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Electrical conductivity of conductive carbon blacks: Influence of

surface chemistry and topology

Article  in  Applied Surface Science · July 2003

DOI: 10.1016/S0169-4332(03)00550-6

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 Applied Surface Science 217 (2003) 181–193

Electrical conductivity of conductive carbon blacks:

influence of surface chemistry and topology
Dana Pantea, Hans Darmstadt, Serge Kaliaguine, Christian Roy*
Département de Génie Chimique, Université Laval, Quebec, Que., Canada G1K 7P4
Received 25 February 2003; received in revised form 21 March 2003; accepted 21 March 2003

Abstract

Conductive carbon blacks from different manufacturers were studied in order to obtain some insight into the relation between
their electrical conductivity and their surface properties. The surface chemistry was studied by X-ray photoelectron spectro-
scopy (XPS) and static secondary ion mass spectroscopy (SIMS), whereas the topology of the carbon black surface was
investigated using low-pressure nitrogen adsorption. All these techniques yield information on the graphitic character of the
surface. In general, the electrical conductivity of the conductive blacks increases with the graphitic character of the surface. For
low surface area conductive blacks, the electrical conductivity correlates well with the surface chemistry. In the case of the XPS
and SIMS data, this correlation is also valid when other types of carbon blacks such as thermal and furnace blacks are included,
confirming the determining influence of the carbon black surface chemistry on the electrical conductivity.
# 2003 Elsevier Science B.V. All rights reserved.

PACS: 79.60.Jv, X-ray photoelectron spectra; 81.70.Jb, 82.80.Ms, secondary ion mass spectroscopy (SIMS); 34.50.Dy, 82.65.Pa, gas–surface
interactions; 73.25.þi, electrical conductivity surfaces

Keywords: Carbon black; Electrical conductivity; XPS; SIMS; Gas adsorption

1. Introduction Carbon black consists of nearly spherical primary

Carbon blacks are widely used in elastomers and
plastics as fillers in order to modify the mechanical,
electrical and optical properties. Electrically conduc-
tive carbon blacks have received special attention in
the manufacture of conductive polymer composites.
They are used in applications like shielding of elec-
trical cables, special electrical parts in cars [1], and in
electrodes for fuel cells [2].
*
Corresponding author. Tel.: þ1-418-656-7406;
fax: þ1-418-656-2091.
E-mail address: christian.roy@gch.ulaval.ca (C. Roy).
particles, which are fused together in aggregates. The
degree of aggregation of the carbon black particles is
commonly known as ‘‘structure’’ and is measured by a
method based on dibutyl phthalate (DBP) absorption
[3]. The specific surface area—inversely proportional
to the particle diameter—and the structure are
regarded as the two most important carbon black
properties. It was observed that the electrical conduc-
tivity of carbon blacks is strongly influenced by the
structure, specific surface area, and other properties
[4–10]. However, to the best of our knowledge, up to
now no research on the influence of surface proper-
ties (e.g. surface chemistry) on the conductivity of

