Fuel 295 (2021) 120627

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Fuel
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Full Length Article

Preparation of isotropic spinnable pitch with high-spinnability by

co-carbonization of coal tar pitch and bio-asphalt
Xiongchao Lin a, *, Zhe Sheng a, Jin He a, Xin He b, Caihong Wang a, Xiaohu Gu c,
Yonggang Wang a
a
School of Chemical & Environmental Engineering, China University of Mining and Technology (Beijing), D11 Xueyuan Road, Haidian District, Beijing 100083, PR
China
b
Department of Petroleum and Chemical Engineering, University of Wyoming, Laramie, WY 82071, USA
c
State Key Laboratory of Coking Coal Resources Development and Utilization, China Pingmei Shenma Group (Pingdingshan), Pingan Road, Xinhua District, Pingdingshan
467000, PR China

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

Keywords: Co-carbonization of coal tar pitch (CTP) with bio-asphalt (BA) was performed to prepare spinnable pitch with
Isotropic spinnable pitch suitable softening point and excellent spinnability for general purpose carbon fiber. The co-carbonization
Coal tar pitch mechanism and the correlation between spinnability and molecular structure of prepared pitch were clarified.
Co-carbonization
BA produced from the pyrolysis of biomass is abundant of aliphatic units and oxygen-containing groups, leading
Bio-asphalt
Cross-linking
to high reactivity during carbonization. The co-carbonization reactions mainly depend on the mutual cross-
linking among CTP and BA molecules, which are principally triggered by active oxygen-containing groups of
BA. The formed cross-linked macromolecules could further promote the polymerization degree of pitch mole­
cules; thus, the spinnable pitch with suitable softening point could be obtained by simply thermal treatment of
blended pitches at a relatively moderate condition (<350 ◦ C). The properties of the pitch could be optimized by
changing the blending ratio of CTP to BA. Moreover, the prepared carbon fibers demonstrated distinct features,
especially surface profiles. It is expected to provide a new strategy for the preparation of isotropic spinnable pitch
in a relatively simple approach.

1. Introduction
Carbon fiber (CF) has been widely used in the fields of aerospace,
automobile, sports equipment, and other high-value composites [1,2].
Generally, CFs are produced from polyacrylonitrile (PAN), mesophase
pitch (MP), and isotropic pitch (IP) [3]. The PAN-CFs and MP-CFs have
been widely used because of their excellent mechanical properties [4].
However, their more extensive applications have been limited due to the
extremely high cost of raw materials and production procedures [5,6].
Recently, huge demands of CFs with moderate mechanical properties
and low cost were created by the automotive industry [7,8]. To some
extent, IP-CF is considered to be a feasible alternative for PAN-CFs and
MP-CFs in the automotive industry due to its reasonable cost and suit­
able mechanical properties. In the past several decades, numerous re­
searches have been performed to prepare IP-CF precursors from low-cost
raw materials, such as coal tar pitch (CTP), ethylene bottom oil, and
biomass [9–14]. Among those raw materials, coal tar pitch is commonly
used as raw material for IP-CFs due to its characteristics of low price,
high carbon content, and high aromaticity. As for coal tar pitch, there is
a great difficulty in producing a spinnable pitch with suitable softening
point for carbon fibers because of the contradiction between its low
reactivity and the formation of mesophase during high-temperature
treatment. In order to solve the problem, several methods, such as air
blowing [15,16], thermal treatment [17,18], bromination-
dehydrobromination polymerization, and adding chemical additives
[19–21], have been used to modify coal tar pitch. Air blowing and
thermal treatment are the most widely used treatment approaches for
increasing the coking value and softening point of the modified pitch.
However, it consumes large amounts of energies to obtain the spinnable
pitch with suitable softening point by thermal treatment alone due to the
requirement of relatively high temperature. Furthermore, it is difficult
to avoid the generation of mesophase and the deterioration of rheo­
logical behavior induced by excessive dehydrogenation [22]. The air
oxidation method is generally adopted to create the macromolecules by

* Corresponding author: D11 Xueyuan Road, Haidian District, Beijing 100083, PR China.
E-mail address: linxiongchao@163.com (X. Lin).

https://doi.org/10.1016/j.fuel.2021.120627
Received 19 August 2020; Received in revised form 16 February 2021; Accepted 4 March 2021
Available online 17 March 2021
0016-2361/© 2021 Elsevier Ltd. All rights reserved.
X. Lin et al. Fuel 295 (2021) 120627

Table 1
Main characteristics of pitch samples.
Sample Elemental analysis (wt.%) C/H SPa (oC) f ab Mwc Yield/%

