Computational Materials Science 220 (2023) 112029

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Computational Materials Science

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

Full Length Article

The evolution of carbon fiber elements and their effects on fiber mechanical
properties from molecular dynamics
Yuanyuan Ma a, b, *, Jiangtao Wang a, b, Kuan Lu c, Yang Xiang a, b, Yaqing Liu a, b, *
a
Shanxi Province 1331 Project Key Innovation Team of Polymeric Functional New Materials, North University of China, Taiyuan 030001, PR China
b
Shanxi Province Key Technology Innovation Platform for the Development and Application of High Performance Carbon Fiber and Its Composites, North University of
China, Taiyuan 030001, PR China
c
State Key Laboratory of Coal Conversion, Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, PR China

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

Keywords: Carbon fibers are ideal light-weight materials for aerospace applications due to their properties such as high
Carbon fiber strength, high modulus. As a result, there are significant efforts aimed at studying the theory of fiber structure
Molecular simulation and fabrication methods. The mechanical performance of carbon fibers can be controlled by the interaction of
Non-carbon element
many complex factors, one of them being the element characteristic. Here, we use the molecular dynamics
Carbonization
Mechanical properties
simulations to predict the evolution of non-carbon elements during heating and their responses to mechanical
behavior. Particularly, the possible structures of N, O and Si are comprehensively studied. It is observed that Si
results in the formation of –C––N–Si chains and –OH residues, which hinders the improvement of the strength
of the carbon fibers. The oxygen-containing groups of the terminal ester can increase the content of adjacent
chain structures that preferentially participate in carbonization. The O groups of hydroxypyridine lead to
significantly lower carbonization onset temperature of polyacrylonitrile (PAN) via the pathway for H2O elimi­
nation, while the reaction rate of the H2O molecules is relevant to the PAN chain length distribution and local
density. Interestingly, in the case of oxygen-modified carbon fibers, the Young’s modulus is predominantly
affected. The release temperature of N, ranked from lowest to highest, is given by the chain-end –CN group >
hydrogenated-CN > unhydrogenated-CN, and the “transfer hopping” effect of the N element on the activated
carbon chains contributes to carbon rearrangement during carbonization. The modified carbon ring structure
comprising of 1.0–3.0 wt% N element is beneficial factor for conferring high tensile strength and large elongation
to the carbon fibers. Our results provide valuable insights for the preparation and screening of high-performance
carbon fibers from an elemental perspective, which can pave the way for a systematic framework for optimizing
their performance.

1. Introduction condensation at high temperature (greater than 1000 ◦ C) in inert envi­

Over several decades, carbon fibers (CFs) have matured into a pivotal
new material system owing to their enhanced mechanical properties,
low thermal expansion coefficient and dimensional stability [1]. Due to
these properties, CFs are increasingly used in the aerospace, military and
civilian industries, and the field is still making rapid progress [2,3]. CFs
can be prepared from different precursors, such as PAN, which is the
most commonly used precursor for producing high-strength CFs [4].
Typically, the process of making CFs involves spinning linear molecular
chains of PAN precursors into heat-resistant ladder-like structures,
which is followed by further carbonization through pyrolysis and
ronment conditions [5]. These CFs have complex microstructure char­
acteristics, which are strongly controlled by the proportion of
crystalline, amorphous and defect components. CFs are commonly
composed of more than 90 % of C and a small amount of N, Si, O residue.
Foreign Si is inevitably introduced due to the penetration of silicone oils
into the loose fibers during oiling. Most silicone oils are modified based
on polydimethylsiloxane (PDMS) [6,7]. Most approaches for mechanical
reinforcement of CFs have used the trial and error route, with the goal of
understanding the influence of structural and elemental characteristics
(microstructure, element, orientation of crystallites, hybrid structure,
porosity, etc.) on the strength-modulus response. Experimental studies,

* Corresponding authors at: Shanxi Province 1331 Project Key Innovation Team of Polymeric Functional New Materials, North University of China, Taiyuan
030001, PR China.
E-mail addresses: yuanm78@nuc.edu.cn (Y. Ma), lyq@nuc.edu.cn (Y. Liu).

https://doi.org/10.1016/j.commatsci.2023.112029
Received 11 October 2022; Received in revised form 30 December 2022; Accepted 13 January 2023
Available online 1 February 2023
0927-0256/© 2023 Elsevier B.V. All rights reserved.
Y. Ma et al. Computational Materials Science 220 (2023) 112029

Fig. 1. An overview of the evolution of the oxidized PAN/PDMS model. (a) A single PDMS chain, and oxidized PAN with three different chain lengths and structures.
Color code: Carbon-gray, Nitrogen-yellow, Silicon-orange, Oxygen-red, Hydrogen-blue. (b) The initial construction of the oxidized PAN/PDMS, where the mixture of
oxidized PAN is artificially divided into three regions along the X-axis to facilitate the understanding between the PAN chain distribution and O release rate (see
Section 3.1.2. for details). (c) The simulated box in (b) is compressed, such that the final density is 1.30 g cm− 3; (right) the large-scale PAN ladder structure at 2100 K
(initial carbonization), and (left) the final carbonized structure at 2800 K. (For interpretation of the references to color in this figure legend, the reader is referred to
the web version of this article.)