0169-4332/03/$ – see front matter # 2003 Elsevier Science B.V. All rights reserved.
doi:10.1016/S0169-4332(03)00550-6
182 D. Pantea et al. / Applied Surface Science 217 (2003) 181–193
conductive carbon blacks was published. This is some-
what surprising since the most important obstacle to the
electron flow in carbon black beds is located at the
interface between the primary particles of the different
carbon black aggregates [11]. Our research group
investigated therefore the relation between the electri-
cal conductivity and surface properties of thermal
blacks [12], furnace blacks [13] and carbon blacks
recovered by pyrolysis of tires [14]. The structure
and surface area of thermal blacks are very similar,
whereas their surface properties differ considerably.
Thus, differences of the electrical conductivities could
be associated to the surface properties. It was found that
the electrical conductivity correlates best with graphitic
character of the first atomic layer on the carbon black
surface as studied by static secondary ion mass spectro-
scopy (SIMS). The term ‘‘graphitic character’’ is used
here to describe how close the structure of the carbon
black surface approaches the structure of a perfect
graphite surface.
These studies gave valuable insight into the factors
influencing the electrical conductivity. However, most
of the carbon blacks that are selected in the industry
based on their conductive properties are the so-called
conductive blacks. As compared to other rubber-grade
carbon blacks produced by the furnace process, con-
ductive blacks have higher electrical conductivities,
usually higher surface areas and structures, and can
contain a significant volume of micropores [15,16].
These properties vary over a wide range. It is therefore
not straightforward to attribute differences in the elec-
trical conductivity to a certain carbon black property.
However, because of the commercial importance of
conductive blacks, this was attempted in the present
work. The surface characteristics of the carbon black
samples were studied by two spectroscopic methods
(X-ray photoelectron spectroscopy (XPS) and static
SIMS) and by low-pressure nitrogen adsorption. By
XPS, the chemistry of the surface and the near-surface
region is investigated, whereas by static SIMS only the
first one or two atomic layers are probed. Low-pressure
nitrogen adsorption, on the other hand, yields informa-
tion on the surface topology. The electrical conductivity
was measured by impedance spectroscopy.
In commercial applications, conductive blacks are
always used in composites. Therefore, an investiga-
tion on the electrical conductivity of conductive
blacks may seem not very valuable. However, it
was observed that a correlation between the intrinsic
electrical conductivity of conductive carbon blacks
and the conductivity of composites containing these
blacks exists [17]. Thus, the findings of the present
work might be relevant to commercial carbon black
applications.
2. Experimental procedures
2.1. Carbon black samples
The conductive carbon blacks were obtained from
different producers: Cabot Corporation, USA (Black
Pearls 2000, Vulcan XC-72), Columbian Chemicals
Canada (Conductex 975, Conductex SC) and Degussa
Canada Ltd. (Printex L, Printex L6, Printex XE-2).
The surface area and structure (DBP number) of the
conductive carbon blacks ranged from 150 to
1635 m2/g and from 115 to 400 cm3/100 g, respec-
tively (Table 1). Of these samples, Conductex SC is
classified as a so-called semi-conductive black [18].
Two of the conductive blacks (Printex XE-2 and Black
Pearls 2000) had considerably higher surface areas
and structures than the other conductive blacks. A
furnace rubber-grade carbon black (ASTM designa-
tion N375) produced by Columbian Chemicals
Canada, a thermal carbon black from Cancarb Ltd.,
Canada (N880), and a commercial graphitised carbon
black (Carbopak Y) obtained from Supelco, USA [19]
were studied for comparison. These reference samples
had ‘‘typical’’ properties for the respective carbon
black type [12,13].
2.2. Sample characterisation
2.2.1. Electrical conductivity by
impedance spectroscopy
The procedure and the set-up used for the electrical
conductivity measurements were already described
elsewhere [12]. Briefly, the carbon black sample
was placed in a glass tube between two metal plun-
gers. The electrical conductivity at different compres-
sion was measured by impedance spectroscopy.
However, because of the low apparent density, a
smaller amount of carbon black sample was used in
the present work (approximately 1 g). It should be
noted that the experimentally determined electrical
 D. Pantea et al. / Applied Surface Science 217 (2003) 181–193 183

conductivity does not depend only on the carbon black
properties. Various parameters of the conductivity
measurement (e.g. cross-sectional area of the glass
tube and the amount of the carbon sample) also have a
significant influence [20,21]. It is therefore not
straightforward to compare conductivity data from
different laboratories. In the present work, values
for the electrical conductivity are reported for all
samples at the same packing fraction (f) of 0.3.
For carbon blacks with a similar particle size (or
similar external surface area) at a given packing
fraction, the number of contacts between the particles
is comparable. Here, f is defined as the ratio of the
volume of the carbon black particles including their
micropores and the volume available of the carbon
sample:
ðm=rHe Þ þ Vmicropore
f¼
Sh
where m is the carbon black mass, rHe the real
carbon black density (as measured by helium dis-
placement), Vmicropore the micropore volume, deter-
mined by the t-plot method from nitrogen adsorption
data, S the transversal area of the hollow glass
cylinder and h the column height of the carbon black
sample.
2.2.2. Nitrogen adsorption
An Autosorb-1 MP apparatus from Quantachrome,
Boynton Beach, FL, USA was used for the nitrogen
adsorption experiments at 196 8C. The adsorption
isotherms were recorded between relative pressures
(P/P0) of 106 and 0.995. Prior to the adsorption
experiment, the carbon black samples were outgassed
at 200 8C until the pressure increase in the closed
sample cell was lower than 1.2 Pa/min. A typical final
dynamic pressure was 0.125 Pa. The BET [22] equa-
tion was used to calculate the specific surface area
from adsorption data between relative pressures of
0.05 and 0.2. The area of a nitrogen molecule adsorbed
at the surface was assumed to be 0.162 nm2. The
external surface area and the micropore volume were
determined by the t-plot method [23]. The nitrogen
adsorption data were also used to calculate the adsorp-
tion potential distribution (APD). The adsorption
potential (A) is defined as the negative change of
the Gibbs free energy of adsorption [19]:
 
(1) P
A ¼ DG ¼ RT ln (2)
P0
where R is the gas constant, T the absolute temperature
and P/P0 the relative pressure. The APD was normal-
ised to the monolayer volume:
DV
APD ¼ (3)
Vmonolayer DA
where DV and DA are the differences in volume of
adsorbed gaseous nitrogen (cm3 STP/g) and in the
adsorption potential, respectively, between two nei-
ghbouring points of the adsorption isotherm, and