C H N S O

CTP 91.42 4.50 1.16 0.85 1.98 1.69 42.7 0.93 410 –
BA 68.44 6.83 1.00 0.58 21.52 0.83 <RT 0.57 1135 –
CBP-0 91.98 4.43 1.08 0.79 1.72 1.73 62.9 – – 89.67
CBP-30 91.13 4.88 0.99 0.40 2.51 1.56 93.7 0.92 670 80.33
CBP-50 89.42 5.19 1.02 0.33 4.13 1.44 133.7 0.84 860 72.58
CBP-70 87.84 5.36 1.06 0.24 5.57 1.36 187.4 0.79 1093 63.91
CBP-100 85.40 5.13 1.24 0.05 8.96 1.39 foaming – – 48.67
CTP-360-6 93.62 4.48 0.99 0.47 0.49 1.74 121.1 0.95 – 75.45
CBP-30-360-6 93.11 4.49 1.02 0.36 0.65 1.73 166.6 0.93 – 67.89
CBP-50-340-4 91.39 4.81 1.05 0.31 1.05 1.58 230.1 0.89 – 69.64
CBP-70-320-1 88.10 5.30 1.07 0.24 5.00 1.38 228.6 0.81 – 62.88
a
Softening point.
b
Carbon aromaticity.
c
Averaged molecular weight.

cross-linking reactions triggered by oxy-radicals [23]. Such oxidation
process usually needs a long reaction time, and produces a large amount
of exhaust gas, leading to the less spinnability of produced pitch and
high cost of tail-gas treatment as well. Besides, adding polymerization
initiators, such as HF/BF3, AlCl3, CH2O, and elemental S, as well as the
bromination-dehydrobromination method could accelerate the poly­
merization and cross-link reaction of pitch molecules. However, such
additives usually cause severe corrosion of equipment, and moreover,
the residual of additives left in the precursor is hard to remove and could
show adverse effects on their performances. Nonetheless, it is worth-
considering to enhance the polymerization reaction by introducing the
accelerants or inducers to solve the problems mentioned above.
Co-carbonization as an effective procedure to modify the carbon­
ization properties of feedstock, was selected for the preparation of
spinnable pitch with suitable softening point and excellent spinnability
[4,11,24–28]. Guo [28] has tried to co-carbonize petroleum pitch with
coal tar pitch to prepare spinnable pitch for carbon fiber. They have
found that the rheological property of spinnable pitch was improved,
but its softening point was still not suitable after co-carbonization. The
formation of mesophase is hard to control due to high-temperature heat
treatment. For a few decades, lignocellulosic biomass, which is derived
from agricultural wastes and forestry, is considered as a promising
feedstock for biofuels and commodity chemicals [29]. Bio-oil is pro­
duced by fast pyrolysis of lignocellulosic biomass without air condition
[30]. Bio-tar is obtained from the heavy components of bio-oil, whose
lighter fractions have been separated to produce useful chemicals [31].
After further vacuum distillation to separate the light components, the
remaining thick or solid components could be called bio-asphalt. Bio-
asphalt (BA) is largely comprised of aromatic structures, substituted and
linked by aliphatic units and oxygen-containing groups [12,21,32],
thus, it has high reactivity during carbonization. Prauchner et al. [21]
studied the thermal polymerization of bio-asphalt. They found that the
polymerization of bio-asphalt could occur at 250 ◦ C by pyrolytic he­
molytic cleavage of C-O. Li et al. [33] prepared mesophase pitch by co-
carbonization of coal tar pitch and bio-asphalt. They noted that the
addition of bio-asphalt could effectively introduce alkyl and naphthenic
structures to improve the rheological property of mesophase by cross-
linking reaction. However, the co-carbonization of coal tar pitch and
bio-asphalt to prepare spinnable pitch for carbon fiber has not been
studied so far. Co-carbonization of bio-tar with ethylene bottom oil [26]

Fig. 1. The flow diagram of experimental process.

