Fibers and Polymers 2011, Vol.12, No.7, 979-982 DOI 10.

1007/s12221-011-0979-2
Communication

Effect of Boric Acid on Oxidative Stabilization of Polyacrylonitrile Fibers

Gang-Ping Wu*, Chun-Xiang Lu**, Ying-Yan Wang, and Li-Cheng Ling1
National Engineering Laboratory for Carbon Fiber Technology, Institute of Coal Chemistry,
Chinese Academy of Sciences, Taiyuan 030001, China
1
College of Chemical Engineering, East China University of Science and Technology, Shanghai 200237, China
(Received October 16, 2010; Revised May 8, 2011; Accepted May 22, 2011)

Abstract: The coating modification of polyacrylonitrile (PAN) fibers with boric acid to enhance the controllability of
thermally oxidative stabilization process. The stabilization process, cross-section morphologies of oxidized and carbonized
products were investigated by means of optical microscopy, SEM, XPS and in-situ thermal shrinkage indicator. The results
indicated that the coating with boric acid on fiber surface was effective to avoid skin-core heterogeneity on the cross section
and, in the stabilization process, that boric acid as a crosslinking agent to tie together the adjacent oxidative molecular chains
was confirmed. It was suggested that the crosslinked structures should play an essential role in controlling the formation of
uniform oxidized structures, which is favorable for tensile properties of carbon fibers.
Keywords: Coating, Polymer, Polyacrylonitrile, Fibers, Boric acid, Stabilization

Introduction companies for carbon fiber production, have also developed

[12,13] boric acid as the stabilizing reaction inhibitor. However,
Carbon fibers are a kind of versatile reinforcement material the mechanism regarding to the role of boric acid on the
with an extensive use in aerospace, sport, building, automobile formation stabilized species, intramolecular cyclization or
and defense applications [1-3]. Among the complicated intermolecular nitrile reactions has not yet well understood.
processing processes to transform the PAN to carbon fibers, Ouyang et al. [14] studied the effect of boric acid on the
oxidative stabilization has been an interest of subject stabilization of poly(acrylonitrile-co-itaconic acid) (P(AN-
because it largely determines the structures and properties of co-IA)) by differential scanning calorimetry (DSC) and
ultimate carbon fibers [4,5]. This process is conducted prior thermogravimetry (TG). They reported that boric acid can
to carbonization in an oxidizing atmosphere at temperatures greatly decrease the activation energy and diminish the
ranging from 200 and 300 oC. A series of exothermic reactions nitrile cyclization by formation of a cross-linking structure.
including cyclization reactions of nitrile groups, dehydrogenation The crosslinking effect of boric acid has also been referred
and oxidative reactions take place to form stabilized fireproof by Yin et al. [15]. They crosslinked poly(vinyl alcohol) (PVA)
structure [6]. Some reactions occurring in the stabilization with boric acid, in which the hydroxyl groups were linked by
were listed in Scheme 1.
The stabilization has been regarded as a time-consuming
process to reduce as much as possible the radial homogeneity
caused by inadequate pick-up of oxygen [7] ; it usually takes
at least one hour to achieve relatively desirable stabilized
structures at this step, which is responsible for the low
productivity of carbon fibers. Therefore, great efforts were
worthwhile to be made to diminish this handicap.
Many attempts have been made to improve the con-
trollability of oxidized species, e.g., the modification through
pre-stabilization stretching in the presence of plasticizers,
such as succinic acid [8], boric acid [9], dimethylformamide
[10] and zinc chloride [11] etc., has been adopted to prepare
small-diameter carbon fibers, which in some way lower the
threshold for uniform oxidation. Grassie and McGuchan
have ever deduced [11] that boric acid acts as an inhibitor of
stabilization reactions from results of differential thermal
analysis (DTA). Toray industries, one of the world’ best
Scheme 1. Some reactions occurring in the oxidative stabilization
**Corresponding author: wgp@sxicc.ac.cn
process of PAN fibers.
**Corresponding author: lucx@sxicc.ac.cn

