mation of glassy epoxy/clay nanocomposites with clay load-
ings of up to 6 wt% on a silicate basis. On a different work,
the diglycidyl ether of bisphenol A and an epoxy resin Epon-
828 underwent self-polymerisation when heated with acidic
onium ion exchanged forms of montimorillonite to form
polyether-clay nanocomposites.[49] As noted, the intercalated
onium ions functioned concomitantly as a clay surface modi-
fier, intragallery polymerisation catalyst, and curing agent.
Depending on the chain length of the diamine, different
orientations of the propylene oxide chains are adopted in the
clay galleries, resulting in basal spacing from approximately
14 Š (lateral monolayer, x = 2.6) to around 45 Š (folded
structure, x = 33.1). From a different perspective, Chenngang
and Curliss[50] examined a low-cost epoxy resin suitable for
use as a composite matrix which was modified with various
modified clays (montmorillonite) and characterized. The or-
ganic treatment of clay was found to be compatible with
aerospace epoxy resin and was used to prepare the nano-
Fig. 2. Synthesis of polyimide±clay hybrid film [47].
ADVANCED ENGINEERING MATERIALS 2004, 6, No. 4 http://www.aem-journal.de
composites. Polyaniline (PANI)/clay composites that are
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composed of both PANI±clay nanocomposite particles and
pure PANI particles, shown on Figure 3, have been
reported.[51]
PANI/clay composite suspensions were prepared via dis-
persion polymerisation of PANI with clay and used as ERFs
by dispersing the composite particles (15 wt.%) in silicone oil
(viscosity g = 0.10 Pa/s and d= 0.96 g/cm3). Dispersion poly-
merisation of aniline was carried out under mechanical stir-
ring (approx. 200 rpm) in a 1000-ml round flask, which was
immersed in an ice bath. Fifteen grams of exfoliated clays
was dispersed in 1 N HCl and then sonicated for 30 min.
Different contents of aniline were dissolved in that solu-
tion and aqueous solution of ammonium persulfate (APS)
was added drop by drop. The molar ratio between the APS
and aniline was set to 2.5. The reaction mixture was stirred
(approx. 200 rpm) for 24 h. The dispersed composite particles
in an aqueous medium were filtered and washed with etha-
nol and water in order to free them from the unreacted ani-
line and APS. In order to reduce the conductivity of PANI
particles prepared by the chemical oxidation process of ani-
line in the presence of acidic dopant, particles were treated
with 3.0 vol.% NH4OH aqueous solution for 24 h. Afterward,
the composite particles composed of both PNC and pure
PANI particles were obtained by sequentially washing, filter-
ing, drying, milling, and sieving.
Singh and Haghighat patent[52] synthesized organically
modified layered aluminosilicates using the sol-gel process
where the organic groups are incorporated into the molecular
structure through the use of organically modified silicon alk-
oxides. The organic functionality was therefore directly
bonded to the structural Si atom by the Si-C bond. The orga-
nically modified aluminosilicate was synthesized using mix-
tures of organically-modified silicon alkoxides and solutions
of aluminum chloride. The standard approach combines an
alcohol solution of aluminum chloride with an alcohol solu-
tion of organically functionalized alkoxysilane. The mixture
is then condensed (crosslinked) to form a gel at appropriate
pH conditions by the addition of NaOH. The gel is aged, fil-
tered, washed with distilled water, and then dried in vacu-
um. That procedure yielded a stable layered organophilic
compound. The resulting material is either precipitated as a
powder, dried and ground to appropriate particle size, or cast
into various shapes and forms. The organically modified
Fig. 3. Microstructure of PANI (left) and PANI/clay (right) composites [51].
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 197
 Njuguna, Pielichowski/Polymer Nanocomposites for Aerospace Applications: Fabrication
layered aluminosilicates is then precipitated as a powder or
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ground and classified it into appropriate size particles for
incorporation with the polymer matrix for direct melt interca-
lation. A unique feature of these organically modified layered
aluminosilicates compounds is that they are especially engi-
neered to delaminate in the presence of a variety of polymer
resins, thus promoting the dispersion of the inorganic layers
in the polymer matrix.
Polansky et al.[29] patented their polymer composite com-
prising an epoxy vinyl ester resin or unsaturated polyester
matrix having dispersed therein particles derived from a mul-
tilayered inorganic material which possesses organophilic
properties. The dispersion of the multilayered inorganic
material in the polymer matrix is such that an increase in the
average interlayer spacing of the layered inorganic material
occurs to a significant extent resulting in the formation of a
nanocomposite. In one of their fabrications, an unsaturated
polyester, such as dicyclopentadiene polyester synthesized
using 50 % ethylene glycol and 50 % diethylene glycol let
down with styrene was blended with unsaturated polyester/
clay composite. The clay was dispersed through shear and
sonication. The final clay loading was between 2 and 6 wt %.