2
X. Lin et al.
was found to be effective to form high softening point pitch. Besides, the
abundance of aliphatic structures introduced by bio-tar could improve
the viscosity-temperature characteristics and spinnability of the pitch.
Bio-tar and bio-asphalt both have high reactivity due to the abundant
oxygen functional groups and alkyl groups. It is possible to make use of
the high reactivity of bio-asphalt to induce the polymerization of coal tar
pitch at relatively low temperature. Meanwhile, bio-asphalt has signif­
icant potential as a pitch precursor since it is renewable, environmen­
tally friendly, and can be considered as a “negative-cost” feedstock [25].
Thus, the bio-asphalt was thought to be an appropriate accelerant or
inducer to co-carbonize with coal tar pitch to prepare spinnable pitch for
CFs.
This study aims to develop the isotropic spinnable pitch for CFs by
co-carbonization of CTP and BA. The polymerization features of the co-
carbonization process would be systematically verified through the
study of functional group variations of CTP and BA. The cross-linking
mechanism induced by the oxygen-containing functional groups will
be briefly illustrated accordingly. Furthermore, the correlation between
spinnability and molecular structure of as-prepared pitch would be
clarified. It is expected to show insight into the co-carbonization char­
acteristics of CTP and BA, and provide a new strategy for the preparation
of isotropic spinnable pitch precursors in a relatively simple processing
method.
2. Experimental
2.1. Materials
The CTP was from the Pingmei Shenma Group in Pingdingshan,
Henan, China. BA was produced by pyrolysis of poplar and pine, and
separation of the light bio-oil. To enhance the quality of prepared carbon
materials, the quinolone insoluble matter of CTP was removed by
dissolution-sedimentation processing with kerosene and wash oil. And
the impurities of BA have been eliminated with tetrahydrofuran (THF)
by filtration and rotary evaporation. Properties of the refined CTP and
BA are shown in Table 1. The specific preparation of CTP and BA is
presented in the supplementary information (SI).
2.2. Preparation of spinnable pitches
Fig. 1 and Fig. S1 show the diagram of the main experiment processes
and the reactor, respectively. A two-steps method for preparation of
spinnable pitch by co-carbonization of CTP and BA was developed. The
co-carbonization reaction was carried out with a 250 ml reactor. The
specific description is provided in the SI.
2.3. Preparation of CFs
The pitch fibers were spun using a laboratory-scale single-hole 500
ml spinning apparatus through a spinneret (diameter = 0.2 mm, length/
diameter = 2). Spinning experiments were performed under 0.1 MPa
with N2 atmosphere at a temperature of SP + 50 ◦ C. The 10 g of the as-
prepared pitch was spun at a winding speed of 400 rpm for 15 min to
evaluate the spinnability. Pitch fibers were then stabilized at 260 ◦ C for
1 h with a heating rate of 0.5 ◦ C/min and an air flow rate of 200 ml/min.
Following, the stabilized fibers were carbonized to 800 ◦ C for 5 min with
a heating rate of 5 ◦ C/min and a 100 ml/min of N2 flow. The carbon
fibers prepared from CBP-50–340-4 and CBP-70–320-1 were labeled as
CF-50 and CF-70, respectively.
2.4. Characterizations
Softening points were determined by Thermal Mechanical Analyzer
(TMA, Rigaku TMA8311, Japan). The pitch sample was heated at a rate
of 5 ◦ C/min under N2 atmosphere and the pressure was exerted by a
probe on the surface of the sample to obtain the softening point.
3
Fuel 295 (2021) 120627
Fig. 2. GPC profiles of raw materials and co-carbonized pitches.
Ultimate analyses were conducted on the Vario MACRO cube elemental
analyzer (Elemental, Germany), and the O content was measure by the
oxygen mode. Molecular weight distributions were evaluated by gel
permeation chromatography instrument (GPC, Waters 515–2410, Mil­
ford, MA). Samples were dissolved in THF with a concentration of 2 mg/
ml and the elution was carried out at a rate of 1 ml/min. Polystyrene
with different molecular weight was used as the reference material to
perform the equipment calibration before measurement. Thermogravi­
metric analysis (TGA, NETZSCH STA 449F3, Germany) was employed to
measure the thermal properties of raw materials. Samples were heated
from 25 ◦ C (room temperature) to 800 ◦ C at a rate of 10 ◦ C/min in a
nitrogen atmosphere.1H NMR and 13C NMR experiments were per­
formed using a Bruker Advance 400 spectrometer (400 MHz), and
samples were dissolved in CDCl3 with tetramethylsilane (TMS) as the
internal standard. Chemical structures of samples were analyzed by
Fourier transform infrared spectrometer (FTIR, Nicolet IS10, USA). The
equal weighted samples were ground with KBr at a weight ratio of 200
(KBr/Sample), and the experiment was operated at a resolution of 4
cm− 1 in the region of 4000–400 cm− 1. Morphologies and diameters of
produced carbon fibers were observed using a scanning electron mi­
croscope (SEM, JSM7401, Japan) with surface coating by platinum. The
tensile strength of carbon fibers was measured according to ASTM
D4018-2011. The tensile strength was obtained from the mean value of
30 tests.
3. Results and discussion
3.1. Analyses of the raw materials
The main characteristics of the CTP and BA are summarized in
Table 1. The CTP contained 91.42 wt% C, 4.50 wt% H and 1.98 wt% O,
whereas the BA had 68.44 wt% C, 6.83 wt% H and an extremely high
proportion of O (21.52 wt%). The higher oxygen content in BA, the
higher reactivity it is, promoting the cross-linking reaction happens even
at low temperature [26,27,34]. The CTP had high carbon content. And
the C/H mole ratios of CTP and BA were 1.69 and 0.83, respectively. The
molecular weight of CTP and BA were 410 and 1135 Dalton, respec­
tively. From GPC curves (Fig. 2), it could be found that the CTP and BA
had significant differences on molecular weight distributions, indicating
different polymerization behaviors during thermal treatment of CTP and
BA.
13
C NMR spectra of the CTP and BA are shown in Fig. 3a. The CTP
had a high concentration of non-oxygenated aromatic carbons (peaks at
X. Lin et al. Fuel 295 (2021) 120627

