Carbon 42 (2004) 2233–2244

www.elsevier.com/locate/carbon

Effects of boron doping in low- and high-surface-area carbon powders

a,*
Young-Jae Lee , Yasuo Uchiyama b, Ljubisa R. Radovic a

a
Fuel Science Program, Department of Energy and Geo-Environmental Engineering, The Pennsylvania State University,
University Park, PA 16802, USA
b
Department of Materials Science and Engineering, Nagasaki University, Japan
Received 10 March 2004; accepted 29 April 2004
Available online 25 May 2004

Abstract
Two distinctive carbon materials (Saran char and SP-1 graphite) were doped with B at different loading to clarify the intrinsic
effect of substitutional B on carbon reactivity. The carbon precursors would be affected in different style by substitutional B due to
different important properties (crystallinity and surface area). The B retentivity depended on the nature of B dopant and carbon
substrate; a less ordered carbon has higher B loading than its counterpart. Graphitization was enhanced by substitutional B, as
expected. Furthermore, the B incorporation was still beneficial for SP-1 although it already had high crystallinity. An interesting
behavior was noticed; the increase in La was greater than Lc . The intrinsic effect of substitutional B in carbon oxidation was proved
to be a catalytic one. Unlike highly ordered SP-1 graphite, Saran char showed both a catalytic effect at low B loading and low
conversion, and an inhibiting effect at high B loading and high conversion. The inductive effect was proposed to explain this catalytic
effect on different crystallite size. Different sizes of carbon clusters were calculated by Gaussian 98W; the extent of the effect of
substitutional B did get smaller to the carbon in bigger size of carbon cluster.
Ó 2004 Elsevier Ltd. All rights reserved.

