Carbon 190 (2022) 92e103

Contents lists available at ScienceDirect

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

Transformation of petroleum asphaltenes to carbon fibers

Shabab Saad a, 1, Ali Shayesteh Zeraati a, 1, Soumyabrata Roy b,
Md Abid Shahriar Rahman Saadi b, Jago
s R. Radovi c c, Ashna Rajeev a, Kristen A. Miller b,
Sohini Bhattacharyya b, Stephen R. Larter c, Giovanniantonio Natale a,
Uttandaraman Sundararaj a, Pulickel M. Ajayan b, *, Muhammad M. Rahman b, *,
Md Golam Kibria a, *
a
Department of Chemical and Petroleum Engineering, University of Calgary, Calgary, AB, T2N 1N4, Canada
b
Department of Materials Science and NanoEngineering, Rice University, Houston, TX, 77005, United States
c
Department of Geoscience, University of Calgary, Calgary, Alberta, TN 1N4, Canada

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

Article history: Petroleum asphaltenes, a by-product of crude oil extraction, are a promising feedstock for the devel-
Received 20 November 2021 opment of high-value carbonaceous materials because of their high carbon content and aromaticity. In
Received in revised form this work, we have studied the efficacy of low-value petroleum asphaltenes as raw materials in pro-
5 January 2022
ducing carbon fibers. We present a facile, yet effective, method to produce carbon fibers without the
Accepted 6 January 2022
need of expensive pre-treatment processing. To do this, extensive physicochemical characterizations
Available online 7 January 2022
were carried out to evaluate asphaltene properties throughout the entire process. Continuous spinning of
green fibers with different diameters (~10e200 mm) was optimized according to the rheological char-
Keywords:
Asphaltenes
acteristics of asphaltenes. We originally developed a multi-step stabilization process to cross-link the
Carbon fibers asphaltene-derived green fibers. This was followed by carbonization of the fibers resulting in fibers with
Oxidative stabilization mechanical strength of ~400 MPa and Young's modulus of ~70 GPa. These are relatively high values
Carbonization obtained without any pretreatment or high temperature carbonization/graphitization. This study pre-
Mechanical properties sents a previously unexplored avenue to develop low-cost carbon fibers from low-value petroleum
asphaltenes.
© 2022 Elsevier Ltd. All rights reserved.

1. Introduction mass fraction of a heavy crude oil or bitumen. Worldwide reserves

Asphaltenes are well-known carbonaceous macromolecules
that reside primarily in crude oil, petroleum residues, and coal
processing [1,2]. Produced during the thermal maturation process
of kerogen in petroleum source rocks, they migrate with crude oils
to reservoirs and after production and processing of crude oil, they
commonly precipitate out [3], poison catalyst surfaces [4], act as
coke precursors in heavy oil processing [4,5] and increase the vis-
cosity of heavy oil [5]. Asphaltenes also cause various production
related issues in certain types of petroleum reservoirs [6,7]. Typi-
cally, they are usually treated as a low-value by-product with no
commercial uses in today's market yet and may represent a large
* Corresponding authors.
E-mail addresses: pma2@rice.edu (P.M. Ajayan), mr64@rice.edu (M.M. Rahman),
md.kibria@ucalgary.ca (M.G. Kibria).
1
These authors contributed equally.
of asphaltenes is currently estimated to be ~1e2 trillion barrels
[8,9]. Disposal of asphaltenes poses detrimental effects on the
environment [3,5] because of their poor biodegradability. Hence,
scalable valorization of this material is key to addressing the
ecological and economic challenges.
Asphaltenes have significant potential as feedstocks for the
synthesis and development of functional carbonaceous materials
and structures because of their high carbon content, aromaticity,
heteroatom content, polar functional groups, and double bond
equivalent (DBE) numbers [5,10]. They can be a cheap feedstock in
producing a wide variety of non-combustible, high-value products
with diverse applications. Over the past few years, asphaltenes
have been employed to fabricate carbon electrodes [5,11] graphene
quantum dots [12,13], porous carbon foam/scaffolds [14], carbon
nanosheets [15,16], and polymer composites [17,18] for applications
ranging from catalysis and energy storage to water treatment and
biological imaging.