13
Fig. 3. NMR spectra of raw materials and co-carbonized pitches, (a) C NMR; (b) 1H NMR.

Table 2 Table 3
Distribution of proton in pitch samples. Band assignments of main peaks in the FTIR spectra.
Sample Hydrogen contents/% σe Peak Assignments
a (cm− 1)
Har HFb Hα c
Hβ d
Hγ f

3450–3400 − OH stretch
CTP 75.66 4.72 10.66 6.46 2.50 0.08
3050–3030 Aromatic CH stretch
BA 23.26 19.76 25.30 26.95 4.73 0.45
2970–2850 Aliphatic CH3, CH2, and CH stretch
CBP-30 70.91 4.56 14.39 8.85 1.29 –
1775–1765 C––O stretch in ester with group attached to single-bonded oxygen
CBP-50 57.96 5.25 16.60 14.99 5.20 –
1735 C––O stretch in ester
CBP-70 50.61 3.49 17.25 19.22 9.43 –
1720–1690 C––O stretch in ketone, aldehyde, and carboxyl
CTP-360-6 78.52 4.37 9.47 5.73 1.92 –
1650–1630 C––O stretch, highly conjugated
CBP-30-360-6 71.71 4.94 13.41 8.15 1.79 –
1600 Aromatic C– –C ring stretch, highly conjugated hydrogen-bonded
CBP-50-340-4 69.18 5.02 13.02 9.74 3.04 –
C––O stretch
CBP-70-320-1 52.25 2.74 15.15 18.88 10.98 –
1510 Aromatic C– –C ring stretch
a 1460–1440 Aliphatic chains CH3− and CH2−
Aromatic proton (9.5–6.0 ppm).
b
Aliphatic protons in methylene groups to two aromatic groups or protons in 1365–1355 Aliphatic chains CH3− or in-plane O–H bend
1275–1200 C–O–C stretch of alkyl aryl ethers, ester CC(–
–O)–O stretch and C–O
α- position to oxygen (4.5–3.3 ppm).
c stretch in phenols
Aliphatic protons in α- position to an aromatic ring (3.3–2.0 ppm).
d 1115–1110 C–O–C stretch of aliphatic ethers or C–O stretch in alcohols
Aliphatic protons in β- position to an aromatic ring (2.0–1.0 ppm). 1030 C–O stretch of aryl alkyl ethers or C–O stretch in alcohols
f
Aliphatic protons in γ- position to an aromatic ring (1.0–0.5 ppm). 900–700 Aromatic CH
e
Substitution degree.

110–140 ppm) and a low content of aliphatic carbons (peaks at 10–50

ppm); while the BA had abundant of aliphatic carbons (peaks at 10–70
ppm), including the methoxy carbons (peaks at around 55 ppm), alco­
holic carbons or/and other etheric carbons (peaks at 60–70 ppm),
oxygenated aromatic carbons (peaks at 140–160 ppm), and carboxyl
carbons (peaks at 160–185 ppm) [21,26,35]. The aromatic fractions of
CTP and BA obtained from 13C NMR were 0.93 and 0.57, respectively,
which is consistent with the C/H mole ratio results. Moreover, 1H NMR
spectra of CTP and BA are shown in Fig. 3b, and their hydrogen distri­
butions are summarized in Table 2 [35–38]. The Har content of CTP was
much higher than that of BA, indicating the rich aromatic structures
with lower substitution degree in CTP. Furthermore, contents of HF, Hα,
Hβ, and Hγ representing proportions of aliphatic structures and lengths
of the alkyl chains to some extent were more abundant in BA than CTP.
According to previous studies [35–38], the HF of coal tar pitch could be
aliphatic protons in methylene group, linking two aromatic groups;
while, in BA, the HF mainly represents the hydrogen atoms on carbons
bonded to an oxygen atom in ethers or alcohols. The oxygen-containing
groups, such as alcohols, alkyl aryl ethers, and aliphatic ethers, are
abundant in BA with a concentration of 19.76%. The substitution degree
of aromatic rings (σ [39]) of CTP and BA were 0.08 and 0.45, respec­
tively, implying that BA has more aromatic ring substituents than CTP.
To further elucidate the structural features of CTP and BA, FTIR
Fig. 4. FTIR spectra of raw materials and co-carbonized pitches.
spectra are demonstrated in Fig. 4, and peak assignments are shown in
Table 3 [32,33,40]. The FTIR spectrum of BA showed high-intensity
peaks at 3405 cm− 1 and 1700 cm− 1, which corresponds to the hydrox­
yl –OH and carbonyl C = O groups in ketone, aldehyde, and carboxyl,

