11 Lignin-Derived Carbon Fibers
Sabornie Chatterjee 1, Tomonori Saito 1 and Priyanka Bhattacharya 2
1
Chemical Sciences Division, Oak Ridge National Laboratory, Oak Ridge, TN, USA
O U T L I N E
1. Introduction
2. Processing
2.1 Spinning
2.2 Thermostabilization
2.3 Carbonization
3. Applications
1. Introduction
Carbon fiber (CF) is an important engineering ma-
terial with high stiffness, great tensile strength,
elevated temperature tolerance, low thermal expan-
sion, lightweight, high flexibility, and high fatigue
resistance (Baker et al., 2012; Baker and Rials, 2013;
Chatterjee et al., 2014a,b; Huang, 2009). CF in general
contains at least 90% carbon obtained by the controlled
pyrolysis of the precursor fiber. A fiber containing
carbon content more than 99% is termed graphite fiber.
The core structure of CF has long chains of graphene
molecules that are arranged hexagonally (Huang,
2009). The orientation of graphite layers, which are
mostly aligned parallel to the long axis of the fiber,
results in high modulus and tensile strength of the fiber.
Based on the modulus, commercial CFs can be divided
into five typesdultrahigh-modulus, type UHM
(modulus >450 Gpa); high-modulus, type HM
(modulus between 350 and 450 Gpa); intermediate-
modulus, type IM (modulus between 200 and
350 Gpa); low modulus and high-tensile, type HT
(modulus <100 Gpa, tensile strength >3.0 Gpa); super
high-tensile, type SHT (tensile strength >4.5 Gpa)
(Chung, 1994). CFs with high tensile strength
(>1.4 GPa) are called “high-performance carbon fi-
bers.” Relatively low tensile strength CFs are called
Lignin in Polymer Composites. http://dx.doi.org/10.1016/B978-0-323-35565-0.00011-4
Copyright © 2016 Elsevier Inc. All rights reserved.
2
Proton Power, Inc., Lenoir City, TN, USA
207 3.1 Structural CFs 209
208 4. Microstructured Carbon Fiber Mats 211
208
5. Conclusions and Future Perspectives 214
209
209 References 215
209
“general purpose carbon fibers.” Highly porous, low
strength fibers are called “activated carbon fibers.”
Additionally, CFs can also be classified based on the
temperature used in the manufacturing procedure.
There are three types of CFs in this categorydType-I,
high-heat-treatment CFs (HTT) (temperature is equal
to or more than 2000  C), Type-II, intermediate-heat-
treatment CFs (IHT) (temperature is about 1500  C),
and Type-III, low-heat-treatment CFs (temperature is
equal to or less than 1000  C).
The properties and classifications of CFs largely
depend on the precursor material and processing
methods (Chatterjee and Saito, 2014). Poly-
acrylonitrile (PAN) is the most commonly used pre-
cursor material for the commercial production of CFs
(Huang, 2009; Chung, 1994). In some cases, petro-
leum- or coal-based pitch and rayon are also used to
make CFs. However, due to the high price of petro-
leum feedstock, CFs produced from PAN are
expensive. Thus, the use of expensive CFs is limited
to high-performance materials, such as secondary
structural materials in the aerospace industry, sports
equipment, satellites, race cars, wind turbine com-
ponents, etc., where high mechanical performance
and low weight are more important than low cost. To
make CFs for economic and general applications,
easily available and inexpensive raw materials should
207
208
be used. Thus, there is an increasing demand for CFs
made from economic and widely available raw ma-
terials such as lignin.
Lignin, the largest aromatic biomass source after
cellulose and chitin with carbon content above 60% is
an attractive sustainable precursor for CFs (Chatterjee
and Saito, 2014; Chatterjee et al., 2014c; Sherine and
Rafael, 2014; Zakzeski et al., 2010; Baker et al., 2005;
Bhattacharya et al., 2013; Chatterjee, 2013; Ragauskas
et al., 2014). The US Renewable Fuels Standard
(RFS) mandates production of 16 billion gallons of
lignocellulosic biofuels (primarily EtOH) by 2022
www.ethanolrfa.org/pages/renewable-fuels-standard
(accessed 03/28/2015). Subsumed under this mandate