Table 1
Properties of the carbon black samples

Sample Surface area (m2/g) Structure, DBP Micropore s at a packing

absorption volume fraction of 0.3
Total BET External t-plot (cm3/100 g)a (cm3/g) (S/cm)
Thermal black 13 10 39 – 0.0b,c
Furnace black 99 88 115 0.003 2.0
Conductex SC 190 123 115 0.03 2.5
Conductex 975 250 142 170 0.05 4.7
Printex L 150 79 116 0.04 3.3
Printex L6 190 98 120 0.04 3.3
Vulcan XC-72 245 110 178 0.06 4.5
Black Pearls 2000 1635 480 330 0.59 2.2b
Printex XE-2 1300 1021 400 0.03 12.3b
Graphitised black 33 – – – –
a
Values obtained from the manufacturer.
b
Extrapolated value from higher packing fractions.
c
The extrapolated value was negative, which has no physical meaning. It is assumed that s is close to 0 S/cm.
184 D. Pantea et al. / Applied Surface Science 217 (2003) 181–193

Vmonolayer the volume of the nitrogen monolayer cal-
culated with the BET equation.
2.2.3. Surface chemistry by XPS
An ESCALAB MK II spectrometer (VG Scientific,
East Grinstead, UK), equipped with a Microlab system
from Vacuum Generators (Hastings, UK) with non-
monochromatised Mg Ka radiation were used. The
pressure in the analytical chamber was lower than
107 Pa, the X-ray power was 300 W, and the spot size
was approximately 1 cm2. The pass energies were 10,
20, and 50 eV for the spectra of carbon, the other
elements, and the survey spectra, respectively. Prior to
the experiment the binding energy (BE) was calibrated
against the following lines: Au 4f7/2 (84.0 eV), the Ag
3d5/2 (368.30 eV) and the Cu 2p3/2 (932.65 eV). The
observed binding energy of the so-called graphite peak
(see Section 3.2.2) was very close to the usual value of
284.5 eV for graphite-like surfaces indicating that no
charging of the surface occurred. After subtraction of a
non-linear background from the spectra, a mixed
Gaussian–Lorentzian product function was used to
describe the symmetric C2–C6 C 1s, O 1s and S 2p
XPS peaks [24]:
I0
I¼
ð1 þ ðmðx  x0 Þ2 =b2 ÞÞ
 exp ðð1  mÞ ln 2ðx  x0 Þ2 =b2 Þ
where I is the intensity, I0 the peak height, x the BE, x0
the peak centre, b a parameter for the peak width that
is nearly 0.5 full width at half maximum (FWHM) and
m the Gaussian–Lorentz mixing ratio; with m ¼ 0 a
pure Gaussian curve is obtained, whereas m ¼ 1 gives
a pure Lorentzian curve. The C1 peak of the carbon
spectrum had an asymmetric shape. Its shape was
described by an exponential tail, added to the high
BE side of the peak [24]:
I 0 ¼ I þ ðI0  IÞð1  TMRÞ exp ðETRðx  x0 ÞÞ
0
where I is the intensity of the asymmetric peak, TMR
the tail mixing ratio and ETR the exponential tail ratio.
A program developed at Université Laval was used to
calculate the relative sensitivity factors for the deter-
mination of the elemental composition on the surface.
This program considers the Scofield photoionisation
cross-sections, angular asymmetry factors, transmis-
sions and the electron mean free path in the calculation.
2.2.4. Static SIMS
A Vacuum Generator SIMSLAB equipped with a
Wien-filtered AG61 ionisation ion gun and an MM12-
12S quadrupole mass spectrometer was used for the
SIMS experiments. The static SIMS spectra were
recorded using Arþ ions with a current density smal-
ler than 1 nA/cm2 and an energy of 1 keVat a pressure
lower than 107 Pa. The total ion dose after recording
the positive and negative SIMS spectra at these set-
tings was lower than 5  1012 ions/cm2. The argon ion
beam diameter was 100 mm, the scanned surface
area was 16 mm2 and the angles of incidence and
emission were 45 and 08 with respect to the surface
normal, respectively. The mass resolution was better
than 0.6 atomic mass units (amu) at 5% peak height.
The carbon black samples were pressed to self-sup-
porting disks. The disks were placed in stainless
steel sample holders where they were only held by
gravity. By investigating the effect of the total ion
dose, it was confirmed that with these experimental
settings true static SIMS spectra were obtained
[25].
3. Results and discussion
(4)
3.1. Electrical conductivity
The electrical conductivity of the conductive
