International Journal of Coal Geology 85 (2011) 219–226

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International Journal of Coal Geology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / i j c o a l g e o

Development of graphite-like particles from the high temperature treatment of

carbonized anthracites
Sandra Rodrigues a,b,⁎, Isabel Suárez-Ruiz a, Manuela Marques b, Deolinda Flores b,
Ignacio Camean a, Ana B. García a
a
Instituto Nacional del Carbón, (INCAR-CSIC), Francisco Pintado Fe 26, 33011-Oviedo, Spain
b
Centro de Geologia da Universidade do Porto, Faculdade de Ciências, Universidade do Porto, Rua Campo Alegre, 687, 4169-007 Porto, Portugal

a r t i c l e i n f o a b s t r a c t

Article history: The aim of this study is the optical and structural (micro-Raman spectroscopy and X-ray diffraction)
Received 27 August 2010 characterization of particles formed during the high temperature treatment (HTT) of anthracites. Two
Received in revised form 2 November 2010 anthracites of different rank, from the Peñarroya–Belmez–Espiel Basin (PBEB, Spain) (Rr = 2.62%), and the
Accepted 2 November 2010
Douro Basin (DB, Portugal) (Rr = 6.25%), were carbonized at 1000 °C in a tube furnace, under nitrogen flow,
Available online 12 November 2010
and then treated at temperatures of 2000 °C and 2500 °C, in a graphite furnace.
Keywords:
After treatment at these high temperatures, the residues obtained show various graphite structures, namely,
Carbonized anthracites flakes, microspheres and crystalline aggregates, in percentages that depend on type of the precursor
Graphite-like particles (carbonized anthracite) and temperature. These structures grow from the dense particles, which are the
High temperature treatment major component of the studied samples. Flakes, microspheres and crystalline aggregates develop and
Optical properties acquire their properties at 2000 °C, and minor changes occurring with the rise in temperature. Moreover,
Micro-structural characterization theses structures exhibit similar characteristics to those of graphite edge planes.
Micro-Raman spectroscopy Dense particles from both samples show an improvement in their microstructure with the rise in
temperature. This improvement is greater in dense particles from the carbonized DB anthracite. In fact at
2500 °C these dense particles show optical and structural properties similar to those found in natural graphite.
This was not found in the case of dense particles from the carbonized PBEB anthracite. These observations are
also supported by the X-ray diffraction parameters which confer the highest degree of crystallinity for the
carbonized DB sample at 2500 °C.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction
Graphitic materials are highly valuable products with many
industrial applications (Chung, 2002; Pierson, 1993). Nowadays,
petroleum coke is the main carbon material used in the manufacture
of synthetic graphite. However, efforts are being made to decrease the
dependence on petroleum by searching for other graphitic material
precursors that graphitize readily. Among these, anthracites were
found to graphitize easily when heated to temperatures above
2000 °C (Franklin, 1951; Oberlin and Terriere, 1975). These high
rank coals are heterogeneous materials and the graphitization
behavior of each anthracite may differ vastly from one another.
Nevertheless, certain physical and chemical properties of anthracites
allow them to be considered as potential precursors of graphitic-like
products, such as: (1) the chemical composition of the raw materials
⁎ Corresponding author. Centro de Geologia da Universidade do Porto, Faculdade de
Ciências, Universidade do Porto, Rua Campo Alegre, 687, 4169-007 Porto, Portugal.
Tel.: + 351 220402489; fax: + 351 220402490.
E-mail address: sandra.rodrigues@fc.up.pt (S. Rodrigues).
(Atria et al., 2002; Suárez-Ruiz and García, 2007); (2) the prior
arrangement of the Basic Structural Units (BSUs) with a preferential
planar orientation in the raw anthracite (Blanche et al., 1995; Duber
et al., 1993; Oberlin and Terriere, 1975; Pusz et al., 2003); (3) the
presence of planar pores (Deurbergue et al., 1987; Oberlin and
Terriere, 1975); and (4) the presence of mineral matter that acts as a
catalyst during high temperature treatment (HTT) (Atria et al., 2002;
Evans et al., 1972; Garcia et al., 2010; González et al., 2005; Oberlin
and Terriere, 1975; Pappano and Schobert, 2009).
In a recent work, Suárez-Ruiz and García (2007) identified
different kinds of particles developed from the graphitization of two
anthracites of relatively close coal rank (Rr = 2.3 and 3.6%) at different
temperatures. This included dense particles, flakes, microspheres and
crystalline aggregates. However, the authors focused their study on
dense particles which are the predominant component of the
materials obtained from high temperature treatment (HTT), paying
less attention to the other components that are present in minor
proportions.
The present work, which is part of an ongoing PhD thesis,
complements a study carried out by Suárez-Ruiz and García (2007).

