Accepted Manuscript

On the morphology and structure formation of carbon fibers from polymer pre-
cursor systems

Muhannad Al Aiti, Dieter Jehnichen, Dieter Fischer, Harald Brünig, Gert

Heinrich

PII: S0079-6425(18)30072-0
DOI: https://doi.org/10.1016/j.pmatsci.2018.07.004
Reference: JPMS 526

To appear in: Progress in Materials Science

Received Date: 30 October 2017

Revised Date: 29 June 2018
Accepted Date: 5 July 2018

Please cite this article as: Al Aiti, M., Jehnichen, D., Fischer, D., Brünig, H., Heinrich, G., On the morphology and
structure formation of carbon fibers from polymer precursor systems, Progress in Materials Science (2018), doi:
https://doi.org/10.1016/j.pmatsci.2018.07.004

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On the morphology and structure formation of carbon fibers from polymer
precursor systems

Muhannad Al Aiti1,2,*, Dieter Jehnichen1, Dieter Fischer1, Harald Brünig1, Gert

Heinrich1,3

1
Leibniz-Institut für Polymerforschung Dresden e.V., D-01069 Dresden
2
Technische Universität Dresden, Institut für Leichtbau und Kunststofftechnik, D-
01062 Dresden
3
Technische Universität Dresden, Institut für Textilmaschinen und Textile
Hochleistungswerkstofftechnik, D-01062 Dresden
*corresponding author; E-Mail: aiti@ipfdd.de

This review paper summarizes and critically discusses the morphology and structure
formation of carbon fibers (CFs) from polymer precursor systems. Throughout this
review, we focus on the key mutual interactions between the polymeric precursor
systems, their physically determined processability into filaments, the thermally
initiated crystal conversion mechanisms, as well as the morphological and physical
properties of the resulting CFs and graphite fibers (GFs). Understanding the behavior of
crystal conversion mechanisms from a polymeric semi-crystalline structure into a
turbostratic, glass-like or even a graphite-like carbonaceous crystalline structure is
essential to carbon and graphite fiber formation. The nature of the crystal conversion
and thermal processing largely determine the recovery degree and behavior of the
carbonaceous crystal orientation. Over the last three decades, CFs and GFs have earned
a significant reputation as lightweight fibrous reinforcement materials, and considerable
advances have been achieved in understanding the structure of CFs and GFs and in
tailoring their performance towards specific applications. The utilization of CFs and
GFs in different thermoplastics and thermosets, as well as in concrete as reinforcements,
is well known thanks to the abundant number of reports and reviews available.
Nevertheless, large-scale utilization of CFs in high-technology sectors, such as the
aerospace industry, is mainly driven by the required performance of the CFs. For
civilian applications such as general engineering and the automotive industry, however,
the large-scale production of CFs is immensely limited by production costs. Numerous

1
reports and reviews are available in the field of CFs and its precursors. Therefore, we
focus on reviewing the less-discussed structure–property relationship and the influence
of the different manufacturing processes on this relationship. Throughout this review,
we identify areas that require future research and development regarding the
morphology and structure formation of CFs from emerging precursor systems, e.g.,
lignin.

Keywords:

carbon fibers, graphite fibers, emerging precursors, lignin, thermally induced crystal
conversion, void formation, turbostratic, glass-like, graphitic, orientation degree,
orientation recovery mechanisms, carbon fiber defects, lattice disorder

Abbreviations:

AA, acrylamide; ALS, alkali softwood; AGU, anhydroglucose unit; acrylamide; AP,
anthracene-derived mesophase pitch; APL, annual-plant lignin; AS, acetylated softwood
lignin; CF, carbon fibers; CL, percynnamoylated lignin; CryL, crystal length; CNT,
carbon nanotube; CP, cellulosic precursors; CP/MAS, cross-polarized magic angle
spinning ; CTE, coefficient of thermal expansion; CW, crystal width; D, dry-spinning;
Df, degree of fibrillation; DL, domain length; DMAc, dimethylacetamide, DMF,
dimethylformamide; dMNP, dimethylnaphthalene-derived mesophase pitch; DMSO;
dimethyl sulfoxide; DP, average degree of polymerization; DR, draw ratio; DSC,
differential scanning calorimetry; DTA, differential thermal analysis; DTG, derivative
thermogravimetric; E, activation energy; EB, elongation at break; EGMA, ethylene
glycol dimethacrylate; EOC, degree of cyclization extent; FTIR, Fourier transform
infrared spectroscopy; FWHM, full-width at half-maximum; G, gel-spinning; GC–MS,
gas chromatography–mass spectrometry; GF, graphite fibers; H, hardwood lignin;
HF/BF3, hydrogen fluoride/boron trifluoride; HM, high modulus; IM-SHT, intermediate
modulus–super high tenacity; K, thermal conductivity; Li, lignin; LM, low modulus; M,
melt-spinning; MA, methyl acrylate; MAA, methacrylic acid; MCMB, mesocarbon
microbeads; MMA, methyl methacrylate; MNP, methylnaphthalene-derived mesophase
pitch; MPP, mesophase pitch precursors; MS, methoxybenzoyl-softwood lignin; NP,

2
naphthalene-derived mesophase pitch; PAN, polyacrylonitrile; PD, packing density; PE,
polyethylene; PET, poly(ethylene terephthalate); PP, polypropylene; -q, orientation
parameter; QI, quinoline insoluble ; QS, quinoline soluble; S, softwood lignin; SEM,
scanning electron microscope; SM_HT, standard modulus–high tenacity; sp², sp²
hybridization of the carbon atoms; sp³, sp³ hybridization of the carbon atoms; SS,
sodium styrene sulfonate; TCP, thermo-chemical-based plasma; TEM, transmission
electron microscope; TGA, thermogravimetric analysis; TM, tensile modulus; TS,
tensile strength; UHM, ultra-high modulus; V, vanillic acid; VA, vinyl acetate; VC,
vinyl chloride; V-PET, vanillic-acid-based polyester; W, wet-spinning; WAXS, wide-
angle X-ray scattering; SAXS, small-angle X-ray scattering, XCr, crystallinity index;
XRD, X-ray diffraction.

3
Contents
1. Introduction ..................................................................................................................... 5
1.1. Material properties of CFs .............................................................................................. 5
1.2. Application aspects of CFs ............................................................................................. 7
1.3. Scope of the present paper ............................................................................................ 11
2. Polymeric precursors for CFs and GFs.......................................................................... 13
2.1. Cellulosic precursors ..................................................................................................... 13
2.1.1. Crystal structures and the fibrillation of cellulose polymorphs .................................... 13
2.1.2. Thermal pyrolysis behavior of cellulose crystals and its mechanisms of
conversion into graphite-like crystals ....................................................................................... 17
2.2. Polyacrylonitrile (PAN) ................................................................................................. 26
2.2.1. Polymerization and possible chemical structure ........................................................... 27
2.2.2. Tacticity and crystal structure ....................................................................................... 28
2.2.3. Thermal behavior of PAN and its conversion mechanisms into the carbonaceous
turbostratic crystal structure ..................................................................................................... 36
2.3. Mesophase-pitch-based precursors (MPPs)................................................................... 45
2.3.1. Formation, fiber properties, and the general mesoscopic structure .............................. 46
2.3.2. Thermal behavior and the process-determined structural changes ............................... 53
2.3.3. Crystal conversion mechanisms and the morphology formation.................................. 54
2.4. Lignin (LI) ..................................................................................................................... 59
2.4.1. General aspects ............................................................................................................. 59
2.4.2. Thermal behavior and the heat-treatment-induced carbonaceous crystal structure
formation .................................................................................................................................. 61
2.4.3. Lignin as a precursor for CFs ....................................................................................... 64
3. Summary, future perspectives, and avenues for further research .................................. 72
3.1. Summary ....................................................................................................................... 72
3.2. Future perspectives ....................................................................................................... 74
3.3. Necessary areas for further research ............................................................................. 75

4
1. Introduction
CFs have been known since 1850. Sir Joseph Wilson Swan demonstrated a device for
manufacturing carbon filaments under a partial vacuum based on cellulose nitrate
filaments manufactured by the Chardonnet method, and he later obtained a US patent in
1885 [1]. Thomas Edison developed ―carbon filaments‖ by dissolving commercial
cotton or other fibrous vegetable substances in a solution of zinc chloride, followed by
extruding the resulting solution through a die [2]. The resulting regenerated cellulosic
filament was coagulated, dried, and carbonized by heating it out of contact with air.
Edison used the charred threads as an illumination source in his 1880 patented
incandescent lamp. However, CFs were soon forgotten with the development of
tungsten. CFs appeared again in the 1950s as a construction material for various air and
aviation applications. This introduction is structured as follows: First, we draw attention
to the material properties of CFs. Second, we give a brief overview of their application
aspects. Finally, we formulate a complex set of questions towards understanding the
nature of the crystallite formation of CFs from different polymeric precursor systems.

1.1. Material properties of CFs

CFs and GFs are generic terms referring to a broad category of fibrous carbon materials
with carbon contents of at least 92 wt% and up to 100 wt% [3]. The term ―GFs‖ is more
or less a misnomer [3-4]. It is used to refer to ultra-high-modulus CFs that possess a
highly oriented graphite-like 3D crystal structure along the fiber axis. The sp³-/sp²-
hybridized carbon atoms are covalently bonded to each other within a single basal layer.
The manner in which the layers stack relative to one another determines the allotropic
crystal form, i.e., glass-like, 2D turbostratic and 3D graphite-like crystal structures,
which should be adequately oriented or aligned parallel to the fiber axis. Beside the
crystallite structures, accessible and inaccessible voids are an unavoidable component of
CFs. Tuning the crystal structure, porosity, and pore geometry of the CFs can impart
them with a wide variety of physical and unique mechanical properties. The crystal
structure predominantly depends on the polymeric precursor system used, the
processing parameters of the fiber formation technique, as well as the thermal
conversion processes. Meanwhile, the formation of voids and their properties depend on
the precursor system, the fiber formation process, and the heat treatment.

5
Various continuous CFs are industrially available with tensile strengths from ~1 to ~7
GPa combined with a low volumetric mass density between 1.76 and 2.22 g·cm-3, high
stiffness in terms of a high tensile modulus of 200-950 GPa and a low elongation at
break of 0.3-2.2 %. Therefore, CFs and GFs withstand high stresses with minimum
deflections and thus are renowned as lightweight reinforcements. These properties are
accessible if a certain basal-plane-based, highly oriented 2D turbostratic crystal
structure or a 3D graphite-like crystal structure can be achieved in the CFs [4]. In
contrast, special types of CFs possess a low elastic modulus (50-150 GPa) and/or low
tensile strength of up to 2 GPa [5]. However, these types of CFs are considered
functional thanks to their special disordered glass-like carbon crystal structure. In
general, these CFs show positive coefficients of thermal expansion (CTEs) and
adequately balanced tensile and compressive strengths combined with a low volumetric
mass density (1.65-1.76 g·cm-3) [5-7]. These special types of carbon fibers are produced
by the Nippon Graphite Fibers Co. Ltd. under the trade name GRANOC XN05, XN10
and XN15. The GRANOC XN05 is produced from isotropic pitch precursor; the other
GRANOC XN10 and GRANOC XN15 are produced with mesophase pitch precursor.
The low temperature in carbonization at 1100°C is the only reason for such properties.
These traits are not observed for CFs based on polyacrylonitrile (PAN), rayon or even
mesophase pitches. Nevertheless, some Japanese patents illustrate the possibility of
producing PAN-based CFs with improved cross-sectional compressive strength via
implementation of ions to de-crystallize the fiber [8], or by configuring the cross-section
of the fiber to increase the geometrical moment of inertia [9].

Fig. 1 summarizes the spectrum of mechanical and physical properties for 100 different
types of commercially available continuous CFs and GFs1. These fibers are produced in
multifilament bundles with numbers of filament ranging between 1,000 and 320,000
filaments. Based on the number of filaments, CFs are classified into low-tow (1,000-
24,000 filaments) and heavy-tow CFs (up to 320,000 filaments). Chopped and ground
forms of CFs and GFs find application in a variety of fields, such as reinforcing cement
mortar and concrete, ceramic compounds [10], carbon–carbon composites for aerospace
applications [11], and electrically conductive fillers [12] have been reported.

1
Around 100 carbon and graphite fiber types from 12 manufacturers were analyzed and represent the
recent range of commercially available CFs. For more details, please refer to supplementary table I.

6
Commercial CFs and GFs can be classified into several different types based on their
tensile elastic moduli and tensile strengths. Table 1 describes the classes of CFs and
GFs, the related ranges of tensile strengths and elastic moduli, as well the polymeric
sources of the corresponding fibers.

Different physical properties of CFs and GFs, such as electrical resistivity (𝜌 = 1.5 up to
25 µΩ∙m) [13-16], conduction-electron magnetic susceptibility [17-19], magneto-
resistance [20], low or even negative CTEs of -1.5 to +3.4 (for disordered low-modulus
CFs) 10-6 K-1) [21], thermal conductivity (K = 5-900 W∙K-1∙m-1) [22-23], exhibit a close
relationship with specific crystal structure and aspect ratio (i.e., the length-to-diameter
ratio) of the fibers. The tensile strengths and tensile moduli of CFs and GFs are
inversely proportional to the diameter of the starting precursor filaments [24-25].
Typical diameters of industrial CFs and GFs range from 5 to 10 µm. In addition to their
unique mechanical and physical properties, CFs have very good chemical resistance
against a wide spectrum of chemicals. However, a severe drawback of CFs and GFs is
their low chemical and thermal stability against strong oxidizing agents (e.g., oxygen)
and intumescing agents (sulfuric acid and nitric acid mixtures) at relatively elevated
temperatures. The presence of oxygen leads to the thermal decomposition of CFs at
high temperatures, thus deteriorating their mechanical properties and changing their
morphology [26-30]. CFs and GFs physicochemically react with different intercalation
agents, which lead to the formation of intercalation compounds (i.e., CFICs and GFICs,
respectively). These agents penetrate the basal layer plans and increase the interlayer
distances of the crystal structure. A large number of acceptor and donor halides are
known to intercalate graphite and thus CFs and GFs as well [31-40]. Intercalation of
CFs and GFs with bromine enhances the Seebeck effect, and the fibers can act as
thermocouples for thermal sensing and structural health monitoring (SHM) in cement
and concrete applications [41-42]. Furthermore, lithium-ion-intercalated CFs and GFs
are promising candidates for rechargeable lithium-ion batteries [43-44].

1.2. Application aspects of CFs

The performance of carbon can be adjusted by tuning the crystallite type, size, disorder,
and orientation. Furthermore, tuning the voids, their accessibility, specific surface area,
and orientation degree provide the fibers with additional unique properties.

7
Activated CFs (ACFs) have been reported in different technical fields as a promising
tunable nano- and micro-porous platform that can selectively absorb various compounds
from liquid and gaseous phases. Mochida et al. reported the potential use of ACFs for
eliminating air pollutants including sulfur oxide (SOx), nitrogen oxide (NOx), ozone-
depleting substances (ODS), and many volatile organic compounds (VOCs). The
achieved desulfurizing ratio of the ACF-based filter was around 95 % [45]. The tailored
pore structure and porosity of ACFs enable their use in the field of the hydrogen storage
[46]. ACFs have also been reported for the preparation of novel green metal-free
catalytic system [47] and for molecular sieve applications with high selectivity [48].
ACFs act as a platform for antiseptic and anti-inflammatory agents such as silver and
can therefore be applied in wound dressing systems [49].

CFs and GFs possess piezoelectric conductivity [50], which enables the real-time, non-
destructive monitoring of fatigue delamination [51-52] and short-term dynamic stresses
(e.g., impact) for SHM [53] and [54]. Although the electrical conductivity of CFs is
lower than that of metals, it is sufficient for conducting high-frequency Foucault
currents (eddy currents), which are induced inductively in the fibers by changing the
magnetic field and its frequency [17]. This significant and very promising characteristic
diamagnetism of CFs and GFs enables non-destructively mapping the permittivity
variations; thus, they can be used to detect defected fiber layers, undulation, and
misalignments in multi-layer carbon-fiber-reinforced composite structures [55-56].

Due to their multi-functionality, CFs and their composites find various applications in
biomedical fields. CFs that were both electrically conductive and stiff were deployed as
ultra-micro electrodes for long-term stable neural recording. These stiff, sharpened
electrodes were easy to implant and were found to provide an excellent sustainable
signal-to-noise ratio [57]. Various unique thermal applications of CFs and GFs and their
thermally stabilized precursors have been reported in different fields. For example,
oxidized or stabilized polyacrylonitrile (ox-PAN) filaments were reported to be flame
retardant with an effective limiting oxygen index (LOI) between 45 and 55 %. The use
of asbestos and asbestos-containing products in thermal insulation and flame retardant
applications is controversial [58]. Ox-PAN possesses a larger fiber diameter (10-20 µm)
and a lower density (1.37-1.45 g∙cm-3) than asbestos (1 µm and 2.5 g∙cm-3, respectively)

8
[59-60]. These materials have long been considered potential candidates for use in heat-
protective clothing [61], fire-blocking fabrics for aircraft seats [62], car disk brakes, and
clutch friction components [63]. Amorphous and thermally less conductive, carbon-
bonded CFs (CBCFs) are effective materials for thermal insulation applications in
vacuum and inert-gas furnaces [64]. Highly thermally conductive GFs, with
conductivities up to 900 W∙K-1∙m-1, show significantly higher thermal conductivities
than copper under ambient conditions, but their density is only one-quarter that of
copper. These kinds of GFs have been successfully used in thermal management
applications as efficient heat transfer elements and radiators for aerospace applications
[65-67].

High-performance intermediate-, high-, and ultra-high-modulus CFs and GFs are in

high demand as lightweight reinforcements for thermoplastics and thermosets. These
composites are considered very promising materials for a wide spectrum of industrial
applications because they combine the traits of anisotropy, high tenacity, and a high
modulus with a very low volumetric mass density. Reported applications of carbon-
fiber-reinforced thermosets in the aviation and aerospace fields include turbine engine
fan blades, floor beams, pylon fairings, landing gear doors, flight control surfaces,
nacelles, cowlings, vertical and horizontal airplane stabilizers, propeller and rotor
blades, acoustic liner panels for engines, engine access doors, thrust reverser buckets,
main and tail rotor blades, and rotor drive shafts for helicopters. An attractive attribute
of graphite-fiber-reinforced thermosets is their superior structural rigidity combined
with negative or near-zero CTEs. Therefore, these types of composites have been
developed for vibration-damping structural elements that maintained the thermal
dimensional stability of the structure in orbit. These dual-use composite materials (e.g.,
GFs/epoxy resin) have been deployed in the antenna booms, backing and mirror support
struts, spars, beam struts and fittings of Hubble space telescopes [68].

In addition to the air and aviation sectors, there is an increasing focus in the European
Union, the USA and Japan on making the electro-automotive sector more eco-friendly
in order to sustainably reduce greenhouse pollutants due to serious concerns about
climate change, including efforts to reduce the weight of new utility and commercial
vehicles. For instance, the European Union CO2-regulation EG Nr. 510/2011 stipulates

9
a CO2 emissions target for new utility and lightweight commercial vehicles of less than
147 g∙km-1 starting in 2020. Under such directives, constructive solutions towards
reducing vehicle weights, in addition to implementing the electric vehicles, should be
developed, which would significantly improve vehicle fuel economy. Efforts to reduce
vehicle weights are a direct reason to choose carbon- and graphite-fiber-reinforced
composites as a structural material in the automotive industry, albeit with some
restrictions regarding damage tolerance and high-volume production technologies.
Although the processing and manufacturing stages of carbon-fiber-reinforced plastics
(CFRPs) releases more CO2 emissions than those of conventional metallic construction
materials, the overall CO2 emissions considering the entire service life of the aircraft or
automotive vehicle fabricated entirely or partially from CFRPs has been estimated to
emit 10-20 % less CO2 than those built with conventional metal materials [69], [70] and
[71]. Moreover, standard and intermediate-modulus carbon-fiber-reinforced
thermoplastics and thermosets can be used in various automotive parts, including key
roof elements, door frames, windshield pillars, steering wheels, transmission tunnels,
brake discs, clutches, tailgates, flooring, and drive shafts. These parts have already been
deployed in high-end and luxury cars. The main issue for the large-scale utilization of
CFs composites in the automotive sector is the cost of carbon fiber production.

For short-time dynamic load scenarios (i.e., impact) CFRP parts should show high
deflection resistance and a high energy of fracture initiation. High-ductility, low-
modulus CFs provide hybrid CFRP with high impact performance and damage
tolerance. For instance, a CFRP with low modulus (tensile modulus of 50 GPa) and
highly ductile CFs in the skin layers (on the compression sides) exhibited a fracture
initiation energy more than twice that of normal CFRPs [7]. These types of composites
have been reported for manufacturing golf club shafts with flexure using conventional
high-strength PAN-based carbon fiber composite to reduce the breakage of the shaft at
the junction between the shaft and the head. Particularly, the largest impact stress is
produced at this junction [72] and in [73].

Although a very wide variety of applications have been reported, current applications of
CFs and GFs still only extend into a small niche because of their high manufacturing
and processing costs. Such niche applications include wind turbine blades for wind-

10
based energy and compressed natural gas (CNG) storage cylinders. Nevertheless, the
economic demand for high-performance CFs and GFs, regardless of the application, is
expected increase overall by 10-19 % per year until 2020 [74].

1.3. Scope of the present paper

CFs and GFs have been discussed in many different review articles [75-80], [81], [82]
and [83]. This paper emphasizes understanding the influence of the polymeric precursor
system, i.e., aerospace-, commodity- and textile-grade PAN, mesophase pitch, and
lignin, on the morphology of the resulting CFs. Additionally, this paper covers the less-
discussed mechanisms underlying the conversion of the polymer crystallite into
turbostratic, glass-like or graphite-like crystal structures and how the orientation of the
original crystals can be recovered through thermal processes. In the case of industrially
manufactured high-performance CFs and GFs, the compositions of the precursor
polymer formulation and the processing parameters, including spinning the polymer
into fibers, stabilization, carbonization, and graphitization, are ideally optimized. In this
paper, we clarify the physically and chemically determined crystal limitations of
converting emerging precursor materials, i.e., lignin and cellulose derivatives, into CFs
with the appropriate crystal type, size, and orientation degree. These new precursors are
physically and chemically different from the "well-established" precursor systems, i.e.,
PAN, isotropic pitch, and mesophase pitch. The nature of technology used to process
these emerging precursors into CFs should be modified and tailored to the physical
limitations of the precursor. Furthermore, we will highlight the less-discussed structure–
property relation for the emerging-precursor-based CFs.

Fig. 2 schematically proposes a network of the complex mutual interactions between

various parameters of the carbon fiber processing stages for conventional precursor
systems. The most important but hidden parameter underlying this complex
manufacturing process is how the initial oriented precursor crystal can be optimally
converted into carbonaceous crystal and how the initial orientation degree can be
recovered or even exceeded. However, the formation mechanisms of glass-like,
turbostratic or the graphite-like crystal structures from precursors ranging from totally
amorphous polymers (i.e., lignin) to highly crystalline bio-polymers (i.e., chitin) have
not been fully investigated. Important challenges for future research include

11
understanding the roles of the hetero-atoms (oxygen and nitrogen) in the polymer
crystal morphologies and their influences on the mechanism of conversion into one of
the aforementioned carbonaceous crystal structures while maintaining or recovering a
high degree of orientation. An additional goal of this paper is to review the unavoidable
thermally induced formation of voids in the fiber structure and how to control this
formation.

Additionally, throughout this article we critically discuss a complex set of questions

towards understanding the following points:

i. High- and ultra-high-modulus CFs with a graphite-like 3D crystal structure

can be fabricated at elevated temperatures by hot stretching of rayon
filaments [84-85], which is a form of regenerated cellulose and belongs to
the category of high-oxygen-content hydrocarbons [86]. Which mechanisms
influence the formation of graphite-like crystals? How can the orientation
degree of the crystals be recovered?
ii. Which key attributes are required to make CFs with reproducible and
sufficient mechanical properties based on emerging precursor systems, i.e.,
non-agricultural and sustainable lignin or naturally abundant chitin?
iii. There are many physically determined limitations in the processing of the
polymeric precursors into CFs, i.e., at level of the fiber formation. How
should the eco-friendly and economical melt-spinning process be modified
in order to overcome the precursor-determined limitations and to reduce
manufacturing costs?

12
2. Polymeric precursors for CFs and GFs
Several types of polymeric precursors with widely varying chemical composition have
been used to develop CFs and GFs at the research scale. The particular chemical
composition of the polymeric precursor system influences its thermal properties in
terms of decomposition, degradation, and stability. It also affects the mechanism of
processing the precursor into filaments and the crystallographic structure of the
resulting fiber, including the crystallite size, crystallinity, and maximum orientation of
the crystals along the fiber axis upon deformation, as well as stresses and the possible
mechanical properties. In the following sections, different precursor systems are
discussed, such as cellulose, PAN, pitch precursors and lignin.

2.1. Cellulosic precursors

Cellulose is the most abundant bio-polymer in the world and has an important, versatile
chemical structure. The linear homo-polymer is composed of repeating β-1,4-glycosidic
linked D-glucopyranose units, which form anhydroglucose units (AGUs). Therefore, it
exhibits polydispersity and linear rigidity, and it highly capable of being chemically
functionalized and forming various rigid polymorphs because its hydroxyl groups are
evenly distributed in the AGUs. Fig. 3 illustrates the molecular structure of cellulose
and its AGU.

2.1.1. Crystal structures and the fibrillation of cellulose polymorphs

To clarify the various crystal modifications of cellulose and to gain more insight into
the chain conformations caused by both intra- and intermolecular hydrogen bonding
behavior, many structural studies have applied synchrotron X-ray and neutron
diffraction, 13C solid-state NMR spectroscopy, infrared spectroscopy, and intra-
crystalline deuteration of cellulose and regenerated cellulose in fibrous forms. The
hydrogen bond network of the cellulose determines the conformation of the cellulose
polymeric chain, including cellulose I (with two different crystal lattice types Iα, Iβ), II,
III, IV and their subtypes cellulose IIII, IIIII, IVI and IVII. Thus, cellulose can form
different crystalline polymorphs, but only if certain conditions are satisfied. Cellulose I
is a naturally occurring polymorph and can be found in native cotton, ramie, sisal, and
different woods. In general, cellulose I forms two allomorphs: cellulose Iα, which

13
crystallizes in a triclinic lattice with one polymer chain in the unit cell, and cellulose Iβ,
which crystallizes in a monoclinic manner with two polymer chains in the crystal unit
cell [87]. Table 2 provides a brief list of the calculated crystallite sizes of different
cellulose polymorphs. Dimorphism occurs when two phases of cellulose I coexist in the
same natural cellulose sample and or even in the same microfibril, which causes a
minimal loss in the overall crystallinity [88]. In cellulose Iβ, the neighboring lattices
gradually shift by about c/4 along the c axis (i.e., along the fiber axis), whereas the
neighboring lattices in cellulose Iα shift in an alternating up and down manner relative to
the c axis. Fig. 4 schematically illustrates the structural differences between the
monoclinic and triclinic forms of native cellulose. These differences are caused by the
different intramolecular hydrogen bonding of the two cellulose I allomorphs, which
exhibit the same intermolecular hydrogen bonding. The most important similarities
between these two crystal phases are that the chains are strictly parallel to the fiber axis,
while the polymer chains are packed in a parallel-up arrangement. Horri et al. claimed
that cellulose Iα is thermodynamically metastable [89]. Therefore, it can be irreversibly
transformed into the more stable allomorph, cellulose Iβ, via solid-state annealing with
high conversion ratios from 77 % to 99 %, depending on the thermal annealing
conditions [90].

