Fullerenes, Nanotubes and Carbon Nanostructures

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Fullerenes, Nanotubes and Carbon Nanostructures

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A STUDY ON THE THERMAL STABILITY TO 1000°C OF

VARIOUS CARBON ALLOTROPES AND CARBONACEOUS
MATTER BOTH UNDER NITROGEN AND IN AIR
a
Franco Cataldo
a
Via Casilina 1626/A , Soc. Lupi Chemical Research Institute , Rome, 00133, Italy
Published online: 23 Aug 2006.
To cite this article: Franco Cataldo (2002) A STUDY ON THE THERMAL STABILITY TO 1000°C OF VARIOUS CARBON ALLOTROPES
AND CARBONACEOUS MATTER BOTH UNDER NITROGEN AND IN AIR, Fullerenes, Nanotubes and Carbon Nanostructures, 10:4,
293-311, DOI: 10.1081/FST-120016451
To link to this article: http://dx.doi.org/10.1081/FST-120016451
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FULLERENES, NANOTUBES, AND CARBON NANOSTRUCTURES

Vol. 10, No. 4, pp. 293–311, 2002
A STUDY ON THE THERMAL

STABILITY TO 1000 C OF
VARIOUS CARBON ALLOTROPES
Downloaded by [134.117.10.200] at 15:45 15 June 2014
AND CARBONACEOUS MATTER

BOTH UNDER NITROGEN
AND IN AIR
Franco Cataldo
Soc. Lupi Chemical Research Institute,

Via Casilina 1626=A, 00133 Rome, Italy
E-mail: cdcata@flashnet.it
ABSTRACT
The thermal behavior of graphite, C60 fullerene, fullerene black

(carbon soot containing fullerenes), extracted fullerene black and
diamond has been analyzed to 1000 C by TGA–DTA (thermo-
gravimetric analysis and differential thermal analysis) under a
nitrogen flow at a heating rate of 20 C=min. Very small weight
losses have been recorded in the case of graphite and diamond.
Furthermore no diamond graphitization has been observed. The
sublimation of pure C60 and the fullerene fraction of fullerene
black (both pristine and extracted) has been observed and
discussed.
The combustion reaction in air flow of graphite, C60 and
C70 fullerenes, fullerene black (both unextracted and extracted),
carbon nanotubes and diamond has been studied by TGA–DTA
at a heating rate of 20 C=min. C70 fullerene and fullerene black
293
DOI: 10.1081=FST-120016451 1536-383X (Print); 1536-4046 (Online)

Copyright # 2002 by Marcel Dekker, Inc. www.dekker.com
294 CATALDO
have been found to be the most reactive carbon materials

with O2. The role played by C70 in the degradation of fullerites
has been discussed. Among the carbon materials examined, the
best resistance to O2 attack has been shown by diamond and
carbon nanotubes. The behavior of graphite is intermediate
between diamond and fullerene blacks. The behavior of C60
fullerene appears closer to that of graphite although it appears to
be more reactive with O2. Samples of graphite and carbon
blacks N375 and N234 have been studied by TGA–DTA in air
flow before and after a radiation treatment with neutrons or
g radiation. The effect of the radiation damage in the combus-
tion reaction of these carbon materials has been discussed.
INTRODUCTION
In a previous work,[1] we have studied by TGA (Thermogravimetric

Analysis) and DTA (Differential Thermal analysis) the thermal behavior of C60
fullerene under nitrogen atmosphere and other C60 fullerene derivatives (the
photopolymer, the ozonized derivative and the chlorinated derivative). Among the
various conclusions it is interesting to remind here that the C60 photopolymer
prepared in solution[2,3] did not revert back to C60 and instead was converted into
disordered carbon.
The present work can be considered a continuation of the former one. In the
present case we have selected a series of carbon materials much more extended
than those adopted in the previous work and we have studied by TGA–DTA their
thermal behavior both under nitrogen flow and air flow. The purpose of this work
is to build a deeper knowledge on the comparative behavior between well known
carbon allotropes like graphite and diamond and other rather ‘‘new’’ carbon
materials like fullerene black, C60 and C70 fullerenes and the well known carbon
black. Furthermore, we have examined the effect of the radiation treatment on the
thermal behavior of graphite and two different grades of carbon blacks in
comparison to the pristine samples.
Despite the large efforts and works devoted to fullerenes and other
carbonaceous materials, the investigations pertaining the thermal behavior (both
under nitrogen atmosphere and in air) of certain carbon allotropes and
carbonaceous matter are relatively limited in number and in scope. The purpose
of the present work is to fill this gap in a relatively comprehensive work.
Furthermore, an increased knowledge on the behavior of carbon materials at
relatively high temperatures will improve further our knowledge on them and may
stimulate a broadening of the application fields. Part of the results of the present
work will be of some help to us and other scientists who are interested in a better
THERMAL STABILITY OF CARBON MATERIALS 295
understanding of the so-called reprocessing cycles of carbon in the interstellar

