CARBON 6 9 ( 2 0 1 4 ) 6 2 6 –6 2 9

Available at www.sciencedirect.com

ScienceDirect

journal homepage: www.elsevier.com/locate/carbon

Letter to the Editor

Carbon fibers from dry-spinning of acetylated

softwood kraft lignin

Meng Zhang, Amod A. Ogale *

Chemical Engineering and Center for Advanced Engineering Fibers and Films, Clemson University, Clemson, SC 29634, United States

A R T I C L E I N F O A B S T R A C T

Article history:
Received 15 October 2013
Accepted 5 December 2013
Available online 11 December 2013
An acetylated softwood kraft lignin was dry-spun into precursor fibers and successfully
processed into carbon fibers with a tensile strength exceeding most values reported in prior
studies on lignin-based carbon fibers. Limited acetylation of lignin hydroxyl groups enabled
dry-spinning of the precursor using acetone (solvent) followed by thermo-oxidative stabil-
ization. Resulting carbon fibers (7 lm diameter) displayed a tensile modulus, strength,
and strain-to-failure values of 52 ± 2 GPa, 1.04 ± 0.10 GPa, and 2.0 ± 0.2%, respectively.
Because of solvent diffusion during dry-spinning, fibers displayed a crenulated surface that
can provide a larger specific interfacial area for enhanced fiber/matrix bonding in compos-
ite applications.
Ó 2013 Elsevier Ltd. All rights reserved.

Currently, three precursor materials are used for commer-
cial production of carbon fibers: polyacrylonitrile (PAN), pitch
and rayon [1]. Of these, PAN is used almost exclusively to
produce high strength carbon fibers. The process involves
generation of certain toxic by-products such as hydrogen cya-
nide (HCN). This environmental problem can potentially be
overcome by the use of naturally occurring biomass, includ-
ing lignin. Unfortunately, most current grades of lignin are
intractable, so its chemical modification is needed for further
processing.
Otani et al. [2] described the use of an alkali-modified solu-
tion of lignin to produce carbon fibers. Later studies have fo-
cused on producing carbon fibers derived from modified-
lignins by melt spinning of steam-exploded lignin [3], organo-
solv lignin [4] and hardwood kraft lignin [5,6]. In a recent
study [7], fractionated softwood kraft lignin in combination
with hardwood kraft lignin was found to be capable of
continuous melt spinning and fast stabilization. But the
as-spun lignin fibers were thick (aprox. 100 lm) with carbon-
ized fibers being about 50 lm in diameter, and no tensile
properties were reported for those fibers. For high strength
purposes, however, other literature studies have established
that much smaller carbon fiber diameters (typically less than
10 lm) are desired [8]. For chemically modified kraft lignin,
other studies have reported its blending with synthetic resins
to increase the bio-derived component of matrices [9], or to
reduce its Tg to enable melt blending [10]. However, carbon fi-
bers produced from prior lignin-based studies in the literature
have exhibited relatively low tensile properties, with pub-
lished strengths of 660 MPa or lower [3–6]. A value of
1.07 GPa was attributed in a review article [11] to a DOE pre-
sentation, but the presentation,1 does not explicitly report