Keywords: A. Char, Graphite; B. Doping, Graphitization; D. Reactivity

1. Introduction stability of carbon for high compatibility of commercial

Carbon fiber reinforced carbon (CFRC) composites
are the materials of choice for high-temperature struc-
tural applications due to their high thermal conductivity
and good chemical resistance at very high temperatures
in an inert atmosphere [1–4]. To this date, however,
the composites have found use in only a limited number
of commercial applications such as rocket nozzles and
exit cones for missiles, as well as high performance
brakes and transmission components for automobiles
[5–7].
The principal reasons for the limited commercial
application of CFRC composites would be their rela-
tively poor oxidation resistance; the oxidation reaction
would result in the catastrophic failure of the compos-
ites. Therefore, it is essential to improve the oxidation
*
Corresponding author. Present address: Department of Inorganic
Chemistry Examination, Korean Intellectual Property Office, Govern-
ment Complex-Daejeon, Dunsan-dong, Seo-gu, Daejeon 302-701,
Republic of Korea. Tel.: +82-42-481-8305; fax: +82-42-472-3459.
E-mail address: youngjae1004@hanafos.com (Y.-J. Lee).
0008-6223/$ - see front matter Ó 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.carbon.2004.04.030
applications; obviously, overcoming this problem will be
the key to new technological developments.
The oxidation protection of carbon has been studied
extensively, primarily using surface coatings and mixing
with oxidation inhibitors (e.g., halogen, silicon and
phosphorus) [8–12]. McKee [13] reviewed the several
coating systems to protect carbon from oxidation, and
emphasized that ‘‘because of the thermal expansion
anisotropy of most carbonaceous materials, satisfactory
coatings have been proved very difficult to develop.’’ He
also stated the addition of inhibitors to carbon have also
met with limited success [13]. The oxidation protection
roles of both coatings and inhibitors can be summarized
following; active sites blockage and oxygen diffusion
barrier formation. Based on these mechanisms, it can
only be expected to result a proportional decrease in the
number of reactive carbon sites, caused by edge site
blockage and a monotonic decrease in the accessible
reactive sites due to surface coating. Therefore, a
development of intrinsic oxidation inhibition system,
which does not suffer from substrate/coating thermal
expansion mismatch, is of great interest.
2234 Y.-J. Lee et al. / Carbon 42 (2004) 2233–2244
Boron and its compounds have often been used for
surface coatings [13–17]. Boron is thought to be capable
of blocking active sites at the edges of graphene layers
and it can also form an O2 diffusion barrier [14–16]. But,
more importantly, B also has the unique property as a
substitutional element in the carbon structure [18]: it can
replace C in the graphene layer, resulting in altering the
electronic structure and providing intrinsic oxidation
inhibition [19]. But unlike a boron-coating layer on the
carbon surface, the role of substitutional B in carbon
oxidation remains somewhat controversial despite the
existence of many relevant studies: substitutional B
has showed both a catalytic and an inhibiting effect on
carbon oxidation [15,16,19–23]. Thomas and Roscoe
[20] found a catalytic effect of substitutional B in the
reaction of steam with carbon. Allardice and Walker
[21] argued that the intrinsic effect of substitutional B is
suppressed by the formation of a boron oxide film, and
this argument was supported by Karra et al. [22]. These
authors found that substitutional B has a catalytic and/
or inhibiting effect and that the dominant factor depends
on B concentration and carbon conversion, and con-
cluded that the entire carbon surface should be covered
by such a protective layer to inhibit carbon oxidation.
Three important characteristic effects of substitu-
tional B have been discussed [19]: (a) graphitization
enhancement; (b) formation of boron oxide layer; and
(c) redistribution of p-electrons in the graphene layer.
Unlike the first two mechanisms the last one is contro-
versial and is not compatible with some experimental
results in which a catalytic effect is observed [20–23]. The
relationship [19] between lowering the indisputable
Fermi level and inhibition of CO desorption should also
be clear. Therefore, it is important to confirm this elec-
tronic effect due to the possibility of intrinsic oxidation
inhibition and it is evident to consider the redistribution
of both r- and p-electrons to study this electronic effect.
The electronic structures of pure and B-doped
graphene layers in large aromatic clusters of carbon
atoms was investigated by the semi-empirical MOPAC
software, resulting in higher electron density of edge
carbon atoms [24]. The key parameter in this analysis
was the charge transfer ability among B, C and O atoms
with Mulliken electronegativity values of 2.0, 2.5 and
3.0, respectively. In contrast, the previous study [19] did
only consider an electron-withdrawing property of B
with respect to C. It is obvious here that both con-
tradicting studies only considered different characteris-
tics of substitutional B: an electron-donating property
due to low electronegativity [19] vs. an electron-with-
drawing property due to one less electron [24]. A more
through analysis of the changes of both r- and p-elec-
tronic systems is required.
Radovic et al. [23] proposed that the sometimes
conflicting results on the effects of B doping are a con-
sequence of the dual action of substitutional B, being an
inhibitor at high temperature, high oxygen partial
pressure and high B loading but a catalyst at low tem-
perature, low oxygen partial pressure and low B loading.
This proposal was based on a scrutiny of the electronic
effect of B using H€ uckel molecular orbital theory. The
conclusion was that three competing effects complicate
the evaluation of electron distribution in the graphene
layer in the presence of substitutional B: (1) reduced
total electron density; (2) decreased contribution of de-
localized p-electrons to the electron density on the
remaining C atoms; and (3) r-electron localization on C
atoms due to higher electronegativity of C with respect
to B.
Zhong et al. [25] have agreed with this analysis. In
contrast, based on the finding that ‘‘the substitutional
boron atoms on the edges dramatically alter the density
distribution of high energy electrons along the edges’’,
Ma et al. [24] have argued ‘‘the mechanism of oxidation
inhibition . . . is chemical inhibition via the reduction of
electron density with high energy at surface sites, and