such as wide-angle X-ray scattering [8], Raman spectroscopy [9], small-
angle X-ray scattering [10] and transmission electron microscopy [11],
have been effectively used to evaluate these attributes of CFs, albeit at
the expense of high cost and being time-intensive. However, due to the
combined influence of many factors, numerous experimental methods
cannot yet precisely explain the detailed structure-properties relation­
ships. In summary, the current production of high-performance fibers
urgently requires in-depth research on the basic theory, which is
essential to understand the relationship between strength-modulus-
elongation and reduce upgrade costs.
Reactive molecular dynamics (MD) can address this problem by
providing complementary molecular-level insights to study the specific
evolution of CFs during high-temperature chemical processes. In prin­
ciple, it can assist in effectively screening the factors that impact per­
formance and achieving optimal design. Recently, reactive force-field
(ReaxFF) has been applied in many research fields, including the me­
chanical properties of fibers, polymer pyrolysis and fiber–matrix inter­
face. Several studies have used ReaxFF to explore various aspects related
to CFs, such as the formation of the PAN rings [12], the effects of micro-
voids of CFs [13] and crystal orientation [14], the structural evolution of
poly-p-phenylene benzobisoxazole/carbonnanotube fillers incorporated
into CFs [15], the effect of skin-core structure ratio in CFs [16], and the
analysis of thermal properties of PDMS [17]. However, the mechanism
of how the fiber structure controls mechanical properties is still lacking,
one of which is the collective effect of many factors.
In this article, we employ the ReaxFF MD approach to predict the
evolution of non-carbon elements (Si, O, N), and the effect of their
structure on the mechanical properties of the CFs. Particularly, the effect
of Si has been ignored in previous studies, whereas it is known that Si is
present in CFs due to the decomposition and diffusion of silicone oils.
Furthermore, the presence of Si has shown to be detrimental to the
mechanical performance of CFs, but no specific reason has been estab­
lished. Additionally, the content of the N element cannot be reduced
arbitrarily, which may lead to the low polarity of the fiber surface and a
worsen interface with the resin.
Here, we systematically construct an oxidized PAN/PDMS model
that includes all possible functional groups, obtain the preferred
elemental structures of Si, O, N by the carbonization, and then analyze
the effect of element content on the mechanical properties of fibers. The
results of this paper not only offer a broader understanding of the PAN-
based elemental evolution and its impact on mechanical properties, but
also provide insights towards the realization of high-performance CFs.
2. Computational details
2.1. ReaxFF potential
Herein, we adopt the MD simulation of the all-atom ReaxFF to
calculate all the different energies involved in the oxidized PAN/PDMS
and large-scale CFs systems. Unlike classical force fields, ReaxFF can
effectively simulate the chemical bond formation and breaking based on
the interatomic potentials of the bond order that can be trained using
empirical or quantum mechanics data. Especially in the study of carbon,
the ReaxFF method has been widely used for modeling rapid reaction
processes in order to better understand the fundamental principles of the
phenomenon. Its wide application in this field is also due to the fact that
results derived from this method are in agreement with the experimental
studies. The ReaxFF is expressed by the following formula to calculate
the potentials on each atom:
Esystem = Ebond + Eover + Eunder + Elp + Eval + Etor + EvaWaals + Ecoulomb + Etrip
(1)
Where, Ebond, Eover, Eunder, Elp, Eval, Etor, EvaWaals, Ecoulomb, Etrip refer
to energies related to the bond, over-coordination penalty, under-
coordination stability, long-pair, valence angle, torsion angle, van der
Waals, coulomb and triple bond stabilization, respectively. A full func­
tional description of ReaxFF potential can be found elsewhere in pre­
vious reports [18,19]. To explore the evolution mechanisms of Si, O and
N atoms of the CF precursors, we adopt the ReaxFF-lg force field [20,21]
to simulate the dual systems mentioned earlier (oxidized PAN/PDMS
and large-scale CFs systems). Because of its force-field accuracy, ReaxFF-
lg force field has been explored and verified by the combustion of en­
ergetic materials [22], the pyrolysis of pitch-based carbon fibers [23],
and the chemical/mechanical properties of carbon fiber matrix

