Advanced Industrial and Engineering Polymer Research 5 (2022) 90e106

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Advanced Industrial and Engineering Polymer Research

journal homepage: http://www.keaipublishing.com/aiepr

Chapter 5: A critical review of carbon fiber and related products from

an industrial perspective
Ton Peijs a, *, Robert Kirschbaum b, Pieter Jan Lemstra c
a
WMG, University of Warwick, Coventry, UK
b
Sakugariconsult, Amsterdam, The Netherlands
c
PlemPolco B.V., Veldhoven, The Netherlands

a r t i c l e i n f o a b s t r a c t

Article history: Because of their exceptional mechanical properties, carbon fibers are being used in composite applica-
Received 19 February 2022 tions where weight saving is key such as in the aerospace and sports sector, with increasing demands
Received in revised form coming from wind energy, aerospace and defense. However, an even more significant increase in de-
25 March 2022
mand in automotive is foreseen if the cost price of carbon fiber could come down substantially. In 2012
Accepted 25 March 2022
the US Department of Energy set a target price level of 10 USD/kg to get carbon fiber into mainstream
cars. These low-cost carbon fibers should possess a tenacity of at least 1.7 GPa with a corresponding
Keywords:
elastic modulus of 170 GPa. Carbon fibers are currently predominantly based on polyacrylonitrile (PAN)
Review
Carbon fiber
precursor fibers, while pitch is used for some high-modulus fibers. The cost price of PAN-based carbon
Precursor fiber fibers is determined for at least 50% by the PAN precursor. Consequently, over the last decade huge R&D
Polyacrylonitrile programs have been undertaken in search of cheaper and more sustainable precursors such as lignin and
Lignin polyethylene. Despite major efforts no significant commercial successes have been obtained up to now in
Cellulose stark contrast with numerous claims in the scientific literature regarding so-called breakthrough tech-
Polyethylene nologies. Next to the recent revival in carbon fiber research another carbon allotrope, the carbon
Carbon nanotubes nanotube (CNT), has received huge attention as the ‘next generation’ reinforcing element for composites.
Fibers and yarns have been made directly from CNTs or have been added into other high-performance
fibers to boost their properties. However, also here despite major research efforts and numerous high
impact publications the results obtained were at best interesting or doubtful with little commercial
success.
© 2022 Kingfa Scientific and Technological Co. Ltd. Publishing services by Elsevier B.V. on behalf of KeAi
Communications Co. Ltd. This is an open access article under the CC BY-NC-ND license (http://
creativecommons.org/licenses/by-nc-nd/4.0/).

1. Preamble discussed extensively as a precursor for low-cost carbon fiber [5e10].

The science and technology of carbon fiber production has been
well documented in numerous papers, reviews and textbooks [1e3].
About 90% of carbon fibers are based on polyacrylonitrile (PAN),
while a small amount is based on rayon or petroleum pitch, notably
some higher modulus grades. The cost of producing carbon fibers is
highly determined by the cost of producing the precursor PAN fiber,
about 50%. In recent years, attention has therefore focused on
alternative cheaper and more sustainable precursors [4] like lignin,
cellulose or polyethylene to lower the cost of producing carbon fibers
with the aim to make inroads into high-volume application areas like
automotive where cost is a major issue. In recent reviews, lignin is
* Corresponding author.
E-mail address: t.peijs@warwick.ac.uk (T. Peijs).
In many of these studies expectations are running high regarding the
potential of lignin as a biobased and cheap precursor for carbon fi-
bers but the question remains; are these predictions realistic?
Another potential reinforcing element based on carbon atoms,
albeit of finite length, are carbon nanotubes (CNTs), which when
compared with carbon fibers, possess extremely high tensile
strengths up to 100 GPa. What can these nano-structures bring us
in fibrous form? Can we expect a next generation super high
strength fiber? Or when used as an additive in other high-
performance fibers, can they upgrade these fibers to the next per-
formance level, e.g. a tensile strength of >10 GPa? Scientists have
claimed that by adding CNTs to polymeric fibers they can increase
their strength [11e13], with some studies claiming similar or higher
strength levels as current aramid and high-performance

https://doi.org/10.1016/j.aiepr.2022.03.008
2542-5048/© 2022 Kingfa Scientific and Technological Co. Ltd. Publishing services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an open access article
under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
T. Peijs, R. Kirschbaum and P.J. Lemstra
polyethylene fibers like Dyneema®. However, also here the ques-
tion arises; are these claims even realistic?
In this paper the various property claims regarding novel routes
towards cheaper carbon fibers and the use of carbon nanotubes as
nanoreinforcements in high-performance fibers are critically eval-
uated and discussed from an industrial perspective.
2. Carbon fibers, a brief history
Sir Joseph Wilson Swan [14] was the first in 1860 to make a
carbon fiber by heating cotton fibers in the absence of air for use in
early incandescent light bulbs followed by Thomas Edison in 1879
who made carbon fibers from cellulose (cotton and bamboo) in the
first light bulbs to be heated by electricity [15]. Cotton is almost
pure cellulose but the mechanical properties of the produced car-
bon filaments were poor though suitable for the main application at
that time, the first light bulbs. However, when Tungsten became the
light bulb filament of choice in the early 1900s, carbon fiber became
obsolete and received little attention for the next 50 years.
The interest in carbon fibers revived in the 1950s, starting in the
USA where Union Carbide opened a new research center, the Union
Carbide Parma Technical Center in Cleveland, OH. This new research
center attracted young scientists who were given the freedom to
explore new avenues, which resulted in a number of key discoveries.
In 1958 a young physicist called Roger Bacon experimented with
equipment akin the early arc streetlamps but operating at much
higher pressures and he could grow thin carbon whiskers with
exceptional mechanical properties. In his 1960 publication Bacon
described these carbon whiskers as rolled-up sheets of graphite
layers extending continuously along the length of the whisker up to a
length of several cm and diameters of 1e5 microns [16]. The
measured strength and stiffness of these carbon whiskers were truly
impressive, a strength up to 20 GPa and a corresponding Young's
modulus of 700 GPa. Although the discovery of Bacon was consid-
ered a real breakthrough invention, the obtained filamentary carbon
fibrous structures were extremely expensive to produce, estimated
at several 10 million USD/kg and they were discontinuous. Much
later in 1991, Sumio Iijima in Japan published his seminal paper [17]
on carbon nanotubes (CNTs), and that paper is now often regarded as
the birth of CNTs using a process quite similar to that of Bacon.
Maybe Bacon made besides carbon whiskers also some thinner
nanotubes but either he did not notice them or simply lacked the
tools to detect them at that point in time. In fact, even as early as
1952, Russian scientists Radushkevich and Lukyanovich already re-
ported hollow carbon fibers, which we would now refer to as multi-
walled carbon nanotubes [18]. Unfortunately, their paper, which
showed the first images of CNTs, was in Russian and nobody took any
notice. In the late 1970's, Endo and coworkers also already showed
images of what would now be called a carbon nanotube [19].
However, electron microscopes at that time were not powerful
enough to reveal the number of walls as in the case of Iijima. Again,
this work did not attract a lot of attention as most carbon research at
that time focused on carbon fibers.
In 1959, one year after Bacon's discovery of carbon whiskers,
Ford and Michell of the same Parma Institute patented a process for
making carbon fibers based on heat-treating rayon up to 3000
C
[20]. Rayon is cellulose, like cotton and bamboo, but is a continuous
fiber obtained via the so-called and well-known viscose process as
developed by Courtaulds in the beginning of the 20th century in the
UK. In 1964 Bacon and Schalamon [21] improved this process by
hot-stretching and orienting the graphite layers and Union Carbide
commercialized in 1965 the carbon fiber “Thornel 25” with a
Young's modulus close to 200 GPa. The US Air Force at that time
heavily supported the R&D in carbon (or graphite) fibers and
composites for rockets, missiles and aircraft structures.
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Advanced Industrial and Engineering Polymer Research 5 (2022) 90e106
While in the USA the emphasis was on carbon fibers based on
cellulose (rayon) as precursor, Akio Shindo [22] of the Osaka
Technical Research Center in Japan started to use polyacrylonitrile
(PAN) in 1961 as a precursor for carbon fiber leading to pilot-scale
production in 1964. In 1963, William Watt and coworkers at the
Royal Aircraft Establishment in Farnborough in the UK had also
started to an R&D programme on PAN fiber from Courtaulds, the
Orlon® grade, and applied for patent protection [23]. This patent
was licensed to Rolls-Royce, Courtaulds and Morganite Modmor in
the UK. Rolls-Royce produced the first carbon fiber Hyfil® which
was used to create composite turbine blades of the RB211 jet
engine. Unfortunately, composite technology was not advanced
enough at that time and these turbine blades were way too brittle
to survive a so-called bird strike test (shooting a dead chicken into
a jet engine) and this was one of the disasters that lead to the
company's bankrupty and its nationalization by the British
government.
The Japanese took back the lead in the manufacturing of PAN-
based carbon fibers, notably Toray Industries, and in 1970 they
signed a technology agreement with Union Carbide bringing the
USA back to the forefront but now with PAN instead of cellulose
precursor technology. Carbon fibers are typically synthesized
through the controlled pyrolysis of a stabilized precursor fiber
(Fig. 1). In the case of PAN, the precursor fibers were first stabi-
lized and stretched over a temperature range of 200e400
C in air
using an oxidization process (thermoset treatment). Then, in a
carbonization process, the stabilized fibers are subjected to tem-
peratures in the range of 800e1500
C in an oxygen-free envi-
ronment to remove non-carbon impurities, including hydrogen,
oxygen, nitrogen, and other non-carbon elements. In a subsequent
step, the carbonized fibers are graphitized using a process
involving temperatures of up to 2500
C. Simultaneous stretching
of the fibers ensures a highly crystalline and orientated structure
(Fig. 1), which results in a higher modulus than those of carbon-
ized fibers. The properties of the resultant carbon fibers are
dependent on their crystallinity, crystalline distribution, carbon
content, molecular orientation, and the proportion of defects.
While the highly oriented microstructure post-graphitization
yields fibers with a higher modulus, they typically have a lower
strength than the fibers after carbonization. Especially in
compression, the highly anisotropic structure of these high
modulus fibers can lead to shear-induced micro-buckling and a
low compressive strength. Finally, an oxidative surface treatment
process is applied together with a sizing to enhance their adhe-
sion to polymer matrices. Again, here the less perfect micro-
structure of the high strength carbon fiber can be an advantage as
it can lead to the introduction of a larger number of reactive
functional groups at the fiber surface.
In the 1970s and 1980s, in the Western world carbon fibers were
of interest to many military applications in view of their light
weight when compared with glass fibers (density carbon fiber is
~1.8 g/cm3 compared with glass fiber 2.5 g/cm3). However, due to
the fall of the iron curtain in 1989, the industrial interest in carbon
fibers for military and defense applications diminished strongly in
the West but R&D in carbon fibers continued in Japan in the typical
‘Kaizen’ approach; continuous small improvements. Since the early
1970s Toray have developed a wide range of PAN-based carbon fi-
bers, with various mechanical and sizing characteristics. Their
Torayca® carbon fibers are divided into two distinct categories: the
T-Series characterized by their high tensile strength and standard
to intermediate modulus and the M-Series characterized by a high
modulus (Fig. 2).
In the 1970s Leonard Singer, again at the Union Carbide Parma
Technical Center in Cleveland, studied mesophase pitch as a
precursor to produce carbon fibers [24]. Pitch is a viscoelastic
T. Peijs, R. Kirschbaum and P.J. Lemstra Advanced Industrial and Engineering Polymer Research 5 (2022) 90e106