The preparation was cured using 0.2 wt.% Co naphthenate
and 1.25 wt.% methyl ethyl ketone peroxide. The resultant
composite exhibited an increase in the basal spacing of the
clay from approximately 19 Š to more than 38 Š, as observed
in the X-ray diffraction pattern.
5. Carbon Nanofibers and Nanotubes
Versatile methods for enabling the growth of carbon nano-
fibers and nanotubes include the use of laser etching, chemi-
cal vapour deposition CVD, sol-gels, substrate supported
catalysts and catalyst particles suspended as an aerosol. Each
of these methods has shown promise for obtaining the high-
quality production of CNT and nanofibers such as the one
shown on Fig. 4. The most employed fabrication procedures
have been reviewed hereby.
5.1 Laser Ablation Method
Laser ablation, first used for the production of fullerenes,
has been developed over the years to produce both SWNT
and MWNT. Its great advantage is the control of space and
Fig. 4. Scanning electron micrograph of a nanotube fibre at 25 nm (left) [53] and nano-
fibres of poly(3,4-ethylenedioxythiophene) (right) [54].
198  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
time of the various interaction processes taking place during
the evaporation experiments, especially in the case of light
originating from laser sources. Laser ablation technique can
be categorised in to Nd;YAG laser and CO2 laser approaches.
The Nd: YAG-laser[55] is a horizontal configuration, which
consists of a quartz-tube mounted in a temperature-con-
trolled furnace, and is the base for almost all pulsed Nd:
YAG-lasers. A target rod, normally made of graphite, is
placed axially in the middle of the controlled high tempera-
ture zone with temperatures near 1200 C. After sealing and
evacuating the tube, a buffer gas (argon) is flowed through it
followed by a pulsed Nd: YAG laser focused onto the target
rod. The carrier Nd: YAG laser is focused onto the target rod.
The carrier gas-flow sweeps most of the carbon species pro-
duced by the laser evaporation out of the furnace zone depos-
iting it as soot on a water-cooled copper rod. By use of 100 %
graphite rod, it was noted that the MWNT yield and quality
significantly depend on the furnace temperatures.[55] SWNT
were only found at temperatures around 1200 C[55,56] after in-
clusion of small percentages of metals with nickel producing
the best results.
Later on, an increase of SWNT by a factor of 10 to100 was
reported[56] after use of bi-metals like cobalt/nickel and nick-
el/platinum. Hereby, the SWNT amounted to 50 vol.% with
an estimated 15 wt.% of the carbonaceous material deposited
as a rubbery sheet of soot material. Further works involved
optimisation of the process with initial laser pulse by Thess
et al.[57] The initial laser pulse (532 nm, 250 mJ, 10 Hz, 5 mm
diameter spot) was followed 50 ns later by a second pulse
(1064 nm, 300 mJ, 10 Hz, in a 7 mm diameter spot coaxial
with the first laser spot). The results were quite rewarding,
SWNT yields from graphite/cobalt/nickel was 70±90 vol.% of
the carbonaceous materials in the obtained samples, consist-
ing of 100±500 SWNT of diameters between 10±20 nm and
10±100 lm length. The tubes were perfectly closed and no
evidence of defects but no presence of MWNT was evident.
Production of SWNT by amounted to approximately 80 g/
day of SWNT. Efforts to increase the production rate by
Rinzler et al.[58] by optimising parameters (laser powers, spot
sizes, timing, gas flow rate, and pressure) achieved 100 g/
day. Modification of the horizontal set-up previously used in
to double quartz-tube system, using dual laser pulses both
operating at a wavelength of 1064 nm, resulted to slightly bet-
ter results 120 g/day but still short of the target. This was
mainly due to the moving plume that was incompatible with
a plume confinement tube thus the optimum temperature of
1200 C could not be reached.
Using a carbon monoxide laser with a wavelength of
10.6 mm operating in continuous wave- mode and taking
advantage of the different light±target interaction, Maser
et al.[59] developed a simple vertical experimental set-up. This
new and totally different approach for production of CNT
consisted of an evaporation chamber in whose centre is
placed a target rod but with no furnace. Samples analysed
from this production approach revealed the soot contains
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Njuguna, Pielichowski/Polymer Nanocomposites for Aerospace Applications: Fabrication

large amount of SWNT with diameters of around 20 nm, After the substrate is etched in diluted high frequency solu-

length exceeding 1 lm, average tube diameter around 1.4 nm
and the diameter distribution ranges from 1.1 to 1.17 nm.
With evaporation rate as high as 200 mg/h on a fifteen min-
utes experiment, a remarkable 80 vol.% yield of SWNT was
observed on web-like soot while 50 mg/h resulted in rubber
like soot with slightly less yield.