consequently, a reduction in the total number of active
sites for gasification of the carbon’’.
Because of these complexities and the apparent lack
of consensus, the scrutiny of a simpler system was
thought to be desirable. Therefore, two well researched
carbon materials, Saran char and SP-1 graphite, were
doped with different amounts of B and examined. Saran
char was used to represent a disordered carbon with
high surface area (
1000 m2 /g) and low crystallinity; in
contrast, SP-1 graphite is a very ordered carbon with a
low surface area (
1 m2 /g) and high crystallinity. At
comparable B doping levels, it is expected that the latter
is more likely to be completely covered by a boron oxide
film during oxidation.
2. Experimental
Two distinctive carbon precursors were selected in
order to explore the effects of substitutional B in carbon:
the low-surface-area Saran char (120 mesh), prepared by
pyrolysis of PVC and PVDC (Dow Chem.) using stan-
dard methods, and the high-surface-area SP-1 graphite
powder (Union Carbide Corp.). Elemental boron
(Union Carbide, 99.999%) was used as the B dopant due
to its high loading retentivity compared to organic
boron compounds [26].
The carbons were mixed with elemental B, at initial
loadings of 0.2, 1.0 and 2.5 wt.%, and placed in graphite
crucibles. These crucibles were placed in a graphitization
furnace (Centorr Vacuum, Inc.) and evacuated before
heat treatment. Argon (UHP, 99.999%) was introduced
to raise the pressure (0.1 MPa); this procedure was re-
peated at least three times in order to further reduce the
residual oxygen concentration. The furnace was then
heated to the final heat treatment temperature (HTT),
 Y.-J. Lee et al. / Carbon 42 (2004) 2233–2244
2450 °C; this HTT was selected because it is known to
ensure the maximum solubility of B in carbon [20] and is
between the melting point (2100 °C) and boiling point
(2600 °C) of elemental B. This temperature was held for
15 min to enhance B diffusion into the samples.
The samples were analyzed after B doping to obtain
their specific properties that would be influenced by the
presence of substitutional B. The B loading after heat
treatment was determined by Galbraith Laboratories
Inc. using inductively coupled plasma (ICP) emission
spectroscopy (Perkin–Elmer P2000) with the detection
limit of 0.05 wt.%: the samples were digested by fusing
with sodium carbonate and dissolving the resulting melt
in water with a small amount of hydrochloric acid.
X-ray diffraction (XRD, Rigaku Geiger-Flex) was
employed to measure the crystallinity changes. The
samples were ground using agate mortar and pestle and
sieved through a 120 mesh screen; a thin film of each
sample was deposited on a glass slide using acetone as a
binder. Scans were made between 10° and 60° (2h) with
a scan speed of 0.5°/min. Silicon powder was added to
each sample as an internal standard.
Oxidation behavior was analyzed in a thermal
gravimetric analyzer (TGA, Mettler TA 4000). For all
the analyses,
10 mg of sample was placed in a silica
crucible and onto the pan in the furnace. Initially, N2
(99.999%) flushed the furnace at 200 cc/min for 30 min.
The temperature was raised to 1000 °C at the rate of 5
°C/min in dry air at 1 atm for non-isothermal analysis;
for isothermal analyses, samples were heated to the de-
sired temperature (750, 775, 800 and 825 °C) at 25 °C/
min in N2 , and then the reactant gas (dry air) was
introduced and the sample weight changes were moni-
tored until complete burnoff.
The changes of surface area with the incorporation of
B were also analyzed using the BET method (N2
adsorption at 77 K, Micromeritics Gemini III analyzer)
as well as the DR method (CO2 adsorption at 273 K,
AUTOSORB-6B analyzer). In the latter case the sam-
ples were outgassed at 300 °C overnight prior to anal-
ysis.
Computational chemistry, as implemented in the
Gaussian 98W software package, was used to analyze
Table 1
Comparison of B doping efficiency for Saran char, SP-1 graphite, coal tar pitch-derived carbon, and PAN- and pitch-based carbon fibers
Initial B loading
0.35 at.% 0.2 wt.%
a
Saran char – 60%
SP-1 graphitea – 36%
PAN-based carbon fibersb 57% – –
Pitch-based carbon fibersa 29% – –
Coal tar pitch-derived carbonc – –
a
From this study.
b
From Ref. [10] for HTT ¼ 2500 °C.
c
From Ref. [27] for HTT ¼ 2300 °C.
2235
several model carbon clusters (graphene layers) and thus
predict some of the key parameters in their structure,
with the expectation of evaluating the effect of substi-
tutional B. In all the calculations, density functional
theory at the B3LYP level, with the 3-21G basis set,
was used for geometry optimization and frequency
calculations. Single point energy calculations were per-
formed at the same level of theory using the larger
6-31G(d) basis set.
3. Results and discussion
3.1. Boron retention analysis
The final B concentration in the samples (Saran char
and SP-1 graphite) is presented in Table 1. Its retention
is quite high in Saran chars; from 60% to 83% as initial
B loading increases; in contrast, it is lower in SP-1
graphite, from 36% to 54%. The discrepancy between
initial and final B loadings is thought to be due to the
migration of B to the crucible during heat treatment.
The efficiency of B doping in both materials could still
be considered quite high compared to other B precursors
or carbon materials. Table 1 compares the efficiencies of
B retention based on the difference between initial and
final B loading in different carbons.
The retention efficiency of B is seen to depend on
both B dopant and the carbon substrate. Elemental B
was retained more than organoborane compounds due
to their vapor pressure difference: there is more loss of B
from the organoborane compounds (tributylborate and
boron oxide) [26]. Coal tar pitch-derived carbon was
also doped with elemental B [27]; the B doping efficiency
increased from 40% to 81% as the initial B loading in-
creased (see Table 1). Carbon fibers that were doped
with organoborane compounds showed relatively low
retention efficiency which depended on the precursor
used: at 0.35 at.% of initial B loading, PAN- and pitch-
based carbon fibers retained 57% and 29% B, respec-
tively.
Despite the different final HTT (2450 °C for Saran
char and SP-1 graphite vs. 2500 °C for carbon fibers vs.
1 wt.% 2 wt.% 2.5 wt.% 5 wt.%
83% – 74% –
51% – 54% –
– – –
– – –
40% 73% – 81%
2236 Y.-J. Lee et al. / Carbon 42 (2004) 2233–2244
2300 °C for coal tar pitch-derived carbon), the results
summarized in Table 1 emphasize the relationship be-
tween B doping efficiency and carbon crystallinity: the
higher the crystallinity of the carbon, the lower the
efficiency of B doping. PAN-based carbon fibers re-