* Corresponding author.
E-mail address: ogale@clemson.edu (A.A. Ogale).
1
C.D. Warren and A.K. Naskar http://www1.eere.energy.gov/vehiclesandfuels/pdfs/merit_review_2012/lightweight_materials/
lm004_warren_2012_o.pdf.
0008-6223/$ - see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.carbon.2013.12.015
 CARBON 6 9 (2 0 1 4) 6 2 6–62 9
and discuss lignin-based carbon fibers. The low strength may
be attributed to the fact that melt-spun precursor fibers are
inherently difficult to stabilize by thermo-oxidative means,
and often partially fuse together during the stabilization-car-
bonization processes that result in surface defects on the
resulting carbon fibers. Solution-based dry-spinning of a high
softening-point lignin grade may reduce surface fusion of fi-
bers during heat treatment, but such dry-spinning of suitably
modified softwood kraft lignin precursor has not been re-
ported in prior literature studies. Therefore, the objective of
this study was to modify a softwood kraft lignin by limited
acetylation to convert it into carbon fibers via dry-spinning of
the precursor fibers.
As-received softwood kraft lignin (SKL, Indulin, Mead-
Westvaco) was washed with acidified DI water until ash con-
tent was 0.14% as measured by ASTM D5630 technique. SKL
showed no softening behavior during the entire heating pro-
cedure even when the temperature reached 300 °C. Acetyla-
tion at 85 ± 2 °C for 2 h with excess acetic anhydride (Ac2O)
concentration (15 ml Ac2O/g SKL) resulted in a thermally fus-
ible material. However, these melt-spun lignin fibers could
not be adequately stabilized due to the presence of thermally
stable acetyl groups that would not crosslink, even when the
thermo-oxidation heating rate was as low as 0.01 °C/min.
Consequently, SKL was reacted with a significantly lower
anhydride concentration (0.66 ml Ac2O/g SKL) for only 0.25 h
to produce acetylated SKL (Ace-SKL).
Fig. 1 displays the FTIR spectra of SKL at different acetyla-
tion levels; spectra were normalized with respect to the peak
at 856 cm 1, which is attributed to C–H bending on aromatic
rings. As the amount of Ac2O decreased from 15 to 0.66 ml/g
SKL, intensity of the hydroxyl peak at 3400 cm 1 increased
significantly. Also, the weight gain of lignin after reaction with
Ac2O moderated from 18% to 5%. Larger content of hydroxyl
group retained by these reaction conditions led to increased
reactivity/crosslinking of the precursor during subsequent
thermo-oxidation step. This enhanced crosslinking enabled
the stabilized fibers to retain the original fiber shape and size
without becoming tacky. At the same time, Ace-SKL obtained
from limited acetylation could be fully dissolved in acetone.
Fig. 1 – FT-IR spectra of acetylated lignin (Ace-SKL) produced from various compositions and reaction times.
627
This optimal composition of Ace-SKL enabled us to process
it into thin fibers (as described next) by solution or dry spin-
ning. Thus, 0.66 ml Ac2O/g SKL concentration and 0.25 h
reaction time were chosen as the conditions for producing
precursor for all subsequent experiments.
Ace-SKL powder was dissolved in acetone to obtain a vis-
cous solution (just under 75 wt.% solid content), which was
transferred into a custom-designed spinning unit fitted with
a 12-hole, 75 lm U spinneret (AJA Inc., Greenville, SC). This
Ace-SKL/acetone solution was successfully dry-spun into lig-
nin fibers; the smallest average fiber diameter achieved was
30 ± 1 lm. SEM micrographs of the as-spun fibers, displayed
in Fig. 2a (left), showed that the fibers were slightly non-circu-
lar with surface crenulations resulting from evaporation of
acetone. Subsequently, Ace-SKL fibers were thermo-oxida-
tively stabilized using a temperature ramp of 0.2 °C/min from
ambient to a maximum temperature of 220 °C under tension,
which led to an extension of up to 800%. The stabilized lignin
fiber diameter reduced to about 12 ± 1 lm. Carbonization was
also performed under tension using a heating rate of 4.5 °C/
min up to 1000 °C (HP50 furnace, Thermal Technology LLC).
An extension of up to 25% could be achieved during carbon-
ization with adequate tension. The carbon fiber size ranged
between 6 and 8 lm, as displayed in Fig. 2b (right). Carbon fi-
bers also preserved the non-circular cross section observed
for precursor fibers.
Wide angle X-ray diffractograms (WAXD, Rigaku) were ob-
tained from a CuKa X-ray source with a wavelength of
0.15406 nm operated under 45 kV and 0.65 mA. WAXD of car-
bon fibers (Fig. 3a) indicated a low degree of graphitic crystal-
linity within the carbon fibers. Integrated azimuthal profiles
for fibers carbonized with and without tension are similar,
with their (0 0 2) peaks located at 2h value of approximately
24°. The azimuthal profile of this peak, Fig. 3b, showed virtu-
ally no molecular orientation in fibers carbonized without
tension, with a Herman’s orientation factor of about 0.1
(fa = [3 < cos2/ > 1]/2). In contrast, for fibers carbonized un-
der tension, the peak at /  0° indicates an observable extent
of molecular orientation with a significantly higher Herman’s
orientation factor of about 0.3.
628 CARBON 6 9 ( 2 0 1 4 ) 6 2 6 –6 2 9
Fig. 2 – SEM images of (a) Ace-SKL as-spun fibers, and (b) carbon fibers. Schematics of fiber cross-section displaying:
(c) convex/sharp notches and (d) concave/smooth notches.
Fig. 3 – Wide-angle X-ray diffraction of carbon fibers derived
from Ace-SKL with an without tension during
carbonization: (a) integrated azimuthal profiles (two-theta
scans) of an aligned carbon fiber tow, with the three small,
sharp peaks (first appearing at 28.4°) are from NIST-grade
640b silicon powder sprinkled on the carbon fiber samples
for accurate location of two-theta peak positions;
(b) azimuthal profile of the 24° peak associated with (0 0 2)
layer planes.
Individual fibers were mounted on paper tabs for tensile
tests, and nominally 25 samples per group of fibers were
tested using a gage length of 10 mm. Fig. 4 displays modulus
and strength of various carbon fibers as a function of fiber
extension-during-carbonization (EDC). As expected, carbon fi-
bers with larger EDC displayed better tensile properties, due
to a higher molecular orientation. After compliance correc-
tion for modulus (using shorter and longer gage lengths of 5
and 25 mm, per ASTM D-3379-5), carbon fibers displayed a
tensile modulus, strength, and strain-to-failure values of
52 ± 2 GPa, 1.04 ± 0.10 GPa, and 2.0 ± 0.2%, respectively. The
largest individual filament tensile strength recorded was
1.3 GPa. In contrast to the doubly-convex crenulations
observed for current fibers (shown schematically in Fig. 2c)
that result in sharp notches, fibers with smoother crenula-
tions (Fig. 2d) will likely possess better mechanical properties.
Thus, further dry-spinning studies will address the role of
spinning conditions in attaining an optimum level/shape of
crenulations.
In conclusion, the tensile strength of present carbon fibers
produced from dry-spinning of partially acetylated lignin is
amongst the highest values reported in the literature. It is also
noted that crenulated carbon fibers obtained in this study
from dry-spinning of ACE-SKL have 35% larger surface area
as compared with equivalent circular fibers that are typically
obtained by melt-spinning. Further, due to the lack of gra-
phitic crystallinity in these lignin-derived carbon fibers, their
surface is expected to be more reactive than that of carbon
fibers possessing graphitic structure (such as those from
mesophase pitch precursor) that tends to be rather inert
due to the stable crystalline form. Therefore, such lignin-de-
rived carbon fibers could possess an intrinsically higher
 CARBON 6 9 (2 0 1 4) 6 2 6–62 9 629