0166-5162/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.coal.2010.11.007
220 S. Rodrigues et al. / International Journal of Coal Geology 85 (2011) 219–226
It is focused on the optical and structural characterization of all the
structures identified during the HTT at 2000 and 2500 °C of two
carboniferous anthracites of different rank (Rr = 2.62% and 6.25%) and
geotectonic settings. Two major techniques were applied: optical
microscopy and micro-Raman spectroscopy. The use of both techni-
ques permitted the various particles found in the heated samples to
be characterized individually. Moreover, a natural graphite was also
selected for comparative purposes.
The optical properties of the materials prepared from the two
carbonized anthracites were studied by means of reflectance-
indicating surface (RIS) characterization, using RIS main reflectance
axes (RMAX%, RINT% and RMIN%) and the parameters Ram, Rev and Rst ,
which had been previously used by other authors to characterize the
textural anisotropy and structure of BSUs (microtexture) of carbona-
ceous materials (Duber et al., 2000; Kilby, 1988, 1991; Marques et al.,
2009; Pusz et al., 2002; Suárez-Ruiz and García, 2007). Additionally,
these optical parameters may also be useful to differentiate between
and/or group together the different graphite-like particles developed
during the high temperature treatment of the materials.
As Micro-Raman spectroscopy is particularly sensitive to crystal-
line structures, it allows the structural characterization of graphitic
materials (Compagnini et al., 1997; Ferrari, 2007; González et al.,
2004; Katagiri et al., 1988; Lespade et al., 1984; Marques et al.,
2009; Nemanich and Solin, 1979; Suárez-Ruiz and García, 2007; Tan
et al., 2004; Tuinstra and Koenig, 1970; Vidano et al., 1981; Wang
et al., 1990). In order to assess the degree of structural order of each
individual graphitic-like particle developed from the heat treated
samples, both regions of the spectra (first and second-order) were
considered. The first-order Raman spectrum is well known in the
literature. Only one band (G band, 1580 cm− 1) is present in highly
ordered graphite (basal plane) (Tuinstra and Koenig, 1970). Discon-
tinuities in the graphite planes (Compagnini et al., 1997; Katagiri
et al., 1988; Tan et al., 2004) or other defects in disordered carbon
materials may lead to the addition of other bands on the first-
order Raman spectrum, such as the D1 band (1350 cm− 1), D2 band
(1620 cm− 1), D3 band (1500 cm− 1) and D4 band (1200 cm− 1)
(Beyssac et al., 2003; Larouche and Stansfield, 2010; Sadezky et al.,
2005). However, most of the studies have been performed on
graphite basal planes (GBP, ab directions), while only a few works
such as those of Compagnini et al. (1997), Katagiri et al. (1988) and
Tan et al. (2004) have studied graphite edge planes (GEP, c direc-
tion). In their experiments the edge planes of graphite produced
very different Raman spectra to those of the graphite basal planes,
since the D1 band was apparent. Despite not being extensively used,
the second-order Raman spectrum is very important in character-
ization of graphitic materials. In fact, some sharp features such as
the splitting of the 2700 cm− 1 band into two components, which
indicates the final stages of the graphitization process (Lespade
et al., 1984), and the disappearance of the 2900 cm− 1 band with
the increase in the degree of structural order (Hishiyama et al.,
2001; Sato et al., 1978) make it possible to study changes in carbon
crystallinity. Hence, identification of such features together with the
Raman parameters obtained from the deconvolution of the spectrum
helps to evaluate the structural order reached by the various kinds
of graphite-like particles developed from the HTT of carbonized
anthracites.
X-ray diffraction parameters, interlaying spacing (d002), and
crystallite sizes along the c axis (Lc) and the a axis (La), were also
obtained in order to determine the evolution of the structural order of
the whole samples during the increase in thermal treatment. It has
been demonstrated that the combined use of both techniques, X-ray
diffraction and Raman spectroscopy, is complementary in the study of
the structural order and the degree of ordering of the crystalline
structures of carbon materials (Cabielles et al., 2008; Cabielles et al.,
2009; Cameán et al., 2010; Cuesta et al., 1998; Marques et al., 2009;
Suárez-Ruiz and García, 2007).
2. Samples and analytical procedures
2.1. Samples
Two anthracites were chosen for this research work. One is from
the Peñarroya–Belmez–Espiel Basin (Spain), is named PBEB, and has a
vitrinite random reflectance (Rr) of 2.62%, whereas the second one is
from the Douro Basin (Portugal), is designated DB, and has a Rr of
6.25%. Both coals come from highly tectonized basins of Carboniferous
age. In addition, the PBEB anthracite shows the effects of fluids
circulation resulting from magmatic activity (Suárez-Ruiz et al., 2006)