As mentioned above, the crystal structure of the cellulose is governed by the inter-
and/or intramolecular hydrogen bonding patterns in the cellulose polymer chains. Table
2 demonstrates the significant differences in the crystal unit cells of common cellulose
polymorphs. We calculated the theoretical volume of one AGU unit for the different
cellulose polymorphs, and cellulose II exhibits the lowest AGU volume of the cellulose
polymorphs except for cellulose Iα. Cellulose I can be converted into cellulose II by the
mercerization process due to intra-crystalline swelling [93]. This process involves
treating the native cellulose I without tension in a concentrated alkali solution, up to 50
wt%, in a temperature range between 20 and 60 °C. Meanwhile, cellulose I can be
regenerated via the rayon process, which involves swelling cotton linters in a caustic
alkali solution, i.e., 17-20 wt% aqueous sodium hydroxide (NaOH) at room
temperature. The converted alkali cellulose must be pressed, shredded into crumbs, and

14
carefully aged via oxidative depolymerization of the cellulose. The oxidative alkaline
scission of cellulose I chains is significantly influenced by the process temperature, the
crystallinity of the input cellulose, and the ripening time. This depolymerization stage
reduces the average molecular weight of the original cellulose [94]. The aged mass is
then treated in carbon disulfide to form cellulose xanthate, which is subsequently
soluble in the alkaline NaOH solution. The concentration of the intermediate cellulose
xanthate in the spinning mass is between 4 and 10 wt%, and the coagulation baths
contain 4-12 wt% of sulfuric acid, 13-25 wt% sodium sulfate and 2-15 wt% zinc sulfate,
which reduces the gel swelling effect during the coagulation stage and increases the
tensile properties of the as-spun filaments [95]. The presence of amine modifiers in the
zinc-containing coagulation baths reduces the unbalanced swelling between the core and
shell of the filaments, thus eliminating the deep and shallow crenulations of the filament
shell [95]. Dissolving the depolymerized cellulose I chains in a polar solution rearranges
the polymer chain, and the conformation of hydroxymethyl groups converts irreversibly
from trans-gauche (tg) into gauche-trans (gt) upon coagulation. Thus, new
intramolecular hydrogen bonds are established [96], and the chains become oriented in
an anti-parallel arrangement in the unit cell after coagulation. Assisted by a molecular
dynamics simulation, Kroon-Batenburg et al. demonstrated that the hydroxymethyl
groups in the regenerated cellulose II preferably exhibit the (gt) conformation [97],
which leads to the antiparallel arrangement of the chains in the crystal cell unit.

Fig. 5 shows projections of the unit cells of cellulose Iβ, II, IIII, and IVI onto the plane
𝑎, 𝑏 and the inter- and intramolecular hydrogen bonding. Cellulose IIII and cellulose IIIII
polymorphs can be developed from cellulose I and cellulose II (i.e., via mercerization or
the rayon process), respectively, via swelling in dry liquid ammonia at -80 °C and the
subsequent decomplexation of ammonia–cellulose I and ammonia–cellulose II by
evaporating the ammonia at -15 °C [108]. Many other specific di- or triamines could
also be used in order to swell and convert cellulose I or II into the polymorph cellulose
III [109]. As shown in Table 2, the crystal structures of cellulose IIII and cellulose IIIII
are monoclinic with one polymer chain per a unit cell. Sarko et al. suggested parallel
and antiparallel arrangements of the polymer chains in cellulose IIII and IIIII,
respectively [102].

15
Hutino et al. reported the existence of a fourth polymorph of cellulose [111]. Two
cellulose IV polymorphs, which are denoted by cellulose IVI and cellulose IVII
depending on the starting material, can be obtained from cellulose III or directly from
cellulose I or cellulose II by thermal conversion in glycerol for 20 min at 260 °C [108,
111]. The unit cell parameters and crystallite sizes of cellulose IVI and IVII are
summarized in Table 2. Interestingly, the unit cell parameters of these two types are
nearly identical to each other, and the small differences in the unit cell parameters (a)
and (b) lie within the experimental error range. The crystal unit cells of these sub-
polymorphs resemble that of cellulose Iβ, with some restrictions regarding the γ angle,
which was found to be 90° by Gardiner et al. [103]. In the case of cellulose IVI, two
polymer chains are packed in the unit cell in parallel, while in cellulose IVII, the
polymer chains are packed in an antiparallel arrangement. Cellulose IV is metastable
and can thus be transformed back into cellulose I or II via acidic treatment [103].

The impact of the crystal structure on the thermal properties is fundamental to further
understanding the thermal conversion of cellulose crystals into high-modulus CFs. Hori
et al. provided clear insights into the thermal expansion behavior of the crystal unit cell
of highly crystalline mercerized cellulose II and its derivative cellulose IIIII by recording
X-ray diffraction (XRD) profiles at temperatures ranging from room temperature to 250
°C with a heating rate of 5 K∙min-1 [112]. They found that the unit cell of cellulose II
expands unevenly perpendicular to the fiber axis along the a (+0.54 %) and b (+3.4 %)
directions and contracts in the longitudinal direction c by 0.09 %. Additionally, the
monoclinic angle, γ, remains almost constant up to 150 °C and increases by about 2° at
250 °C [112]. The authors attributed these changes to the nature of the cellulosic chain,
which consists of strong AGUs reinforced by bifurcated O3···O5/O6 intramolecular
hydrogen bonds [112]. The crystal structure and the packing arrangement of the
polymer chains affect the size of the crystal domains and their arrangement within the
nanocrystalline fibrils. All cellulose polymorphs were found to be semi-crystalline.
Both the fringed-micelle models, as well as the folded chain model, have been used to
describe the parallel/antiparallel chain arrangements and the antiparallel chain packing,
respectively. Okano et al. proposed a model of a native cellulose fiber consisting of
parallel chains positioned in microfibrils with amorphous transition regions. The same
model was applicable to cellulose II [113]. During mercerization or regeneration of

16
cellulose I into cellulose II, the parallel-packed arrays of microfibrils with antiparallel-
arranged chains of cellulose I convert into antiparallel-packed fibrils [113]. Fink et al.
used electron micrographs and X-ray scattering data of different cellulose microfibrils
from different sources to suggest a general fringed-micelle model for the
supramolecular structure of cellulose morphology and aligned crystal domains (see Fig.
6) [114]. The single crystals agglomerate to form the elementary fibril, which is bonded
to the adjacent fibrils by non-crystalline (amorphous) regions. Table 3 shows the
structural data of selected cellulosic polymorphs.

The cellulose I, cellulose II (mercerized), cellulose IIII, cellulose IIIII (based on

mercerized cellulose II) and cellulose IVI and IVII polymorphs have been discussed in
the literature as staple (i.e., discontinuous) fibers, which cannot be stretched in the
subsequent processes and hence are unsuitable for manufacturing continuous CFs [120-
121]. Cuprammonium rayon fibers show a significant amount of amorphous regions
between the elementary fibrils, which can additionally introduce brittle fracture zones
into the resulting CFs. The aforementioned high content of nano- and macro-scale
internal voids results in weak filaments after carbonization, although the dimensions of
the elementary fibrils are much larger than those of rayon (please refer to Table 4). As
shown in Table 3, lyocell exhibits a higher degree of polymerization and higher
crystallinity than rayon. However, it fibrillates in the wet state (with a degree of
fibrillation in the range of 4-6); furthermore, considerably fewer lateral conjunctions
exist between the elementary fibrils or the microfibrils. However, the higher
crystallinity and degree of polymerization could impart some degree of structural order
to the carbonized fibers. Table 4 compares the mechanical properties of CFs based on
carbonized rayon and lyocell fibers. Unfortunately, no data are available for stress-
graphitized lyocell fibers. Therefore, the stress-graphitizing behavior of lyocell fibers is
an urgent area for future research.

17
2.1.2. Thermal pyrolysis behavior of cellulose crystals and its mechanisms of
conversion into graphite-like crystals
Under atmospheric pressure, cellulosic materials thermally decompose, excluding any
solvents present, at onset temperatures between 320 and 350 °C, without the presence of
a melting stage. Fig. 7 illustrates the thermogravimetric analysis (TGA) of cellulose at
atmospheric pressure with helium and nitrogen purges and at different heating rates,
wherein the char residues after pyrolysis under nitrogen or helium are less than 10 wt%.
Madorsky et al. studied the pyrolysis behavior of cellulose I and cellulose II under
vacuum at temperatures up to 390 °C. Conducting the pyrolysis under vacuum prevents
the degradation products from reacting with oxygen (which occurs during pyrolysis in
air), and the volatiles can be quickly removed from the pyrolysis zone, which is more
difficult in the case of pyrolysis under inert gas and atmospheric pressure [122].
Assisted by infrared analysis, Madorsky et al. concluded that the main product of the tar
produced by the pyrolysis of cellulose I and II was levoglucosan. Additionally, it was
reported that the yield of the tar fractions of cellulose I is around 52 wt%. In other
words, approximately one out of every two structural units of cellulose I (cotton)
vaporizes as a levoglucosan molecule. In the case of cellulose II (rayon), the tar yield is
about 30 wt%, which means that approximately one out of every three structural units
converts into levoglucosan [122]. The second highest volatile fraction is water, which is
around 21 % for cellulose I and 29 % for rayon. Theoretically, the amount of volatile
water should be 27 % for cellulose I and 37 % for cellulose II. The obvious differences
between the theoretical and actual values are due to the formation of CO2, CO, and CH4,
as well as H- and O-containing chars [122]. Schwenker et al. investigated the pyrolysis
mechanisms of cellulose I under air in a temperature range between 350 °C and 375 °C
[123]. Levoglucosan was detected to be the main pyrolysis product [124], which
undergoes two further pyrolysis mechanisms. First, it forms low-molecular-weight
volatiles in air, and second, it further polymerizes into aromatic compounds, which form
the final chars. Bacon et al. proposed a simplified ideal pyrolysis mechanism of rayon
(cellulose II), which shifts the residue yield to a maximum of approximately 29.6 wt%
[125].

This pyrolysis mechanism suggests the existence of a pyrolyzed monomer consisting of

four carbon atoms with a molecular weight of 48 g∙mol-1 as a result of the pyrolysis of

18
one glucose unit of cellulose. The glucose unit has a molecular weight of 162 g∙mol-1.
Bacon et al. reported that cellulose II fibers (rayon) with a small diameter between 8 and
15 µm yield 10-21.5 % residues under an ideal pyrolysis schedule including first
heating to 400 °C at a heating rate of 10 K∙min-1 and then up to 900 °C at 50 K∙min-1.
Coarser cellulose II fibers with diameters of 100-500 µm lead to increased residue
yields of up to 29.5 %, which are close to the ideally calculated maximum yield of 29.6
% [125]. In the same study, Bacon et al. observed that the filaments shrank
anisotropically by up to 30 %. In other words, the characteristic length yield of the
resulting fibers after carbonization stage was around 70 %. In summary, an ultimate
residue yield between 10 and 20 % is characteristic of cellulose II and could be further
increased towards the theoretical yield with the appropriate pyrolysis parameters and the
presence of bulky crystals [128]. Considering the aforementioned thermal studies, Tang
et al. suggested, with the assistance of a complementary elemental analysis, a simplified
general carbonization mechanism based on four successive stages for the carbonization
of highly crystalline regenerated cellulose II fibers (Fortisan-36, expired trademark of
Celanese Corporation), viscose rayon, and textile cotton yarns (see Fig. 11) [128].

Pastorova et al. investigated the chemical transformation of cellulose at low-temperature

pyrolysis of microcrystalline cellulose up to 390 °C by following the transformation via
Fourier transform infrared (FTIR) spectroscopy [129]. In the FTIR spectrum (see Fig. 8)
of the char produced by pyrolysis at 250 °C, the decreasing intensity of the O–H
stretching band (3100-3600 cm-1) relative to that of microcrystalline cellulose can be
attributed to dehydration. At 220-250 °C, two new stretching bands appear at wave
numbers of 1620 and 1700 cm-1 (-C=C- and >C=O stretching bands, respectively).
These two bands appear in the cellulose spectrum, although the crystal structure of the
cellulose is preserved [84-85, 125, 128, 130-131]. The bands that develop between 250
and 390 °C at wave numbers between 800 and 1000 cm-1 indicate that some aromatic
structures exhibit out-of-plane bending. Tang et al. plotted the atomic ratio H/C against
O/C (van Krevelen diagram) at different charring temperatures for cellulose triacetate II.
The extent of the decrease in these ratios between 200 and 280 °C was attributed to the
dehydration reaction. Between 280 °C and 400 °C, the decarbonylation and
decarboxylation were assumed to be the predominant reactions during the pyrolysis.

19
The further decrease in the H/C ratio up to temperatures of 600 °C indicated
dehydrogenation, de-ethanation, and de-methanation (Fig. 9).

In their study, Plaisantin et al. used solid-state cross-polarized magic angle spinning
(CP/MAS) 13C NMR to understand the conversion mechanisms of cellulose-II-based
fibers (rayon) into CFs during different pyrolysis stages [132]. The authors proved that
the critical pyrolysis temperature range between 300 and 500 °C is characterized by the
dehydration of the glucopyranose unit, cleavage of the AGU's chair configuration, and
rearrangement to form ketone or ester groups [132]. At higher temperatures, aliphatic
and phenolic carbon signals disappear, while an aromatic carbon signal appears. The
NMR spectrum of the chars produced at 650 °C shows that aromatization is achieved
[132] (see Fig. 10).

To investigate the influence of the pyrolysis mechanism of cellulose II on the structural

properties of the fibers, Bacon et al. investigated the anisotropic shrinkage phenomena
of cellulosic fibers [125]. The pyrolysis mechanisms suggested that two monomers,
each based on four carbon atoms containing residue, result from the pyrolysis of one
unit cell of cellulose II with an antiparallel arrangement. As shown in Table 2, the
length of the cellulose II crystal unit along the vector 𝑐 was detected to be 10.31 Å. If
these two linear monomers can align themselves along the fiber axis of the original
cellulose unit cell, i.e., via stretching during the earlier pyrolysis stages and/or any
further thermal treatment, these two monomers could be expected to further polymerize
into an ideal graphitic unit cell with a characteristic unit cell height of 8.52 Å [133]
(Fig. 12a).

If the monomers could perfectly re-orient to develop a graphitic unit cell, this would
result in an ideal characteristic length yield of (8.52/10.21)100 %=82.6%. This
mechanism was suggested by Bacon et al. and defined as a longitudinal re-
polymerization mechanism [125]. As the orientation of the cellulosic crystals is not
perfect (see Table 3), the experimentally determined length yield should be less than the
theoretical values. Bacon’s pioneering experimental work on this issue found that upon

20
hot stretching of about 150 %, a maximum length yield of 76 % could be achieved,
which is particularly close to the ideal calculated length yield. The second suggested re-
polymerization mechanism is the traverse polymerization of the two adjacent
monomers. This assumption suggests that each monomer reacts in a traverse way with
the adjacent monomer within the single-crystal unit cell. This reaction would form a
polymer chain in the traverse direction of the fibers being pyrolyzed, which could
produce a graphitic unit cell with a length of 0.492 nm [133]. The length yield
according to this assumption is calculated as (4.92/10.31)100%=47.7% (see Fig. 12b).
The discrepancy between the theoretical length yield (47.7 %), determined under the
assumption of traverse re-polymerization of the four carbon residue monomers, and the
experimental length yield of 76 % could be the first criterion that excludes the
possibility of traverse polymerization during the formation of the graphite-like crystal
structure from cellulose. Notably, the calculated yield lengths of carbonized cellulose
fibers deviate from the experimental values by about 8-10 %, which was
physicochemically explained by Bacon et al. [125]. The weight yields of the ideally
carbonized cellulosic fibers were found to be as high as 28.5 %, whereas these weight
yields are approximately 29.6 %. Bacon et al. attributed this small deviation to the tar
molecules being outgassed during the low-temperature degradation of cellulose
(temperatures up to 500 °C). Additionally, these molecules are thermally unstable and
could partly cleave into smaller fractions (Fig. 11). The nearly 1 % weight deviation led
Bacon et al. to assume that the tar molecules (levoglucosan) could further thermally
decompose, thereby leaving some carbon atoms in other adjacent crystal unit cells being
formed before they can completely leave the fiber during the low-temperature
carbonization. In order to decrease or even inhibit the formation of tars, a pre-pyrolysis
step under oxygen or other reactive atmospheres, i.e., hydrochloric acid, chlorine,
bromine, or iodine, is required. Although these reactive atmospheres have some
technical disadvantages, such as their corrosivity and the required post-treatment of the
reactive gases, they have been reported in some patents for use during carbonization (up
to 1,600 °C) and graphitization (up to 3,000 °C) [134], [135] and [136]. Shindo et al.
claimed in their patent [135] that the use of gaseous hydrochloric acid increases the
carbonization yield from 27 % (in the case of stabilization under oxygen) up to 41 wt%.
Byrne et al. suggested the stabilizing role of halogens. These halogens can form

21
furfurals, which condense and cross-link with the adjacent molecules during the thermal
treatment [137]. Theoretically, the carbon yield of pure cellulose is 44.4 % [80],
whereas the maximum carbon yield at 600 °C achieved by Byrne et al. [138] was 43 %
via the water regeneration of cellulose dissolved into phosphorous-based ionic liquids.
This process increased the crystallinity, inhibited the formation of volatile oxygen
species, i.e., levoglucosan, and decreased the depolymerization reaction temperature by
70 °C (see Fig. 13).

Unfortunately, only a few attempts have been undertaken to determine the lattice strain
of the cellulose crystal unit cell during different hot stretching steps and to determine
the conversion mechanisms of the cellulose unit cell into graphite-like unit cell. To
deliver more insights into the changes in the physical nature of cellulose during the
pyrolysis, Bacon et al. investigated the mechanical properties of Villwyte rayon at each
step during the pyrolysis and carbonization at temperatures of up to 1,300 °C [84].

The tensile strength, Young’s modulus, and elongation at break decrease very rapidly
during the first stages of the thermal decomposition (Fig. 14). Additionally, Bacon et al.
found out that the mechanical properties are sensitive to temperature in the critical
pyrolysis range of cellulose in the temperature region between 240 and 290 °C.
Accordingly, Bacon et al. plotted the mechanical properties as functions of the weight
losses and not as a function of temperature (Fig. 14).

Bacon et al. showed that the XRD patterns of pyrolyzed rayon fibers with weight losses
in the range of 10-20 % remain unchanged, indicating that the pyrolysis occurs in the
amorphous regions. The tensile strength was also found reach a minimum in the weight
loss range of 30-50 %, which suggests that cellulose crystal the decomposition of the
was complete. At this point, the tensile strength increased again, which could be
attributed to the remarkable formation and recovery of a new crystal structure. This
crystal structure healed itself in the carbonization zone (Fig. 14a). The tensile strength
and Young’s modulus were found to sharply increase at a weight loss of 70 % onwards,
and the tensile strength doubled from the initial value. The Young's modulus increased
slightly during the initial stage of pyrolysis and then decreased during the rest of the

22
pyrolysis, when the crystal structure of cellulose began to disappear (in the weight loss
range of 10-20 %). Fig. 14b reveals a sharp decrease in the elongation at break of
pyrolyzed cellulose filaments at the beginning of the carbonization region, which would
be attributed to the development of the initial carbonaceous crystals.

The continuous decrease in the elongation at break during the progress of the
carbonization stage can be considered as evidence that brittle carbonaceous crystal
domains form. The thermal healing of the crystal structure has been suggested at this
level as a predominant factor in the carbonization progress [84].

The Raman spectra of cellulose-based CFs and GFs treated at different temperatures
provide key insights into the lattice disorder of the carbonaceous fibers derived from
cellulose precursors. Raman spectra are very sensitive to any bulky lattice disorder,
which breaks down the translational symmetry. In addition, the wavelength of the
Raman laser is relatively long compared to the lattice dimensions of the carbonaceous
materials [139], which enables reproducibly measuring the lattice disorder and detecting
micro-scale voids fluctuations of up to 1 µm.

Kong et al. studied the Raman spectra of CFs and GFs based on commercial high-
modulus regenerated liquid crystalline BoCellTM fibers [140]. Fig. 15a clearly
demonstrates how the development of lattice disorder in BoCellTM-based CFs depends
on the heat treatment. The presence of both D- and G-bands (Fig. 15a) results from
mixed phases of sp2- and sp3-hybridized carbon atoms. The G-band at wave numbers
between 1575 and 1582 cm-1 is assigned to the vibrational mode E2g of the graphite unit
cell [141]. The D-band at 1350-1370 cm-1 is caused by the breakdown of the lattice
symmetry and is attributed to the A1g vibrational mode of the graphite single layer. The
D-band arises due to a small crystal height in the carbonaceous structure, i.e., a low
number of basal layers, and any structural disorder caused mainly by sp³-hybridized
carbon atoms [139, 142]. The 2D-band between 2690 and 2730 cm-1 is present only in
the graphitic and graphite-like materials and is physically an overtone of the D-band
[139, 141-143]. In some cases of the pyrolytic graphite, the D'-band (~1620 cm-1) can
be observed as a shoulder of the G-band. This band appears in the spectrum pyrolytic

23
graphite because of the nonzero phonon density at frequencies above the G-band, which
become Raman-active due to crystal defects, i.e., at the boundary surface between single
graphitic crystals [144]. The ratio of the intensities of the D- and G-bands, ID/IG,
increases with the increasing heat treatment temperature up to 1,500 °C; thus, one
would expect a substantial increase in the sp3 carbon content. Hence, the lattice
structure of cellulose-based carbonaceous crystals at this treatment temperature stage
may be highly disordered [139].

Additionally, Fig. 15 a) exhibits no significant second-order 2D-band in the range of

2500-2800 cm-1. The appearance of this band is characteristic of the 1D planar lattice of
graphene or the 3D graphite lattice structure [139]. After graphitization under tensile
stress, the Raman spectra of BoCellTM-based GFs show a well-ordered graphite-like
lattice structure. For instance, the sample D in Fig. 15b shows a decreased intensity ratio
α = ID/IG of about 0.19 and a characteristic 2D-band at 2666 cm-1. These observations
are evidence for a well-ordered 3D oriented graphite structure. Fig. 15d (sample B0-
2200) shows the Raman spectra of rayon-based graphitized fibers at 2,200 °C. Bacon et
al. effectively compared the XRD patterns of cellulosic precursor fibers with different
degrees of the preferred molecular orientation with the resulting graphitized fibers.

Hence, a crucial and simple conclusion was arrived at by Bacon et al. from Fig. 16,
namely, that the higher preferred orientation of the cellulose crystals along the fiber axis
is responsible for the formation of the oriented graphite layers along the fiber axis. In
addition, the equatorial reflection (101) of the rayon fiber crystals was found to be
responsible for the formation of the (002) reflection of the GFs, whereas the orientation
angles of the oriented cellulose films and the graphitized cellulose films were found to
be approximately equal, 13° and 12°, respectively. Therefore, the ideal pyrolysis
program in the critical temperature range (250-500 °C) of cellulose and the crystallinity
of the cellulosic precursor fibers significantly determine the intermediate pyrolysis
products and the weight yield of the pyrolysis process. Combined with a sufficient
tensile stress applied to the pyrolyzed fiber during further pyrolysis, i.e., the
carbonization and graphitization, the perfection of the lattice graphite structure is the
main heat-induced healing effect of the lattice crystal structure if the fibers are hot

24
stretched. Bacon et al. found that rayon-based cellulose precursors should be stretched
during the carbonization stage at approximately 900 °C [84]. Fig. 17a reveals the
influence of hot stretching during carbonization at 900 °C on the Young’s modulus of
the stress-free graphitized fibers, while Fig. 17b illustrates the effect of the stretching
during the graphitization at 2,800 °C of Villwyte rayon precursor fibers already
carbonized under stress, where an effective stretching of 100 % during graphitization
increases the Young’s modulus up to 90∙106 psi (ca. 621 GPa).

In order to obtain further insights into the finite fiber crystal structure and its thermally
induced conversion mechanisms into turbostratic and graphite-like crystal structures,
additional wide- and small-angle X-ray scattering (WAXS and SAXS, respectively)
measurements of the carbonized and graphitized fibers were conducted by Ruland et al.
[146] and [130]. In these studies, the Villwyte rayon precursor and the Fortisan-36
precursor, which is a cellulose triacetate II precursor, were used to produce GFs. Three
significant structural changes were found to occur during the thermal treatment of the
cellulosic precursors:

 Complete loss of the cellulosic crystal structure in the critical heat treatment
range between 240 °C and 280 °C;
 Nucleation of small crystal centers in the highly disordered and misoriented
structure of the carbonized fibers between 280 °C and 900 °C; and
 Thermally and mechanically (i.e., hot stretching) determined further recovery of
the graphite-like structure and the accompanying preferred orientation of the
developed fibers between 900 °C and 2,800 °C.

When sufficient stress is applied to fibers during the carbonization and graphitization
stages, the degree of preferred orientation of the crystals exceeds that of the precursor
fibers to some extent (i.e., in the case of rayon) [146]. The same study demonstrated that
cellulose-triacetate-II-based GFs were significantly less oriented than those based on
rayon processed under the same conditions, although the degree of orientation of the
starting material Fortisan-36 was roughly twice that of Villwyte rayon (see Fig. 18).
This difference could be attributed to the significant differences in the size of the crystal
unit cell of the starting materials (see Table 2).

25
In order to understand the predominant longitudinal polymerization process of cellulose
II filaments described by Tang et al. and Bacon et al. [125, 128], Ruland et al. [130]
investigated the fiber structure in the range of 10-1,000 Å (using a Kiessig camera with
a maximum Bragg spacing of 350 Å and a Kratky camera with a maximum Bragg
spacing of 3,000 Å) and correlated the results with the results of the preferred
orientation of the fibers. Fig. 19 schematically illustrates small-angle diagrams of the
stress-free graphitized fibers of rayon (Villwyte) and cellulose triacetate II (Fortisan-36)
heat treated at different temperatures.

