Vol. 44 No.

2 SCIENCE IN CHINA (Series B) April 2001

Evolution of the composition and structure of PAN carbon

fiber during preoxidation
LI Xiaojia (9̤), LUO Qianhua (å/), ZHU Yijun (K¢Š)
& WANG Haizhou (º:)

Central Iron & Steel Research Institute, Beijing 100081, China

Correspondence should be addressed to Wang Haizhou (email: hzwang@ncschina.com)

Received December 25, 2000

Abstract Using scanning electronic microscope, X-ray diffraction analysis, PYR-GCMS and IR
etc., we studied the evolving process of the composition and structure of PAN carbon fiber during
preoxidation. In the initial stage of preoxidation, PAN filament tows disappear and become
semi-thaw. At first, reactions happen between the copolymers and esters disappear. The mole-
cules annularly crosslink and the index of cyclation slowly increases. It is easy to fix the structure
and form defects during the initial and the medium stages, which are most reactive. More traction
is advised in these stages to minimize the structural deficiencies. In the medium stage of preoxida-
tion, the fiber was reshaped into new sheet stacks and gradually changed to sheet sectors, and
this structure tends to be stable in the final stage. Induced by acid and ester copolymer, PAN fiber
forms a very stable cycle structure in the final stage. Besides, monomer, dimmer and trimer obvi-
ously decrease. In the final stage of the preoxidation, there exists only the fragment of CN, and
it also disappears at last. The index of cyclation rises with the process of preoxidation and the
structural shape stabilizes.
Keywords: PAN carbon fiber, preoxidation, evolution of the composition and structure, structural deficiencies.

During the past 20 years, PAN carbon fiber has entered a new era of high-speed development.
Especially with the growth of modern industry of navigation and spaceflight, high performance
fiber-enhanced materials are getting their use in structural materials of navigation[1 3]
. The exten-
sive application of carbon fiber complex materials boosts the development of carbon fiber industry
greatly. In order to produce high performance PAN carbon fiber, PAN fiber usually needs to be
preoxidized under low temperature to make the thermoplastic PAN change into cycle or
heat-resistant scalar form compound, so that it can endure the high temperature of the next step.
With carbonization under high temperature, the hydroxyl groups in preoxidized PAN carbon fiber
begin to cross-link and condensate and finally form condensed aromatic ring topping structure.
Next, we treated the surface of the carbon fiber to get the final product. The microstructure and
inner-defects will directly influence the tensile strength, elastic modulus and discreteness[4 7]
.
The long duration of preoxidation process and the complexity of chemical reaction will
greatly influence the final structure and formation of the inner-defects[8, 9]. By using scanning
electronic microscope, X-ray diffraction analysis, PYR-GCMS and IR to follow the process of
preoxidation,we explored the rules of the composition and structural evolvement, during the PAN
 No. 2 EVOLUTION OF COMPOSITION AND STRUCTURE OF PAN CARBON FIBER 197

carbon fiber preoxidation, and the reason for inner-defects. We hope that we can provide some
academic bases for process optimization of PAN carbon fiber’s preoxidation.

1 Experimental

1.1 Equipments
Carbo Elba 1102 elementary analyzer (Heraeus, Germany), ST-02 elementary analyzer,
APD-10 automatic powder X-ray diffraction analyzer (Philip, Holand), S-530 scanning electronic
microscope (Hitatch, Japan), FEM-100CX transmission electronic microscope (Electricity, Japan),
FTS-65 FT-IR spectrometer, FRJ tubing degradationer (Fangshan, Nanjing), GC-14A chromato-
graph (Shimadzu, Japan), QP-2000 mass spectrometer (Shimadzu, Japan).

1.2 Sample preparation

1.2.1 Sample preparation for scanning electronic microscope. Embedded and fixed the fila-
ments of original and preoxidized PAN with resin, then put them in a bottle of dry ice for quick
frozen. Broke off the sample and took the cross section for analysis.

1.2.2 Sample preparation for elementary and diffraction analysis. On the two sides of the pre-
oxidation oven, cut off the preoxidation filament and drew it out quickly, then divided it equally
into 8 parts with each reflecting the different preoxidation periods.
2 Results and discussion
2.1 Change of fracture graph of filament during preoxidation by SEM

2.1.1 Fracture graph of PAN original filaments.

By the scanning electronic micrograph we can clearly
see the filament tow in the fracture graph of PAN
original filaments. The fracture graph of original
filaments of different brands is a little different be-
cause of the diverse technic applied. Some look like
dogtooth with relatively big diameter, sparse structure
and flimsy strength. The fracture graph of qualified
original filament looks orderly, fine and even (fig. 1).