tained more B than pitch-based carbon fibers at 0.35
at.% of initial B loading (see Table 1). Saran char and
SP-1 graphite show the same trend at all loadings: the
more disordered Saran char retained more B than the
more ordered SP-1 graphite.
This preferential doping of less ordered carbon agrees
with the study by Jones and Thrower [28]: three different
pyrolytic graphite samples were doped with B at iden-
tical conditions. The authors observed that the B
retention decreased as the degree of crystallinity ðd0 0 2 Þ
increased. Further evaluation of the relationship be-
tween B retention and carbon crystallinity will be pre-
sented in next.
3.2. Crystallinity changes
The X-ray diffraction patterns were examined for
both Saran char and SP-1 graphite, and crystallinity
parameters such as the d-spacing ðd0 0 2 Þ and the crys-
tallite height ðLc Þ from (0 0 2) peak and the crystallite
width ðLa Þ from (10) in Saran char and (101) in SP-1
graphite are presented in Table 2. The d-spacings are
very much affected by B doping and heat treatment, and
in different ways, as expected.
The decrease of d0 0 2 in Saran char is very significant
in B-loaded samples. Despite its non-graphitizable
character the crystallinity was dramatically improved by
the presumed presence of substitutional B; it is intrigu-
ing, however, to observe that the d0 0 2 of B-doped sam-
ples was even lower than that of perfect graphite (0.3354
nm). As-received Saran char has a very broad XRD
pattern; its estimated d-spacing is
0.35 nm, even larger
than that of completely turbostratic carbons (0.344 nm).
It is, therefore, also intriguing to note that the nominally
0.0% B sample (<500 ppm) becomes much more ordered
(d0 0 2 ¼ 0:3375 nm < 0.344 nm) upon heat treatment to
Table 2
Effect of substitutional B on the changes in crystallite parameters of Saran char and SP-1 graphite
Samples (initial B loading, wt.%) d0 0 2 (nm)
Saran char (0.0) 0.3375
Saran char (0.2) 0.3343
Saran char (1.0) 0.3346
Saran char (2.5) 0.3342
SP-1 graphite (0.0) 0.3351
SP-1 graphite (0.2) 0.3353
SP-1 graphite (1.0) 0.3346
SP-1 graphite (2.5) 0.3342
a
Lc of both Saran char and SP-1 graphite was obtained from (0 0 2) peak.
b
La of Saran char from (10) peak.
c
La of SP-1 graphite from (101) peak.
2450 °C. This is tentatively attributed to the graphitizing
effect of low levels of B doping in this sample; even
though no B was deliberately added to it, some boron
must have diffused into it from other parts of the furnace
(or the crucible). The other possible explanation for this
intriguing result, a calibration problem, was discarded,
because a silicon standard was used and all the peak
positions were calibrated accordingly. The fact that the
d-spacing of B-doped samples is lower than that of
perfect graphite is a clear signature of the presence of
substitutional B, as discussed below for SP-1 graphite.
No significance is attached to the observed small chan-
ges in d-spacing in Table 2 as a function of boron
loading (see Table 1); the reproducibility is considered to
be ±0.0005 nm.
The changes in Lc and La in Table 2 are also inter-
esting: the increase in La is larger than that of Lc in both
carbons, and increases in both Lc and La of Saran char
are larger than those of SP-1 graphite. As described in
Section 3.1, there is preferential doping of less ordered
carbon. The enhancement of graphitization by substi-
tutional B is not controversial and has been studied
extensively [19,26,27] even though its mechanism is still
unclear (see below). Here we postulate that the increase
in crystallinity of Saran char is greater than that of SP-1
graphite due to higher B retention.
An interesting and often ignored effect of substitu-
tional B on carbon crystallinity should be mentioned
here: when an increase in Lc is compared to that of La , the
latter is greater than the former. The very same effect is
observed here: 100% vs. 111% for Saran char and 8% vs.
14% for SP-1 graphite. We have reported earlier that the
increase of La is considerably greater than that of Lc [27]
in the presence of B. A similar trend has been observed in
B-doped carbon nanotubes by Redlich et al. [29]: sub-
stitutional B promoted a substantial increase (by at least
a factor of 10) in the length of carbon nanotubes. As the
authors stated, the elusive mechanism of growth of La in
B-doped carbons still remained to be resolved.
At this point, the reasons for the d-spacing decrease
beyond that of perfect graphite must be discussed. The
Lc (nm)a La (nm)
1.5 5.6b
1.6 6.8b
2.5 8.9b
2.9 11.8b
34.6 60.5c
34.6 66.6c
40.8 70.8c
37.4 68.7c
 Y.-J. Lee et al. / Carbon 42 (2004) 2233–2244
enhancement of graphitization by substitutional B is
well documented [30,31] and beyond controversy. The
incorporation of B into the carbon lattice, up to
2.35
wt.% [32], results in an increase in crystallite height and
width and a decrease in interlayer spacing [19,27,28].
The proposed mechanism in the presence of boron by
Hagio et al. [33] is that boron’s electron deficiency with
respect to carbon causes a decrease in the repulsive
interaction between the p-electron clouds of adjacent
graphene layers, allowing these layers to come closer
together. In contrast, Hishiyama and Inagaki [34] place
emphasis on the attractive p–p interaction and argue
that the presence of substitutional B decreases the p-
electron density in the graphene layers and the resulting
decrease in p–p overlap should lead to an increase in d-
spacing. The same effect would be observed, of course, if
some of the doped B is interstitial, rather than substi-
tutional.
More convincing evidence has been presented by
Hunter and Sanders [35]. The argument by Hagio et al.
is not necessarily obvious if the nature of p–p interac-
tions is considered in more detail [35]: electron defi-
ciency in the aromatic ring causes an increase in
repulsion for face-to-face interaction between adjacent
p-systems, suggesting the opposite effect to that argued
by Hagio et al. It remains to be seen whether the same
conclusion applies to the ABAB sequence of graphene
layers. Furthermore, the argument by Hagio et al. [33] is
still not sufficient to explain the intriguing experimental
fact that the increase in La is greater than the increase in
Lc [27].
3.3. Oxidation behavior
Figs. 1 and 2 show the non-isothermal TGA results.
The comparison of oxidation behavior between B-doped
and B-free samples is interesting: it reveals the catalytic/
inhibiting effects of substitutional B.
Fig. 1. Non-isothermal TGA of SP-1 graphite.
2237
Fig. 2. Non-isothermal TGA of Saran char.
The oxidation behavior of the low-surface-area SP-1
graphite is quite straightforward. It starts to oxidize at

