December 2010, Volume 1, No.

2
International Journal of Chemical and Environmental Engineering

Preparation and characterization of

polyacrylonitrile/ acrylamide-based activated
carbon fibers developed using a solvent-free
coagulation process
1,2
Norhaniza Yusof and 1,2*Ahmad Fauzi Ismail
1
Advanced Membrane Research Technology Centre (AMTEC)
2
Faculty of Petroleum and Renewable Energy Engineering, Universiti Teknologi Malaysia,
81310 Skudai, Johor Bahru, Malaysia
*Corresponding author: afauzi@utm.my

Abstract
Polyacrylonitrile (PAN)/ acrylamide (AM) fibers were fabricated using dry-jet wet spinning system via solvent free coagulation
process. Activated carbon fibers (ACFs) were formed from the PAN/AM fibers through carbonization and activation. The ACFs are
aimed to be used as a precursor for natural gas storage application which may also suppress the natural gas storage problem. The
fabrication aspects in this study can be divided into several sections: dope formulation, spinning process, pyrolysis processes
including carbonization and activation steps. The manipulation of the dope formulation and heat treatment parameter are discussed.
By understanding the available methods, one can choose and optimize the best technique during the fabrication of PAN/AM-based
carbon fiber. The microstructures of the fibers were characterized using FESEM. The effects of the AM loading and heat treatment
parameter on the thermal property of PAN fibers were studied using DSC, TGA and Vario Elemental Analyzer III. Fibers fabricated
from 18 wt. % PAN and 5 wt. % AM compositions had better thermal properties compared to the homopolymer PAN precursor.

Keywords: Polyacrylonitrile, Acrylamide, Activated Carbon fiber, Solvent-free coagulation process, Dry-jet wet spinning.

1. Introduction fuel source. The feature of NG can simultaneously

Carbon fiber is a well-known material in many
applications particularly in composites. It has become an
important and attractive material due to its high strength
and modulus, high thermal, corrosion resistance and light
weight. A common cliché for carbon fiber composites is
that it is stronger than steel, stiffer than titanium and
lighter than aluminum is being noted and practiced [1].
Nowadays, carbon fibers are considered in a variety of
specialized applications such as aerospace, automobile,
chemical industry, general engineering, missile, nuclear
field, reinforcement in composite materials and textile. In
particular, carbon fiber composites are quite popular in
the automotive application due to the reduction of vehicle
weight in order to reduce fuel consumption. Furthermore,
environmental pollution cause by gasoline and diesel fuel
emission has driven public awareness to substitute them
with alternative clean energy. The combustion of gasoline
and diesel fuel emits a high ratio of carbon oxides,
nitrogen oxides, and sulfur dioxide, which is dangerous
from the point of view of nature protection. Natural gas
(NG) is definitely a more reliable fuel for vehicles
because it is relatively cleaner compared to gasoline. The
oil crisis in 2008 also increased interest in diversifying the
address the environmental problems as well as promote
future energy security.
NG stored under ambient temperature conditions is
very unreliable as transportation fuel mainly due to its
limited driving range as a result of its low volumetric
energy density [2]. Hence, the suitability of NG in
automobile application depends on the ability to store an
adequate amount of it in the vehicle fuel tank and one of
its ways is through compression of NG [3]. In the
compression method, the NG is stored and compressed
supercritical fluid at a very high pressure 20-50 MPa [3-
5].
The main hurdle for compressed natural gas (CNG)
vehicles is to have pressure vessel that can withstand high
pressure while being lightweight, high temperature
resistance and high corrosive material resistance. The best
alternative is to meet the above demand by selecting
carbon fiber (CF) as CNG pressure vessel. The various
unique properties of CF; namely lighter than aluminum,
stronger than steel, capable of withstanding great
extremes in heat and high pressure, and almost
impervious to corrosion and fatigue, make carbon fiber
 composites the perfect choice for CNG pressure vessel
[6].
Another latest finding in carbon fiber composites
area is the development of activated carbon fiber (ACF)
as an adsorbent media for natural gas and hydrogen
storage [2, 4, 6-7]. As compared with conventional
activated carbons (AC), ACFs have very fast adsorption/
desorption rates in gas and liquid filtration [7]. Moreover,
ACFs are also easy to handle and able to avoid the
problems arising from the packing of the granules or
powders of conventional AC. All of these features have
contributed to the increasing attention and wide use of
ACFs in various fields [7].
Hence, the development of Polyacrylonitrile (PAN)-
based activated carbon fiber (ACF) using the solvent free
coagulation process for precursor formation is important
and beneficial as it is receiving great attention nowadays
and also very environmental friendly. However, the
production of a high quality carbon fiber via solvent free
coagulation is fairly new and a lot of new information is
yet to be discovered. This process may involve many
steps that must be controlled and optimized. Therefore,
the objectives of this study are to investigate the
manipulation of comonomer content in PAN precursor
fibers and to study the pyrolysis process parameters to
provide an avenue for further enhancement of the
performance of PAN-based activated carbon fibers in the
future.
2.2 Dry-jet-wet spinning in solvent-free coagulation bath
The dry-jet-wet spinning technique was used to
produce PAN fibers. The unique feature of the spinning
process is to use 100% tap water in the coagulation bath,
which has been guaranteed to be environmentally
friendly and economical [8-9]. In the dry-wet spinning
process, the dope is extruded and traveled through an air
gap of 1 cm before dropping into coagulation bath. In
particular, PAN fibers were spun using a spinneret with
ten holes, each having a diameter of 0.35 mm. The
coagulation bath temperature was set at 17 oC. The
spinning parameters were tabulated in Table 1.
2.3 Pyrolysis Process
Carbolite (Model CTF 12/65/550) wire wound tube
furnace with Eurotherm 2416CC temperature control
system was used in the pyrolysis process in this study. In
this research, PAN/AM fibers were pyrolyzed at three
process regions for stabilization, carbonization and
activation processes as shown in Table 2.
Table 1 Dry-wet spinning process specification
Spinning Dope PAN/AM/DMF
AM weight % in Polymer 5.0 wt. %
Polymer Concentration 18 wt %
Dope Temperature Ambient Temperature