The diffraction patterns of the precursor Fortisan-36 remain unchanged up to 320 °C,
whereas the crystal structure of rayon fibers disappears at 280 °C. Identical periodic
density fluctuations (around 200 Å) were detected in the direction of the fiber in this
pyrolysis stage for both fibers [130]. Ruland et al. attributed these density fluctuations
to the probable dissimilarity in the decomposition behavior of both the amorphous and
crystalline domains during the early pyrolysis stage (up to 320 °C). Moreover, the
inhomogeneity between the pyrolysis of the two domains exhibited a memory effect and
influenced the fiber structure, even at high temperatures (i.e., 2,800 °C). Therefore,
cellulosic fibers with fewer amorphous domains should be chosen as precursors.
Additionally, SAXS investigations by Ruland et al. demonstrated that needle-like,
inaccessible pores oriented along the fiber axis with an average diameter of 10-30 Å and
lengths of over 200 Å formed simultaneously with the recovery of the preferred
orientation [130]. The preferred orientation of these pores, which started to form at 900
°C, was mechanically determined (hot stretching) and increased with the increasing heat
treatment temperature, as shown from the SAXS in reciprocal space for the Villwyte
rayon fibers. The scattering of these pores replaced the scattering of the microfibrillar
structure above 1,700 °C for Villwyte rayon and 2,100 °C for Fortisan-36 (see Fig. 19).
Extended research work regarding the temperature dependence of the equatorial
orientation distribution of the microvoids and the length of the microvoids for the
thermal treatment between 200-2800 °C is still required. Additionally, the geometrical
parameters of the voids, its orientation and content of the microvoids should be

26
correlated to the hot stretching parameters and the molecular packing of the cellulose
precursor fibers.

2.2. Polyacrylonitrile (PAN)

Butadiene–acrylonitrile rubber was developed in 1926 by I.G. Farben Industrie under
the trademarked name Buna N. In 1944, Du Pont patented the acrylonitrile process in
order to improve the fiber properties based on PAN [147]. In 1961, Shindo et al. first
patented the use of PAN as a precursor material for manufacturing CFs [148]. In 1966,
Johnson et al. filed a patent for an improved method to produce high-strength CFs
[149], wherein the authors demonstrated that the oriented PAN fibers should be
stabilized under tension in order to improve the mechanical properties of the resulting
CFs. PAN and its copolymers are currently the predominant precursor materials for
manufacturing CFs, with a market share of 90 %.

2.2.1. Polymerization and possible chemical structure

All textile-grade PAN consists of homo-PAN or copolymers. High-grade copolymers of
PAN are used to produce CFs. Fig. 20 illustrates the chemical structures of homo-PAN
and some of its possible copolymers.

PAN can be synthesized via aqueous dispersion polymerization assisted by a redox

system consisting of a catalyzer, e.g., sodium persulfate, potassium persulfate and
iron(III) ions, and activators, e.g., sodium bisulfite. Co-monomers such as vinyl acetate,
methyl methacrylate, and vinyl chloride are easy to incorporate into the polymer
structure using this polymerization technique. Another method for polymerizing PAN is
suspension polymerization, wherein a radical initiator dissolved in oil is suspended in an
aqueous solution of the water-soluble monomers [150]. Molecular weights up to
800,000 g∙mol-1 and PAN fibers with high tenacities and tensile moduli have been
reported to be achievable [151]. Another polymerization method is solution
polymerization, wherein the acrylonitrile monomers are dissolved in a solvent with a
high chain-transfer constant, i.e., dimethylacetamide (DMAc), dimethylformamide
(DMF) or dimethyl sulfoxide (DMSO) [152].

27
Surprisingly, two component PAN-based polymer, first component with extremely high
average molecular weight between1,000,000 to 15,000,000 g∙mol-1 and second
component with weight average molecular weight between 150,000 to 1,000,000
g∙mol-1 could be achieved [157]. The weight average molecular weight ratio of the first
component to the second component is between 2 to 45 and the weight ratio of the first
component to the second component is 0.001 to 0.3. Utilizing such synthesis pathways
enables ultra-high-strength CFs (tensile strength up to 7.2 GPa) [157]. Additional
criteria for the PAN-based carbon fiber precursors include the stereoregularity of the
polymer and the introduction of a meso-triad sequence with at least 35 % isotacticity
into the polymer structure [158].

2.2.2. Tacticity and crystal structure

2.2.2.1. Tacticity
Many researchers have attempted to clarify the stereoregularity of homo- and co-PAN.
In the family of vinyl polymers, including PAN, polypropylene, polystyrene,
polyvinylchloride (PVC), and polyvinyl alcohol (PVA), the stereoregularity is well
known to considerably influence the crystallization behavior of these polymers. For
most vinyl polymers, the presence of carbon–carbon backbone chains with regularly
spaced, isotactic or syndiotactic fashioned side groups facilitates the crystallization,
while the size and spatial arrangement of the side groups significantly affect the
crystallization behavior. In some cases, such as polystyrene (except the polystyrenes
polymerized via the Ziegler–Natta method), PVA and PVC, the side groups are
randomly distributed along the carbon–carbon backbone chain, and thus, these polymers
are atactic. The random distribution of the side groups prevents the chains from aligning
with sufficient regularity, and the polymer becomes amorphous and glassy. Atactic
polystyrene and polymethyl methacrylate are glassy and amorphous, and thus,
processing them into fibers with sufficient tenacity is impossible due to their
insufficient crystalline order.

At this point, the question arises as to how fibers can be developed with sufficient
mechanical properties, especially in the case of PAN. In addition to PVA and PVC,
PAN was found to possess a so-called pseudo-crystalline structure or orthorhombic
pseudo-hexagonal crystal unit cell [159-161]. Using high-resolution pulsed 13C-NMR at

28
a low frequency of 22.6 MHz (Fig. 21i), Schaefer et al. investigated the stereoregularity
of two types of homo-PAN synthesized utilizing the free-radical catalyst method and
the organometallic catalyst method [162]. The authors found that the homo-PAN
synthesized with organometallic catalyst showed three peaks in the vicinity of the –CN
and –CH carbon peaks, which they assigned to the isotactic (I), heterotactic (H) and
syndiotactic (S) triads of the –CN carbon peaks (see Fig. 21i). The measured ratio of the
possible triad tacticity was found to be 5(I):2(H):3(S). Therefore, the detected
stereoregularity was correspondingly found to be low. Furthermore, they attributed the
higher intensity of the 13C-NMR chemical shift of PAN to isotactic PAN because the
abundance of meso-diads in the PAN could increase the intensity of the 13C-NMR peaks
of both the isotactic and heterotactic triads. The pentad tacticity of redox-synthesized
PAN using high-frequency high-resolution 13C-NMR at frequency of 100.7 MHz was
carefully elucidated by Kamide et al. [163]. Fig. 21iia shows the peak assignment of the
–CN carbon in relation to pentad tacticity.

Additionally, Kamide et al. investigated the influence of the racemo (r) and meso (m)
configurations of the CN carbon nuclei of PAN on the triad and pentad tacticity of the
homo-PAN (Fig. 22a and b). Based on the triad sequence, Kamide et al. found that 26.6
% of this polymer is isotactic (I) with the (mm) sequence, 49.1 % is heterotactic (H)
with (mr) sequence, and 24.3 % is syndiotactic (S) with (rr) sequence. The observation
of pentad tacticity explains that only 7.6 % of the CN carbon nuclei are isotactic with a
(mmmm) sequence. It is well known that a polyvinyl polymer can be defined as atactic
and less stereoregular when the ratio H:(S+I) exceeds or is on the order of the value of
2:(1+1). The polyvinyl then becomes completely atactic, as in the case of the homo-
PAN discussed by Kamide et al. Some patents report that the (mm) content should
exceed 0.35-0.5, and the expression I+3S should be equal to or greater than 1 in order to
consider the PAN isotactic [164-165]. For specific applications, e.g., manufacturing
CFs, the content of the (mm) triad sequence should exceed 0.4, and the expression I+3S
should be greater than 0.95 [164, 166-167]. In some cases, highly isotactic PAN can be
synthesized with (mm) content of 0.52 ((mmmm) content is 0.39) [168] or larger than
0.7, as reported by Nakano et al. [169], or even larger than 0.8, as reported by

29
Minagawa et al. in [170]. PVC shows a similar behavior with low stereoregularity; for
instance, an atactic polymer configuration was observed for both polymers in [171].

2.2.2.2. Crystal structure

Chiang et al. investigated the influence of the polymerization mechanism on the
stereoregularity of the resulting homo-PAN and its crystal structure [172-174].
Additionally, Chiang et al. investigated the crystallization behavior of homo-PAN
synthesized with the NaAlEt3S(i-Pr) catalyst [173]. The authors found that homo-PAN
can form crystalline platelets from diluted solutions of propylene carbonate. These
crystals can be re-dissolved in propylene carbonate at elevated temperatures. Chiang et
al. found that the dissolution temperature changes linearly with the crystallization
temperature and possesses a value of 175 °C for the investigated type of homo-PAN.
Homo-PAN synthesized with a coordination- type catalyst exhibited a lower dissolution
temperature of 125 °C with platelets of infinite height [173]. Furthermore, Chiang et al.
investigated 12 different synthesis pathways to produce homo-PAN. Among the various
resulting homo-PAN, different dissolution temperatures were detected. These
differences have been attributed to variations in the perfection of the crystals, although
the infrared diffraction and XRD patterns did not demonstrate any differences [172]. In
order to understand the ability of PAN to develop a crystal structure, the possible intra-
and intermolecular interactions of PAN should first be considered. Olivé et al. [175]
investigated the modes of the inter- and intra-dipolar interactions between the highly
polar nitrile side groups. Fig. 23a illustrates the possible interactions between nitrile
groups. The polar nitrile groups from two adjacent polymer chains experiencing
maximum attractions can align themselves, thus orienting the chains in an anti-parallel
arrangement. Meanwhile, adjacent nitrile groups on the same polymer chain or on two
different adjacent chains can repel each other. Another possibility is the maximum
repulsion and the polymer chains become oriented in parallel, as shown in Fig. 23a.
Additionally, the polar nitrile group of a given chain could attract a proton center, i.e.,
hydrogen atoms, from the backbone chain of an adjacent chain, leading to a parallel
end-to-end orientation [175]. These inter- and intramolecular interactions cause the

30
predominantly irregular helical conformation of the PAN backbone chains (see Fig. 23b
and Fig. 25d).

For PAN to form filaments with the desired tenacity, sufficient crystalline order should
exist, at least in the quasi-oriented fiber structure. Lindenmeyer et al. investigated the
influence of the orientation-induced crystal structure of PAN. A typical XRD diagram
of oriented PAN fibers consists of two sharp equatorial diffractions and a third very
weak off-equatorial reflection (see Fig. 24a) [177]. This equatorial reflection could be
assigned to a 2D orthorhombic (pseudo-hexagonal) unit cell with an interchain
displacement of 6 Å. Klement et al. successfully determined the diffraction spacing of
single crystals of PAN, and they detected 12 different (hkl) reflections [178], [179] (see
Fig. 24b). The interchain distance determined from the single-crystal X-ray
measurements was 5.2 Å. Table 5 summarizes selected dimensions of the orthorhombic
unit cell of single-crystal PAN.

In Table 5, we calculated the volume fraction of the unit cell and found that the specific
volume fraction per polymer chain in a single crystal of PAN is around 0.63-0.88 nm³.
The lattice spacing calculated by Lindenmeyer et al. [177] for the homo-PAN fibers
yielded orthorhombic unit cell dimensions of a = 1.06 nm and b = 0.582 nm and an
average distance between monomers along the c axis of 0.23 nm (estimated from the
lateral packing of the chain and the polymer density). The weak off-equatorial reflection
could be attributed to different configurations along the polymer chain with no preferred
distribution [177]. Furthermore, Lindenmeyer et al. found that the model of para-
crystalline materials could describe the crystal nature of PAN [177]. Fig. 25a
schematically shows the differences between the hexagonal crystal order and its
orthorhombic modifications. In the hexagonal order, the aspect ratio of the unit cell
dimensions satisfies the ratio 𝑎 𝑏 = 3, and the (200) planes possess the same spacing
as the (110) planes. For both orthorhombic modifications of the hexagonal crystal, the
ratio 𝑎 𝑏 becomes either greater or less than 3. In the case of PAN, the crystal expands
perpendicular to the (200) planes, and thus, the spacing between the (110) planes

31
decreases. This was confirmed by Lindenmeyer et al. for single-crystal platelets of
PAN, wherein the (200) planes exhibit a slightly larger spacing than the (110) planes,
and the aspect ratio 𝑎 𝑏 for PAN is greater than 3. This result was confirmed by
Kumamaru et al. [179] for a syndiotactic-rich (57 % syndiotacticity) homo-PAN.
Obviously, the syndiotacticity of PAN with the helical distribution of the nitrile groups
enables the PAN chains to exhibit a regular conformation with no appreciable
intramolecular dipolar repulsions between the nitrile groups of the adjacent polymer
chains. The grid surfaces in Fig. 25b illustrate the nitrogen atoms. In this case of a
helical distribution of these atoms along the backbone chain, an electrostatically stable
interaction between the adjacent polymer chains could be assumed. In their study on the
laterally ordered PAN (i.e., with regularly repeating chain-to-chain spacing), Bohn et al.
discussed the structural factors that lead to the thermal expansion the PAN
orthorhombic crystal unit cell [182]. The XRD measurements at different temperatures
between 25 and 140 °C clearly demonstrate a glass transition in the homo-PAN fibers at
around 85 °C, which confirmed by dilatometry measurements [182] (see Fig 26). Above
the glass transition temperature, both the linear and cubical CTEs increase to average
values of 2∙10-2 %∙K-1 and 3.8∙10-2 %∙K-1, respectively. From these observations, Bohn
et al. assumed that the longitudinal expansion of the PAN fibers is negligible and
calculated the cubical CTE above the glass transition temperature from the XRD data.

Surprisingly, the calculated value of 4∙10-2 %∙K-1 was in good agreement with the
dilatometer measurements, which indicates that the polymer is nearly 100 % laterally
ordered. However, the bulk polymer exhibited a glass transition temperature, which
suggested the existence of amorphous regions and confirmed the hybrid single-phase
morphology of the PAN. Hinrichsen et al. found this hybrid single-phase morphology to
be parallel to the fiber axis using SAXS techniques, and the length of the periodical
structure (ordered domains) was found to be 105 Å [185].

32
In the case of PAN fibers, the crystal unit cells aligned themselves laterally and formed
elementary fibrils with a thickness on the order of 50 Å [186]. These fibrils consisted
mainly of long-period rod-like domains. The ordered domains exhibited lengths of 80-
140 Å, and the amorphous disordered domains were around 40-70 Å in length [183].
Fig. 25c illustrates the aforementioned hybrid single-phase model, and Fig. 25d
illustrates the molecular conformation of a PAN chain with a characteristic rod diameter
of 6 Å. These elemental domains align themselves parallel to the fiber axis in response
to the rigorous axial extension ratio during the wet-, dry-, or pseudo-melt-spinning of
the polymer into fibers, and they form fibrils with a thickness on the order of 100-1,000
Å (see Fig. 25c). Minami et al. measured the dynamic mechanical behavior of undrawn
PAN fibers at a constant frequency of 110 Hz within a temperature range of -100 to 300
°C [187]. The dissipation factor (tan𝛿) shows two distinct peaks indicating two different
transitions at 110 °C and 160 °C. The authors associated these transitions with a double
glass transition in this polymer. This phenomenon confirms the observations of
Andrews et al. in [188] and [189]. Drawing the PAN fibers in boiling water influences
the glass transition observed at 160 °C, as observed by Minami et al. in [190]. With the
increasing draw ratio, the dissipation factor peak at 160 °C broadens, decreases in
height, and then completely disappears at a draw ratio of 7. These findings agree with
the results of Sawai et al. [168], as illustrated in Fig. 27ii). This observation allows the
assumption that the laterally ordered domains and the disordered regions undergo glass
transitions at different temperatures, which could be evidence for the hybrid single-
phase morphology of the crystal structure of PAN. The peak at 160 °C could be
assigned to the amorphous disordered domains; thus, the higher draw ratio (i.e., the
increased orientation) leads to increased chain packing in these regions and restricts the
chain mobility. The peak at 110 °C appears at the same temperature after drawing (draw
ratio of 7), which could be attributed to the amorphous phase in the rod-like laterally
ordered domains. Subsequently, Sawai et al. studied the influence of the stereoregularity
and draw ratio on the dynamic mechanical relaxation PAN fibers and films [168]. A
series of PAN with different (mm) meso-triad content between 0.25 (atactic PAN) and
0.48-0.68 (isotactic PAN) was studied in terms of the orientation state, and different
draw ratios between 1 and 60 were applied. In both isotactic and atactic PAN, four

33
relaxations at the frequency of 3.5 Hz of the type α, αc, βc, and γ were detected at 150,
150, 100, and 25 °C, respectively.

In Fig. 27ic, iic, and iiic, an α relaxation at 150 °C is clearly observed in the undrawn
gel films of the atactic and isotactic PAN, which is thus independent of the initial
stereoregularity. The drawing process alters the magnitude and shape of the loss factor
tan δ due to the increased crystallinity of the films and the reduced chain mobility in the
laterally amorphous (disordered) domains. Both isotactic and atactic PAN show βc
relaxation at around 100 °C (Fig. 27ic). The higher content in the (mm) sequence
increases the magnitude of the βc relaxation peak of the loss factor tan δ (Fig. 27ic). The
increased drawing of the fibers reduces the temperature and the magnitude of the βc
relaxation in both isotactic and atactic PAN fibers (Fig. 27iic; Fig. 27iiic, respectively)
[168]. Fig. 27ib, Fig. 27ic, and Fig. 27iiic show the γ relaxation of the atactic PAN,
which increases with decreased isotacticity and increased drawing. The authors
attributed the γ relaxation to the locality of the syndiotactic sequences and the short
isotactic sequences, which assume a planar zigzag conformation in the para-crystalline
phase [168]. Additionally, the authors demonstrated the αc relaxation at 150 °C only in
highly drawn atactic PAN, which was assigned to the molecular motion related to the
first order of the crystal/crystal transition [168].

In an extended study, Akira et al. [191] examined the reversible crystal/crystal transition
of drawn films of ultra-high molecular weight (UHMW) homo-PAN via the WAXS
technique. Fig. 28b illustrates the influence of the temperature on the (200) and (110)
reflections of the orthorhombic crystal structure of ultra-drawn films of UHMW homo-
PAN. At 150 °C, both orthorhombic (200) and (110) reflections disappear and merge
into a single (100) reflection at the Bragg reflection angle of 16.7°. At this point, the
crystal becomes truly hexagonal. Furthermore, Fig. 28b clearly shows that the
hexagonal (100) spacing increases more rapidly with increasing temperature than the
other that of the orthorhombic reflections. This could be evidence that the molecular
motion in the crystal becomes active at temperatures above 150 °C. Upon cooling, the
crystal converts back into the original orthorhombic form and the (200) and (110)
reflections appear again at temperatures below 150 °C, which additionally proves that

34
the crystal/crystal transition at 150 °C is reversible [191]. The crystal/crystal transition
above 150 °C directly influences the ductility of the ultra-drawn films of UHMW homo-
PAN. The same study found that the drawability of the films increases rapidly above
150 °C.

Gupta et al. critically reviewed interpretation methods for the WAXS diffraction
diagrams of various homo- and copolymer PAN fibers. Fig. 28a compares the results of
different methods to interpret the WAXS curves of the crystalline and amorphous
components of finely cut homo-PAN fibers. The crystalline peak with the highest
intensity was associated with the (200) reflection and occurs at 2𝜃 of 16.4°-17.2°. The
second crystalline and less intense reflection is the (110) reflection, which occurs at a
2𝜃 of around 30°. A broad, diffuse scattering maximum occurs between 25° and 27°
[184], which was attributed to the rotational disorder in the laterally ordered regions.
The crystallinity interpretation methods a) and b) in Fig. 28a are quite contradictory;
thus, the crystalline (110) reflection is considered an amorphous component. Matta et al.
[192] utilized another method to determine the crystallinity of PAN fibers used as a
precursor to produce CFs. In this method, they prepared a nearly amorphous standard
film. The diffraction pattern of this film was superimposed onto the patterns of finely
cut fiber samples, and they determined crystallinity values between 64 and 70 %. The
70 % crystallinity of the fibers was achieved by additionally hot stretching the fibers
above the glass transition temperature under a nitrogen atmosphere. The reasons for the
increased crystallinity after hot stretching was intensively studied by Bahl et al. [193].
Utilizing hot stretching above the glass transition temperature of the PAN, longer
periods of rod-like domains were achieved (from 80 Å to 107 Å), and the crystallinity
was increased by 35 %. Additionally, the intensity of the (200) reflection at a diffraction
angle 2θ of 17° increased, suggesting that new (200) planes contributed to this
reflection. The influence of the stress-induced orientation and the resulting crystal phase
transition of PAN with different stereoregularities was studied by Sawai et al. [168].
Fig. 29b shows the decreased full-width at half-maximum (FWHM) of the azimuthal
distribution plots of the (200) reflection before and after hot stretching. Lower FWHM
values indicate higher degrees of orientation in the hot-stretched PAN fibers.

35
Bahl et al. attributed these structural improvements to both the alignment of the
molecular chains along the fiber axis and the partial removal of the amorphous regions
between two well-ordered crystalline portions (see Fig. 29a). Unfortunately, no
sufficient data regarding the tacticity of the PAN used in this study and the portions of
the (mm) meso-triad (isotactic portion) and the (mr) (syndiotactic portion) was provided
by the authors. Chair et al. extensively studied the influence of the molecular weight
distribution of PAN on the crystallinity, orientation degree, and Young’s modulus of the
precursor fibers for producing CFs from different textile-grade and high-performance
PANs. The authors found a narrow correlation between the orientation degree and the
distribution of the molecular weight of the precursor polymer [196]. Notably, textile-
grade PANs could be possible precursor systems for CFs if the number and mass
averages (Mn and Mw, respectively) of the molar mass of the polymer exceed 26,000
g∙mol-1 and 124,000 g∙mol-1, respectively, in addition to some other factors [196].
Introducing itaconic acid to textile-grade PAN is important for the production of CFs, as
reported by Fu et al. in [197]. The crystallinity values of textile-grade PAN fibers were
found to be around 44 %. In addition, the achieved tensile strength and Young’s
modulus are around 1.6 GPa and 160 GPa, respectively [196]. These metrics of the
mechanical properties of PAN-based CFs are functions of the crystalline content and the
orientation degree of the precursor fibers [196]. In their report, Warren et al. illustrated
the possibility of forming CFs from low-cost, commodity-grade PAN for the
automotive sector [198]. They obtained CFs tows (with 26,000 filament) with a tenacity
in the range of 2.14-2.69 GPa and a Young’s modulus of 200-228 GPa [198].

Thünemann et al. analyzed synchrotron SAXS patterns of both homo-PAN and its
copolymer precursor fibers, only a weak equatorial scattering could be detected due to
structural micro-voids in the fiber. This weak scattering indicates the existence of a
homogeneously disordered structure of alternating laterally ordered and laterally
disordered phases [199]. The influence of various co-monomers, i.e., methyl
methacrylate, 2-hydroxyethyl methacrylate, methacrylonitrile and vinyl acetate, on the
crystal morphology of copolymer PAN has been investigated by several authors [184,
200-204]. Frushour et al. additionally studied the influence of the type and

36
concentration of the co-monomer introduced into PAN on the morphology of the crystal
structure [205]. Depending on the size and type of the co-monomer, the morphology
does not change up to a critical concentration of the co-monomer introduced into the
polymer structure. Fig. 30 shows these conclusions for three types of co-monomers,
vinyl acetate, methyl methacrylate, and methacrylonitrile, wherein the FWHM of the
(200) reflection is plotted against the mole percent of the co-monomer. Up to a fraction
of 10 mol% for both vinyl acetate and methyl methacrylate, few changes are introduced
to the average chain separation of 6 Å (Bragg reflection of (200)). To achieve the same
effect with methacrylonitrile, around 20 mol% is needed because methacrylonitrile is
smaller than the vinyl acetate and methyl methacrylate co-monomers, which are
approximately the same size. This higher requirement is also due to the polarity
resemblance between PAN and the co-monomer methacrylonitrile [205].

2.2.3. Thermal behavior of PAN and its conversion mechanisms into the carbonaceous
turbostratic crystal structure

2.2.3.1. Physically determined fusibility and the exothermal boundaries

Utilizing a differential thermal analysis (DTA), Thompson et al. studied the exothermal
behavior of PAN with different molecular weights was studied between 250 °C and 325
°C [206]. The observed temperature of the exothermal peaks was found to strongly
depend on the molecular weight, the temperatures of the exothermal peaks and the glass
transition decrease with the decreasing molecular weight of the polymer [206]. Using
ultrafast differential scanning calorimetry (DSC), Furushima et al. delivered extended
structural insights into the melting and crystallization behavior of homo-PAN over a
wide range of ultra-high heating rates up to 10,000 K∙s-1 and cooling rates up to -7,500
K∙s-1 [207]. Using conventional DSC, Furushima et al. approximately determined the
apparent activation energy of the glass transition of homo-PAN to be 162 kJ∙mol-1, and
the exothermal activation energy was found to be 249 kJ∙mol-1. For a sufficiently high
heating rate (up 60 K∙min-1), melting will occur before the cyclization reaction of the
nitrile groups. The endothermal melting occurs over the temperature range of 340-360
°C and can be detected with ultrafast DSC measurements, as shown in Fig. 31a. Upon
ultrafast cooling (Fig. 31b), no exothermal peak was detected in the range of 340-360

37
°C, and an exothermal crystallization peak in the range of 200-250 °C could be
detected. Highly isotactic PAN shows a lower activation energy (around 171 kJ∙mol-1)
for the exothermal reaction, according to Zhang et al. in [208].

These results are in good agreement with the early observations of Hinrichsen et al.
[209]. They detected a high-temperature melting-like transition in homo-PAN, which
suggests the rigid-like nature of the PAN chains. In order to investigate the influence of
solvents on the melting and glass transition temperatures of the PAN, Krigbaum et al.
studied these transition points with different polymer fractions in DMF and γ-
butyrolactone (see Fig. 32b). The long extrapolation of the curves at higher homo-PAN
contents provides an apparent melting temperature of 317 °C and a glass transition
temperature of around 104 °C [210]. In most cases, higher exothermal activation energy
leads to the scission of the homo-PAN chains [211]. In order to prevent the scission of
the main chain of PAN, especially when used as precursors for CFs, co-monomers in
small amounts are essential to moderate the exothermal cyclization reaction of the
nitrile groups. A wide range of monomers has been reported to moderate the exothermal
peak, such as Methacrylic acid, itaconic acid, vinyl acetate, and vinyl bromide [78,
212]. As reported in section 2.2.2.2 on the crystal structure of PAN, the incorporation of
copolymers expands the crystal structure of PAN. Slade et al. in [213] studied the
influence of the vinyl acetate content on the melting endotherm of the PAN copolymer
(see Fig. 32 b). According to the Flory relationship (equation 1), the extrapolated
melting temperature of the homo-polymer is 322 °C.