Laplaze et al.[60] used a concentrated light for the produc-
tion of nanotubes in a reaction chamber consisting of a Pyrex
balloon flask located on a water-cooled brass support. De-
pending on the pressure and flow conditions, deployment of
nickel/cobalt and nickel/yttrium in the graphite mixture
resulted in soot containing either bamboo-like MWNT, or
MWNT and SWNT together or only SWNT in the form of
long bundles. Though the production rates were lower than
the laser experiments, the use of solar radiation is comparable
to the one of carbon dioxide laser approach.
5.2 Arc Discharge Method
This technique has been in use for a long time for the pro-
duction of carbon fibers. Thus, it is very likely that nanotubes
were observed before 1991 but not recognized as such.[61] This
technique involves the use of two high-purity graphite rods
as the anode and cathode. The rods are brought together un-
der a helium atmosphere and a voltage is applied until a
stable arc is achieved. The exact process variables depend on
the size of the graphite rods. As the anode is consumed, a
constant gap between the anode and cathode is maintained
by adjusting the position of the anode. The material then
deposits on the cathode to form a build-up consisting of an
outside shell of fused material and a softer fibrous core con-
taining nanotubes and other carbon particles.[62] Arc dis-
charge was the first method available for the production of
both MWNT[63,64] and SWNT.[65,66] MWNT produced by arc
discharge are long and straight tubes closed at both ends with
graphitic walls running parallel to the tube axis. To achieve
SWNT the electrodes are doped with a small amount of
metallic catalyst particles such as cobalt, iron or nickel mixed
with graphite powder results in a deposit containing
SWNT.[61,61,65±68] SWNT are usually assembled in ropes but
some single tubes can also be found in the deposits. Laser
ablation is a related method where the graphite±catalyst
target is vaporized by a laser.[68]
REVIEWS
tion with distilled water, the specimen is placed in a quartz
boat. The boat is positioned in a CVD reaction furnace, and
nano-size fine catalytic metal particles are formed after an
additional etching of the catalytic metal film using NH3 gas at
a temperature in 750 to 1050 C.
Various forms of carbon fibers, filaments, and MWNT
have been synthesized by CVD in the past. To understand the
gravity effect, CNT were synthesized using thermal chemical
vapour deposition with substrates located at different orien-
tations relative to the gravity vector.[68±70] The diameters of
these CNT were quite uniform with the length of the CNT up
to several tens of micrometers. Thermal CVD has advantages
of variety in products and hydrocarbon sources, adequacy for
synthesis of high quality materials, and controllability of
microscopic structures. However, this method lacks homoge-
neity on substrate as change in the flow of the reaction gas
leads to unstable gas supply. It is also sensitive to the temper-
ature change and position in the chamber.
5.4 Plasma enhanced CVD
Plasma CVD requires specialised plasma equipment but
has an advantage of low temperature synthesis over thermal
CVD as well as better control over length, diameter and struc-
ture of nanotubes. Bower et al.[72] showed that in microwave
plasma-enhanced CVD (MPECVD) alignment of the CNT
results from the self-bias that is imposed on the surface of the
substrate from the microwave plasma, Figure 5.
CNT can be synthesized on soda lime glass, especially for
production of display devices, at less than 550 C, at which
soda lime glass begins to melt. The power supplies for dis-
charge of plasma CVD excitation are DC source or microwave
source. The plasma method generates glow discharge in a
chamber or a reaction furnace by a high frequency applied to
both electrodes. A substrate is placed on the grounded elec-
trode. In order to form a uniform film, the reaction gas is sup-
plied from the opposite plate. C2H2, CH4, C2H4, C2H6, CO
gases are typically used to synthesize CNT. Catalytic metal,
such as Fe, Ni, and Co are used on a Si, SiO2, or glass sub-
strate using thermal CVD or sputtering. The deposited metal

5.3 Thermal CVD Method

Chemical vapour deposition of hydrocarbons over metal
catalysts has been a classical method to produce carbon mate-
rials. Thermal CVD is a simple pyrolysis, usually performed
in a flow reactor inside a tubular oven. The CVD process can
also be assisted by a hot filament and/or by a microwave or
plasma. The synthesis method of CNT using thermal chemi-
cal vapour deposition demands first the Fe, Ni, Co, or alloy of Fig. 5. The influence of MPECVD on the structure of nanotubes (top) and nanotubes
the tree catalytic metals be initially deposited on a substrate. aligned normal to the surface of a glass fibre in the bottom [72].

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 Njuguna, Pielichowski/Polymer Nanocomposites for Aerospace Applications: Fabrication
on substrate can be etched using ammonia or hydrogen gas.
REVIEWS
After nanoscopic fine metal particles are formed, carbon
nanotubes are grown on the metal particles on the substrate
by glow discharge generated from high frequency power.