Fig. 1. Structure development of a carbon fiber during carbonization and graphitization. (Adapted from Marsh H, Griffith G. Proc. Int. Symp. on Carbon, Toyohashi, Tokyo, Japan
1982).

Fig. 2. Classification of Toray's high-performance Torayca® carbon fibers. (Image courtesy of Toray).

92
T. Peijs, R. Kirschbaum and P.J. Lemstra
material that is composed of aromatic hydrocarbons and can be
obtained from crude oil and coal. Pitch is isotropic, but can be
made anisotropic viz. in a layered form, by heat treatment and
stress. Singer and his assistant Allen Cherry designed a so-called
‘taffy-pulling’ device to align the molecules and then heated this
material to convert it into highly oriented carbon fiber. The
properties of these mesophase pitch-based carbon fibers are
impressive with elastic moduli approaching 1000 GPa and a very
high thermal conductivity. However, tensile strength and
particularly compressive strength are typically lower than for
PAN-based carbon fibers which is again related to their highly
intrinsic anisotropic structure.
Generally, carbon fibers are synthesized through controlled
pyrolysis of the stabilized precursor fibers (Fig. 1) [43,51]. The
precursor fibers were first stabilized and stretched over the
temperature range 200e400
C in air using an oxidization pro-
cess (thermoset treatment), which strongly depended on the
natural chemistry of the precursor. Then, in the carbonization
process, the stabilized fibers were subjected to high temperatures
over the range 800e1600
C in an oxygen-free environment to
remove noncarbon impurities, including hydrogen, oxygen, ni-
trogen, and other noncarbon elements. Further, the carbonized
fibers were graphitized using a graphitization process involving
higher temperatures of up to 3000
C and stretching, resulting in
a 50e100% elongation. The stretching of the fibers ensured a
preferred crystalline orientation, which resulted in the desired
modulus being higher than those of carbonized fibers. The
properties of the resultant carbon fibers were relevant to their
crystallinity, crystalline distribution, carbon content, molecular
orientation, and the proportion of defects. Finally, surface
oxidation treatment processes and epoxy sizings are applied to
the carbon fibers, i.e., post-treatments to enhance their adhesion
to the composite matrices.
3. Carbon fiber producers
Carbon fiber producers come and go. Some established key
player companies nowadays are listed in the table below but many
companies have left the sector in the past like Asahi, BP, ICI, Cour-
taulds and BASF. Carbon fibers in Europe were ‘born’ at Courtaulds
and BASF was also very active in the 1980s and developed novel
routes like melt-spinning of PAN but, unfortunately, at the end of
the cold war they disappeared from the scene. The total name plate
capacity (2022) is in the order of some 160 ktons/annum with an
annual growth rate in the past decades of some 5% (Table 1). These
numbers are presented at the annual carbon fiber conference by
Roberts and Pichler and published in ‘Composite World’. The car-
bon fiber market is projected to grow at a rate of more than 8% from
Table 1
Carbon fiber producers and capacity.
Manufacturer Country 2022 (kton)
Toray (incl. Zoltek) Japan 55
Hexcel USA 16
Mitsubishi Chemical Carbon USA 16
Fiber & Composites
Teijin Japan 14
SGL carbon Germany 13
Formosa Plastics Taiwan 9
Solvay (Cytec) USA 4,4
DowAksa USA/Turkey 3
Hyosung South Korea 2 4.2. Solution(gel)-spinning of PAN
Various China 21,8
Various Rest of world 5 After the discovery of solution(gel)-spinning of UHMW-PE at
Total Approx. 160
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Advanced Industrial and Engineering Polymer Research 5 (2022) 90e106
7 billion USD in 2020 to 8.9 billion USD by 2031, with increasing
demand coming mainly from wind energy, aerospace and defense.
In China carbon fiber manufacturers also come and go. Currently
(2022) carbon fiber manufacturers include (name plate capacity in
kton/annum between brackets): HengShen (8); CNBC (6), Jilin-
Jinggong (9), Zhongjian Technology (3), Sinopec Shanghai Pet-
rochem (2), Weihai Guangwei (2,5), Bluestar (1,5) and a dozen
other smaller players.
4. Precursors for carbon fibers
4.1. Polyacrylonitrile
The precursor for the production of carbon fibers is at present
almost exclusively polyacrylonitrile (PAN), and its copolymers as
mentioned before. PAN can be made via solution, suspension and/
or emulsion-polymerization processes and they all classify as
radical polymerizations. Polymers produced via radical polymeri-
zations such as polystyrene (PS), polyvinylchloride (PVC) and
polyacrylonitrile (PAN) result in so-called atactic polymers and are
not crystallizable in contrasts with stereoregular polymers like e.g.
isotactic polypropylene (i-PP). In this respect poly(vinyl alcohol)
(PVOH), is an exception due to the small size of the eOH side group
and atactic PVOH is therefore still crystallizable. But in the case of
PVC and PAN, the side-groups -CL and eCN respectively, are rather
voluminous and prevent the predominantly atactic chain to
crystallize.
However, during the standard (radical) polymerization pro-
cesses a slight preference for syndiotactic placement of the
monomer units prevails, resulting in relatively short syndiotactic
sequences which can form tiny crystallites of the fringed-micelle
type. At least that is the explanation for the small amount of
crystallinity, up to 10% max, in PVC [25]. In the case of PAN the
normal X-ray fiber diffraction pattern consists of just two sharp
equatorial peaks respectively d1 ~0,53 nm and d2 ~ 0,30 nm and
based on this limited information various models have been pro-
posed to explain the crystallinity in PAN. The models proposed
range from a hexagonal packing of rod-like chains of PAN with no
chain-axis order [26] to a planar zig-zag packaging of syndiotactic
sequences [27]. Between these two extremes more complex
models have been proposed involving not only short syndiotactic
sequences to form orthorhombic crystal structures but also co-
crystallization with helical isotactic units [28]. The issue is not
clear yet and maybe will never be resolved due to the lack of ac-
curate information from X-ray diffraction patterns.
A more important question is how crystallinity and resulting
morphology will develop during spinning of PAN from solution and
the effect - if any - of as-spun fiber morphology on final carbon fiber
properties. The standard way of producing PAN fibers is via wet-
spinning and in this case the spinneret is immersed in the coagu-
lation bath and a complex interplay will start induced by mutual
diffusion of non-solvent/solvent into the as-spun fibers. L-L (liquid-
liquid phase separation) will occur and L-S (liquid-solid) viz. crys-
tallization. The structure development can be arrested by passing
through the so-called Berghmans’ point (B.P.) when the concen-
trated domains vitrify [29] upon passing the glass transition tem-
perature. As a consequence of coagulation, the as-spun fibers and
quenched fibers show distinct skin-core effects with voids and the
fiber structure and morphology as a whole is far from
homogeneous.
DSM in which dilute solutions of UHMW-PE in a solvent are spun
T. Peijs, R. Kirschbaum and P.J. Lemstra
using an airgap [30e32] and in view of the higher temperatures of
the spinnerets and subsequent quenching in water, attempts have
been made to use this technique for high molar mass PAN. The basic
concept of solution(gel)-spinning is that the filaments after leaving
the spinnerets are quenched into a bath containing a non-solvent
for both polymer and its solvent. The function of the quench bath
is to induce thermo-reversible crystallization/gelation, L-S separa-
tion, without mass transfer due to mutual diffusion, so no L-L phase
separation. The developed crystals act as physical crosslinks
embedded in a large amount of solvent and the quenched filaments
have a gelatinous character, viz. crystals surrounded by solvent,
which is much more homogeneous than coagulation processes
involving mass transfer with the formation of concentrated poly-
mer domains, voids and a distinct core-shell character.
In the case of industrial solution(gel)-spinning processes of
UHMW-PE, typically concentrations are used of approximately 10%
so the as-spun and quenched filaments contain up to 90% of solvent
which are referred to as gel-fibers. UHMW-PE as such is a very fast
crystallizing polymer and the formation of gel-fibers occurs almost
instantaneously, even in a small airgap of around 10 mm between
spinneret and the surface of the (water) quench bath. Also in PVC,
which is much less crystallizable than UHMW-PE with only some
10% maximum crystallinity, gels develop very fast and PVC solu-
tions in di-octyl-phthalate form elastic and transparent (due to the
small crystals which do not scatter light) gels upon quenching in
e.g. water. These PVC gels are highly stretchable [25].
In a recent paper, Wang et al. [33] discussed the difference be-
tween standard wet-spinning with coagulation and air-gap spin-
ning, which they denote as dry-jet wet spinning. In the case of
using a small airgap they report a smoother surface of the PAN fiber,
which is not explained in detail while also no carbon fiber prop-
erties are presented. It has to be noted that dry-jet wet spinning is
very different from solution(gel)-spinning because in dry-jet wet-
spinning of PAN the as-spun filaments surpass a small airgap but
then immerse in a coagulation bath and mass transfer processes
take place. Nevertheless Wang et al. claim a much smoother fiber
surface upon dry-jet wet-spinning. Whether this precursor will
render better carbon fibers is not mentioned in their publication. To
avoid mass transfer upon coagulation, leading to the unavoidable
skin-core effects and voiding, the question remains if homogeneous
gelatinous PAN filaments can be produced. In the 1980s and 1990s
several companies like Courtaulds, DSM, Akzo Nobel etc. tried to
perform solution(gel)-spinning using high molar mass PAN and
preventing coagulation viz. mass transfer by using a quench bath
with non-miscible solvents for the spinning dope. The problem
encountered was that the rate of crystallization and hence gelation
in the case of PAN is rather slow. The rate of crystallization/gelation
can be enhanced by adding a very small amount of bivalent metal
compounds appr 0,01e0,2 mol% per mole acrylonitrile units and
crystallization/gelation became feasible rendering virtually trans-
parent gel filaments [34]. PAN fibers could be obtained possessing
tenacities up to 1.8 GPa and corresponding Young's moduli of appr.
20 GPa. However, these favorable properties of PAN were not re-
flected in better carbon fiber properties despite many attempts in
industrial labs at DSM, Courtaulds and Akzo Nobel. These results
are not available in the public domain but known to the authors.
In a press release in 2015, the Georgia Institute of Technology
announced that in the group of professor Satish Kumar a new
technique for producing carbon fibers was developed that claimed
to set a new milestone in the strength and stiffness of carbon fibers.
The work reported was part of a 4-year program (USD 9.8 million)
sponsored by the Defense Advanced Research Project Agency
(DARPA). Kumar and coworkers claimed a breakthrough technol-
ogy by using solution(gel)-spinning of high molecular weight PAN.
However, upon studying their papers [35] more carefully, the
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Advanced Industrial and Engineering Polymer Research 5 (2022) 90e106
question arises whether real gel-spinning was achieved by
quenching the as-spun filaments into cold methanol. Moreover,
their claimed breakthrough properties were not all that impressive
when compared with current state-of-the-art high strength carbon
fibers with strength levels up to 7 GPa.
4.3. Melt-spinning of PAN
For solution-spinning of PAN either aqueous ionic media such as
ZnCl2 or NaSCN solutions in water are used or polar organic sol-
vents such as DMF, DMAc, DMSO. The overall speed in these
solution-processes is low; < 500 m/min in the case of wet-spinning
and <1500 m/min for dry-spinning. Melt-spinning has the advan-
tage that no environmentally less benign solvents have to be used
and the speed can be much higher e.g. several thousands of meters
per minute in melt-spinning polypropylene (PP) and polyesters
(PET).
The major drawback in the case of PAN is its thermal instability
with a melting point just above 300
C whereas the complex re-
action of intra- and intermolecular cyclization, well-known as
‘stabilization’ in the carbon fiber community, sets in from 222
C.
Hence, melt-processing of PAN homopolymer seems to be next to
impossible. The standard way to process intractable polymers is
either by using external plasticizers or changing the molecular
structure. For several decades, therefore, efforts have been made to
make PAN melt-processable. It is important to distinguish ap-
proaches via an external plasticizer (mixture of polymer with ad-
ditives) and internal plasticization (copolymerization). In both
cases, the interaction of the nitrile (-CN) groups is disturbed and
melting occurs below the decomposition temperature.
Already back in the 1970s Du Pont and American Cyanamid filed
a series of patents regarding melt-spinning of PAN homopolymer
and copolymers using all kinds of plasticizing solvents [36,37]. The
largest internal plasticization patents are held by Standard Oil
wherein initially all conceivable comonomer classes are described
and claimed [38]. In a review paper by Udakhe and Goud [39]
numerous patents are mentioned regarding melt-spinning of PAN.
Seemingly more interesting and easier to handle is to use only