4
X. Lin et al.
Fig. 5. TGA analyses of CTP and BA.
which were hardly found in CTP. Meanwhile, peaks in the region of
1300–1000 cm− 1 of BA, representing C-O stretching vibrations of phe­
nols, ethers, esters, and alcohols, were stronger than those of CTP. The
results show that BA has more abundant oxygen-containing groups than
CTP. Furthermore, the absorption peak at around 3050–3030 cm− 1 and
900–700 cm− 1 are assigned to aromatic –CH groups, whose intensities
are stronger in CTP than those in BA. Intensive peaks of aliphatic –CH,
–CH2, –CH3 groups at around 2970–2850 cm− 1 and 1460–1440 cm− 1
were observed in BA. Thus, compared to CTP, BA contained more
abundant aliphatic structures and substituents. Besides, the C = C ab­
sorption bands at 1600 cm− 1, which should be attributed to the aromatic
rings, were clearly observed in both CTP and BA samples.
TG and DTG curves from TGA are shown in Fig. 5. From the TG
profile, the initial weight loss temperature of BA was much lower than
that of CTP, and the weight loss of BA was higher than CTP at the same
temperature in the full temperature range. The DTG curves of CTP and
BA exhibited different ranges of weight loss with peaks at 178 ◦ C and
375 ◦ C, respectively. More importantly, BA had more than 60% weight
loss below 300 ◦ C. However, only 30.86% weight loss was observed in
CTP even at 350 ◦ C. This was attributed to the release of both volatile
and small molecules produced by thermal polymerization reactions.
Thus, due to the special structure of BA, it is a possible method to co-
carbonize CTP with BA to produce isotropic spinnable pitch by the
polymerization reaction.
3.2. Analyses of co-carbonized pitches
Table 1 shows the main properties of the co-carbonized pitches. The
CBP-0 was prepared from CTP alone. Its softening point slightly
increased from 42.7 ◦ C to 62.9 ◦ C, and the elemental analysis changed
little after thermal treatment. In contrast, the CBP-100 had apparent
changes after thermal treatment. The pitch lost its flow properties and
showed foaming morphology reflecting its high degree of cross-linking
polymerization [32]. It could be seen that the hydrogen and oxygen
content decreased obviously, and the carbon content increased, sug­
gesting the loss of aliphatic side chains occurred during thermal treat­
ment. These results show that the polymerization reaction in CTP was
weak, whereas, occurred drastically in BA. As for co-carbonized pitches,
compared with elemental analysis of raw hybrid pitches calculated from
Table 1, the carbon content increased and hydrogen content decreased
after co-carbonization of CTP and BA, leading to the higher aromaticity
and higher thermal stability of the co-carbonized pitches [27]. As shown
in Fig. 5 and Fig. S2, the thermal gravimetric analysis presents the
thermal behavior of raw materials and co-carbonized pitches. This result
also could prove this conclusion. Notably, the oxygen content markedly
5
Fuel 295 (2021) 120627
decreases. Such phenomena were similar to the polymerization of alone
BA. On the other hand, with the increasing of BA concentration, the co-
carbonized pitch exhibited a decreasing carbon content, an elevated
hydrogen, and oxygen content. This was attributed to the abundant
hydrogen and oxygen content in BA. The softening points increased from
93.7 ◦ C to 133.7 ◦ C and 187.4 ◦ C, illustrating that the BA is conducive to
enhance the polymerization reaction and has a great influence on the
increment of the softening point. Furthermore, the softening point could
be an indicator of the polymerization degree [32]. The polymerization
degree of the co-carbonization reaction was determined by the con­
centration of BA. The co-carbonization of CTP and BA prevented the