800 °C, compared to 700 °C for Saran char, as ex-
pected. Unlike Saran char, for which a catalytic effect is
observed at low B loading here, there is no evidence of a
catalytic effect of substitutional B; oxidation resistance
increases monotonically with increasing B content.
There are four conceivable explanations for this trend:
(1) a monotonic decrease in the reactive surface area
(RSA) of the material, caused by a progressive increase
in crystallinity; (2) a monotonic decrease in the intrinsic
reactivity of the carbon reactive sites, as a consequence
of the electronic effect of substitutional boron; (3) a
proportional decrease in the number of reactive carbon
sites, caused by their blockage with edge-bound boron
atoms; and/or (4) a monotonic decrease in the accessible
RSA, caused by surface coating with a protective B2 O3
layer.
Scenario 3 is illustrated schematically in elsewhere
[13]; scenario 2 can also be depicted in the same sche-
matic except B atom is located in the middle of graphene
layer instead of edge site. A hypothetical graphene layer
can be drawn with the B atom either as a basal plane site
within the graphene layer (scenario 2), or as an edge site
chemically bound to the graphene layer (scenario 3).
Based on the results shown in Fig. 1 (and discussed
below), as well as the study of Radovic et al. [23], here
we can discard only scenario 2. Which one of the
remaining explanations is dominant remains uncertain,
but they all have the same undisputed effect: an increase
in oxidation resistance. Scenario 4 can easily be visual-
ized as either interstitial or separate-phase boron form-
ing a protective B2 O3 film at the graphene layer edge
upon contact with reactive O2 ; of course, a similar result
is obtained if the C–B bonds shown here are weaker
than the C–C bonds.
The results for Saran char summarized in Fig. 2 de-
serve closer scrutiny. At the higher B loadings there is a
clear inhibiting effect, especially at higher conversion
levels. At the lower B loadings, on the other hand, there
2238 Y.-J. Lee et al. / Carbon 42 (2004) 2233–2244