is the inevitable availability of an enormous amount of
lignin as a coproduct of biofuel manufacture.
Assuming that a commercial biorefinery produces
80 gallons biofuel ton 1 biomass and that the biomass
averages 20 wt% lignin, operation at the legislated
levels of the RFS will afford 40 million tons of lignin
on an annual basis. This remarkable level of renewable
carbon production and availability is an attractive
target for downstream chemical processing and con-
version to higher-value chemicals and materials.
However, the heterogeneous structure of lignin has
frustrated efforts to selectively convert this abundant
biopolymer into low-molecular-weight aromatics.
From the industrial perspective, conversion of lignin to
materials such as CFs has more economic potential.
2. Processing
A typical process to produce CF from purified lignin
can be divided into three main steps (Scheme 1):
(1) spinning, (2) thermal stabilization, and (3)
carbonization (Baker et al., 2012; Baker and Rials,
2013; Chatterjee et al., 2014a,b; Lin et al., 2012).
For the processing of graphite fibers from appro-
priate precursor fibers, an additional step of
Scheme 1 Processing of lignin carbon fibers.
L IGNIN IN P OLYMER C OMPOSITES
graphitization is used. Sometimes lignin is washed or
solvent fractionated (Chatterjee and Saito, 2014) and
dried under vacuum prior to spinning and thermally
pretreated under vacuum for a few hours to remove
volatile components in it. In some cases, chemical
modifiers or additives are added to lignin before or
during spinning. The production of good quality
CFs requires highly pure lignin. The use of lignin
with less heterogeneity (narrow-molecular-weight
distribution) results in an increase in the molecular
weight of the entire fiber during the thermal stabili-
zation step. This helps to form uniformly structured
CFs during carbonization.
2.1 Spinning
Spinning controls the tenacity, diameter, and
morphology of the precursor fibers. Depending on the
nature of lignin, different spinning methods such as
melt spinning or extrusion, dry spinning or solvent-
assisted spinning, wet spinning, electrospinning, or
melt-blown (for lignin CF mats) are used.
In a melt spinning method, lignin is molten by rapid
heating to a temperature between 100 and 250  C.
Lignin is an amorphous thermoplastic polymer and
so, its spinning temperature is related to its Tg (glass
transition temperature), Ts (softening temperature),
and molten viscosity (Saito et al., 2012, 2013, 2014;
Luo et al., 2011). To avoid early cross-linking of
lignin fibers, the melt spinning of lignin is generally
conducted at a lower temperature than the Tg of the
corresponding lignin. For melt spinning of lignins, it
must have a low softening temperature which will
allow melt flowing (Baker and Rials, 2013; Luo et al.,
2011; Braun et al., 2005; Kadla et al., 2002a,b). As
the source of the lignin has a huge impact on lignin’s
property, the spinning temperature of various lignins
varies with the type of lignin. The temperature for
melt spinning of organosolv (Alcell) hardwood lignin
is in the range of 138e165  C, which is lower than
11: L IGNIN -D ERIVED C ARBON F IBERS
that of kraft hardwood lignin (195e228  C) (Baker
and Rials, 2013; Chatterjee et al., 2014a,b; Luo et al.,
2011; Braun et al., 2005; Kadla et al., 2002a,b). The
lignin melt is then extruded through spinneret to form
the fiber, which is collected on a winder. In some bulk-
scale productions, lignin melt is passed through a
blower of air. To minimize the oxidation of lignin
fiber, in some cases, spinning is performed under
inert gas (e.g., nitrogen and argon) atmosphere.
In a dry spinning method, a suitable solvent is used
to dissolve lignin. The lignin solution is then
extruded and subsequently heat dried to obtain the
fibers (Zhang and Ogale, 2014).
In a wet spinning method, lignin is dissolved in a
suitable solvent or solvent mixture. The lignin solu-
tion is then extruded with or without heating. The