1 1 𝑅
−𝑇 ° =− 𝑙𝑛𝑁2 eq. 1
𝑇𝑚 𝑚 Δ𝐻𝑢

where Tm is the melting temperature of the copolymer, 𝑇𝑚 ° is the melting point of the
homo-polymer, Δ𝐻𝑢 is the heat of fusion of the major component, and N2 is the mole
fraction of the copolymer.

In their patent [214], Coxe et al. were the first to describe melt-spun fibers from the
binary compound of PAN (molecular weight: 15-250 kg∙mol-1) and water. Water
enables melting PAN and its copolymers at temperatures above the boiling point of
water and below the exothermal cyclization reaction temperature of the nitrile groups.
In [204] and [215], Frushour et al. investigated the influence of the water concentration

38
on the melting behavior of PAN vinyl acetate copolymer. The increased water content
depresses the melting point of the polymer until a critical water level, after which the
melting point of the homo- and co-PAN remains constant, and a two-phase system
forms, namely, a liquid molten phase of polymer hydrate and pure water) (Fig. 33).

From the results of such studies, Porosoff et al. reported in their patent [216] a
generalized phase diagram of the PAN/water binary system, as shown in Fig. 34a and
34b. In region I of both figures, line FAG indicates that a single-phase fusion melt of
homo-PAN hydrate (Fig. 34a), co-PAN (co-monomer: 10.7 wt% methyl methacrylate)
hydrate (Fig. 34b) occurs at a water content of 15-40 wt% in the case of homo-PAN and
5-30 wt% in the case of PAN methyl methacrylate copolymer. In this region, the water
is hydrogen bonded to the polymer chain. In region II, both homo- and co-PAN develop
a molten single phase of polyacrylonitrile/water and a free water phase. Region III
indicates that at water concentrations below a critical value of 20 wt% in the case of
homo-PAN (Fig. 34a) and below the melting temperatures (line FAE) a single phase of
solid PAN/water could develop. In the same region III and at higher water
concentrations (above 20 wt% in the case of homo-PAN), a two-phase composition
could be obtained composed of a solid single phase of PAN/water and a phase of free
liquid water [216].

Water has been reported to be used as a major plasticizing agent in many other patents
for the pseudo-melt-spinning (i.e., spinning of pseudo-melts under high pressure to
prevent the plasticizer from evaporating) of PAN [217-220]. Some of these patents have
also reported the co-usage of small-molecule diluents. In some studies, an exothermal
crystallization peak was detected in the high-pressure DSC curves upon cooling. This
peak indicates the re-formation of the crystal structure and could be evidence for the
fusibility of the single-phase PAN/water system. Table 6 shows the melting points of
some different types of PAN.

39
Utilizing high-pressure DSC, Bajaj et al. illustrated the endothermal crystallization
behavior of the PAN/water system for homo-PAN and some of its copolymers, i.e.,
itaconic acid and methyl methacrylate [225]. In Fig. 35a homo-PAN clearly shows a
melting point at 186 °C in the second heating run and a single exothermal crystallization
peak at a maximum of 171 °C during cooling. The incorporation of co-monomers, i.e.,
itaconic acid, reduces the melting peak in the second heating run to 170 °C (Fig. 35b).
In the first heating run of the PAN/itaconic-acid copolymer, two distinct melting points
were detected (155 and 168 °C), which could be attributed to the different hydration
characteristics of the hydrophobic nitrile groups and the hydrophilic carboxylic groups
both present in the copolymer [225].

2.2.3.2. Influence of the thermal stabilization on the fiber structure

To develop PAN-based CFs, PAN must be stabilized via thermal oxidation. This critical
step is necessary to control the exothermal cyclization reactions of the nitrile side
groups. During the stabilization step, different structural and morphological changes are
introduced into the precursor fiber, such as the shrinkage of the precursor fibers, density
changes, chemical cyclization reactions, void formation, and crystal type conversion.
From the process point of view, the stabilization process is the most time-consuming
step for manufacturing CFs [226]. Bahl et al. investigated the influence of the thermal
oxidative stabilization step on the load-free shrinkage of fibers from different PAN
copolymers [227]. Fig. 36a shows that less equilibrium shrinkage occurs for the same
fibers under air than those obtained under pure oxygen. Utilizing the WAXS technique
[228], Bahl et al. studied the influence of the pre-oxidation time on the mechanical
properties of the pre-oxidized fibers. Additionally, the authors defined a so-called
aromatization index, which was calculated from the ratio of the diffraction intensity of
the aromatic structure IA at the newly developed diffraction angle 2𝜃 = 25.5° to the sum
of the intensities of the aromatic structure IA and the IP of the main (200) reflection of
the PAN at 17.5°. The broad peak at the diffraction angle 25.5° indicates the amorphous
nature of the sheet-like arrangements of ladder-like polymer chains [228]. The
maximum aromatization of around 90 % could be achieved with an oxidation duration
of 40 h at 205 °C. At the same cyclization temperatures but under nitrogen, less

40
aromatization of around 13 % was achieved after 16 h of thermal treatment. The CFs
developed from oxygen-stabilized PAN with the aromatization index of 90 % possess
less tenacity than CFs produced under same conditions but after a shorter stabilization
treatment (around 9 h). This was attributed to the over-oxidation of the chemical
structure of the oxidized PAN fibers. Additionally, the authors investigated the
influence of the heating rate on the stabilization and the resulting CFs. They found that
heating rates of around 1-3 K∙min-1 were optimum to obtain CFs with the highest
tenacity [228]. These results were supported by Fitzer et al., who investigated the ideal
heating rate and the optimum stabilization temperature of PAN at 270 °C [226]. The
ideal pyrolysis process included isothermal stabilization at 230 °C for 30 min and a
subsequent increase in the temperature to 270 °C at a heating rate of 0.7 K∙min-1 [226].
Wang et al. found that an oxygen content in the PAN in the range of 15-21 wt% leads to
the optimum stabilization [229]. Jain et al. investigated the stabilization treatment of the
PAN fibers applied without allowing shrinkage [230], and they recorded the shrinkage
stress generated during stabilization under air at 265 °C. The results are illustrated in
Fig. 36b. The authors attributed the initial decrease in stress to the orientation of the
laterally disordered regions of the crystal, which act as tie chains between the ordered
domains [230].

Both HWD (hot-water drawn) and HTD (high-temperature drawn) fibers exhibit
crystallite sizes of 5.4 and 13 nm and apparent crystal orientation degrees of 70 and 92
%, respectively. The higher crystallinity and orientation degree of HTD fibers explain
the higher shrinkage-induced stress in the HTD fibers relative to that in the HWD fibers
because the higher crystallinity achieved in the fibers reduces the orientation relaxations
in any subsequent thermal process. The prevented or constrained relaxation minimizes
or even hinders any misorientation of the polymer crystals in the subsequent thermal
treatment.

Fitzer et al. extensively investigated the dynamic shrinkage of PAN fibers with different
chemical polymer compositions, i.e., homo-PAN, 1 % itaconic acid co-PAN, 6 %
methyl acrylate with 1 % itaconic acid co-PAN, and 6 % methyl acrylate co-PAN [226].
Two different shrinkage stages were detected; the first one was thermally induced

41
entropy shrinkage, which was mostly completed below 200 °C. The thermal energy
introduced to the filaments allows the amorphous regions in the polymer chains to
shrink in order to positively change its entropy. Above 200 °C, the larger chemical
shrinkage becomes predominant. Fig. 37 clarifies that the chemical composition of the
PAN influences the chemical shrinkage. Higher co-monomer contents shift the chemical
shrinkage to a higher level and decrease the onset temperature of the chemical reactions.
Furthermore, the authors studied the influence of the heating rate and the final
stabilization temperature on the tensile strength of the CFs, and their results are shown
in Fig. 38. Heating rates of 1-2.5 K∙min-1 and stabilization temperatures of 270-280 °C
were found to be ideal for the production of high-tenacity CFs [226].

The isothermal shrinkage of PAN fibers drew the attention of Takaku et al. to another
important aspect of the PAN precursor stabilization process. They studied the density
changes of acrylonitrile co-PAN fibers during isothermal stabilization under air at
different temperatures and different dwell times [231], as shown in Fig. 39a. The lower
the stabilization temperature is, the longer is the required dwell time to achieve the same
density value [231]. Furthermore, in the same study, the authors investigated the
influence of the density of the stabilized precursor fibers on the density of the resulting
CFs (see Fig. 39b). Clearly, the higher the density of the stabilized fibers, the lower the
density of the resulting CFs [231].

Utilizing FTIR, Lee et al. studied the stabilization mechanisms of PAN under air and at
250 °C for different time segments (5-180 min) (see Fig. 40) [232]. The starting PAN
fibers show clear bands at wave numbers of 2939 (VC-H in CH2), 2243 (VC≡N of the
nitrile groups), 1454 (δC-H in CH2), and 1360 cm-1 (δC-H in CH) [232]. During the
cyclization, a new band appears at 1595 cm-1, which was assigned to –C=N– stretching.
Dalton et al. investigated [233] the influence of applying tension during the thermal
stabilization on the WAXS patterns of the fibers. A new equatorial broad peak at 25.5°
could be detected, which the authors assigned to the Bragg spacing d = 3.5 Å and
ascribed to the stacked ladder polymer chains.

Rahaman et al. [77] summarized the cyclization reaction model of the PAN, as shown in
Fig. 41. Two major reactions are assumed to occur during the thermal stabilization of
PAN, as shown in Fig. 41. The first reaction is the dehydrogenation of the backbone

42
chain, and the second one is the cyclization of the nitrile groups. Both of these reactions
are very important to introducing the ladder polymer structure, which becomes visible
in the XRD patterns as a broad ―amorphous halo‖ peak at a reflection angle of 25.5°.
Fitzer et al. found that oxygen acts as an initiating center for the subsequent intra-chain
cross-linking because of the higher activation energies detected in air than those
detected in nitrogen atmosphere [234].

At temperatures between 200 and 300 °C, inter-molecular cross-linking between the
adjacent chains occurs, and the original WAXS patterns of the precursor fibers
disappear completely at 314 °C, as reported by Gupta et al. in [235]. In summary, the
following points should be considered in order to optimally stabilize PAN-based fibers:

 The diffusion of oxygen into the fiber should be ensured, which depends on the
diffusion ratio and the diameter of the fibers.
 The fiber should be prevented from overheating (caused by the exothermal
nature of the PAN cyclization reaction) by choosing a very low heating rate to
inhibit the fragmentation and scission of the polymer chains and by
implementing suitable co-monomers, i.e., itaconic acid.
 The fiber must be prevented from shrinking in order to minimize the orientation
relaxation and the de-orientation phenomena in the subsequent CFs.

Fig. 42a and b show the final tenacity and the Young’s modulus of PAN-based CFs,
which are strongly influenced by the initial stabilization treatment and the different final
heat treatment temperatures. After the stabilization stages, the fibers are subjected to
carbonization and graphitization under an inert atmosphere and at elevated temperatures
between 500 °C and 2,800 °C to convert the crystal structure into the turbostratic or
partially graphite-like crystal structure.

Rahaman et al. in [77] reviewed the possible stabilization mechanisms for CFs. They
evaluated the gases that evolved during the carbonization step, the largest portion of
which was hydrogen cyanide (HCN), followed by ammonia (NH3) and nitrogen, and
lower amounts of H2O, CO2, CO, CH4, and H2. These evolved gases are responsible for
the fiber weight loss and the generation of nanopores and voids in the fiber structure.

43
Two structural changes occur simultaneously during the stabilization and the early
carbonization stage of the homo-PAN and co-PAN fibers, namely, the formation of a
lamellar system and void formation.

In an extensive article, Walenta et al. reported unambiguously that during the early
oxidative stabilization stages of co-PAN, the lamellar system starts to form in the
laterally disordered regions of the PAN crystal structure and proceeds to the laterally
ordered regions [238]. These results are in good agreement with the results of Warner et
al. in [183]. They deduced that the selective prior degradation of the PAN structure in
the laterally disordered regions gives rise to the SAXS patterns at defined stabilization
time intervals [183]. Utilizing the synchrotron SAXS technique, Thünemann et al.
investigated the lamellar mesophase formation in PAN fibers during the oxidative
stabilization and the pre-carbonization in the temperature range of 25-500 °C [199]. The
scattering-invariant calculations demonstrated that the first lamellar mesophase (α-
phase) appears between 200 and 300 °C for co-PAN precursors and between 250 and
350 °C for homo-PAN precursors. For homo-PAN fibers, the α-phase shows a period
length of 13 nm. The second lamellar mesophase (β-phase) arises at temperatures above
350 °C for co-PAN and at 400-500 °C for homo-PAN fibers. The β-phase has a period
length on the order of 5 nm for homo-PAN [199]. Thünemann ascribed the lamellar α-
phase to a two-phase system of pristine and cyclized PAN segments. Meanwhile, the
lamellar β-phase was caused by a different two-phase system of cyclized and
aromatized PAN segments [199].

Furthermore, Thünemann et al. used the SAXS technique to investigate the formation,
size, and orientation behavior of microvoids for homo-PAN and co-PAN between 190
°C and 470 °C [237]. In the precursor fibers, microvoids were already present because
of the fiber formation process (wet-spinning process). These initial microvoids were on
the order of 1 vol%. In the final stabilization stage, the voids content reached 10-20
vol%[237]. Fig. 42c and d reveal the dependence of the void length and relative void
volume for both homo-PAN and co-PAN on the temperature of the critical stabilization
and pre-carbonization stages. Additionally, Thünemann et al. claimed that between the
α and β phase, the polymer chain cyclizes completely. After the β-phase, the fibers

44
become fully aromatized [237]. Both Fig. 42c and d clearly show that the cyclization
causes an increase in the void length L and the relative volume of the voids Vrel for both
homo-PAN and co-PAN fibers. Above 350 °C, the aromatization reactions cause a rapid
increase in the relative volume of the voids in both homo-PAN and co-PAN fibers.

During carbonization and graphitization, the ladder-like stabilized polymer chains,

which show a broad XRD peak at 25.5° that indicates the stacking of the polymer
chains, condense with adjacent chains via dehydration and condensation reactions. Ko
et al. used Raman spectroscopy to examine changes in the hybridization state of the
carbonaceous bulk crystal structure at different heat treatment stages [239]. The
intensity ratio ID/IG obviously increased with the increasing thermal treatment
temperature up to 1,800-2,000 °C. Above 2,200 °C the intensity ratio decreased, and the
content of the sp2-hybridized carbon atoms increased to around 40 % after a heat
treatment at 2,800 °C (see Fig. 43i). The higher content of sp3-hybridized carbon atoms
in PAN-based CFs during the early carbonization stage suggests that the morphology of
the carbon crystal structure is turbostratic. This was recently corroborated via ReaxFF
molecular dynamics simulations conducted by Saha et al. [240]. Due to the diffusion
gradient of oxygen in the PAN precursor fiber during the stabilization stage, PAN-based
CFs exhibit a core-shell morphology. This phenomenon was first discussed by Butler et
al. [241].

Utilizing high-resolution transmission electron microscopy (TEM), Bennett et al.

showed that fully stabilized PAN fibers possess a thin skin with a thickness of 100-150
nm [243]. The thermal treatment of PAN at 2,500 °C induces a 3D crystal structure,
wherein the crystal dimensions Lc (ca. 50 Å) and La|| are identical in the core and sheath.
In the other dimension (i.e., perpendicular to the fiber axis), the crystal thickness on the
surface is around 70 % higher than that in the core [243]. Bennett et al. concluded that
the misoriented crystals in the skin considerably limit the intrinsic strength of PAN-
based CFs. Furthermore, Reynolds et al. found in their study [244] that the crystallites
in the skin region induced at elevated temperatures (2,500 °C) are significantly
disoriented. Based on this observation, they assumed that these regions are responsible
for the failure of the fiber (graphitized at 2,000-2,500 °C) at lower stresses (see Fig. 42

45
a). Additional parameters that influence the heterogeneity of the core-shell structure of
the fiber include the spinning parameters and the precursor system [241, 243-244]. Li et
al. studied the structural heterogeneity of PAN-based CFs and GFs [242]. The authors
used Raman spectroscopy to map the cross-section of the PAN-based CFs. The core-
shell structural differences were found to intensify during the graphitization process.
The authors examined fracture propagation during tensile tests, and cross-sectional
scanning electron microscope (SEM) images showed that the fracture surface was
rough. In contrast, in the case of the graphitized fibers, no specific fracture source was
found.

In their study, Warren et al. investigated the residence time requirements for prospective
advanced oxidation and stabilization routes for PAN-based CFs [198]. Extended
evaluations of the thermo-chemical-based plasma (TCP), ultraviolet, and electron beam
methods show that TCP is the most energy-saving and acceptable alternative
stabilization route (see Table 7). The TCP technique induces the necessary level of
cross-linking without damaging the precursor fiber as the other stabilization methods
do. Additionally, the TCP method possesses can be directly integrated into the
continuous stabilization process, leading to a single, seamless process [198]. These
results have been supported by different authors [245-250], who showed that an
additional thermal post-treatment is required in order to fulfill the criteria of fully
stabilized fibers. Additional in-depth studies are necessary to investigate the influence
of such emerging techniques on the morphology. Suggested areas for future research
will be discussed in section 4 of this paper.

2.3. Mesophase-pitch-based precursors (MPPs)

Pitch precursors are the second most abundant precursor systems for the industrially
well-established highly ductile CFs and high-modulus GFs. Optically isotropic pitch
precursors (IPPs) are extracted mainly from the impregnated-pitch precursors and are
used to develop CFs with balanced tensile and compressive strengths. These fibers build
up regions with low elastic moduli (50-150 GPa) and low tensile strengths (1-2 GPa).
Meanwhile, ultra-high-modulus CFs are based on optically anisotropic, thermotropic,

46
and/or lyotropic mesophase pitch precursors (MPPs), which are thermally and/or
catalytically derived from suitable petroleum fractions or coal-tar pitch.

2.3.1. Formation, fiber properties, and the general mesoscopic structure

2.3.1.1. Formation and fiber properties

Utilizing MPPs to manufacture ultra-high-modulus CFs began with the study of coking
processes of coals under inert atmospheres. Via polarized light microscopy, Mackowsky
et al. observed the conversion of optically anisotropic beads into a mosaic structure
from the solid state into the softened state and vice versa [251]. Subsequently, Brook
and Taylor investigated the solubility of anisotropic spherules during the initial stage of
graphitization in the liquid phase [252]. In their patent [253], Otani et al. claimed the
formation of pitch-based CFs utilizing PVC-based pitch as the precursor. At this stage,
Otani et al. did not recognize the presence of mesophase spheres in the PVC-based
pitch. The ability of PVC to form graphitizable anisotropic mesophase spheres was later
investigated by Marsh et al. [254]. Collett et al. investigated the rheological
characteristics of two coal-tar pitches during the transformation into the mesophase
utilizing shear rheological measurements [255]. They suggested that depending on the
shear behavior and the viscosity–temperature curves, the system can be regarded as an
emulsion of mesophase domains in the isotropic phase at low temperatures (240-380
°C). At higher temperatures above 420 °C, the emulsion transforms from an isotropic
liquid phase into a mesophase. Utilizing a heat treatment, Lewis et. al. demonstrated a
vacuum-assisted process to partially transform isotropic pitch into a mesophase pitch
suitable for producing CFs [256]. They achieved a mesophase yield of 90 wt% with
treatment temperatures in the range of 350-450 °C. Singer et al. thermally converted
petroleum-pitch, coal-tar pitch, and acenaphthylene pitch into mesophase pitch by
pyrolysis with a mesophase yield of 50-90 wt% [257]. CFs could be produced from
these three precursors with ultra-high-modulus of 75∙106 psi (ca. 517 GPa). Many
patents have discussed the conversion of petroleum pitch into an immiscible mesophase
and isotropic pitch solution utilizing the pyrolysis technique, and these patents have
shown that the low mesophase content, difficult-to control molecular weight of the
resulting mesophase pitch, long processing times of 30-60 h, and the associated low-
molecular-weight isotropic pitch substances reduce the feasibility of processing the as-

47
produced mesophase pitch into precursor fibers [258], [259], [260], [261] and [262]. In
order to overcome the thixotropic characteristic of the thermally synthesized high-
molecular-weight mesophase pitch, Otani et al. hydrogenated this pitch in order to
considerably increase its H/C atomic ratio up to 1.2. Mesophase pitch with a higher
molecular weight has been claimed to be thermally unstable, and it tends to form coke.
This thermally induced coke considerably increases the viscosity of the mesophase
pitch, thus inhibiting the melt-spinning process. The hydrogenation of the mesophase
pitch enables the formation of totally quinoline-soluble (QS), latently anisotropic
mesophase pitch with good spinnability [263]. Carbonaceous crystals with a high
apparent orientation degree (80 %) could be obtained, and the Young's modulus and
tensile strength of the Dormant-mesophase-derived CFs reach up to 390 GPa and 1.96
GPa, respectively. In order to realize processable (i.e., spinnable) mesophase pitches, it
is important to control their properties including their molecular structure, QS, and
quinoline-insoluble (QI) fractions, the H/C atomic ratio, the molecular weight and
molecular weight distribution, the softening temperature, and the processing viscosity.
Depending on the heat treatment and synthesis time, mesophase pitch transforms into
different structures. Honda et al. illustrated the transformation sequence of the bulk
mesophase pitch as follow [264]:

Stage 1: Nucleation of mesophase spherules from high-molecular-weight fractions

Stage 2: Condensation of the planar molecules and the growth of mesophase spherules
Stage 3: Macroscopic coalescence of the spherules, without a detected increase in the
molecular weight, as reported by Mochida et al. [265].
Stage 4: Formation of the softened mesophase

Zimmer et al. proposed the formation of mesophase pitch when the aromatic molecules
condense in an appropriate way to form parallel sheets with a characteristic lamellar
structure in the form of a simultaneously thermotropic and lyotropic liquid crystal (see
Fig. 44a). This liquid crystal could form when the molecular weight of the condensed
polyaromatic hydrocarbon exceeds 1,500-2,000 g∙mol-1 [266]. Honda et al. [264] and
Brooks et al. [267] illustrated the model of mesophase spherules (Fig. 44), which show
complex patterns in polarized light in both the softened and solid states (see Fig. 44e)
[266]. The accumulation of oriented polycondensed aromatic hydrocarbons is

48
additionally responsible for the spherule formation. Via electron diffraction, Brooks et
al. investigated the existence of a considerable degree of crystallographic order in the
direction perpendicular to the lamellae [268]. Furthermore, Brooks et al. attributed the
spherical shape of the mesophase spherules to surface tension forces, which become
obvious when two spherules coalesce and further transform into a larger sphere. After
carbonization, the spherules show stacked carbonaceous lamellae. These observations
have been recently confirmed utilizing a high-temperature centrifugal solvent extraction
technique on the mesophase spherules using N-methyl pyrrolidone as the solvent for the
isotropic pitch (see Fig. 44b and 44c) [269]. Brook et al. found that the mesophase
spherules transform into ellipsoidal bodies after graphitization for 1 h at 2,800 °C. This
shape transformation occurs because the interlayer distances decrease and approach the
characteristic interlayer distances of natural graphite [270]. The anisotropic content of
petroleum pitch and mesophase pitch is an important parameter of these material
classes. A quantitative reflected polarized light microscopy method is applied according
to the standard procedure ASTM D 4616 to determine the mesophase content in
petroleum pitches with mesophase content of up to 20 %. Alternatively, high-
temperature centrifugation can be used to separate the mesophase pitch from the
isotropic pitch for mesophase pitches with mesophase contents of up to 100 % [271]
and [272]. In a brief report, Chwastiak et al. studied the solubility of different
mesophase pitches at different mesophase contents and in different polar solvents
(toluene, pyridine, and quinoline). As shown in Fig. 45a, the highest solubility was
found in quinoline and the lowest solubility in toluene.

According to this observation, Chwastiak et al. suggested that mesophase domains

include high-molecular-weight insoluble fractions and low-molecular-weight soluble
fractions [274]. This is obvious in Fig. 45a, wherein the strongest solvent, quinoline,
can dissolve only 75 % of the 100 % mesophase pitch. Honda et al. classified the
mesophase pitches into three different categories [264, 275]:

1- insoluble and infusible mesophase domains,

2- soluble mesophase domains, and
3- fusible mesophase domains.

49
The insoluble and infusible mesophase pitch was found to be the mesophase spherules
separated as QI fractions. These fractions are graphitizable and are technically called
mesocarbon microbeads (MCMBs) with diameters of 1-40 µm. They are promising
precursors for electrodes of lithium-ion batteries [276]. MCMBs have been synthesized
via high-temperature heat treatment from different precursors, i.e., the QS coal-tar pitch,
asphalt and naphtha-tar pitch, as reported by Honda et al. in [264]. Akezuma et al.
investigated the physicochemical parameters influencing the solubility and fusibility of
mesophase pitch [275]. A QI mesophase (QImeso) was polycondensed by heat treating
hydrogenated coal-tar pitch. Further, a QS mesophase (QSmeso) was synthesized from
the toluene-soluble and hydrogenated fractions of coal-tar pitch. The softening
temperature was detected by high-temperature reflected polarized light microscopy. No
softening temperature was detected for the QImeso fractions, even at 500 °C. The as-
synthesized QSmeso softens at 450 °C. In the FTIR spectra, the characteristic intensity
ratio of the aliphatic C–H band at 2920 cm-1 and the aromatic C–H band at 3050 cm-1
was detected to be 2.48 and 3.17 for QSmeso and QImeso, respectively. This suggests that
the QImeso fractions possess higher aromaticity than QSmeso. Fig. 45b illustrates the
changes in the interlayer spacing d002 and the crystallite thickness Lc(002) versus the
heat treatment temperature. QSmeso shows a higher Lc thickness (above 1,000 Å) than
QImeso (ca. 700-800 Å) and lower d002 (3.77 Å) values at 2,770 °C [275], which
indicates its better graphitizability. The Raman intensity ratios ID/IG of graphitized
QSmeso and QImeso are around 0.3 and 0.5 at 2,770 °C, respectively. These results agree
with the XRD data and suggest the higher graphitizability of QSmeso [275]. Fig. 46a
illustrates fundamental processes for converting iso-phase pitches into isotropic and/or
anisotropic mesophase pitches. Pseudo-mesophase pitches, i.e., dormant mesophase
pitch [263] and premesophase pitch [277], are hydrogenated mesophase pitches with no
optical anisotropy. Neomesophase pitch consists of more than 90 % of mesophase pitch
and possesses a QI fraction lower than 25 % [278]. In this patented method, extraction
with pyridine and quinoline was disclosed as a unique method for separating the
mesophase from the pitch by removing the lightest and heaviest polyaromatic fractions.
Dauché et al. investigated supercritical fluid (SCF) extraction utilizing toluene as a
solvent for the fractionation of an isotropic petroleum pitch and produced several
mesophase fractions with 100 % optical anisotropy, different average molecular

50
weights, and hence, different softening temperatures [279]. Fig. 46b illustrates the
differences in the processing and structural properties of CFs produced from isotropic,
premesophase, mesophase, and dormant mesophase pitches. The as-spun precursor
fibers and the stabilized fibers (annotated as infusible fibers) made from dormant
mesophase and premesophase were found to possess an anisotropic and isotropic
texture, respectively.