2. Materials and Methods Spinneret Diameter 350 µm

2.1 Materials Air Gap Distance 1 cm
PAN in powder form was obtained from Aldrich, No of holes for the spinneret 10 holes
USA. Meanwhile, acrylamide (AM) purchased from Coagulation Bath Composition 100% tap water
Sigma Aldrich, Germany was used as an additive. The
Coagulation Bath Temperature 17 oC
blending technique of PAN and AM in DMF to form
finely dispersed slurry was reported earlier [8-9].
Eighteen weight percent of PAN/DMF solution was
prepared, into which different amounts of AM ( 0% and
5%) were added. The slurry was heated continuously until
a highly viscous dope solution became ready for spinning
process.

Table 2 Pyrolysis temperature and other heat treatment parameters

Pyrolysis Process Pyrolysis Type of Gas Heating Rate Gas Flowrate Soaking time
Temperature (oC) (oC/min) (l/min) (min)

Oxidation stabilization 275 Compressed Air 2 0.2 30

Carbonization 600 Nitrogen (N2) 3 0.2 30

Activation 800 Carbon dioxide 5 0.2 30

(CO2)

80
 2.4 Characterization methods
Differential Scanning Calorimetry (DSC) was used
to measure the heat evaluated by the exothermic reaction
of the PAN fibers. DSC was carried out by a Mettler
Toledo differential scanning calorimeter (DSC) model
DSC822. The measurements were made in a dry nitrogen
environment at a heating rate of 10 oC/min. The samples
were then heated at programmed temperatures from 100–
400 °C at a heating rate of 10 °C/min under nitrogen
atmosphere. The weight loss of the fibers during heat
treatment process was characterized by thermogravimetric
analysis (TGA). The analysis was performed with a ramp
of 10 oC/min at the temperature ranging from 50 to 850
o
C. Vario elemental analyzer III was used to investigate
the elements contained in the fiber in weight percentage.
The outer surface and cross section morphologies of the
precursor and PAN-based carbon fibers were observed
under JEOL JSM-5610LV scanning electron microscopy
(SEM). The fiber samples were prepared by fracturing it
after immersing in liquid nitrogen for few minutes to
reduce damage on morphology.
3. Results and Discussion
3.1 Effects of comonomer addition to properties of PAN-
based carbon fiber
The effect of addition of acrylamide on the thermal
properties of the PAN precursor was investigated by DSC
experiments. The pyrolysis of homopolymer PAN is
uncontrollable because of difficulties involved in the
initial oxidation stage. The difficulty arises due to the
sudden and rapid evolution of heat, coupled with a
relatively high initiation temperature. This rapid surge of
heat can cause chain scission resulted in poor carbon fiber
properties [10]. Referring to the structure of
polyacrylonitrile in Figure 1, the acrylonitrile molecule
has a highly polar nitrile group that may cause a
polymerization via free radical or anionic polymerization.
The dipole-dipole interaction may also cause fiber
shrinkage upon heat treatment. This shrinkage is believed
to have the ability to disrupt the fiber orientation,
ultimately leading to poor mechanical properties.
Fig 1.The molecular structure of PAN
Figure 2 shows the trend of exothermic curve in
PAN fibers with additional of 5% AM and also the
homopolymer PAN for the purpose of comparison. The
exothermic regime of AM containing PAN precursor is
much broader and the cyclization reaction started at lower
81
temperatures compared to the PAN homopolymer
precursor which started at the temperature of 317.7 oC.
The exothermic process is the result of thermal stabilizing
processes and cyclization of nitrile group contributed to
the evolution of large amount of heat released from the
PAN fiber samples [5, 10]. Figure 2 depicted the presence
