Carbon Vol. 36, No. 4, pp.

3455362, 1998
0 1998 Elsevier Science Ltd
Pergamon Printed in Great Britain. All rights reserved
0008.6223/98 $19.00 + 0.00

PII: MOOS-6223(97)00185-l

THE EFFECT OF PROCESSING ON THE STRUCTURE AND

PROPERTIES OF CARBON FIBERS*

D. D. EDIE
Center for Advanced Engineering Fibers and Films and Department of Chemical Engineering,
Clemson University, Clemson, SC 29634-0909, USA

(Received 25 August 1997)

Abstract Even though the same three process steps (fiber formation, stabilization, and carbonization)
are used to produce both polyacrylonitrile-based (PAN-based) and pitch-based carbon fibers, their final
properties differ significantly. This is a direct result of the precursors used to produce these two types of
carbon fibers (polymeric versus liquid-crystalline). Liquid-crystalline materials readily orient during fiber
formation, creating fibers with a high degree of molecular orientation, whereas polymers form fibers
with less ordered, fibrillar structures. Carbon fibers with high degrees of molecular orientation exhibit
high moduli and thermal conductivities. By contrast, carbon fibers with more discontinuous and less
ordered, fibrillar structures tend to develop higher tensile strengths. Thus, it is not surprising that PAN-
based carbon fibers have become the preferred reinforcement for high-strength composites. However,
recent studies have proven that, by disrupting molecular orientation during fiber formation, the strengths
of pitch-based carbon fibers can be improved significantly. Alternatively, linearizing the molecular
orientation during fiber formation can yield pitch-based fibers with enhanced thermal conductivities.
Researchers now realize that understanding and controlling structure during the fiber formation step is
critical if the properties of carbon fibers are to be optimized. Controlling the structure during fiber
formation can also permit milder conditions to be used during subsequent process steps, As a result,
research into precursor fiber formation offers the best opportunity for improving properties and reducing
production costs for both PAN-based and pitch-based carbon fibers. Q 1998 Elsevier Science Ltd. All
rights rcscrved.

Key Words A. Carbon fibers, fiber formation, structure/properties, PAN, A. mesophase.

1. INTRODUCTION the conditions used to form the precursor fiber. Post-

treatment steps (in this case crosslinking and carbon-
Carbon fibers are, perhaps, the most successful new
ization) merely refine and perfect the as-spun struc-
carbon product to be commercialized in the past
ture. This is not to say that fiber properties cannot
3.5 years. Their high strength and stiffness, combined
be dramatically altered during post-treatment.
with their light weight, make these fibers attractive
However, the fundamental fiber structure needed to
for high-volume applications ranging from sporting
develop high strength or high thermal conductivity
goods to aircraft structures. Today, carbon fibers are
must be created during the initial fiber formation
also being developed for a new class of applications,
step. This paper details the processes used to form
thermal management. Like other products, commer-
the two dominant classes of carbon fibers, polyacry-
cial carbon fibers must exhibit consistent mechanical
lonitrile-based (PAN-based) and mesophase pitch-
and transport properties, and the optimum properties
based (pitch-based). Then, the relationship between
may differ for each application. Because of this, the
structure and properties for both classes of carbon
control of structure and the interaction between the
fibers is discussed. Finally, recent breakthroughs in
structure and properties has been extensively studied
the control of structure for pitch-based fibers will be
since high performance fibers were first commercial-
reviewed and the possible implications for PAN-
ized by Union Carbide in the 1960s.
based fiber producers discussed.
Nearly all commercial carbon fibers are produced
Although considerable progress has been made
by first converting a carbonaceous precursor into
over the past 35 years, the origin and development
fiber form. The precursor fiber then is crosslinked in
of structure as well as the relationship between
order to render it infusible. Finally, the crosslinked
structure and properties are still not completely
precursor fiber is heated at temperatures from 1200
understood for carbon fibers. Therefore, this review
to cu 3000°C in an inert atmosphere to drive off
article indicates areas where researchers are in general
nearly all of the noncarbon elements, converting the
agreement and points out phenomena that are still
precursor to a carbon fiber. Like other commercial
subject to debate.
fiber processes, the final properties are, to a great
Unlike people, all carbon fibers are not created
extent, determined by the material, the process, and
equal. The fundamental structural characteristics of
*Based on Plenary lecture given at Curbon ‘97 at The PAN precursor fibers differ from those of mesophase
Pennsylvania State University, 13-~18 July 1997. pitch precursor fibers. Because of this, certain proper-
345
346 D. D. EDK