water to facilitate processing of PAN and its copolymers. Hirotaka
et al. developed a process of melt-spinning homo- and copolymer
PAN using water, starting from hydrous PAN crumb containing
30e60 wt% water and dewatering in the molten state at tempera-
tures >140
C and pressures above the autogenous pressure until
the polymer concentration is > 70 wt% [40]. In the patent appli-
cation no mention is made of carbonization of the melt-spun PAN
fibers and melt-spun PAN fibers with water and/or other plasti-
cizers are generally not suitable for subsequent carbonization into
to high-quality carbon fibers in view of fiber inhomogeneity as a
result of evaporation/extraction of plasticizers.
In the 1980s BASF made a major effort in melt-spinning of PAN
and subsequent carbon fiber formation [41] which were qualified
for use in the B2 bomber at that time. At BASF a mixture of water
and acetonitrile was used as plasticizers in melt-spinning and PAN
precursor fibers could be produced which were quite suitable to
render carbon fibers with a strength up to 4 GPa with corre-
sponding moduli in the range of 275e300 GPa. A lower production
cost compared with solution-spun PAN was claimed of up to 30%
and increased line speeds with a factor of 4. In 1991 the program
was terminated due to the end of the cold war. However, the efforts
made by the BASF team are not lost in history and a dedicated team
at Oak Ridge National Laboratory in close collaboration with Vir-
ginia Tech have been pursuing this line of research. In parallel, the
Fraunhofer Institute for Applied Polymer Research in Germany
claims that their ComCarbon® technology will make melt-spinning
possible at low cost [42].
T. Peijs, R. Kirschbaum and P.J. Lemstra
More recently, Ionic liquids (ILs) have attracted attention as
potential “green plasticizers” that may be applied to the production
of high-strength carbon fibers [43e45]. Ionic liquids (ILs) are liquid
salts at room temperature that offer many advantages over tradi-
tional solvents including negligible vapor pressures, low toxicity,
good thermal stability, and can yield carbon upon controlled
carbonization [45]. ILs have been used as plasticizers for other
polymeric systems, where ILs were shown to reduce glass transi-
tion temperatures and melt viscosities [44]. In their study, re-
searchers at Deakin University demonstrated that a lower carbon
fiber stabilization temperature was required after impregnating the
PAN precursor fibers with ILs [45]. The process should potentially
lead to energy savings and is currently commercialized by LeMond
Carbon in the US. However, if the process can lead to significant cost
reductions remains to be seen as the majority of carbon fiber
manufacturing cost is in producing the PAN precursor rather than
the stabilization and carbonization steps.
4.4. Electrospinning of PAN
In the fiber world a general belief is that tensile strength in-
creases with decreasing fiber diameter and this phenomenon has
been well-established for the case of inorganic glass fibers where
strength is governed by defects (Griffith theory) but the question
arises whether this is also the case for oriented organic fibers.
Pennings et al. [46] claimed that the tensile strength of PE fibers
increased with decreasing fiber diameter. However, this statement
is not valid because in their studies the PE fiber diameter was
reduced by increasing the draw at temperatures below but close to
the melting temperature and with increasing draw ratio the mo-
lecular orientation increases as well. Comparing fibers with varying
diameter but at the same draw ratio and modulus, a measure of
chain orientation, on the other hand showed that there is no direct
relationship between tensile strength and fiber diameter, all
strength values were similar and independent of the fiber diameter
[47].
In the case of PAN and notably the resulting carbon fiber thereof
the question remains whether the fiber diameter has an influence
on the tensile strength. In the case of glass fibers, the strength in-
creases because during hot-drawing the surface flaws, which are
crack initiators, are eliminated whereas in the case of carbon fibers
the internal fiber structure/morphology is inhomogeneous
compared with the homogeneous amorphous glass fibers. A
method to make carbon fibers with ultra-low diameters is elec-
trospinning, a versatile tool for the production of polymer fibers in
the nanometer to micrometer range [48]. For an in-depth review of
the mechanical properties of electrospun fibers with a particular
focus on methodologies to generate high performance nanofibers
the reader is referred to the reviews by Yao et al. [49] and Peijs [50].
Although some evidence exists of confinement induced molecular
orientation in the case of ultra-fine nanofibers, the orientation and
particularly levels of chain extension achieved in electrospun
polymer fibers is often rather limited due to the absence of a post-
drawing step [49,50]. Zussman et al. created electrospun PAN-
derived carbon nanofibers with different fiber diameters possess-
ing Young's moduli of approximately 60 GPa and tensile strengths
between 0.3 and 0.9 GPa. Inferior mechanical properties of these
electrospun PAN-based carbon nanofibers compared to commercial
carbon fibers resulted mainly from the relatively poor molecular
orientation and disarrangements in the core-shell structure of
these carbon nanofibers [51]. PAN-based carbon nanofibers were
also prepared by Zhou et al. [52] and Young's moduli of 40e60 GPa
and tensile strengths of 0.3e0.6 GPa were achieved. Optimized
process conditions for strong carbon nanofibers based on PAN were
reported by Chasiotis and coworkers [53]. and Young's moduli as
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Advanced Industrial and Engineering Polymer Research 5 (2022) 90e106
high as 200 GPa and tensile strengths up to 3.5 GPa upon carbon-
ization were reported, making these fibers approach but not exceed
the mechanical performance of baseline T300 carbon fiber. In a
review by Jadhav et al. [54] various other potential applications of
electrospun carbon nanofibers are mentioned like in energy con-
version and storage devices e.g. supercapacitors, lithium-ion bat-
teries and solar cells, catalysis, sensors and biomedical fields.
However, for the moment electro-spinning is still very much in the
academic domain and difficult to scale-up although recent alter-
native developments such as rotor-jet spinning may have slightly
better potential for scale-up of ultra-fine fibers [55].
5. Alternative precursors to PAN
The cost to produce the precursor PAN fiber depends on the
number of filaments in the yarn, expressed as tow, but is at least 50%
of the total cost of carbon fiber production [56] and the precursor
holds the major share in determining the final price of the carbon
fibers as already mentioned before. In 2012 the USA administration
legislated that the average fuel economy of cars and light trucks sold
in the USA for the year 2017 should be 35 miles per gallon and should
increase to 55 miles per gallon by 2025 [57]. The USA Department of
Energy (DOE) studies suggested that carbon fiber reinforced plastics
could reduce the weight of cars by 50%. The price of PAN fibers as
precursor for carbon fibers is determined for a large extent by the
price of oil but in 2012 when this legislation was put in place the
price of carbon fibers was >30 USD/kg which is acceptable for ap-
plications where weight saving is key like in aerospace and defense
but for mainstream cars this price is too high. As a target for the
automotive industry a price level was set at <15 USD/kg and pref-
erably down to 10 USD/kg. Furthermore, this low cost carbon fiber
should at least possess a tenacity close to 2 GPa (minimum 1.7 GPa)
with a corresponding modulus close to 200 GPa (minimum
170 GPa). Subsequently, research efforts intensified in trying to find
alternative precursors to replace PAN, not only to reduce cost price
but also in a pursuit to lower their environmental impact through
the use of biobased feedstock. Cellulose was revisited as well as
another major component of wood - lignin - which seemed very
promising in view of its high carbon content.
5.1. Lignin
Lignin is a macromolecular polyaromatic compound, and not a
polymer as often mentioned in literature. Lignin was first discov-
ered by the French agronomist P.O. Payen in 1838 and the name
stems from the Latin word “Lignum” meaning wood. Lignin acts in
wood as a kind of ‘glue’ and provides UV-protection to trees. Lignin
is a polyaromatic polyol and constitutes, after cellulose, the second
largest component in wood and most other lignocellulosic plants.
The amount of carbon in lignin is relatively high, approx. 60e65%,
and therefore lignin is regarded as a promising raw material for
carbon fiber with respect to giving a high carbon yield. Lignin looks
promising since its molecular structure contains already abundant
aromatic (benzene) units in sp2 configuration (Fig. 3). As a ‘glue’
and UV-stabilizer for cellulose in the cell wall of plants lignin is
plentiful available as waste in paper production and from so-called
‘biorefineries’ which break down lignocellulosic structures into
their main components, refine those and then transform them into
product streams. Cellulose and hemicellulose are mostly converted
into (bio)fuels, whereas the lignin can be used among others as a
precursor for carbon fiber.
The most commonly available lignin is the so-called Kraft lignin
which accounts for 85% of the total lignin production in the world.
Kraft pulping is a process of separating cellulose from hemicellu-
lose and lignin in high temperature by treating the woody materials
T. Peijs, R. Kirschbaum and P.J. Lemstra
Fig. 3. Chemical structure of lignin.
with an aqueous solution of sodium hydroxide and sodium sulfide.
Through this process, lignin and a large portion of hemicellulose are
obtained in the form of black liquor, which subsequently undergoes
a delignification process to separate lignin-hemicellulose complex
through a precipitating process. Lignin in solid phase is then
washed with acidic solution and dried. More recent technologies
often related to ‘biorefineries’ are ‘organosolv’ pulping using a
solvent to extract lignin from lignocellulosic feedstock at temper-
atures in the range of 140e220
C whereby lignin breaks down by
hydrolytic cleavage into fragments that are soluble. Solvents which
can be used are acetone, methanol, ethanol and organic acids like
formic and acetic acid. Next to organosolv pulping other techniques
have been developed to extract lignin e.g. supercritical extraction
[58]. In conclusion there is plenty of lignin on this planet and it is
very cheap.
However, to convert lignin into a fibrous structure is easier said
than done. The major problem encountered during melt- or
solution-spinning of lignin is that lignin as a macromolecular
compound lacks the characteristic elongational viscoelastic prop-
erties of synthetic polymers required for melt- and/or solution-
spinning. The next problem encountered is that the as-spun
lignin fibers have to be stabilized before the final carbonization
step because they easily melt during thermal conversion. In order
to achieve a thermoset material, i.e. an infusible non-sticky stabi-
lized fiber for conversion into the final carbon fiber, the lignin
precursor has to be stabilized at low heating rates and unrealistic
long stabilization times are reported, as discussed below. The first
carbon fibers produced based on lignin started already in the 1960's
[59] by Otani et al., and the first commercial production of carbon
fibers based on lignin started in the early 1970s by the Japanese
company Nippon Kayaku Seizo Co., Ltd. under the trade name
Kayacarbon® but production stopped after a few years due to
competition from PAN-based carbon fibers showing much better
properties.
5.2. Melt-spinning of lignin
The cheapest way to make fibrous precursors based on lignin is
via melt-spinning but many problems are encountered. Kraft lignin
often contains too many (inorganic) impurities which are detri-
mental for extrusion/spinning. Organosolv lignin is purer but also
shows poor melt-spinnability which can be improved by polymeric
additives like PEO [60] or by chemical modification or fractionation
[61e67]. Furthermore, even after obtaining an as-spun lignin fiber
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Advanced Industrial and Engineering Polymer Research 5 (2022) 90e106
the next problem is stabilization as mentioned above. Summarizing
the problems encountered with melt-spun lignin are:
 Lignin as a non-polymeric substance lacks the viscoelastic
properties which makes fast melt-spinning impossible if not
challenging;
 Due to the lack of melt-strength (elongational viscosity) it is
next to impossible to produce lignin fibers with the required
small diameters needed for effective carbonization;
 Polymeric additives can be used to improve spinnability but
these additives interfere with the subsequent carbonization
process, hence only small amounts (<10%) can be added;
 Stabilization of the as-spun lignin fibers prior to carbonization is
delicate and slow and the purer the lignin the longer the sta-
bilization times needed;
 The ultimate tensile properties of carbon fibers obtained via
lignin do not even match the targets set for a commodity carbon
fiber for automotive, viz. a tensile strength of 1.7 GPa and a
corresponding modulus of 170 GPa. The best reported values in
literature, if true, are typically a tenacity of appr. 1 GPa and
moduli up to 100 GPa.
A possible way out of the challenges encountered during direct
melt-spinning of lignin could be the use of a bi-component spin-