https://doi.org/10.1016/j.carbon.2022.01.011
0008-6223/© 2022 Elsevier Ltd. All rights reserved.
S. Saad, A.S. Zeraati, S. Roy et al.
Owing to outstanding mechanical properties (high tensile
strength and modulus along with low density), carbon fibers are
one of the attractive materials [19e21] for various applications
including automotive, aerospace, and construction industries
[22,23]. Currently, commercial-grade carbon fibers are produced
from polyacrylonitrile (PAN) and pitch (isotropic and anisotropic)
precursors with suitable physicochemical properties (e.g., high
thermal stability, DBE, high aromaticity, high softening point, etc.)
[24e26]. However, the production of commercial-grade carbon fi-
bers from these precursors is plagued with high cost of raw ma-
terials and complex processing (~USD 18e35/kg carbon fiber for
PAN, ~USD 15e20/kg carbon fiber for pitch precursors) [8,27].
Additionally, PAN and pitch-based carbon fibers are not affordable
for large scale applications [8,27] and thus fail to cater to the
extensive commercial scope available. Therefore, an inexpensive
precursor from low-value by-products can lead to a paradigm shift
in carbon fiber production technology and its commercial viability
[28e30]. Transforming asphaltenes to carbon fibers can potentially
offer a six-fold increase in value-proposition for a barrel of oil and is
expected to revitalize the incumbent PAN and pitch-based fiber
industry [8]. Utilization of inexpensive feedstock like petroleum
asphaltenes in carbon fiber manufacturing could cut down pre-
cursor cost by ~90% and reduce the production cost from ~USD
18e35/kg (PAN-based carbon fibers) to < USD 9/kg eventually [8].
As a result, we anticipate valorization and diverse applications of
asphaltene-derived carbon fibers.
So far, only coal-based asphaltenes or isotropic/petroleum
pitches with low asphaltene content have been used to produce
carbon fibers [28e30]. To the best of our knowledge, the efficacy
and potential of petroleum asphaltenes as a raw precursor for
carbon fiber processing is yet to be reported. Developing pathways
through which petroleum asphaltenes can be directly transformed
to carbon fibers without any energy intensive steps (e.g., pre-
processing or pre-treatments) are appealing. In this study, we
employed petroleum asphaltenes as inexpensive feedstocks for
carbon fiber development in the absence of any conventional pre-
processing techniques. Asphaltene properties were systematically
evaluated by extensive physicochemical characterizations (e.g.,
assessment of chemical structure, aromaticity, shear viscosity,
softening point, thermal stability, etc.) and tailored towards the
formation of carbon fibers. We proposed a multi-step stabilization
approach that can effectively stabilize petroleum based asphaltene-
derived green fibers. A detailed discussion on how this multi-step
stabilization approach affect the morphologies/structures of
asphaltene-derived carbon fibers is also provided. We envisage that
this work will foster attention towards developing inexpensive
processing routes to produce carbon fibers valorizing underutilized
low-value resources (e.g., petroleum asphaltenes), and thereby
create considerable technoeconomic dividends for the booming
carbon fiber industry.
2. Experimental section
2.1. Materials
Toluene (99.5%), n-Pentane (99%), Methanol (99.8%), and
ammonium hydroxide (NH4OH) were purchased from Sigma-
Aldrich and were used as received. Two batches of asphaltene
samples (Alberta oil sands asphaltenes) were received from Inno-
Tech Alberta. The batches are labeled as RP (raw powder with
higher asphaltene content of ~76%) and gel (with lower asphaltene
content of ~22%) asphaltenes. More information can be found in
Tables S1 and S2.
93
Carbon 190 (2022) 92e103
2.2. Solvent extraction
The gel sample (as received) has a low concentration of pentane
insoluble asphaltenes. To increase the asphaltene content without
performing any chemical modifications, solvent extraction was
employed [53,54]. The gel sample was mixed with n-pentane (1:40
v/v) in a beaker and continuously stirred using a magnetic stir bar
at room temperature for 12 h. After completely dispersing the raw
asphaltene material in the alkane solvent phase, the remaining
insoluble asphaltenes were separated through vacuum filtration
using a 0.22 mm filter paper. The obtained asphaltenes from the gel
sample (which was named SEG) were collected from the filter pa-
per and dried at room temperature for 24 h. The process yield is
about ~98% (pentane washed asphaltenes) which is calculated with
respect to the initial and final mass and with minor losses during
collection. It is worth mentioning that the gel sample was used in
this study as a precursor for carbon fiber production alongside the
powder sample to demonstrate the value of gel asphaltenes with an
additional solvent extraction step. Since gel type asphaltenes are
produced in large quantities like powder asphaltenes in the oil
sands industry, it is important to highlight the efficacy of gel
samples in producing high value carbon fibers.
2.3. Fiber preparation
The RP and SEG asphaltene samples were melt-spun using a
conventional melt spinning apparatus through a single-hole spin-
neret (diameter ¼ 150 mm, L/D ¼ 5). Different winding rates were
used to produce green fibers with different diameters. During this
process, the samples were extruded at a temperature 40e50  C
above the sample softening points under a shear rate of 0.1e10 s1.
The extrusion temperatures were 230  C and 240  C for RP and SEG
samples, respectively. After preparing green fibers, they were sta-
bilized in the air following a multi-step stabilization route (Fig. S5).
They were first heated from ambient temperature to 260  C with a
slow heating rate of 1  C/min. Then the fibers were soaked at 260  C
for 4 h. Next, the temperature was ramped up from 260  C to 350  C
at a heating rate of 5  C/min. The fibers were then soaked at 350  C
for 2 h before cooling down to room temperature. The stabilized
fibers were then carbonized at two different temperatures: 500  C
(30 min) and 800  C (30 min) under N2 at a heating rate of 5  C/min.
2.4. Characterization
2.4.1. Rheological measurements
The rheological behavior of the RP, SEG, and gel asphaltenes was
studied using Anton Paar MultiDrive MCR 702 Rheometer at
different temperatures under N2. The analyses were performed
with 25 mm diameter parallel plates and a gap size of 1.0 mm under
nitrogen atmosphere to prevent any reaction/degradation. To reach
a stable temperature, a rest time of 10e15 mins in the rheometer
was used after loading the sample. It is worth mentioning that we
also used the rheological results to estimate the softening points.
The lowest temperature (~180  C) at which the precursor material
exhibits fluidic behavior (viscosity ~110-120 Pa-s at shear rate of ~1
s1) was estimated as the softening point. In all cases, the samples
were loaded first and then heated under nitrogen until the soft-
ening point followed by trimming and running the experiments at
different temperatures.
2.4.2. Softening point measurements
The softening point of gel asphaltenes was determined using a
standard ball and ring apparatus (ASTM D36) raw bar [55,56]. The
standard ball and ring apparatus consist of two horizontal holders