which is not the case of the Douro Basin sample (Pinto de Jesus, 2003).
For the graphitization process the two raw anthracites were
previously carbonized at 1000 °C in a tube furnace, under nitrogen
flow, at a heating rate of 2 °C/min and for a residence time of 1 h. The
carbonized samples (precursors of the graphitized materials) were
then heated to temperatures of 2000 °C and 2500 °C in a graphite
furnace, under argon flow, at a heating rate of 10 °C/min, and the
samples being kept at these temperatures (2000 and 2500 °C) for 1 h.
The materials obtained from the high temperature treatment were
identified by a code that includes the designation of the precursor
anthracite, the letter “C” for carbonization process and then the HTT
graphitization treatment temperature, (e.g.) PBEBC/2000 or DBC/
2500. For comparison purposes, a natural graphite from Mozambique
was selected. This sample was obtained from the archives of Porto
University, and no geological information is available.
2.2. Analytical procedures
2.2.1. X-ray diffraction
The diffractograms were recorded on a Bruker D8 powder
diffractometer equipped with a monochromatic Cu Kα X-ray source
and an internal standard of silicon powder. Diffraction data were
collected by step scanning using a step size of 0.02° 2θ and a scan step
of 2 s. For each sample, three diffractograms were obtained, employ-
ing a different representative batch of sample for each run. The mean
interlayer spacing, d002, was evaluated from the position of the (002)
peak by applying Bragg's equation. The mean crystallite sizes, Lc and
La, were calculated from the (002) and (110) peaks, respectively,
using the Scherrer formula, with values of K = 0.9 for Lc and 1.84 for La
(Biscoe and Warren, 1942). The average number of aromatic layers
bNN was determined in the stacks as bNN = Lc/d002, following the
procedure described by Laggoun-Defarge et al. (1994). The broaden-
ing of the diffraction peaks due to instrumental factors was corrected
by using a silicon standard. Typical standard errors for the crystallite
sizes were 2% and 9% lower than the values reported for Lc and La,
respectively. The d002 values are much more precise, with standard
errors lower than 0.1%. This technique gives an indication of the
degree of graphitization (increase in structural order) of the whole
sample.
2.2.2. Optical microscopy
Optical characterization of the samples to obtain the RIS
parameters was performed on pellets with randomly oriented
particles using a MPV-Combi (Leitz) microscope equipped with a
100× oil immersion objectives in polarized light. The magnification
was chosen to avoid problems due to surface heterogeneity and the
small size of the particles. For each particle three reflectance points
(R1, R2 and R3) were measured by rotating the microscope stage 45°
from each point (Ting, 1981). The maximum and minimum apparent
reflectances (R′max% and R′min%) were calculated using Ting's
equations (Ting, 1981). On the basis of these values the RIS main
axes (RMAX%, RINT% and RMIN%) and parameters (Ram, Rev and Rst) were
obtained following the procedures described by Kilby (1988, 1991)
and later modified by Duber et al. (2000). In the case of the graphite
the main axes of the RIS were obtained taking in to consideration the
 S. Rodrigues et al. / International Journal of Coal Geology 85 (2011) 219–226
different graphite planes. The sections parallel to the natural cleavage
surfaces (a–b directions, graphite basal planes, GBP) hold the true
RMAX% value (Kwiecinska et al., 1977; Kwiecinska and Petersen, 2004;
Marques et al., 2009). While cleavage surfaces which slope towards
the basal surface or, in extreme cases, are perpendicular to these (c
direction, graphite edge planes, GEP) reflect the true RMIN%. Since
graphite is an optically uniaxial mineral, the RINT% RIS axis is equal to
the RMAX% value (Duber et al., 2000; Kilby, 1988) and the RIS
parameters (Ram, Rev and Rst) can be obtained. The optical photo-
micrographs were taken on a Zeiss Axionplan microscope, in oil
immersion, polarized light and with a 1λ retarder plate. Leica
software was used to capture and analyze the corresponding images.
2.2.3. Micro-Raman spectroscopy
The Raman scattering measurements were performed on a Jobin
Yvon LabRam HR UV 800 spectrometer using a laser wavelength of
Argon 532 nm (24.3 mV). A microscope equipped with a 100× lens was
used to focus the excitation laser beam onto the particle and to collect
the Raman signal. For each graphitic structure two spectra were
obtained and about ten spectra in the case of dense particles. These
spectra were recorded in the range of 1000–1800 cm− 1 in the first-
order region and from 2300 to 3500 cm− 1 in the second-order region.
Each spectrum was subjected to peak fitting with LabSpec software in
order to resolve the curve using Lorentzian line shapes and/or
Lorentzian/Gaussian combination line shapes. The parameters obtained
from the decomposition of the spectrum include: the peak position