Machinenbau GmbH
ning process as recently developed by Fourne
in Germany [68]. They used a special (melt-processable) polyvinyl
alcohol (PVOH) grade (Mowiol® from Kuraray) as spin carrier with
a core of pure lignin. The PVOH outer shell can be washed away
with water, leaving behind the pure lignin fibers that can be sta-
bilized and carbonized. The measured properties of the resulting
carbon fibers were: a tensile strength of approximately 1 GPa and a
corresponding Young's modulus of 80 GPa. Researchers from the
German Institutes of Textile and Fibre Research in Denkendorf
(DITF) together with the University of Limerick have been also
working within the EU funded LIBRE project on melt-spinnable
systems by either modifying lignin chemically or mixing it with
meltable additives like thermoplastic elastomer polyurethane
(TPU) [69] or biobased PE [70]. Samples with TPU content greater
than 30% showed good melt processability and carbonization yield
(35% carbon yield). Different softwood lignin O-acyl derivatives
were also synthesized, of which cinnamoylated softwood lignin
(CL) showed superior processability. Tensile strengths up to 0.9 GPa
and elastic moduli up to 60 GPa were reported [61]. More recently a
tensile strength of 1.8 GPa and modulus of 200 GPa has been
claimed by the DITF team.
5.3. Solution-spinning of lignin
In view of the difficulties encountered in melt-spinning of lignin
and lignin/mixtures the next possibility is solution-spinning. So-
lution-spinning of lignin as such is difficult since lignin, albeit being
a macromolecular compound, is not a polymer as mentioned above.
Chemically modified lignin shows a better spinnability as shown by
Zhang and Ogale [71] using chemically modified lignin via acety-
lation which is soluble in acetone. They performed dry-spinning
and after carbonization obtained a carbon fiber with a tenacity of
1.1 GPa. However, the penalty which had to be paid as a result of the
use of chemically modified lignin was the extreme low heating
rates for stabilization. They obtained thermo-oxidatively stabiliza-
tion using a temperature ramp of 0.2
C/min from ambient to a
maximum temperature of 220
C under tension which took
1000 min! In a later study, Ogale and coworkers [72] used acetic
acid to simultaneously fractionate, solvate and clean Kraft lignin
and used dry-spinning to obtain carbon fibers with a tensile
strength of nearly 1.4 GPa and a corresponding modulus of 98 GPa.
T. Peijs, R. Kirschbaum and P.J. Lemstra
To improve spinnability without the need of chemical modifi-
cation and added cost, a polymeric additive can simply be added to
lignin in a common solvent. Many polymers have been tried but
obviously only PAN and cellulose are the most realistic in view of
their proven ability to carbonize. Husman from Zoltec reported the
spinning of PAN/lignin mixtures with a lignin content up to 45% but
at higher lignin loadings unacceptable voids were obtained [73].
The prediction at that time (2014) by Zoltec was that carbon fibers
could be made with a strength of 2.4 GPa and a corresponding
Young's modulus of 200 GPa but these expectations did not
materialize. However, Kumar and coworkers claimed more recently
[74,75] that solution-spinning of PAN with a PAN/lignin ratio of 70/
30, and PAN with lignin þ3% CNTs with DMAc as a solvent resulted
in carbon fibers with a tensile strength of 1.7 GPa for PAN/lignin and
1.6 GPa for PAN/ligin/CNT. However, these values were not better
than for pure PAN when carbonized under identical conditions
(carbonization 1100
C). Kumar c.s. also claimed new milestones in
developing high-strength and high-modulus carbon fibers [74]
with their so-called gelspinning technology. However, the term
gelspinning is here misleading since they use as a quench medium
methanol at 50
C and the solvent used for spinning, DMAc, is
soluble in methanol and consequently, cannot be gelspun (see
section on definition of solution-gelspinning). Moreover, they
stored the as-spun fibers in methanol for 12 h and the question is
how much lignin and carbon nanotubes may have leached out.
5.4. Cellulose/lignin mixtures
Cellulose has a beneficial molecular structure which makes it
possible to produce carbon fibers with reasonable properties. Un-
fortunately, cellulose has a low carbon content (44 wt%) and after
conversion even is reduced to some 10e30%. Consequently, mixing
cellulose with lignin with a high carbon content (60e65%) seems an
obvious way to boost the overall carbon content. Several research
groups focus on cellulose-lignin mixtures notably in Nordic coun-
tries like Sweden and Finland. The Bentsson group at the Rise
Research Institutes in Sweden has published numerous papers on
dry-jet wet spinning of cellulose/lignin mixtures and tenacities
were obtained of approximately 1 GPa max with a corresponding
Young's modulus of about 70 GPa. The authors claim that their fi-
bers are better than glass fibers [76e78], which is a rather odd
conclusion given that the strength of glass fiber is 2 GPa or more,
while it also seems odd in the context of pursuing a cheaper or
more sustainable carbon fiber. Even when compared with the set
targets for a commodity carbon fiber with a strength of 1.7 GPa and
modulus of 170 GPa, the obtained results by Bentsson c.s. are rather
disappointing.
A serious player in the area of cellulose/lignin nowadays is Stora
Enso Oyj (Finland). In a series of patent applications by Garoff et al.
several methods are described. They first started with melt-
spinning [79], which was subsequently abandoned and followed-
up by solution-spinning of cellulose/lignin mixtures in NMMO
(N-methylmorpholine-N-oxide) hydrate at an elevated tempera-
ture of 90
C using air-gap spinning [80]. The resulting precursor
yarn was stabilized at 240
C to form a precursor yarn. This stabi-
lized precursor yarn was then treated in a stretch-precarbonization
step at an applied stretch of 200% to give a highly oriented inter-
mediate carbon fiber. This intermediate fiber was then carbonized
to a carbon fiber at 2000
C at 0% stretch for 5 min. The resulting
highly oriented carbon fiber, had an average elastic modulus of
100 GPa and tensile strength of 1.1 GPa with maximum values of
105 GPa for modulus and 1.27 GPa for strength. In subsequent
patent applications, methods were described to prevent lignin
leaching out of the as-spun fiber in the precipitation bath by adding
specific salts [81] as well as the use of a water-free spin finish to
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Advanced Industrial and Engineering Polymer Research 5 (2022) 90e106
prevent fiber fusion [82] after carbonization with tenacities in the
order of 16e35 cN/tex and corresponding moduli in the range of
900e1500 cN/tex.
Recently Stora Enso Oyj teamed up with Cordenka GmbH & Co
KG (Germany) owned by Beautiful Mind Capital (BMC), a private
equity firm based in London and Shanghai and the largest producer
of industrial rayon. In their envisaged future carbon fiber process
the solution routes employing NMMO as solvent have been shelved
into history and cellulose is converted into viscose and mixed with
lignin to form the spinning dope based on acquired patents from
Kelheim Fibres GmbH [83]. The dope is spun into precursor fiber
that is thermally converted to carbon fiber. The ambition is that
their NeoFiber® shall be a cost-competitive biobased baseline
carbon fiber with the lowest carbon footprint in the world. Stora
Enzo aims to produce carbon fibers based on lignin/viscose mix-
tures having an elastic modulus of at least 230 GPa, and preferably
also a tensile strength of at least 3 GPa and the target for the
moment is to compete with PAN-based carbon fibers like T300
from Toray, viz. the lower end of the property spectrum of current
PAN-based carbon fibers but at a substantially lower carbon foot-
print (Fig. 4).
5.5. Polyethylene
Theoretically, polyethylene (PE) is the ultimate precursor in
terms of carbon content consisting for 92% of carbon. The Inter-
national Union of Pure and Applied Chemistry (IUPAC) has defined
carbon fibers as filaments, reels or lines that contain more than 92%
so in terms of carbon content PE fiber is already there! Hence, PE is
seemingly the ultimate candidate for producing carbon fibers
below the 10 USD/kg target.
Unfortunately, in terms of molecular structure the arrangement
of polymer chains in a PE fiber is as far away as possible from the
graphitic and notably turbostratic structure in carbon fibers.
Whereas the C-atoms in PE molecules and fibers are connected
together in linear arrays with covalent sp3 bonds and relatively
weak Van der Waals interactions between the chains, the C-atoms
in carbon fibers are connected in planes with sp2 bonded carbon
atoms in graphitic sheets which are haphazardly folded, or crum-
pled together in (turbostratic) carbon. The first and main problem
encountered is how to stabilize the PE precursor fibers in view of
their low melting temperature, 135e150
C before carbonization.
Any PE fiber will just melt upon heating. In the case of PAN pre-
cursor, stabilization occurs relatively far below the melting point.
But in the case of PE no chemical reaction will occur at any tem-
perature below the melting temperature. Consequently, PE fibers
Fig. 4. Biobased precursor and carbon fiber produced by Stora Enso e Cordenka (Image
courtesy of Stora Enso - storaenso.com).
T. Peijs, R. Kirschbaum and P.J. Lemstra
have to be treated with aggressive chemicals such as chlor-
osulphonic acid or concentrated sulphuric acid to induce cross-