Reaction gas, such as C2H2, CH4, C2H4, C2H6, CO is supplied
to the chamber during the discharge. Growth rate of CNT un-
der the plasma enhancement has been reported to be 40 times
faster than the thermal CVD.[72]
Zhua et al.[68] synthesized CNT using thermal CVD with
substrates located at different orientations relative to the
gravity vector.[69±71] As noted earlier, the diameters of these
CNT were quite uniform with the length of the CNT up to
several tens of micrometers. With the substrate surface nor-
mal either along or against the gravity vector, different
growth orientations of CNT were observed by scanning elec-
tron microscopy. The Raman spectra were similar for samples
synthesized at different locations. These results suggest that
gravity affects the growth of long CNT with small diameters
phenomenon. Thus the CNT growth orientations could be
controlled by gravitation.
Vertically aligned MWNT on different nickel-coated sub-
strates by plasma enhanced hot filament CVD at low temper-
atures below 650 C have been achieved.[74] Acetylene and
ammonia gas with flow rate of 80 sccm and 160 sccm respec-
tively, were used as the carbon source and a catalyst. The
grown CNT were characterized by scanning electron micros-
copy (SEM) to investigate the effect of growth parameters on
their morphology. Transmission electron microscopy (TEM)
was used for microstructure analysis of nanotubes. The sur-
face roughness of the nickel layer increased as NH3 etching
time increased. The diameters of the nanotubes decreased as
well as the density of nanotubes as NH3 etching time in-
creased. The diameter of the nanotubes was 30±70 nm. A
nickel cap was observed on the top of the grown nanotube
and a very thin amorphous-carbon-like layer was found on
the nickel cap. The morphology and microstructure of CNT
were measured using SEM and TEM. Highly oriented CNT
obtained in this work can be applied to the field emission dis-
play.
5.5 Vapour Phase Growth Method
The phase growth has produced the highest level of SWNT
occurring at around 1200 C and 10 atm[73] by use of carbon
monoxide as the carbon source. Fabrica-
tion of CNT for nanocomposites using
other hydrocarbon gases at high gas
pressure (gas±nitrogen or nitrogen±ar-
gon, pressure up to 1300 atm) has been
cited too.[75] This method is the most
favoured choice for most researchers and
is tipped to be viable for mass produc- (a)
tion. The vapour phase growth is a syn- Fig. 6. Nanofibre extrusion tool: (a) is the side view of the extruder while (b) shows the extrusion process for uni-
thesis method that involves directly sup- form diameter composite strand [78].
200  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
plying reaction gas and catalytic metal in the chamber
without a substrate. A mass flow controller is placed in one
corner and a boat for catalytic metal powder in the chamber.
Relatively low temperature is kept in the first furnace while
higher temperature is maintained in the hot second furnace
where the synthesis occurs. Catalytic metals vaporized from
powder are normally in atomic form, formed as fine particles
down to several tenths of nanometres in the chamber amid
collisions among the atoms. When fine catalytic particles va-
porized from metal powder in the low temperature area
reach the second furnace, decomposed carbons in the hot sec-
ond area are adsorbed, diffused to catalytic metal particles,
and synthesized as CNT.
As a matter of interest, vapour phase growth was chosen
by van Hattum et al.[75] to investigate the properties of com-
posites reinforced with PAN fibers and vapour grown carbon
fibers (VGCF) for polyproplene matrix. Controversially, their
work found the strength of the VGCF reinforced composites
was similar to those reinforced with PAN fibers but the stiff-
ness was marginally lower. VGCF with epoxy and poly
(phenylene sulphide) matrix has also been prepared.[20] The
work reflected on the importance of mixing the two products
as the determining factor of the VGCF composites. Thermal
conductivity properties of VGCF/ABS (acrylonitrile±buta-
diene±styrene tetrapolymer) and VGCF/epoxy composites
with various fiber volume fractions were measured. Thermal
conductivity increased with an increase in fiber volume frac-
tion. However, these increases were not significant enough to
make these VGCF fiber/organic matrix composites candi-
dates for thermally conductive materials.[76]
Another investigator[77] extruded a polycarbonate sheet
with aligned VGCF in a polymer flow during extrusion to
produce an improved thermoplastic. A twin-screw extru-
der[78] as the one shown on Figure 6 was used to shear mix
and extrude fiber/polyproplene mixtures through a converg-
ing-annular die that generated fiber alignment along the flow
direction.