is a clear catalytic effect of B on the reactivity of heat-

treated Saran char, which was not seen in the case of SP-
1 graphite. One obvious hypothetical explanation is as
follows: Saran char has a much higher surface area than
SP-1 graphite and an equal degree of protection of the
edges of its crystallites, either by a B2 O3 film or a more
stable C–B bond, cannot be achieved at the same B
loading. The other explanation is the following: because
of the much smaller sizes of the crystallites in Saran char
(see Table 2), it is much more likely that substitutional B
will be closer to the graphene edges, rather than buried
in the basal plane where its electronic effect on the edges
may not be as pronounced; the presence of substitu-
tional B then manifests itself not as an inhibiting effect
Fig. 4. Isothermal TGA of Saran char at 800 °C.
but, quite the contrary, as a catalytic effect: the affinity
of O2 for the reactive carbon sites becomes greater, as
suggested by Radovic et al. [23].
The isothermal reactivity results confirm these trends
and strengthen the proposed explanation. They are
summarized in Figs. 3 and 4 in the form of burnoff plots,
and in Figs. 5 and 6 in the form of oxidation rate vs.
conversion plots. As boron loading increases, there is a
monotonic increase in oxidation protection of SP-1
graphite (Fig. 3). The differences in oxidation behavior
of Saran char and SP-1 graphite are clearly noticed at
early reaction time. In Fig. 4, the Saran char with 0.2
wt.% B has higher burnoff than the B-free one. As the
reaction continues, the B-doped sample becomes more
oxidation-resistant than its B-free counterpart due to the
formation of boron oxide film. An interesting compar-
ison can be made between 1.0% and 2.5% B samples in
Fig. 5. Oxidation rate of SP-1 graphite at 800 °C.
Fig. 4. The oxidation behavior of these two samples is
similar to that of the others (0.0% and 0.2% B); the
higher B-content sample (2.5%) has a lower oxidation
resistance than the lower B-content one (1.0%) in the
early stage of the reaction, but the reverse is true as
reaction continues. This trend cannot be explained by
postulating the formation of a boron oxide film that
inhibits carbon oxidation, because the difference in B

Fig. 6. Oxidation rate of Saran char at 800 °C.