2
Y. Ma et al.
Fig. 2. (a) Basic building unit, (b) initial and (c) final configurations of CFs system. The final fiber density is 1.70 g cm− 3.
composites [24].
2.2. Element evolution model—the oxidized PAN/PDMS system
For accurate compliance with the experiment, the stabilized PAN end
group structures are denoted as a six-membered ring containing an ester
group, and their regular sequence structures are designed to have the
ketone, hydroxyl, and unreacted cyano end groups [5,15,25]. As shown
in Fig. 1a, the length of the PAN chains is varied according to the ring
number, which are denoted as L6, L10 and L16. Therefore, the oxidized
PAN/PDMS system consists of 72 L6, 60 L10, 42 L16, and 50 PDMS
(C30O13Si14H90) with a size of 110 × 50 × 80 Å, as shown in Fig. 1b. The
mass fraction of PDMS is about 30 wt%. It should be noted that each
chain in the PAN system is initially parallel to the X-axis (the orientation
of the PAN chain mainly depends on the pyridine rings on it, ignoring
the edge structural distortion caused by the cyano end groups), and the
PDMS material is separated from the PAN model as its penetration into
the PAN system is not considered in the initial stage. The following steps
are performed with the MD process to obtain the elemental evolution: i)
the system is subjected to energy minimization and compressed to 1.30
g cm− 3 at 300 K by imposing periodic boundary conditions under the
NPT ensemble (a constant pressure of 0.3 GPa in the z-direction); ii) it is
then equilibrated at 300 K for 0.2 ns; iii) next, it is heated from 300 K to
2800 K within 1.8 ns; iv) the system is then maintained at 2800 K for 1.0
ns to complete the carbonization; v) finally it is cooled to 300 K in 0.2 ns
to analyze the evolution of all the carbon structures. A default time step
of 0.25 fs is selected, and the temperature and barostat are controlled by
the Nose-Hoover thermostat throughout the processes. The exemplar
snapshots of the trapezoidal (at 2100 K) and turbostratic graphite
structures (at 2800 K) of CFs are displayed in Fig. 1c, which are obtained
from the OVITO software package. The temperature in the simulation is
set to be higher than the experiment, which is done so that the chemical
processes are accelerated and the reaction energy barrier can be sur­
mounted. The LAMMPS package from lammps.sandia.gov is imple­
mented throughout. The bond order cutoff for molecule recognition of
all systems is 0.3.
2.3. Model construction of elements affecting mechanical properties of
CFs—system of large-scale CFs
It is necessary to establish a large-scale CFs system to explain the
effect of elements on its mechanical properties. Generally, the presence
3
Computational Materials Science 220 (2023) 112029
of these elements causes structural instability, due to the removal of the
high content of heteroatoms fastened to the host carbon structure in the
oxidized PAN/PDMS system. The initial configurations of the CFs system
are composed of 15 trapezoid structures with lengths of 1.1 nm, 30 with
lengths of 2.5 nm, and 55 with lengths of 5.2 nm, as shown in Fig. 2a-b.
The idealized hydrocarbon structures are stacked by Bernal (ABA)
structural units, which are randomly placed in the cell with an orien­
tation range of 0-±10◦ (the X and Y axis as the reference). The removal
of zigzag and armchair H at 900 K and the carbonization process
(heating from 900 K to 2800 K, equilibrating at 2800 K and cooling from
2800 K to 300 K) are in conformity with previous reports [14]. The force
field, temperature control and timestep are the identical to the param­
eters presented in Section 2.2. Thus, the final structure of the CFs with a
density of 1.70 g cm− 3 is consistent with those obtained by KMC-MD
method [6] and experimental high resolution transmission electron
microscope images of cross-sections [4], as shown in Fig. 2c. Its struc­
tural characteristics are identified in accordance with previous reports
via X-ray diffraction (XRD) profiles, ring alignment of Herman’s orien­
tation factor (HOF), pore size distribution and degree of graphitization
[14,26].
CF models with heteroatoms can be constructed by deliberately
replacing some carbon atoms in the large-scale CFs system with the
structure of a specific element (Section 3.1). This is an efficient and
straightforward strategy to investigate the effect of elements on me­
chanical properties of CFs. The N, Si and O content range of the
heteroelement-based CFs are selected to be 1.0–8.0 wt%, 0.3–1.5 wt%,
and O 1.0–3.0 wt%, respectively. This is based on the typical content of
commercially available samples. These modified systems are subject to
strain increments in the x-axis with a constant velocity of 25.0 m s− 1
until the occurrence of fractures is observed in the fiber.
3. Results and discussion
3.1. Element structure evolution analysis of CFs
3.1.1. Si element evolution
Findings related to the evolution of Si element in the oxidized PAN/
PDMS model are first discussed in this section. At about 900 K, formation
of methyl radicals preferentially occurs due to shortening of the Si–Si
bond in the siloxane, followed by stretching and further breaking of the
Si–C bond, in agreement with the previous reports [17,27,28]. At
higher temperatures in the range of 900–1200 K, de-polymerization and
Y. Ma et al. Computational Materials Science 220 (2023) 112029

–
Fig. 3. Pyrolysis products of PDMS, and reactive pathways between PDMS and PAN. (a) Si-(OH)n monomolecular, N– –C-Si-(OH)n, and “cage-like structure silanol”
structure. Color code: Carbon-gray, Nitrogen-yellow, Silicon-orange, Oxygen-red, Hydrogen-blue. (b) Si–C, Si single atom, and (c) Si–O bonds in PDMS participate
in non-six-membered ring reactions of oxidized PAN, including the long chain, –CSiN-tricyclic, –Si–ONO– and –Si–NCN-tetracyclic, or larger rings. (d) The
formation pathways of silicon rings and silanols. From (a) to (d), the oxidized PAN fragments are denoted in black, PDMS fragments are denoted in red, and the
symbol “R” refers to the main carbocycles of PAN. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of
this article.)