containing the gel sample (each supporting a steel ball) immersed
S. Saad, A.S. Zeraati, S. Roy et al.
in a water bath. Then the water bath containing these two holders
was heated at a controlled rate using a temperature regulator. The
softening point was measured as the mean of the temperatures at
which the sample in these two holders softened enough to allow
each ball (covered in asphaltenes) to drop and fall a distance of
25 mm within the water. For RP and SEG samples with softening
points higher than 100  C, shear viscosities measured through
rheological characterizations were used to estimate the softening
points.
2.4.3. Fourier Transform infrared spectroscopy (FTIR)
The chemical structure of the RP, SEG, green, and stabilized fi-
bers was studied with a Frontier™ Fourier Transform IR spec-
trometer in the range of 400e4000 cm1 at room temperature.
2.4.4. Thermogravimetric analysis (TGA)
Thermal stabilities of RP, gel, SEG asphaltenes as well as green
and stabilized fibers were investigated using TA Instruments Q50
Thermogravimetric analysis (TGA) Analyzer in the range of
20e800  C with a heating rate of 10  C/min under nitrogen. This
characterization was helpful to identify if the asphaltenes and
green/stabilized fibers were thermally stable enough to undergo
extrusion, stabilization, and carbonization steps at different tem-
peratures above 200  C. We also performed more analyses in air to
have more insights into the oxygen uptake with a heating rate of
0.5  C/min.
2.4.5. Microscopy
The mesophase content in RP, gel, and SEG asphaltenes was
quantified with cross-polarized light microscopy (Olympus BX-
51P). Thin films of different asphaltene samples were prepared in
coverslip chambers by heating in an inert environment at high
temperatures of ~350  C for 2 h. Cross-polarized images were
captured from multiple areas and an average was reported for the
mesophase content. Image analysis was performed using ImageJ
and the mesophase content was calculated according to ASTM
D4616-95 [43,45,57]. The percentage of mesophase in the asphal-
tene samples was determined by manual counting (diameter
>4 mm considered) in volume percentage by taking ten observa-
tions of each sample in different directions before averaging them
out. According to the standard test method (ASTM D4616-95), the
following equation can be used to determine mesophase content by
microscopy analysis [43,45,57]:
mesophase counts
% mesophase content ¼  100 (1)
1000 ðtotal countsÞ
Bright-field optical microscopy was also performed on green
fibers using the ECHO Revolve R4 inverted microscope to study
their respective diameters.
2.4.6. Fourier Transform ion cyclotron resonance mass spectroscopy
(FT-ICR MS)
All asphaltene samples (RP, gel, SEG) were analyzed using a 12T
Bruker SolariX by ultrahigh-resolution Fourier transform ion
cyclotron resonance mass spectrometry (FT-ICR MS) coupled with
atmospheric pressure photoionization in positive-ion mode (APPI-
P) as per previously published methods [58], in order to measure
the relative abundance of different compound classes, and other
relevant molecular parameters that can be derived from FT-ICR MS
data, e.g. average molecular weights, DBE (double bond equivalent)
and carbon number distribution. Briefly, an aliquot of the sample
stock solutions was diluted to 0.25 mg/mL in toluene and then
infused into the ionization source using a syringe pump set to
deliver 200 mL/h. A krypton lamp at 10.6 eV was used as the ion
94
Carbon 190 (2022) 92e103
source. The transfer capillary temperature and nebulizer pressure
were set to 400  C and 0.5 bar, respectively. The instrument was
calibrated beforehand using a known reference sample. FT-ICR MS
raw data were processed using the CaPA (Aphorist, Inc.) software
package. Compositional boundaries, in terms of element atom
content abundances for the fitting algorithm, were set to C4e95
H0e200 N0e4 S0e4 O0e15 and double bond equivalent (DBE) ranges
for detected species were set between 0 and 50. DBE is a measure of
hydrogen deficiency in a molecular formula, as a result of double
bonds and/or cyclic structures in the molecule. To manipulate and
visualize the several layers of compositional data generated in each
FT-ICR MS analysis, the Ragnaro €k (Aphorist, Inc.) software was
employed.
2.4.7. X-ray photoelectron spectroscopy (XPS)
The surface elemental compositions and chemical states of the
asphaltene components were analyzed by X-ray photoelectron
spectroscopy (PHI Quantera II with monochromated Al Ka at 1486.6
and 26 eV pass energy, 50 W, 15 kV, and 200 mm diameter X-rays
were shot on the sample). The XPS survey scan spectra in the
1100e0 eV binding energy range were recorded in 0.5 eV steps with
a pass energy of 140 eV. High-resolution spectra were recorded in
0.1 eV steps with a pass energy of 26 eV.
2.4.8. Solid state Nuclear Magnetic Resonance (ssNMR)
Solid state 13C MAS NMR (ssNMR) spectra were obtained on a
Bruker Advance III, two channel spectrometers with a 4.7 T magnet
(50.3 MHz 13C). Samples were spun in a 4 mm outer diameter zir-
conia rotor barrel with a Kel-F [poly (chlorotrifluoroethylene)] rotor
cap. Direct 13C pulse MAS spectra were acquired using standard
Bruker pulse programs modified to incorporate a fixed waiting
period before each experiment in a series of repetitive experiments
(i.e., with different relaxation delays: 10 s, 30 s, 90 s, 180 s). Direct
13
C pulse spectra were obtained with 12 kHz MAS and a spectral
width of 50000 Hz (994 ppm), which results in any spinning
sidebands at multiples of ±238 ppm from a center band. Experi-
ments used a 2.5 ms, 90 13C pulse, and a short Hahn echo33 (total
duration ¼ 8ms) immediately preceded FID acquisition. Using the
integrated intensities of the aromatic and aliphatic domains, the
aromaticity factor (fa ) of AOAs can be calculated by the following
equation [22,29,32,36,59]:
CAr
fa ¼ (2)
CAr þ CAl
where, CAr and CAl represent the aromatic and aliphatic fractions of
asphaltenes, respectively.
2.4.9. Scanning electron microscopy (SEM)
Surface morphology, size and cross-sections of extruded, stabi-
lized, and carbonized fibers were studied by a field emission SEM
(FEI Quanta 250 FEG) equipped with a Bruker QUANTAX energy-
dispersive X-ray spectroscopy (EDS) system, which was used for
EDS mapping.
2.4.10. Mechanical testing
For tensile testing experiments, an ARES G2 Rheometer was
used. The fibers were first glued at both ends to laser cut paper
strips with a rectangular cut in the center of length 20 mm before
mounting them in the tensile tester. Once each end of the fiber is
fastened to the grips, the small paper strips on both sides of the
fiber were cut before running the experiment. The diameter of the
fractured fiber was determined by SEM to calculate the cross-
sectional area of the fractured surface allowing conversion from
measured force to calculated stress values.
S. Saad, A.S. Zeraati, S. Roy et al.
3. Results and discussion
3.1. Structural and physicochemical properties of asphaltenes
In this work, we investigated the transformation of two distinct
forms of petroleum asphaltenes (i.e., powder and gel-like). It is
important to analyze factors such as softening point, carbon con-
tent, molecular weight (MW) distribution, aromaticity, shear vis-