(frequency, cm− 1), full width at half maximum (FWHM, cm− 1) of the
bands, and the band area ratios, ID1/IG, IG/Iall (Sheng, 2007), and I2900/
I2700 (Zaida et al., 2007). The Raman properties of the graphite were
evaluated by also taking into account the two crystallographic directions
of graphite, i.e., graphite basal planes (GBP) and graphite edge planes
(GEP). Several authors (Compagnini et al., 1997; Katagiri et al., 1988;
Tan et al., 2004) had already identified different features of GBP and
GEP in the Raman spectra. Therefore both sections of this mineral
were analyzed. The values of the Raman parameters presented in Table 2
are the mean values obtained from the deconvolution of the spectrum
of each particle.
3. Results and discussion
3.1. Structural order as determined by X-ray diffraction analysis
Table 1 summarizes the results of the X-ray diffraction for the
treated samples and natural graphite. In the heated samples the effect
of increasing temperature is a reduction in the interlayer spacing
(d002), and an increase in the crystalline sizes along the c-axis (Lc) and
along the a-axis (La), there being also a significant increase in the
number of aromatic layers (bNN). Despite the improvement in the
structural organization of the PBEBC samples from 2000 to 2500 °C, as
can be seen in Table 1, these samples are less ordered than the
corresponding graphitized materials obtained from the DBC samples.
In fact, the DBC/2000 sample shows a higher degree of structural
ordering than PBEBC/2500. Furthermore, DBC/2500 results in graphite
material that exhibits properties comparable to those of Mozambique
natural graphite (Table 1). Indeed, the d002 interlayer spacing
Table 1
X-ray diffraction parameters of HTT materials at 2000 and 2500 °C and natural graphite
(not submitted to any thermal treatment).
Samples d002 (nm) La (nm) Lc (nm)
PBEBC/2000 0.3467 8.0 4.1
PBEBC/2500 0.3438 10.9 5.7
DBC/2000 0.3420 29.0 8.0
DBC/2500 0.3375 47.4 27.3
Natural Graphite 0.3371 32.1 24.3
221
obtained for DBC/2500 (0.3375 nm) is very close to the value obtained
for the natural graphite (0.3371 nm), which is within the values
reported by Kwiecinska and Petersen (2004) for that type of
materials. The crystallite sizes, La and Lc, are higher in the DBC/2500
sample than natural graphite (Table 1), which indicates that the DBC/
2500 sample has undergone strong three-dimensional ordering.
3.2. Development of graphite-like structures
Optical microscopy showed that when the temperature rises from
2000 to 2500 °C, different kinds of graphite-like particles develop.
These graphite-like particles include dense particles, flakes, micro-
spheres and crystalline aggregates, some of which are present in
natural graphite (Kwiecinska and Petersen, 2004). Fig. 1 shows that
flakes, microspheres and crystalline aggregates are present in small
percentages in all the samples. However, the percentages in which
these types of structures are found increase with temperature,
especially in the DBC sample, with a total amount of 30% (vol.) at
2500 °C. However the percentage of the dense particles decreases.
This suggests that the structures mentioned above (flakes, micro-
spheres and crystalline aggregates) grow or are formed from the
dense particles (Fig. 2a and c). In any case, the dense particles are the
predominant component in all the analyzed samples at the tempera-
tures of 2000 and 2500 °C.
The flakes and microspheres are particles that have a strong optical
anisotropy. The flakes have an elongated shape (Fig. 2a) while the
microspheres are round in morphology (Fig. 2b). The crystalline
aggregates are very small particles that grow out of dense particles in
the form of aggregates (Fig. 2c).
The dense particles appear as irregular plates of variable size, some
of which develop porosity. Most of these particles are strongly
anisotropic (Fig. 2d). However, in the DBC/2500 dense particles, two
main optical features are observed as in the case of graphite: i) basal
planes oriented parallel to the polished surface that have isotropic
optical behavior (Fig. 2e) and are similar to GBP, and ii) sections which
deviate from or are even perpendicular to the basal plane, display an
anisotropic optical behavior (Fig. 2f) and are similar to GEP.
3.3. Evolution of the Raman spectroscopic characteristics in the graphite-
like structures
Table 2 shows the main parameters obtained from the micro-
Raman spectroscopy analysis for all the identified graphite-like
particles. The exceptions are the microsphere particles in the
PBEBC/2000 sample that, due to their small size, could not be
subjected to micro-Raman measurements.
All the spectra obtained from the flakes, microspheres and
crystalline aggregates of the studied samples exhibit three bands in
bNN
12
17
23
81
Fig. 1. Development and evolution of the graphite-like structures during the high
72
temperature treatment (HTT) of PBEBC and DBC carbonized anthracites.
222 S. Rodrigues et al. / International Journal of Coal Geology 85 (2011) 219–226