lignin fiber obtained is then collected either by drying
or by using a coagulation bath, where the lignin fiber
precipitates. The precipitated fiber is dried to obtain
the lignin fiber.
In electrospinning, lignin solution is spun using an
electrical voltage-driven method; lignin solution is
released from a spinneret to a collector (Wang et al.,
2013; Ruiz-Rosas et al., 2010; Lallave et al., 2007).
While passing through the spinneret, the lignin so-
lution becomes electrically charged due to the po-
tential difference between the spinneret and the
collector. The combined effect of the electrical
charge on the liquid surface and the surface tension
of the liquid helps to form a drop on the tip of the
spinneret needle. At one point, the repulsions be-
tween surface charges exceed the surface tension of
the liquid drop which results in the lignin solution
stream from the spinneret to the collector. After rapid
evaporation of the solvent, the lignin fibers are ob-
tained. One major advantage of the electrospinning
method is that it can produce nanodiameter fiber mats
(20e300 nm diameter) from any source of lignin.
The fiber obtained after spinning generally has
very low strength. This fiber is thermostabilized and
carbonized to form the moderate-to-high strength CF.
2.2 Thermostabilization
Thermo-stabilization stabilizes lignin fibers and
induces cross-linking in lignin, which raises the Tg of
lignin (Luo et al., 2011; Braun et al., 2005; Kadla
et al., 2002a,b; Dallmeyer et al., 2014a,b). This
converts the nature of lignin from thermoplastic to
thermoset. The conversion of thermoplastic lignin to
a thermoset material helps lignin fibers to maintain
209
the fiber form at higher temperatures. Thermo-
stabilization also prevents fiberefiber fusion and
deformation of lignin fibers during carbonization.
The effect of thermostabilization on the lignin fiber
can be tuned by changing the heating rate at different
stages of thermostabilization. In a typical thermo-
stabilization process, lignin fiber is first heated from
the room temperature to about 100e105  C at a rate
of 1  C min 1 (Luo et al., 2011), and then the fiber is
held at that temperature for 1 h to remove moisture
from the sample. Subsequently, the fiber is heated to
200  C at a rate of 0.25  C min 1 and at that tem-
perature the fiber is held for 24 h to further oxidize
and cross-link the lignin and raise the Tg value. Ther-
mostabilization initially increases the oxygen content
of lignin fiber with the increase of temperature. After
reaching the maximum, increase in temperature
decreases the oxygen content in lignin fibers. With
a slower heating rate, at low temperatures, auto-
oxidation, molecular rearrangement, and radical
couplings occur. These reactions introduce carbonyl
type functional groups in lignin. At a molecular level,
cleavage of aliphatic side chains and b-O-4 bonds
occur. These changes as a whole decrease the aryl
ether content of lignin. At high temperatures, dehy-
dration, cross-linking, condensation, and elimination
reactions occur, which result in the release of gases
such as CO and CO2 from lignin through the for-
mation of keto, ester, and anhydride linkages
(Chatterjee et al., 2014a,b; Luo et al., 2011).
2.3 Carbonization
The thermostabilized lignin fiber is carbonized at
the next step by heating at temperature 1000  C or
higher. Carbonization is conducted in an inert gas
atmosphere that prevents the combustion of lignin
fibers. During carbonization, all elements except
carbon are removed from the material. Due to the
release of vapors and gases from the fiber, imper-
fections and defects form in the fiber which, in turn,
changes the surface and porosity of the fiber. Thus,
by changing the rate of heating, the morphology and
brittleness of lignin-derived CFs can be controlled.
3. Applications
3.1 Structural CFs
The use of lignin to make CF has been studied for
more than 60 years (Luo et al., 2011). In 1966, Otani
210
et al. reported the production of CFs from lignin by