At a similar exercise[27] an addition of 11.5 vol.% of carbon
nanofibers doubled the pure strength of polypropylen. Sand-
ler et al.[18] prepared poly (ether ether ketone) (PEEK) nano-
composites containing vapour-grown carbon nanofibers
using a Berstorff co-rotating twin-screw extruder with a
length-to diameter ratio of 33. Macroscopic PEEK nanocom-
posite master batches containing 0, 5, 10 and 15 wt.% carbon
nanofibers were prepared while matrix ductility was main-
(b)
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Njuguna, Pielichowski/Polymer Nanocomposites for Aerospace Applications: Fabrication
tained up to 10 wt.%. Later work showed that it is indeed pos-
sible to produce an improved anistropic composite by align-
ment of VGCF suspended in polymer flow during extru-
sion.[78] It has also now been shown that aligned composites
could be obtained by mechanically stretching the nanocom-
posites.[79]
For the preparation of carbon nanofibers in large quantities
two methods are used, one being decomposition of different
polymers (mainly polyacrylnitrile) which is a multi-step pro-
cess and requires high temperature (1000±1300 C) for carbo-
nisation. Carbon nanofibers with high surface area can be
synthesized in a simple one-step reaction under relatively
mild conditions in the decomposition of acetylene over SnO-
doped Fe3C binary catalyst prepared by direct precipitation
method (if it is necessary, carbon nanofibers can be purified
by dissolving the catalyst (e.g. Co/silica and Fe/silica) in
hydrochloric acid at 80 C).[80] Catalytic pyrolysis of lower
hydrocarbons over supported transition metal (Fe, Co, or Ni)
catalysts is also in use for the production of this material
albeit in smaller quantities. Mechanical properties of catalyti-
cally grown carbon fibers are probably better than those of
conventional polyacrylnitrile-based fibers.[81]
5.6 Flame and Electrolysis Methods
It has been demonstrated that flame synthesis of SWNT
via a simple laboratory-scale diffusion flame is possible.[82] A
metal nanoparticles catalyst formed from a metallocene low-
ers the energetic constraints for the formation of a CNT and
hence acting as an effective interface between the gas-phase
reactants and solid carbon precipitate. In Flame synthesis
method, combustion heat is a heating source of carbon nano-
tubes produced from combustion of CH4 in the small amount
of oxygen atmosphere. MWNT and SWNT are synthesized
by flowing hydrocarbon source like C2H2 and catalytic pre-
cursors in the diffusion flame atmosphere. As the tempera-
ture range of 600±1300 C is not uniform in the flame atmo-
sphere, the tubes contain a great amount of amorphous
carbons and show poor crystalline. It facilitates mass produc-
tion and is promising in the application to electrolytic materi-
als. A laminar diffusion flame (flow rates were 150 sccm of
acetylene and 1750 sccm of nitrogen) served as the hot, reac-
tive hydrocarbon environment for the synthesis in a labo-
ratory-scale diffusion flame at atmospheric pressure condi-
tions.[82] Nitrogen dilution of the fuel acetylene or ethylene
produced a fuel concentration commensurate with that typi-
cally used in the floating catalyst approach conjunction with
high-temperature furnaces. Metallocene vapour was en-
trained within the inert gas that was the major component of
the pyrolysis flame with an estimated introduction rates
ranged between 0.1 and 2 mg/min. A metal nanoparticles
catalyst formed from a metallocene lowers the energetic con-
straints for the formation of a CNT and hence acting as an
effective interface between the gas-phase reactants and solid
carbon precipitate.
ADVANCED ENGINEERING MATERIALS 2004, 6, No. 4 http://www.aem-journal.de
MWNT can also be synthesized using electrolysis method,
REVIEWS
which involves the electrolysis of molten lithium chloride
using a graphite cell in which the anode has a graphite cruci-
ble. The temperature of the graphite crucible is approximately
600 C in the argon atmosphere. MWNT with 2±10 nm in
diameter and 0.5 lm or more in length are synthesized when
DC power at less than 3-20 A and 20 V is applied as amor-
phous carbons and encapsulated CNT are synthesized as
by-products.
A structural change in nanofibers owed to high-tempera-
ture heat treatment has been reported.[83] The synthesis of the
carbon nanofibers was carried out in a horizontal alumina
reactor with an inner diameter of 50 mm, and a length of
1100 mm. An alumina plate used as the substrate was first
immersed in 0.2 M nickel nitrate /ethanol solution, and was
removed and dried. Subsequently, it was placed in the reactor
and reduced in hydrogen at 700 C for one hour. The growth
of CNT was carried out through the decomposition of
acetylene at atmospheric pressure at 700 C. The flow rate of
C2H2, hydrogen and nitrogen was 20, 200, and 100 sccm,
respectively. After a one-hour reaction, the reactor was cooled
in nitrogen, and the synthesized carbon nanofibers were
taken out. The graphitisation of the nanofibers was carried
out at 2500 C for one hour in argon after which they were
dispersed in acetone by ultrasonic vibration for 30 min, and
then the dispersion was dropped on a carbon-coated copper
grid for observation in a high-resolution transmission elec-
tron microscope. The as-synthesized nanofibers have diame-
ters ranging from 10 to 300 nm, probably because of the wide
distribution in the size of the Ni catalyst particles. Two struc-
tures, platelet and herringbone, were found to dominate after
heat-treatment at 2500 C and exhibited many 'round head'
and nanotube-like structures on their surface.