Fig. 2. Optical photomicrographs of different kinds of particles found in the graphitized samples. Images were taken in oil immersion (50×), polarized light and with a retarder plate
of 1λ. a) Flakes from the DBC/2500 sample; b) Microspheres from the PBEBC/2500 (see white arrow); c) Crystalline aggregates from the DBC/2000 sample; d) Dense particles from
the PBEBC/2500 sample; e) Isotropic dense particle from the DBC/2500 sample; f) Anisotropic dense particle from the DBC/2500 sample.

the first-order region, two major G and D bands (Table 2) and a well
defined D2 band (1620 cm− 1). However, additional bands of low
intensity that represent structural defects appear at 1500 cm− 1 (D3
band) in the flakes and crystalline aggregates spectra of the PBEBC/
2000 sample. Moreover, there is another band at around 1278 cm− 1
(D4 band) which was only observed in the flakes spectra from PBEBC/
2000 sample. The defect bands (D3 and D4) tend to disappear with
increasing temperature. The second-order region displays four bands
at around ~ 2460 cm− 1, ~2700 cm− 1, ~2940 cm− 1 and ~3240 cm− 1
in the spectra of the above mentioned graphite-like particles.
No correlation was found between the micro-Raman parameters
and the increase in temperature for flakes, microspheres and
crystalline aggregates (Figs. 3 and 4). In fact, a homogenization of
the values of the Raman parameters and an approximation towards
the values of the natural graphite edge planes (GEP) was observed for
these structures (Table 2).
The Raman spectra of the dense particles from the PBEBC/2000 and
PBEBC/2500 samples exhibit five bands in the first-order region, the
D1 and G bands (Table 2), D4 band (~ 1160 cm− 1), D3 band
(~1570 cm− 1) and D2 band (1620 cm− 1), and four bands in the
second-order region (Table 2) at similar positions to those already
mentioned for the particles described above. With the increase
heating temperature, the D1 and G bands of the dense particles in the
PBEBC samples tend to become narrower and to move to the lower
frequencies (Table 2). Moreover, a decrease in the band area ratio ID1/
IG and I2900/I2700, and an increase in IG/Iall ratio were observed
during HTT (Figs. 3 and 4). These results show an improvement in the
degree of structural ordering of the dense particles in the PBEBC
sample with thermal treatment.
The DBC/2000 dense particles show similar Raman spectra to those
of the PBEBC graphitized samples (Figs. 3 and 4). The Raman
parameters revealed that the dense particles of the DBC/2000 sample
have values close to those of the dense particles in the PBEBC/2500
sample (Table 2). This suggests that the DBC/2000 dense particles
already have a high degree of structural organization even at lower
temperatures.
The Raman spectra of the dense particles from DBC/2500 were
obtained bearing in mind the orientation of the particles relative to
the polished surface, that is, particles (basal plane) parallel to the
polished surface and dense particles perpendicularly orientated to the
basal plane. The D1, G and D2 (1620 cm− 1) bands are present in the
first-order region. However, the basal dense particles of DBC/2500
have other striking features that deserve mentioning such as a very
low intensity D1 band and a narrow G band (Table 2, Fig. 3). The
second-order Raman spectrum of the DBC/2500 dense particles
exhibit four bands: 2460, 2700, 2940 and 3240 cm− 1. Once again,
 S. Rodrigues et al. / International Journal of Coal Geology 85 (2011) 219–226 223