cosity and thermal stability of asphaltenes prior to melt extrusion.
Hence, softening point was measured to identify the minimum
temperature at which the asphaltenes start exhibiting fluidic
behavior under shear. This behavior is extremely important to
design the melt extrusion of asphaltenes to produce continuous
uniform green fibers. The gel-like sample had a low softening point
of about 40  C (Tables S1 and S2) due to low asphaltene content
(~22% pentane insoluble asphaltenes), whereas the raw powder
(RP) sample (~76% pentane insoluble asphaltenes) had a softening
point of about 180  C. The very low softening point of the pristine
gel-like sample suggests that this category of asphaltene is not
suitable for industrial fiber processing. Therefore, we performed
solvent extraction process for the gel-like sample, hereafter
referred to as solvent extracted gel (SEG) (Table 1). Through solvent
extraction the softening point of SEG increased to ~180  C (four
times of the pristine gel sample).
We assessed carbon content, aromatic hydrocarbons, molecular
weight distribution, and flow behavior of these two samples (i.e.,
RP and SEG) for carbon fiber processing. We first performed solid
state Nuclear Magnetic Resonance (ssNMR) studies to identify the
aromatic and aliphatic fractions of the asphaltene samples. Fig. 1a
shows the solid state 13C NMR (13C ssNMR) spectra for RP and SEG
asphaltenes. Typically, 13C ssNMR is known to provide a wider
chemical shift dispersion than 1H NMR and helps with the accurate
identification of various functional moieties of asphaltenes [31,32].
As can be seen, both RP and SEG samples contain significant
aliphatic and aromatic domains. The extreme heterogeneity of
asphaltenes results in overlapping signals from various compo-
nents and few, if any, signals demonstrate characteristics for of a
specific structural environment. Straight chain alkyl groups and
alkyl groups with methyl branches appear as relatively minor
components yet such species are known from pyrolysis and other
studies to be common components of many petroleum asphaltenes
[7]. Their distinctive signals [33] are however not readily evident
above the broad aliphatic band dominated by alicyclic CH2 groups
in naphthenic fragments in both RP and SEG samples [32,34,35]. A
significant part of the broad aromatic band can have overlapping
contributions from CH and quaternary carbons. Thus signals from
different types of quaternary aromatic carbons (interior bridgehead
carbons of condensed aromatic ring systems, bridgehead carbons
on the periphery of the ring system, and alkyl-substituted aromatic
carbons) are found in different chemical shift ranges [33].
Table 1
Summary of different physicochemical properties (carbon content, double bond
equivalent, aromaticity, elemental ratios, and average molecular weight) of
asphaltenes derived from FT-ICR MS characterization (for comparison all parameters
were weighted based on the total ion intensity of the sample).
Parameters RP asphaltenes SEG asphaltenes
Carbon Number 27.88 34.10
DBE 11.08 14.20
Aromaticity Index 0.40 0.41
O/C 0.010 0.006
H/C 1.256 1.218
N/C 0.002 0.005
S/C 0.024 0.027
Average MW (Da) 396.37 484.72
95
Carbon 190 (2022) 92e103
Heteroatoms such as oxygen and nitrogen result in significantly
shielded signals for the adjacent aromatic carbons. The “fjord”
carbons in the polyaromatic hydrocarbon (PAH) structures
[29,32,34] could potentially decrease the molecular stability of
asphaltenes due to steric hindrance between hydrogen atoms in
these regions. This steric hindrance might explain the lower soft-
ening points of ~180  C in both RP and SEG asphaltenes compared
to coal based asphaltenes [22,24,29].
We used different relaxation delay times (e.g., 10 s, 30 s, 90 s,
180 s, etc.) in 13C NMR studies to validate complete relaxation of
both aromatic and aliphatic domains in RP and SEG samples
(Fig. S1). We observed that the relaxation of the aliphatic carbons is
essentially complete with a 10-s relaxation delay, whereas the ar-
omatic carbons relax much more slowly, requiring about a 90-s
relaxation delay. Interestingly, both RP (~41%) and SEG (~40%)
asphaltenes have similar aromaticity factors after 90-s relaxation
delay. This is further reflected in their close softening points
(~180  C for both RP and SEG) as mentioned previously.
The carbon content and chemical structure of different asphal-
tenes were studied using X-ray Photoelectron Spectroscopy (XPS).
The elemental analysis (Fig. 1b) shows that both RP (~93% carbon)
and SEG (~94% carbon) samples are rich in carbon content with a
low oxygen (~3.7% and ~2.3% oxygen for RP and SEG, respectively)
and sulfur content (~3.3% and ~3.7% sulfur for RP and SEG,
respectively). Generally, a high level of adventitious carbon in both
these asphaltene samples (RP and SEG) make them promising
candidates for carbon fiber production. More information about the
chemical structure (elemental survey and high resolution XPS
spectra) of different asphaltene samples can be found in Figs. S2eS4
and Tables S3eS5.
Fourier transform ion cyclotron resonance mass spectroscopy
(FT-ICR MS) was performed on RP and SEG asphaltenes to further
study their aromaticity, MW distribution, DBE, and heteroatom
content. Fig. 1c illustrates FT-ICR MS mass spectra for different
asphaltenes where they show a similar MW distribution, with RP
sample having a mass distribution slightly skewed towards the
lower MW range. RP asphaltenes have a lower DBE number but a
similar aromaticity index compared to SEG sample. This suggests a
slightly higher concentration of highly condensed aromatic struc-
tures in the SEG sample (Table 1 and Fig. 1d) than RP, which is
apparent from its higher average MW (484.72 Da for SEG, 396.37 Da
for RP) as well. Moreover, from the DBE distribution profile of hy-
drocarbon radicals observed (Fig. S5) it is clear that, SEG asphal-
tenes have a wider DBE distribution than RP asphaltenes.
In contrast, the compound class distributions of the samples
(Fig. S5e) obtained from analysis of FT-ICR MS data, suggest that the
RP sample has significantly higher overall oxygen content with
slightly lower overall sulfur content relative to SEG sample (Table 1
and Fig. 1d). More diverse oxygen speciation and likely higher ox-
ygen content in RP asphaltenes is apparent through the presence of
oxygen and multiple oxygen radicals (e.g., O, O$, O2, O2$, OS$, etc.)
seen in the FT-ICR MS compound class distributions (Figs. S5c and
e). The presence of more diverse oxygen speciation could help in
the formation of oxygen mediated cross-linked structures within
asphaltenes for subsequent stabilization steps. Unlike the RP sam-
ple, the SEG sample contained fewer oxygen-containing species,
but contained a wider DBE distribution of oxygen radicals. In all
cases, wider DBE distribution profiles of SEG asphaltenes
(Figs. S5aed) explain how the SEG sample had a slightly higher
average MW relative to the RP sample. This phenomenon can also
be related to the complex molecular structure of SEG and its spe-
cific rheological behavior.
The rheological behavior of asphaltenes were thoroughly stud-
ied to gain insights into their flow properties (e.g., viscosity at
different temperatures and shear rates) for potential application in
S. Saad, A.S. Zeraati, S. Roy et al. Carbon 190 (2022) 92e103