carbon black samples increased upon compression
(Fig. 1). Several factors are responsible for this
(5)
Fig. 1. Electrical conductivity of carbon blacks as a function of
compression.
 D. Pantea et al. / Applied Surface Science 217 (2003) 181–193
Fig. 2. Electrical conductivity of carbon blacks as a function of the
packing fraction.
behaviour. Upon compression at relative low pres-
sures—as used in the present work—the carbon black
aggregates rearrange themselves into in a denser
packing. The number of contacts between them in-
creases, leading to a higher electrical conductivity of
the carbon black bed.
As mentioned above, in the present work, the
conductivities of the different carbon blacks at the
same packing fraction are compared. It is therefore
interesting to regard the dependence of the conduc-
tivity on the packing fraction. This is shown in Fig. 2.
In order to minimise overlapping curves, the data are
presented in two graphs. For all samples, the con-
ductivity increased with increasing packing fraction
in a linear fashion. However, because of the different
compressibility of the various carbon blacks, impor-
tant differences exist. The highest pressure reached
during the compression experiments was approxi-
mately 2000 kPa (Fig. 1). Under this pressure, the
packing fraction of the thermal carbon black was
approximately 0.6, whereas in the case of the con-
ductive black Printex XE-2 the packing fraction was
approximately four times lower (Fig. 2). This obser-
vation might be attributed to the differences in the
basic carbon black properties. The thermal carbon
black had a very low surface area and structure,
whereas Printex XE-2 had the highest surface area
185
and structure of all samples studied (Table 1). The
behaviour of the other samples was in between these
extreme cases. The corresponding packing fractions
under a pressure of 2000 kPa ranged from 0.27 to
0.34. For all these samples, extrapolation to a con-
ductivity of zero yielded packing fractions between
0.16 and 0.22 (Fig. 2). This indicates that at these
packing fractions the physical contact between the
carbon black aggregates was so weak that no transport
of electrons occurred.
At a packing fraction of 0.3, the electrical conduc-
tivity varied considerably for the carbon black samples
studied (Table 1). It should be considered, however,
that for the conductive black Printex XE-2 and the
thermal black the conductivity was extrapolated over a
wide range. Thus, the conductivities reported for these
samples are only indicative.
The conductivity increases in the order: thermal
carbon black < rubber-grade furnace black < semi-
conductive black (Conductex SC) < conductive
blacks. Within the conductive carbon blacks, there
was no clear correlation between the conductivity and
the surface area. However, as mentioned in the litera-
ture [10], the electrical conductivity increased in
general with increasing structure (Table 1). An excep-
tion was found for one of the high surface conductive
blacks (Black Pearls 2000). Furthermore, for other
types of blacks (e.g. thermal and furnace grades) no
dependence of the conductivity on the structure was
observed [12,13]. Since our previous investigations
established for other types of carbon blacks the impor-
tance of the graphitic character of the surface, this
property is discussed in Section 3.2.
3.2. Graphitic character of the surface
3.2.1. XPS survey spectra
XPS is a very useful tool to study the graphitic
character of the surface and near-surface region of
graphite-like carbonaceous solids. First information
can be obtained from the surface elemental composi-
tion. A perfect basal graphite surface only contains
carbon. Indeed on the graphitised carbon black—our
standard for a well-ordered graphite-like surface with
very few defects—only carbon was detected (Table 2).
On the other carbon black samples studied, in addition
to carbon, oxygen and/or sulphur were found. The
concentration of these elements on the conductive
186 D. Pantea et al. / Applied Surface Science 217 (2003) 181–193