melt spinning and dry spinning methods (Otani et al.,
1966). The first commercial pilot plant for lignin-
based CFs was set up in early 1970s by Nippon
Kayaku Co. in 1974.
In 1992e1993, Sudo and coworkers showed that
by using hydrocracking, phenolation, or hydro-
genolysis followed by heat treatment under vacuum,
lignin could be converted into a molten viscous ma-
terial with suitable properties for thermal spinning
(Sudo and Shimizu, 1992; Sudo et al., 1993). Sudo
et al. made CFs from steam-exploded birch hard-
wood lignin. The steam-exploded lignin was cata-
lytically hydrogenated to lower its softening point to
110  C, which facilitated the melt spinning of lignin.
The fibers were of modest mechanical properties
with a moderate tensile strength of 0.660 GPa.
Uraki et al. (1995) also prepared melt-spun CFs
from birch hardwood. However, they used an orga-
nosolv process to extract the lignin. The CFs had a
tensile strength of about 0.035 GPa and a modulus of
39.1 GPa.
After 2000, several research groups such as Kadla
et al. and Baker et al. started working intensively on
developing lignin-derived CFs. Kadla et al. (2000a,b)
worked on the preparation of CFs from various lig-
nins. While comparing melt spinnability of organo-
solv (Alcell) lignin, hardwood kraft lignin, and
softwood kraft lignin, Kadla et al. found that while
both organosolv lignin and hardwood kraft lignin
were suitable for melt spinning, softwood kraft lignin
could not be melt-spun as in this case, charring
occurred before melting. Organosolv lignin was
found to have the lower spinning temperature
(138e165  C) than hardwood kraft lignin
(195e228  C). After thermostabilization and
carbonization the fibers obtained from organosolv
lignin showed strength and modulus of 0.388 and
40 GPa, respectively. The strength and modulus of
the kraft hardwood-based CF were 0.422 and 40 GPa.
Baker et al. conducted a significant amount of
research on lignin-derived CFs (Baker et al., 2005,
2012; Baker and Rials, 2013). This group worked on
the process optimization for the production of CFs
from different lignins. In one study, organic solvent-
washed hardwood kraft lignin was found to be more
spinnable than as-received hardwood kraft lignin
(Figure 1). The CFs obtained from the organic
solvent-washed lignin showed a tensile strength of
0.517 GPa. In another study, they found by using a
thermal pretreatment of organosolv (Alcell) lignin,
L IGNIN IN P OLYMER C OMPOSITES
the Tg and Ts could be increased which finally
enhanced the tensile strength and yield of Alcell
lignin-derived CF. Using a thermal pretreatment they
were able to increase the tensile strength of organo-
solv lignin-based CFs from 0.338 to 0.710 GPa
(Figure 2).
In 2012, Lin et al. reported the synthesis of CFs
from softwood lignin (Lin et al., 2012), which was
obtained by solvolysis of cedar wood chips by
polyethylene glycol and sulfuric acid. Interestingly,
the softwood lignin was easily converted to lignin
fibers by melt spinning at 145e172  C. After ther-
mostabilization and carbonization, the CF obtained
in this case showed tensile strength and modulus up
to 0.457 and 26.2 GPa, respectively.
In a recent work, Zhang and Ogale (2014) reported
the production of high tensile strength (w1.04 GPa)
CFs from acetylated softwood kraft lignin. The CFs
(with about 7 mm diameter) were made using a
solvent (acetone)-assisted spinning method. The
fibers were found to have high surface area due to
their crenulated structure.
Several researchers tried to obtain better quality
CFs by using lignin synthetic polymer blends (Kubo
and Kadla, 2004, 2005). Kadla et al. developed a
method to enhance the melt spinnability of hardwood
kraft lignin by using ligninepolyethylene oxide
(PEO) blends as precursors. A blend of commercially
available unmodified kraft hardwood lignin and PEO
was melt-spun, thermally stabilized, and carbonized
to make moderate strength CFs (up to 0.422 GPa
tensile strength and 40 GPa modulus). In this case,
the use of PEO enhanced the fiber spinnability
without affecting the properties of the fiber. The same
group also used other synthetic polymerelignin
blends to make CFs (Kubo and Kadla, 2004, 2005).
In one study, fibers made from unmodified hardwood
kraft and organosolv lignin were found to be brittle.
The use of blends of lignin and synthetic polymers
such as poly(ethylene terephthalate), PEO, and
polypropylene was found to reduce the brittleness
and showed improved tenacity. Kadla et al. also
employed an electrospinning technique to produce
CFs from ligninesynthetic polymer blends
(Dallmeyer et al., 2014a,b). They studied the effect of
viscoelasticity of DMF (N,N-dimethyl formamide)
solution of softwood kraft lignin on its properties,
especially electrospinnability. In another study by
this group, the relation between the fluid properties of
the blend and fiber diameters was studied. It was
found that, using lignin precursors with different
11: L IGNIN -D ERIVED C ARBON F IBERS 211