Fig. 4 – Tensile strength and modulus of carbon fibers produced from acetylated lignin precursor fibers under various levels of
tension during carbonization. Solid circles represent tensile strengths. Open diamonds represent modulus values (without
compliance correction), whereas open square represents modulus value corrected for system compliance.

fiber–matrix interfacial bond strength when used in poly-
meric composites.
Acknowledgments
The authors gratefully acknowledge financial support from
SERDP WP-1758 (ARL project monitor: Dr. John LaScala). The
authors would also like to acknowledge Marlon Morales and
Dr. Y.P. Jeon for helping with WAXD and fiber spinning
measurements.
R E F E R E N C E S
[1] Fitzer E, Manocha LM. Carbon reinforcements and carbon/
carbon composites. Springer; 1998 (pp. 17–28).
[2] Otani S., Fukuoka Y., Igarashi B., Sasaki K. Method for
producing carbonized lignin fiber. US patent 3,461,082. 1969.
[3] Sudo K, Shimizu K. A new carbon fiber from lignin. J Appl
Polym Sci 1992;44:127–34.
[4] Uraki Y, Kubo S, Nigo N, Sano Y, Sasaya T. Preparation of
carbon fibers from organosolv lignin obtained by aqueous
acetic acid pulping. Holzforschung 1995;49:343–50.
[5] Kadla J, Kubo S, Venditti R, Gilbert R, Compere A, Griffith W.
Lignin-based carbon fibers for composite fiber applications.
Carbon 2002;40:2913–20.
[6] Baker DA, Gallego NC, Baker FS. On the characterization and
spinning of an organic-purified lignin toward the
manufacture of low-cost carbon fiber. J Appl Polym Sci
2012;124:227–34.
[7] Norberg I, Nordström Y, Drougge R, Gellerstedt G, Sjöholm E.
A new method for stabilizing softwood kraft lignin fibers for
carbon fiber production. J Appl Polym Sci 2013;128:3824–30.
[8] Chae HG, Choi YH, Minus ML, Kumar S. Carbon nanotube
reinforced small diameter polyacrylonitrile based carbon
fiber. Compos Sci Technol 2009;69:406–13.
[9] Thielemans W, Wool RP. Lignin esters for use in unsaturated
thermosets: lignin modification and solubility modeling.
Biomacromolecules 2005;6:1895–905.
[10] Jeong H, Park J, Kim S, Lee J, Cho JW. Use of acetylated
softwood kraft lignin as filler in synthetic polymers. Fiber
Polym 2012;13:1310–8.
[11] Baker DA, Rials TG. Recent advances in low-cost carbon fiber
manufacture from lignin. J Appl Polym Sci 2013;130:713–28.