Fig. 1. (a) 13C ssNMR spectrum of RP and SEG asphaltenes representing the aliphatic (up field band) and aromatic peaks (downfield band). Both asphaltene samples have an
aromaticity of about 40%; (b) Carbon (C1s), oxygen (O1s), and sulfur (S2p) atomic contents (elemental %) in RP and SEG asphaltene samples obtained from XPS analysis; (c) MW
distribution profiles; and (d) Radar plot of RP and SEG asphaltenes showing normalized intensities of average MW, aromaticity index, carbon number, DBE, and heteroatom ratios
obtained from FT-ICR MS characterization. The results were obtained from atmospheric pressure photoionization in positive-ion mode, APPI (þ). (A colour version of this figure can
be viewed online.)

carbon fiber production. From literature, the suitable viscosity insights about this, we plotted the viscosities at constant shear
range to maintain an ideal flow for smooth and continuous extru- rates (e.g., g_ ¼ 1 s1, g_ ¼ 10 s1, g_ ¼ 20 s1) as a function of tem-
sion of fibers is found to be in the range of ~1e20 Pa-s under low perature (Fig. 2c and d). Fitting the experimental data through close
(~1 Pa-s) to high (~100 Pa-s) shear [22,23,36] along with some exponential fits, the slope of the line can be calculated using an
shear-thinning behavior at both these low and high shear rate re- Arrhenius equation [22,37e39]:
gions. Fig. 2a and b demonstrate the viscosity of RP and SEG sam-
ples as a function of shear rate at different temperatures. Both RP
and SEG asphaltenes display slight shear thinning at low shear rates h ¼ 3m0 eEa =RT (3)
ðg_ < 100 s1 Þ until temperatures of ~240  C. At higher shear rates
where m0 is a constant, Ea is the flow activation energy (energy for
ðg_ > 100 s1 Þ, both RP and SEG samples show shear thinning
segmental movement), R is the gas constant and T is the temper-
behavior at some temperatures (e.g., 180  C and 210  C). For both
ature. From the Arrhenius equation, the fraction Ea =R represents
the samples, as we increase temperature from 180  C to 270  C, the
the slope for each of the lines at specific shear rates. The slope
average viscosity decreases by almost an order of magnitude at
describes the “flow activation energy”, of the samples at specific
every 30  C interval under low shear rates. This trend in viscosity
temperatures and is directly proportional to the stress generated
reduction can be attributed to the softening point of the samples. To
during extrusion. The viscosity dependence on temperature in-
clarify this further, we conducted rheological experiments below
creases by increasing the shear rate (with increasing slopes) for
180  C, where asphaltenes exhibited solid like behavior. Thus, no
both samples. This implies that spinning RP and SEG asphaltenes at
shear could be applied till the temperature reached 180  C where
high shear rates (e.g., g_ ¼ 20 s1) would generate higher stress
the asphaltenes started exhibiting fluid-like behavior. In this way,
causing the extruded jet of material to degenerate into drops,
through rheological analysis, we confirmed that the softening
eventually breaking the filament [22,37e39]. In addition to that,
points for both RP and SEG asphaltenes are close to~180  C. As a
higher stress correlates to the need for higher flow activation en-
result, we were able to identify a suitable temperature range (yel-
ergy (Ea).
low box in Fig. 2a and b) where both asphaltene samples exhibited
Table 2 shows the Ea changes in both RP and SEG samples under
appropriate viscosities (~1-20 Pa-s) for extrusion above the soft-
different shear rates. The Ea for SEG is higher than RP at any chosen
ening temperature. Temperatures between 240  C and 270  C
shear rate resulting from its close dependence on the irregularity of
satisfied the viscosity conditions for both the samples and showed
the hydrocarbon chains [37e39]. FT-ICR MS and 13C ssNMR char-
promise for smooth and continuous extrusion within a shear rate of
acterizations demonstrated that the RP sample has similar average
~1e10 s1. This observation aligns well with the ideal temperature
aromaticity in comparison to SEG with a similar MW distribution
for melt spinning (yellow boxes in Fig. 2a and b) according to
profile. However, SEG asphaltenes (~484.72 Da) have a slightly
literature. This is usually ~50e90  C higher than the respective
higher average MW relative to RP asphaltenes (~396.37 Da), which
softening points of the precursors [22,23,36].
suggests the presence of higher MW compounds within the SEG
Another factor that can disrupt the continuous extrusion of
hydrocarbon chains (Table 1). A higher maximum intensity of SEG
asphaltenes is the temperature dependent viscosity. To have more
asphaltenes in the hydrocarbon DBE distribution profile (HC$ class)
96
S. Saad, A.S. Zeraati, S. Roy et al. Carbon 190 (2022) 92e103