reorganization of the cleaved PDMS backbone leads to the emergence of
cyclosiloxane oligomers formed from intramolecular, cyclic, and four-
center transition-states. Following the departure of the methyl group
and further silicon diffusion, the formation of –Si–N– bond arising
from the combination of cyclosiloxane oligomers and –CN end group of
PAN is observed. At temperatures beyond 1200 K, continued scission of
the PDMS backbone is observed. Main products formed are methane
molecules resulting from the CH3 combination with H, and “cage-like
structure silanol” (Si–OH)n groups, and smaller molecules including
shorter Si–O, Si–C, C–Si–O bonds, various C1(CH2), C2(C2H4, C2H3
radical) hydrocarbons and H2/H2O. Fig. 3a shows the structural details
of (Si–OH)n groups, including the single silanol (left), reunited silanol
(right), and structures where –OH can be substituted by –CN (center).
It is observed that the formation of Si–O bond also involves the
recombination between different PDMS chains. And a low proportion of
Si–C bond is formed by the rearrangement of free Si atoms/short Si
chains and dissociated –CH3. In the temperature range of 1200 K to
2800 K, the final configuration of the PAN is enriched in Si impurities,
including Si–C bond, free Si atoms and Si–O bond, as shown in Fig. 3b-
c. Si enrichment severely damages the mechanical properties of PAN,
which is attributed to the increased proportion of long chains and non-
six-membered heterocycles (Fig. 3b-c). The mechanical properties of

Fig. 4. (a-b) Snapshots of Si-limited carbon rearrangement at 2800 K, including Si-(OH)n and silicon-containing heterocyclic structures. Color code: Carbon-gray,
Nitrogen-yellow, Silicon-orange, Oxygen-red, Hydrogen-blue, 5-, 6-, and 7-membered carbon rings around Si are denoted as crimson. (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this article.)

4
Y. Ma et al. Computational Materials Science 220 (2023) 112029

Fig. 5. Evolution of O functional groups, including terminal esters and pyridone. (a-b) The conversion of the esters to pentanol. (c-d) The first case, and (e) the
second case of intramolecular evolution: amyl alcohol induces ring/chain-opening of intramolecular adjacent and sub-adjacent pyridine, where (d) further explains
the N transfer in the activated carbon chain. (f-j) Intermolecular evolution between the cyano and the cyclopentanol. Color code: from (a) to (j), the O atom of the
terminal ester involved in the reaction-blue, and the O atom of the pyridine-pink, the evolution of sub-adjacent pyridine-purple, other elements-black. (For inter­
pretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

non-six-membered heterocycles are observed to be lower than the six-
membered rings. Herein, three pathways are proposed to describe the
increase in the non-six-membered ring structures: (i) The first pathway
arises from the reaction of the Si–O, Si–C bonds with pyridine N, cyano
N, –OH or –C– – O– of the oxidized PAN to form the long chains, as
illustrated in Fig. 3b (left); subsequently, these chain structures are
distorted due to the Si intervention, which is no longer capable of
forming rings. Additionally, the N, O atoms permanently lose their
ability to induce the formation of trapezoidal structures and reorganize
carbocycles during carbonization. (ii) The second reaction leads to the
formation of the non-hexacyclic structures between the free Si atom, the
Si–O, Si–C bonds and the –C– – N– structures of PAN. For instance,
–C–Si–N– tricyclic, –Si–ONO– and –Si–NCN-tetracyclic and
larger rings (Fig. 3b-c), yield a significant decrease in the mechanical
behavior of the final CFs. (iii) The third pathway is the formation of
terminal silanols, which originates from the capture of –H by Si–O
bonds of the above chain and ring structures (Fig. 3c-right). Fig. 4a-b
show the phenomenological snapshots of the described Si-confined ring
recombination. Si-induced delayed N release at 2100–2800 K is detailed
in the section of “3.1.3 N element evolution”. Fig. 3d summarizes the
specific pathways from PDMS to the formation of complex heterocycles,
where the PDMS preferentially pyrolyzes into Si–C(O) radicals and
reacts with the –CN radicals in PAN (the dangling –CN and a small
proportion of pyridine) to obtain –CSiN– three-membered heterocy­
cles. These structures further proceed to recombine from PDMS/PAN
structures to form Si-NCN-four-membered or larger heterocycles. It can
be concluded from these results that the silica impurities is composed of
inorganic SixNy, SixO(H)y and SixNyOz, which is far richer than
previously reported experimental data [29].
3.1.2. O element evolution
As shown in Fig. 1a, two types of oxygen-containing functional
groups are contained in the pyridone or hydroxypyridine, and ester
(from the ester comonomer) structure. From the details of the molecular
trajectories, it can be seen that different oxygen functional groups have
different evolutionary paths and roles.
According to the results of the simulations, the evolution of the
terminal esters of the PAN structure are classified into two categories,
namely, intramolecular and intermolecular mechanisms. In the first case
of the intramolecular evolution, ring-opening conversion of the pyridine
makes the PAN transform into a chain structure, as shown in Fig. 5c-d. In
this case, the –C– – O structure of the terminal esters collides to form a
–OH group at 1300–1500 K, resulting from the combination of H
radical species (Fig. 5a-b). The conversion of the esters to pentanol
(green area—oxygen atoms are denoted as blue) is observed to arise
from the departure of H2O/–OH, which is due to its lower thermal
ability. Next, this pentanol induces the conversion of the adjacent pyr­
idone structure to pyrrolidone, followed by the opening of the next
adjacent pyridine N ring (Fig. 5c and Fig. 6a). Finally, the formation of
the PAN carbon chains occurs, as the N species successively transfer to
the end of the PAN chain and are eliminated by N2, as shown in Fig. 5d.
In the second case of the intramolecular evolution, the pentanol can
directly induce the ring-opening of the CN-bonds of two adjacent
pyridine-like 6-membered rings into long chains on the same molecule
at 2000 K, as shown in Fig. 5e and Fig. 6b. These long carbon chains
involve the carbon rearrangement at higher temperatures, which