6. Conclusions
Prospects on PNC mainly depends on the success in fabri-
cation procedures. Unlike traditional filled polymer systems,
nanocomposites require relatively low dispersant loadings
(~ 2 wt%) to achieve significant property enhancements. The
fabrication of homogeneous materials requires control of not
only the individual building blocks but also the higher level
architecture by which the ªmoleculesº assemble. As cited on
this work, various fabrication methods both old and new are
being employed to maximise good interficial bonding for the
PNC. Synthesis of 'pure' nanoparticles is one of the key issues
to best enhancements on polymeric materials normally used
in aerospace. Fabrication of carefully selected PNC for aero-
space applications has been discussed and the current chal-
lenges outlined. Further work is underway examining the
characterisation methodologies and properties utilisation as
to date for the PNC covered in the present work.
Final version: February 10, 2004
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 201
 Njuguna, Pielichowski/Polymer Nanocomposites for Aerospace Applications: Fabrication
± [23] V. Lordi, N. Yao, J. Mater. Res. 2000, 15, 2770.
REVIEWS
[1] D. W. Steuerman, A. Star, R. Narizzano, H. Choi, R. S.
Ries, C. Nicolini, J. F. Stoddart, J. R. Heath, J. Phys.
Chem. B 2002, 106, 3124.
[2] S. Iijima, Nature 1991, 354, 56.
[3] See http://www.fibrils.com.
[4] J. Njuguna, K. Pielichowski, Polymer Aero. Sci. Tech.
2003, submitted.
[5] A. Star, J. F. Stoddart, D. Steuerman, M. Diehl, A. Bou-
kai, E. W. Wong, X. Yang, S. W. Chung, H. Choi, J. R.
Heath, Angew. Chem. Int. Ed. 2001, 40, 721.
[6] A. P. Davey, J. Coleman, A. Dalton, S. Maier, A. Drury,
D. Gray, M. Brennan, K. Ryder, M. Lamy De La Cha-
pelle, C. Journet, P. Bernier, D. Carroll, W. Blau, H. J.
Byrne, P. M. Ajayan, S. S. Lefrant, Synthetic Metals 1999,
103, 2559.
[7] G. M. Odegard, V. M. Harik, K. E. Wise, T. S. Gates,
NASA/TM-2001-211044, August 2001, p. 17.
[8] C. Park, Z. Ounaies, K. A. Watson, R. E. Crooks,
J. Smith Jr., S. E. Lowther, J. W. Connell, E. J. Siochi, J. S.
Harrison, L. St. Terry, Chem. Phys. Lett. 2002, 364, 303.
[9] J. G. Smith Jr, K. A. Watson, C. M. Thompson, J. W.
Connell, 34th International SAMPE Technical Conference,
Maryland, November 4±7, 2002.
[10] C. Park, Z. Ounaies, K. A. Watson, ICASE Report No.
2002-211940-2002-36, Hampton, Virginia.
[11] C. A. Cooper, R. J. Young, M. Halsall, Comps. Part. 2001,
32, 401.
[12] P. M. Ajayan, L. S. Schadler, C. Giannaris, A. Rubio,
Adv. Mater. 2000, 12, 750.
[13] K. Yoshino, Y. Kawagishi, S. Tatsuhara, H. Kajil, S. Lee,
M. Ozaki, Superlattices and Microstr. 1999, 25, 325.
[14] H. W. Kroto, J. R. Heath, S. C. O'Brien, R. F. Curl, R. E.
Smalley, Nature 1985, 315, 162.
[15] P. Glatkowski, P. Mack, J. L. Conroy, J. W. Piche,
P. Winsor, United States Patent No.6265466.
[16] P. Glatkowski, P. Mack, J. L. Conroy, J. W. Piche,
P. Winsor, US Patent Application Pub. No. US2002/
0143094 A1.
[17] R. L. Cook, A. R. Barron, K. J. Gleason, D. B. Mac-
Queen, G. L. Siparsky, Y. Koide, C. T. Vogelson, United
States Patent No. 6369183.
[18] J. Sandler, P. Werner, M. S. P. Shaffer, V. Demchuk,
V. Altstädt, A. H. Windle, Compos. Part A. 2002, 33,
1033.
[19] R. W. Siegel, S. K. Chang, B. J. Ash, J. Stone, P. M. Aja-
yan, R. W. Doremus, L. S. Schadler, Scripta Mater. 2001,
44, 2061.
[20] H. D. Wagner, O. Lourie, Y. Feldman, R. Tenne, Appl.
Phy. Lett. 1998, 72, 188.
[21] H. Yamanashi, H. Ushijima, M. Katsumata, M. Endo, in
The 21st Biennial Conference on Carbon, Buffalo, June
1993, p. 88.
[22] X. Gong, J. Liu, S. Baskaran, R. D. Voise, J. S. Young,
Chem. Mater. 2000, 12, 1049.