medium and around certain circumstellar environment.[4,5]
EXPERIMENTAL
C60 and C70 fullerenes were obtained from Southern Chemical Group LLC
or from Fluka. In any case their purity was confirmed to be higher than 99% by
UV spectroscopy and HPLC. The samples of fullerene black (FB), and extracted
fullerene black (EFB) were prepared according the procedure of Wudl et al.[6]
Under the name ‘‘fullerene black’’ we identify the raw soot formed from resistive
heating of graphite under Kratschmer-Hufmann conditions and containing about
6% of C60 and C70 fullerenes. Under the name ‘‘extracted fullerene black’’ we are
referring to FB samples which have been extracted with toluene but which still
contain a residual amount of C60 and C70 fullerenes and all their superior
homologues which are not extractable with toluene.
The graphite sample used in the present work was from Aldrich with a
particle size of 1–2 microns of synthetic origin (not natural).
Carbon nanotube sample was purchased from Aldrich and used as received.
Carbon black samples used were standard grades N375 and N234 types
from Cabot Corp. Both samples were produced by a furnace process.[7]
Diamond samples employed in this study were two gemstones of 0.65 carat
each having a neat yellow color.
Neutron irradiation of graphite and N234 carbon black was made for 5
hours on samples sealed in PE vials at a neutron flux of 2 1012 n cm2 s2
(mixed thermal and fast neutrons) at the Pavia (Italy) nuclear reactor Triiga Mark
2 from General Atomic.
Gamma irradiation of N375 carbon black sample was performed in a Co60
cell at the Istituto di Chimica Nucleare of CNR, Moterotondo (Italy) at a dose rate
of about 5 kGy=h for a total dose of 1 MGy.
The surface area of the carbon materials studied was estimated by the
iodine absorption method according to the ASTM D1510 procedure which gives
the mg iodine absorbed by each g of material under analysis. The iodine value is
in general numerical agreement with the N2 surface area measurement made
according to the BET method and expressed in m2=g.[8]
Simultaneous TGA–DTA measurements were performed on a Linseis
apparatus L81 þ DTA. The measurements under N2 flow (0.35 L=min) and under
air flow (2 L=min) were performed at a heating rate of 20 C=min.
The FT-IR spectra were recorded on a Perkin Elmer 1710 Spectrometer on
KBr pellets.
296 CATALDO
RESULTS AND DISCUSSION
Study of the Thermal Behaviour Under N2 Flow
Graphite
Figure 1 shows the TGA curves recorded over a set of carbonaceous