(a) (b)

(c) (d)

(e) (f)

Figure 1 Scanning electron microscopy images of (a,b) lignin fibers extruded from an organic solvent-extracted
kraft hardwood lignin; (c,d) oxidized lignin fiber at heating rates of (c) 0.05  C min 1 and (d) 0.025  C min 1
showing different degrees of fusion; (e,f) carbon fiber, carbonized to 1000  C at 2  C min 1 after stabilization
at a heating rate of 0.01  C min 1.
Reproduced from Baker et al. (2012). Copyright (2012, John Wiley and Sons).

softening temperatures, CFs with different morphol-
ogies could be produced by controlling the heating
rate during thermostabilization.
At present, lignin CFs with average tensile
strength as high as 1.07 GPa with a modulus of
82.7 GPa can be prepared from modified lignin
(Baker and Rials, 2013; Zhang and Ogale, 2014;
Warren and Naskar, 2012). Synthesis of such higher-
performance lignin CFs requires highly pure lignin
with optimized processing parameters. Especially,
contamination had a major effect on the properties of
CFs. Based on their research, the ORNL team
described a general specification of lignin for the
production of CF (Table 1) (Luo et al., 2011). A
comparison of mechanical strengths of different fi-
bers is given in Table 2.
4. Microstructured Carbon Fiber
Mats
While the major research on lignin-derived CFs
for high-performance and general purpose applica-
tions is aimed toward the increase of the fiber
strength for mechanical or structural applications,
several researchers have been trying to develop lignin
212 L IGNIN IN P OLYMER C OMPOSITES

(a)

(b) (c)

Figure 2 (a) Fused lignin carbon fiber mats after carbonization; (b,c) scanning electron microscopy images of
lignin carbon fiber mats with different degrees of fusion and density.
Reproduced from Tenhaeff et al. (2013). Copyright (2014, John Wiley and Sons).

CF materials for nonstructural applications. In such

Table 1 ORNL Specification for Lignin Feedstock to cases, researchers are developing lignin CFs with
be Used as a Carbon Fiber Precursor (Luo et al., 2011)
controlled porosity and high surface area. Some of
Specification Value the high surface area porous CFs are termed activated
CFs.
Lignin content 99 (wt%)
Recently, Tenhaeff et al. (2013) reported the
Ash content <0.1 (wt%) synthesis and application of lignin CF mats for en-
Volatile material content <5% (at 250  C) (wt%) ergy storage applications (Figure 2). This group of
Particulate matter Removal of all researchers produced three-dimensional carbon
particulate matter mats from solvent-extracted organosolv lignin.
>1 mm in diameter Electrodes made from highly porous CF mats do not
Residual carbohydrates <500 ppm
need any binders. Most importantly, due to high
porosity, these electrodes are less affected with
electrolyte solutions. The electrically networked

Table 2 Structural Properties of Carbon Fibers from Different Precursors (Lin et al., 2012)

Acetylated
Hardwood Hydrogenated Softwood
Precursor PAN Pitch Kraft Lignin Lignin Kraft Lignin

Prepared by Zoltec Zytec (2009) Kadla Sudo Ogale

Diameter (mm) 7.2 11 46  8 7.6  2.7 w7
Tensile strength (GPa) 4.137 1.56 0.605 0.660  230 1.04  0.10
Tensile modulus (GPa) 242 172 140 40.7  6.3 52  2
PAN, polyacrylonitrile.
11: L IGNIN -D ERIVED C ARBON F IBERS 213

(a) 200 µm (b) 200 µm (c) 20 µm

(d) 3 µm (e) 200 µm (f) 40 µm

Figure 3 Scanning electron microscopy images of lignin carbon fibers. (a) Unmodified Alcell hardwood lignin
(AHL); (b) phthalic anhydride-modified AHL; (c) close-up and cross section of a phthalic anhydride-modified
AHL-based carbon fiber with a hollow center; (d) fused lignin carbon fiber mat (AHL); (e,f) examples of fiberefiber
fusion in phthalic anhydride-modified kraft softwood lignin (KSL).
Reproduced from Chatterjee et al. (2014a,b). Copyright (2014, The Royal Society of Chemistry).