of acrylamide reduced the stabilization initiation
temperature and facilitated the process which made the
cyclization occur in a broader thermal range. For the
homopolymer PAN, a very sharp peak was obtained,
meaning sudden and rapid energy release occurred at a
high initiation stabilization temperature. It was also found
that the amount of energy released was also very large
compared to the other samples containing AM.
With addition of AM, the exothermic peak became
broader and shifted to lower initiation temperature at 275
o
C. It proves that AM unit acts as initiation sites of nitriles
and promotes the nitriles cyclization. This result was also
in accordance with the reported work by previous
researchers that claimed comonomers often acts as an
initiator for the stabilization reaction and facilitate the
process, thus cyclization occurs at lower temperatures and
in broader thermal ranges [5, 10, 11]. AM has amide
groups that can form cyclic structures with adjacent nitrile
groups of PAN. These cyclic structures propagate to the
larger structure through nitrile oligomerization and
dehydrogenation and subsequently slow down the
propagation steps [12]. By slowing down the propagation
steps, sudden and rapid energy release can be controlled,
which will prevent the structure of PAN fibers from
damage.
Fig 2(a) DSC curve of homopolymer PAN

Fig 2(b) DSC curve of PAN/AM 5 %
3.2 Effects of heat treatment on PAN-based carbon
fiber
Pyrolysis is a conversion process which is
compulsory to convert PAN fiber precursor into carbon
fiber. Oxidative stabilization forms the ladder structure to
enable the fibers undergo further pyrolysis process at
higher temperatures [13]. Meanwhile, carbonized fibers
are the fibers that have undergone heat treatment in an
inert condition to remove the non-carbon elements as
volatile gases. The pyrolysis process was further done to
the PAN/AM fiber. From the elemental analysis results
with Vario Elemental Analyzer depicted in Figure 3 for
PAN/AM fibers, the carbon content continuously
increased while the other elements decreased with the
increasing temperature and the activation time.
Carbonized fibers show low content of Hydrogen and
Oxygen due to effective dehydrogenation and
oligomerization during oxidative stabilization.
From the TGA thermogram in Figure 4, it was
observed that, weight loss significantly occurred around
300-350°C for PAN/ AM fiber. The onset of thermal
decomposition of PAN fiber with the AM attached to the
PAN structure took place at two temperature region (i.e.
273ºC and 385ºC). The reason was possibly due to the
glassy temperature of polyacrylonitrile at 317°C.
However in the region at 400-850°C TGA temperature,
the loss was slower. This indicated that AM which
attached to the PAN structure could cyclize the structure
faster than others and then stabilized the PAN structure.
From the percentage loss, it has been determined
that, the total weight loss of PAN/AM fiber prepared by
dry-jet wet spinning method via solvent free coagulation
process is less, which means that the yield of carbon is
high. It is also shown in the Figure 4 that after for about
50 % weight loss the losing rate was slow. It is perhaps
due to the molecular cross linking that occurred in PAN
structure which could inhibit the weight loss of PAN
fiber. It is commonly believed that a cross-linked polymer
would naturally be more thermally stable than the
corresponding thermoplastic polymer. It is believed that
molecular crosslink in the PAN polymer could crystallize
the PAN structure. Zhu and coworkers discovered that
PAN in a crystal structure would decelerate the weight
loss in order to produce high carbon yield [14].