linking, a method originally developed by Noeske et al. in the
1950s.
In the 1990s Zhang et al. [84] used UHMW-PE fiber as precursor
for carbon fiber. In their experimental procedure they immersed
UHMW-PE, both partly and fully drawn, in concentrated sulphuric
acid starting at 135
C, so close to the melting temperature (the
standard melting temperature of isotropic HDPE is 135
C but in
oriented fibers the melting temperature increases to approximately
145
C) and gradually increasing the temperature to 180
C over a
period of 1 h. Subsequent carbonization was done at 1100
C for
2 min in nitrogen atmosphere. Carbon fibers were obtained with a
tensile strength up to 2 GPa and corresponding moduli of approx-
imately 200 GPa. They found that the partly drawn fibers were
more susceptible for sulphonation, which shows the importance of
crystallinity. Chemicals cannot penetrate the PE crystals and in fully
oriented UHMW-PE fibers the crystallinity is very high (>80%) and
chains are aligned almost in parallel to the fiber axis. In partly-
drawn UHMW-PE fibers the crystallinity is less and hence the
amorphous fraction is higher in which the chemical reactions take
place. In the case of partly-drawn fibers the so-called stabilization
time in sulphuric acid could be reduced to 45 min. These results
indicate that ‘some’ carbon fiber can be made out of PE fibers but
this is of little practical use because the solution(gel)-spun UHMW-
PE fibers are intrinsically expensive in view of the required solvent
recovery processes and the use of expensive twin-screw extruders.
Commercial UHMW-PE fibers like Dyneema® and Spectra® are
>20 USD/kg. The copy-paste UHMW-PE fibers produced in China,
often referred to as “Chineema” fibers, are cheaper but not below 10
USD/kg, hence also they are not a suitable precursor for producing
carbon fibers at the price level required.
Melt-spinning of PE is the cheaper alternative for solution(gel)-
spinning. Postema et al. [85] started from melt-spun LLDPE (linear-
low-density-polyethylene) and used chlorosulphonic acid for sta-
bilization/crosslinking at room temperature for different periods of
time. Subsequent carbonization was done at 900
C in nitrogen
atmosphere for 5 min. It was found that long stabilization times in
chlorosulphonic acid of 24e40 h were needed to fully ‘crosslink’ the
structure in order to survive the carbonization step without fiber
breakage. Carbon fiber strengths were reported of 1.1 GPa with
moduli of 60 GPa. The original work of Zhang and Postema and
coworkers in the 1990s was followed up by many other research
groups notably at Institute for Textile Technology (ITA) at RWTH
Aachen (Germany) where a dedicated group of PhD students and
post-docs were/are working on PE fiber precursors for carbon fi-
bers. Wortberg et al. used melt-spun HDPE fibers as the starting
material for making carbon fibers via treatment in sulphuric acid.
They claim that HDPE gave the best results for carbon fibers, albeit
not substantiated in their paper [86] which is remarkable because
HDPE has a high crystallinity compared with LLDPE and LDPE,
while Postema et al. claimed that HDPE is not suitable [85]. Wort-
berg et al. used stabilization times in sulphuric acid of 6 h. In later
work [87] they claim that a lower crystallinity and low(er) orien-
tation of the PE fiber is beneficial for stabilization time but at the
expense of reduced final carbon fiber properties. For the chemical
stabilization of the PE fiber, fiber diameter is the controlling factor
and should be preferably <18 mm. PE fiber precursors were treated
in hot (120
C) sulphuric acid (96 wt%) for 4 h. The carbonization of
the sulphonated fibers was carried out by a heating step between
250 and 900
C. Analogous to the PAN-based carbon fiber route the
PE based carbonization is divided in two zones with different
temperature and tensile profiles. The carbon yield was approxi-
mately 75% and with stretching carbon fibers with a tensile
strength of 1.9 GPa and modulus of 178 GPa were produced. The
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Advanced Industrial and Engineering Polymer Research 5 (2022) 90e106
research team claim a total production cost of PE-based carbon fi-
bers of <10 Euro/kg based on a 1.500 tons/annum plant. Of course,
these cost data are speculative but the various assumptions made
[61] seem rather optimistic in view of the many hours needed for
stabilization by sulphuric acid (>4 h). However, the ITA-Aachen
team is convinced that the stabilization time can be reduced to
approximately 2 h by inducing the right morphology (crystal size)
in the as-spun PE fibers. In the meantime, the prestigious Paul
Schlack Prize was awarded at the Dornbirn conference in 2017 to
the ITA-Aachen researchers Andreas de Palmenaer and Gisa
Wortberg for their technology.
5.6. Some concluding remarks about precursors other than PAN
Numerous papers and patents have been published regarding
low-cost carbon fibers based on alternative precursors to PAN.
Many tens of millions of dollars for example in the USA have been
spent on this topic e.g. at Georgia Tech in the group of Satish Kumar
and notably at the Oak Ridge National Laboratory (ORNL, Tennesee,
USA) in their Carbon Fiber Technology Facility. This facility was
funded by the Department of Energy (DOE) as a dedicated user
facility for carbon fiber innovation identifying high potential, low-
cost precursors for carbon fibers. Here, industry can validate con-
version of its carbon fiber precursors at a semi-production scale.
Lignin has been and still is of prime interest as a low-cost precursor
for carbon fibers. Many press releases can be found from the Oak
Ridge National Laboratory - Carbon Fiber Technology Facility as
well as reports on the internet claiming the most promising results
but in terms of lignin-based low-cost carbon fibers there are is little
positive and proven competitive data. Moreover, ORNL- CFTF seems
to move away from biobased feedstock for carbon fibers and since
in 2020 a new project was started funded by the DOE of around 10
million USD to transform coal into high-value carbon fibers and
composites in collaboration with the University of Kentucky's
Center for Applied Energy Research (CAER). This project, entitled
“C4WARD: Coal Conversion for Carbon Fibers and Composites”,
seeks to develop the fundamental and translational science and
engineering necessary to create energy-efficient and cost-effective
processes for manufacturing carbon fibers with tunable properties.
It will address challenges associated with coal processing, vari-
ability in coal feedstocks, and carbon fiber manufacturing scale-up
from laboratory to semi-production scale.
When reviewing papers and patents on ‘low-cost’ carbon fibers
one can conclude that the target set by the DOE in 2012 of a (cheap)
carbon fiber with a strength of 1.7 GPa and modulus of 170 GPa is
seemingly only matched by a few fibers including those based on
PAN/lignin mixtures and polyethylene. However, even here the
proposed methods and technologies are still far from a commer-
cially viable process. The main problems are still the long times
needed for stabilization, extraction etc. and consequently the
feedstock (lignin or PE) might be cheaper but subsequent pro-
cessing seems more expensive and cumbersome than the current
standard routes for conversion of PAN into carbon fiber. The route
currently pursued by Stora Enso Oyj might be the way forward and
they had ample experience with melt-solution-spinning of PAN and
PAN mixtures and finally have chosen for viscose/lignin mixtures.
Nevertheless, the main advantage of PAN remains its continuous
carbon backbone and nitrile groups that are ideally positioned for
cyclization to occur, enabling the formation of a ladder polymeric
structure during stabilization, as a first stage towards the sheet-like
carbon structure of the final carbon fiber. The ability of PAN to
maintain its oriented structure during stabilization, which takes
approximately 1 h or less, is the key to success for achieving PAN-
based carbon fiber with exceptional mechanical properties.
Depending upon the precursor fiber, carbon fiber may be
T. Peijs, R. Kirschbaum and P.J. Lemstra
Fig. 5. Schematic illustration of turbostratic (left) and graphitic (right) carbon structures. Reproduced and adapted with permission from Dasgupta K, Sathiyamoorthy D. Materials
Science and Technology. 2003; 19(8):995 (Copyright Elsevier, 2003).
turbostratic or graphitic (Fig. 5), or exhibit a hybrid structure with
both graphitic and turbostratic parts present. In turbostratic carbon
fiber the sheets of carbon atoms are haphazardly folded, or crum-
pled together and the distance between the parallel graphene
sheets is greater than that in graphite.
Carbon fibers derived from PAN are turbostratic whereas carbon
fibers derived from mesophase pitch are graphitic after heat treat-
ment at temperatures exceeding 2200
C. Turbostratic carbon fibers
tend to have a higher ultimate tensile strength and compressive
strength, whereas heat-treated mesophase-pitch-derived carbon
fibers can have a very high Young's modulus up to 900 GPa.
Last but not least, a parallel route towards biobased carbon fi-
bers is to produce the precursor PAN from biobased resources e.g.
acrylonitrile via biobased glycerol. Companies like Solvay, who
aquired in 2017 European Carbon Fiber GmbH, a German producer
of large tow (50k) PAN precursor fiber, and DowAksa are active in
this area and might make the routes via lignin, cellulose etc.