monolithic mats were prepared by air-driven
melt spinningethermal stabilizationecarbonization
route. The degree of fiberefiber fusion and mat
density were controlled by the rate of heating. The
electrochemical performance of lignin CF mat-
based electrodes was found to be comparable with
that of commercial carbon-based anodes. The
compositional and electrochemical characterization
showed that carbonized lignin had a disordered
nanocrystalline microstructure.
Chatterjee et al. (2014a,b) designed and pro-
duced unique mesostructured porous CFs from
organosolv (Alcell) and softwood kraft lignins. A
combination of chemical modifications and CF
processing techniques was used to synthesize these
CFs. In this work, lignin was first modified by
converting its hydroxyls to different ester groups.
Esterification of lignin increases the melt spinn-
ability of these lignins. This effect was especially
significant in case of phthalic anhydride-modified
softwood lignin. This was most probably due to
the incorporation of the phthalic moiety to lignin
that increased the aromatic content of lignin.
Furthermore, esterified lignins were melt-spun,
thermally stabilized, and carbonized at a low tem-
perature to make microstructured CFs. The esteri-
fied lignins had higher thermal stability than the
unmodified lignin, which resulted in less mass loss
during carbonization. This result showed that by
tuning the chemical modification, the meso and
microstructures of lignin-derived CFs could be
controlled. In addition, by changing the carbon-
ization temperature profile, the graphitic or disor-
dered structures of these fibers can be adjusted. The
combined process was able to preserve the het-
erogeneous core structure of lignin that resulted in
nanocrystalline domains in the resulting CFs. The
produced CFs were found to have a void at the core
with a microporous surface morphology (Figure 3).
Acetic anhydride-modified lignin-derived CFs
showed a surface area of about 37.42 m2 g 1.
Kadla et al. reported the synthesis of CF mats
interconnected with submicron fibers (Dallmeyer
et al., 2014a,b). The interfiber bonding increased the
mechanical strength of the CF mats. The CF mats are
made from a blend of kraft lignin/PEO in DMF using
electrospinning. The electrospun fibers were ther-
mostabilized at 250  C and carbonized at the range of
600e1000  C. The surface area of the material was at
the range of 370e456 m2 g 1. The produced fibers
showed low-to-moderate tensile strengths
(0.32e0.76 GPa). However, the CFs had high elec-
trical conductivity (8.3  10 4  1.9  10 4e19.6
 3.0 S cm 1). In another recent work, this group
made moisture-responsive materials from kraft lignin
blends using electrospinning (Dallmeyer et al.,
2013). Lignin blends were prepared by mixing PEO
with different fractions (or fraction mixtures) of
214
(a) (b)
Wet surface t=0
(e) (f)
Dry surface, t = 0 t = 10 s
Figure 4 Reversible, moisture-responsive shape change of a thermostabilized (5  C min 1) film (made from
blends of lignin fractions). (aed) When placed on a moist paper; (eeh) after moving to a dry paper.
Reproduced from Dallmeyer et al. (2013). Copyright (2013, American Chemical Society).
lignin. The fractionation of softwood kraft lignin was
conducted using a sequential addition of organic
solvents. Different blends (containing different frac-
tions or fraction mixtures) of lignins have different
physical properties. In particular, the thermal flow
behaviors of different lignin fractions are different,
which in turn changes the interfiber fusion during
oxidative thermostabilization. By carefully tuning
the relative amount of various lignin fractions and
the extent of fiber flow and interfiber fusion, the
electrospun lignin-derived materials with different
morphologies were prepared, which were success-
fully transformed to moisture-responsive materials
capable of reversible changes in shape (Figure 4)
(Dallmeyer et al., 2013).
Rojas et al. developed cellulose nanocrystals-
reinforced nanofibrous mats by electrospinning of
softwood kraft lignin (Figure 5) (Ruiz-Rosas et al.,
2010; Ago et al., 2012). They electrospun a mixture
of polyvinyl alcohol, lignin, and celullose nano-
crystals, which produced defect-free nanofibrous
mats with up to 90% of lignin and 15% of cellulose
nanocrystals.
L IGNIN IN P OLYMER C OMPOSITES
(c) (d)
t=2s t = 10 s
(g) (h)
t = 30 s t = 45 s
5. Conclusions and Future
Perspectives
CFs can be considered as one the most economi-
cally attractive applications of lignin. Lignin CFs, if
properly customized, could attract large markets in
automotive, aerospace, renewable energy, and energy
storage system/electronic industries. Among these
industries, lignin CFs have major potentials in auto-
motive and energy storage/electronic industries as in
these cases; only moderate-to-high strength CFs are
required. The global market demand for CFs is esti-
mated to reach about 102,460 metric tons in 2020
(Composites World Carbon Fiber Conference, 2012).
As the precursor cost is about 50% of the CF pro-
duction cost, an abundantly available inexpensive
precursor, such as lignin, would have a huge potential
compared to PAN or other petroleum-based raw ma-
terials. However, lignin’s heterogeneous structure
varies with the source. The presence of impurities in
lignin alters the physical and chemical properties of
lignin. The heterogeneity in lignin quality also com-
plicates the process development and optimization.
11: L IGNIN -D ERIVED C ARBON F IBERS 215