Fig. 6. (a), (b) and (c) correspond to the snapshots of the molecules shown in (c), (e) and (j) in Fig. 5, respectively. Color code: from (a) to (c), background carbon-
gray, Nitrogen-yellow, Oxygen-red, Hydrogen-blue. C atoms in different PAN chains—other colors. Different chains are marked with a specific color to distinguish.
(For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

5
Y. Ma et al.
Fig. 7. (a) The gas molecule release as a function of time during heating (1.8 ns) and carbonization (1 ns), where the slope reflects the release rate. Snapshots of the
morphology of π-conjugated N-containing graphite structures from (b) the A region and (c) the B region. Color code: from (b) to (c), Carbon-gray, Nitrogen-yellow,
Oxygen-red, Hydrogen-blue. (For interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)
generate the macrocycles and longer carbon chains. These features are
identified as amorphous regions of the fiber. It should be noted that both
cases of the intramolecular reactions temporarily decrease the content of
trapezoids. However, the structure of the formed long carbon chain
participates in carbon rearrangement earlier than the trapezoidal
structure. It can be summarized that a single factor related to the ester-
induced increase in the chain ratio alone does not necessarily lead to a
decrease in the mechanical properties of the fiber. In the intermolecular
mechanism, a new conjugated π plane between the cyano and the
cyclopentanol is formed, as shown in Fig. 5f-j. The conjugation process
of the three fused terminal ring, with one ring being a 7-membered and
the other two being 5-membered, is shown in Fig. 5j and Fig. 6c. These
results suggest that intermolecular evolution is a favorable case, which
results in an increase in the number of five, six and seven-membered
rings, and is conducive to the reconstruction of trapezoidal structures.
To the best of our knowledge, such a feature has not been reported
before.
The oxygen evolution of pyridine or pyridone tautomers can be
traced as follows: firstly, the O-containing groups serve as initiators for
the carbonization, which is in good agreement with the previous reports
[15,30]; secondly, the intermolecular –C– – N– bonds of different PAN
chains occur at 950 K due to the removal of –OH on pyridine, when two
adjacent PAN approach each other. In subsequent steps, the H2O for­
mation occurs via the combination of –OH and –H species, which can
promote the release of nearby –H radicals to obtain the initial nitrogen-
containing graphite clusters at 1300 K. This temperature is 300 K lower
than the temperature at which only H2 is removed to form the nitrogen-
containing graphitic structures. Furthermore, the formation of H2O has a
higher and more concentrated release rate than that of H2, as shown in
Fig. 7a. Then the larger π-conjugated N-containing graphite structures
occur at 1700–2300 K due to the dehydration and dehydro poly­
condensation, as shown in Fig. 7b-c.
It is also observed that the chain length distribution of PAN has a
significant effect on the release rate of H2O/H2 molecules and the size of
the merged graphite plane, as shown in Fig. 7b-c. According to the
synthetically divided chain distribution interval in Fig. 1b, the A region
(PAN chain ratio-40 %L6, 40 %L10 and 20 %L16) comprises of x-axis
6
Computational Materials Science 220 (2023) 112029
values in the range of about 0–45 Å, the B region (25 %L6, 25 %L10, 50 %
L16) comprises of the range of about 45–85 Å, and the C region (62.5 %
L6, 37.5 %L10) comprises of the range of about 85–110 Å. Among these
regions, the removal temperature of H2O/H2, ranked from lowest to
highest, is given by A region ≈ B region < C region. This is because, at
the locally low-density C region, which is mainly composed of the L6 and
L10 short chains, the high flexibility of the short chains is not conducive
to the collision of –C– – N– bonds and further formation of new
–C– – C– bonds in PAN. Thus the formation of N2 occurs before H2O/H2
formation, which is consistent with the report of Saha et al. [12].
However, premature N2 elimination is unfavorable for the construction
of large-scale N-containing graphite structures.
From the trajectories, it can be observed that the size of the π con­
jugated plane in the regions is given by A region > B region ≫ C region.
It can be speculated that the polymerization degree of PAN and the chain
length distribution affect the fiber toughness and modulus. In the A re­
gion, –OH/–H structures on the high proportion of short and medium
chains, can be twisted and easily docked on the –C– – N/C– bonds of a
low proportion of long chains. This results in the formation of large-scale
monolayer N-containing graphitic structures with a dimension of about
37.60 × 26.60 Å, as shown in Fig. 7b. In the B region, the presence of a
high proportion of long chains is more likely to form a small-sized ABA
stack structure (Fig. 7c) due to the difficulty involved in torsion (about
32.04 × 9.32 Å). Except for the crystalline region, the rest of the space in
the region is occupied by the amorphous structure. The composition
ratio of crystalline structure and amorphous structure is an important
parameter that affects fiber performance.
3.1.3. N Element evolution
As shown in Fig. 1a, the nitrogen-containing functional groups
include the chain-end group –CN, hydrogenated and unhydrogenated
amino groups. Among them, two hydrogenated amino groups in the L16
PAN chains are adjacent to the end cyano groups. Most studies have
focused on unhydrogenated amino groups, while studies relating to the
other two have been rarely reported.
The initial carbonized structure is characterized by the formation of
large-scale N-containing trapezoidal PAN, which arises from the
Y. Ma et al. Computational Materials Science 220 (2023) 112029