ties are easier to develop in PAN-based carbon fibers, 2.2 Production of PANprecursorJibers
while other properties are easier to develop in pitch- Although PAN fibers can be produced by either
based carbon fibers. Therefore, to understand struc- wet or dry spinning processes, wet spinning is used
ture and properties of these two classes of carbon to produce nearly all precursor fibers used in commer-
fibers, one must begin by detailing the materials and cial PAN-based carbon fiber processes. The solution
processes used to form the precursor fibers. used in a wet spinning process normally consists of
from 10 to 30% by weight of PAN or (PAN copoly-
mer) dissolved in a polar solvent, such as sodium
2. PAN-BASED CARBON FIBERS
thiocyanate, nitric acid or dimethylacetamide. This
Nearly all commercial fibers are produced using solution is first filtered and then extruded through a
one of three techniques: melt spinning; wet spinning; spinnerette into a coagulation bath [3,4] (see Fig. 1).
or dry spinning. In melt spinning the precursor is The coagulation bath can contain various solutions,
merely melted and extruded through a spinneret ranging from water and sodium thiocyanate or
containing numerous small capillaries. As the precur- dimethylacetamide to ethylene glycol and dimethyla-
sor emerges from these capillaries, it cools and solidi- cetamide or dimethylformamide. The rate of fiber
fies into fiber form. In wet spinning a concentrated formation is controlled by adjusting parameters such
solution of the precursor is extruded through a as the solution concentration, the concentration of
spinneret into a coagulation bath. The solvent is the coagulation bath, the bath temperature, the draw-
more soluble in the coagulation fluid than it is in the down rate, and the rate of extrusion [ 51.
precursor. Therefore, as the solution emerges from Mass transfer at the fiber/liquid interface is rela-
the spinneret capillaries, the precursor precipitates tively slow in the wet-spinning process. The reason
into fiber form. Dry spinning also involves spinning is that the solvent concentration of the coagulation
a concentrated solution through a spinneret. bath is relatively high. Because of this the solvent
However, in dry spinning the solution is extruded can diffuse radially through the solidifying fiber faster
into a drying chamber. Here, the solvent evaporates than it can diffuse away from the fiber surface. As a
and the precursor precipitates into fiber form. result, the solvent concentration is relatively uniform
Because melt spinning converts a pure precursor across the fiber’s cross-section during solidification.
directly into fiber form and does not involve the Therefore, the fiber shrinks uniformly in the radial
added expense of solvent recycling and recovery, it direction, giving the circular cross-section that is
is the preferred fiber formation process. However, characteristic of wetspun PAN. However, if the poly-
either wet or dry spinning must be employed if the mer concentration in the spinning solution is low, a
precursor degrades at or near its melting temperature. relatively rigid fiber skin can also form in this process
before the center of the fiber has solidified, yielding
2.1 Production of PANprecursor a dogbone-shape fiber.
PAN is an atactic, linear polymer containing highly As the PAN solution is forced through the spin-
polar nitrile pendant groups. Because of its highly neret capillaries, the shear field tends to orient the
polar nature, pure PAN has a glass transition temper- solidifying polymeric structure parallel to the direc-
ature of ra 120°C and tends to decompose before it tion of flow. In fact, various studies have found that
melts. Therefore, PAN precursor fibers must be pro- a solvent can decrease the entanglement of polymers
duced by either wet- or dry-spinning processes using during extrusion and enhance orientation. Like many
a highly polar solvents. Actually, PAN homopolymer other polymers, PAN tends to precipitate into fibril
is rarely, if ever, used as a carbon fiber precursor. form. Various processing parameters, such as coagu-
Commercial PAN precursor fibers normally contain lation bath temperature, solvent concentration and
from 6 to 9% of other monomers, such as itaconic stretch, can influence the fibrillar structure and its
acid, acrylic acid, methacrylic acid, methyl acrylate, orientation within the as-spun PAN fiber (see Fig. 2)
vinyl bromide, etc. [1,2]. These additions lower the [5]. In other words, wet-spinning yields a precursor
glass transition temperature and affect the reactivity fiber in which the PAN molecules are organized into
of the polymer structure. Both of these changes can fibrils which, in turn, are generally oriented parallel
dramatically influence subsequent process steps. to the fiber axis. Electron micrographs of as-spun

Storage tank
Dry and heated-draw
A

Coagulation bath Wash bath P

Fig. 1. Schematic of wet-spinning process used to produce PAN precursor fibers [4].
 Effect of processing on carbon fibers 341

(a) 0°C (b) 30°C (c) 50°C

Fig. 2. Effect of coagulation bath temperature on the fibril and pore structure of wet-spun PAN fiber after 6 x stretch [5].

Tension Coti

Exhaust Gases

Oxiied Fiber Wind-up

Tension Contml

Fig. 3. Schematic of commercial PAN stabilization oven [2].

fibers show that these fibrils are joined together in a
three-dimensional network [6].
After being spun into fibers, the orientation within
the PAN is enhanced by stretching. Although the
maximum degree of crystallinity within the PAN fiber
is only 50%, this step is essential for producing
final carbon fiber with adequate strength and modu-
lus. Like most polymeric fiber processes, stretching
does not greatly increase the crystallinity or the
molecular order within the PAN; rather, it enhances
the axial orientation of the PAN fibrils. This fibrillar
network appears to be the precursor of the graphene
network that develops during final heat treatment.
2.3 Stabilization of PANprecursorfibers
The primary function of the stabilization step is to
crosslink this as-spun structure, insuring that both
the molecular and the fibrillar orientation will not be
lost during final heat treatment. To accomplish this,
either the inherent stiffness of the PAN molecules
must be increased or the molecules must be “tied”
together in order to eliminate, or at least limit
relaxation and chain scission during the final carbon-
ization step [7,8]. In most commercial processes, the
PAN precursor fiber is stabilized by exposing it to
air at temperatures ranging from 230 to 280°C.
Tension must be applied during this step to limit
a relaxation of the polymer structure (see Fig. 3). Most
would agree that both cyclization and dehydrogena-
tion can occur during the stabilization step.
Cyclization, in particular, is highly exothermic, but
the exotherm is reduced when PAN copolymer pre-
cursors are employed. Evidently, the comonomer acts
as an initiator for the stabilization reaction [9].
Numerous studies [lO,ll] have shown that the rate
of oxidative stabilization is affected by the copolymer
composition of the PAN precursor fiber, the temper-
ature and even the applied tension. Although most
researches agree that a ladder polymer forms during
this process, its exact structure is still in doubt. In a
recent review article, Bashir [ 121 pointed out that the
cyclization reaction may be stereospecific. In fact, a
study by Colman et al. [ 131 suggests that cyclization
would occur preferentially in isotactic sequences.
348 D. D. EIIII:

However, Chen et al. [14] found that syndiotactic minimized by applying tension during heat treatment
sequences were equally capable of cyclization. The [ 181. By contrast, the degree of preferred orientation
problem may be that the polymer chains within the within the fiber and, thus, the modulus of the PAN-
fibril form an irregular rod-like helix due to the based carbon fibers increase continuously as heat
intramolecular repulsion of the nitrile groups. These treatment temperature is increased [17]. Because of
fibrils, in turn, contain both crystalline and amor- this, the various grades of PAN-based carbon fiber
phous regions. Gupta and Harrison [ 151 found that available from a particular manufacturer are, nor-
intramolecular reactions within the rod-like helix mally, the result of changes in heat treatment
dominate at lower temperatures (below ca 290°C) temperature.
whereas intermolecular reactions between adjacent
helices occur between 300 and 380°C. Perhaps both 2.5 Structure of PAN-based carbonJibers
Colman et al. and Chen et al. are correct - intramolec- Pioneering studies by Diefendorf and Tokarsky
ular reactions are stereospecific, but intermolecular [ 191, Johnson [20] and others showed that the struc-
reactions are not. ture of PAN-based carbon fiber is fibrillar in nature,
Thus, one might expect a stereoregular precursor mimicking the fundamental structure of the poly-
polymer to offer advantages. However, to date, no meric precursor fiber. Diefendorf and Tokarsky also
research in this area has been reported. showed that the amplitude of the undulation in the
fibrillar structure was highest in the center and lowest
2.4 Carbonization of stabilized PANJibers near the surface of the PAN-based carbon fibers.
Once stabilized, the PAN fiber is carbonized at This indicated that the modulus of a PAN-based
1000~1500°C in an inert atmosphere [2,8]. During carbon fiber varies throughout its cross-section. In a
this step most of the noncarbon elements within the recent study Huang and Young [21] confirmed this
fiber are volatilized in the form of methane, hydrogen, skin-core structural difference in PAN-based carbon
hydrogen cyanide, water, carbon monoxide, carbon fibers using Raman spectroscopy. Both Johnson [20]
dioxide, ammonia and various other gases [6,16]. and Endo [22] employed wide-angle X-ray diffraction
The evolution of these compounds decreases the mass to show that the layer planes of PAN-based carbon
of the fiber by from 55 to 60 wt%. As a result the fibers have no regular three-dimensional order. Also.
fiber shrinks in diameter. Therefore, in a typical PAN by subjecting longitudinal and transverse sections to
process, the precursor fiber might begin with an small-angle X-ray diffraction and transmission
as-spun diameter of 35 pm and then be stretched to electron microscope (TEM) analysis, Johnson [ 201
a diameter of 10.5 ,nm. Finally, shrinkage during showed that needle-shaped voids exist between crys-
carbonization yields a carbon fiber with a diameter tallites in the outer skin of the fiber and that. in this
of 7 pm. In other words, small carbon fiber diameters region, the layer planes are essentially parallel to the
are a characteristic of the high weight loss of PAN surface. However, in the core region, Johnson found
during processing. Even though the diameter of most that the layer planes were folded extensively, often
PAN-based carbon fibers is smaller than that of most through angles of 180”. Based on these results,
pitch-based carbon fibers, the as-spun diameter of Johnson developed the three-dimensional schematic
the precursor fiber is actually significantly greater. representation of the microstructure of PAN-based
Initially, increasing the final heat treatment temper- carbon fiber shown in Fig. 5. Guigon rt al. [23] have
ature increases tensile strength. However, as Fig. 4 proposed that the microtexture of PAN-based carbon
shows, the tensile strength suddenly drops when heat fibers is even more complicated~“crumpled sheets”
treatment temperatures exceed 1600°C [ 171. Fitzer form these fibrils.
claims that this decrease is associated with the release
of nitrogen and that the reduction in strength can be

40 -

I ,.., I I ,, I I I * , I,, , , I,,

500 ,000 1500 2000 2500

Final Heat Treatment Temperature (“C)

Fig. 4. Influence of final heat treatment temperature on the Fig. 5. Microstructure of PAN-based carbon fiber proposed
tensile strength of PAN-based carbon fiber [ 171. by Johnson [20].
 Effect of processing on carbon fibers 349

!
I
Tensile stress causes basal Catastrophic failure occurs if
Misoriented crystallite linking two

crystallites parallel to fiber axis. plane rupture in La direction. crystallite size 5 critical flaw size.

(4 (b) cc>
Fig. 6. Reynolds and Sharp mechanism for tensile failure of carbon fibers [20].

Each of these studies show that the PAN-based failure mode explains the difference between the flaw
carbon fibers contain extensively folded and sensitivity (and, therefore, the tensile strength) of the
interlinked turbostratic layers of carbon with nongraphite, fibrillar PAN-based carbon fiber and
interlayer spacings considerably larger than those of graphitic, mesophase pitch-based fiber. Recent work
graphite. As a result, PAN-based carbon fibers have by Dobb ef al. [24] indicates that inter-crystalline
a low degree of graphitization. The turbostratic layers and intra-crystalline disorder, most likely caused by
within PAN-based carbon fibers appear to follow the the fibrillar structure of the PAN-based carbon fiber,
original fibril structure of the PAN precursor fiber. is responsible for the superior compressive strength
Although the turbostratic layers within these fibrils of this class of carbon fiber.
tend to be oriented parallel to the fiber axis, they are Obviously, the fundamental fibrillar structure of
not highly aligned. As first proposed by Johnson PAN-based carbon fibers is created during initial
[20], it is this fibrillar structure that makes PAN- fiber formation. However, little if any research into
based fibers less prone to flaw-induced failure. He this fiber formation process has been done since
based his argument on the brittle-failure mechanism PAN’s adoption as a carbon fiber precursor. Instead,
proposed by Reynolds and Sharp. As discussed as the above review indicates, nearly all recent PAN-
above, the crystallites within PAN-based carbon based carbon fiber research has concentrated on
fibers are not perfectly aligned, and misoriented stabilization and carbonization. By contrast, research
crystallites are relatively common (see Fig. 6(a)). in pitch-based carbon fibers has concentrated on
When a stress is applied parallel to the fiber axis, the perfecting precursor chemistry and the development
crystallites align until their movement is restricted by of structure during fiber formation. As will be seen,
a disclination in the structure (Fig. 6(b)). If the stress pitch researchers appear to have chosen the more
is sufficient, the misoriented crystallite will rupture critical area for control and optimization of fiber
and relieve the stress within the fiber (Fig. 6(c)). properties.
When the size of the ruptured crystallite (perpendicu-
lar to the fiber axis) is larger than the critical flaw
3. PITCH-BASED CARBON FIBERS
size, a catastrophic failure occurs, and the fiber
breaks. Even if the rupture crystallite is smaller than Its highly condensed aromatic structure gives meso-
the critical flaw size, catastrophic failure can occur if phase pitch (the precursor for pitch-based carbon
the crystallites surrounding the disclination are con- fibers) relatively good thermal stability. Because of
tinuous enough to allow a crack to propagate into this, mesophase pitch precursor fibers are melt spun.
neighboring crystallites. According to Johnson, this As previously mentioned, melt spinning is the pre-
350 D. Eon