excess polymerization, which might occur in BA. The CTP and BA pre­
sented good synergism during the co-carbonization reaction. The CBP-
30, which has the highest proportion of CTP, had the highest yield of
80.33% and fa of 0.92. These values present a decreasing tendency with
the increasing of BA.
Molecular weight distributions were examined by GPC, as shown in
Fig. 2. The average molecular weight of CBP-70 is 1093 Dalton, with
those of CBP-50, CBP-30 gradually decreasing to 860 and 670 Dalton,
respectively. It is clearly illustrated that the low molecular weight region
gradually decreased as the content of BA increased, which is in agree­
ment with variations of softening points related to concentrations of BA
in pitches.
Fig. 3b shows the 1H NMR spectra of the co-carbonized pitches, and
the results were processed in Table 2. As shown in Table 2, contents of
Har in the co-carbonized pitches decrease in the order of CBP-30 > CBP-
50 > CBP-70, indicating a larger proportion of alkyl structures and fewer
aromatic structures in co-carbonized pitch with the higher weight ratio
of BA. Particularly, the co-carbonization treatment could sharply reduce
the HF content of mixed pitches regardless of the mixing ratio of CT and
BA. This was mainly because the HF of BA, which mostly represents the
oxygen-containing groups (such as methoxyl, alcohol, ether, and ester),
could be easily involved in the polymerization reaction and released
from the system as the form of volatile molecules. Among the co-
carbonized pitches, the CBP-50 has the highest concentration of HF,
which should be mainly assigned to methylene group bridged aromatic
structures. Proportions of Hα and Hβ hydrogens decrease in all samples
after the co-carbonization reaction. However, contents of Hγ in CBP-50
and CBP-70 surpassed those in respective raw hybrid pitches due to
the competition between breakage of alkyl chains and the new chains
formed by combining with units from the breakage of alkyl ether. These
results show that the increase of softening point is mainly attributed to
polymerization reactions triggered by the decomposition of oxygen-
containing groups, instead of breakage of alkyl chains. The 13C NMR
spectra of the CTP, BA, and co-carbonized pitches are presented in
Fig. 3a. Compared to BA, the oxygen-containing groups, such as
methoxyl, carboxyl, alcohol, phenol, and oxygenated aromatic carbons,
were apparently weaker or even merged in CBP-30, CBP-50, and CBP-
70. Generally, the higher reactivity of bio-asphalt was induced by the
high content of oxygen-containing side chains, and the polymerization
of bio-asphalt mainly involved pyrolytic cleavage of C-O bonds [21].
Combining with above-mentioned results and literature, the co-
carbonization reaction was mainly triggered by the pyrolytic cleavage
of C-O bonds of BA, and the linked side chains were released, leading to
the formation of larger molecules through the heavier free radical
fragments by bonding with aromatic rings of CTP and BA.
Besides, in order to understand the variations of functional groups
through the co-carbonization process, FT-IR spectra of CBP-30, CBP-50,
and CBP-70 are shown in Fig. 4. For the co-carbonized pitches, in­
tensities of peaks corresponding to aliphatic structures (2970–2850
cm− 1: C–H stretching vibration, 1450 cm− 1 and 1377 cm− 1: C–H
deformation vibration) become stronger with the increasing of BA
content, while intensities of peaks corresponding to aromatic structures
(3043 cm− 1 and 875–745 cm− 1: aromatic nucleus C–H) decreases with
the BA content. Thus, the higher weight ratio of BA in raw hybrid pitch,
the more aliphatic structures the co-carbonized pitch has. As for oxygen-
X. Lin et al. Fuel 295 (2021) 120627