Table 2
Raman parameters from the first- and second-order Raman spectra of individual particles developed during HTT (2000 and 2500 °C) of two carbonized anthracites (PBEBC and DBC),
and natural graphite (not submitted to any thermal treatment).

Particles Sample D1 Band G Band First-order 2700 Band 2900 Band Second-order
ratios ratio

Frequency FWHM Frequency FWHM ID1/G IG/Iall Frequency FWHM Frequency FWHM I2900/I2700
(cm− 1) (cm− 1) (cm− 1) (cm− 1) (cm− 1) (cm− 1) (cm− 1) (cm− 1)

Flakes PBEBC/2000 1346 41 1580 21 1.08 0.40 2699 63 2936 91 0.27

PBEBC/2500 1352 38 1584 20 1.54 0.37 2704 73 2943 76 0.29
DBC/2000 1350 38 1583 18 1.12 0.44 2704 77 2945 66 0.20
DBC/2500 1349 39 1581 21 1.52 0.37 2700 75 2942 72 0.26
Microspheres PBEBC/2500 1350 40 1583 21 1.48 0.37 2702 75 2940 81 0.30
DBC/2000 1350 40 1584 20 1.52 0.37 2701 80 2942 76 0.34
DBC/2500 1348 38 1581 21 1.43 0.38 2699 76 2941 71 0.27
Crystalline aggregates PBEBC/2000 1348 37 1582 24 1.21 0.41 2699 54 2940 80 0.22
PBEBC/2500 1349 38 1583 21 1.33 0.39 2702 76 2941 73 0.27
DBC/2000 1349 40 1583 20 1.04 0.45 2703 69 2943 71 0.21
DBC/2500 1349 37 1582 23 1.15 0.44 2699 60 2942 71 0.20
Dense particles PBEBC/2000 1353 53 1589 40 2.25 0.25 2696 95 2944 109 0.43
PBEBC/2500 1351 42 1586 37 1.34 0.34 2696 68 2944 86 0.26
DBC/2000 1353 42 1587 38 1.33 0.38 2699 73 2944 95 0.36
DBC/2500 Basal Plane 1349 38 1582 25 1.65 0.35 2698 68 2941 77 0.31
DBC/2500 Basal Plane 1348 35 1580 16 0.48 0.65 2719 36 2943 68 0.13
Natural graphite GEP 1348 42 1582 23 1.75 0.33 2700 79 2940 81 0.35
GBP – – 1580 13 0.00 1.00 2719 32 – – 0.00

PBEBC — carbonized anthracite from Peñarroya–Belmez–Espiel Basin (Rr = 2.62%). DBC — carbonized anthracite from Douro Basin (Rr = 6.25%).
DBC/2500 Basal plane — dense particles perpendicularly oriented to basal dense particles. DBC/2500 Basal plane — basal dense particles.
GEP — Graphite edges planes (section of natural graphite perpendicular to the basal plane). GBP — Graphite basal plane.

the DBC/2500 basal dense particles show features that are not
observed in the dense particles perpendicularly oriented to the basal
plane. These included: i) the 2700 cm− 1 band split into a doublet,
indicating a dislocation to higher positions (2720 cm− 1, Table 2) with
a shoulder at 2680 cm− 1; and ii) a very low intensity 2900 cm− 1
band. These two features are indicative of a higher degree of structural
ordering of the materials (Cuesta et al., 1994; Ferrari, 2007; Hishiyama
et al., 2001; Lee, 2004; Sadezky et al., 2005). Thus, sections of the
dense particles of the DBC/2500 sample which are perpendicular to
the basal plane exhibit values of micro-Raman parameters close to
those obtained for the flakes, microspheres, crystalline aggregates
and the GEP of the studied natural graphite. However, the basal
sections reveal micro-Raman structural properties similar to the GBP
(Figs. 3 and 4).
The micro-Raman parameters make it possible to group the
various graphite-like particles into three main groups (Figs. 3 and 4):
(i) the DBC/2500 basal dense particles; (ii) the PBEBC/2000, PBEBC/
2500 and DBC/2000 dense particles; and (iii) the flakes, microspheres,
crystalline aggregates from all the samples, and the DBC/2500 dense
particles which are perpendicular to the basal dense particles.
The micro-Raman results show that: i) the increase in tempera-
ture from 2000 to 2500 °C, leads to an improvement in the structural
organization of the dense particles; ii) the rise in temperature during
HTT also promotes an improvement of the structural and textural
characteristics of the flakes and crystalline aggregates of the PBEBC/
2000 sample as reflected by the removal of the D3 and D4 defect
bands; iii) the micro-Raman properties of the flakes, microspheres
and crystalline aggregates tend to approach those of GEP in natural
graphite; iv) the DBC/2500 dense particles show a higher degree
of structural order, and have two paths with respect to their
orientations on the polished surface, one in the direction of GBP,
corresponding to the dense particles parallel to the polished surface
with basal planes characteristics, and the other in the direction of
GEP, represented by the dense particles perpendicular to the basal

Fig. 3. Relationship between Raman parameters of the first-order spectrum, G band FWHM (cm− 1) and the band area ratio IG/Iall of the graphite-like particles, and the GEP and GBP
of natural graphite (not submitted to any thermal treatment). The association between particles also permitted the discrimination of three groups.
224 S. Rodrigues et al. / International Journal of Coal Geology 85 (2011) 219–226

Fig. 4. Relationship between Raman parameters from de first (G band FWHM) and the second-order (band area ratio I2900/I2700) of Raman spectrum of the graphite-like particles
and the GEP and GBP of natural graphite (not submitted to any thermal treatment).