Table 2 It was suggested that the electrical conductivity of

Elemental composition of the carbon black surface by XPS
carbon blacks increases with decreasing concentration
Sample Element (at.%) of non-carbon elements on their surface [27]. Indeed, for
the samples of the present investigation, the highest
Carbon Oxygen Sulphur
a
conductivity was found for the carbon black without
Thermal black 98.1 1.9
Furnace black 97.2 2.0 0.8
oxygen and sulphur on the surface (Printex XE-2;
Conductex SC 99.2 0.8 a Tables 1 and 2). However, conductive carbon blacks
Conductex 975 99.0 0.7 0.3 with similar conductivities differed considerably in their
Printex L 99.4 0.4 0.2 surface elemental composition (e.g. Conductex 975 and
Printex L6 99.6 0.2 0.2 Vulcan XC-72). Furthermore, plotting the conductivity
a
Vulcan XC-72 99.7 0.3
Black Pearls 2000 99.8 a
0.2
of conductive blacks as a function of the concentration
Printex XE-2 100.0 a a of oxygen, sulphur, or oxygen plus sulphur revealed that
Graphitised black 100.0 a a
no correlation exists between these properties (not
a
Element not detected (five scans).
shown). It can be concluded that the concentration of
non-carbon elements on the carbon black surface is not a
determining factor for the electrical conductivity. Thus,
additional information on the graphitic character was
carbon blacks (0.0–1.0 at.%) was considerably smal- extracted from the XPS detail spectra.
ler than on the thermal and rubber-grade furnace
blacks (1.9–2.8 at.%). Conductive blacks are pro- 3.2.2. XPS carbon spectra
duced at higher temperatures as compared to thermal In the present work, the C 1s spectra were fitted to six
and rubber-grade furnace black. The high tempera- peaks: a peak for carbon atoms in graphite-like, poly-
tures favour the removal of oxygen and sulphur con- aromatic structures (the so-called graphite peak, C1,
taining functional groups. On one conductive carbon [28,29]), three peaks for carbon atoms with one, two
black (Printex XE-2) neither oxygen nor sulphur at all and three bonds to oxygen and/or sulphur atoms (e.g.
was found. This indicates that the defect sites created C–OH, C¼O and COOH (C2–C4) [28,29]), and finally
upon removal of the non-carbon elements healed and two p ! p peaks (C5 and C6, respectively [30,31]).
a highly ordered carbon surface with a low reactivity The BE of the C1 peak was 284.45 eV, the other peaks
was formed. Prior to the XPS experiments, the carbon were shifted from the C1 peak by 1:5
0:1 eV (C2),
black samples were stored in vials. No special mea- 3:0
0:1 eV (C3), 4:5
0:1 eV (C4), 6:3
0:3 eV
sures were taken to restrain the access of oxygen or (C5), and 9:5
0:5 eV (C6) to the high BE side. The
moisture. However, when the highly ordered surface C2–C6 peaks were symmetrical, whereas the C1 peak
of Printex XE-2 was in contact with the atmosphere, had an asymmetrical shape. The C1 peak may contain
no reaction with oxygen took place. The opposite contributions from carbon atoms in an aliphatic envir-
behaviour was reported for activated carbons. Upon onment [28]. Since the carbon spectra consisted of
heating activated carbons in nitrogen, most of the non- overlapping peaks, a strict fit routine was used. The
carbon elements could be removed. However, as soon asymmetry of the C1 peak obtained by the fitting routine
as the heat-treated samples were exposed to air, new is strongly correlated to the areas of the peaks assigned
oxygen-containing functional groups were formed. It to carbon–oxygen and carbon–sulphur groups (C2–C4).
was concluded that after removal of the non-carbon The concentration of these groups depends of course on
elements, no healing occurred and the defects the surface concentration of oxygen and sulphur. There-
remained on the surface of the activated carbon fore, the following constraint was added to the fitting
[26]. procedure:

area of C2 peak þ area of C3 peak þ 2ðarea of C4 peakÞ concentration of oxygen þ concentration of sulphur
¼
total area of the carbon signal concentration of carbon
(6)
 D. Pantea et al. / Applied Surface Science 217 (2003) 181–193 187

Many parameters such as the peak position [34], the

Fig. 3. C 1s XPS spectra normalised to the same height (left) and
to 10% of the maximum intensity (right), respectively.
The area of the C4 peak is multiplied by a factor of two
because this peak was assigned to –COOH groups,
where one carbon atom is bonded to two oxygen
atoms. Since the escape depths of carbon and oxygen
are different, it has to be assumed that no concentra-
tion gradient exists in the volume probed by XPS [32].
The carbon black C 1s spectra were dominated by
intense, asymmetric C1 peaks and weaker p ! p the electronic environment of the carbon atoms on the
peaks (Fig. 3). The spectra are typical for carbonac-
eous solids with a graphite-like surface such as carbon
fibres [28,29], and ordered mesoporous carbons [33].
asymmetry of the C1 peak [35], its FWHM [36], and
the area of the p ! p peak [37] depend on the
graphitic character of the surface. For the samples
of the present investigation, however, the peak posi-
tion and asymmetry of the C1 peak were not suitable
parameters to describe the graphitic character. The
differences between the peak positions were too small
(<0.1 eV) to allow a reliable analysis based on this
parameter. In previous investigations [12–14], the
asymmetry of the C1 peak was used as a measure
for the graphitic character. In the fit procedure used,
the peak asymmetry is characterised by two para-
meters (ETR and TMR; Eq. (5)). One of these para-
meters was kept constant, whereas the other was
allowed to vary. Thus, the peak asymmetry could be
described by the variable parameter. In the present
investigation, however, it was not possible to obtain
‘‘good’’ fits for all spectra when either ETR or TMR
were fixed. This indicates that the differences between
the carbon spectra of the conductive carbon blacks
were larger as compared to the thermal and rubber-
grade furnace blacks studied earlier.
For these reasons, in the present investigation, the
FWHM of the C1 peak and area of the p ! p peak
were used to describe the graphitic character of the
surface. The FWHM depends on the heterogeneity of
surface. Differences in the environment of certain
carbon atoms will slightly shift the position of the
signal corresponding to these atoms and cause a