Coal-tar-derived mesophase Petroleum-derived mesophase

Fig. 7. Typical polynuclear aromatic hydrocarbons in mesophases produced from coal-tar and petroleum [32]

ferred fiber formation process because it avoids Chwastiak [32] found that if an inert gas spurge was
solvent-related issues. Initially, it was felt that this used to agitate the pitch during thermal polymeriza-
less complicated spinning process, combined with the tion, a spinnable 100% mesophase product could be
potential low cost of the precursor, would make produced. A single-phase precursor is preferable for
pitch-based fibers a low-cost alternative to PAN- melt-spinning processes because it avoids the stability
based carbon fibers. While this may come to pass problem associated with two-phase extrusion,
eventually, the economics of pitch fiber processing Nevertheless, based on a recent TEM study by Fitz
are not quite this simple. Also, as researchers have Gerald et (I/. [33], it would appear that some commer-
discovered, the fundamental structure of pitch-based cial pitch-based fibers are still produced from a mixed
carbon fibers is very different from that of PAN- mcsophase/isotropic pitch precursor.
based carbon fibers, and each structure offers certain Diefendorf and Riggs developed an alternative
advantages. Like PAN-based fibers, the structure of technique, solvent extraction. that produced a spinn-
pitch-based fibers is largely developed during fiber able 100% mesophase precursor from an isotropic
formation. feed [34]. In their process a portion of highly aro-
matic pitch was extracted using a solvent mixture
3.1 Production of’mesophase pitch such as benzene and toluene. The extraction step
Like PAN-based carbon fibers, the peculiarities of removes the smaller disordering molecules and con-
pitch-based fibers are the direct result of the precursor centrates the higher molecular weight material. The
and the process used to convert it to fiber form. In higher molecular fraction can be converted to 100%
this case, the precursor is mesophase pitch, a liquid mesophase by heating it to between 230 and 400°C
crystalline material consisting of large polynuclear for only 10 minutes. In either the thermal polymeriza-
aromatic hydrocarbons. The properties of meso-
phase, its formation, and mode of growth have been
the subject of numerous articles [25-281.
The first commercial mesophase precursors were
produced by Union Carbide using a thermal polymer-
ization process. Evidently, the original process pro-
duced a mixture of isotropic and mesophase pitch
[29,30]. These early patents claim that small amounts
of isotropic pitch are needed to reduce the viscosity
of the polymerized mesophase and, therefore, the
spinning temperature. These mixed precursors were
prepared by thermally polymerizing a highly aromatic
isotropic pitch feed (originating from either petro-
leum or coal tar) at temperatures of 400-410°C for
as long as 40 hours [29,30]. Coal tar pitch produces Quench Air
a mesophase product with higher aromaticity.
whereas petroleum pitch yields a mesophase product
with a more open structure and a higher content of
aliphatic side chains (see Fig. 7) [9.31]. As revealed Variable Speed
Winder -
by Lewis [30], agitation during heat treatment pro-
duces a lower molecular weight mesophase and cre-
ates an emulsion of the mesophase and isotropic Fig. 8. Schematic of melt-spinning process used to product
pitch, making the material easier to spin. Later mesophase pitch precursor fibers [39].
 Effect of processing on carbon fibers 351

Quench Cross Air winder Spinning

Temperature Velocity Velocity Temperature

Fig. 9. Predicted influence of major process variables during mesophase melt spinning [41].

tion or the solvent extraction process, a free radical but uses large amounts of solvents. Supercritical
mechanism is believed to be responsible for polymer- extraction and catalytic polymerization produce rela-
ization of the carbonaceous material. Although tively uniform products with narrow molecular
solvent extraction does reduce the molecular weight weight distributions. However, supercritical extrac-
distribution somewhat prior to heat treatment, this tion has yet to be proven on a commercial scale, and
reaction mechanism still tends to create a product processes using HF-BF, catalysis are being subjected
with a relatively broad molecular weight distribution. to increasing environmental regulations.
Recently, Thies and coworkers [35] developed a The mesophase products produced by these four
variation of this solvent-extraction process that uses processes differ considerably, but they also exhibit
a supercritical fluid instead of a conventional liquid many similarities. For instance, each process yields a
solvent. In this process, an aromatic isotropic feed product with a different molecular weight distribution
pitch is initially dissolved in an aromatic solvent, and a different concentration of aliphatic side chains
such as toluene, at supercritical conditions. The on the individual mesophase molecules. Consequently
resulting homogeneous solution is then fractionated their viscous characteristics differ and, as will be
in a conventional manner, using changes in either explained later, their rate of stabilization differs as
temperature or pressure, to produce pitch fractions well. However, all of these mesophase products con-
of relatively narrow molecular weight distribution. tain a range of molecular weights, with an average
Recent tests have demonstrated that the process can from 800 to 1200. Because of this these mesophases
be used to produce 100% mesophase fractions of a reach a viscosity of 200 Pa s-l or lower well below
desired molecular weight and softening point [ 361. their degradation temperature. Also, although some-
Mochida [37] also has developed a process which what irregular, the individual mesophase molecules
produces a spinnable 100% mesophase precursor with are, in general, disc-like in shape. Recent work by
a relatively narrow molecular weight distribution. Korai and Mochida [38] indicates that mesophase
This process, recently commercialized by Mitsubishi molecules can form a substructure and that the
Gas Chemical Company, uses a strong Lewis acid chemical nature of the molecule influences the size
catalyst (HF-BF,) to catalyze a pure chemical feed, of this substructure.
such as naphthalene or methyl-naphthalene, to a While coalesced mesophase can exhibit compli-
100% mesophase product. As Mochida has shown, cated extinction patterns caused by disclinations, no
the use of HF-BF, greatly reduces the molecular grain boundaries appear to be present [ 391. In other
weight distribution of the mesophase product com- words, one might expect bulk mesophase to behave
pared to that produced by thermal polymerization. as an ideal liquid crystalline fluid-a single-domain
Each of these processes are being explored, and, liquid crystal. As will be seen, this appears to be
to varying degrees, used on a commercial scale. While both true and false.
each process and its mesophase product offer certain
advantages, they also suffer from some disadvan- 3.2 Production of mesophase pitch precursor
tages. Thermal polymerization avoids the use of jibers
solvents, but produces a product with a broad molec- As previously mentioned, the mesophase pitches
ular weight distribution (and perhaps even a two- used to form carbon fibers soften and flow well below
phase mixture). Solvent extraction produces a pro- their degradation temperature. Therefore, they can
duct with a narrower molecular weight distribution, be melt spun into fiber form. The schematic for a
352 D. D. EDK