materials. The behavior of 2 mm size graphite synthetic particles is very clear:
the weight loss involves only about 3% of the original weight at 900 C
confirming our previous results[1] on rather different graphite grade. The
weight loss may be ascribed essentially to the moisture vaporization. Since
graphite sublimation is known to occur at about 3367 C,[9] all the weight loss
recorded is due to moisture. The DTA of the graphite sample used in the
present work shows a very weak and broad exothermal transition at about
850 C. Probably this transition is associated to the rearrangement of a small
fraction of b-graphite to the a-form. In fact it is known[9] that b-graphite is
produced by mechanical treatment such as grinding of the a-form. The
thermal treatment of b-form at about 1000 C causes the complete reversion to
the a-graphite. The transformation is exothermal and involves a DH of
0.14 kcal g atom1.[9] The difference between a and b graphite involve the fact
that the graphene sheets are arranged in a way that the carbon atoms of
alternate layers are vertically above each other in the case of a-form. Instead,
in the case of b-form the graphene sheets are staggered such that the carbon
atoms of every third layer are vertically above each other.
Diamond
Diamond samples were heated in the TGA (see Fig. 1) under N2 flow. The
weight loss measured was less than 1% of the original weight at about 900 C,
thus somewhat negligible. The surface of each face of the diamond samples was
originally smooth since we have used two gemstones with brilliant cut in this
study. After the thermal treatment the surface of the stones has lost its smoothness
and appears slightly rough and opalescent like a frosted glass. We interpret this
morphology as due to a light volatilization of carbon from the surface of diamond
which may account for the 1% weight loss. In fact in this case the weight loss
cannot be attributed to the desorption of moisture or other adsorbed molecules
due to the original smoothness of the surfaces. An additional feature observed on
the diamonds thermally treated was the change in color which passed from dark
yellow to a pale yellow after the thermal treatment. About this phenomenon we
will refer in another communication.[10]
Thermogravimetric analysis on carbon materials under N2 flow at 20 C=min.