Table 3
Carbon XPS spectra, relative peak areas and FWHM of the C1 peaks

Sample Area of C 1s peaks (%) FWHM C1

peak (eV)
C1 C2 C3 C4 C5 C6
(C–C, C–H) (C–OH) (C¼O) (COOH) (p ! p (I)) (p ! p (II))
a a a
Thermal black 88.5 2.0 9.5 1.02
a
Furnace black 88.5 2.6 0.6 7.7 0.6 1.20
a a
Conductex SC 91.9 1.1 6.8 0.2 1.10
a a
Conductex 975 89.8 1.1 8.9 0.2 1.04
a a
Printex L 91.8 0.6 7.4 0.2 1.08
a a
Printex L6 91.8 0.4 7.4 0.4 1.08
a a
Vulcan XC-72 91.4 0.3 7.8 0.4 1.07
a a
Black Pearls 2000 88.8 0.2 10.8 0.2 1.05
a a a
Printex XE-2 89.6 9.7 0.7 0.99
a a a
Graphitised black 90.5 8.9 0.6 0.82
a
No peak detected.
188 D. Pantea et al. / Applied Surface Science 217 (2003) 181–193
Fig. 4. Correlation between electrical conductivity (packing
fraction ¼ 0.3) and the FWHM of the XPS carbon C1 peak.
broadening of the observed peak. In a defect-free
graphene layer the electronic environment of all car-
bon atoms is the same. The corresponding XPS spec-
trum shows a narrow peak. An example is the
spectrum of the graphitised carbon black. For this
sample, the smallest FWHM of all carbon blacks
studied was found (0.82 eV; Table 3). The largest
FWHM (1.19 eV) was observed for the furnace black,
indicating a low graphitic character of its surface. Of
the conductive carbon blacks, the sample with the
highest conductivity also had the smallest FWHM
(0.99 eV, Printex XE-2). In fact, for the low surface
area conductive carbon blacks, a good correlation
between the FWHM and the electrical conductivity
exists (upper graph in Fig. 4). The correlation was still
reasonably good when high surface area conductive
blacks and the furnace blacks were included (lower
graph in Fig. 4). This suggests that the graphitic
character of the carbon black surface is indeed a major
factor determining the electrical conductivity.
It should be noted, however, that this correlation
does not apply to the thermal black. The thermal black
had a very low conductivity (Table 1), whereas its
FWHM was comparable to that of conductive blacks
having a much higher conductivity. This observation
may be explained as follows: the basic building units
of carbon black particles are graphene layers, arranged
roughly parallel to the surface [3]. Since the carbon
black particles are spherical, the graphene layers are
curved. This curvature will introduce some heteroge-
neity in the electronic environment of the carbon
atoms on the surface and broaden the XPS carbon
peak. The thermal black has an average particle
diameter of approximately 300 nm, whereas the dia-
meter of furnace black and the conductive blacks
studied here is at least 10 times smaller (inverse
relation between specific surface area and particle
diameter; Table 1). Thus, the curvature of the graphene
layers on the surface of the furnace and conductive
blacks is much more pronounced as compared to the
thermal black. Consequently, one can expect for these
samples a more important broadening of the XPS
carbon peak. The influence of the curvature on the
electrical conductivity, however, is most probably
much smaller since even in a ‘‘curved’’ graphene layer
the p electron system remains intact.
As mentioned above, in the present work the relative
area of the p ! p peak was used as second parameter
to describe the graphitic character of the carbon black
surface. It can easily be seen in the right-hand side of
Fig. 3 that the area of the p ! p peak differs con-
siderably. A larger p ! p peak is usually associated
with a larger polyaromatic system [37]. However, for
the graphitised carbon black, a smaller p ! p peak
than for some of the other blacks was found (Table 3).
Again, this could be related to the curvature of the
graphene layers on the surface of the carbon blacks
[38]. Nevertheless, for the low surface area conductive
carbon blacks, a good relation between the area of the
Fig. 5. Correlation between electrical conductivity (packing
fraction ¼ 0.3) and the relative area of the p ! p peak.
 D. Pantea et al. / Applied Surface Science 217 (2003) 181–193
p ! p peak and the electrical conductivity was
observed (upper graph in Fig. 5). However, no correla-
tion was found when the furnace and the high surface
area conductive carbon black was included (lower
graph in Fig. 5). It can be concluded that the FWHM
is a more robust XPS parameter for the description of
the graphitic character of carbon black surfaces than
the area of the p ! p peak. A similar conclusion was
reached for ordered mesoporous carbons [33].
3.2.3. Static SIMS spectra, negative ions
Static SIMS was used as second surface spectro-
scopic method. The SIMS spectra of carbon blacks
show intense signals of C2H and C2 fragments.
Most of the C2H fragments originate from the edges
of graphene layers, whereas the C2 signal is assigned
to particles removed from the basal plane of the
graphene layers [25,39]. According to STM observa-
tions the surface of carbon black particles consists of
overlapping graphene layers, similar to tiles on a roof
[40]. Making the reasonable assumption that most of
the carbon atoms at the edges of the graphene layers
have bonds to hydrogen atoms (i.e. the concentration
of dangling bonds and bonds to oxygen and sulphur
atoms are low), the C2H/C2 ratio is a measure for
the concentration of these edges. A low C2H/C2
ratio indicates a low concentration of edges or large
graphene layers. An example is the graphitised carbon
black with a C2H/C2 ratio of 0.17. On the other
hand, for 3,4-benzo-fluoranthene, the reference com-
pound for a small polyaromatic system, a C2H/C2
Fig. 6. SIMS spectra (negative ions) normalised to the height of
the C2 peak.
189
ratio of 2.20 was found (Table 5). For the other
samples, the C2H/C2 ratio decreased in the order:
thermal black > rubber-grade furnace black > low
surface area conductive blacks > high surface area
conductive blacks (Fig. 6), confirming the XPS obser-
vation that the graphitic character increases in the same
order (with the exception of the thermal black). In the
case of the low surface area conductive carbon blacks,
a good correlation between the C2H/C2 ratio and the
electrical conductivity was observed (upper graph in
Fig. 7). The correlation is still reasonably good when
the furnace and thermal blacks are included. However,
this was not the case if the two high surface area
conductive blacks are included as well.
3.2.4. Low-pressure nitrogen adsorption
Like the two spectroscopic methods discussed above,
the low-pressure portion of the carbon black nitrogen
adsorption isotherms yields information on the graphi-
tic order of the surface. One important difference is that
adsorption of inert molecules (such as nitrogen)
depends on the surface topology, whereas it is essen-
tially insensitive to the chemical nature of the surface.
On a perfect graphite surface, all adsorption sites have
the same energy. Thus, the first monolayer is formed in a
relative narrow pressure range. An example is the
nitrogen adsorption isotherm on graphitised carbon
black. The monolayer formation is marked by a step
increase of adsorption between P/P0 of approximately
5  105 and 4  105 (left graph in Fig. 8). If a
Fig. 7. Correlation between the electrical conductivity (packing
fraction ¼ 0.3) and the SIMS C2H/C2 peak ratio.
190 D. Pantea et al. / Applied Surface Science 217 (2003) 181–193