Fig. 6. Mechanism of co-carbonization reaction between CTP and BA.

containing groups, the broad absorption peak at 3421 cm− 1, which is

ascribed to the hydrogen-bonded –OH, was observed. Peaks in the re­
gion of 1300–1000 cm− 1 representing the C-O links were clearly iden­
tified in co-carbonized pitches, implying the remaining oxygen-
containing groups after co-carbonization. Particularly, the stretching
vibration peak at around 1695 cm− 1 represents active C– – O in ketone,
aldehyde, and carboxyl functional groups, which disappeared in co-
carbonized pitches. While, the C– – O (peak at 1600 cm− 1) with lower
activity still existed after co-carbonization.
Thermal gravimetric analysis of the co-carbonized pitches is shown
in Fig. S2. The CBP-0 received the lowest residual weight, whereas CBP-
100 had the highest one. Also, with the increasing of the BA concen­
tration, the co-carbonized pitch showed an increasing residual weight.
However, Fig. 5 illustrated that the residual weight of BA was lower than
that of CTP. Thus, these results suggested that the polymerization re­
action occurred during co-carbonization, furthermore, the polymeriza­
tion degree was elevated with the increase of BA, which is in agreement
with the main properties of samples and NMR analysis.
The probable reaction mechanism during the co-carbonization was
proposed on the basis of the above analyses and given in Fig. 6.
As shown in Table 1, the softening point of CTP-360–6 is only
121.1 ◦ C, even though sample CTP-360–6 was obtained at a relatively
higher thermal treatment temperature. Therefore, it is confirmed that it
is difficult to prepare a suitable spinnable pitch by thermal polymeri­
zation method with CTP alone. These results clearly demonstrate that
the softening point of feedstock is significantly enhanced even samples
were treated at a relatively low temperature by co-carbonization with
BA. Furthermore, the feedstock with more content of BA can be prepared
to obtain a higher softening point of the co-carbonized pitch under the
same reaction condition. Moreover, abundant aliphatic structures are
introduced into co-carbonized pitches due to the high aliphatic com­
ponents in BA.
3.3. Analyses of prepared pitches
The suitable softening point of spinnable pitch, which should be over
220 ◦ C, is a critical requirement to guarantee the sufficient oxidation of
pitch fibers completed in a short time [27]. Accordingly, the co-
carbonized pitches should be subjected to further thermal treatment to
increase the softening point. Table 1 shows the main properties of pre­
pared pitches produced by co-carbonized pitches at various thermal
treatments which could effectively enhance the softening point for the
preparation of isotropic carbon fibers. As shown in Table 1, the C/H
mole ratio of CBP-30-360-6 and CBP-50-340-4 significantly increased
from 1.56 and 1.44 to 1.73 and 1.58, respectively; whereas the value of
CBP-70-320-1 had a slight increase from 1.36 to 1.38, which implied
that the dehydrogenation polymerization occurred in the further ther­
mal treatment, but the aromaticity, as well as thermal stability, were
more deeply enhanced in CBP-30-360-6 and CBP-50-340-4 than those of
CBP-70-320-1 after thermal treatment. Besides, the oxygen content
decreased slightly from 5.57 to 5.00 in the case of CBP-70-320-1, while
those for CBP-30-360-6 and CBP-50-340-4 decreased more obviously.
This suggests that the active oxygen-containing groups basically release
in the first step of co-carbonization and the residual needs a relatively
Fig. 7. 1H NMR spectra of as-prepared pitches.
high reaction temperature to decompose. Generally, the heteroatoms
release during the carbonization of carbon fiber preparation, decreasing
the mechanical properties of obtained materials. Thus, the high oxygen
content in CBP-70-320-1 is a disadvantage to the mechanical properties
of prepared carbon fibers. Yields of CBP-50-340-4 and CBP-70-320-1 are
both higher than 60%, with the former one reaches around 70%.
CBP-70-320-1 with a softening point of 228.6 ◦ C is produced by a
thermal treatment temperature of 320 ◦ C and reaction time of 1 h. The
softening point of CBP-50-340-4 is similar to that of CBP-70–320-1, but
its thermal treatment conditions (340 ◦ C and 4 h) are more severe.
Furthermore, for CBP-50-340-4 and CBP-70-320-1, their softening
points could increase to over 250 ◦ C with a longer thermal treatment
time of 2 h and 1 h under 340 ◦ C and 320 ◦ C, respectively. It should be
noted that the softening point of CBP-30–360-6 is 166.6 ◦ C, and was
obtained at a higher temperature (360 ◦ C) and longer reaction time (6
h). However, even if the thermal treatment conditions increased to
380 ◦ C and 6 h, the softening point of CBP-30–360-6 was just around
180 ◦ C, which was still lower than that of the spinnable pitch require­
ment. This might be due to more cross-linked macromolecules created in
co-carbonization with the higher weight ratio of BA, promoting the
polymerization reaction and finally resulting in the high and suitable
softening point of pitches under moderate thermal treatment. As for CTP
and CBP-30, thermal treatment temperature needs to be over 380 ◦ C to
receive pitches with a softening point over 220 ◦ C.
The 1H NMR spectra of prepared pitches are shown in Fig. 7, and the
hydrogen distributions are summarized in Table 2. As shown in Table 2,
since the release of aliphatic structures and reactions of polymerization
were taken place in the further thermal treatment, contents of Har hy­
drogens in prepared pitches were enhanced, compared to their corre­
sponding co-carbonized pitches. Compared to CTP-360-6, pitches
prepared by co-carbonization with BA contain more aliphatic structures.
Particularly, hydrogen distributions of CBP-70-320-1 are slightly