Fig. 8. (a-c) Mechanisms of gas molecules released by terminal cyano and hydrogenated-CN groups. (d1, e1) Conventional and (d2, e2) Si-intervened reaction
mechanisms for (d) intramolecular and (e) intermolecular removal of N2 from unhydrogenated-CN groups. Color code: from (a) to (e), terminal cyano group-green,
hydrogenated-CN-blue, unhydrogenated–CN-red, the foreign introduced elements Si/Si–OH, or other chains-pink, other elements-black. (For interpretation of the
references to color in this figure legend, the reader is referred to the web version of this article.)

removal of H2O/H2 and formation of new –C– – C–/–C– – N– bond at
2700 K, as shown in Fig. 7b-c. In Fig. 7a, the initial carbonization line
(the left vertical brown line), can be identified from the pronounced
phase distinction line in the gas release plots. With continuous annealing
at a higher temperature of 2800 K, the N-containing gases are explo­
sively released in the form of N2 and NH3, as shown in Fig. 7a (the right
vertical brown line). Other types of gases, such as HCN, NH2, HNO, CNO,
etc. are not accounted for.
A detailed analysis of the reaction pathway shows that the release of
N-containing functional groups occurs in the following sequence: chain-
end group –CN > hydrogenated-CN > unhydrogenated-CN, as shown in
Fig. 8. The chain-end cyano structure pyrolyzes to the cyano, carbon-
chain, and ladder PAN radical species at about 1300 K, as shown in
Fig. 8a-b. Next, HCN is eliminated when the cyano radical species
encounter the H. The carbon chains can directly participate in the sub­
sequent carbonization after further cracking (Fig. 8b). Besides, the
hydrogenated-CN radicals are formed at 1750 K due to the ring-opening
evolution caused by the radical reaction between the A site and other
chains (Fig. 8c). In this case, two adjacent –C– – N– bonds on the same
molecules are broken and N2 is eliminated, as also shown in Fig. 8c. The
N2 removal temperature in this reaction pathway is much lower than the
reaction temperature between the unhydrogenated-CN bonds. It is hy­
pothesized that the hydrogenated-CN and the chain end groups syner­
gistically affect the low-temperature release of N species. Studies have
shown that N2 elimination density of the hydrogenated-CN is higher
than that of unhydrogenated-CN in other PAN structure types [30].
In the evolution of unhydrogenated-CN, conventional intramolecular
and intermolecular N2 molecules form after 2700 K (Fig. 8d1 and e1), in
conformity with the literature [12]. However, the intervention of Si
impurity delays the conventional N2 elimination, which is not conducive
to subsequent carbonization. Simulation results suggest two detrimental
mechanisms. In the first mechanism, the cross-linking between the
–Si–O–/–Si–C– bonds and the N atoms in adjacent pyridine six-
membered rings occurs (Fig. 8d). –Si–N– bonds are not eliminated
in the mechanism. However, Si with another dangling bond reacts with
the nearby –CN bonds on the same molecules, resulting in the forma­
tion of an oversized heterocycle or chain structures, as shown in
Fig. 8d2. In the second mechanism, formation of –Si–N– bonds be­
tween two different molecules results in a stable “–N–Si–N bridge”
structure (Fig. 8e). Due to the increased –CN–CN– bond distance in
this structure, the intermolecular N2 elimination is hindered in these
molecules, as shown in Fig. 8e2.
After the gas molecules are released, the residues in the system are
mainly carbon-based. The sp-type alkyne C chains can self-assemble into
stable ring clusters, mainly composed of 5-, 6- and 7-membered carbon
rings, which gradually increase with carbonization time, as shown in
Fig. 9a. A detailed study of the simulated trajectories aids in under­
standing the crucial role of the N atoms in carbonation recombination. It
is observed that not all of the N atoms are immediately released via the
formation of N2 and NH3 gases. Some N atoms are constantly transferred
and can hop on the reactive carbon chains, and then participate in the
conformation of new super-large rings or cleavage. Such mechanisms
are relatively rare and have only been reported by Mao et al. [15]. The
carbon clusters production pathway is shown in Fig. 9b-i, each of which
is extracted from a single MD trajectory.
For the large-size trapezoidal PAN structures arising from the A and B
regions, opening of the rings occurs for –CN– groups of pyridine rings,
which transforms them into an active long-carbon chain at 2000 ps, as
shown in Fig. 9b. At 2063 ps, the additional nitrogen-containing carbon
chain is inserted into the existing long-carbon chain with the N as the