(a-1) (a-2) (a-3) (a-4)

(b-1) (b-2) (b-3) (b-4)

Figure 5 Field emission scanning electron microscopy micrographs (scale bar: 5 mm) of lignin-based fibers
obtained by electrospinning of aqueous solutions containing polyvinyl alcohol (PVA) at concentrations of 10%
(upper row, (a) series) and 5% (bottom row, (b) series). The different ligninePVA mass ratios of the obtained,
solid fibers are 0:100 (1); 20:80 (2); 50:50 (3); and 75:25 (4).
Reproduced from Ago et al. (2012). Copyright (2012, American Chemical Society).

All these result in inconsistencies in the quality of CFs
from batch to batch. Thus, intensive research is
required to understand the basic chemistry and to
optimize the processing technology to produce good-
quality CFs from lignin.
References
Ago, M., Okajima, K., Jakes, J.E., Park, S.,
Rojas, O.J., 2012. Biomacromolecules 13, 918.
Baker, D.A., Gallego, N.C., Baker, F.S., 2012. Journal
of Applied Polymer Science 124, 227.
Baker, D.A., Rials, T.G., 2013. Journal of Applied
Polymer Science 130, 713.
Baker, F.S., Griffith, W.L., Compere, A.L. (Eds.), 2005.
Process Report. Oak Ridge National Laboratory.
Bhattacharya, P., Penmetsa, V., Steele, P., Mitchell, B.,
2013. Journal of Forest Products and Industries
2, 47.
Braun, J.L., Holtman, K.M., Kadla, J.F., 2005. Carbon
43, 385.
Chatterjee, S., Saito, T., 2014. Polymer Precursor-
Derived Carbon, vol. 1173. American Chemical
Society, p. 153.
Chatterjee, S., Clingenpeel, A., McKenna, A.,
Rios, O., Johs, A., 2014a. RSC Advances 4, 4743.
Chatterjee, S., Jones, E.B., Clingenpeel, A.,
McKenna, A.M., McNutt, N.W., Rios, O.,
Keffer, D.J., Johs, A., 2014b. ACS Sustainable
Chemistry and Engineering 2, 2002.
Chatterjee, S., Saito, T., Rios, O., Johs, A., 2014c.
Green Technologies for the Environment, vol. 1186.
American Chemical Society, p. 203.
Chung, D., 1994. Carbon Fiber Composites, first ed.
Butterworth-Heinemann.
Chatterjee, S., 2013. Biofuels 4, 571.
Composites World Carbon Fiber Conference,
Dec 4e6, 2012, La Jolla, California, U.S.A.
http://www.compositesworld.com/news/carbon-
fiber-2012-supply-and-demand-forecast (accessed
03/28/2015)
Dallmeyer, I., Lin, L.T., Li, Y., Ko, F., Kadla, J.F.,
2014a. Macromolecular Materials and Engineering
299, 540.
Dallmeyer, I., Ko, F., Kadla, J.F., 2014b. Industrial and
Engineering Chemistry Research 53, 2697.
Dallmeyer, I., Chowdhury, S., Kadla, J.F., 2013.
Biomacromolecules 14, 2354.
Huang, X., 2009. Materials 2, 2369.
Kadla, J.F., Kubo, S., Gilbert, R.D., Venditti, R.A.,