2.1.2 Fracture graph of preoxidation. Semi-thaw

can be observed in the initial stage of preoxidation by
Fig. 1. The fracture graph of PAN original filament
scanning electronic microscope. The tows of the obtained by scanning electronic microscope.
original filament disappears and looks like stacks.
The gap increases and the fibers clearly shrink. In the medium stage of the preoxidation, carbon
fibers are reshaped into new sheet stacks, and gradually change to sheet sectors.The frame formed
in the medium stage of preoxidation tends to be stable in the final stage. Except that the sheet
structure is becoming clear, there is little change during the carbonization (fig.2).
 198 SCIENCE IN CHINA (Series B) Vol. 44

Fig. 2. The fracture graph of carbon fiber and PAN filaments during different preoxidized stages. (a) The ini-
tial stage, (b) the medium stage, (c) the final stage, (d) carbon fiber.
2.2 Formation of the inner-defects during preoxidation
The structure of PAN original filament undergoes the following process: filament tow
semi-thaw sheet stacks sheet sectors. It displays semi-thaw sheet stacks during the back part of
initial stage and the front of medium. It is very easy to form some inner-defects. During the initial
and medium stages, PAN original filament maybe forms big structural holes and consolidates with
each other. These defects cannot be eliminated and will exist in the final carbon fiber leading to
macroporous structural deficiencies and even hollows inside. The sheet texture is thick and sparse.
Sometimes, lots of bi-connected structures even appear (fig.3).

Fig.3. The fracture graph of preoxidized filaments with bugs. (a) The initial stage, (b) the medium stage, (c) the final stage.
 No. 2 EVOLUTION OF COMPOSITION AND STRUCTURE OF PAN CARBON FIBER 199

2.3 Elemental changes during preoxidation

Different technics bring about different
concentrations of the main elements such as
C, H, O and N in PAN original fibers. The
concentrations of C, H and N decrease during
the initial stage, whereas the decreasing rate
is not as acute as in the medium stage, but is
the same to the increase of oxygen. But the
distinction is blurry because the initial stage
is very short. During the medium stage, the Fig. 4. The elemental changes during preoxidation.
concentrations of C, H and N plummet, and
the concentration of O hoicks. The reaction is very fierce and becomes relatively mild in the final
stage (fig.4).

2.4 Changes of the index of cyclation during preoxidation

According to the analysis of wide and narrow angular X-ray diffraction, the PAN fiber
(C3H8N)n has no strictly crystalloid structure, but has the similar and relatively ordered area. The
typical X-ray spectrum has two acute peaks (near 2θ = 17 and 2θ = 30, corresponding to S1 and
S2). With cyclation and dehydrogenation, the linear PAN changes to trapezoidally shaped
heat-resistant structure during oxidation. The peak value
and positions of S1 and S2 also change. So we used A =
S2/(S1−S2) as the index to evaluate the degrees of preoxi-
dation or cyclation. Here, A is the index of preoxidation;
S1 and S2 are the diffractive intensity. We can acquire the
values of S1 and S2 directly from the spectrum and esti-
mate the degree of preoxidation by A.
The index of cyclation increases slowly in the initial
stage and hoicks in the medium and final stages (fig. 5).
Fig. 5. The change of the index of cyclation At last, peaks S1 and S2 are superposed.
during preoxidation.

2.5 Evolvement of chemical compounds during preoxidation

PYR-GCMS results show in fig.6 that during the initial stage, the ester (CN CH == CH
CH2 COOCH3), carboxylic acid (CN CH2 COOH) and CN CH2 CH2 CN in the original
filament disappear (corresponding to peaks 27, 26 and 7). At the same time, polycircular com-
pounds increase. In the initial stage, copolymers join in the reaction first, and molecules cross-
link with each other. It brings forth the decrease of CN CH2 CH2—CN and the increase of
aromatic ring CN (peak 15). Because of the induced cyclation of carboxylic acid polymer dur-
 200 SCIENCE IN CHINA (Series B) Vol. 44

ing the medium stage, the fiber forms a very stable macromolecular structure gradually. And this
decreases the peaks of monomer (peaks 1 5), dimmer (peaks 9 12), trimer (peaks 19 21) and
heterocyclic compound (peaks 13, 14, 16 and 22). In the last stage, the degree of cyclation is very
high, and there lie only a few peaks, such as CN CH2 CH2 CN, CN CH(CH) CH (CH)
CN, CH == CH(CN) CH2 CH2 CN and CH2 == CH2 NH fragment. Finally, the CN
fragment totally disappears. In the initial stage, the fiber quickly cycles, releases heat and melts.
Some consolidate and even form inner structural deficiencies.