content between these two samples is almost twofold

Fig. 3. Isothermal TGA of SP-1 graphite at 800 °C.
(see Table 1).
Not only the formation of boron oxide diffusion film,
but also the development of crystallinity (see Table 2)
due to the incorporation of substitutional B would lead
to an increase in oxidation resistance. It is difficult to
 Y.-J. Lee et al. / Carbon 42 (2004) 2233–2244
assess whether the formation of boron oxide or an in-
crease in crystallinity would have a major role in oxi-
dation resistance. This comparison brings up the
additional question whether the formation of boron
oxide alone is enough to inhibit carbon oxidation. In
Fig. 6, the rapid decrease of oxidation rate for 2.5% B-
doped Saran char can be explained by the formation of
boron oxide only. In Fig. 5, B-doped Saran char has
higher oxidation rate than B-free Saran char despite its
higher degree of crystallinity (see Table 2). Furthermore,
the rate for 2.5% B char is even higher than that of 0% B
sample at the beginning of the reaction in Fig. 6. But,
the reactivity of B-doped sample substantially decreases;
in contrast, that of 0% B sample slowly increases.
Eventually, the B-free sample shows higher oxidation
rate than the 0.2% B sample.
The temperature dependence of the reaction in the
presence and absence of B is summarized in Figs. 7 and
8. The activation energy values for Saran char are in the
range expected for disordered carbon [36]. The values
for SP-1 graphite are higher, which is also consistent
with much of the literature, even though its trend is not
well understood and has been neglected in most dis-
cussions. In the presence of B there is no consistent
trend for both carbons, suggesting that several elemen-
tary processes (adsorption, surface reaction, diffusion
through B2 O3 film and desorption) may be contributing
in different degrees to the rate-determining step of this
reaction [37]. Indeed, such a lack of clear trend is also
evident from a cursory analysis of the relevant litera-
ture.
Tang [38] impregnated carbon fibers with either li-
quid organoborane or inorganic borate and measured
the activation energy of reaction in air: the Ea of
treated fibers (200 kJ/mol) was twice higher than that
Fig. 7. Arrhenius plots of reactivity for SP-1 graphite at 0% burnoff
with activation energy (kcal/m).
2239
Fig. 8. Arrhenius plots of reactivity for Saran chars at 0% burnoff with
activation energy (kcal/m).
of untreated fibers. McKee [13] used graphite to study
the effect of B in oxidation. They found that B-treated
and untreated graphite has around 51.4 and 46.2 kcal/
mol of Ea , respectively, but the energy was little chan-
ged with increasing the additive loading. The authors
suggested that active site blockage by the formation of
boron oxide film is accounted for the increase in oxi-
dation resistance. McKee later chosen [39,40] carbon
composites to study the effect: the matrix was mixed
with inhibitors (zirconium boride and boron carbide).
The rate of the modified composites was reduced by
a factor of 4–5 at
30% of burnoff, and a rapid de-
crease of the rate was observed as gasification was
proceeded.
Ehrburger and coworkers [14,41] also studied oxida-
tion behavior of carbon composites. The composites was
impregnated with orthoboric acid and heated to convert
it to boron oxide. With the disagreement of McKee’s
results, they observed almost same activation energies
regardless B treatment (153–158 kJ/mol) despite the rate
was lower in the treated sample. Furthermore, the
amount of additive was seen to be important in the ex-
tent of the effect: the inhibition factor was almost linear
increase up to 20 wt.% of boron oxide loading. Al-
though quite opposite results were observed compared
to McKee’s, the authors suggested the same mechanism
for oxidation inhibition: active site blockage.
Thomas and Roscoe used graphite single-crystals
doped with B in both wet and dry O2 at 1110 K [20]. In
dry O2 , the reaction of graphite was inhibited by sub-
stitutional boron; while in wet O2 , the opposite effect
was observed. They concluded that boron oxide affected
the reaction catalytically due on its moisture sensitivity
and volatility.
Karra et al. [22] also reported a catalytic effect of B in
the oxidation reaction of carbon black, saran char and
2240 Y.-J. Lee et al. / Carbon 42 (2004) 2233–2244
glassy carbon doped with B at 1, 2 and 5 wt.%. Iso-
thermal oxidation study between 600 and 675 °C
showed that B acts an inhibitor of oxidation at high B
levels, higher temperatures and high carbon conver-
sional levels. Conversely, B also acts as a catalyst at low
B levels, low temperatures and lower conversion levels.
High surface areas of all samples compared to that of
graphite were thought to contribute to the defection of
the catalytic effect. At low boron levels, a B2 O3 film
barrier could not cover the entire surface of all samples
and this revealed the two competing effects of B on
carbon oxidation: boron oxide film formation and
intrinsic catalytic effect. This intrinsic catalytic effect of
B is thought to be a consequence of the weakening of C–
C bonds and the strengthening of the C–O bonds. It was
proposed by Allardice and Walker using B-doped SP-1
graphite [21].
Even if they did not observe a catalytic effect in the
reaction with wet oxygen, as Thomas and Roscoe did
[20], they found that reaction rate increased after boron
oxide was removed from the surface by water treat-
ment. They also reported that the overall activation
energy of the reaction decreased as the B content in-
creased. The conclusion from this study is that the
intrinsic catalytic effect of substitutional B was over-
shadowed by inhibition due to boron oxide in barrier
formation.
There is also no consistent trend with increasing
carbon burnoff. There is no evidence, for example, of
increasing importance of diffusion of O2 through the
B2 O3 film with increasing B loading; it is reliable to be
indicative that the activation energy of B-doped graphite
and that of oxygen diffusion through molten boron
oxide [21].
There is also no evidence of decreasing importance of
diffusional limitations for O2 in the pores of Saran char
with increasing burnoff; this would be manifested in a
consistent increase in apparent activation energy. In this
regard, a comparison of the relevant surface areas in
Table 3 is useful. The fundamental reason for the
selection of Saran char and SP-1 graphite was the fol-
lowing: at comparable B loadings, the surface of Saran
char (initially
1000 m2 /g) is less likely to be completely
covered by a B2 O3 film. Under such conditions, each of
Table 3
Surface area measurement of SP-1 graphite and Saran char
Initial B loading (wt.%) SP-1 graphite
N2 at 77 K, BET (m2 /g)a N2 at 77 K, BET (m2 /g)a
0.0 1.7 0.37
0.2 1.9 0.34
1.0 1.8 0.26
2.5 1.8 0.35
a
Measurement performed at Pennsylvania State University.
b
Measurement performed at Quantachrome (courtesy of C.A. Leon y Leon).
the four scenarios mentioned in Section 3.2 can be
scrutinized with a greater degree of independence from
the others.
However, as seen in Table 3, the surface area of Saran
char dramatically decreases upon heat treatment to the
temperature required for B substitution. The residual
porosity of this material (glassy-carbon), which obvi-
ously exists because its apparent density is still much
lower than that of graphite [42,43], is closed and even
CO2 at 273 K cannot access the pores that are closed to
N2 at 77 K. So, the main difference between these Saran
char and SP-1 graphite samples is in their crystallite
dimensions: although the surface areas are much less
different after heat treatment (and even the latter are
somewhat higher than the former), Saran char crystal-
lites are still much smaller than those of SP-1 graphite
(see Table 2). There is no question that SP-1 graphite
possesses less reactive sites than the heat-treated Saran
char: as Figs. 7 and 8 shows, for example, despite its
higher surface area, it is less reactive than Saran char. Its
larger crystallites raise the possibility that the catalytic
effect of substitutional B is absent (see Fig. 1) because B
is ‘‘buried’’ in the graphene layers and exerts very little
influence on the edge carbon atoms. A computational
chemistry study of this ‘‘inductive effect’’ [44] is de-
scribed next.
3.4. Theoretical analysis
The observed differences in the effect of B doping on
the oxidation resistance of Saran char vs. SP-1 graphite
point to the following assumption: because Saran char
has smaller crystallites than SP-1 graphite, substitu-
tional B in Saran char has a higher probability to affect
the edge carbon atoms than in SP-1 graphite. This
so called ‘‘inductive effect’’ is explored in more detail
below.
Four different model clusters were analyzed. The
electronic effect of substitutional B is expected to depend
on the size of the graphene layer and the location of
substitutional B in it. Structures I and II, presented in
Fig. 9, are the basic sets with the same three benzene
rings but different spin multiplicities ðMÞ. The important
issue of the appropriate value of M is still unresolved;
Saran char
N2 at 77 K, BET (m2 /g)b CO2 at 273 K, DR (m2 /g)b
0.41 4.25
0.39 0.52
0.39 0.46
0.48 0.33
 Y.-J. Lee et al. / Carbon 42 (2004) 2233–2244
Fig. 9. Schematic representation of structures I and II; in the presence
of B the atom is substituted at positions 8 and 1 in structures I and II,
respectively.
what is well known is that at least some of the edge
carbon atoms are not conventional free-radical sites [45];
they are not bound to any heteroatoms but are somehow
stabilized. Here for simplicity all the edge sites are sat-
urated with hydrogen. Structures III and IV in Fig. 10
are the extended sets with the same seven benzene rings
and different spin multiplicities. Each set of structures
was compared in the absence and presence of B. The
comparison between structures I and III, and between II
and IV, was evaluated primarily in terms of bond angles
and lengths, as well as atomic charges. To verify the
compatibility of our calculations some of the properties
of these model carbon clusters (e.g., the dipole moment
and the vibrational frequencies) were examined. As ex-
pected, the effect of B on the dipole moment was more
important in structure II than in structure I. Both in the
absence and presence of B, the vibrational frequencies
were all positive, indicating that even in the case of the
odd-electron phenalene (structure I) a stable structure
was found (for M ¼ 2); furthermore, the values obtained
for the three ring cluster agreed with the experimental
values for anthracene [46]. Therefore the choice of both
the density functional theory (B3LYP) and the medium-
size basis sets (3-21G and 6-31G(d) is thought to be
appropriate for our purposes).
Table 4 presents the bond angle comparison. The
effects of the presence of B are discussed in detail by
Radovic et al. [23]. Here the focus is only on the extent
2241
Fig. 10. Schematic representation of structures III and IV; in the
presence of B the atom is substituted at position 1 in structures III and
IV.
of substitutional B effect based on the distance from the
B atom. The differences observed in structure I do be-
come smaller in structure III. For example, at a dis-
tance of 0.284 nm (structure I) the presence of B
changes the bond angle at C5 (bond 4–5–6) by 2.93%,
but the difference at C20 (bond 15–20–21) and C21
(bond 20–21–22), at a distance of 0.430 and 0.515 nm,
in structure III is reduced to 0.43% and 0.32%,
respectively.
The same trend is also observed in the bond length
comparisons, presented in Table 5. In structure II the
change in C8–C9 in the presence of B is 1.61%; the
same bond in structure IV (C12–C13) changes by
1.04%. Indeed, the differences in structures III and IV,
especially at the extended parts (e.g., C20–C21 and
C21–C22 in structure III, and C14–C24 and C23–C24
in structure IV), become smaller than in structures I
and II.
Atomic charges are also compared and presented in
Table 6. At a distance of 0.247 nm from B, C4 in
structure I changes by 30.13%; C20 (0.426 nm) and C21
(0.515 nm) in structure III change 12.14% and 9.91%,
respectively. The differences at C23 and C24 in structure
IV do also become smaller (2.57% and 5.26%) in com-
parison with the differences in structure II (29.43% and
11.49% at C4 and C5, respectively).
2242 Y.-J. Lee et al. / Carbon 42 (2004) 2233–2244