In contrast, the premesophase and dormant mesophase-pitch-based CFs and GFs show a
fibrillated and anisotropic structure along the fiber axis, which indicates that mesophase
pitches are extremely sensitive to shear forces introduced in the spinning dies and
advantageously orient the lamella along the fiber axis. The only crucial drawback is the
shear-induced interlayer shearing on the level of the planar lamella, which thus
drastically decreases the stacking thickness of the lamella in the fiber (by around 50 %),
as reported by Yang et al. in [281]. This shearing deteriorates the graphitizability of the
as-spun fibers, even if the starting mesophase pitch is well graphitizable. This
phenomenon could be attributed to Franklin's findings on the graphitizability of carbons
[282], which indicate that the higher the stacking in the starting material is, the more
graphitizable is the graphite precursor. In order to recover crystal thickness after melt-
spinning, solid-state annealing should be performed at temperatures 𝑇𝐴 between the
glass transition temperature 𝑇𝑔 and the softening temperature 𝑇𝑆 , which must satisfy the
equation TA = (TA + 2TA)/3, as reported by Yang et al. [281]. Fig. 47 shows the
influence of annealing the precursor fibers on the resulting GFs with naphthalene-based
mesophase pitch as the precursor. As shown in this figure, annealing decreases the
intensity of the D-band (1360 cm-1) and increases the intensity of the G-band (1580 cm-
1
), whereas the G'-band (1620 cm-1) becomes weakened in the Raman spectra. The
degree of graphitic ordering (ID/IG) decreases by around 27 % for GFs derived from
annealed precursor relative to that derived from non-annealed precursors [281]. Honda
et al. reviewed the mechanical characteristics of CFs and GFs based on premesophase
and dormant mesophase pitches [283]. Premesophase-based CFs and GFs exhibit tensile
strengths of 2.94 and 3.42 GPa and tensile moduli of 197 and 588 GPa, respectively.
Dormant-mesophase-based CFs and GFs possess comparatively lower tensile strengths

51
of 2.45 and 1.96 GPa and tensile moduli of 196 and 392 GPa, respectively. A
challenging task for using thermally condensed coal-tar pitch or petroleum pitch to
produce thermally processable, 100 % optically anisotropic mesophase pitch is to
maintain a low softening temperature to prevent any further polycondensation or
stabilization (post-polymerization) reactions during the subsequent processing, i.e.,
melt-spinning [284-287].

Different patents claim various modifications to the thermal coking process for
petroleum pitch in order to prepare mesophase pitch with a low molecular weight and a
low softening temperature between 230 and 350 °C. These patented processes include
one- and two-stage atmospheric pressure methods, vacuum-assisted method or
atmospheric pressure method under a vigorous nitrogen flow and stirring [257, 260,
288] and [289], respectively. The atmospheric pressure method was implemented in
order to remove the low-molecular-weight fractions, which prevent the formation of 100
% optically anisotropic mesophase pitch. Mesophase pitches prepared with this method
exhibit low molecular weights (less than 1,000 g∙mol-1) and relatively high softening
temperatures (around 350 °C). Mesophase pitches prepared by vacuum-assisted
methods show a lower softening temperature (300-320 °C). Starting polyaromatic
hydrocarbons with introduced alkyl side groups were found to be advantageous in terms
of a lower softening temperature for the formed mesophase pitch and high oxidation
reactivity, as reported by Mochida et al. [290]. Alternatively, mesophase pitch can be
catalytically synthesized from ethylene tars or utilizing aluminum chloride (AlCl3) as a
catalyst for non-dehydrogenative polymerization, as reported by Mochida et al. [291-
292] and Lewis et al. [293]. Several studies found that AlCl3 cannot be completely
removed from the formed mesophase pitch by acid washing, and trace amounts of solid
aluminum hydroxide and alumina on the order of 10-20 ppm remain in the mesophase
pitch [294-295]. Technically, the aluminum chloride cannot be recycled from the pitch
by acid washing; thus, it converts into aluminum hydroxide, and the remaining traces
degrade the mechanical properties of the resulting GFs, as reported by Mochida et al.
[296]. Mochida et al. [297-301] and Korai et al. [302] reported a novel method for
preparing mesophase pitches from aromatic hydrocarbons using HF/BF3 (hydrogen

52
fluoride/boron trifluoride) as a Friedel–Craft catalyst for the cationic polymerization and
at relatively low temperatures between 200 and 300 °C. HF and BF3 can be easily
recovered in gaseous forms from the reaction mixture by simple atmospheric
distillation; thus, they possess low boiling points of 19.5 °C and -100.3 °C, respectively.
HF/BF3 is already known as a catalyst for the synthesis of anthracene in a corrosion-
resistant Monel autoclave, where the formation of higher condensates were discovered
by Meyer et al. in [303]. The aforementioned characteristics of HF and BF3 are very
advantageous for producing highly pure mesophase pitches. In order to obtain highly
graphitizable mesophase pitch, the purity and graphitizability of the starting material
requires special attention. In all the pioneering works of Mochida et al., Yoon et al., and
Thies et al., highly graphitizable and simple polycyclic aromatic hydrocarbon (PAH)
species and/or mixtures of them were chosen as starting materials, e. g., naphthalene,
methyl-naphthalene, anthracene, and pyrene [281, 294, 296-299, 302, 304-307]. Fig. 48
summarizes the graphitizability in terms of La, Lc, and d002 at different heat treatment
temperatures for different pure, oxygen-free and oxygen-containing PAHs studied
utilizing the WAXS technique by Kinney et al. [308]. Additionally, all the chars derived
from benzene derivatives, i.e., biphenyl, benzoic acid, and phthalic acid, were found to
yield carbons with high d002 values (above 0.344 nm), even at high graphitizing
temperatures of 3,000 °C. Chars based on oxygen-containing coumarin or 2-naphthoic
acid, however, graphitize very well, and their graphitizability characteristics are
comparable with those of anthracene and naphthalene.

Yoon et al. prepared an 100 % optically anisotropic mesophase pitch from a mixture of
methylnaphthalene and naphthalene as starting materials and HF/BF3 as a catalyst,
obtaining 100 % optically anisotropic mesophase pitch with a low softening temperature
between 228 and 235 °C. This pitch combined the traits of low softening temperature,
spinnability, and affinity for oxidative stabilizing reactions. These properties were
introduced to the structure by the alkyl side groups.

53
Fibers with diameters of 11 and 9 µm were graphitized from these precursors at 2,500
°C and for 2 min at a heating rate of 100 K∙min-1 and show tensile moduli of 960 and
975 GPa, respectively[305]. Korai et al. derived CFs from heterocyclic nitrogen-
containing hydrocarbons (quinoline and isoquinoline) using the strong Friedel–Craft
catalyst HF/BF3. The produced pitches were optically isotropic, and the tensile strength
and tensile modulus of the carbonized fibers were 0.9 GPa and 41 GPa, respectively.
Fig. 49 illustrates the expected chemical structure of mesophase pitch molecules based
on naphthalene, methylnaphthalene, and anthracene synthesized via the Friedel–Craft
catalyst HF/BF3.

2.3.1.2. General mesoscopic structure

To obtain more insights into the structure of the anisotropic, insoluble, and infusible
mesophase pitch, Mochida et al. utilized a high-resolution microscope, diamagnetic
susceptibility measurements, H-NMR, and 13C-NMR to investigate the structure of
MCMBs. The measurements show that the molecules constituting the microbeads are
planar and have diameters of 6-15 Å with molecular weights in the range of 400-3,000
g∙mol-1. These small condensed-ring compounds were found to be connected by
methylene bridges and anchored to each other by π-π van der Waals forces, which
induce the self-assembly of the mesogen molecules [265]. According to these findings,
Mochida et al. generalized the morphological structure of mesophase pitch and
described the morphology by the Spider Wedge model, as shown in Fig. 50.

2.3.2. Thermal behavior and the process-determined structural changes

Mesophase pitch possesses lyotropic (liquid crystal in solution) and thermotropic (liquid
crystal in the molten phase) characteristics. The softening temperature is commonly
used to describe the softening transition from the solid state into the liquid state, and
this point is related to the molecular constitution of the mesophase pitch [296, 306,
309]. In general, mesophase pitches are glass-like and brittle at ambient temperature.
The mesogens are not folded but show a planar and lamellar stacking. The glass
transition temperature of mesophase pitch is influenced by different parameters, such as

54
the heterogeneity and the characteristic broad molecular weight distribution of
mesophase pitch, the mesophase content [310], and the initial stacking height of the
lamella [309]. Table 8 illustrates the glass transition temperatures Tg and the softening
temperatures Ts of some mesophase pitches synthesized via the HF/BF3 method.

Khandare et al. utilized the expansion measurements via a dilatometer to investigate the
CTE of 100 % mesophase pitch (Mitsubishi AR) [310]. Fig. 51a shows that the CTE
reaches a maximum at the glass transition temperature, and the error range was reported
to be ± 2 K [310].

The dimethylnaphthalene-derived mesophase pitch has been reported to possess high

stacking values (Lc at the reflection (002)) (see Fig. 51b) [304, 312]. This additionally
influences the glass transition temperature of the polymer [309]. The stacking height of
the lamella is sensitive to the chemical constitution and any temperature changes.
Mochida et al. used XRD data to study the stacking height changes at different
temperatures since mesophase pitch derived from aromatic hydrocarbons exhibits a
definite (002) reflection [312-313]. Fig. 51b clearly shows that the stacking thickness
decreases with increasing temperature above the glass transition region. This was
attributed by Korai et al. to the possible molecular mobility [296, 309, 313]. Even in the
molten state, as illustrated in Fig. 51b, mesophase pitches with different molecular
constitutions still exhibit a 2D molecular ordering expressed by the Lc(002) value. The
same figure shows how the initial stacking and its response to thermal changes are
strongly influenced by the molecular structure of the mesophase pitch. In addition,
methylnaphthalene-based mesophase pitch shows three times higher stacking than
naphthalene-based mesophase pitch. This initial stacking height is decisive for different
processing stages, such as melt-spinning, solid-state annealing, fiber stabilization, and
graphitization, of mesophase pitch and the resulting GFs.

It is important to report the structure of mesophase pitch in fiber form, where the
molecules are subject to high shear rate (>104 s-1), induced stresses in the spinning die,
and extensional forces in the fiber-building zone between the spinning die and the

55
solidification point. The as-spun fibers were reported by Yang et al. [281] to possess
lower Lc values than the starting mesophase pitch. Thanks to solid-state annealing, the
stacking height could be recovered to higher values than that of the starting pitch [281]
(see Fig. 51c). The as-spun mesophase pitch precursor fibers were reported to possess
macro-, meso- and microscopic structures [312, 314].

2.3.3. Crystal conversion mechanisms and the morphology formation

In order to investigate the crystal conversion mechanisms, Mochida et al. [315] studied
solvent (pyridine and tetrahydrofuran)-extracted naphthalene-derived mesophase pitch
fibers. The solvent extract shows rod-like microdomains in the insoluble fraction with
pores only on the surface [315]. Fig. 52i illustrates the morphological surface structure
of the as-spun mesophase pitch precursor fibers as well as THF- and pyridine-extracted
mesophase pitch precursor fibers. The surface of the as-spun mesophase pitch fibers has
a wavy texture. The solvent-extracted fibers show a uniform fibril ordering with fibrils
on the order of 100 nm in width and connecting pleat units 30 nm in width. The cross-
section of the fibrils in the as-spun precursor fibers is roughly elliptical with a diameter
of 50-100 nm, as reported by Mochida et al. in [315]. This shape will be inherited by the
subsequent carbonized and graphitized fibers. Fig. 52ii clearly shows the fibrils and the
connecting pleat units in the carbonized (b) and graphitized (c) states. The stabilized
fibers (a) show the same wavy surface morphology as the as-spun fibers. The size of
the fibril and pleat units are smaller than that observed in the extracted [296].

The formation mechanism suggested by Mochida et al. in [314] claims that the initial
self-assembly of the planar molecules persists in the fibers, even after the considerable
shear and extensional deformation applied in the spinning die and fiber formation zone,
respectively. The microstructure and the assembly of the as-spun, stabilized, carbonized,
and graphitized fibers are thus inherited from the assembly units of the aromatic
molecules [314-315]. As clearly shown in Fig. 51, mesophase pitches retain a
characteristic lattice structure, even in the molten state. The as-spun fibers show a
definite (002) reflection, which indicates that the fibers inherit the assembly

56
characteristics of the mesophase pitch itself [315]. Fig. 53i shows the dimensions of the
graphitic unit and the pleat unit from the high-resolution SEM micrographs of GFs, and
Fig. 53ii illustrates the domain units in the mesophase-pitch-based CFs. In contrast with
the given domain length of 20-40 nm and pleat unit length of 10-20 nm, Fitz Gerald et
al. claimed that the domains are ribbon-like structures with an extended length of up to
100 µm aligned along the fiber axis. These structures exhibit an elliptical cross-section
with a long axis of 0.5-3 µm and a short axis on the order of 0.2 µm. These structures
were observed in mesophase-pitch-based GFs, where the origin mesophase pitch was
synthesized by heat treating the isotropic pitch (Thornel® GFs) [316]. Fig. 53iii
illustrates the generalized morphology of mesophase-pitch-based precursor fibers and
their conversion into GFs, showing the graphite units and the pleat units.

Fitz Gerald et al. [316] and Mochida et al. [314] claimed that the homogeneous
distribution of the graphitizable domains over the cross-section and along the precursor
fiber axis significantly influences the pleat-like structure, which could be initiated in the
spinning die during the melt-spinning process. An important parameter governing this
structural formation is the spinning temperature, as reported by Otani et al. (see Fig. 54)
[317]. The extent of ordering of the domains, the existence of folded layers, and the
presence of flaws affect the fracture initiation and propagation behavior and directly
influence the tensile modulus of the GFs [316]. Otani et al. reviewed the influence of
the processing temperature during melt-spinning on the viscosity of mesophase pitch
and on the macroscopic alignment variations of the domains in the fiber cross-section,
as shown in Fig. 54. Carbonizing and graphitizing extensively influence the degree of
graphitic ordering, measured as the intensity ratio of the D-band and G-band (ID/IG) of
the fiber shell. In Fig. 55i, the G-band obviously increases in value and becomes narrow
with the increasing heat treatment temperature. Inversely, the D-band shows a lower
intensity with the increasing carbonization and graphitization temperature. ID/IG
increases in the carbonization stages due to the swelling phenomena of the fibers upon
the extensive evaporation of the low-molecular-weight fractions at the carbonization
temperature (1,000-1,200 °C), as reported by Mochida et al. [315]. At elevated

57
temperatures, ID/IG decreases (0.1-0.2), indicating higher graphitic ordering (see Fig.
55ii).

Thermosetting or oxidative stabilization is an important step to transform the

mesophase-pitch-based precursor fibers into infusible fibers. This step significantly
influences the morphology of the GFs. The extent of the oxidation of naphthalene-based
mesophase pitch profoundly influences the mechanical performance of the subsequent
CFs and GFs, as reported by Drbohlav et al. in [318] and [322]. Drbohlav et al. found
that the oxidative conversion (under air) into the infusible state results in a weight gain
and is governed by the aliphatic content in the pitch. They described two main reaction
paths [318]:

a. Low-activation-energy reaction, wherein the weight of the fibers increases with

the increased oxygen uptake (weight-gain reaction) due to the formation of
hydro peroxide intermediates and ketones.
b. The weight-loss regime, wherein the weight of the fibers decreases despite the
increased oxygen uptake (weight-loss regime), which is caused by the thermally
initiated hemolysis of the pitch molecules.

Fig. 55a shows the influence of the stabilization temperature of the Mitsubishi AR
mesophase pitch. At relatively low temperatures, i.e., 240 °C, the weight-gain reaction
competes to become the predominant reaction, and the weight gain reaches a maximum
of 10 %. After a dwell time of around 240 min, the weight decreases, indicating that the
weight-loss reaction becomes the predominant one. At a high oxidation temperature,
i.e., 340 °C, the weight-loss reaction becomes the predominant reaction. Drbohlav et al.
[318] calculated the ratio of the time-dependent weight change (dw/dt) to the initial
mesophase pitch weight (w) (see Fig. 55b). The authors recorded the ratio for the
weight-gain reaction during the first 15 minutes of the stabilization process and for the
weight-loss reaction between 240 and 480 min of the stabilization process. The
Arrhenius plot (see Fig. 55b) shows that both weight-gain and weight-loss reactions
show different activation energies [318]. Fig. 55b clearly shows that the weight-loss
reaction exhibits a higher activation energy than the weight-gain reaction, indicating
that the weight-gain reaction occurs faster than the weight-loss reaction [318].

58
Miura et al. evaluated the influence of the gas formation and chemisorbed oxygen
during the stabilization reaction on the micropore volume of the mesophase pitch fibers
[319]. The authors indicated that the gas formation reactions (CH4, H2, CO2, and H2O)
increase the volume of the surface micropores. The authors claimed that the volume of
hydrogen and carbon is higher than the volume of the chemisorbed oxygen [319]. Fig.
55c shows that the total micropore volume increases linearly with the amount of
evolving water during the stabilization reaction, which means that the micropore
volume increase is due to the water evolution during the stabilization reaction.
Matsumoto et al. studied the oxygen distribution profile in mesophase pitch fibers
thermally stabilized under air at a low heating rate of 0.5 K·min-1 [321]. The stabilized
fibers at 350 °C were found to show a homogeneous (flat) oxygen concentration across
the fiber cross-section. In contrast, mesophase pitch fibers stabilized at 250 °C show an
oxygen gradient up to 2.5 µm from the fiber surface and a constant oxygen
concentration beyond this distance . This indicates limited oxygen diffusion at the low
stabilization temperature [321]. Fig. 55e shows the weight gain at a low heating rate
(0.5 K·min-1) for a wide stabilization temperature range. The low heating rate clearly
suppresses the weight-loss reactions. The oxygen uptake of the mesophase pitch fibers
during the stabilization is ruled by different parameters, such as the minimized
stabilization dwell time and the maximized carbon yield of the resulting GFs [321].
Additionally, the low oxygen uptake of the core of the fibers increases the potential of
the fibers to adhere to each other. This adhesion is caused by the insufficiently
stabilized molecules in the fiber core, which can diffuse from the core to the surface of
the fiber in the subsequent carbonization process [321]. Fig. 55f shows the influence of
the stabilization temperature on the glass transition temperature of the stabilized
mesophase pitch fibers at a heating rate of 0.5 K·min-1. At stabilization temperatures
below 200 °C, the glass transition temperature increases slowly. At higher temperatures,
the glass transition drastically increases, indicating that the weight-gain reactions
proceed significantly above 200 °C. The fibers stabilized at 350 °C show no glass
transition, indicating that the fibers are fully stabilized [321].

The higher aliphatic content of the mesophase pitch has been found to accelerate the
stabilization process, which is exothermal because of the formation of oxygen
functional groups and decomposition reactions [323] and [324]. A low heating rate, i.e.,

59
0.1 K∙min-1, in the stabilization process leads to high tensile strengths in the GFs
derived from the same precursor pitch (up to 4.70 GPa), as reported by Yoon et al. in
[324]. The stabilization process changes the morphology of the fiber structure. The
stabilization parameters, such as time, temperature, heating rate and the partial oxygen
pressure, play an important role in the formation of a core-shell structure [325-326]. The
oxygen diffuses from the gas phase through the solid phase towards the core and reacts
with the high-activity components in the mesophase pitch, i.e., aliphatic carbon. This
reaction causes further polymerization and leads to the infusibility of the fiber. The
diffusion coefficient depends on the oxygen partial pressure and the reactivity of the
mesophase pitch [325]. Over-oxidized precursor fiber surfaces release more low-
moleculare-weight compounds during the subsequent carbonization, thus obtaining
carbonized fibers with high surface porosity [326]. Unfortunately, no data in the
available literature discuss the in situ void formation phenomena and its temperature
dependence of mesophase-based CFs during thermal processing.

60
2.4. Lignin (LI)

2.4.1. General aspects

Lignin is the generic term for a complex set of aromatic-rich, condensed amorphous
polyphenols. Industrially, it is a byproduct of the pulp and papermaking processes
utilizing different extraction methods. Lignin is an associated matrix in vascular plants
and functionally supports the cellulosic tissues, comprising around 20-30 % of the dry
woody mass.

Three monolignols act as a source for the synthesis of lignin, namely, ρ-coumaryl,
coniferyl and sinapyl alcohol (see Fig. 56). According to the chemical composition,
lignin can be classified into three types: softwood, hardwood, and annual-plant lignin.
The main monomer of softwood lignin is coniferyl alcohol, which has only one
methoxy group in the C3 position. Hardwood lignin is chemically based on coniferyl
and sinapyl alcohol. ρ-Coumaryl alcohol is an essential monomer in the annual-plant
lignin, e.g., grasses, [327]. The results of Kinney et al. (see Fig. 48) suggest that these
monolignols could not develop a satisfactory graphitic crystal structure, even at elevated
heat treatment temperatures.

In general, lignin is inexpensive and has a significant aromatic character, making it a

suitable candidate for the development of carbonaceous chars, adhesives, fillers, and
combustion feedstock. Kraft pulping is the dominant process for recovering lignin and
industrially covers around 95 % of the lignin market volume [328].

In the pulping process, a hot aqueous solution of sodium hydroxide and sodium sulfide
is used to free the cellulose from lignin, where attention must be paid to reducing the
recalcitrance of the woody or lignocellulosic mass. The resulting byproduct solution
called ―black liquor‖ undergoes different processes to extract lignin from the solution.
Only 2-3 % of the lignin regenerated from pulping process finds further technical usage.
The rest is used as an energy source "fuel" as an integral part of the recovery process in
the pulping industry. The production capacity of lignin from pulping processes
worldwide is estimated to be around 50 million tons/year [329-330]. However, some
crucial drawbacks limiting the further technical utilization of lignin as a precursor for

61
CFs include the impurities the ash and carbohydrate contents, the low molecular weight,
the broad molecular weight distribution, and the chemical structure, e.g., the content of
methoxy groups, which reduces the glass transition temperature and increases the cross-
linking ability, thus also influencing the softening behavior of lignin above the glass
transition temperature, as reported by Horvath et al. [331] and Kubo et al. [332].

Cellulose can be chemically and/or semi-mechanically extracted from the wood via the
kraft pulping process (sulfate process), sulfite process, soda pulping, and organosolv
pulping. Different processes to extract pure lignin from the black liquor of the kraft
process have been patented and commercialized, namely:

 LignoBoostTM [333],
 LignoForce SystemTM [334], and
 Sequential Liquid-Lignin Recovery and Purification (SLRP-process) [335].

These processes recover lignin from black liquors with a low ash residue content (1-3
wt%), low sulfur content (1-3 wt%), and high purity and reproducibility of precipitation
products, as expressed by their Klason-lignin content of 60-90 wt%. Additionally, the
impurities in lignin including carbohydrate substitutes linked to the lignin and
carbohydrates with high molecular weights can be extracted via dialysis. The
organosolv extraction process can yield sulfur-free lignin with a low ash content (< 0.1
wt.%) [336-338]. In this process, the lignin can be directly recovered from the woody
biomass instead of the black liquor (in the case of kraft process). A hot aqueous solution
of inorganic-free solvents (ethanol or acetone and water) is used as the solvent in this
process. Recently, Klett et al. [338] and Thies et al. [339] systematically demonstrated a
multistage fractionation and purification process to extract ultraclean kraft lignin
(overall ash content <100 ppm) with a controlled high molecular weight and a narrow
molecular weight distribution.

For carbon fiber production, lignin should be extensively purified, i.e., via aqueous acid
washing [338, 340-341], in order to remove any contaminating alkali metals or free
sulfur and to reduce the possible flaws generated in the fibers by the ash, as reported by
Baker et al. [342].

62
2.4.2. Thermal behavior and the heat-treatment-induced carbonaceous crystal structure
formation
The thermal stability of lignin and lignin derivatives is chiefly affected by their
chemical structure, the pyrolysis atmosphere, and the processing schedule. Fenner et al.
described the pyrolysis of lignin as a two-stage process [343]. The critical
decomposition was reported to occur in the early pyrolysis stage between 120 and 300
°C, when phenyl propane side chains decompose and yield low-molecular-weight
fractions, i.e., formic acid, formaldehyde, water, and carbon dioxide [343]. Major
decomposition reactions were reported to occur in the range of 300-480 °C. Degradation
in this region can be characterized by the cleavage of the backbone chain, where
monomeric phenols sublimate into the vapor phase. If any possible cross-linking
reaction occurs in this phase, the cross-linked molecules then possess high molecular
weights that restrict the ability to evaporate. High-molecular-weight phenols were also
detected in the vapor phase [343].

Brodin et al. in [344] investigated the thermal behavior of softwood, hardwood kraft
lignin, and the methylated kraft lignin during a thermal treatment utilizing the TGA and
pyrolysis-gas chromatography–mass spectrometry (Py-GC–MS) techniques. The
heterogeneous structure of lignin, which consists of non-repetitive or random chemical
bonds, was found to accelerate the release of volatile products between 200 and 600 °C
[344]. In this temperature range, all lignin types lose around 40 % of their mass.
Oxidative pre-treatment of kraft lignin was found to induce specific chemical changes in
the material, i.e., cross-linking, and the treated lignin types become more thermally
stable.

Bährle et al. investigated in situ the formation of radicals during the thermal pyrolysis of
softwood and hardwood lignin [345]. Utilizing the in situ high-temperature electron
paramagnetic resonance spectroscopy between 350 °C and 550 °C, the authors observed
that radicals form more frequently during hardwood lignin pyrolysis than during that of
softwood lignin. They attributed this to the high methoxy group content in hardwood
lignin [345]. This observation supports the findings of Wang et al. [346], who reported
that during the pyrolysis of hardwood lignin, more methanol was detected due to the
high content of methoxyl groups [346].

63
Hardwood lignin is known to mainly consist of coniferyl (guaiacyl) and sinapyl alcohol,
which are bonded in the polymeric chain of the lignin by ether bonds. Different authors
[346-348] have reported that the ether bonds are thermally nonstable and can easily
decompose at elevated temperatures.

Cui et al. showed that the investigated softwood kraft lignin is highly susceptible to
thermal treatments that elevate its glass transition temperature. It unavoidably
undergoes some radical polymerization, which increases the molecular weight due to
irreversible cross-linking [349]. Remarkably, the progressive elimination of the
phenolic hydroxyl groups via methylation was found to drastically reduce the glass
transition temperature and to thus increase the thermal processability [349]. The same
findings were proven by Pucciariello et al. for the annual-plant lignin (straw lignin)
[350]. In their study, no glass transition temperature could be detected in the DSC
measurements during the second heating. In order to overcome these limitations and to
make lignin thermally fusible, many chemical modification methods have thus been
reported to reduce the inter- and intramolecular interactions caused by the hydroxyl
groups, i.e., methylation [349, 351], alkylation [349], and esterification [352].