Figure 1.
298 CATALDO
It has been reported that the transition from diamond to graphite occurs
already at 1030 C in the absence of oxygen;[9] if the conversion is complete,
always polycrystalline graphite is obtained without any preferred orientation.
Hence our study on the thermal behavior of diamonds was also conducted with
the basic idea to verify this aspect of the allotropic transition from diamond to
graphite with the possibility to observe new carbon morphologies. Unfortunately
we have not observed any hint of graphitization in our samples. This fact suggests
that very long heating at 1030 C is needed to observe such a transition.
C60 Fullerene
Concerning C60 fullerene, the TGA under N2 (Fig. 1) shows that C60 is
rather stable to the thermal treatments provided that air or O2 are excluded from
the system; the unique phenomenon observed is the gradual sublimation of C60
which seems to start very slowly at 400–450 C but becomes appreciable only
above 800 C and ends at 900 C. These results are in good agreement with the
results of early investigators[11] who have studied the C60 sublimation under
different conditions than those used here. In fact in the mentioned work[11] the
heating rate was only 5 C=min and inert gas used was Ar instead of N2. However,
it was found that the sublimation begins at 550 C, becomes appreciable at about
720 C and is completed at 900 C. Always a residue remains in the crucible of the
thermobalance after the sublimation. This residue accounts for the 15 to 10% of
the weight of the original sample and it appears to be composed by a ‘‘non-C60’’
carbonaceous matter.[11] It has also been established the C60 fullerene sublimation
can be described by a first order reaction.[11] The maximum rate of sublimation of
C60 occurs at 790 C at a heating rate of 2 C=min, it is shifted to 835 C at
5 C=min and it reaches 870 C at a heating rate of 9.6 C=min. From these data the
energy of activation for sublimation E# has been found to be 44.4 kcal=mol in
agreement with the heat of sublimation of C60 which is 40.1 kcal=mol.
Fullerene Black and Extracted Fullerene Black
Figure 1 shows also the thermal behavior of FB and extracted EFB (see
the experimental section for a definition of these two materials). The TGA
shows that FB and C60 are almost coincident up to 500 C. However above
this temperature the weight loss of FB become linear with temperature while
this is not the case of fullerene. Thus, the interesting conclusion drawn from
these two TGA curves is that C60 and also higher fullerenes are sublimed
more easily from FB rather than from C60 crystalline solid. This is quite
reasonable if we consider that all fullerenes are highly dispersed in the FB
matrix and are not in crystalline form or, if they posses a crystalline form, the
crystals must be very small and dispersed into the FB matrix. Conversely, in
the case of C60 fullerene, we are dealing with much larger crystals than those
which may exist in the FB matrix. Therefore their sublimation requires much
more energy and higher temperature than the case of FB. The sublimation
from FB involves also a re-condensation of the sublimate along the quartz
tube of N2 gas outlet from the TGA apparatus. In the case of pure C60
sublimation we got the formation of large dark-violet crystals of C60. In the
case of FB we obtained the deposition of C60 crystals together with a more
volatile brown fraction which condensed at longer distance from the crucible
than pure C60. There are no neat evidences about the sublimation of the
superior homologues of C60. The EFB shows an onset weight loss already at
250 C (Fig. 1). We believe that this is due to trapped toluene which was used
to extract C60 and C70. However the weight loss extends linearly up to 620 C
until a plateau is reached. It is hard to admit that all the weight loss (which
amounts to 9.5% at 900 C) of extracted FB was due to trapped toluene. It is
obvious to think that some residual C60 and also its superior homologues have
been released.
In this context it is useful to recall the weight loss and hence the residual
matter remained in the TGA crucible. As reported above the residue (under N2)
was about 10% in the case of pure C60, was 82.6% in the case of FB and 90.5% in
the case of EFB.
Thus the total volatile ‘‘sublimable fullerenic matter’’ is 17.4% in the case
of FB but it is reduced to much less than 9.5% in the case of EFB. This means
that with toluene extraction it is possible to remove only 17.4 7 9.5 ¼ 7.9% of the
total ‘‘sublimable fullerenic matter’’ from FB (assuming negligible the toluene
residue in the EFB). The value of 7.9% up to 10% at best is the usual yield of
C60 þ C70 fullerenes which can be extracted with toluene from graphite.[6]
Therefore sublimation should be a better more efficient technique in the
separation of fullerenes from the FB but it should be taken into account that this
thermal treatment causes also a conversion of C60 to other carbonaceous matter
by about of 10% of the original value.
Based on the above data, we may affirm that the production of fullerenes
according to the modified Kratschmer-Huffman conditions[6] is able to produce
about 20% of fullerenic matter from graphite (17.4 þ 1.74 ¼ 19.1%) but only
50% of this amount can be recovered during the toluene extraction.
It must be emphasized that in addition to the extractable or volatile
fullerenic matter, also the residual EFB can be regarded more as a defective
graphite (i.e., graphite containing fullerene-like structures[12]) rather than a pure
and simple furnace or flame-derived carbon black.[13]
Concerning the DTA signal, surprisingly the three different materials
namely C60 fullerene, FB and EFB do not show any peculiar feature which is able
300 CATALDO
to differentiate the thermal behavior of one of these three materials from the
others.
Study of the Thermal Behavior Under Air Flow
Fullerenes and Fullerene Blacks Versus Graphite
The study of the thermal behavior in air of fullerenes has attracted a certain
attention of the investigators in recent years.[11,13–17] It has already been reported
that C60 fullerene is more reactive with O2 than graphite and C70 is even much more
reactive.[11,13,15–17] Surprisingly, EFB is more reactive with oxygen than pure C60
and C70[13] and carbon nanotubes are less reactive than fullerenes. Moreover, the
presence of C70 in a sample of C60 accelerates its reaction with O2.[15]
In Fig. 2 we show our experimental TGA curves recorded in a relatively
high air flow rate, thus in combustion conditions which are much more dramatic
than those adopted by any other previous investigator.[11,13,15–17] With so drastic
conditions there is the risk to loose in sensitivity and in the possibility to
differentiate the behavior of the different materials examined but in this way we
are approaching a more realistic burning conditions in a furnace. Despite the
conditions adopted, in Fig. 2 it is possible to appreciate the completely different
behavior of the carbon materials studied. The highest reactivity in combustion
reaction can be qualitatively estimated from the TGA curves of Fig. 2 in the
following order:
FB > C70 > EFB > C60 > Graphite > Diamond ¼ nanotubes
However, precise and quantitative data can be verified from the DTA results
which have been recorded simultaneously with the TGA curves. Some of these
data are reported in Fig. 3 and are summarized in Table 1. From these data the
reactivity with oxygen must be definitively arranged in the following scale (from
the highest reactivity to the lowest):
EFB > C70 > FB > C60 > Graphite > Diamond ¼ nanotubes
From the DTA data (Fig. 3 and Table 1) it can be deduced that the most reactive
material in the combustion reaction is EFB. In fact its onset temperature of
reaction lies at 315 C and Fig. 3 shows a very broad exothermal signal with three
consecutive peaks at 582 C, 686 C, and 790 C. It is reasonable to think that this
very high reactivity is due to the very high surface area of EFB (160 m2=g, see
Table 1). The high surface area favors the combustion at relatively low
temperature (DTA onset only 315 C); however the reaction is not so fast at the
initial stages and develops slowly and then it is prolonged to very high
temperatures. It looks like the initial ignition causes some surface clumping or
Thermogravimetric analysis on carbon materials under air flow at 20 C=min.