7
Y. Ma et al. Computational Materials Science 220 (2023) 112029

Fig. 9. (a) Evolution of 5-, 6- and 7-membered carbon rings during carbonization (1 ns). The carbon rearrangements of (b-e) the PAN ladder structure and (f-i) the
single chain without intervening PAN trapezoidal structure. Color code: background carbon-gray, background nitrogen-yellow, background other elements-white;
highlight elements of the PAN structure: Carbon-dark green, Nitrogen-pink; highlight elements of the single chain: Carbon-light green, Nitrogen-orange. (For
interpretation of the references to color in this figure legend, the reader is referred to the web version of this article.)

Table 1 Table 2
Summary of the evolution of N, Si and O elements in the fiber structure. Structural parameters of the constructed fiber models.
elements Surface Functional groups Embedded into the carbon rings Microstructure Density Crystallite d002 6-membered Porosity
(g cm− 3) size (nm) (nm) ring (%) (%)
N –C–N– or –C– –N– (on the –C– –N– in 5-, 6-, 7-membered
chain); rings 1.70 1.92 3.45 91.08 % 9.52 %
–C–N–Si(OH)n n = 1,2,3 Hybridization (%) HOF
(terminal structure)
sp sp2 sp3 Initial Final
0.82 93.13 6.04 − 0.47 − 0.38
Si –C–Si– (on the chain); –C–N–Si– in odd rings
–C–N–Si–(OH)n n = 1,2,3 (mostly);
(terminal structure) –C–N–Si–O– in four-
membered rings the rings, as listed in Table 1. The mechanical properties of fibers
–C–O–C– in three-membered modified with the hetero-elements embedded in the ring are better than
O rings; –C–O–C– in six-membered fibers with surface functional group modification.
–C–OH; no ester group; rings (few) The trajectory trait did not search for surface functional groups that
–Si(OH)n n = 1,2,3 (terminal
structure)
were esters, which may be attributed to the relatively small size of the
computational system in our simulations. However, experimental X-ray
photoelectron spectroscopy (XPS) results for O functional groups on
insertion point, as shown in Fig. 9c. Then at 2125 ps, the new long- desized fibers typically show relatively low ester peaks [31]. Further
carbon chain captures the additional carbon atoms from the surround­ investigation is needed to explain this discrepancy. From the statistical
ings and melts into a 9-membered carbon ring, as shown in Fig. 9d. analysis of Fig. 1c, the number of non-carbon elements embedded within
Subsequently, this 9-membered carbon ring transforms into two smaller the rings is as follows: about 20 % of N and 1 % of O elements are
rings with 5- and 7-membered rings, as shown in Fig. 9e. For the PAN detected in the 5-, 6- and 7-membered rings, and about 15 % of the Si
chain structures from the C region, the chain evolves into 5-membered atoms are detected in the odd-numbered rings through the formation of
rings and shorter carbon chains due to the removal of conventional the –N–Si– structure.
intramolecular N2, as shown in Fig. 9f-h. Irrespective of whether these 5-
,6- and 7-membered carbon rings are from the trapezoidal PAN or PAN 3.2. Analysis of the effect of elemental structure on mechanical properties
chain, they can act as nucleating agents for carbon plane growth. As
shown in Fig. 9i, additional carbon atoms are assembled alongside the The structural parameters of the constructed CFs are listed in Table 2.
existing 5-,6- and 7-membered carbon rings to form larger ring clusters. A detailed inspection of XRD pattern reveals a sharp d002 peak near 2θ =
28◦ and two broad peaks near 2θ = 45◦ and 70◦ . The interlayer-spacing
3.1.4. Non-carbon functional group structures is determined to be 3.45 nm, and crystallite sizes of 1.92 nm in graphite
The evolution of N, Si and O elements in the PAN/PDMS system is is calculated from the Scherrer formula, as shown in Fig. 10a. The CF
subdivided into two structures, namely, one where the elements form model also has a high degree of graphitization, which is reflected by the
surface functional groups and the other where they are embedded within low HOF value (-0.38), the high proportion of sp2 hybridization (93.13

8
Y. Ma et al. Computational Materials Science 220 (2023) 112029

Fig. 10. (a) The XRD and (b) the pore parameters for constructing CFs models.