Steudle et al. [353] investigated the acetylation of lignin with different acetylation
agents. The substitution of hydroxyl groups of lignin with acetic anhydride, benzoyl
chloride and benzoic acid chloride was found to enhance the fusibility but reduce the
overall mass yield at elevated temperatures.

Prauchner et al. studied the formation of the graphitic structure from coal tars prepared
from eucalyptus wood chips, which contain up to 30 wt% cellulose [354]. Two phases
were found in the carbonized and graphitized structures at the heat treatment
temperature 2,300 °C. The first phase is the less ordered phase (lignin based) with a
characteristic turbostratic lattice structure (d002: 3.5 Å and Lc: 65 Å), and the second
phase (cellulose based) is a well-ordered phase with a 3D graphite-like lattice structure
(d002: 3.39 Å and Lc: 175 Å). Unfortunately, the authors did not provide details
regarding the La size of the crystal structure of either of the detected phases at different
heat treatment temperatures [354]. Recently, Tenhaeff et al. in [355] and Rios et al.
[356] investigated via wide-angle XRD the phenomenological morphology formation
upon heat treatment of AlcellTM lignin fiber mats formed by melt blowing. The fibers

64
were carbonized up to 2,000 °C. The (002), (100), and (110) reflections in the selected-
area electron diffraction indicate the development of short-range graphite lattice order
(Lc: 14 Å (002)) in the fiber with no preferred orientation along the fiber axis [355].
Raman spectra of the graphitized fibers at 2,000 °C show the development of the D-
band, G'-band (at 1620 cm-1), and G-band. The FWHMs of the Raman bands of the
graphitized fibers at 2,000 °C demonstrate the enhanced perfection of the lattice
structure after the graphitization step [355]. These observations support the model of the
formation of non-oriented nanocrystalline graphite-like lattice structure discussed
above.

Davé et al. [357] utilized hot-stage optical microscopy to investigate the thermotropic
liquid-crystalline behavior of four lignin-like model compounds:

a- non-phenolic biphenyl (5-5),

b- phenolic biphenyl (5-5),
c- β-ether model (β-O-4), and
d- phenyl coumaran (β-5)).

The authors indicated that the dimeric lignin-like model compounds exhibit
thermotropic liquid crystal behavior in the low-temperature range between 98 and 128
°C. These compounds are thermally unstable upon further heating at higher
temperatures. In contrast, lignin shows weak anisotropic melt behavior at 200 °C, which
has been attributed to the 3D molecular diversity and the thermally induced cross-
linking of the structure [357].

Although all reported lignins are amorphous, lignin can be transformed into a
carbonaceous nanocrystalline structure at elevated temperatures due to the nucleation of
disordered aromatic rings. For illustration purposes, three different lignin types
(softwood BioChoiceTM, hardwood AlCellTM, and annual-plant soda lignin) were
carbonized in powder form at 1,200 °C (heating rate of 10 K∙min-1) under nitrogen for
10 min without any thermally oxidative pre-stabilization. The as-prepared, non-
oriented, thermally induced crystal structure was analyzed via Raman spectroscopy with
a laser wavelength of 532 nm. In Fig. 57, we plotted the Raman intensity ratio ID/IG of
the as-prepared nanocrystalline structure of lignin and other highly oriented CFs and

65
GFs based on PAN, mesophase pitch, and isotropic pitch, versus the line FWHM of the
observed graphitic G-band. According to the pioneering study of Schwan et al. [358],
the intensity ratio increases proportionally to the increasing FWHM of the G-band until
it reaches a maximum at a G-band of 47 cm-1. At this level, the carbonaceous crystal
width La is small, ~1 nm. For comparison, Fig. 57 shows that carbonized lignin powder
cannot develop a considerable crystal width La, but the moderate FWHM of its G-band
suggests that it is theoretically possible to achieve a turbostratic structure with lattice
disorder comparable to that of CFs based on PAN or isotropic pitch. The challenging
task in the case of lignin is developing an oriented crystal structure along the fiber axis
during the fiber formation. Maintaining the high molecular weight of the lignin with
high inconsistency [338-339], is also required. The high molecular weight could
increase the possibility of forming conjunctions between the later carbonaceous
turbostratic nanocrystals.

2.4.3. Lignin as a precursor for CFs

Otani et al. investigated the formation of needle-like whiskers from lignin powder
heated at 500 °C. The authors found that softened lignin can be deformed and oriented
into whiskers during a certain stage of the heat treatment. Furthermore, they developed
the first lignin-based CFs via melt-spinning [359]. In [360], Otani et al. illustrated
different methods for producing carbonized fibers from alkali-lignin, thiolignin, and
ligninsulfonate from different resources (softwood, hardwood and mixtures of them)
utilizing melt-spinning and dry-spinning. They also reported that the fibers were
carbonized and graphitized at temperatures up to 2,500 °C. However, insufficient
mechanical properties were obtained among different processing variations, as
illustrated in Table 9. The microstructure and void geometry of lignin–PVA fibers were
investigated by Tomizuka et al. utilizing SAXS. The radius of gyration varied in the
range of 8-16 Å. Open and closed voids with weak, circular, long periodic patterns were
observed in the carbonized and graphitized fibers [361]. Johnson et al. investigated the
lattice structure of lignin–PVA-based CFs and GFs utilizing WAXS [362]. At 1,500 °C,
the fibers showed undefined lattice structures and a high void content. At the
graphitization temperature of 2,000 °C, the fibers exhibited a variety of continuous and

66
discontinuous regions of graphitic lattices [362]. Mansmann et al. patented a method for
manufacturing CFs from blends of lignin, poly(ethylene oxide) (PEO), and acrylamide–
acrylic acid block copolymer utilizing the dry-spinning method [363]. Possible
mechanical properties are summarized in Table 9 (under ref. [363]). Uraki et al. utilized
the melt-spinning process for manufacturing precursor fibers from a spinnable softwood
acetic acid lignin. The carbonized fibers, which had a large specific surface area (1200
m²∙g-1), were used as ACFs for filtration purposes [364]. The pulping process used an
aqueous solution of acetic acid to prevent the acetylation of lignin and thus improved
the processability of the as-extracted softwood acetic acid lignin via melt-spinning
[365].The mechanical properties of the carbonized fibers are also summarized in Table
9 (ref. [364] and ref. [365]). Fractionation of wood utilizing high-pressure steam with
subsequent solvent extraction was reported by Sudo et al. in different publications [366-
368]. A subsequent hydrogenolysis treatment was used in order to make the lignin
fusible. The chloroform-soluble and carbon-disulfide-insoluble fractions were heated to
300-350 °C for 30 min, which provided a fusible material [366] with a softening
temperature of around 145 °C. Via melt-spinning at a winding speed of 100 m∙min-1,
continuous precursor fibers were developed. The CFs produced at 1,000 °C exhibited a
diameter of 7 µm. The mechanical characteristics of these fibers are summarized in
Table 9 under ref.[366].

Kadla et al. blended different types of commercially available kraft lignin (i.e.,
organosolv hardwood lignin AlCellTM and softwood kraft lignin IndulinTM) without any
chemical modification with PEO, and they prepared precursor fibers by melt-spinning
followed by carbonization [340]. Prior to blending with PEO, all types of lignin were
subjected to acid washing in order to remove the alkali metals and to reduce the ash
content. Additionally, lignins thermally treated at 145 °C for 1 h under vacuum in order
to remove the low-molecular-weight volatiles from the structure [340]. Utilizing DSC
measurements, a single glass transition temperature was detectable over the entire
composition range of softwood lignin–PEO blends, which indicates the miscibility of
the two polymers [369]. The concentrations of the PEO in the blends were between 5
and 25 wt%. This blending reduces the spinning temperature to around 45 °C and
increases the subsequent oxidative thermosetting times. The CFs resulting from the
blend with a PEO concentration of 5 wt% and a high molecular weight of 600 kDa were

67
reported to provide maximized mechanical properties. The crucial drawback of these
fibers was their brittleness and low elongation at break. The properties of the carbonized
fibers are shown in Table 9 (ref. [340]). Recently, Imel et al. studied in detail the impact
of PEO on the assembly of lignin in solution and its possible influence on the resulting
CFs [370]. The addition of PEO was found to anisotropically direct the self-assembly of
the hardwood and softwood lignin by lengthening the cylindrical building blocks that
make up the larger global aggregates. The presence of PEO potentially prevents
interactions among the cylindrical building blocks of lignin and, consequently, limits
the growth of the lignin aggregates. The radius of gyration of the softwood lignin
blended with 10-20 wt% PEO was found to be 50 % lower than that of the original
softwood lignin [370]. Hardwood lignin blended with PEO at different ratios shows a
constant radius of gyration. Imel et al. attributed this to the higher content of methoxyl
groups, which produces a less branched structure and prevents PEO from interfering
with the self-orientation of the hardwood. This behavior could be evidence for the
possible spinnability of lignin molecules into fibers [370]. Fig. 58 schematically
illustrates the extended straightening of hardwood and softwood lignin.

Annual-plant lignin shows a more complex structure, and its radius of gyration uniquely
depends on the PEO loading. These results are in good agreement with the studies of
Kubo et al. on the effects of kraft lignin structure on the PEO miscibility [369] and on
the relationship between the thermal properties, chemical structure, and blend behavior
of PEO and organosolv lignin [371].

The addition of a small amount of hardwood AlcellTM to PEO was reported to induce an
increase in the PEO crystalline domain size [371]. In another study, Kubo et al.
investigated the possibility of producing CFs from hardwood kraft lignin thermally
blended with two recyclable polymers, poly(ethylene terephthalate) (PET) and
polypropylene (PP). Hardwood kraft lignin was found to be immiscible with PP, and the
resulting CFs were morphologically hollow and/or porous and possessed extremely low
tensile strengths and tensile moduli (see Table 9; ref. [372]).

68
In [373] Baker et al. reported the development of CFs via melt-spinning hardwood kraft
lignin and an organic purified lignin at an operating temperature of 86 °C. The
mechanical properties of the fibers are summarized in Table 9 under ref. [373].
Furthermore, Baker et al. in [374] and [375] illustrated that thermally pretreating
different types of hardwood lignin maintains the high molecular weight of lignin and
results in a wide spectrum of lignins with different Tg (glass transition temperature) and
Ts (softening temperature) values, which were further evaluated for their multifilament
melt-spinning properties. Lignin fiber tows could be spun at a speed of 1,500 m∙min-1
via melt-spinning. These fibers were studied for their oxidative thermo-stabilization and
carbonization characteristics. The initial heat treatment prior to the melt-spinning
increased the carbon yield of the fibers from 33 to 55 % (Table 9, ref. [375]). The slow
carbonization rates were also reported to intensify gasification extension, which creates
a large amount of pores and voids [374]. After the high thermal heat treatment, these
lignin-based CFs demonstrate a low degree of graphitic structure, which was
nonetheless comparable to that of PAN-based CFs (d002 = 3.408 Å; Lc = 33 nm at 2,700
°C) [374]. Compere and Griffith et al. [376-380] utilized a series of miscible polymer
blends consisting of desalted softwood kraft lignin (Indulin AT) and PET, PP, and
polyethylene (PE). Wide-angle XRD data of the powder lignin graphitized at 2,400 °C
proved the existence of a graphite-like crystal structure. CFs derived from the melt-spun
lignin–PET polymer blend (carbonized at 1,600 °C) show a broad characteristic (002)
diffraction ring at an atypical 2θ value between 28° and 29°, which looks rather like an
amorphous maximum [377]. In turn, this indicates that the oriented crystallization
gained by the melt-spinning, which is due to the flow-induced molecular pre-orientation
in the die capillary and the extensional-force-induced orientation in the fiber building
zone, disappears in one of the subsequent thermal treatment processes (e.g., oxidative
stabilization, carbonization). The graphitization at 2,400 °C does not improve the
orientation of the lignin–PET-based GFs. (For the mechanical properties, see Table 9,
ref. [377].)

In their patent, Eckert et al. modified commercial softwood lignin via acetylation with
(but not limited to) acetyl chloride, acetic anhydride, and acetic acid in order to mask the –
OH groups and to induce the fusibility of the polymer. After acetylation, the softwood
lignin could be melt-extruded into precursor fibers with a wide range of fine diameters

69
(10-100 µm) [381]. A patent filed by Berlin et al. discloses the enhancement of lignin
fusibility via acetylation with acetic anhydride in pyridine as a solvent [382]. The
acetylated lignin was then melt-spun into fibers, without blending with a thermally
spinnable polymer. The thermal properties (Tg, Tm) were not clearly observed in the
TGA or DSC results. The reported mechanical properties of the CFs are shown in Table
9 (ref. [382]).

Steudle et al. reported in [353] and [383] the formation of CFs from different lignins,
i.e., cinnamon lignin and commercial softwood kraft lignin (Indulin AT). These lignins
were subjected to acetylation reactions in a pyridine medium with different modifiers,
i.e., methacrylic anhydride, benzoyl chloride, hexanoyl chloride, decanoyl chloride,
cinnamic acid chloride, methacrylic anhydride, p-toluenesulfonyl chloride and/or a
mixture of them. In order to increase the spinnability of the developed lignin
derivatives, they were blended with 5 wt% of a polyester synthesized from vanillic acid
and ethylene glycol. The blended modified lignin and vanillic-acid-based polyester (V-
PET) were found to be miscible via DSC and TEM measurements. Low melting points
between 120 and 220 °C could be achieved for the different modifications. The
mechanical characteristics of the carbonized and graphitized fibers are summarized in
Table 9 under ref. [353] and [383]. Percynnamoylated softwood-lignin-based CFs show
a high ID/IG intensity ratio (1.4) at a high graphitization temperature (2,200 °C). The
WAXS data show expanded interlayer spacing d002 = 0.353 nm, low crystal thickness Lc
= 1.7 nm, and low crystal width La = 4 nm. This indicates that the crystal unit of the
graphitized fibers theoretically consists of only 4 or 5 carbonaceous layers. The
orientation degree from the (002) reflection of the graphitized fibers shows a maximum
of 49 % [383]. Bordin et al. investigated the optimum thermal oxidative stabilization
program for lignin fibers as precursors for CFs [390]. The yield of carbonized lignins,
as evaluated by TGA at 1,000 °C, was reported to increase with longer stabilization
times, higher temperatures, and slower heating rates. The highest yield was achieved at
280 °C with a heating rate of 0.28 K∙min-1 and a holding time of 2 h. Norberg et al.
investigated a one-pot method to stabilize fibers based on lignin blends (90 wt%
softwood lignin and 10 wt% hardwood lignin) under nitrogen [391]. With a heating rate

70
of 1 K∙min-1 and a total treatment time of 255 min, they were able to develop fully
stabilized CFs without the skin–core structure [391]. These fundamental findings are of
great interest since the introduction of hardwood lignin makes the processing time
during the stabilization process 26 times shorter [391]. Several carbonizable and
graphitizable polymers, e.g., PAN and cellulose, have been utilized to produce miscible
lignin blends to improve the performance of lignin-based CFs. In many studies, partial
substitution of PAN through lignin has been reported to reduce the cost of the CFs. Two
main pathways have been reported for this purpose. The first reported technique is the
in situ copolymerization of acrylonitrile oligomers with commercially available and
purified hardwood lignin, as reported by Maradur et al. in [392]. Unfortunately, no data
regarding the crystal structure of the wet-spun fibers were provided by the authors. The
TGA analysis of the AN (acrylonitrile)–lignin copolymer showed a mass yield of 48 %
at 800 °C. A very sharp exothermal peak between 285 and 308 °C was detected in the
DSC measurements, which the authors attributed to the cyclization reactions of the
homo-acrylonitrile domains in the AN–lignin-copolymer [392]. Additionally, the
incorporation of lignin was found to accelerate the oxidative stabilization reactions.
These findings were recently corroborated by Xia et al. [385]. In their study, they
utilized lignosulfonate esterified with acryloyl chloride and copolymerized the resulting
polymer with acrylonitrile. The aim of the esterification was to decrease the –OH
content in the lignosulfonate and thus to prevent any hydrogen bonding at the inter- and
intramolecular level [385]. The heat release of the exothermal reaction was found to be
very slow during the initial stage compared with that of homo-PAN. The authors
attributed this slow exotherm to the phenolic hydroxyl groups of lignin acting as radical
scavengers, which consume some radicals for the cross-linking reactions [385]. The
mechanical properties of the resulting CFs are summarized in Table 9 under ref. [385].
Youe et al. reported the formation of nanocarbon fiber mats from electrospun
copolymers of pure lignin (extracted with methanol) and PAN [393]. The XRD patterns
show crystal size Lc up to 20 nm. A heat treatment temperature of 1,400 °C achieved a
typical graphitic crystal ordering ratio of PAN (ID/IG) of 1.01 [393]. The authors
indicate that the in situ chemically modified structure of the lignin-g-PAN copolymer
could produce 2D turbostratic structure upon carbonization [393]. The second pathway
to produce miscible lignin/PAN blends is blending in solution since PAN and lignin are

71
soluble in some organic solvents, including DMSO, DMF, and DMAc. Husman et al.
produced hybrid lignin/PAN precursor fibers via wet-spinning [386-388]. The
properties of the developed CFs are summarized in Table 9 ref. [386-388]. In different
works, Liu et al. [389, 394] investigated the morphological, structural, and mechanical
properties of CFs produced from PAN/lignin (70/30 w/w %) blends via a gel-spinning
technique. A bath of methanol at -50 °C was used to coagulate the fibers with an
orientation air gap of 3 cm. Hot stretching the as-spun fibers in a glycerol bath at 165 °C
with a draw ratio up to 13 increased the crystallinity of the PAN/lignin fibers from 49 %
to 60 %. Analogously to Fig. 27, the loss factor obtained from a dynamic mechanical
analysis of the PAN/lignin fibers at a frequency of 1 Hz between 25 °C and 150 °C (Fig.
59) shows two significant peaks. The low-temperature peak in the tan δ plot of the PAN
precursor fibers is referred to as the βc relaxation temperature (80.3 °C) of the chain
motion in the para-crystalline regions. The βc relaxations in the PAN/lignin fiber show a
higher, broader tan δ peak at a lower temperature (76.9 °C). This phenomenon was
attributed by the authors to the extra free volume created by the presence of branched
annual-plant lignin molecules incorporated in PAN, which makes the molecular motion
less restricted [389]. Carbon nanotubes incorporated into the polymer blend restrict the
molecular motion, and shift the βc relaxation to a lower temperature.

The mechanical properties of the investigated CFs are illustrated in Table 9 under ref.
[389]. Recently, Li et al. reported the fractionation of kraft lignin via the laccase
enzyme into a water-soluble fraction of (30.2 wt%) and a water-insoluble fraction (69.8
wt%) with the aid of a laccase-mediator system HBT (1-hydroxybenzotriazole hydrate)
[395]. No improvement in the thermal stability of the polymer was reported, and the
overall mass yield at 950 °C was around 40-50 % for both lignin fractions. The authors
processed the fractionated lignin with PAN into nanofibers. The carbonized fiber mats
from the insoluble lignin fractions showed a higher transverse modulus (measured by
nanoindentation), which increased by more than 40 % relative to those of the raw kraft
lignin. More importantly, the carbon fiber made from the insoluble lignin fraction had a
comparable or higher transverse modulus than pure PAN-based CFs [395]. Table 9
clearly shows that, except in the case of PAN/lignin blends, lignin-based CFs show low

72
tensile strengths of 0.245-1.1 GPa and low Young’s moduli of 32-140 GPa. The
graphitized fibers also show low values of tensile strengths (0.1-0.9 GPa) and low
Young’s moduli (up to 48 GPa). Additionally, in some cases, the developed CFs
possess low elongation at break, less than 1 %. The incorporation of carbonizable
polymers with defined crystal structures more effectively enhances the formation of
lignin-based CFs. For the CFs fabricated from lignin, attention should be paid to
modifying the lignin to form a defined crystal structure and repeated monomer
sequences.

73
3. Summary, future perspectives, and avenues for further research

3.1. Summary
In this article, we attempted to critically review a complex set of polymeric precursor
systems for carbon and graphite fiber formation. Elucidating the critical transformation
from a polymeric crystal into a carbonaceous one and its influences on the morphology,
mechanical properties, and fine fiber structure involves physical, chemical, and process-
determined structural changes. We reviewed the available literature in depth to reveal
the origins of the crystal structure formation and the structure–property relation.
Furthermore, we identified a set of physical and morphological criteria that should be
fulfilled by a precursor system in order to obtain low-cost CFs with sufficient
performance. These criteria include but are not restricted to:

1- General requirements: Having a low ash content (<<100 ppm), a high molecular
weight, and a narrow molecular weight distribution are the most important
criteria for any carbon fiber precursor. Additionally, the precursor should show
desirable processability into fibers via eco-friendly processes with low operating
costs, i.e., melt-spinning or pseudo-melt-spinning.
2- The crystal structure: The polymeric precursor system should present a
repetitive 3D crystal unit cell, i.e., cellulose, cellulose triacetate, or para-
crystalline unit cell with side groups enabling carbonization, i.e., PAN or even
2D lamellar clusters of large carbonizable or graphitizable condensed molecules,
i.e., mesophase pitch. The crystal unit cells should build larger domains or
crystal clusters. The content of the conjunction clusters between the crystalline
domains should be as minimal as possible, which largely depends on the fiber
formation process. This structural arrangement enables homogeneous
decomposition behavior along the domain during the critical early stage of the
appropriate thermal treatment.
3- Carbonizable monomer sequence: The monomer sequence of the polymeric
precursor should enable the development of intermediate educts, which can be
further carbonized or graphitized assisted by hot stage processes (i.e., hot
stretching), as is the case with cellulose, PAN and mesophase pitch. This could

74
 be realized if the monomer unit exhibits a low volume and is homogenously
distributed along the polymer chain.
4- Orientation degree of crystalline structure: The polymeric chain should be able
to be oriented along the fiber axis. This is very important to obtaining
intermediate educts (carbon skeleton) at defined positions in the fiber, which
could recover the orientation of the fibers after carbonization via longitudinal
"re-polymerization" of the carbon skeleton assisted by external elongation
deformation (hot stretching), i.e., cellulose and cellulose triacetate. Carbon or
GFs should possess a crystalline structure with an orientation degree above 80
%.
5- Processability: The polymeric precursor polymer should possess the physical
ability to be processed into fibers via melt- or pseudo-melt-spinning, gel-
spinning, dry-spinning, jet-wet-spinning, or wet-spinning. In the reviewed recent
developments, low-cost, textile-grade PAN could be processed into hydrated
fibers via pseudo-melt-spinning. The resulting CFs are of considerable interest
to the automotive industry since the pseudo-melt-spinning process offers an
economically viable alternative with better ecological perspectives than the
established conventional wet-spinning processes.
6- The stabilization: Before any thermal treatments, the precursor system should be
optimally stabilized to prevent the fibers from fusing during the subsequent
thermal treatment stage. The stabilization is the most critical step because
morphological and structural heterogeneities can arise in the fiber (e.g., the
core–shell structure). Novel, low-energy processes for cross-linking the fiber
structure, which would suppress the formation of the core–shell structure, are
still under development, e.g., TCP treatments.
7- For high- and ultra-high-modulus CFs and CFs with balanced tensile and
compression strengths, it is important that the precursor system can develop a
wide crystal unit in terms of La (110), and the aspect ratio La/Lc should be in the
range of 1.5-2.2.
8- Controlled void formation: Nano and micro-voids are unavoidable due to the
decomposition reactions, chain scission reactions, and evaporation of low-
molecular-weight compounds at elevated temperatures under atmospheric

75
 pressure. For high-performance CFs, the micro-void content should not exceed
10-20 vol%, and voids should show a preferred orientation along the fiber axis.
The micro-voids should not be longer than 40 nm, and their diameter should be
below 0.5 nm [130-131, 146, 199, 396-398].
9- Costs and price elasticity of demand: The generalized breakdown of costs of
PAN based carbon fibers shows that 50 % of the costs are caused by the PAN
precursor fibers (including polymer manufacturing, conventional fiber formation
process (wet-spinning) and fiber packaging). Around 22 % of the costs are
caused by the conventional, production limiting and thermo-oxidative
stabilization step. Additional 15 % of the costs are caused by the subsequent
carbonization step. The price target of the low cost carbon fibers for automotive
sectors and non-aerospace applications should be in the range of 5 - 12 € per
Kilogram. The availability of low-cost carbon fibers at the mentioned price
target assumes (i) the realization of a significant reduction in production cost for
the precursor polymers, i. e. implementation of low cost emerging precursor
systems like lignin, textile grade PAN and the binary system lignin/textile grade
PAN with lignin shares up to 50 % by weight, (ii) development of advanced
manufacturing technologies (pseudo-melt spinning technology, novel
stabilization processes), and (iii) the scalability of the mentioned technologies
into industrial manufacturing processes. Oka Ridge National Laboratory (USA)
and its partners have been developing scalable technologies for the production of
low cost textile grade PAN based carbon fibers for automotive sectors. The
targets of tensile strength and tensile modulus of the low cost carbon fibers for
this application are 1.73 GPa and 173 GPa, respectively. Low cost textile grade
PAN based carbon fibers with strengths greater than 2.4 GPa and moduli higher
than 240 GPa have been achieved with cost target less than 15 US$ (~12.8 €) per
Kilogram. For widespread utilization in most high volume applications, i. e.
automotive industry and wind energy sectors, the priority requirements are (i) to
reduce the costs by means of the implementation of high volume precursor
systems (textile grade PAN) and preferably sustainable precursor systems
(lignin, chitin, cellulose) and (ii) to increase the production volume by
introduction of seminal production methods in fiber formation, stabilization and

76
 carbonization processes. The price elasticity of demand of low-cost carbon
fibers could also be supported by implementation of high volume, oil-
independent and sustainable emerging precursors, i. e. lignin. For lignin-based
low cost carbon fibers the positive cost potential could be influenced by other
different factors, i. e. carbon yield, purification (reduction of ash content;
elimination of nano-cellulose; removal of sugars and sand particles) and
unification of the molecular fractions. Furthermore, the low cost conversion of
lignin into a fusible semi-crystalline structure, which is the most important, less
investigated criterion for lignin based carbon fibers manufacturing, is still the
most challenging task.

3.2. Future perspectives

In the recent decade, interest in efficient, high-volume fabrication of economically
viable CFs for the lightweight construction sector has considerably increased. For the
large-scale incorporation of CFs into materials for the automotive sector, the total
manufacturing costs remain the main hindrance. Utilizing new emerging precursor
systems, e.g., lignin, necessitates modifying and adjusting the conventional
manufacturing processes because these precursors are different in nature than
conventional PAN or mesophase pitch. Different research programs, clusters, and
facilities have been initiated worldwide to investigate the formation of low-cost CFs
based on lignin, polyolefin, and textile-grade PAN. Table 10 summarizes a list of
selected research projects and their formulated objectives.