Upon heat treatment of the activated carbon fibers Fig 3 Elemental Percentage of various elements of PAN/ AM fibers
(ACFs), the reaction between carbon and regenerated gas
caused the weight loss of the fiber, and the corresponding
carbon yield at activation times from 30 to 60 minutes
was in the range of 88.82 to 91.61%. The carbon content
of ACFs increased with activation time, but the nitrogen
content of ACFs was negatively related to the activation
time. This result demonstrates that nitrogen continues to
be eliminated from the carbonized fibers during
activation, and carbon monoxide is formed by the reaction
of carbon constituent of the carbonized fiber with CO2
and air, reducing the weight of the emerging ACFs. The
formation of new carbon basal planes and the evacuation
of a large amount of nitrogen were continuous during
activation, thus increasing the carbon content.
82

Fig 4 TGA curves of PAN/AM fibers
The cross-section of PAN/AM precursor fibers which
had been fabricated in this study by the solvent-free
coagulation process was observed using SEM, as depicted
in Figure 5(a). Referring to the SEM micrograph, it shows
that the fibers fabricated have a round shape cross section.
Some finger-like micropores are observed from the
PAN/AM, extending from the circumference to the center
of the fiber. These finger-like micropores were formed
during the solvent or nonsolvent exchange that occurred
in the free solvent coagulation bath. However, it was
observed that the cross section of precursor fiber was
much smaller than the original size of spinneret with
reduction of 61.7 %. The jet stretch applied during the
spinning of the precursor fiber contributes to the cross
section reduction of the fiber. The high jet stretch helped
outward diffusion of solvent and aligned the polymer
chains thus prevented more non-solvent to diffuse to the
core of PAN/AM fibers. Besides, the high jet stretch
reduces the probability for appearance of defects in the
PAN/AM fibers structure [15]. The alignment of PAN
polymer chains also helped in removal of the non-solvent
inside the as-spun fiber thus prevented the pores
formation. Hence, figure 5(b) shows the surface area of
precursor PAN/AM fibers with no pores detected on the
surface area of the fiber.
Fig 5 (a) Cross section of PAN/AM precursor fiber
83
Fig 5 (b) Surface area of PAN/AM precursor fiber
Meanwhile, figure 6(a) and 6(b) show the cross-
section and surface area of PAN/AM activated carbon
fiber which had undergone activation process. The first
step during the fiber conversion process is oxidation
stabilization at 275oC. Stabilization is the most essential
process since it allows the subsequent polymer
degradation reactions during carbonization to proceed
without collapse of the fiber or loss of orientation [16].
The heating rate for carbonization process was set at 3
o
C/min with nitrogen flow rate set at 2 L/min until
temperature of 600oC before constant heating for 30
minutes which is also known as soaking time.
The next step after carbonization will be activation of
the fibers in moisturized carbon dioxide which is also
known as physical activation process. During the
activation process, carbon dioxide etched the carbon basal
planes of carbonized fibers, and this reaction promoted
degradation of the structures and formed new flaws.
Therefore, the surface area of fiber increased remarkably
after activation. The loss of volatile components and the
subsequent reorganization of the remaining structures are
widely known to increase surface areas and its porosity.
Thus, from the micrographs depicted in Figure 6 (a) and 6
(b), it reveals that prior to activation; porosity is increased
whilst the cross section is decreased together with the loss
of volatile components.
Fig 6(a) Cross section of PAN/AM activated carbon fiber

Fig 6 (b) Surface area of PAN/AM activated carbon fiber
4. Conclusion
Based on the results of the study, the following
conclusions can be drawn;
PAN-based ACFs were successfully fabricated using
PAN as the polymer with AM as the comonomer via
environmental friendly solvent-free coagulation process.
The presence of AM comonomer in the PAN fibers
enables the production of carbon fiber precursor with
good thermal properties. The fibers fabricated from a
dope containing 18 wt% PAN and 5 wt % AM exhibited
superior exothermic trend process.
The carbon content of ACFs increased with
activation time, but the nitrogen content of ACFs was
negatively related to the activation time.
The activation steps increases the porosity of
PAN/AM fibers and its cross section is decreased together
with the loss of volatile components.
ACKNOWLEDGEMENT
The authors gratefully acknowledge the generous
financial support from Ministry of Higher Education
Malaysia and Universiti Teknologi Malaysia to support
one of the author i.e. Norhaniza Yusof for her Ph.D study.
84
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