the manifold it enters a metering pump. The purpose

of this positive-displacement pump is to minimize
any pressure fluctuations created by the rotating
extruder screw. The metering pump forces the molten
precursor into the spin pack. Normally, the spin pack
houses a filter, which is capable of removing any
Radial Onion-skin Random small solid particles from the molten precursor. As
the precursor exits the pack, it is forced through a
plate containing numerous small holes (i.e. the spin-
neret). Finally, as the molten precursor exits these
holes, it is simultaneously quenched by the surround-
ing atmosphere and drawn down by the windup
device, forming solid fibers. At first glance, this would
appear to be a relatively simple process. In fact, the
Flat-layer Radial-folded Line-origin melt spinning is simple. However, melt-spinning
mesophase is far from simple.
Fig. 10. Transverse textures of mcsophasc-pitch-based By applying heat, mass and momentum balances,
carbon fibres [56]. Edie and Dunham [41] showed that the mesophase
melt-spinning process is extremely sensitive to small
typical melt-spinning process that might be used to changes in process conditions. Although their model
produce mesophase pitch precursor fibers [40] is did not account for the liquid crystalline behavior of
shown in Fig. 8. The precursor (in this case, meso- the mesophase precursor, it nevertheless demon-
phase pitch) is loaded into the feed hopper of the strated that, at typical process conditions, the tensile
extruder as solid chips. The extruder’s rotating screw stress on mesophase fibers is ca 20% of that required
conveys the chips into the melting section of the to break the fiber (see Fig. 9), and experimental
extruder where the chips are heated, forming a vis- measurements confirm these predictions. In compari-
cous melt. Then the molten precursor is conveyed son, during melt spinning the tensile stress developed
into the pumping section of the extruder. In this within a nylon fiber is < 1% of the breaking strength
section of the extruder the channel narrows, increas- of the filament. This stability problem is the direct
ing the fluid pressure. The molten precursor, now at result of two peculiarities of mesophase: its highly
a relatively high pressure, exits the extruder and flows temperature-dependent viscosity, and the brittle
through the transfer manifold. As the precursor exits nature of as-spun mesophase fibers.

7 I I I I I I
I I I

PAN-based fibers Current PAN-based fibers

(Prior (Amoco, Hercules,
6 Akzo Nobel, Mitsubishi)

1
Isotropic-pitch-based fibers Mesophase-pitch-based fibers
l v (Textron) (Prior to 1YYO)

0 I I I I I , I I I
C) 100 200 300 400 500 600 700 800 900 1 10

Fiber Modulus, GPa

Fig. 11. Mechanical properties of commercial PAN-based and mesophase pitch-based carbon fibers as of 1989 compared to
the properties of current commercial PAN-based and pitch-based fibers.
 Effect of processing on carbon fibers 353

vr = “8 = 0

n,=cosw(r)

ne = sin o(r)

n, = 0

(4

Fig. 12. Predicted transverse molecular orientation for mesophase pitch flowing through a circular capillary a.nd transl
texture of carbonized mesophase fiber extruded from a circular capillar [57].

Because its viscosity is highly temperature-depen- so the stabilization process involves simultaneous
dent, mesophase pitch fibers draw down and cool diffusion and reaction. However, unlike PAN precur-
very quickly during fiber formation. In fact, at typical sor fibers, the as-spun structure of mesophase precur-
melt-spinning conditions, mesophase fibers are sor fibers is already highly oriented, so tension does
already 100°C below their glass transition temper- not need to be applied during stabilization. Most
ature by the time they are 2 cm from the spinneret. mesophase precursor fibers can be stabilized by
As a result, they can break easily during spinning exposing them to air at temperatures ranging from
and are extremely difficult to handle before they are 230 to 280°C. Often, the temperature begins near the
carbonized. Although the rheology of mesophase softening temperature of the mesophase and is
makes control of the melt-spinning more difficult, its increased in a series of steps during the stabilization
liquid crystalline nature gives this precursor advan- process. Numerous studies [43-451 have shown that
tages compared to polymeric precursors such as the rate of oxidative stabilization is affected by the
PAN. As Yoon et al. [42] showed, unlike polymeric temperature, the concentration of oxygen, and the
fibers, the molecular orientation within a mesophase chemical structure of the mesophase molecules. Most
precursor fiber can be improved by increasing spin- researchers agree that, during the initial stages of
ning temperature. oxidative stabilization, the mesophase fiber gains
weight; ketones, aldehydes and carboxylic acids are
3.3 Stabilization of mesophasepitch precursor formed; and water is given off [43,44]. At higher
fibers temperatures, the fiber begins to lose weight as CO,
Because mesophase pitch is a thermoplastic mate- is evolved. However, the exact nature of the reactions
rial, the as-spun structure must be thermoset to that occur during the stabilization step is still the
prevent relaxation during final heat treatment. Like subject of active research. As in the PAN carbon
the PAN carbon fiber process, oxidative stabilization fiber process, the objective is to uniformly crosslink
is normally employed to crosslink the as-spun fibers, the precursor fiber as fast as possible with a minimum
354 D. D. EDW