plane; v) in the basal dense particles of the DBC/2500 sample, the
splitting of the 2700 cm− 1 band and the very low intensity of the
2900 cm− 1 band show that these materials have acquired a
tridimensional order; and vi) the two last features are also supported
by the values of the X-ray diffraction parameters obtained for the
DBC/2500 sample.
3.4. Evolution of the optical properties in the graphite-like structures
The optical properties that characterize the RIS of the various
graphite-like structures are presented in Table 3. It was not possible to
obtain the RIS parameters for the flakes from PBEBC/2000 and for the
microspheres from PBEBC/2000, PBEBC/2500 and DBC/2000 due to
their small size and/or because of their absence. No optical data were
obtained for crystalline aggregates due to their peculiar morphology
(see Fig. 2c). For the flakes and microspheres, the values of the optical
parameters change only slightly with the increase in temperature.
Indeed, they all tend to exhibit similar values at both temperatures
(Table 3, Fig. 5). Because of the lack of enough data no statistical
conclusions can be obtained.
The PBEBC dense particles evolve with the increase in temperature
of the thermal treatment. In fact, there is an increase in the values
of the RMAX% and the anisotropy parameters, Ram, B and [(RMAX% −
RMIN%)/RMAX%)], and a decrease in the Rev values. All of these results
are related with an improvement in the structural and textural
organization of the materials that seems occur at 2500 °C (Table 3,
Fig. 5). These findings are in good agreement with those previously
reported by Suárez-Ruiz and García (2007) for dense particles in the
same range of temperature treatment.
The dense particles from DBC/2000 experience an improvement in
their microtexture (structure of BSUs and spatial arrangement of
BSUs, i.e., texture) at lower temperatures treatment when compared
with the same particles from PBEBC/2500 at 2500 °C (Fig. 5).
In view of the similarities that the dense particles share with
graphite (e.g., optical features, micro-Raman characteristics and the
tridimensional features which can be seen by X-ray data) the RIS
parameters from DBC/2500 dense particles were calculated using
the same criteria as for the graphite. The projection of the R′max and
R′min values of the DBC/2500 dense particles onto the Kilby cross-
plot make it possible to separate sections with different optical
behaviors due to the different orientations relative to the polished
surface. The dense particle sections parallel to the plane of
measurement (basal planes) have very high R′max% and R′min%
and, thus, low bireflectance values. These particles contain the true
RMAX% value. The sections that are perpendicular to the basal plane
sections have high R′max% but very low R′min% values. Consequently
they have very high values of bireflectance, and hold the true RMIN%
value (Table 3).
Similar results were obtained when the two planes of natural
graphite (GBP and GEP) were projected. Basal planes (GBP) hold the
true RMAX% value whereas the cleavage surfaces (GEP) comprise the
true RMIN% value (Table 3). Similar values were found for the dense
particles from DBC/2500 and natural graphite, as Table 3 and Fig. 5
shows.
Taking into account the optical properties obtained for the various
structures identified (Table 3, Fig. 5) it is possible to group together
particles with similar optical parameters, as follows: (i) dense
particles from DBC/2500; (ii) dense particles from PBEBC/2000,

Table 3
Optical properties of individual particles developed during HTT (2000 and 2500 °C) of two carbonized anthracites (PBEBC and DBC), and natural graphite (not submitted to any
thermal treatment).

Particles Flakes Microspheres Dense particles Natural

graphite
Sample/HTT PBEBC/2500 DBC/2000 DBC/2500 DBC/2500 PBEBC/2000 PBEBC/2500 DBC/2000 DBC/2500

RIS characteristics
RIS axes RMAX% 9.81 11.32 9.10 8.35 8.89 9.21 13.60 18.20 20.57
RINT% 3.41 2.99 3.30 3.42 7.73 8.51 12.09 18.20 20.57
RMIN% 0.09 0.45 0.13 0.10 4.28 2.80 3.18 0.08 0.16
RIS parameters Ram 0.429 0.445 0.419 0.404 0.132 0.198 0.225 0.331 0.330
Rev 1.45 2.47 1.58 1.40 6.65 6.03 8.06 3.00 4.05
Rst 10.37 17.07 9.65 6.36 − 16.04 − 24.27 − 22.33 − 30.00 − 30.00
Anisotropy parameters B% 9.72 10.87 8.97 8.25 4.60 6.41 10.42 18.12 20.41
(RMAX% − RMIN%)/RMAX% 0.99 0.96 0.99 0.99 0.52 0.70 0.77 1.00 0.99

PBEBC — carbonized anthracite from Peñarroya–Belmez–Espiel Basin (Rr = 2.62%).