202  2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim
[24] L. S. Schadler, S. C. Giannaris, P. M. Ajayan, Appl. Phys.
Letts. 1998, 73, 3842.
[25] O. S. Carneiro, Compos Sci Techn. 1998, 58, 401.
[26] D. Qian, E. C. Dickey, R. Andrews, T. Rantell, Appl.
Phys. Letts. 2000, 76, 2868.
[27] G. G. Tibbetts, J. McHugh, J. Mater. Res. 1999, 14, 2871.
[28] Z. Jia, Z. Wang, C. Xu, J. Liang, B. Wei, D. Wu, S. Zhu,
Mater. Sci. and Eng. A 1999, 271, 395.
[29] C. A. Polansky, J. E. White, J. M. Garces, A. Kuperman,
D. Z. Ridley, United States Patent No. 6287992.
[30] K. Lozano, E. V. Barrera, J. Appl. Polym. Sci. 2001, 79,
125.
[31] R. Haggenmueller, H. H. Gommans, A. G. Rinzler, J. E.
Fischer, K. I. Winey, Chem. Phys. Lett. 2000, 330, 219.
[32] R. Andrews, D. Jacques, D. Qian, T. A. Rantell, Acc.
Chem. Res. 2002, 35, 1008.
[33] R. Krishnamoorti, Y. Koray, Current Opinion in Colloids
and Interface Sci. 2001, 6, 464.
[34] Y. Kojima, A. Usuki, M. Kawasumi, A. Okada, T. Kur-
auchi, O. Kamigaito, J. Polym. Sci.: Polym. Chem. 1993,
31, 983.
[35] B. Hoffmann, C. Dietrich, R.. Thomann, C. Friedrich,
R. Mulhaupt, Macromol. Rapid Commun. 2000, 21, 57.
[36] E. P. Giannelis, R. Krishnamoorti, E. Manias, Adv.
Polym. Sci. 1999, 138, 107.
[37] R. Krishnamoorti, E. P. Giannelis, Macromolecules 1997,
30, 4097.
[38] R. Krishnamoorti, A. S. Silva, in Polymer/Clay Nanocom-
posites, John Wiley & Sons, 2000, 315.
[39] J. Ren, A. S. Silva, R. Krishnamoorti, Macromolecules,
2000, 33, 3739.
[40] C. A. Mitchell, R. Krishnamoorti, Polymer nanocompos-
ites. ACS, 2001.
[41] A. P. Davey, J. Coleman, A. Dalton, S. Maier, A. Drury,
D. Gray, M. Brennan, K. Ryder, M. Lamy De La Cha-
pelle, C. Journet, P. Bernier, D. Carroll, W. Blau, H. J.
Byrne, P. M. Ajayan, S. S. Lefrant, Synthetic Metals 1999,
103, 2559.
[42] J. Sloan, A. I. Kirkland, J. L. Hutchison, M. L. H. Green,
Acc. Chem. Res. 2002, 35, 1054.
[43] J. W. Gilman, T. Kashiwagi, S. Lomakin, J. D. Lichten-
han, in Proceedings of the Inter. Wire and Cable Symposium,
1997, 46, 761.
[44] J. Zhua, C. A. Wilkie, Polym Interf. 2000, 49,1158.
[45] J. Zhua, P. Startb, K. A. Mauritzb, C. A. Wilkie, Polym.
Degr. and Stab. 2002, 77, 253.
[46] B. K. Kim, J. W. Seo, H. M. Jeong, Eur. Polym. J. 2003,
39, 85.
[47] K. Yano, A. Usuki, A. Okada, J. Polym. Sci.: Polym. Chem.
1997, 35, 2289.
[48] A. Thess, R. Lee, P. Nikolaev, H. Dai, P. Petit, J. Robert,
Science 1996, 273, 483.
[49] T. Lan, P. D. Kaviratna, T. J. Pinnavaia, J. Phys. Chem.
Solids 1996, 57, 1005.
http://www.aem-journal.de ADVANCED ENGINEERING MATERIALS 2004, 6, No. 4
Njuguna, Pielichowski/Polymer Nanocomposites for Aerospace Applications: Fabrication
[50] C. Chenggang, D. Curliss, 46th Inter'l SAMPE Symposium
and Exhibition, 2001, 1, 362.
[51] Y. T. Lim, J. H. Park, O. O. Park, J. Colloid and Interface
Sci. 2002, 245, 198.
[52] A. Singh, R. Haghighat, United States Patent No.
6057035.
[53] P. Poulin, Carbon 2002, 40, 1741.
[54] S. Iijima, T. Ichihashi, Nature 1993, 363, 603.
[55] T. Guo, P. Nikolaev, A. G. Rinzler, D. Tomanek, D. T.
Colbert, R. E. Smalley, J. Phys. Chem. 1995, 99, 10694.