Figure 2.
302 CATALDO
Figure 3. Differential thermal analysis signals recorded during the combustion of

fullerenes and fullerene black in air flow. ‘‘Fullerite’’ is FB and ‘‘Extracted fullerite’’ is
toluene-EFB.
agglomeration so that after an initial burst, the reaction slows down and revamps
at much higher temperatures. These results appear in agreement with the work of
Schlogl and colleagues[13] where the mentioned reaction spike has been recorded
under combustion conditions different from those adopted here.
The DTA data of Table 1 and Fig. 3 shows also that fullerene C70 has its
onset reaction with oxygen at only 426 C, thus at much lower onset temperature
than C60 fullerene whose onset reaction temperature lies at 527 C. This can
be visually appreciated also from the DTA signals reported in Fig. 3: when the
reaction between O2 and C60 is just at the beginning C70 is already burnt out in
large part. This is suggested by the C70 DTA peaks which lie at 457 C and 504 C
while for C60 the DTA peaks appears at much higher temperature i.e., 665 C and
Table 1. Thermogravimetric Analysis in Air Flow of Carbon Materials
Iodine DTA Signal Combustion=Decomposition ( C) DTA Combustion TGA Max

Surface Enthalpy Decomposition
Area, m2=g Onset Peak 1 Peak 2 Peak 3 H (mV s=mg) Rate ( C)
Extracted fullerene 160 315 582 686 790 3,823
black
Fullerene C70 n.d. 426 457 504 6,272
Fullerene black 21 443 485 3,009 506
Fullerene C60 7.2 527 665 820 4,063 822
Graphite 15 609 638 697 815 4,476
Graphite treated >15 570 697 782 4,450
with neutrons
N375 carbon black 90 505 558 615 702 4,947
N375 treated with 90 532 563 648 738 4,000
gamma rad
THERMAL STABILITY OF CARBON MATERIALS
(1 MGy)
N234 carbon black 120 523 568 620 691 4,367
N234 treated with <120 531 560 720 4,449
neutrons
303
304 CATALDO
820 C. Reverting back to the TGA curves (Fig. 2), the different behavior between
C70 and C60 is striking. In fact when C60 starts to decompose, C70 has already lost
50% of its weight while for C60 the maximum decomposition rate occurs only at
822 C. The C70 decomposition reaction slows down at about 700 C according to
TGA due to the formation of a 10% residue which is completely burnt out
at 850 C. Conversely for C60 the reaction slows down only at 850 C with about
15% residue.
The strikingly different behavior observed between C60 and C70 is the key
for the interpretation of the different behavior between EFB and FB.
Extracted fullerene black is largely free from C70 but possesses a very high
surface area (see Table 1) and the superior homologues of fullerenes and
fullerene-like structures. Previously we have discussed the effect of the high