Table 1. Current mechanical and electrical properties of commercial pitch-based carbon

fibers

Density Average tensile Average tensile Average electrical

(g cm? strength (GPa) modulus (CPa) resistivity(@ mm’)

Amoco
P-25 1.90 1.38 159 13.0
P-55s 2.00 I .90 379 8.5
P-l% 2.00 2.10 517 7.0
P-loos 2.16 2.41 758 2.5
P-loos 2.16 2.07 758 2.5
P-120 2.17 2.41 827 2.2
P-120s 2.18 2.41 827 2.0
K-800x 2.18 2.93 931 1.6
K-l 100 2.20 3.10 931 I .2

Nippon
XN-5OA 2.14 3.83 520 7.0
XN-70A 2.16 3.63 720 4.0
XN-8-A 2.17 3.63 785 3.0
XN-85-A 2.17 3.63 830 3.0
YS-SOA* 2.09 3.83 520 7.0
Y S-7OA* 2.14 3.63 720 6.0
YS-50* 2.09 3.73 490 7.0
YS-60* 2.12 3.53 590 7.0
YS-70* 2.14 3.53 690 6.0
YS-80* 2.15 3.53 785 5.0

Mitsubishi
Kasei Co.
K133 2.08 2.35 440
K135 2.10 2.55 540
K137 2.11 2.65 640
K139 2.12 2.75 740
K321 I .90 1.96 180

Textron
Carboflex+ 1.57 0.55 35 60.0

*Coal tar mesophase pitch precursor.

+Isotropic pitch precursor.

addition of noncarbon elements. Currently, stabiliza- carbonization. In other words, even though the diam-
tion is the slowest step in the pitch-based carbon eters of most commercial pitch-based carbon fibers
fiber process, taking from 30 minutes to >2 hours are larger than those of most PAN-based carbon
for most mesophase precursors. Therefore, the search
continues for new stabilization techniques and new
mesophase structures that can be more readily
crosslinked.

3.4 Carbonization of stabilized mesophase pitch-

based$bers
Once stabilized, the pitch fiber is carbonized at
1500-3000°C in an inert atmosphere [46,47]. During
this step most of the noncarbon elements within the
fiber are volatilized in the form of methane, hydrogen,
water, carbon monoxide, carbon dioxide and various
other gases. Because the mesophase precursor fiber
is 90% carbon and it gains only 6-8 wt% of oxygen
during stabilization, the yield of the pitch-based
1.44
carbon fiber process ranges from 70 to 80-consider- 0.95 0.97 0.99 1 01 1.03 1.05

ably higher than that of the PAN-based process. Dimensionless Temperature, TTT,
However, the lower mass loss also means that, typi-
cally, a 12-pm-diameter precursor fiber must be spun Fig. 13. Temperature variation in elastic constants for splay,
K,, and bend, K, [60]. The temperature is scaled by the
if a 10 pm final diameter is desired. By comparison, transitional temperature T, at which K, = K3, and the scaling
a fully-drawn AN precursor fiber with a diameter of constant for the Frank elastic constants is K, the cross-over
15 pm would yield the same size carbon fiber after value of K, and K3.
 Effect of aroce
. :ssing on carbon fibers 355

(4

Fig. 14. Predicted transverse molecular orientation for mesophase pitch flowing through a rectangular capillary and tra msverse
texture of carbonized mesophase fiber extruded from a rectangular capillar [57].

fibers, the as-spun diameter of the precursor fibers result of the transverse microstructure and axial
are actually significantly smaller. Needless to say, molecular orientation created as the liquid crystalline
smaller as-spun ‘diameters tend to increase process- precursor flows through a capillary and then is
ing costs. extended during fiber formation. Unless relaxation
Increasing the final heat treatment temperature occurs during thermosetting, this transverse micro-
improves the degree of preferred orientation within structure and axial orientation is merely perfected
the fiber and, thus, the modulus of the pitch-based during carbonization. The transverse texture of early
carbon fibers. As with PAN-based carbon fibers, the commercial mesophase carbon fibers was either radial
various grades of fiber available from a particular or flat-layer (see Fig. 10). Thus, in the transverse
manufacturer often are produced by merely changing direction the graphene layer planes fan out from the
this temperature. center of the fiber, and in the axial direction the layer
planes tend to align parallel to the fiber axis. As
3.5 Structure of mesophase pitch-based carbon Bright and Singer [52] first demonstrated, the
jb ers transverse texture can affect fiber graphitizability.
Since the early studies by Otani [48], Singer [49], Although this early study did not reveal how fiber
Bacon [50] and Barr et al. [51], researchers have texture could be varied, a later patent [53] disclosed
recognized that melt spun mesophase fibers can that fibers with random transverse textures could be
develop remarkably high moduli. This is the direct produced by disrupting the flow during extrusion.
356 D. D. EDII+

Assuming p = 90” and solving the Leslie-Ericksen equations yields

(b)
Fxg 15. Predicted effect of converging flow prior to extrusion through a rectangular capillary and transverse texcurc of
carbonized mesophase fiber extruded from a rectangular capillary with a converged entry region [57].

Fig. 16. High resolution SEM images of near-surface microtcxture in a mesophase-pitch-based carbon fiber [611
 Effect of processing on carbon fibers

+z*O
3 16

4 12

56
5
24
Go
0 0.5 1 1.5 2 2.5 3
Channel Radius (mm)
Fig. 17. Observed and predicted microstructure during flow of AR mesophase through entry region of capillary
(y,=3 seconds-‘) [67].