Fig. 2. Rheological measurements showing viscosities of (a) RP and (b) SEG asphaltenes as a function of shear rate at different temperatures. Yellow boxes show suitable viscosity
ranges for extrusion; Dependence of shear viscosity as a function of temperature for (c) RP and (d) SEG asphaltenes; the dotted red, blue, and black lines show the closest fitting of
experimental data with the theoretical model; (e) Thermogravimetric analysis (TGA) profile and (f) Differential thermogravimetry (DTG) profile of RP and SEG asphaltenes under N2
flow from 25  C to 800  C with a heating rate of 10  C/min. (A colour version of this figure can be viewed online.)

Table 2
Flow activation energy (Ea) of RP and SEG asphaltenes as a function of shear rate.
Shear Rate (1/s) Ea (kcal/mole)
RP
1 ~17.7
10 ~19.6
20 ~20.9
in Fig. S5a also implies that SEG could contain more heterocyclic
groups (e.g., phenols, ethers, etc.) than RP. Large cyclic groups in the
SEG structure would increase the flow activation energy due to
higher steric rotation effects. Thus, more energy is required for
segmental motion in case of SEG and makes melt extrusion more
challenging.
The Ea values for RP asphaltenes (average ~19.4 kcal/mol for
asphaltenes, ~18 kcal/mol for linear polystyrene) are similar to
linear polystyrenes [37,39], suggesting a high linearity to the
average asphaltenes’ structures. Alternatively, the higher Ea values
(average ~26.4 kcal/mol) for SEG asphaltenes indicate less linearity
and probable structural similarities to branched polystyrene (or of
various blends) containing large phenol or functional groups (thus
more irregularity because of heavily extended functional groups)
[37,39]. Higher concentration of linear chains within the RP
asphaltenes (as indicated by lower Ea values) is expected to facili-
tate its smooth extrusion.
Thermal stability is another important factor to understand the
extrudability and stability of asphaltene-derived green fibers.
Typically, both extrusion and stabilization are carried out above the
softening point (up to ~100  C above softening point) which ne-
cessitates the asphaltenes to exhibit high thermal resilience. The
TGA and DTG profiles of different asphaltenes used in this study are
shown in Fig. 2e and f (Fig. S6 for gel sample), respectively. The RP
sample retains most of its weight (>90%) up to 400  C. Interestingly,
the SEG sample has a similar thermal stability to that of the RP
SEG
sample (no clear peaks in DTG profile below 400  C) in agreement
~22.8
with the close softening point and aromaticity of these samples.
~27.4
~29.0 Asphaltenes generally contain highly ordered aromatic sheets and
high MW components and can easily increase the degree of
aromaticity and softening points of a carbonaceous sample
[10,40,41]. The removal of functional groups and thermal degra-
dation of low MW components led to dramatic weight loss at
temperatures above ~400  C for both RP and SEG asphaltenes. The
TGA results suggest that RP and SEG are suitable precursors for both
melt extrusion and stabilization as only ~10% weight is lost at
temperatures around 400  C.
3.2. Melt-spinning of green fibers from asphaltenes
Based on the TGA and bulk rheology studies, an extrusion
temperature of 240  C (since 240  C showed appropriate viscosity
for continuous melt spinning) was selected for both RP and SEG
asphaltenes for the melt-spinning process. Fig. 3aee illustrates
optical microscopy and SEM images of green fibers prepared from
RP asphaltenes. We could continuously spin RP and SEG samples
with different diameters (~10e200 mm), which can be controlled
with the winding rate (~236 m/min resulting in thinner fibers).
Green fibers as thin as ~10 mm were produced and stored carefully
for stabilization and carbonization steps.
Generally, precursor materials (e.g., asphaltenes, pitch, etc.) for
carbon fiber processing can generate mesophase under applied
shear. Thus, mesophase content is widely studied as a means to
control the final mechanical properties of petroleum and pitch-
97
S. Saad, A.S. Zeraati, S. Roy et al. Carbon 190 (2022) 92e103

Fig. 3. (aec) Bright field optical microscopy images of green fibers extruded at 240  C from RP asphaltenes with different diameters. The fibers were spun continuously at 240  C
with different winding rates resulting in different fiber diameters; (dee) Scanning electron microscopy (SEM) images of green fibers extruded from RP asphaltenes. Figure (e) shows
the cross-section of an extruded fiber; (feg) Cross-polarized microscopy images of (f) RP and (g) SEG asphaltenes after extrusion demonstrating mesophase content. (A colour
version of this figure can be viewed online.)

based carbon fibers [22,42e44]. Normally, higher mesophase con-
tent results in higher mechanical properties. Cross-polarized mi-
croscopy was employed to measure and compare the mesophase
content of RP and SEG asphaltenes before and after melt extrusion.
Mesophase spheres can be detected in both RP and SEG samples
(Fig. 3f and g) after extrusion. These mesophase spheres are
immiscible within the surrounding isotropic material and can be
clearly observed with cross-polarized microscopy [43e45]. After
spinning the asphaltene samples at 240  C under shear (g_ ~1-10
s1), the average mesophase content in RP and SEG samples was
calculated to be ~28% and ~14%, respectively. Interestingly, the
overall mesophase content in the SEG sample has increased by ~9%
in comparison to its control gel sample (Fig. S7) after solvent
extraction. Such an increase in mesophase content arises from the
higher concentration of asphaltenes in the SEG sample.
3.3. Stabilization and carbonization of green fibers
Stabilization is the first step of thermal treatment after spinning
98
of green fibers in a typical carbon fiber processing. This is usually
done while maintaining the fibers under airflow, typically at a
single temperature, to cross-link the structure and stabilize them
for subsequent carbonization or graphitization steps [28,42].
However, in our study, single-step oxidation did not yield proper
stabilization of the RP and SEG derived green fibers (Fig. S8). The
single-step stabilization at 270  C for 1 h at a heating rate of 1  C/
min under air, failed to develop strongly oxidized functionalities
(e.g., ethers, carboxylic acids, ketones, etc.) within the RP and SEG
green fibers (Fig. S10). In some cases, single-step stabilization only
leads to the formation of some ether stretches in the stabilized fi-
bers but was very inconsistent in terms of ketones or carboxylic
acid group formations. This confirms the ineffectiveness of single-
step stabilization that can be accredited to the extreme heteroge-
neous structure of petroleum asphaltenes.
To overcome the challenge, we developed a multi-step (2-step)
oxidative stabilization technique (260  C and 350  C) to stabilize
thin green fibers (~10e60 mm) produced from RP and SEG asphal-
tenes. In thicker fibers (~60e200 mm), oxygen does not completely
S. Saad, A.S. Zeraati, S. Roy et al. Carbon 190 (2022) 92e103