obsolete.
6. Fibers based on carbon nanotubes
As mentioned above, in 1958 Roger Bacon [16] already produced
what he called graphite whiskers in a DC arc at Union Carbide and
reported very impressive properties like a strength level of
approximately 20 GPa and a corresponding stiffness of 700 GPa. In
1978 Morinobu Endo used a vapor growing technique as part of his
PhD studies at the University of Orleans in France [19]. He could
produce very small diameter carbon filaments of around 7 nm, but
these filaments were not recognized as carbon nanotubes at that
time. After the discovery of fullerenes by Kroto et al. [88] in 1985
researchers started to explore various carbon allotropes. In 1990,
Richard Smalley postulated the concept that if a buckyball get big
enough, it becomes a carbon cylinder. While many can claim the
discovery of carbon nanotubes (CNTs) it was not until Iijima's
seminal ‘Helical microtubules of graphitic carbon’ paper in 1991
[17] that caused a new revolution in carbon science (Fig. 6).
The reported properties of CNTs are truly amazing [89,90], viz. a
Young's modulus of 1000 GPa, which is some 10e20% higher than
ultra-high modulus pitch-based carbon fibers. However, it is the
theoretical predictions regarding strength that are truly amazing at
around 100e200 GPa [11,91e93]. Moreover, in CNTs the individual
C-atoms are linked via sp2 bonds and consequently, CNTs could be
in theory even stronger than diamond. Furthermore, CNTs are
elastic in the sense that they can bend, twist, kink, and finally
buckle without damaging the tubular structure, with the nanotube
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Advanced Industrial and Engineering Polymer Research 5 (2022) 90e106
being able to return back to its original structure, of course within
deformation limits. Although tensile strengths in the order of
100 GPa have been measured for SWCNTs, often lower values are
measured due to imperfections and experimental levels for
strength are likely to be more in the range of 30e60 GPa [11,94,95].
In addition, most strength data is often on multi-walled carbon
nanotubes (MWCNTs), which typically have lower strength levels
than SWCNT.
It is beyond the scope and context of this review on carbon fibers
to discuss in detail the structure and chemistry of CNTs but as a small
recap for the reader. There are single-wall carbon nanotubes
(SWCNTs) with a sub-division, the arrangement of the atoms, in
armchair, chiral, and multi-walled carbon nanotubes (MWCNTs).
MWCNTs come in two morphologies. When a carbon nanotube
contains another nanotube inside and the outer nanotube has a
greater diameter than thinner nanotube, it is called a Russian Doll
model. On other hand, when a single graphene sheet is wrapped
around itself manifold times, the same as a rolled-up scroll of paper,
it is called the Parchment model. MWCNTs have typically a lower
strength than SWCNTs because they contain more defects and load
is mostly carried by the outer walls. This is particularly true when
these nanotubes are embedded in a polymer matrix and load needs
to be transferred from the outer wall into the inner walls. Here the
inner walls are often not loaded due to low stress transfer from wall
to wall [96,97]. Carbon nanotubes are often pictured like rigid rods
but due to their high aspect ratio they can be highly flexible and can
entangle like macromolecules, which has important consequences
for processing and properties. However, when embedded in a
polymer matrix they can be oriented together with the host mac-
romolecules into highly oriented nanocomposites structures (Fig. 7).
Very early on it was already recognized that an interesting
approach to fully exploit the potential of CNTs would be to align
them parallel in a fibrous structure or yarn [11e13,98,99]. In this
respect CNTs are to some extent similar to the process of making
strong fibers based on macromolecules. In both cases the strength
of the assembly is dependent on the stress transfer between the
tubes or molecules of finite length. In the case of UHMW-PE fibers,
tensile strength is limited (<5 GPa) by the relatively weak Van der
Waals forces between the macromolecules while the strength of
the individual PE chain is in the order of 20 GPa [100,101]. Similar
arguments will hold for an assembly of aligned CNTs with strength
level of 50e100 GPa for the individual tubes [94,95,102], while the
strength of an assembly of tubes of finite length will be controled by
interaction forces or friction between the tubes. Strong PE fibers
can therefore be made only from ultra-long PE molecules which are
T. Peijs, R. Kirschbaum and P.J. Lemstra
Fig. 6. High-resolution TEM images of Iijima's MWCNTs consisting of two and seven
graphene shells published in 1991 (top). Reproduced and adapted with permission
from Iijima S. Nature. 1991; 354(6348):56 (Copyright Springer Nature, 1991). Infinite
graphite layer with (n, m) nanotube naming scheme describing how a nanotube is
rolled up (bottom, image courtesy of The Royal Society of Chemistry).
oriented and extended in a parallel array in order for the weak Van
der Waals interactions between the chains to activate the covalent
bonded C-atoms within the polymer chain. Translating this concept
to CNTs would mean that we need CNTs with ultra-high aspect
ratios (preferably > 106).
Several groups have aimed to develop macroscopic yarns made
solely out of CNT as a direct replacement for carbon fiber yarns by
spinning aligned arrays of nanotubes [103e110]. Many of these
studies found their way into high impact journals but properties of
these yarns were often modest at best. Fig. 8 shows one of the
earlier examples of spinning such yarns by Ray Baughman and
coworkers using a process that involved simultaneous drawing and
twisting from a nanotube forest [107]. Single-ply yarns like shown
Fig. 7. CNTs dispersed in polystyrene matrix using charge contrast imaging with SEM showing random organization (left, image courtesy of Dr. J. Loos). Oriented CNTs in a
polypropylene matrix after solid-state drawing (right, image courtesy of Dr. D. Hua).
100
Advanced Industrial and Engineering Polymer Research 5 (2022) 90e106
in Fig. 6c had a very low tensile strength of around 250 MPa, while
two-ply yarns reached strength of around 400 MPa. After infiltra-
tion with PVOH the singles reached a strength of 800 MPa. Moduli
were at best 25 GPa and hence properties of these yarns were well
below those of baseline carbon fibers.
The reasons for these low values are rather obvious and a
fundamental issue with all twisted CNT yarns. Nanotubes in these
twisted yarns are oriented at a helix angle with the yarn axis
(Fig. 8c), while ultimate strength is determined by twist and inter-
tube friction rather than intrinsic nanotube strength, meaning that
properties are governed by yarn mechanics rather than intrinsic
CNT properties. Around the same time as Baughman c.s., Windle
and coworkers at the University of Cambridge reported an inter-
esting methodology to directly spin CNT fibers from an aerogel
formed during the synthesis by chemical vapor deposition (CVD)
[108e110]. Windle c.s. used a vertical reactor (temperature
>1000
C) to produce CNTs using a CVD process from methane as
carbon source and iron as the catalyst (Fig. 9). As the CNTs grow in
the gas-phase they entangle due to their very high aspect ratio
(>105), forming an elastic smoke which can be drawn out of the
reactor continuously at reasonable high winding speeds, in the
order of 100 m/min.
From a commercial point of view this process has some signif-
icant advantages as it promised a continuous production of CNT
fibers. Koziol et al. [110] reported a maximum tensile strength and
modulus for their spun yarns of 9 GPa and 350 GPa, respectively.
While moduli approached the values for carbon fiber and the best
reported tensile strength value even exceeded those of any other
man-made fiber, these values were only based on a single mea-
surement at an ultra-short gauge length of 1 mm. In fact, the ma-
jority of their yarns showed mostly modest strength values
(<2 GPa). While the strength of spun yarns based on CNTs of finite
lengths is normally determined by nanotube-nanotube interactions
and friction rather than intrinsic nanotube strength it can be ex-
pected that strength will increase if yarns are tested at unrealisti-
cally low gauge lengths. In fact, as mentioned earlier, normally the
failure mode of a spun yarn at the nanotube level would be rather
similar to the mechanism at the molecular level in highly oriented
and chain extended polymer fibers like Dyneema®. PE molecules
possess strengths in excess of 20 GPa while the maximum experi-
mental strength in real fibers is at best 7 GPa upon fast loading
[111]. In PE fibers the weak intermolecular Van der Waals in-
teractions between PE chains lead to a mechanism of chain slippage
limiting the ultimate tensile strength [31,32], while in the case of
CNT yarns a mechanism of nanotube slippage is operative. In the
case of ultra-low gauge lengths less tube ends are present in the
fiber reducing tube slippage. Hence, rather than as a direct
replacement to carbon fiber these yarns may have more potential in
functional textiles, where properties such as electrical conductivity
and flexibility are also importnat. Vilatela and Windle [112], for
example, compared some textile relevant properties such as knot
T. Peijs, R. Kirschbaum and P.J. Lemstra Advanced Industrial and Engineering Polymer Research 5 (2022) 90e106