6
X. Lin et al.
Fig. 8. FTIR spectra of as-prepared pitches.
changed when compared with CBP-70, which is in agreement with the
elemental analysis results. This could contribute to its most moderate
thermal treatment conditions when compared to other samples. Among
prepared pitches, CBP-50-340-4 possesses the most HF, which demon­
strates that it composes the highest concentration of linear structures
linked by methylene bridges. These structures can improve the flexi­
bility of molecules and thus contribute to the spinnability of pitches.
Meanwhile, excess aliphatic structures without bridging, have negative
effects on carbon fiber preparation, since they are unstable during the
thermal treatment procedure. Thus, the CBP-50-340-4 shows the best
properties for carbon fiber preparation.
Fig. 8 shows the FTIR spectra of the prepared pitches produced by
further thermal treatment of co-carbonized pitches and CTP. Peaks
corresponding to the aliphatic structures become stronger with the
increasing of BA concentration, which is similar to the result of spectra
of the co-carbonized pitch. Peaks around 1300–1000 cm− 1, which is
attributed to C-O links, were clearly obvious in prepared pitches. It can
be seen that the as-prepared pitches with the addition of BA have the
more intense peaks, suggesting the oxygen was introduced into prepared
pitches during co-carbonization. It further confirms that the as-prepared
pitches have more abundant aliphatic structures with the addition of BA.
It is widely known that [41], under the carbonization process, the
main reaction of coal tar pitch should be attributed to polymerizations of
aromatic groups and cracking of aliphatic chains. In general, it is hard to
increase the softening point of the pitch at a relatively low temperature
due to its low reactivity. By the co-carbonization with BA, active oxygen-
containing groups can promote the cross-linking reaction to create
macromolecules. Thus, the isotropic pitches with high and suitable
softening points can be obtained by co-carbonization with BA at
Fig. 9. SEM images of carbon fibers, (a) CF-50, (b) CF-70.
7
Fuel 295 (2021) 120627
relatively low temperature.
3.4. Analyses of spinning features of prepared pitches
As mentioned above, pitches with suitable softening points were
successfully spun into pitch fibers at an extrusion rate of 400 m/min at a
temperature of around 50 ◦ C above their softening points to demonstrate
their spinnability. Results show that both CBP-50-340-4 and CBP-70-
320-1 with a softening point of around 230 ◦ C could be spun into
pitch fibers smoothly over 15 min without breakage, indicating that the
prepared pitches have excellent spinnability. Furthermore, pitch fibers
were subjected to consecutive heat treatments (stabilization and
carbonization) to obtain carbon fibers. The photos of pitch fibers and
stabilized fibers of CBP-70-320-1 are supplied in the Fig. S3. Morphol­
ogies of carbon fibers were observed by SEM and are shown in Fig. 9. It
can be seen that carbon fibers exhibit no fusing properties, which sug­
gests that the stabilization process is sufficient to keep fibers from
melting in the next carbonization process. From the cross-sections of CF-
50 and CF-70, the fibers showed random structure, which meets the
typical microscopic characteristics of isotropic fibers [42]. The optical
microstructure also demonstrated the isotropy of CBP-50-340-4 and
CTP-70-320-1, as shown in Fig. S4. Besides, fibers of CF-50 have ho­
mogeneous and smooth surfaces with an average diameter of 12 μm.
While fibers of CF-70 have an average diameter of 13 μm with partial
fibers presenting some apparent small holes in the surface. This might be
attributed to the releases of volatile materials during the carbonization.
These results are in agreement with characteristics of microstructures of
CBP-70-320-1, which have more unstable aliphatic chains than CBP-50-
340-4, tending to decompose and release during the carbonization
process. These defects will reduce the mechanical properties of carbon
fibers. The tensile strength of CBP-50-340-4 and CBP-70-320-1 was 786
and 543 MPa, respectively. The former one was higher than the other
bio-asphalt based carbon fiber prepared by Qiao at al. (632 MPa) [13]
and could reach the target value of commercial general-purpose carbon
fibers (780–1000 MPa). Since the tensile strength depends largely on the
diameter of the fiber, the tensile strength has the potential to be further
improved and optimized. The optimal mixing ratio and a deeper syn­
ergistic effect of co-carbonization of CTP and BA on mechanical prop­
erties of carbon fibers are still under investigation. In summary, the
spinnable pitch precursor with the suitable softening point for isotropic
carbon fibers can be successfully manufactured by co-carbonization of
CTP and BA.
4. Conclusion
CTP was processed to produce isotropic spinnable pitch for general
purpose carbon fiber by co-carbonization with BA. Under the same
thermal treatment condition, the polymerization reaction of CTP was
weak, whereas the BA occurred drastic polymerization. The co-
carbonization reaction was mainly triggered by the pyrolytic cleavage
of C-O bonds of BA, and the linked side chains were released, the heavier
free radical fragments could combine with aromatic rings of CTP and BA
X. Lin et al.
to form larger molecules. Besides, the polymerization degree of the co-
carbonization reaction was determined by the concentration of BA.
Co-carbonization of CTP and BA also prevents excessive polymerization,
which might occur in BA alone. CTP and BA presented good synergism in
co-carbonization reaction. The isotropic spinnable could be obtained
under more moderate thermal treatment conditions with the increase of
BA concentration. Excessive addition of BA brought some defects to the
prepared carbon fibers. When the weight ratio of CTP to BA was 1:1, the
average diameter and tensile strength of carbon fibers were 12 μm and
786 MPa, respectively. Through this study, it is expected to enlighten the
co-carbonization characteristics of CTP and BA, providing a new strat­
egy for the preparation of isotropic spinnable pitch in a relatively simple
method.
CRediT authorship contribution statement
Xiongchao Lin: Conceptualization, Data curation, Project adminis­
tration. Zhe Sheng: Methodology, Writing - original draft. Jin He:
Methodology. Xin He: Writing - review & editing. Caihong Wang:
Investigation, Data curation. Xiaohu Gu: Investigation. Yonggang
Wang: Investigation, Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Acknowledgments
This work was supported by the National Natural Science Foundation
of China [grant numbers 21978319, 21406261]; National Key Research
and Development Program [Grant number 2016YFB0600303031]; and
Yue Qi Young Scholar Project of China University of Mining & Tech­
nology, Beijing.
Appendix A. Supplementary data
Supplementary data to this article can be found online at https://doi.
org/10.1016/j.fuel.2021.120627.
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