These initial mesophase-pitch-based carbon fibers mechanical and thermal properties appear to be the
with radial and flat-layer transverse textures readily result of optimizing the transverse textures for a
developed three-dimensional crystallinity (see given property and utilizing improved mesophase
Fig. 10). Although this structure made pitch-based precursors.
carbon fibers more flaw-sensitive than PAN-based
fibers with their more random, fibril structure, it gave 4.1 Control of structure
them superior lattice-dependent properties. As Beginning with the work by Hamada et al. [54],
Fig. 11 shows, prior to 1990, PAN-based carbon Matsumoto [55] and Edie et al. [56] it became
fibers were characteristically high strength but low apparent that the texture of mesophase fibers was
modulus, whereas pitch-based carbon fibers were created, and thus could be controlled, during melt
high modulus but low strength. spinning. Hamada et al. [54] changed transverse
structure by disrupting the flow profile prior to
extrusion, whereas Matsumoto [55] and Edie et al.
4. NEW DEVELOPMENTS
[ 561 used extrusion capillaries with either nonuniform
Obviously, structure controls the properties of the or noncircular cross-sections. Since that time numer-
final carbon fiber (either PAN-based or pitch-based). ous researchers have demonstrated that flow during
In this review, the author has tried to demonstrate extrusion can be controlled to create mesophase fibers
that the carbon fiber structure can be controlled by with a variety of textures, each with certain advan-
changing the chemistry of the precursor, by con- tages. Mesophase fibers with random or radial-folded
trolling the development of structure as the precursor textures tend to exhibit higher tensile and compressive
fiber is formed, or by modifying the conditions used properties [ 57,581. By comparison, fibers with linear
to heat treat the precursor fiber. Over the past transverse textures appear to develop better lattice-
10 years pitch-based carbon fiber researchers have dependent properties, for example, thermal conduc-
focused on these first two factors, and their efforts tivity [ 261.
are beginning to yield results. As Fig. 11 shows, new
pitch-based fibers are now being introduced with 4.2 Modeling the development of structure
strengths approaching those of PAN-based fibers. While viscous effects control the rate and distribu-
Also, as Table 1 shows, new pitch-based fibers with tion of flow during extrusion, elastic effects appear
extremely low electrical resistivities (and, thus, high to control the development of structure prior to and
thermal conductivities) are also being introduced for during extrusion. Recent research by McHugh and
thermal management applications. These improved Edie [59,60], Rey [61] and Wang and Rey [62] show
358 D. D. EDIE
 Effect of processing on carbon fibers 359

Fig. 19. Pleat-like structure observed in mesophase pitch-based carbon fibers [64].

that continuum theories (such as Leslie-Ericksen’s), is actually a gel, and that deformation of this gel
first developed for rod-like liquid crystals, can be during fiber formation creates this complex micro-
extended to predict the development of structure structure. Fathollahi and White [68] contend that
during the melt spinning of mesophase. Edie and this complex substructure is the result of disclinations
McHugh showed that the mesophase structure that are deformed during extrusion and fiber forma-
observed as mesophase passes through circular capil- tion. This argument would be consistent with liquid
laries (as well as the transverse texture of carbonized crystal theory. In fact, as Fig. 17 shows, Fleurot and
fibers) matches that predicted by liquid crystal theory Edie [69] have now demonstrated that the liquid
(see Fig. 12). Wang and Rey [62] have shown that crystal theory of Marruchi successfully predicts the
both the radial and the onion-skin structure occur deformation of this disclination structure during the
naturally (either during flow or in a stagnant fluid). extrusion of mesophase pitch precursors. Thus, in
Apparently the stable form depends on the relative some ways, Fleurot and Edie are using classical liquid
size of the elastic constants for bend and splay (see terminology to explain observations such as those
Fig. 13). Rey would predict that high temperatures reported by Oberlin and coworkers. Fleurot and Edie
would favor the formation of onion-skin textures, have already developed “visual” computer models,
low temperatures would favor radial textures and based on first principles, which can even simulate
random textures would occur at intermediate vortices which can develop prior to flow through the
temperatures. spinneret capillary (see Fig. 18) [69]. The next objec-
McHugh found that this same liquid crystal theory tive is to include the development of this substructure,
correctly modeled the development of molecular generated by the deformation of the mesophase
orientation as mesophase was extruded through disclinations.
rectangular capillaries (see Fig. 14) and correctly Additional complications remain before first prin-
predicted that converging flow prior to extrusion ciples can be used to predict the final structure of a
would linearize the transverse structure of a meso- mesophase fiber for a given process. As Fig. 19 shows,
phase fiber. Recent results by Robinson and Edie Mochida et al. [64] have detected “pleat-like” struc-
[63] prove this to be true. Converging flow prior to tures in carbonized mesophase fibers. More than
extrusion not only linearizes the transverse texture likely, crystallization and shrinkage during final heat
of the fiber (see Fig. 15), but it also dramatically treatment must be included if the model is to account
improves the thermal properties of the fiber. for these structures.
Based on these studies, it would appear that the Although mesophase pitch-based carbon fibers are
texture of pitch fibers now can be predicted. However, a newer product than PAN-based carbon fibers,
Robinson and Edie [63] and Mochida et al. [64] researchers are beginning to develop a far better
have shown that, although this texture represents the understanding of how to predict and control their
gross structure, the microtexture [as the high reso- structure. The primary reason for this advance is
lution scanning electron microscopy (SEM) photo in that, while most PAN-based fiber research has
Fig. 16 shows] contains irregular kinks and bends. focused on heat treatment, most mesophase pitch-
Lafdi et al. [65-671 proposed that mesophase pitch based fiber research has concentrated on precursor
360 D. D. EDIE

Table 2. Current mechanical and electrical properties of commercial PAN-based carbon fibers

Density Average tensile strength Average tensile modulus Average electrical resistivity
(8 cm? (GW (GPa) (nD m-‘)