The objectives of these research works clearly reveal the future path of carbon fiber
research. Promising approaches for the conversion of emerging low-grade precursor
systems into CFs are available in the most recent patent literature. These approaches can
be divided into two major categories related to the precursor and the manufacturing
process:

 Precursor: In these approaches, we expect low-cost precursor fibers from the

textile-grade PAN spun via the pseudo-melt-spinning technology [408], low-

77
 cost polymer blends of PAN and lignin [409], and low-cost CFs based on PE
[410].
 Manufacturing processes: In these approaches, novel stabilization methods are
expected to reduce the dwell time and increase the output of the stabilization
process. Examples include (i) the plasma-assisted stabilization of PAN
precursors [411-413]; (ii) the microwave-assisted plasma stabilization process
for PAN precursors [414], and (iii) high-density oxidized PAN fibers via TCP
technology [415]. Additionally, a novel carbonization method called magneto-
carbonization was reported in [416].

3.3. Necessary areas for further research

Despite rapid progress in the field of carbon fiber development, many fundamental and
technological bottlenecks need to be addressed to achieve low-cost CFs from emerging
precursor systems. In particular, some emerging precursors, particularly lignin, possess
no defined crystal structure and are generally non-fusible materials. Despite lignin/PAN
blends, Table 9 shows that lignin-derived CFs exhibit poor mechanical performance.

For purified lignin precursors, three systematic research avenues are recommended to
investigate the fundamentals of lignin-based CFs and their formation processes:

1. Crystal or pseudo-crystal structure formation: The lignin chains should be

assembled into at least 2D unit cells, i.e., with PAN, to potentially orient the
polymeric chains along the fiber axis.
2. Top-down research strategy: Defined lignin fractions with increased molecular
weight and molecular weight consistency should be precisely fractionated and
isolated [339].
3. Controlled thermal degradation behavior of lignin: The thermal degradation
behavior of the amorphous lignin and co-crystallized lignin with PAN should be
investigated. The investigation should cover the early degradation phase
between 200 °C and 500 °C. Additionally, the crystal conversion mechanism
and developed crystal size, type, and lattice disorder should be investigated.

78
Extensive research is needed to further develop fiber formation technology. In
particular, pseudo-melt-spinning technology would overcome the physically determined
processability limitations, i.e., the non-fusibility of PAN, lignin, or textile-grade
PAN/lignin blends under ambient conditions.

Furthermore, additional research ion the influence of novel stabilization and

carbonization processes on the structure–property relation is required, particularly the
impact of the core–shell structure or cross-sectional heterogeneity on the mechanical
performance.

Table 11 rationally summarizes the necessary research and development areas required
to lower costs of carbon fibers. It also gives the targets of price and application
according to the precursors and the limitations and problems to solve to achieve the goal
according to each precursor.

Acknowledgments:

This work was supported by the Leibniz-Institut für Polymerforschung Dresden e. V.,
and the Technische Universität Dresden. Diagrams and graphics were reproduced using
OriginLab. The authors gratefully acknowledge the technical support of Ms. Friederike
Kaiser and Mr. Lucas Wulff.

This research did not receive any specific grants from any other funding agencies in the
public, commercial, or not-for-profit sectors.

79
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Page 98 of 173
Fig. 1: Properties spectra of commercially available continuous carbon and graphite fibers.

Page 99 of 173
Fig. 2: Mutual interactions between the polymeric precursor systems, the fiber formation
mechanisms, the thermal conversion processes and the resulted mechanical, physical and
structural properties of carbon and graphite fibers.

Page 100 of 173

Fig. 3: The general molecular structure of cellulose and its AGU

a)
b)

Fig. 4: a) Schematic illustration of the planar chains shifting of cellulose Iα and Iβ. Each two
rectangle blocks represent one AGU unit. Reproduced from [91] with kind permission from
Elsevier; b) Triclinic unit cell of cellulose Iα (dashed lines) and monoclinic unit cell of
cellulose Iβ (solid lines). Reproduced from [92] with kind permission from Royal Society of
Chemistry.

Page 101 of 173

 Cellulose Iβ Cellulose II

Cellulose IIII Cellulose IVI

Fig. 5: Projections of the unit cell of cellulose Iβ, II, IIII, IVI onto the plan 𝑎, 𝑏 (denoted by
(a)) and the inter- and intramolecular hydrogen bonding (denoted by (b)). Reproduced from
[110] with kind permission from Elsevier.

Page 102 of 173

 b)
a)

c) d)

Fig. 6: a) General supermolecular structure of cellulose microfibrils. Reproduced from [114]

with kind permission from Springer International Publishing AG; b) Optical micrographs of
the fibrillation of Lyocell fibers in wet state, no scale has been provided from the source;
Fibrillation index (FI) in this case is around 9 and has been calculated by the ratio of the sum
of fibril lengths into a defined fiber length to the length of the fiber. Reproduced from [119]
with kind permission from John Wiley & Sons, Inc.; c) Cross section of Lyocell fiber and the
SEM micrographs of the micro fibrillary structure of the Lyocell; d) Cross section of typical
lobulated Rayon fiber and the related SEM micrographs of the fibrillary structure. Both c) and
d) micrographs are reproduced from [118] with kind permission from Elsevier.

Page 103 of 173

 c)

b)
a)

d)

Fig. 7: First-order pyrolysis kinetic of cellulose at different heat rates; a) under helium for 2
K·min-1 with a decomposition ratio of 0.57 %∙K-1 and b) for 80 K∙min-1 with a decomposition
ratio of 0.43 %·K-1; both degradation curves show an activation energy of E = (238 ± 10)
kJ∙mol-1. Reproduced from [126] with kind permission from American Chemical Society; c)
TGA (thermogravimetric analysis)-curves of cellulose pyrolyzed at different heating ratio:
heating ratios for the curves in c) and d) from left to right: 1 K∙min-1; 15 K∙min-1; 150 K∙min-1
; The diagram d) reveals the associated DTG-curves and the experimentally calculated
activation energies. Both diagrams c) and d) are reproduced from [127] with kind permission
from American Chemical Society.

Page 104 of 173

Fig. 8: FTIR-spectra of microcrystalline cellulose pyrolyzed at different temperatures
indicating the chemical transformations throughout the pyrolysis. Reproduced from [129]
with kind permission from Elsevier.

Page 105 of 173

Fig. 9: Van Krevelen diagram for charred cellulose triacetate II. Reproduced from [128] with
kind permission from Elsevier.

Page 106 of 173

 13
Fig. 10: Solid state C CP/MAS NMR spectra of cellulose II (Rayon) fibers pyrolyzed at
different temperatures. Reproduced from [132] with kind permission from Elsevier.

Page 107 of 173

Fig. 11 Suggested four carbon atoms residue model per glucose unit for the conversion of
cellulosic materials into graphite. Reproduced from [128] with kind permission from Elsevier.

Page 108 of 173

 a)

b)

Fig. 12: (a) Longitudinal and (b) traverse re-polymerization mechanisms of the four carbon
residue monomer, with the crystallographic dimensions of the unit cell of cellulose and the
natural graphite. Reproduced from [125] with kind permission from Elsevier.

Fig. 13: TGA curves of triethylammonium phosphate (Tea)H2PO4 regenerated cellulose fibers
(red curve) and pure cellulose fibers (black curve). Reproduced from [138] with kind
permission from Royal Society of Chemistry.

Page 109 of 173

 a)

b)
Fig. 14: Mechanical properties of Villwyte Rayon filaments thermally stabilized under
oxygen for 18 min at various pyrolysis stages and carbonized at 1,300 °C. Republished with
permission of Taylor and Francis Group LLC Books from [84]; permission conveyed through
Copyright Clearance Center, Inc.

Page 110 of 173

a) b)

c) d)

Fig. 15: Raman spectra of a) liquid crystalline BoCellTM fibers and carbonized fibers of it at
different temperatures; b) for the graphitized fibers with the intensity ratio of the first-order
Raman spectrum α = ID/IG; c) dependence of the intensity ratio of the first-order Raman
spectrum to the treatment temperatures; d) Raman spectra of Rayon-based graphite fibers
(sample denoted with B0-2200). The diagrams a), b) and c) are reproduced from [140] with
kind permission from Springer International Publishing AG; the diagram d) is reproduced
from [145] with courtesy of Royal Society of Chemistry.

Page 111 of 173

Fig. 16: XRD patterns of differently oriented Rayon based precursor fibers; upper row
increased orientation from left to right; lower row reveals the graphitized counterparts of the
upper raw. Reproduced from [125] with kind permission from Elsevier. The red rectangle
shows the equatorial reflection of the (101) cellulose reflection and the green dashed rectangle
illustrates the (002) equatorial reflection of the graphite fibers.

Page 112 of 173

 a)

b)
Fig. 17: The influence of the mechanical stretching of the Villwyte Rayon precursor fibers on
the mechanical properties of the stress graphitized fibers; a) effect of stretching during
carbonization at 900 °C on the Young’s modulus of the stress-free graphitized fibers at 2,800
°C; b) effect of stretching during graphitization to 2,800 °C on the Young’s modulus of the
stress graphitized fibers. Both diagrams are republished with permission of Taylor and
Francis Group LLC Books from [84]; permission conveyed through Copyright Clearance
Center, Inc.
Page 113 of 173
 1,0

Villwyte Rayon
Fortisan-36
0,8

0,6
-q [-]

0,4

0,2

0,0
10 100 1000
Temperature [°C]

Fig. 18: Preferred orientation (-q) of graphite fibers based on cellulose II and cellulose
triacetate II for various heat-treatment temperatures up to 2,800 °C (q is the orientation
parameter: q = 0 random, q = 1 perfect oriented at  = 0, and q = -1 perfect oriented at  =
/2). Reproduced from [146] with kind permission from AIP Publishing LLC.

Page 114 of 173

Fig. 19: Intensity distributions of the small-angle diffractions (2D patterns) for carbonized and
graphitized Villwyte Rayon (cellulose II) and Fortisan-36 (cellulose triacetate II) for various
heat treatment temperatures. Reproduced from [130] with kind permission from John Wiley
& Sons, Inc..
Page 115 of 173
 Homo-PAN

Poly(acrylonitrile-co-methylacrylate)

Poly(acrylonitrile-co-methylacrylate-itaconic acid)

Poly(acrylonitrile-co-methylmethacrylate-co-itaconic acid)

Fig. 20: Chemical structure of homo-PAN and different PAN copolymers, the aforementioned
copolymers have been reported to be used for the manufacturing of carbon fibers [153-156].

Page 116 of 173

i)

ii)

Fig. 21: i) 13C-NMR spectrum from a solution of organometallic synthesized Homo-PAN

dimethyl sulfoxide. Reproduced from [162] with courtesy of American Chemical Society; ii)
13
C-NMR spectra from a solution of redox synthesized Homo-PAN in DMF-d7 a) –CN carbon
region; b) –CH2 carbon region and c) is assigned to –CH carbon region. Adapted by
permission from Macmillan Publishers Ltd: Polymer Journal [163], copyright (1985). The
assignments of the nitrile carbon and the methylene carbon are according to the reference
[163].

Page 117 of 173

a)

b)

Fig. 22: Schematic illustration of a) the racemo (r) sequence of the nitrile groups. The C-CN
planes are parallel alongside the planar zig-zag polyvinyl backbone of PAN and b) the meso
(m) sequence of the nitrile groups in a trans-trans conformation. The nitrile group presents in
a meso-interaction with the adjacent nitrile group. Adapted by permission from Macmillan
Publishers Ltd: Polymer Journal [163], copyright (1985).

Page 118 of 173

 a)

b)
Fig. 23: a) Three types of dipolar interactions of the nitrile groups in the PAN (data from
[175]); b) possible model structure of perturbed chains alignment of atactic PAN. Reproduced
from [176] with kind permission from John Wiley & Sons, Inc..

Page 119 of 173

a) b)
Fig. 24: a) X-ray diffraction pattern of oriented PAN fibers. Reproduced from [176] with
courtesy of John Wiley & Sons, Inc.; b) X-ray diffraction patterns of solution crystallized
PAN platelets (single crystal). Reproduced from [179] with kind permission from Elsevier.

Page 120 of 173

a) b)

c) d)
Fig. 25: a) Schematic differences between the hexagonal and two possible orthorhombic
(pseudo-hexagonal) modifications of the PAN (the circles represent the packing cylinders of
the helically packed polymer chains). Reprinted from [177], with the permission of AIP
Publishing; b) 𝑎, 𝑏 projection of the orthorhombic pseudo-hexagonal unit cell of PAN [176];
c) packing morphology of crystal structure in a highly oriented PAN fiber (fiber axis is
parallel to the polymer rods) [183]; d) molecular rod conformation of PAN chain (black
dashes represent the –CN groups) [184]. b) and d) are reproduced from [176] with courtesy of
John Wiley & Sons, Inc.; and c) is reproduced from [183] with kind permission from Springer
International Publishing AG
Page 121 of 173
 7

DILATOMETER READINGS
5.290

4
5.270
d SPACING, Å.

5.250 3

5.230
2

5.210
1
20 40 60 80 100 120 140
Temperature, °C.

Fig. 26: Volumetric thermal expansion and the d110 spacing (calculated from the (110)
reflection) dependence on the temperature of homo-PAN fibers: Open circles refer to the d110
spacings and the dots assigned to the dilatometer readings. Reproduced from [182] with kind
permission from John Wiley & Sons, Inc.

Page 122 of 173

i) ii) iii)
Fig. 27: i) Dynamic storage modulus (E’) (a), loss modulus (E‖) (b), and loss factor (tan δ) (c)
at 3.5 Hz versus temperature for drawn fibers at a draw ratio of 16 (●) isotactic PAN fiber
with (mm) content of 0.68: (▼) isotactic PAN with (mm) content of 0.48; and (○) atactic
PAN fiber with (mm) content of 0.25; ii) influence of the draw ratio on the dynamic storage
modulus (E’) (a), loss modulus (E’’) (b) and the loss (tan δ) (c) at 3.5 Hz on the isotactic PAN
with (mm) content of 0.68: (∆) a gel film; (□) a fiber with a draw ratio of 16 and (●) a fiber
with a draw ratio of 60; iii) influence of the draw ratio on the dynamic storage modulus (E’)
(a), loss modulus (E’’) (b) and the loss (tan δ) (c) at 3.5 Hz on the atactic PAN with (mm)
content of 0.25: (∆) a gel film; (□) a fiber with a draw ratio of 16 and (●) a fiber with a draw
ratio of 60. i), ii) and iii) are reprinted from [168], Copyright 2017 American Chemical
Society.

Page 123 of 173

 (a)

Ac
Ac
Aa

INTENSITY (arbitrary units)

(b)

Ac Aa

(c)

Aa

Ac Ac

5 10 15 20 25 30 35 40
DIFFRACTION ANGLE (2, deg.)

a)

0.55

0.54
Lattice Spacing [nm]

(200)o (100)h
0.53

0.52
(110)o

0.51

0.50
0 50 100 150 200 250 300
Temperature [°C]
b)
Fig. 28: a) Different extrapolation methods of crystalline and amorphous regions in the X-ray
diffraction patterns reviewed by Gupta et al. (method c) [184], method a) has been discussed
by Hinrichsen et al. [194] and method b) has been developed by Bell et al. [195]; Reproduced
from [184] with kind permission from John Wiley & Sons, Inc.; b) Temperature variations of
orthorhombic (200)o and (110)o and hexagonal (100)h spacings for an ultra-drawn films at a
draw ratio 30 of ultra-high molecular weight homo-PAN. Reproduced with kind permission
from [191]. Copyright (2017) American Chemical Society.

Page 124 of 173

a)
INTENSITIY I

 18°

 33°

A
B

0
 
b)
Fig. 29: a) Schematic illustration of the influence of the hot stretching on the supramolecular
structure of PAN; b) plots of the azimuthal distribution of the (200) reflection of (A) PAN
fibers and highly oriented PAN fibers (B). Reproduced from [193] with kind permission from
Elsevier.

Page 125 of 173

Fig. 30: Influence of the co-monomer content on the FWHM of the (200) reflection measured
by wide angle X-ray scattering. Copyright (© 2017) from [205] by Frushour, B. G.;
Reproduced by permission of Taylor and Francis Group, LLC, a division of Informa plc.

Page 126 of 173

a)

b)
Fig. 31: a) Heating rate dependence of the DSC curves of PAN; b) ultrafast DSC curves for
PAN at a rate of -2,000 K∙s-1. Reproduced from [207] with kind permission from Elsevier.

Page 127 of 173

 300
y-butyrolactone
dimethylformamide

T (°C)

200 tM

100

tG

0.2 0.4 0.6 0.8 1.0

v2
a)

1
EXO

2
No. %VA MP °C
3 1 2.7 306
2 7.3 277
T

4
3 8.8 257
4 9.1 254
5 5 12.4 237
6
6 18.9 173
ENDO

7 7 26.1 165
8 8 38.5 81

0 100 200 300 400

T, °C
b)
Fig. 32: a) Melting (Tm) and glass transition (Tg) temperatures of PAN dissolved in
dimethylformamide (dots) and γ-butyrolactone (open circles) against the volume fraction of
polymer. Reproduced from [210] with kind permission from John Wiley & Sons, Inc.; b)
DTA melting points of acrylonitrile-vinyl acetate copolymers, vinyl acetate content between
2.7 and 38.5 wt%. Reproduced from [213] with kind permission from Elsevier.

Page 128 of 173

 360

340

320

300

280

260
Melting Point, °C

240

220

200
0 % VA

180
7.3 % VA
160
11 % VA
140

120

100
0.0 0.1 0.2 0.3 0.4 0.5 0.6
Water Weight Fraction, W (H2O)

Fig. 33: Dependence of the polymer melting point on the water content for homo-PAN and
PAN/vinyl acetate copolymer at different vinyl acetate fractions. Reproduced from [215] with
courtesy of Springer International Publishing AG.

Page 129 of 173

 a)

b)
Fig. 34: a) Phase diagram of homo-PAN and water, b) phase diagram of co-PAN and water
(co-monomer: 10.7 wt.% methyl methacrylate). Both figures are adapted from the open
source U.S. Patent No. US 4163770 A [216].

Page 130 of 173

 171 °C

Exo
Cooling
Heat Flow

143 °C

163 °C
Endo

193 °C
175 °C

First Heating
186 °C

110 130 150 170 190 210

Temperature (°C)

a)

148°C
Exo

Ⅱ Heating run

Ⅰ Heating run 181°C

Heat Flow

Cooling cycle 152°C

170°C
155°C

168°C
Endo

100 120 140 160 180 200

Temperature (°C)

b)
Fig. 35: High-pressure DSC thermograms of a) homo-PAN and b) PAN / itaconic acid
copolymer (IA content 3.2 mole %) under autogenous water vapor pressure, heating rate 5
K∙min-1. Reproduced from [225] with courtesy of Elsevier.

Page 131 of 173

 215°C Ⅰ
27
205°C Ⅱ
215°C Ⅲ
224°C Ⅳ
24

21

18
SHRINKAGE (%)

15 IN PRESENCE OF OXYGEN.

IN PRESENCE OF AIR.
12

0
0 100 200 300 400 500 600 700 800 900 1000
PREOXIDATION TIME (min.)
a)

30
CL, 265 °C
HWD Fibers
HTD Fibers
Stress Generated x 102 [g/den]

24

18

12

0
-20 20 60 100 140
Heating Time [min]
b)
Fig. 36: a) Thermally induced isothermal shrinkage of load-free co-PAN filaments at different
temperatures and oxidation mediums. Reproduced from [227] with courtesy of Elsevier; b)
shrinkage induced stress during thermal stabilization of constant length (CL) of HWD and
HTD filaments (HWD: hot water drawn, and HTD: high temperature drawn filaments).
Reproduced from [230] with kind permission from Springer International Publishing AG.

Page 132 of 173

 80 AREA OF PHYSICAL ENTROPY SHRINKAGE AREA OF CHEMICAL REACTION SHRINKAGE

70
% 6 % MA
60
SHRINKAGE

50 AMOUNT OF
CHEMICAL REACTION
SHRINKAGE 6 % MA + 1 % ITA
40

30
1 % ITA
20
HOMO
10

0
Tstart Tfinal
-10
0 50 100 150 200 250 300 °C 350
TREATMENT TEMPERATURE IN AIR (heating rate 5 °C/min)

Fig. 37: Influence of chemical composition of PAN fibers on the nature of dynamic stress-free
shrinkage curves measured during the in air stabilization at heating rate 5 K∙min-1.
Reproduced from [226] with kind permission from Elsevier.
TENSILE STRENGTH OF THE CARB. FIBRE (1350°C)

3600
MPa
3400

3200

3000

2800 FINAL HTT DURING

STABILIZATION

260°C
2600 270°C
280°C
2400 290°C

0 1 2 3 4 5
LINEAR HEATING RATE DURING STABILIZATION °C/min

Fig. 38: Effect of heating rate and final stabilization temperature on tensile strength of carbon
fibers. Reproduced from [226] with courtesy of Elsevier.
Page 133 of 173
 1.5

Density [g.cm-3]

1.4

1.3

20 50 100 200 500

Stabilization time [min]

a)

1.9
Density of carbon fibers [g.cm-3]

1.8

1.7
1.3 1.4 1.5
-3
Density of stabilized fibers [g.cm ]
b)
Fig. 39: a) Variation of density with stabilization time for acrylic fibers. Stabilization
temperature: (O) 240 °C; (∆) 255 °C; (□) 270 °C; b) density plots of carbon fibers against that
of stabilized fibers. Stabilization temperature: (O) 240 °C; (∆) 255 °C; (□) 270 °C.
Reproduced from [231] with kind permission from John Wiley & Sons, Inc..

Page 134 of 173

 a)

b)
Fig. 40: a) FTIR spectra of (a) virgin PAN and its stabilized fibers at 250 °C for different time
segments (b - g); b) degree of cyclization extent (EOC) detected from FTIR spectra and
calculated via equation: EOC = I1595/(I1595+I2243). Reproduced from [232] Scientific Research
Publishing Inc. (open access source).

Page 135 of 173

Fig. 41: Proposed chemical reactions during the stabilization of PAN. Reproduced from [77]
with kind permission from Elsevier.

Page 136 of 173

 4000 400

MN/m² GN/m²

3000 300

2000 200
Tensile Strength

Youngs Modulus
Stabilization Treatment Stabilization Treatment
230 °C --> 260 °C/ 40 min
230 °C --> 270 °C/ 40 min 230 °C --> 260 °C/ 40 min
SAF SAF
230 °C --> 290 °C/ 40 min 230 °C --> 270 °C/ 40 min
1000 230 °C --> 290 °C/ 40 min
100

1200 1600 2000 2400 2800

1200 1600 2000 2400 2800
HTT °C
HTT °C

a) b)

H
120
homopolymer homopolymer
H H
copolymer copolymer H c
c c c
100

10
Vrel

80
L [nm]

60

40
1
200 250 300 350 400 450
200 250 300 350 400 450
T [°C]
T [°C]
d)
c)
Fig. 42: Influence of the heat treatment on mechanical properties (a: tensile strength; b:
Young’s modulus) of PAN based carbon fibers; the precursors were stabilized at various
conditions under tension. Reproduced from [236] with kind permission from Springer
International Publishing AG; c) Temperature dependence of the length L of microvoids for
homo-PAN fibers (circles) and co-PAN fibers (squares); d) temperature dependence of the
relative volume Vrel of microvoids for homo-PAN fibers (circles) and co-PAN fibers
(squares). Figures c) and d) are reproduced with kind permission from [237]. Copyright
(2017) American Chemical Society.

Page 137 of 173

 1.0

0.8
Relative Intensity

0.6

0.4

0.2

0.0
1000 1400 1800 2200 2600 3000
Temperature (°C)

i)

ii) iii)
Fig. 43: i) Relation between intensity ratio ID/IG and heat treatment temperature for different
PAN fibers (open circles represent carbon and graphite fibers developed from PAN fibers
oxidized in potassium permanganate; open rectangles represent carbon and graphite fibers
derived from PAN oxidized in air). Reproduced from [239] with kind permission from John
Wiley & Sons, Inc.; ii) SEM images of fracture surface of carbon fibers treated at various
temperatures. The arrow indicates the fracture source during the tensile experiment; iii) Raman
mapped images of (a) the as-received and (b) 2,500 °C-treated carbon fibers. The color bars based
on the values of AD/AG are given to the right of each image. The white blanks are singular points
due to the zero signal area outside the cross-section of the fiber. Both figures ii) and iii) are
reproduced from [242] with kind permission of The Royal Society of Chemistry.

Page 138 of 173

a)

b) c)

e)
d)
Fig. 44: a) Model of the carbonaceous mesophase - a lamellar liquid crystal reproduced from
[266] with the courtesy of Elsevier; b) SEM-micrograph of mesophase spherules obtained by
solvent extraction from mesophase pitch using N-methyl pyrrolidone; c) cross section of two
connected carbonized mesophase spheres with obvious lamellar morphology. (b) and c) are
reproduced from [269] with kind permission from Elsevier); d) structure model of mesophase
spherules. (reproduced from [264] with kind permission from Elsevier); e) reflected polarized

Page 139 of 173

light micrograph of polished sections of mesophase spheres derived from acenaphthylene
pitch. (reproduced from [273] with courtesy of Royal Society of Chemistry).

a)

b)
Fig. 45: a) Solubility of pitches with different mesophase contents prepared from a precursor
petroleum pitch. Reproduced from [274] with courtesy of Elsevier; b) changes in d002 and
Lc(002) of QSmeso and QImeso with heat treatment temperature. Reproduced from [275] with
kind permission from Elsevier.

Page 140 of 173

a)

b)
Fig. 46: a) Typical preparation methods of precursor pitch for high performance carbon fibers.
Reproduced from [280] with kind permission from Springer International Publishing AG; b)
influence of melt spinning on the structure of pitch based fibers and fundamental procedures
for manufacturing of low compressive strength isotropic and ultra-high modulus anisotropic
carbon fibers from different pitch types. Reproduced from [264] with courtesy of Elsevier.

Page 141 of 173

Fig. 47: Raman spectra of graphite fibers derived from annealed and non-annealed
naphthalene based mesophase precursors (NPGF: naphthalene based mesophase pitch based
graphite fibers). Reproduced from [281] with kind permission from Elsevier.

Page 142 of 173

 1000

100
Lc [Å]

10

1000
La [Å]

100

10
5 600 °C, 800 °C, 1000 °C, 2500 °C, 3000 °C
4
d002 [Å]

3
2
1
0
l

in

se
id

ne

ne
ne
y

on
en

ar

ac

ro
re

ce
le

in
m
ph

t
th
c

ra
ex
qu
ht
ou

oi

an
Bi

th
ap

D
h

ra
C

An
en
ht
N

th
ap

Ph
An
N
2-

Fig. 48: Crystallite parameters (Lc, La, d002) of different carbonized and graphitized chars
produced from different hydrocarbons. Data obtained from [308].

Page 143 of 173

Methylnaphthalene based mesophase pitch

Naphthalene based mesophase pitch

Anthracene based mesophase pitch

Fig. 49: Typical molecular structures of mesogen molecules in several mesophase pitches
synthesized via the HF/BF3 method. Reproduced from [309] with kind permission from John
Wiley & Sons, Inc..