Fig. 8. Images of a carbon nanotube yarns simultaneously drawn and twisted during spinning from a nanotube forest (A, B), together with an image of the helical twisted yarn
structure (C) and knotted yarn showing yarn flexibility (D). Reproduced and adapted with permission from Zhang M et al. Science. 2004; 306(5700):1358. (Copyright AAAS, 2004).

Fig. 9. Schematic of a direct spinning process by Windle and coworkers. The liquid feedstock is mixed with hydrogen and injected into the hot zone of the CVD, where an aerogel of
nanotubes forms. This aerogel is captured and wound out of the hot zone continuously as a fiber or film. Reproduced and adapted with permission from Li et al., Science. 2004;
304(5668) (Copyright AAAS, 2004).

strength and knot strength efficiency of CVD spun yarns and
compared them with Dyneema®, Kevlar® and T300 carbon fiber.
Tensile strength values reported for their yarns were more realistic
at 1e1.5 GPa using a gauge length of 20 mm. Interestingly, these
values were similar for both unknotted and knotted yarns, indi-
cating 100% knot efficiency. Other fibers like Dyneema®, Kevlar®
and carbon had a significantly lower knot efficiency, although
Dyneema® still possessed a higher actual knot strength.
More recently various other groups have also reported nanotube
yarns. A Korean group developed an optimized spinning method
that can produce highly aligned and densified CNT fibers. A tensile
strengths of around 4 N/tex (~5 GPa), modulus up to 190 N/tex
(~250 GPa) and an electrical conductivity up to 2200 Sm2/kg were
achieved [113]. Even more impressive results were obtained by
Wang et al. by using a similar technology but with a simple cylin-
drical horizontal oven in which the CNTs are produced in a
continuous process exiting the reactor [114,115]. The CNTs in the
‘smoke’ are condensed by spraying e.g. acetone or by quenching
into water or ethanol and a film or fiber could be wound on a
bobbin. Subsequently, the fiber or film was densified by pressurized

101
T. Peijs, R. Kirschbaum and P.J. Lemstra Advanced Industrial and Engineering Polymer Research 5 (2022) 90e106

Fig. 10. Schematic of Nanocomp Technologies' CNT sheet manufacturing process (left). Reproduced and adapted with permission from Singleton JW et al. Results in Materials. 2020;
5:100059 (Copyright Elsevier, 2020), together with CNT aerogel exiting the reactor (right, image courtesy of Nanocomp Technologies Inc.).