diffuse from the fiber surface to the core, eventually resulting in
hollow fibers following carbonization (Supplementary Informa-
tion). Therefore, we explicitly worked with thin green fibers to
achieve effective stabilization and carbonization. During stabiliza-
tion, low energy cross-linked structures are first formed at lower
temperatures that improve the thermal stability of fibers to tolerate
subsequent higher stabilization temperatures (Fig. S9). To confirm
the extent of cross-linking and formation of oxidized structures, we
compared the FTIR spectra of green and stabilized fibers from both
RP (Fig. 4a) and SEG (Fig. S11). Formation of peaks corresponding to
ethers (~1100-1300 cm1), ketones (~1700 cm1) and carboxylic
acid (~1770 cm1) functional groups in both RP and SEG stabilized
fibers confirms the effectiveness of this multi-step stabilization
approach [29,46,47]. In the multi-step stabilization profile, low
temperatures help in the oxidation of compounds having a high
affinity towards oxygen (e.g., CH3 radicals) whereas high temper-
atures aid in the formation of oxidized functional groups and
subsequently oxidized cross-links in compact rings or condensed
structures (e.g., cyclic rings or aromatic sheets). Furthermore, FTIR
spectra of RP green fibers (Fig. 4a) portray some peaks at higher
wavenumbers (~3400-3600 cm1) that were possibly related to the
presence of some freely available eOH groups [26,29,41,46e48].
Interestingly, those were later absent in the stabilized fibers, which
confirms the consumption of all free eOH groups in the formation
of cross-linked networks within the microstructures of stabilized
fibers.
Multi-step oxidative stabilization is further verified by SEM and
TGA analyses. SEM imaging at the cross-section of a stabilized fiber
combined with the EDS mapping confirms the presence of oxygen
and its diffusion in a radial direction towards the core of the fiber
(Fig. 4b). DTG analysis was performed on green fibers in air at a very
slow heating rate of 0.5  C/min to imitate the oxygen uptake in the
asphaltene-derived green fibers. The results demonstrate up to
~3e5% increment in fiber mass within different temperature ranges
(e.g., ~100  Ce180  C, ~240  Ce300  C for RP in Fig. 4c; Fig. S11 for
SEG fibers at the temperature of ~100  Ce170  C, ~230  Ce270  C).
This increase in the mass of green fibers (due to oxygen uptake) at a
range of temperatures suggests the importance of stabilization at
multiple temperatures to cross-link the extremely heterogeneous
structure of petroleum asphaltenes.
Fig. 4dee illustrate SEM and optical images of the stabilized fi-
bers in which they retained their shape and contained solid cores.
Apart from improved functionalities within the microstructure, fi-
bers from both RP and SEG samples were mechanically stable and
flexible after oxidative stabilization. The green fibers, which were
fragile after extrusion, were bendable after stabilization and could
be twisted in any form or shape. This mechanical behavior can be
attributed to the presence of strong cross-linked structures within
the stabilized fibers. Along with FTIR, microscopy and DTG/TGA
results, XPS analysis also confirmed significant oxidation of the

Fig. 4. (a) Fourier-transform infrared (FTIR) spectra demonstrating chemical cross-linking and oxidized functional groups after multi-step stabilization in fibers prepared from RP
asphaltenes; (b) Cross-section and the corresponding EDS mapping of a stabilized fiber after multi-step stabilization which shows the diffusion of oxygen in a radial direction from
the surface toward to the core (arrows); (c) Differential thermogravimetry (DTG) and TGA profiles of RP green fibers in the air from 100  C to 300  C at a slow heating rate of 0.5  C/
min to determine O2 uptake at different temperatures; arrows and highlighted regions show mass increases at different temperature; (d) SEM image of the cross-section of fiber
after multi-step stabilization; (e) Photographs of fibers before and after the multi-step stabilization showing improved flexibility as the stabilized fiber can be twisted without
breaking. The green fibers have a brittle nature. (A colour version of this figure can be viewed online.)