Table 4
Ratio of the C2H/C2 SIMS peaks and position of the monolayer
formation peak as determined by low-pressure nitrogen adsorption

Sample Ratio of the Position of the

C2H/C2SIMS monolayer formation
peaks peak (kJ/mol)

3,4-Benzo-fluoranthene 2.20 –
Thermal black 1.40 5.0
Furnace black 0.68 5.1
Conductex SC 0.28 4.6
Conductex 975 0.17 4.8
Printex L 0.20 4.8
Printex L6 0.25 4.9
Vulcan XC-72 0.21 5.3
Black Pearls 2000 0.15 5.4
Printex XE-2 0.21 5.3
Graphitised black 0.17 5.4

carbon black, confirming again the high graphitic char-

acter of these materials (Table 4). For the low surface
Fig. 8. Low-pressure nitrogen isotherms (graphs on the left-hand
side) and adsorption potential distribution, monolayer layer area conductive blacks, a reasonably good correlation
formation peak (graphs on the right-hand side). between the electrical conductivity and the nitrogen
adsorption data was found (upper graph of Fig. 9).
However, when the other blacks were included, no
graphite surface contains defects, the strengths of the correlation existed (lower graph of Fig. 9). In contrast
adsorption sites differ [41,42]. In the corresponding to the other blacks, the conductive carbon blacks con-
isotherm, the monolayer formation occurs over a larger tain significant volumes of micropores (Table 1). The
pressure range and is shifted to higher pressures (iso- formation of the first nitrogen monolayer [19] and the
therms of the other blacks in Fig. 8). This behaviour can filling of micropores [44] occur in the same pressure
be used to study the graphitic character of a carbon
surface by nitrogen adsorption. It is not easy to deter-
mine from the adsorption isotherms directly at which
pressure the monolayer is formed. A convenient way to
circumvent this problem is to calculate the APD. The
APD can be regarded as the derivative of adsorption
isotherm (Eq. (3)). The monolayer formation is indi-
cated by the so-called monolayer formation peak. For a
series of graphitised carbon blacks, it was observed that
with decreasing graphitic character of the bulk (as
determined by XRD) the monolayer formation peak
was shifted to lower adsorption potentials (correspond-
ing to higher pressures) [19]. Good correlations
between the APD and the surface spectroscopic results
were also found for thermal carbon blacks [43] and
ordered mesoporous carbons [33]. For furnace blacks,
however, the APD depended very little on the surface
chemistry [13]. In the present work, the position of the Fig. 9. Correlation between the electrical conductivity (packing
monolayer formation peak of the two high surface area fraction ¼ 0.3) and the APD position of the monolayer formation
conductive blacks was very close to the graphitised peak.
 D. Pantea et al. / Applied Surface Science 217 (2003) 181–193 191

range. The shape of the low-pressure nitrogen isotherm Table 5

Oxygen XPS spectra, relative peak areas
and consequently the APD is therefore influenced by
these micropores. Thus, it might not be possible to Sample Area of O 1s peaks (%)
compare APDs of carbonaceous materials with differ-
O1 (C¼O, O2 (C–OH) O3 (H2O,
ent micropore volumes. C–O–C) O2,ads)