Fig. 11. Stress–strain curves of fibers modified with different contents of (a) N, (b) Si, and (c) O elements. (d) The local stress distribution map in 0.003Si-
based fibers.

of the elongated pores arranged along the X-axis is in the range of

Table 3 0.4–5.0 nm. These parameters are consistent with experimental results
Mechanical properties of fibers modified with different contents of N, Si, O
involving high-performance fiber indicators [4]. In summary, the con­
elements.
structed large-scale fiber model is reliable and can be used to analyze the
Microstructure Strength (GPa) Young’s Modulus (GPa) Strain (%) mechanical properties of hetero-element modified fibers.
original 22.3 330.9 6.7 The stress–strain curves and strength-modulus-strain properties of
0.01 N-based 24.1 258.4 9.3 hetero-element modified CFs are summarized in Fig. 11a-c and Table 3,
0.03 N-based 23.0 265.5 8.6
respectively. Notably, even if a single factor is controlled, there is no
0.05 N-based 20.6 259.1 7.9
0.08 N-based 21.8 251.6 8.6 perfectly linear relationship between elemental content and mechanical
0.003Si-based 19.4 276.8 7.0 properties. When N contents are increased from 1.0 to 8.0 wt%, the
0.007Si-based 21.0 277.9 7.6 nitrogen-modified fibers exhibit a 19.7–24.0 % decrease in Young’s
0.015Si-based 20.7 273.3 7.6 modulus and a 17.9–38.8 % increase in elongation, as compared with
0.01O-based 22.1 252.2 8.8
0.03O-based 22.2 234.6 9.4
the pristine CFs. Interestingly, 1.0–3.0 wt% N-modified fibers show a
3.1–8.1 % increase in tensile strength and a 28–30 % increase in elon­
gation, which can be considered as the optimum concentration range for
%) and 6-membered rings (91.08 %). Additionally, the pore morphology the preparation of high-performance fibers. In contrast, Si modification
analysis in Fig. 2c shows that most of the pores have elongated profiles. demonstrates an unfavorable response to mechanical properties.
As shown in Fig. 10b, the porosity is found to be 9.52 %, and the length Increasing Si content from 0.3 to 1.5 wt%, results in a Young’s modulus

9
Y. Ma et al.
and elongation of about 275.0 GPa and 7.0 %, respectively. However,
decrease in tensile strength of CFs is about 5.8 %-13.0 %, which is the
largest reduction among all the modified elements. The stress distribu­
tion diagram of the 0.003Si-based fibers is extracted to probe the
possible causes for this reduction, as shown in Fig. 11d. It can be
ascertained that the tricyclic, tetracyclic and macrocyclic rings are more
prone to stress concentration compared to the 5-, 6-, and 7-membered
carbon rings. The presence of the odd and four-membered rings
arising from the –C–N–Si–/–C–N–Si–O– bonds, will undoubt­
edly aggravate the stress concentration in these rings of Si-modified CFs.
Furthermore, the 0.03O-based fibers show the lowest Young’s modulus
of 234.6 GPa among the modified fibers and the highest elongation of
9.4 %. It can be seen that the tensile strength and elongation obtained
though simulations are higher than the reported experimental data. This
is attributed to the fact that the large pores (perpendicular to the fiber
axis) in the experimental samples act as stress concentration points,
which results in brittle fracture at much lower stress and strain levels.
4. Conclusion
ReaxFF simulations utilized to comprehensively study the evolution
of non-carbon elements during the carbonization of CFs and their effects
on mechanical properties. The findings provide a fundamental analyt­
ical framework and a guiding direction for testing and validating
elemental evolution in order to prepare high-performance fibers. The
main conclusions are as follows:
(1) The introduction of Si leads to the formation of the –C–N–Si–
chains and –OH residues, which seriously decreases the me­
chanical properties of fibers, especially the tensile strength, even
at low content addition of embedded carbon rings.
(2) The oxygen-containing groups of the terminal ester can increase
the content of adjacent chain structures that preferentially
participate in carbonization. Compared to the –H, the O groups
of hydroxypyridine can reduce the initial carbonization temper­
ature of the PAN structure by about 300 K. After carbonization,
more than 95 % of the O atoms are involved in the formation of
surface groups, such as –C/Si–OH and ethers. The O groups
embedded into the carbocycles have a detrimental effect on
Young’s modulus response of CFs.
(3) The release temperature of the N atoms ranked from lowest to
highest follows this pattern: chain-end group-CN > hydrogenat­
ed-CN > unhydrogenated-CN. The N element plays a critical role
in carbon reorganization during the carbonization, where it is
continuously transferred on the activated carbon chains to
participate in the formation of new supercycles. Embedding
1.0–3.0 wt% N into carbon rings is beneficial, as it imparts the
CFs with high tensile strength and large elongation.
Data availability
Data related to this article is available from the corresponding author
upon reasonable request.
CRediT authorship contribution statement
Yuanyuan Ma: Conceptualization, Methodology, Formal analysis,
Investigation, Data curation, Visualization, Writing – original draft,
Funding acquisition. Jiangtao Wang: Software, Validation, Formal
analysis. Kuan Lu: Data curation, Writing – review & editing. Yang
Xiang: Visualization, Writing – original draft. Yaqing Liu: Project
administration, Funding acquisition.
Declaration of Competing Interest
The authors declare that they have no known competing financial
10
Computational Materials Science 220 (2023) 112029
interests or personal relationships that could have appeared to influence
the work reported in this paper.
Data availability
Data will be made available on request.
Acknowledgements
This work is supported by the Shanxi Provincial Key Natural Science
Foundation (No.201901D111006(ZD)) and Shanxi Provincial Key
Research and Development Project (No.202102040201010).
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