Page 144 of 173

Fig. 50: Spider Wedge model for describing the structure of mesophase pitch precursors.
Reproduced from [265] with kind permission from Elsevier.

Page 145 of 173

 60 mNA
CTE
dL/L
300 4000
50
250 3500

3000
200 40 PP

Lc (Å)
2500

CTE x 106· °C-1

150 CTP
dL/L x 104

2000 30
100
1500 NA
50 20
1000 ANT

0
500
10
-50 0

-100 -500
0 50 100 150 200 250 300 0
0 100 200 300 400 500

T [°C] Temperature (°C)

Tg = 212 °C

a) b)
6

Annealing
Pitch
5

Spun
4 Fiber Spinning
Lc [nm]

Shear Thinning

1
0 100 200 300 400 500
Temperature [°C]
c)
Fig. 51: a) Plots of dL/L and CTE versus T for 100 % mesophase Mitsubishi ARA-24 pitch.
Reproduced from [310] with kind permission Elsevier; b) stacking height of the layers in the
mesophase pitches derived from: mNA: methylnaphthalene, PP: petroleum pitch, CTP: coal
tar pitch, NA: naphthalene and ANT: anthracene. Reproduced from [313] with kind
permission from Elsevier; c) schematic diagram for change of stacking height of mesophase
pitch during spinning and solid-phase annealing (lines - solid: heating, dashed: spinning; dot:
cooling). Reproduced from [281] with kind permission from Elsevier.

Page 146 of 173

 i) ii)
Fig. 52: i) HR-SEM micrographs of longitudinal surfaces of (a) as-spun, (b) THF and (c)
pyridine extracted fibers observed from a tilted view (10°); ii) HR-SEM micrographs of
longitudinal surfaces of (a) stabilized, (b) carbonized and (c) graphitized fibers. Reproduced
from [296] with kind permission from Elsevier.

Page 147 of 173

i)

iii)
ii)

Fig. 53: i) HR-SEM micrographs of longitudinal sections of mesophase pitch based

graphitized fibers at 2,500 °C ((a) graphitized fibril unit, (b) pleat unit); and STM images of
longitudinal section of (A) thickness of the fibril, (B) thickness of the pleat unit, (C) the
thickness of the graphitic unit. Reproduced from [309] with kind permission from John Wiley
& Sons, Inc.; ii) three-dimensional schematic picture of domain units in mesophase pitch-
based carbon fibers. Reproduced from [314] with kind permission of Elsevier; iii) origin of
graphitic and pleat units in graphite fibers Reproduced from [296] with kind permission of
Elsevier.

Page 148 of 173

Fig. 54: Variation of cross section morphology of mesophase pitch based graphite fiber with
varying the spinning temperature (in other words: the zero shear viscosity) for two different
mesophase pitches. Reprinted with permission from [317]. Copyright (2017) American
Chemical Society.

Page 149 of 173

 15.00
-10
380 240
200
290 270 220
10.00

340
Weight Change [%]

ln R [1/w (|dw/dt|)]
-12
5.00
320

290
0.00

-14
270
-5.00

240
-10.00 -16
0.00 60.00 120.00 180.00 240.00 300.00 360.00 420.00 480.00 0.14 0.16 0.18 0.20 0.22
Time [Minutes] 1/T (K) x 100
a) b)
0.05

12
Total micropore volume [cc/g-yarn]

0.04
10
D/G Ratio (Arca)

0.03 8

6
0.02

0.01
2

0.00 0
0 2 4 6 8 0 500 1000 1500 2000 2500
Amount of H2O produced [mol/g] Heat Treatment Temperature, °C

c) d)

10 350

0
Weight Gain [wt.%]

300
Tg [°C]

-50

250

-100 200
300 400 500 0 100 200 300 400
Temperature [°C] Temperature
Reached in Oxidation [°C]
Reached in Oxidation
e) f)
Fig. 55: a) Weight change curves for mesophase pitch oxidation (filled circle = 240 °C, filled
square = 270 °C, filled diamond = 290 °C, filled triangle = 320 °C, filled cross = 340 °C) ; b)
Arrhenius type plot of mesophase pitch oxidation data (filled circle = weight-loss process,
filled square = weight-gain process). Figures a) and b) are reproduced from [318] with kind
permission from Elsevier; c) change in total micropore volume against amount of H2O

Page 150 of 173

produced from mesophase pitch. Reproduced from [319] with kind permission from Elsevier;
d) plots of ID/IG ratio versus heat treatment temperature. Reproduced from [320] with courtesy
of Elsevier; e) weight gain of pitch fiber by oxidation at heating rate of 0.5 K·min-1; f) glass
transition temperature Tg of pitch fiber after oxidation at heating rate of 0.5 K·min-1. Figures
e) and f) are reproduced from [321] with kind permission from Elsevier

i) ii) iii)
Fig. 56: Monolignols of lignin; i) ρ-coumaryl alcohol, ii) coniferyl alcohol, iii) sinapyl alcohol

Page 151 of 173

Fig. 57: Correlation of Raman FWHM of the G-band with the intensity ratio ID/IG of different
graphite and carbon fibers, and for different pyrolyzed lignin at 1,200 °C; EM: Young’s
modulus; fiber type and code are restricted information. MPP: Mesophase pitch based
graphite fibers; PAN: PAN based carbon fibers; IP: isotropic pitch based carbon fibers. The
coordinates in the brackets are (x: FWHM of the G-band; y: Intensity ratio ID/IG).

Page 152 of 173

 a)

b)
Fig. 58: Illustration of an extended straightening of a) hardwood lignin chain and b) softwood
lignin chain when PEO (green) is introduced. Reprinted with permission from [370].
Copyright (2017) American Chemical Society.

Page 153 of 173

Fig. 59: tan δ plot versus temperature of different precursor fibers (PAN/lignin 70/30 w/w %)
(DR = 13) at 1 Hz. Reprinted with permission from [389]. Copyright (2017) American
Chemical Society.

Page 154 of 173

Table 1: Classification of commercially available continuous carbon and graphite fibers with
regard to their mechanical properties.

Class Tensile Tensile elastic Density Polymeric

strength modulus (g∙cm-3) precursor
(GPa) (GPa)
Lower Upper Lower Upper Lower Upper
limit limit limit limit limit limit
Low modulus 1 2 - 3.5 50 200 1.65 1.9 isotropic pitch
(LM)
Standard modulus - 2.5 4.5 - 5 200 280 1.76 2 PAN
High tenacity
(SM-HT)
Intermediate 3.5 7 280 350 1.76 1.88 PAN
modulus – Super
high tenacity (IM-
SHT)
High modulus 1 5 350 600 1.8 2 PAN, Rayon,
TM
(HM) BoCell
Ultra-high modulus 2 4 600 950 2 2.22 mesophase pitch,
(UHM) Rayon

Page 155 of 173

 Table 2: Unit cell characteristics of common cellulose polymorphs and cellulose triacetate
given by the three edge vectors (𝑎, 𝑏, 𝑐 ) of the crystal parallelepiped and the angles between
the vectors (α:( 𝑎,𝑐 ); β: (𝑏,𝑐 ); γ: (𝑎, 𝑏)); PD - packing degree, V - volume of the unit cell and
CV - volume of one AGU unit (CV = V/PD). The unit cell volume of different polymorphs
and the cellulose derivatives cellulose triacetate I and II was calculated using the formula:
𝑉 = 𝑎𝑏𝑐 1 + 2 cos 𝛼 cos 𝛽 cos 𝛾 − 𝑐𝑜𝑠 2 𝛼 − 𝑐𝑜𝑠 2 𝛽 − 𝑐𝑜𝑠 2 𝛾 ; For comparison
purposes we listed the unit cell dimensions of α-chitin and chitosan with a deacetylation
degree of 100 %.

Unit cell characteristics

Polymorph
a b c α β γ PD V CV
type Ref.
(nm) (nm) (nm) (°) (°) (°) (-) (nm³) (nm³)
0.674 0.593 1.036 117 113 81 1 [87] 0.278 0.278
Cellulose Iα
0.671 0.596 1.040 118.08 114.8 80.37 1 [98] 0.266 0.266
0.801 0.817 1.036 90 90 97.3 2 [87] 0.678 0.334
Cellulose Iβ
0.778 0.820 1.038 90 90 96.5 2 [99] 0.654 0.327
Mercerized 0.810 0.903 1.031 90 90 117.1 2 [100] 0.598 0.299
Rayon 0.909 0.769 1.031 90 90 117.3 2 [101] 0.569 0.285
Cellulose IIII,
1.025 0.778 1.034 90 90 122.4 1 [102] 0.588 0.588
IIIII
Cellulose IV1 0.803 0.813 1.034 90 90 90 2 [103] 0.675 0.338
Cellulose IV2 0.799 0.810 1.034 90 90 90 2 [103] 0.669 0.335
Cellulose
triacetate 0.594 1.143 1.046 90 90 95.4 1 [104] 0.636 0.636
CTAI
Cellulose
triacetate 2.468 1.152 1.054 90 90 90 4 [105] 2.996 0.749
CTAII
α-Chitin 0.471 1.878 1.030 90 90 90 2 [106] 0.912 0,456

Chitosan 0.894 1.697 1.034 90 90 90 4 [107] 1.569 0.392

Page 156 of 173

Table 3: Structural data of selected cellulosic polymorphs, which have been investigated for
manufacturing carbon fibers [115-117]; DP - average degree of polymerization; Df - degree of
fibrillation in the wet state (min=0/max=6) (Data from Ref. [118]); CW - crystal width; CryL:
crystal length; DL - domain length; 𝜒𝐶𝑟 - crystallinity index.

Total
Elementary fibril 𝜒𝐶𝑟 Df
Cellulosic fiber DP orientation
(nm) (%) (-)
(-)
CW CryL DL
1,600-
Cotton 6.2-13 3.2-7.2 12.8-25 70-79 0.62-0.70 2
2,000
~250-
Rayon 7.7-10 2.9-4.9 12-15.4 35-48 0.39-0.95 1
500
~600-
Lyocell 3.9 2.5-4.6 14.3 57-75 0.62-0.94 4-6
800
Cuprammonium
~500 4.2 14.3 25 42 - 2-3
Rayon

Page 157 of 173

Table 4: Mechanical properties based on Rayon and Lyocell, Data from Ref. [84, 117]; The
effective streching is the ratio of cross sectional area of the stress-graphitized filaments and
the unstressed graphitized filaments [84]. Rayon Villwyte is an expired trade mark of the
cellulosic precursor manufactured by Midland Ross Corporation and used by Union Carbide
a)
Corporation for the production of high modulus carbon fibers. Applied effective streching
of 100 % at 2,800 °C for up to 40 min dwell time.

Precursor fibers Carbon fibers

Carbonized at 1,300 °C
As spun and dry Stress-graphitizeda)
without hot streching
Rayon Rayon Rayon
Lyocell Lyocell Lyocell
Villwyte Villwyte Villwyte
Tensile No
0.31 0.93 0.82 1.07 3.79
strength (GPa) published
Young’s data
15.1 12.6 79.2 96.6 750
modulus (GPa) avialable

Page 158 of 173

Table 5: Unit cell characteristics of single para-crystal of PAN – Comparison of literature
data. V - unit cell volume and CV - volume of one monomer unit (CV = V/PD). The unit cell
volume of the single para-crystal was calculated using the formula: V = abc.

Unit cell characteristics

Ref. a b c α β γ PD V CV
(nm) (nm) (nm) (°) (°) (°) (-) (nm³) (nm³)
[178] 2.118 1.160 - 90 90 90 2 - -
[179] 2.10 1.19 0.504 90 90 90 2 1.259 0.629
[180] 2.148 1.155 0.709 90 90 90 2 1.759 0.879
[181] 1.07 1.21 - 90 90 90 2 - -

Page 159 of 173

Table 6: Reported endotherm melting temperatures from high pressure DSC diagrams of
different PAN co-polymers; MA - methyl acrylate; VA - vinyl acetate; VC - vinyl chloride;
SS - sodium styrene sulfonate; MMA - methyl methacrylate; MAA - methacrylic acid.

PAN Plasticizer
Melting
Acrylonitrile Comonomers Water Auxiliaries Ref.
point (°C)
(wt.%) (wt.%) (wt.%) (wt.%)
MA, VA, VC
85 30 - 150-170 [214]
(15)
ethylene
MA(6),
93.6 13.3 carbonate 170-180 [221]
SS(0.4)
(2.9)
20 - 153
90 MA(10)
16 AN (24) 116
[222]
40 - 133
81 MMA(19)
16 AN (24) 96
85.5 MMA (14.5) 18 - 148
[216]
92 MMA (8) 18 - 161
nitromethane
MA(5.5),
93 16 (5), 125 [223]
MAA(1.5)
methanol(5)
MA(5.5), acetonitrile
93 13 130 [219]
MAA(1.5) (14)
88 unspecified 23 - 155
ethylene
[224]
88 unspecified 21 carbonate 147
(2.3)

Page 160 of 173

Table 7: Residence time requirements for prospective oxidation and stabilization routs; data
from [198].

Method Process time Thermal post treatment time Total time

(min) (min) (min)
e-Beam seconds 40-50 40-50
Ultraviolet 6-7 20-24 26-31
Thermochemical 5-10 20-24 25-34

Page 161 of 173

Table 8: Glass transition and softening temperatures of different 100 % optically anisotropic
mesophase pitches; NP: naphthalene-derived mesophase pitch, MNP: methylnaphthalene-
derived mesophase pitch, dMNP: dimethylnaphthalene-derived mesophase pitch, AP:
anthracene-derived mesophase pitch, Mitsubishi AR: mesophase pitch produced by
Mitsubishi Gas Chemicals.

Mesophase NP MNP dMNP AP Mitsubishi

type AR
Tg (°C) 163 144 183 - 212
Ts (°C) 228 225 249 238 - 275 260
Ref. [309] [309] [309] [311] [310]

Page 162 of 173

Table 9: Mechanical properties of carbonized and graphitized fibers for different lignin types and different processing methods (fiber formation,
carbonization and graphitization); L - lignin type (H: hardwood; S: softwood; ALS: alkali softwood); P - plasticizer or blending polymer; SM -
spinning method (M: melt-spinning; D: dry-spinning; W: wet-spinning; G: gel-spinning); δ - tensile strength; E - Young’s modulus; ε - elongation at
break; T - heat treatment temperature. AM - acrylimide; AA - acrylamide; MS - methoxybenzoly-softwood lignin; V - vanillic acid; EGMA -
ethylene glycol dimethacrylate; V-PET - vanillic acid based polyester; CL - percynnamoylated lignin; AS - acetylated softwood lignin; PAN* - 34
% higher molecular weight of PAN; APL - annual plant lignin; CNT - carbon nanotubes.

Carbon fibers Graphite fibers

P:L
Ref. L P SM δ E ε T δ E ε T
(GPa) (GPa) (%) (°C) (GPa) (GPa) (%) (°C)
H M 0.784
S+H
M 0.686 2,000
(1:1)
H M 0.294 800
[360] S+H
M 0.245 900
(1:1)
S glycerin 1:10 M 0.490 1,000
H PVA 1:2 D 0.294 1,500
S PVA 1:1 D 0.490 1,500 0.147 2,500
ALS PEO+AM/AA 5:95 D 0.833 34.3
[363] ALS PEO+AM/AA 4:10 D 1.08 32.4 1,000
ALS PEO 1:10 D 0.882 39.2

Page 163 of 173

[364] S M 0.45 1.2 1,000
[365] S M 0.35 39.1 1,000
[366] S M 0.66 40.7 1.6 1,000
S M 0.339 33 1.2
H PEO 3:95 M 0.458 59 0.79
[340] 1,000
H M 0.388 40 1
H PEO 5:95 M 0.339 33 1.2
H M 0.605 61 1.4
H PP 5:95 M 0.332 57 0.89
[372] 1,000
H PET 25:75 M 0.703 94 1.06
H PET 5:95 M 0.669 84 1.10
[373] H M 0.517
[375];
H M 1.07 86
[374]
[377] S PET M 0.949 127.6 1,200
[382] S M 0.550 60 1,000
[353] S V(8)+EG(5) 13:87 M 1.1 140 0.6 1,400
MS V(5)+EGMA(5) 10:90 M 0.7 210 0.4 2,200
MS V-PET 10:90 M 0.9 140 0.6 1,800
[353]
V(5)+
ZL 10:90 M 0.9 48 2 2,200
EGMA(5)

Page 164 of 173

[383] CL V(5)+EGMA(5) 10:90 M 0.52 32.2 1.65 1,400 0.4 31.7 1.3 2,200
[384] AS M 0.599 1.1
[385] LS AN 21:9 W 1.25
[386] L PAN 35:65 W 1.68 201 0.76
[387] L PAN* 35:65 W 1.93 198 0.85
[388] L PAN 25:65 W 2.24 217 0.98
[389] APL PAN 30:70 G 1.74 230 0.8 1,100
[389] APL PAN/CNT 30:70:3 G 1.4 200 0.7 1,100

Page 165 of 173

Table 10: The objectives of the recent worldwide research activities on low cost carbon fiber
precursors and processes.

Project/Facility General information and selected fundamental research scopes Ref.

CARBOPREC CARBOOREC (Renewable source nanostructured precursors [399]
for carbon fibers) is funded by the European Union within the
funding program FP7-NMP. The research scopes are:
 Development of high purity cellulosic precursor fibers
with increased carbonization yield up to 35 wt.%
 Development of high purity lignin precursor fibers
with increased carbonization yield up to 50 wt.%
 Replacement of the conversional oxidative stabilization
rout with plasma assisted stabilization technology
CFTF The CFTF (Carbon Fiber Technology Facility) is initiated by [400]
the Oak Ridge National Laboratory. The research scopes of
this new research facility are:
 Industrially scalable low cost carbon fibers from
textile-graded PAN and lignin
 Melt-spinning and pseudo-melt-spinning of precursor
fibers
 Conventional (thermal) and advanced microwave and
plasma conversion (stabilization and carbonization)
technologies
EUCARBON EUCARBON (European Space Qualified Carbon Fibres and [401]
Pre-impregnated Based Materials) is a European research
project funded by the European Union within the Seventh
Framework Programme. The research scopes are addressed as
follow:
 Space qualified high and ultrahigh modulus carbon
fibers
 Developing of space qualified pre-impregnated
composites and epoxy resins

Page 166 of 173

  Adjusting the thermal and electrical conductivity via
the composites via the implementation of carbon nano-
tubes.
FIBRALSPEC FIBRALSPEC (Functionalized Innovative Carbon Fibers [402]
Developed from Novel Precursors with Cost Efficiency and
Tailored Properties) is a European research project funded by
the European Union within the Seventh Framework
Programme. The scopes are:
 Development of novel carbon fiber precursors from
different polymers: textile-graded PAN, lignin,
polyolefin
 Functionalization and activation of carbon fibers
 Mathematical modelling of the mechanical properties
of carbon fibers
 Carbon fibers recycling
Greenlight Greenlight (Cost effective lignin‑based carbon fibres for [403]
innovative light‑weight applications) is a research project
funded by the European Union within the program H2020-
EU.3.2.6. The main research scopes are:
 Development of economically viable carbon fibers on
the base of the renewable lignin and via melt spinning
processes
 Investigation of the ideal conversion conditions of the
lignin precursor fibers into carbon fibers
LiCaFib LiCaFib (Lignin-based Carbon Fibers) is a research project [404]
funded by the Federal Ministry of Education and Research of
the Federal Republic of Germany. The main research scopes
are:
 Development of lignin-based carbon fibers with a
tensile strength of 1.5 GPa and tensile modulus of 150
GPa.
 Modification of the fiber spinning technology
 Investigation of the optimal thermal conversion

Page 167 of 173

 processes (stabilization and carbonization) of the lignin
precursor into the carbon fibers
 Structure-property-correlation of the lignin based
carbon fibers
LIBRE LIBRE (Lignin Based Carbon Fibres for Composites) is a [405]
research project funded by the European Union within the
funding program H2020-EU.3.2.6. The main objectives of the
research project are (selected):
 Development of precursor fibers from blends of
modified lignin and biopolymers
 Reduction of the energy consumption of the thermal
conversion processes through the implementation of
microwave or radio frequency heating technologies
 Functionalization of the carbon fiber surfaces via non-
aqueous processes
MAI Green MAI Green is a research project in the Leading-Edge Cluster [406]
MAI Carbon, which is funded by the Federal Ministry of
Education and Research of the Federal Republic of Germany.
The main research scopes are:
 Cost-effective and optimized conversion processes of
the precursor fibers into carbon fibers
 Customization of the lignin precursors
 Tailored approaches for the processing lines of lignin-
based carbon fibers
NEWSPEC NEWSPEC (New cost-effective and sustainable polyethylene [407]
based carbon fibres for volume market applications) is a
research project within the research cluster Carbon Fibres &
Advanced High Performance Composites Cluster, which is
funded by the European Union within the funding program
FP7-NMP. The main research scopes are:
 Investigation the low cost polyethylene as a precursor
for carbon fibers
 Implementation of the electron beam technology for

Page 168 of 173

 cross-linking and stabilization
 Functionalization of the carbon fiber surface utilizing
the atmospheric plasma technology
 Investigation and validation of the in-line quality
control systems using the transportable confocal micro
Raman system

Page 169 of 173

Table 11: The necessary research and development (R&D) areas to lower the costs of carbon fibers.

Precursor Key research and development Key research and development Target properties Price
Material Process and level
-1
Material Properties Criterion R&D strategy Process Criterion R&D strategy applications (€·kg )
+ thermally Fusibility + tuning the pseudo-melting Wet spinning + low volume Alternative spinning TS > 2.4 GPa ~ 7 - 12
stabilizable points via different aprotic production methodologies to TM > 240 GPa
+ high solvents incl. water strength high-volume EB > 1 %
carbon yield + eco-friendly aprotic carbon fiber (achieved by
(> 50 - 60 %) solvents manufacturing ORNL, USA
+ well known + stabilizing aprotic [400])
crystal solvents
conversion Possible annual
mechanisms Purity + low cost removal of Pseudo-melt + sealed spinning + compounding production
and pore sodium ions spinning system ( extruder, under high pressure volume > 1,000
formation + replacement of the fiber formation and sealed extruders tons per year
pathways NaSCN as a solvent in the zone) + tuning the
+ high synthesis + take-up and rheological behavior Main applications:
volume winding under high under consideration Automotive
availability pressures of the implemented industry and wind
Textile + low cost + compounding co-monomers, mills
grade synthesis under high aprotic solvents and
PAN pressure and under molecular weight
gas sealed + production speed
conditions limitations of the
+ high pressure / pseudo melt spinning
gas sealed (take-up; throughput
rheometry profiles)
+ scalability for high
production volumes

Physical + co-monomers to Stabilization + low productivity + elimination of the

chemistry passively reduce the and due to the stabilization step: low
pseudo-melting points carbonization necessary dwell energy stabilization,
+ impact of different aprotic time i.e. microwave
solvents on the crystal + high energy assisted chemical
structure consumption plasma stabilization
+ thermal stability of the (achieved by Carbon

Page 170 of 173

 expanded crystal structure Fiber Technology
+ thermal conversion Facility, ORNL, USA
pathways of the expanded [400])
crystal structure into + chemically
turbostratic carbonaceous designed
forms stabilization
pathways (smart
systems, i.e. via
defined aprotic
solvents)

Lignin + high Fusibility Under consideration the Pseudo-melt Beside the + compounding TS > 2.0 GPa ~ 4 - 10
volume low cost benefit and spinning aforementioned under high pressure TM > 210 GPa
availability sustainability: points: and in sealed EB > 1 % (at low
and + initiation of a semi- + viscoelastic extruders carbonization
sustainability crystalline order  with no behavior of the + tuning the temperatures (up
+ low cost chemical modification pseudo melt rheological behavior to 1,200 °C)
+ carbon + fusibility of the semi- + adjusting the flow under consideration
yield (25 - 40 crystalline order properties of the implemented Sustainable low
%) + pseudo-melts and its (plasticizing effect co-monomers, cost fibers with
+ green viscoelastic and flow of low and medium aprotic solvents and better carbon foot
carbon foot behavior molecular weight molecular weights of print due to the
print + implementation of lignin) lignin lignin shares.
+ technical lignin/textile grade PAN + fiber formation + production speed
waste compounds (lignin shares zone and take-up limitations of the Possible annual
up to 50 %) speed limitations pseudo melt spinning production
(take-up; throughput volume
profiles) (low (scalability
molecular weights of criterion of the
lignin pseudo-melt
+ scalability for high spinning
production volumes technology) >
1,000 tons per
year

Main applications:
Automotive
industry and wind

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 mills
Purity + low cost purification, Stabilization + pore + elimination of the
fractionation, isolation and development stabilization step: low
unification of the molecular mechanisms energy stabilization,
weight of Kraft Lignin + controlling of pore i.e. microwave
(Achieved by Klett et al. true length, tilt assisted chemical
[338] and Thies et al. [339]) angle and specific plasma stabilization
+ unified higher molecular surface (S/V) (Achieved by Carbon
weight >10 kDa and purity + porosity Fiber Technology
level for sodium ions <<100 + thermal treatment Facility, ORNL, USA
ppm (~25 ppm Klett et al. determined crystal [400])
[338]) recovery + chemically
+ overcome the mechanisms designed
consistency problem stabilization
(brittleness) pathways (smart
systems, i.e. via
defined aprotic
solvents)

Physical + thermally stabilizable Carbonizatio + high energy + adjusting the

chemistry + increasing the carbon n consumption porosity and the pore
yield (25 - 45 %) development
+ thermally induced crystal mechanisms
conversion mechanisms + low cost and
+ orientation of the physically initiated
molecules alongside the conversion of the
fiber axis  semi- amorphous lignin into
crystalline order is semi crystalline order
necessary in the starting
+ controlling the pore precursor
development mechanisms + orientation of the
 amorphous region pores (tilt angle of
content in the lignin based the pore axis with
fibers respect to the fiber
+ lattice disorder of the axis)  semi-
carbonized structures are crystalline order is
comparable to PAN-based necessary
carbonaceous structure + fundamental

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 research regarding
the relationship
between the
molecular weight and
the porosity of the
resulting carbon
fibers
+ orientation
recovery
mechanisms
Poly- + high Physical + sulfonation via sulfuric Sulfonation + low productivity + low cost pollutants TS: 1.7 – 2.8 GPa < ~10
ethylene volume chemistry acid process due to the required treatment processes TM > 170 GPa (without
availability + tuning the crystal dwell time + sulfonation EB > 1 % pollutants
+ low cost structure after the wet + low energy processes with treatment
synthesis sulfonation stabilization higher productivity Main applications: costs)
+ melt + crystal conversion + technical Automotive
processable mechanisms concerns (high industry and wind
into fibers + pollutions concerns (high concentration mills
+ high SOx amounts) during the sulfuric acid
density carbonization bathes)
polyethylene + pollutants
(HDPE) elimination after
carbonization (EU-
directive
2010/75/EU for
industrial air
pollution)

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