rolling and stretching which had a large effect on properties. In the copper in electrical applications might even be more challenging as
case of fibers a tensile strength in excess of 4 GPa was reported and replacing carbon fiber in structural applications, the aim to use both
in the case of films even close to 10 GPa. All these academic mechanical and functional properties of these yarns may prove
achievements mentioned above look impressive but it should be essential for commercial success.
noted that these tensile properties were nearly always obtained by
using very low gauge lengths.
7. Carbon nanotubes as additive in fibers
Scale-up from laboratory to industrial scale is another challenge
in the continuous production of CNT fibers, tapes and films. A major
Next to the direct spinning of CNTs into fibers they have been
effort was undertaken by Nanocomp Technologies Inc. (Merrimack,
used as additives in polymeric fibers to improve mechanical
NH, USA), who claim to produce the longest CNTs which are
properties [11e13]. In fact, the reinforcement of 1D objects like fi-
1e10 mm long but only 3e5 nm in diameter, hence giving an aspect
bers with 1D nanostructures like CNTs suggests that such oriented
ratio > 106. Hydrogen and other common gases are mixed with
systems can lead to novel ‘designed’ fibers with additional levels of
industrial fuels and a catalyst and injected into a furnace. In the
hierarchical reinforcing or toughening mechanisms. In contrast to
furnace the mixture is heated to >800
C and a ‘cloud’ comprising
the above-described spun yarns that contain CNTs only, in the case
of numerous CNTs is exiting and harvested in the form of sheets
of polymer fibers the CNT content is typically well below 10 wt%. To
and/or fibers as shown in Fig. 10.
obtain a certain degree of CNT (and polymer) orientation, as-
According to Nanocomp their Miralon® fiber grade possessed a
prepared CNT-polymer mixtures are often spun into fibers by
tensile strength approaching aramid fibers and due to the lower
means of melt-, solution- or electrospinning. Similar to macro-
density the specific strength could compete with carbon fibers. An
molecules the excellent intrinsic mechanical properties of CNTs can
important characteristic of these continuous CNT fibers is again their
only be completely exploited if uniaxial orientation is achieved (see
high knot-strength because they are small and flexible in contrast to
Fig. 7). In general, reinforcing standard plastics with CNTs has not
carbon fibers. A carbon fiber loses >90% of its strength upon knotting
been all that successful until now despite many attempts [117,118].
while the Miralon® fibers retains their strength due to the fact that
The problems are: a) to disperse CNTs homogeneously in a viscous
they are composed of millions of flexible and entangled millimeters
polymer melt is very difficult; b) the CNTs are flexible and entangle
long CNTs. Expectation was running high at Nanocomp and many
giving rise to a huge increase in melt-viscosity and c) the adhesion
future applications were envisaged. Unfortunately, the dream did not
between the CNTs and the polymer matrix is often poor. Surface
materialize and Nanocomp was taken over by Huntsman in 2018 and
modification of CNTs to improve adhesion seems the way to go
from the website of Huntsman the current Miralon® yarns look less
[119] but results remain far from impressive. Moreover, the effect of
impressive than originally anticipated (Table 2).
improved mechanical properties is only observed to some extent
Conyar BV, a spin-off company from Teijin Aramid also devel-
with SWCNTs of high aspect ratio's (>1000) and only when fully
oped CNT fibers via spinning in chlorosulphonic acid aiming for a
aligned. However, when all these conditions are being met, i.e.
high specific electric and thermal conductivity. In their patent
SWCNTs, good dispersion, alignment and stress transfer, in princi-
application [116] they claim low specific resistivities and the aim is
ple high reinforcing effects could be expected.
to apply these fibrous CNT yarns in high quality audio systems such
Significant efforts have therefore been made to produce CNT
as marketed by Van Den Hul Cables (The Netherlands). These cables
reinforced polymer fibers from a range of polymers, incl. PP, PET, PA,
promise great dynamics and maximum detail, and while replacing
PAN and PVOH [11e13]. Although many of these studies reported
some form of increased fiber properties, only few studies actually
achieved effective nanotube reinforcement, while none of these
Table 2 nanocomposite fibers possessed mechanical properties that could
Mechanical properties of Miralon® nanotube yarns.
compete with commercial high-performance fibers like UHMW-PE,
Miralon® Property Base yarn High-strength yarn aramid or carbon. In order to reveal the true reinforcing efficiency
Density (g/cm3) 0,6 0,8 of CNTs in these nanocomposite fibers, the effective stress carried by
Diameter (mm) 150 240 the CNTs needs to be back-calculated using the rule of mixtures
Tensile Strength (GPa) 0,25 1 relationship Scf ¼ Scnt x Vcnt þ Spf x Vpf, where Scf is the tensile
Tensile Modulus (GPa) 5 46 strength of the composite fiber, Scnt is the stress carried by the CNT,
Strain-at-break (%) 27 3,5
Vcnt is the CNT volume fraction, Spf is the stress carried by the polymer
102
T. Peijs, R. Kirschbaum and P.J. Lemstra
fiber (read: matrix), and Vpf is the polymer volume fraction. Using
data reported in literature it can be shown that the effective stress
carried by the nanotubes at composite failure often does not even
exceed 2e3 GPa, i.e. close to the strength of a baseline carbon fiber
[11,12] and well below the strength of T1000 (7 GPa). Only few
nanocomposite fibers attained a reinforcing efficiency in the order of
tens of GPa, for example [120e122], albeit still well below the ulti-
mate strength of CNTs (~100 GPa). Highly effective nanotube rein-
forcement was however achieved in oriented PVOH by Wang et al.
[123,124]. In their study a threefold increase in strength from 400 to
1200 MPa was reported with the addition of only 1 wt% SWCNT,
translating into an effective stress carried by the nanotube of 88 GPa,
i.e. comparable to the ultimate tensile strength of SWCNTs. However,
again, although above studies reported effective nanotube rein-
forcement, the majority of these fibers possessed overall mechanical
properties that were below those of commercial high-performance
fibers with tensile strengths of 3e5 GPa.
Despite these rather modest results in textile grade fibers, the
prospect of substantially improving the tensile strength of high-
performance polymer fibers through the introduction of CNTs
remained intriguing [11e13,125e129]. The problem related to
dispersing long and flexible CNTs which entangle upon mixing with
viscous polymer melts can be avoided by adding CNTs in the
spinning dope of for example UHMW-PE solutions consisting
typically of appr. 10% UHMW-PE in decalin or paraffin [32]. The
diameter of a single CNT is estimated to be from 0.43 nm [130] to
5.1 nm [131]. Assuming a diameter of 0.5 nm and an aspect ratio of
10,000, which can be achieved as discussed above, then the CNTs, if
oriented, nearly form a perfect match with the stretched and
aligned UHMW-PE molecule in a PE fiber. The length of an extended
PE molecule (Mw for UHMW-PE is appr. 5  106 g/mol) in a fiber like
Dyneema® is typically in the order of 1 mm (based on Mn) to 50 mm
(based on Mw) and the aligned CNT is appr. 5 mm (aspect ratio 104)
to 50 mm (aspect ratio 105). Lengthwise, CNTs and PE molecules are
therefore not too far apart and the interaction between PE mole-
cules, CNTs and solvent is similar, viz. Van der Waals interactions.
Despite the small diameter, the CNTs are not expected to co-
crystallize with PE molecules in the standard orthorhombic lat-
tice, at least the authors have not seen literature reports about co-
crystallization, but the aligned CNTs should reside between the
microfibrils in the fiber. The breaking strength of a PE molecule is
estimated to be appr. 20 GPa [100,101] and with an elastic modulus
of 180 GPa [132]. The strength of a SWCNT is estimated, as dis-
cussed above, in the order of 100 GPa, and the elastic modulus is in
the order of 1000 GPa. So, all the prerequisites seem to be in place to
fabricate a fibrous composite structure based on a UHMW-PE ma-
trix and embedded SWCNTs possessing superior levels of strength
and stiffness. However, despite many efforts made in industry, e.g.
DSM Dyneema, and several research institutes, no significant re-
sults have been obtained so far. Similar disappointing results were
reported for other high-performance polymer fibers like aramid
[133] and polybenzoxazole (PBO) [134].
In a recent article by Peijs and Goutianos [135] the disappointing
reinforcement of high-performance fibers by CNTs was analyzed
and discussed in detail. The main reason given by the authors for
these disappointing reinforcing effects was directly related to the
intrinsic highly anisotropic (1D) structure of oriented polymer fi-
bers. Using analytical and numerical models, Goutianos and Peijs
could show that the low intrinsic shear strength of these fibers
effectively limits the stress transfer between the nanotube and the
oriented polymer and as such limits the effective reinforcement by
the nanotubes. A further complication of the reinforcement of a
high-strength and high-modulus matrix is that a relatively high
(>10 vol%) CNT content is required to ensure significant reinforce-
ment. Since it has been proven difficult to homogeneously disperse
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Advanced Industrial and Engineering Polymer Research 5 (2022) 90e106
individual CNTs in polymers at such high concentrations this will
remain a challenge as agglomeration will inevitably lead to reduced
reinforcing efficiency. Nevertheless, there are some reports of
positive effects of the addition of CNTs to (less anisotropic) carbon
fibers notably by Minus and coworkers [136,137] where the addi-
tion of as little as 1% of CNTs increased the tensile strength of
carbonized PAN fibers by 60%, suggesting an effective CNT stress
contribution of 67 GPa. Although the authors ascribed the increase
in properties to some extent to changes in the carbonization pro-
cess and graphitic structure as a result of the presence of CNTs, that
is, a matrix effect rather than a direct nanotube reinforcement ef-
fect, the high reinforcing efficiency was here probably also aided by
the higher shear properties of carbon fibers as compared to more
anisotropic UHMW-PE and aramid fibers.
8. Conclusion
Carbon fibers have impressive tensile properties and combine
strength and stiffness (elastic modulus) with a relatively high
compressive strength. However, carbon fibers are inherently brittle
due to their close to 3D structure in contrast with aramid and poly-
ethylene fibers which are highly anisotropic 1D structures that
exhibit high toughness but lack compressive strength. The current
tensile strength of carbon fibers such as Toray's T1000 approaches
values as high as 7 GPa, while fibers with moduli as high as 800 GPa
are also available. The total production volume of carbon fibers was
appr. 150 kton/annum in 2021 but the projected growth is some 8%
per annum until 2030 with increasing demands coming from wind
energy, aerospace and defense. The demand for carbon fiber is ex-
pected to grow dramatically with expanding opportunities for
lightweighting in automotive, especially in electrical vehicles to
compensate for the heavy battery pack. Although the field of carbon
fibers has achieved a high level of maturity and the offering by
market leader Toray has not significantly changed since the mid-
1980s, there has been a recent resurgence in carbon fiber research.
Driven by the need for cost reduction significant research efforts have
been devoted to develop cheaper and more sustainable precursor
fibers based on lignin or polyethylene, while developments in carbon
nanomaterials have seen a dramatic interest in novel multifunctional
fibers based on carbon nanotubes. Although the properties of lignin-
based carbon fibers are not satisfactory from a current perspective,
these fibers are pushing the boundaries of the requirements set for
the automotive industry, viz. a tensile strength of 1.7 GPa and an
elastic modulus of 200 GPa. Future perspective for fibers based on
carbon nanotubes look less promising, as despite enormous research
efforts and numerous publications in high impact journals little has
materialized into real commercial products.
An area that was not covered in this review but has tremendous
business opportunities is in the area of recycling and recovery of
carbon fiber [138]. Companies such as carboNXT (Germany) and
Gen2Carbon (UK) are developing technology to recover carbon fi-
bers from manufacturing waste and end-of-life composite parts
and returning it back to the market as a technically acceptable
alternative to virgin carbon fiber but with a significantly reduced
environmental footprint. As the energy required to recover carbon
fiber from e.g. end-of-life aerospace or wind turbine parts is much
lower than the embodied energy for virgin fiber, the use of recov-
ered carbon fiber might be a viable alternative to the development
of low-cost carbon fiber for use in automotive applications.
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
T. Peijs, R. Kirschbaum and P.J. Lemstra Advanced Industrial and Engineering Polymer Research 5 (2022) 90e106

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