2002a. In: Hu, T.Q. (Ed.), Chemical, Modification,
Properties, and Usage of Lignin, first ed. Kluwer
Academic/Plenum Publishers, New York. p. 121.
216
Kadla, J.F., Kubo, S., Venditti, R.A., Gilbert, R.D.,
Compere, A.L., Griffith, W., 2002b. Carbon 40, 2913.
Kubo, S., Kadla, J.F., 2004. Macromolecules 37, 6904.
Kubo, S., Kadla, J.F., 2005. Journal of Polymers and
the Environment 13, 97.
Lin, J., Kubo, S., Yamada, T., Koda, K., Uraki, Y.,
2012. Bioresources 7, 5634.
Luo, J., Genco, J., Cole, B., Fort, R., 2011. Bio-
Resources 6, 4566.
Lallave, M., Bedia, J., Ruiz-Rosas, R., Rodrı́guez-
Mirasol, J., Cordero, T., Otero, J.C., Marquez, M.,
Barrero, A., Loscertales, I.G., 2007. Advanced
Materials 19, 4292.
Ragauskas, A.J., Beckham, G.T., Biddy, M.J.,
Chandra, R., Chen, F., Davis, M.F., Davison, B.H.,
Dixon, R.A., Gilna, P., Keller, M., Langan, P.,
Naskar, A.K., Saddler, J.N., Tschaplinski, T.J.,
Tuskan, G.A., Wyman, C.E., 2014. Science 344.
Ruiz-Rosas, R., Bedia, J., Lallave, M.,
Loscertales, I.G., Barrero, A., Rodrı́guez-
Mirasol, J., Cordero, T., 2010. Carbon 48, 696.
Sherine, O.O., Rafael, L. (Eds.), 2014. Green Tech-
nologies for the Environment, vol. 1186. American
Chemical Society.
Saito, T., Brown, R.H., Hunt, M.A., Pickel, D.L.,
Pickel, J.M., Messman, J.M., Baker, F.S., Keller, M.,
Naskar, A.K., 2012. Green Chemistry 14, 3295.
L IGNIN IN P OLYMER C OMPOSITES
Saito, T., Perkins, J.H., Jackson, D.C., Trammel, N.E.,
Hunt, M.A., Naskar, A.K., 2013. RSC Advances 3,
21832.
Saito, T., Perkins, J.H., Vautard, F., Meyer, H.M.,
Messman, J.M., Tolnai, B., Naskar, A.K., 2014.
ChemSusChem 7, 221.
Sudo, K., Shimizu, K., 1992. Journal of Applied
Polymer Science 44, 127.
Sudo, K., Shimizu, K., Nakashima, N., Yokoyama, A.,
1993. Journal of Applied Polymer Science 48, 1485.
Tenhaeff, W.E., Rios, O., More, K., McGuire, M.A.,
2013. Advanced Functional Materials.
Uraki, Y., Kubo, S., Nigo, N., Sano, Y., Sasaya, T.,
1995. Holzforschung 49, 343.
Wang, S.-X., Yang, L., Stubbs, L.P., Li, X., He, C.,
2013. ACS Applied Materials and Interfaces 5,
12275.
Warren, C.D., Naskar, A.K. (Eds.), 2012. Presentation
Bat 2012 DOE Hydrogen and Fuel Cells Program
and Vehicle Technologies Program Annual Merit
Review and Peer Evaluation Meeting.
Zakzeski, J., Bruijnincx, P.C.A., Jongerius, A.L.,
Weckhuysen, B.M., 2010. Chemical Reviews 110,
3552.
Zhang, M., Ogale, A.A., 2014. Carbon 69, 626.

Otani, S., Yamada, K., Koitabashi, T., Yokoyama, A.,
1966. Carbon 4, 425.