Fig. 6. The PYR-GCMS spectrum of PAN original filament in the different stages of preoxidation. (a) Original;
(b) (g) the preoxidized filaments in the different stages ((b) initial, (c) (e) medium, (f), (g) last); (h)carbon fiber.
 No. 2 EVOLUTION OF COMPOSITION AND STRUCTURE OF PAN CARBON FIBER 201

The curve of circular index from X-ray diffractive analysis and elemental analysis show that
the concentration of oxygen is about 11.80%. We can infer that the index of cyclation increases
slowly in the initial stage, and hoicks in the medium and final stages, and then gets stable. This is
accordant with PYR-GCMS, implying that the circular reaction is over and the preoxidation tends
to be complete. So, the carbonization process is the further circular macromolecular cross-linking.
At the same time, it is accompanied by denitrogenation, dehydrogenation and microstructure
changes.
IR spectrum can also prove the obvious decrease of ester group in the initial stage. Mean-
while, some new specific peaks appear. There is a weak shoulder peak at about 2200 cm−1, which
is the absorption band of C == C C N. This implies that in the initial stage, an unsaturated
structure is formed. With the process of preoxidation, this band will gradually disappear. At 810
cm−1, the band of C H of aromatic ring continuously enhances, implying that the cyclation and
dehydrogenation finally lead to the formation of the aromatic ring structure. In the final stage, all
CN disappear, and only a few bands of C == C , N == C , OH and C H of aromatic
ring remain. It implies the complete formation of circular structure. This evolution agrees with
PYR-GCMS very well.

3 Conclusions

(i) The preoxidation procedure of PAN carbon fiber can be divided into 3 stages: initial, me-
dium and final. During the preoxidation, the structure of PAN original filament experiences the
process from filament tow to semi-thaw sheet stacks and to sheet sectors finally.
(ii) In the initial stage, PAN filament tows disappear and become semi-thaw. Copolymers join
the reaction to start up the cyclation. Esters disappear and the molecules annularly cross-link.
NC C C CN groups decrease and aromatic ring CN increases. Correspondingly, C, H de-
crease and O increases in the preoxidation filament. The index of cyclation slowly increases.
The initial and medium stages are the most reactive periods during preoxidation. The struc-
ture tends to be stable and these are the most sensitive stages for the formation of structural de-
fects. So, during this stage, the rate of temperature increase should be slowed down, and thus the
traction should be strengthened to reduce the interspace.
(iii) In the medium stage, the PAN original filament rearranges into new sheet stacks, and
changes into a divergent shape of sheet sectors gradually, which tends to be stable in the final.
During this period, levels of C, H, N groups plummet while levels of O groups dramatically in-
crease. Because of the very stable circular structure gradually induced by the carboxylic acid co-
polymers, the peaks of monomer, dimmer, trimer and heterocyclic compounds clearly decrease in
PYR-GCMS spectra.
(iv) During the final stage of preoxidation, only CN fragment remains, but also disappears
at last. The index of cyclation increases with the process of preoxidation. Double peaks overlap.
 202 SCIENCE IN CHINA (Series B) Vol. 44

And, the structural graph becomes stable and does not change any more.

References
1. Luo Yifeng, Perspective of world carbon fiber at the beginning of new century, High-tech Fibers and Their Application,
2000, 25(1): 1 7.
2. Wo Xiyuan, Comparison and preliminary analysis of several kinds of domestic and abroad fibers, High-tech Fibers and
Their Application, 2000, 25(4): 30 36.
3. Donnet, J. B., Bansal, R. C., Carbon Fiber (translated by Li Rengyuan, Guo Meili), Beijing: Science Press, 1989, 12 27.
4. Dobiasova, L., Stary, V., Valvada, V. et al., Analysis of carbon fibers and carbon composites by symmetric X-ray diffrac-
tion technique, Carbon, 1999, 37(3): 421 426.
5. Buttry, D. A., Pen, J. C. M., Donnet, J -B. et al., Immobilization of amines at carbon fiber surfaces, Carbon, 1999, 37(12):
1929 1940.
6. Brasquet, C., Rousseau, B., Strade-Szwaekopf, H. et al., Observation of activated carbon fibres with SEM and AFM cor-
relation with adsorption data in aqueous solution, Carbon , 2000, 38(3): 407~422.
7. Vickers, P. E., Watts, J. F., Perruchot, C. et al., The surface chemistry and acid-base properties of a PAN-based carbon fi-
bre , Carbon, 2000, 38(5): 675 690.
8. Edie, D. D., The effect of processing on the structure of carbon fibers , Carbon , 1998, 36 (4): 345 362.
9. Paiva, M. C., Bernardo, C. A., Nardin, M., Mechanical , surface and interfacial characterization of pitch and PAN-based
carbon fibres , Carbon, 2000, 38(9): 1323 1338.