[56] T. Guo, P. Nikolaev, A. G. Rinzler, D. Tomanek, D. T.
Colbert, R. E. Smalley, Chem. Phys. Letts. 1995, 243, 49.
[57] A. Thess, R. Lee, P. Nikolaev, H. Dai, P. Petit, J. Robert,
Science 1996, 273. 483.
[58] A. G. Rinzler, J. Liu, H. Dai, P. Nikolaev, C. B. Huff-
man, F. J. Rodriguez-Macias, P. J. Boul, A. H. Lu,
D. Heymann, D. T. Colbert, R. S. Lee, J. E. Fischer, Rao,
P. C. Eklund, R. E. Smalley, Appl. Phys. A. 1998, 69, 29.
[59] W. K. Maser, E. Muæoz, A. M. Benito, M. T. Martínez,
G. F. de la Fuente,Y. Maniette, E. Anglaret, J L. Sauva-
jol, Chem. Phys. Letts. 1998, 292, 587.
[60] D. Laplaze, P. Bernier, W. K. Maser, G. Flamant,
T. Guillard, A. Loiseau, Carbon, 1998, 36, 685.
[61] C. Journet, P. Bernier, Appl. Phys. A. 1998, 67, 1.
[62] See http://www.iljinnanotech.co.kr.
[63] T. W. Ebbesen, P. M. Ajayan, Nature 1992, 358, 220.
[64] S. Iijima, T. Ichihashi, Nature 1993, 363, 603.
[65] D. S. Bethune, C. H Kiang, M. S. deVries, G. Gorman,
R. Savoy, J. Vazquez, R. Beyers, Nature 1993, 363, 605.
[66] J. Abrahamson, P. G. Wiles, B. L. Rhoades, Carbon 1999,
37, 1874.
[67] W. K. Maser, J. M Lambert, P. M. Ajayan, O. Stephan,
P. Bernier, Synthetic Metals 1996, 77, 243.
[68] S. Zhua, H. Ching, J. C. Cochrane, S. Lehoczky, Y. Cui,
A. Burger, J. Crystal Growth 2002, 234, 584.
______________________
ADVANCED ENGINEERING MATERIALS 2004, 6, No. 4 http://www.aem-journal.de
[69] Z. F. Ren, Z. P. Huang, J. W. Xu, J. H. Wang, P. Bush,
REVIEWS
M. P. Siegal, P. N. Provencio, Science 1998, 282, 1105.
[70] W. Z. Li, S. S. Xie, L. X. Qian, B. H. Chang, B. S. Zou,
W. Y. Zhou, R. A. Zhao, G. Wang, Science, 1996, 274,
1701.
[71] P. Nikolaev, M. J. Bronikowski, R. K. Bradley, F. Roh-
mund, D. T. Colbert, Chem. Phys. Letts. 1999, 313, 91.
[72] C. Bower, W. Zhu, S. Jin, O. Zhou, Appl. Phys. Letts.
2000, 77, 830.
[73] G. Rinzler, J. H. Hafner, P. Nikolaev, L. Lou, S. G. Kim,
D. Tomanek, P. Nordlander, D. T. Colbert, R. E. Smal-
ley, Science 1995, 269, 1550.
[74] A. M. Cassell, J. A. Raymakers, J. Kong, H. Dai, J. Phys.
Chem. B. 1999, 103, 6484.
[75] F. W. J. van Hattum, C. A. Bernardo, J. C. Finegan
G. G. Tibbetts, R. L. Alig, M. L. Lake, Polym. Compos.
1999, 20, 683.
[76] D. Dutta, M. Husband, D. Ciminelli, J. W. Hager, The
22nd Biennial Conference on Carbon, San Diego, 1995,
p.292.
[77] G. G. Tibbets, D. W. Gorkiewicz, D. C. Hammond Jr.,
US Patent No. 50248181991.
[78] R. J. Kuriger, M. K. Alam, D. P. Anderson, R. L. Jacob-
sen, Compos. Part A. 2002, 33, 53.
[79] F. W. J. van Hattum, C. A. Bernardo, J. C. Finegan
G. G. Tibbetts, R. L. Alig, M. L. Lake, Polym. Compos.
1999, 20, 683.
[80] K. Hernadi, A. Fonseca, J. B. Nagy, A. Fudala, D. Ber-
naerts, I. Kiricsi, Appl. Catal. A: Gen., 2002, Vol. 228;
pp. 103±113.
[81] G. G. Tibbetts, M. Endo, C. P. Beetz Jr., SAMPE J. Sept/
Oct. 1986, p. 30.
[82] R. L. Vander Wal, T. M. Ticich, V. E. Curtis, Chem. Phys.
Letts. 2000, 323, 217.
[83] Z. Guo-Bin, S. Hideaki, U. Yasuo, Carbon 2003, 41, 856.
 2004 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 203