T-40 1.81 5.65 290 14.5

T-50 1.81 2.90 390 9.5
T-300 1.76 3.65 231 18
T-650-35 1.77 4.28 255 14.5
T-650142 1.78 4.62 290 14.2

Akzo Nobel-Fortafil
Fortafil 3(C) 1.80 3.80 227 16.7
Fortafil 5(C) 1.80 2.76 345 9.75

Hercules
AS4C 1.77 3.86 226
AS4D 1.78 4.21 241
IM4 1.73 4.14 276
AS4 1.79 3.93 221
IM6 1.76 5.24 276
IM7 1.77 5.38 276
IM8 1.80 5.45 303
IM9 1.79 6.43 290
UHM 1.87 3.45 441

Textron
Avcarb 99 1.74 1.90 262 11.0

Toray
T300 1.76 3.53 230
T300J 1.78 4.21 230
T300H 1.80 4.41 250
T700S 1.80 4.90 230
T800H 1.81 5.49 294
TlOOOG 1.80 6.37 294
M35J 1.75 4.70 343
M40J 1.77 4.41 377
M46J 1.84 4.21 436
M50J 1.88 4.12 475
M55J 1.91 4.02 540
M60J 1.94 3.92 588
M30 1.70 3.92 294
M30S 1.73 5.49 294
M30G 1.73 5.10 294
M40 1.81 2.74 392

Zoltek
PANEX 33 3.60

chemistry and fiber formation. Once perfected, the properties is a direct result of the as-spun structure
ability to predict the development of structure during of the two precursor fibers.
fiber formation could lead to mesophase-pitch-based The fibrillar texture of the PAN precursor inhibits
carbon fibers with properties engineered for specific the development of graphitic structure during carbon-
applications. This approach represents the future of ization, making these fibers less flaw-sensitive. By
materials processing, and it could revolutionize comparison, liquid crystalline mesophase can pro-
carbon fiber manufacturing. duce a precursor with an extremely high degree of
molecular orientation parallel to the fiber axis. The
transverse structure can be disrupted during extrusion
5. SUMMARY
to decrease graphitizability and improve strength, or
Table 2 shows a tabulation of the properties of it can be linearized to increase graphitizability and
several commercial carbon fiber products, as listed enhance thermal conductivity.
in the manufacturers’ product data sheets, and these Although it is likely that PAN-based fibers will
same data are plotted in Fig. 11. Obviously, current continue to dominate strength-based applications for
commercial PAN-based carbon fibers exhibit higher the next few years, thermal management applications
tensile strengths, but lower moduli, than do meso- are likely to create a large market ideally suited for
phase-pitch-based carbon fibers. This balance of mesophase pitch fibers. Researchers are just begin-
 Effect of processing on carbon fibers 361

ning to understand how to control mesophase struc- 13 Colman, M. M., Sivy, G. T., Painter, P. C., Snyder, R.
ture during fiber formation and optimize final fiber W., Gordon, B., , IIICarbon, 1983, 21, 255.
14. Chen, S. S., Herms, J., Peebles, L. H. and Uhlmann,
properties. In the future, this knowledge could lead D. R., J. Mater. Sci., 1981, 16, 1490.
to pitch-based carbon fibers with mechanical proper- 15. Gupta, A. and Harrison, I. R., New aspects of the
ties equal to or greater than those of PAN-based oxidation stabilization of PAN-based carbon fibers.
fibre. However, new low-cost production techniques Carbon, 1996,34, 142771445.
16. Fitzer, E., Heine, M. and Metzler, W., Gaseous pro-
must also be developed if pitch-based carbon fiber
ducts during heat treatment of polyacrylonitrile. In
manufacturers hope to compete with PAN-based Carbon ‘86, Proceedings of the Fourth International
fibers in strength-related applications. Carbon Conference, Baden-Baden, Germany, 30
June-4 July 1986.
17. Fitzer, E. and Frohs, W., The influence of carbonization
Acknowledgements-The author would like to thank Steve and post treatment conditions on the properties of PAN-
Linder, Director of Manufacturine. Technoloev. Office of based carbon fibers. In Carbon ‘88, Proceedings of the
Naval Research, for his continuingsupport of%e work in International Carbon Conference, Newcastle upon
mesophase-pitch-based carbon fibers. Thanks are also due Tyne, U.K., pp. 2988300, 18-23 September 1988.
to Albert Bertram, technical monitor of the current Office 18. Fitzer, E., PAN based carbon fibers-present state and
of Naval Research project on high thermal conductivity trend of the technology from the viewpoint of possibilit-
carbon fibers (Contract No. N00014-95-1-1345). The author ies and limits to influence and to control the fiber prop-
is also grateful to the National Science Foundation for erties by the process parameters, Carbon, 1989, 27(5),
supporting his fundamental research into the development 621-645.
of structure through Grant No. OSR-9108 772-004. The 19. Diefendorf, R. J. and Tokarsky, E., Polym. Eng. Sci.,
advice and helpful interaction of industrial colleagues at 1975, 25(3), 150-159.
Amoco Performance Products, Inc., in particular Drs Roger 20. Johnson, D. J., Structure property relationships in
Bacon, Grish Deshpande and Chris Levan, is gratefully carbon fibers, J. Phys. D: Appl. Phys., 1987, 20(3),
acknowledged. The author would like to thank Dr Rosa 287-291.
Menendez and Professors Erich Fitzer, Brian Rand, Carlos 21. Huang, Y. and Young, R. J., Effect of fiber microstruc-
Bemardo, Isao Mochida, Charles Fain and Mark Thies. ture upon the modulus of PAN- and pitch-based carbon
Their advice, comments and ideas have been invaluable. fibers, Carbon, 1995, 33(2), 97-107.
Finally, the author would like to thank his current and 22. Endo, M., J. Mater. Sci., 1988, 23(2), 598-605.
former graduate students for their dedication, their creativ- 23. Guigon, M., Oberlin, A. and Desarmot, G., Fibre Sci.
ity and their hard work. Technol., 1984, 20, 55.
24. Dobb, M. G., Guo, H., Johnson, D. J. and Park, C.
R., Structureecompression property relations in carbon
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