Thermal black 44.2 50.9 4.8

3.3. Oxygen- and sulphur-containing surface
Furnace black 28.9 64.6 6.5
functional groups Conductex SC 32.5 62.9 4.6
Conductex 975 56.2 39.1 4.7
In the previous sections the influence of the gra- Printex L 40.0 47.1 12.9
phitic character on the conductivity was discussed. Printex L6 50a 50a a,b
b b b
Vulcan XC-72
However, in addition to carbon other elements are b b b
Black Pearls 2000
present on the surface of some of the commercial Printex XE-2 b b b

carbon blacks (Table 2). Thus, in this section the Graphitised black b b b

possible influence of the chemical nature of oxygen a

and sulphur containing functional groups is discussed.
Because of the high electronegativity of oxygen, the
BEs of oxygen atoms in different functional groups
differ only little. In the present work, the XPS oxygen
spectra were fitted to three peaks: a peak for oxygen
atoms with two bonds to carbon (e.g. C¼O, C–O–C,
O1, BE ¼ 531:1
0:1 eV), a peak for oxygen atoms no bonds to oxygen (e.g. C–S–C, S1, BE of the S 2p3/2
with one bond to carbon (e.g. C–OH, O2, BE ¼
0:1 eV) and to three doublets for sul-
532:8
0:1 eV), and to a peak for oxygen atoms in
adsorbed water and/or water (O3, BE ¼ 537:1
(S2–S4, BE ¼ 165:5, 167.7, and 169.8 eV, respectively
0:3 eV; Fig. 10) [29]. In most of the oxygen spectra,
the O2 peak was more intense than the O1 peak
(Table 5), indicating that there was more C–OH type
than C¼O type oxygen on the carbon black surface.
No correlation between the chemistry of the oxygen
groups and the conductivity was found.
Very weak peak, fit results only give a rough indication.
b
No peak detected.
With two exceptions (Conductex SC, Printex XE-2)
sulphur was found on all conductive blacks. The
spectra were fitted to a doublet for sulphur atoms with
peak ¼ 163:8
phur atoms with one, two and three bonds to oxygen
[45]). For the blacks studied, the area of the S1 doublet
accounted for approximately 60–70% of the total peaks
area (Fig. 11), whereas the relative concentrations of the
various sulphur–oxygen groups differed considerably
(Table 6). However, no correlation between the chemi-
cal nature of the sulphur groups and the conductivity
was found. It can be concluded that oxygen and sulphur

Fig. 10. O 1s XPS spectra normalised to the same height. Fig. 11. S 2p XPS spectra normalised to the same height.
192 D. Pantea et al. / Applied Surface Science 217 (2003) 181–193

Table 6 the exception of high surface area conductive blacks,

Sulphur XPS spectra, relative areas of the doublets
whereas for the XPS parameter this was the case for all
Sample Area of the S 2p doublet (%) blacks, except the thermal black.
S1 S2 S3 S4
(C–S–C) (C–SO–S) (C–SO2–S) (C–SO3H)
a a a a
Acknowledgements
Thermal black
Furnace black 66.7 12.3 7.5 13.5
Conductex SC 67.7 17.6 9.4 5.3 The authors acknowledge Dr. A. Adnot for record-
Conductex 975 60.0 13.5 13.8 12.7 ing and useful discussion of the XPS and SIMS spectra
Printex L 68.5 14.8 9.5 7.2 and Dr. S. Mikhailenko for assistance in the electrical
Printex L6 68.5 17.2 6.7 7.6 conductivity measurement. Furthermore, we are
Vulcan XC-72 71.5 14.8 8.5 5.3
thankful to Mr. Peter Donnelly (Cancarb Ltd., Med-
Black Pearls 2000 62.6 7.4 16.9 13.1
Printex XE-2 a a a a icine Hat, Alta., Canada), to Mr. D.D. Colli (Cabot
Graphitised black a a a a Corporation, Special Blacks Division, Billerica, MA,
a USA), to Columbian Chemicals Canada, Hamilton,
No doublet detected.
Ont., Canada, to Mrs. N. Janowsky (Degussa Canada
Ltd., Burlington, Ont., Canada), and to Dr. W.R. Betz
functional groups had only a very limited influence on (Supelco, Bellefonte, PA, USA) for providing carbon
the electrical conductivity. This is most probably due to black samples.
the low concentration of these elements on the carbon
black surface.
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