surface area of the EFB in the burning behavior but now we should add the
additional observation that the surface of EFB is also characterized by several
different types of sites. This may account also for the very broad DTA signal of
Fig. 3. On the other hand, FB is characterized by a low surface area of only
21 m2=g, much lower than the extracted FB but it contains C70 fullerene which
has been indicated by several authors[11,13,15,16] as an oxidation promoter in the
decomposition of C60 even when it is present in small amounts. In fact the onset
reaction of FB with O2 in our conditions lies at 443 C which is close to the onset
value of pure C70 (426 C, Table 1). Also the first (and unique in this case) peak
temperature is found at 485 C for FB, very close to that of C70 at 457 C.
Therefore, we may affirm that the combustion reaction of FB is driven by the
presence of C70 fullerene while in the case of EFB the reaction is initially due to
the very high surface area of this material and then by the copious distribution of
different sites on the surface. The TGA curve (Fig. 2) of FB approaches that
of C70 fullerene although the FB weight loss is even much faster than the case of
pure C70. We can exclude that this behavior is due to a simultaneous sublimation
of volatile components from FB. Conversely, the TGA curve of EFB (Fig. 2) and
also its DTA signal (Fig. 3) approaches more closely the behavior of C60
fullerene. Also in this case EFB undergoes a weight loss much more pronounced
than that of C60 in perfect symmetry with the couple FB=C70 previously
discussed.
Both FB and especially EFB left an orange residue in the crucible of the
thermobalance. In the case of the EFB the amount recovered was about 15% of
the initial weight. The FT-IR in KBr of this residue showed the following bands:
3400; 1743; 1705; 1650; 1565; 1440; 1384; 1161; 1125; 1000; 940; 887; 828;
744; 684; 620 cm1. All these bands suggest both the aromatic nature as well as
the highly oxidized state of the residue with ketonic, aldehydic, carboxylic, and
hydroxylic groups.
Table 1 shows that graphite is much less reactive in comparison to
fullerenes and FB, in agreement with earlier works.[11,13] First of all it is
important a simple annotation that the surface area of the graphite used in this
work is almost comparable to that of FB while fullerenes have a lower surface
area due to their crystal structure. The onset reaction of graphite with O2
occurs at 609 C in our conditions, at 166 C higher temperature than FB
which has the same surface area of graphite and at 82 C higher temperature
than C60 fullerene. Despite the higher onset temperature recorded for graphite
combustion, the most intense exothermal event for graphite occurs at 638 C
(see Fig. 4) corresponding to peak 1 of Table 1 while for C60 fullerene the
most intense event occurs only at 820 C (see Fig. 3) corresponding to peak 3
of Table 1. In fact, it is curious to observe the relative correspondence
between the three exothermal peaks of graphite and those of EFB or C60
fullerene suggesting that after a specific inception of the process due to the
specific chemical structure of the surfaces of these carbon solids, then a
certain thermal rearrangement to a common general structure occurs leading
after a certain point to a similar combustion response. This of course is not
applicable to the case of C70 fullerene and FB which burn so fast at low
temperature that this rearrangement is not possible or is not complete. The
TGA curve of graphite and C60 fullerene (Fig. 2) do not show so enormous
differences as suggested by the DTA data.
The Case of Diamond and Nanotubes
Diamond and carbon nanotubes are two carbon materials having a

completely different structure and the carbon atoms have a completely different
degree of hybridization. In the case of diamond an sp3 hybridization of the carbon
atoms must be advocated together with a very compact structure and, in the case of
the sample used, a very low surface area. The combination of these aspects has led
to an extremely low reactivity of diamond with O2. In fact the TGA curve (Fig. 2)
shows the onset for the reaction with O2 at about 800 C in our conditions. Above
this temperature an appreciable reaction can be observed by a rapid weight loss.
The oxidation resistance of carbon nanotubes is even more surprising since
they have the chemical structure of a graphene sheet rolled up in a cylinder shape
with two fullerenic caps which close the cylinder. This structure recalls in any
way the fullerene structure and can be defined a fullerene-like structure.[12]
Therefore one must expect a behavior closer to fullerenes and FB. Instead,
experimentally we have found a behavior closer to diamond. In fact the TGA
curve of Fig. 2 shows the onset reaction with O2 at about 820 C, a temperature
comparable to that of diamond. Notwithstanding this surprising result, we should
observe that other investigators[16,18] have already reported that nanotubes have a
greater apparent oxidative stability than fullerenes even though nanotubes and not
fullerenes have exposed edge sites.
306 CATALDO
Figure 4. Differential thermal analysis signals recorded during the combustion of

graphite and carbon blacks in air flow. The continuous line pertain to the pristine samples
the dotted lines to the radiation-treated samples. Graphite and N234 carbon black were
treated with neutrons, while N375 carbon black was treated with g radiation (see
experimental section for details).
Radiation Treated Graphite and Carbon Black Versus Pristine Samples
In this latest section we report the thermal behavior in air of three different
carbon materials radiation-treated in comparison to pristine samples. The purpose
of this part of the work is to verify whether the radiation treatment is able to
increase the reactivity of graphite or certain carbon blacks with air during a
controlled combustion experiment in the TGA–DTA apparatus.
Recently, in a series of papers[19,20] we have discussed about the radiation
damage induced in carbon materials by g radiation and by neutrons and about the
effect of the radiation treatment on the rubber absorption power of graphite and
carbon black.[21] Furthermore, we were able to evaluate the effect of the radiation-
treated graphite and carbon black on the reinforcement of rubber compounds.[22–24]