99
S. Saad, A.S. Zeraati, S. Roy et al.
Fig. 5. (aeb) Carbon (C1s), oxygen (O1s) and sulfur (S2p) atomic contents in green (GF) and stabilized fibers (ST) extruded from RP and SEG asphaltenes, respectively; (ced) High-
resolution C1s spectra of green and stabilized fibers extruded from RP and SEG asphaltenes, respectively. XPS analysis demonstrates the increment in oxygen content and oxygen
functional groups contents after multi-step stabilization which shows a successful stabilization. (A colour version of this figure can be viewed online.)
stabilized fibers (Fig. 5, more details on Figs. S12eS13 and
Tables S6eS7). The overall oxygen content after multi-step stabi-
lization in RP and SEG stabilized fibers increased to ~22 at% and
~18 at%, respectively. This is further corroborated by an increase in
the amount of oxygen functional groups (Fig. 5ced) which confirms
the efficacy of the proposed multi-step stabilization approach for
asphaltene-derived green fibers. It is worth mentioning that no
defects or abrasions were noticed on the surface of the stabilized
fibers via SEM analysis.
After successful stabilization, the RP and SEG stabilized fibers
were carbonized by a two-step approach (30 mins at 500  C fol-
lowed by 30 mins at 800  C) under nitrogen with a heating rate of
5  C/min. Typically, carbonization at higher temperature and for
longer time results in higher mechanical properties for mesophase
pitch-based carbon fiber [49,50]. Due to the heterogeneous struc-
ture of the asphaltene precursor, it is difficult to perform a single-
step carbonization at high temperature for long time. Thus, a
lower temperature carbonization (at 500  C) step was designed to
equip the fibers for higher temperature carbonization. High tem-
perature carbonization at 800  C for 30 mins was employed to in-
crease the carbon content and mechanical properties. Both the
carbonization temperatures and dwell times were optimized with
respect to the maximum carbon content achieved in the final car-
bon fibers. Carbon fibers produced (Fig. 6a) from RP asphaltenes
retained structural integrity. A solid cross-section with almost no
defect on the surface of the carbon fiber affirms the efficacy of the
proposed stabilization/carbonization approach. After carboniza-
tion, the fibers demonstrated an average elastic modulus and ten-
sile strength of ~70 GPa and ~400 MPa, respectively. It is worth
mentioning that the results were obtained for carbon fibers that
were prepared without any pre-treatment on the precursor. Pre-
treatment of the precursor towards higher mesophase content
and lower impurities combined with longer carbonization time at
higher temperature would increase the overall mechanical
100
Carbon 190 (2022) 92e103
properties. The mechanical properties of the carbon fibers prepared
in this work are comparable (same order of magnitude) with the
ones derived from heat-treated pitches or asphaltenes [30,51,52].
XPS analysis confirmed the effectiveness of the carbonization
approach where lower concentration of oxygen and defects (func-
tional groups) was observed (Fig. 6ced, more details on
Figs. S14eS15 and Tables S8eS9). The results demonstrate that the
amount of oxygen was significantly reduced (from ~22 at% to ~9.4 at
%) after carbonization. Future studies would focus on how to
improve the mechanical properties by optimizing the physico-
chemical characteristics of asphaltenes such as the mesophase
content and aromaticity. For example, desulfurization combined
with thermal treatment can be carried out to decrease impurities
and improve the mesophase content. Both can assist to improve the
fiber quality and mechanical properties. Additional studies would
include understanding the kinetics of oxygen diffusion through
asphaltene-derived green fiber microstructures andcarbonization
at higher temperature for longer time to further enhance the me-
chanical properties.
4. Conclusions
In conclusion, we explored how high aromaticity combined
with high carbon content in petroleum asphaltenes make them an
excellent candidate as precursors for low-cost carbon fiber pro-
duction. Through extensive physicochemical characterization, we
have demonstrated that our asphaltenes have high carbon content
combined with an appreciable amount of mesophase formation
and an optimal softening point which make them suitable pre-
cursors for spinning into fibers. RP asphaltenes have an aromaticity
of about 40%, a mesophase content of ~28%, and softening point of
~180  C. As such, a continuous extrusion process was designed to
prepare green fibers with diameters of ~10e200 mm from the
asphaltene samples. Then, we developed a multi-step stabilization
S. Saad, A.S. Zeraati, S. Roy et al. Carbon 190 (2022) 92e103

Fig. 6. SEM images of asphaltene-derived carbon fibers (carbonized at 800  C). The solid core of the fiber after the carbonization affirms the efficiency of the proposed multi-step
stabilization and carbonization; (b) Young's modulus and tensile strength of the carbonized fiber derived from RP asphaltenes; (c) elemental composition obtained from XPS
demonstrating lower concentration of oxygen after carbonization; (d) high-resolution C1s of carbonized fibers at 800  C. (A colour version of this figure can be viewed online.)

approach to effectively cross-link the extremely heterogeneous
structure of asphaltene-derived green fibers. A two-step carbon-
ization approach has then been developed to fabricate structurally
stable carbon fibers with an average tensile strength of ~400 MPa
and average elastic modulus of ~70 GPa. The mechanical properties,
obtained in this study after minimal optimization, are expected to
have further improvement upon better control of the process pa-
rameters. Our inexpensive way of producing carbon fibers from low
value asphaltenes opens multiple opportunities for applications in
structural engineering, energy storage, and smart composite
materials.
Bhattacharyya: Writing e review & editing. Stephen R. Larter:
Validation, Resources, Writing e review & editing. Giovannianto-
nio Natale: Validation, Resources, Writing e review & editing.
Uttandaraman Sundararaj: Resources, Writing e review & editing.
Pulickel M. Ajayan: Validation, Resources, Funding acquisition,
Writing e review & editing. Muhammad M. Rahman: Conceptu-
alization, Validation, Supervision, Funding acquisition, Resources,
Project administration, Writing e review & editing. Md Golam
Kibria: Conceptualization, Supervision, Visualization, Formal
analysis, Resources, Funding acquisition, Project administration,
Writing e review & editing.

CRediT authorship contribution statement Declaration of competing interest

Shabab Saad: Conceptualization, Methodology, Validation,
Formal analysis, Investigation, Writing e original draft, Writing e
review & editing. Ali Shayesteh Zeraati: Conceptualization,
Methodology, Formal analysis, Data curation, Writing e review &
editing, Visualization. Soumyabrata Roy: Methodology, Validation,
Formal analysis, Data curation, Visualization, Writing e review &
editing. Md Abid Shahriar Rahman Saadi: Validation, Formal
analysis, Investigation, Writing e review & editing. Jago
s R.
Radovic: Methodology, Validation, Formal analysis, Investigation,
Data curation, Visualization, Writing e review & editing. Ashna
Rajeev: Validation, Investigation, Writing e review & editing.
Kristen A. Miller: Writing e review & editing. Sohini
101
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.
Acknowledgments
The authors would like to thank Alberta Innovates (AI) for the
financial support. The authors also thank Paula Berton, Afrooz
Eshraghian, and Christopher Debuhr for their assistance with TGA,
melt spinning process, and SEM imaging. The authors also
acknowledge Oak Ridge National Lab on helping with the melt
spinning process. The authors would like to acknowledge Dr. Paolo
S. Saad, A.S. Zeraati, S. Roy et al.
Bomben for his advice throughout this project. Bruker are thanked
for continued support of the FT-ICR MS facility at the University of
Calgary and Melisa Brown is thanked for help with FT-ICR MS
analysis. The additional support of the research from the CFREF
funding program managed through the global research initiative
(GRI), at the University of Calgary is acknowledged. Natale ac-
knowledges the support of John R. Evans Leaders- Canada Foun-
dation of Innovation (Fund number-37984).
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.carbon.2022.01.011.
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