Table 4
Comparison of selected bond angle between structures I, II, III and IV
Structure Bond B-free (deg) B-doped (deg) Difference (%)
I 13–8–10 119.9898 114.8182 4.31
4–5–6 120.8613 124.4071 2.93
II 2–1–3 121.6613 117.6997 3.26
4–5–6 121.6614 124.0003 1.92
III 15–20–21 120.8059 121.3277 0.43
20–21–22 120.7956 120.4113 0.32
IV 6–5–14 119.9950 120.3310 0.28
14–24–23 121.2220 120.7860 0.36

Table 5
Comparison of selected bond length between structures I, II, III and IV
Structure Bond B-free (nm) B-doped (nm) Difference (%)
I 8–10 0.14327 0.15017 4.82
5–6 0.13929 0.14183 0.92
II 1–3 0.14008 0.15366 9.69
8–9 0.14283 0.14053 1.61
III 20–21 0.13893 0.13852 0.30
21–22 0.13979 0.14076 0.69
IV 12–13 0.13719 0.13861 1.04
23–24 0.13719 0.13687 0.23

Table 6
Comparison of selected atomic charge between structures I, II, III and IV (Mulliken population analysis)
Structure Atom B-free B-doped Difference (%)
I 4 )0.20862 )0.14576 30.13
5 )0.12392 )0.16626 34.17
II 4 +0.14632 +0.10296 29.63
5 )0.29615 )0.26212 11.49
III 20 )0.21781 )0.19137 12.14
21 )0.12362 )0.13589 9.91
IV 23 )0.20791 )0.20257 2.57
24 )0.20766 )0.19675 2.57

4. Conclusions low crystallinity of carbon was favor over the high

To further clarify the intrinsic effect of substitutional
B on carbon reactivity, two distinctive carbon materials
(Saran char and SP-1 graphite) were selected and doped
with B at 2450 °C at different loading, 0.2, 1.0 and 2.5
wt.%. The carbon materials were chosen due to quite
different property in crystallinity and surface area. It
was expected that those characteristics would be affected
by substitutional B in different style, and this would play
a role to elucidate the nature of substitutional B, espe-
cially in carbon oxidation.
The B retentivity in carbon depended on the nat-
ure of B dopant and carbon substrate: elemental B
was superior to organoborane compounds, and the
crystallinity. As-received Saran char had high surface
area with less ordered structure: in contrast, SP-1
graphite had low surface with highly ordered struc-
ture. Saran char retained more B than SP-1 graphite
in all cases.
It was true that substitutional B enhances graphiti-
zation, so that the crystallinity of both carbons was
improved. The d-spacing, and crystallite length and
width increased with B doping in all cases. Despite SP-1
graphite had already highly ordered structure, the B
incorporation was still beneficial. But, the increase in
Saran char was greater than that of SP-1 graphite.
Furthermore, the increase in La was greater than Lc , and
it is agreed with the previous study [27].
 Y.-J. Lee et al. / Carbon 42 (2004) 2233–2244
The intrinsic effect of substitutional B in carbon
oxidation was proved to be a catalytic one. In oxidation
study it was not observed in SP-1 graphite due to its
ordered structure and low surface area, but in Saran
char due to its less ordered structure and high surface
area at low B loading: it is agreed with the study by
Radovic et al. [23]. At low B loading it was clear to see
the catalytic effect of substitutional B in Saran char;
furthermore, the high B loading sample (2.5%) had
higher oxidation rate than the B-free one at the begin-
ning of the reaction, eventually the rate substantially
decreased in the high B loading Saran char. The
‘‘inductive effect’’ was proposed to explain this catalytic
effect based on different crystallite size between Saran
char and SP-1 graphite. The idea is that the B atom at
edge site or close to edge site would have pronounced
effect compared to the one in the center of graphene
layer.
Different carbon clusters were created and used for
computational chemistry with the help of Gaussian
98W. The difference in bond angle and length, and
atomic charges was evaluated and compared. The extent
of the effect of substitutional B did get smaller to the
carbon in bigger size of carbon cluster. Specially, the
effect was weaker as far as the carbon atom from the B.
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