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980 Fibers and Polymers 2011, Vol.12, No.7
B-O bonds. The oxidized structure was quite comparable
with that of PAN, so it is reasonable to conclude that the
oxidized PAN fibers could also be crosslinked by boric acid.
But our knowledge about the cross-linking structures formed
by boric acid is still inadequate, for example, weather this
structure is favorable for obtaining the homogeneous
oxidized PAN structures or not is still doubtful.
In this study, we have confirmed the formation of the
crosslinking structures of PAN fibers with boric acid during
oxidative stabilization, and the effect on the heterogeneity of
cross-sections of stabilized fibers were investigated. The
presence of boric acid was found favorable in occurring of
crosslinking reactions, and forming of uniform cross-section
structures for oxidized fibers. As far as we know, the similar
results have not been reported.
Experimental
Materials
The PAN fibers, which containing 1 wt% itaconic acid,
were supplied by the Institute of Coal Chemistry, Chinese
Academy of Sciences. The major properties were listed in
Table 1.
Surface Coating and Stabilization
The PAN fibers were soaked in 1 M H3BO3 bath and kept
fiber length constant. Thereafter, the as-coated acrylic fibers
were dried at 50 oC for 24 h. Stabilization was carried out in
a batch process using the constant tension modes, and the
amount of shrinking or stretching would be recorded.
Observation and Measurements
The oxidized fibers were embedded in epoxy resin, and
sectioned with glass knife. The cross section morphologies
were observed in an optical microscope. The cross section
morphology of carbon fibers was examined under a JSM-
6360LV scanning electron microscope. X-ray photoelectron
spectroscopy (XPS) measurement was carried out in a
procedure described in a published paper [16].
Results and Discussion
Skin-core Heterogeneity in Oxidized and Carbonized
Fibers
The PAN fibers were made infusible by heating in the air
at a constant rate of 2 oC/min. In both cases, the samples
were continuously changing color and slowly darken upon
heating. Figure 1 showed the images of cross sections of
Table 1. Properties of PAN fibers
Tensile strength Elastic modulus Elongation
PAN fibers
(GPa) (GPa) at failure (%)
P 0.46 6.7
Gang-Ping Wu et al.
Figure 1. Cross section images of the oxidized acrylic fibers;
(a) heated to 230 oC, uncoated oxidized fibers; density: 1.234 g/
cm3 and (b) heated to 230 oC, coated oxidized fibers; density:
1.218 g/cm3.
Figure 2. SEM images of carbon fibers derived from (a) uncoated
acrylic fibers and (b) coated acrylic fibers.
oxidized acrylic fibers with a density of 1.21-1.24 g/cm3.
From the density indicated, it could be seen that the
oxidative stabilization of coated acrylic fiber was delayed as
compared with uncoated fiber.
A structural difference between the sheath and core was
noticed in the oxidized acrylic fibers without any boric acid,
so called sheath-core heterogeneity, which will make a
hollow low grade carbon fiber. In the fibers coated with
boric acid, however, the “sheath-core” effect has not been
observed. Oxidative stabilization of acrylic fibers had been
reported to be reaction-limited or oxygen-diffusing limited
[17]. The reaction-limited oxidation has a comparable reacting
rate with cyclization, which approaching a full stabilization;
whereas the oxygen-diffusing limited oxidation had a rather
low oxygen diffusing rate from fiber outer to inter portion,
therefore the core species might not be fully oxidized as a
result. This suggested that boric acid could play an essential
role in avoiding the skin-core heterogeneity during oxidative
stabilization.
Figure 2 shows the SEM images of carbon fibers obtained
from the carbonization of oxidized fibers to 1300 oC. Some
hollow carbon fibers could be observed in the carbon fibers
Density Crystallinity Orientation index
(g/cm3) (%) (%)
12.79 1.182 35.3 82.9
Effect of Boric Acid on Oxidative Stabilization
derived from fibers without boric acid. Obviously, the void
was derived from the sheath-core heterogeneity in oxidized
fibers. However, almost no such void could be found in
carbon fibers derived from fibers coated with boric acid.
Formation of Cross-linking Structures
Figure 3 shows the wide-scan XPS spectrum of the pristine
PAN fibers, which possessed C, O, N, and Si peaks. However,
the XPS spectrum of the coated oxidized fiber sample
showed the C, O, N, B peaks; further, the coating effect is
observed in the B1s region, as shown in Figure 4.
The boron peak at 192.2 eV is identified [18] as B-O
bonding in pure additive, after oxidative stabilization, a main
peak with binding energy of 194.4 eV could be observed.
The B1s peak was very close to the binding energy of boron
in B-O bonding, with an increase of 2.2 eV. The shift of B1s
signals towards higher binding energy compared to boric
Figure 3. XPS narrow scanning results of boron for oxidized fibers
coated with boric acid.
Figure 4. Thermal shrinkage behavior of coated and uncoated
acrylic fibers during oxidative stabilization.
Fibers and Polymers 2011, Vol.12, No.7 981
Figure 5. Thermal shrinkage behavior of coated and uncoated
acrylic fibers during oxidative stabilization.
acid seems should be assigned to B1s in boronate. Just
recently, Ouyang et al. have deduced [14] that boric acid can
react with hydroxyl groups in the acrylic backbone during
oxidative stabilization, acting as a kind of crosslinking agent
for the polymer chains. It was interesting that there exhibited
the peaks in 186-199 eV binding energy range corresponding
to BN bonding (boron nitride) and the peaks corresponding
to phenylboronate [19]. This has further verified that there
occurred crosslinking reactions between boric acid and
hydroxyl groups.
The degree of crosslinking for oxidized acrylic fibers can
be somehow in-process inspected by thermal shrinkage
under constant tension, as shown in Figure 5.
The oxidized acrylic fibers coated with boric acid
demonstrated an extension maximum of 1.7 % at about
225 oC, a decrease by 43 %, as compared with uncoated
oxidized fibers. This could further prove that the polymer
could be linked together to prevent backbone-sliding, perhaps
borate crosslinking structures acting as tie molecules.
The coated oxidized acrylic fibers were made with more
crosslinked structures, being less dense than those of
uncoated fibers, which enhance the diffusion of oxygen into
the core region. This can account for the even cross-section
morphology for as coated acrylic fibers, shown in Figures 1
and 2.
Conclusion
In summary, boric acid plays an important role in the
formation of oxidized acrylic fibers. Boric acid acts as a
crosslinking agent to tie together the adjacent oxidative
molecular chains. The crosslinked structures should be less
dense than the structures formed by nitrile cyclization; as a
result, the oxidation of core species could be enhanced,
which was beneficial for the mechanical properties of
ultimate carbon fibers.
982 Fibers and Polymers 2011, Vol.12, No.7
Acknowledgements
The authors gratefully acknowledge the support by the
Key Program of National Natural Science Foundation of
China (Project No. 50333070).
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