The general conclusion of our works was that the lower the surface area of the filler,
the lower is the concentration of ‘‘active sites’’ on it (see Ref. 12 for a definition of
‘‘active site’’). The radiation treatment induces the formation of new active sites.
These sites have various natures but Raman spectroscopy suggests that
the radiation treatment induces the formation of fullerene-like sites.[19,20] The
consequences of the radiation treatment are manifested by an increase on the rubber
absorption power of the black filler[21] and in an increase in the mechanical
reinforcement of a rubber compound.[22] However, the increased absorption power
of rubber is more clearly observed on fillers with low surface area, and with a low
concentration of active sites rather than on filler with a high surface area which
already have an high concentration of surface active sites. Hence, it appears that the
radiation damage caused by neutron bombardment is able to increase the activity of
low surface area fillers like graphite but this effect is less clear on high surface area
and relatively disordered materials like carbon black N234.[21]
In Fig. 5 we report the TGA curves recorded in an air flow (see experimental
section) of graphite and two carbon blacks having different surface area (see also
Table 1 for a DTA summary). In Fig. 5 it can be seen that the surface area of the
carbon material used greatly influences the combustion reaction. In fact, the
combustion starts and goes to completion first with N234 carbon black which has
a surface area of 120 m2=g, followed by N375 carbon black with 90 m2=g. The
less reactive carbon material is graphite with only 15 m2=g of surface area and an
highly ordered crystalline structure, significantly different from the highly
disordered and nanocrystalline carbon black. An additional observation from
Fig. 5 is that the neutron-damaged N234 gives a TGA curve completely
coincident with that of the pristine N234; instead g-treated N375 seems to be
slightly more reactive in comparison to its reference pristine counterpart. Finally
no significant differences can be observed in the case of neutron-damaged
graphite in comparison to pristine graphite.
The DTA response to the combustion is reported in Fig. 4 and the data are
summarized in Table 1. First of all we notice in Fig. 4 that the DTA signal is
308 CATALDO
Figure 5. Thermogravimetric analysis on graphite and carbon blacks N375 and N234 pristine and after radiation damage.
broader and more intense for the pristine N375 and pristine graphite sample in
comparison to the radiation-treated samples, but this rule does not apply in the
case of N234 where the DTA signals of the radiation treated and untreated
materials appear almost the same.
The other interesting aspect is the DTA onset temperature for the
combustion reaction which is the lowest for N375 carbon black, followed by
N234 and finally by graphite (see Table 1). Table 1 shows also that the
neutron damage lowers the onset temperature for the combustion of graphite
from 609 C of the pristine material down to 570 C for the damaged material.
However the effect on the DTA onset is exactly the opposite in the case of
both N375 (g-treated) and N234 (neutron-treated) in comparison to the pristine
materials. The reason of this opposite behavior is not clear also considering
that the g-treatment of N375 has not changed at all the surface area of this
material. Conversely, it is reasonable to assume a slight lower surface area in
the case of N234 due to the neutron damage in comparison to the pristine
material. In the case of graphite the neutron bombardment should have caused
a slight increase in the surface area and this may justify the lower onset
temperature of combustion.
CONCLUSIONS
In a N2 flow diamond and graphite are stable up to about 1000 C. The

minimum weight loss observed has been attributed to moisture in the
case of graphite and also to a slight vaporization of carbon. The
graphitization of diamond reported in literature[9] to occur at 1030 C
has not been observed.
C60 fullerene, under a nitrogen flow sublimates. The sublimation starts
very slowly at about 400–450 C and it becomes very strong at
T > 800 C at a heating rate of 20 C=min.
Fullerene black, which is the raw carbon soot containing fullerenes
shows a sublimation behavior. The sublimation of fullerenes from FB is
more pronounced than from pure C60 crystals due to the high dispersed
state of these molecules in the FB matrix.
Concerning the behavior of various carbon materials in an air flow at a
heating rate of 20 C=min, hence in a dynamic combustion conditions,
although the TGA and its derivative curve (whose peak corresponds to
the maximum decomposition rate) shows the following reactivity trend
from the most reactive:
FB > C70 > EFB > C60 > Graphite > Diamond ¼ nanotubes
310 CATALDO
The DTA onset temperature suggests instead the following trend:

EFB > C70 > FB > C60 > Graphite > Diamond ¼ nanotubes
Which is almost the same trend with an inversion between FB and
EFB.
It has been verified that C70 fullerene is very reactive with air. Its
presence both in FB and as impurity in C60 accelerates the combustions
also of these carbon solids.
Thermogravimetric analysis and differential thermal analysis studies on
graphite and carbon black N375 and N234 in a air flow has shown that
the combustion of these solids is dependent from their surface area and
degree of crystallinity. After radiation damage of these materials by

neutron bombardment or by g radiation the behavior of the carbon
solids in combustion does not change in a very clear cutway.
ACKNOWLEDGMENT
I wish to thank ASI, the Italian Space Agency, Viale Liegi 26, 00198 Rome,
Italy for the kind financial support of the present work.
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Received April 20, 2002

Revised May 24, 2002
Accepted August 5, 2002

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Fullerenes, Nanotubes and Carbon Nanostructures

A STUDY ON THE THERMAL STABILITY TO 1000°C OF

To link to this article: http://dx.doi.org/10.1081/FST-120016451

PLEASE SCROLL DOWN FOR ARTICLE

FULLERENES, NANOTUBES, AND CARBON NANOSTRUCTURES

A STUDY ON THE THERMAL

AND CARBONACEOUS MATTER

Soc. Lupi Chemical Research Institute,

The thermal behavior of graphite, C60 fullerene, fullerene black

DOI: 10.1081=FST-120016451 1536-383X (Print); 1536-4046 (Online)

have been found to be the most reactive carbon materials

tion reaction of these carbon materials has been discussed.

In a previous work,[1] we have studied by TGA (Thermogravimetric

THERMAL STABILITY OF CARBON MATERIALS 295

understanding of the so-called reprocessing cycles of carbon in the interstellar

RESULTS AND DISCUSSION

Study of the Thermal Behaviour Under N2 Flow

Figure 1 shows the TGA curves recorded over a set of carbonaceous

THERMAL STABILITY OF CARBON MATERIALS 297

Thermogravimetric analysis on carbon materials under N2 flow at 20 C=min.

Fullerene Black and Extracted Fullerene Black

THERMAL STABILITY OF CARBON MATERIALS 299

Study of the Thermal Behavior Under Air Flow

Fullerenes and Fullerene Blacks Versus Graphite

THERMAL STABILITY OF CARBON MATERIALS 301

Thermogravimetric analysis on carbon materials under air flow at 20 C=min.

Figure 3. Differential thermal analysis signals recorded during the combustion of

Table 1. Thermogravimetric Analysis in Air Flow of Carbon Materials

Iodine DTA Signal Combustion=Decomposition ( C) DTA Combustion TGA Max

fullerene-like structures. Previously we have discussed the effect of the high

THERMAL STABILITY OF CARBON MATERIALS 305

The Case of Diamond and Nanotubes

Diamond and carbon nanotubes are two carbon materials having a

Figure 4. Differential thermal analysis signals recorded during the combustion of

THERMAL STABILITY OF CARBON MATERIALS 307

Radiation Treated Graphite and Carbon Black Versus Pristine Samples

treated graphite and carbon black on the reinforcement of rubber compounds.[22–24]

THERMAL STABILITY OF CARBON MATERIALS 309

 In a N2 flow diamond and graphite are stable up to about 1000 C. The

The DTA onset temperature suggests instead the following trend:

degree of crystallinity. After radiation damage of these materials by

1. Cataldo, F. Fullerene Sci. Technol. 2001, 9, 55.

THERMAL STABILITY OF CARBON MATERIALS 311

19. Cataldo, F. Carbon 2000, 38, 634.

Received April 20, 2002

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