DBC — carbonized anthracite from Douro Basin (Rr = 6.25%).
 S. Rodrigues et al. / International Journal of Coal Geology 85 (2011) 219–226
Fig. 5. Relationship between Ram and RMAX% RIS parameters of the graphitized particles (except crystalline aggregates) and the natural graphite (not submitted to any thermal
treatment). The association between particles allowed the discrimination of the three groups to be done (see text).
PBEBC/2500 and DBC/2000; (iii) flakes (from both samples and at
both temperatures) and microspheres from DBC/2500.
The results presented above show that: i) the increase in
temperature treatment from 2000 to 2500 °C leads to an improve-
ment in the microtexture of the dense particles: ii) the high
temperature treatment of the previously carbonized anthracites
changes the microtexture of the flakes and microspheres particles
slightly, but more importantly, it leads to an increase in the amount of
these particles; iii) the DBC/2500 dense particles show an evolution
towards the characteristics of natural graphite, which suggests they
have a higher degree of structural order than the PBEBC/2500 dense
particles; and iv) this is also supported by the values of the X-ray
diffraction and Raman parameters, which show that the DBC/2500
sample has the highest degree of crystallinity and display values
similar to those of natural graphite. As stated above, both techniques
make it possible to differentiate between various kinds of particles
and show the way in which they evolve during high temperature
treatment (HTT). Hence, on the basis of the optical and structural
characteristics of these graphite-like particles and by comparing them
with the properties of natural graphite planes (GBP and GEP), it is
possible to discriminate between various groups of particles.
4. Conclusions
A detailed characterization of the different particles developed
during HTT was carried out by optical microscopy and micro-Raman
spectroscopy. Micro-Raman spectroscopy also showed that at 2000 °C
particles such as crystalline aggregates, flakes and microspheres
already have similar properties to those of GEP in natural graphite,
and that minor changes occur in the microstructure of these particles
with the increase in temperature from 2000 to 2500 °C in the PBEBC
and DBC samples.
Moreover, the dense particles in the DBC sample heated at 2500 °C
display properties that are close to those of the natural graphite
studied in this work, highlighting the graphitic characteristics of the
material produced from the DB carbonized anthracite at this
temperature. In contrast, the PBEBC/2500 dense particles do not
exhibit such characteristics, i.e., they do not have properties similar to
those of natural graphite. These findings are also supported by the X-
ray diffraction results obtained for these samples.
The higher graphitability evidenced by the DB anthracite may be
due to the rank of the original material (Rr = 6.25%) and the
constraints associated with the tectonic structure of the Douro
225
Basin, namely pressure. However, the nature of the mineral matter
may also have had an influence on the ease with which DB anthracite
can be graphitized. Ongoing research may or may not clarify these
points. In summary, the results obtained for the DB anthracite show
that this coal as could be used as a precursor of graphitic materials.
Moreover, the knowledge acquired about the individual properties
of the components present in the graphitized samples may suggest
ideas for future applications.
Acknowledgments
S. Rodrigues benefited from a PhD scholarship financed by FCT —
Fundação para a Ciência e Tecnologia, Portugal, Ref: SFRH/BD/38126/
2007. This author is also grateful for all technical support given by
INCAR – Instituto Nacional del Carbón (CSIC, Oviedo, Spain).
References
Atria, J.V., Rusinko Jr., F., Schobert, H.H., 2002. Structural ordering of Pennsylvania
anthracites on heat treatment to 2000–2900 °C. Energy & Fuels 16, 1343–1347.
Beyssac, O., Goffé, B., Petitet, J.-P., Froigneux, E., Moreau, M., Rouzaud, J.-N., 2003. On the
characterization of disorder and heterogeneous carbonaceous materials by Raman
spectroscopy. Spectrochimica Acta. Part A 59, 2267–2276.
Biscoe, J., Warren, B., 1942. An X-ray study of carbon blacks. Journal of Applied Physics
13, 364–371.
Blanche, C., Rouzaud, J.-N., Dumas, D., 1995. New data on anthracite graphitizibility.
22nd Biennal Carbon Conference, Extended Abstracts, pp. 694–695.
Cabielles, M., Montes-Morán, M.A., Garcia, A.B., 2008. Structural study of graphite
materials prepared by HTT of unburned carbon concentrates from coal combustion
fly ashes. Energy & Fuels 22, 1239–1243.
Cabielles, M., Rouzaud, J.-N., Garcia, A.B., 2009. High-resolution transmission electron
microscopy studies of graphite materials prepared by high-temperature treatment of
unburned carbon concentrates from combustion fly ashes. Energy & Fuels 23, 942–950.
Cameán, I., Lavela, P., Tirado, J.L., García, A.B., 2010. On the electrochemical performance
of anthracite-based graphite materials as anodes in lithium ion batteries. Fuel 89,
986–991.
Chung, D.D.L., 2002. Review graphite. Journal of Materials Science 37, 1475–1489.
Compagnini, G., Puglisi, O., Foti, G., 1997. Raman spectra of virgin and damaged graphite
edge planes. Carbon 35 (12), 1793–1797.
Cuesta, A., Dhamelincourt, P., Laureyns, J., Martínez-Alonso, A., Tascón, J.M.D., 1994.
Raman microprobe studies on carbon materials. Carbon 32, 1523–1532.
Cuesta, A., Dhamelincourt, P., Laureyns, J., Martínez-Alonso, A., Tascón, J.M.D., 1998.
Comparative performance of X-ray diffraction and Raman microprobe techniques
for the study of carbon materials. Journal of material chemistry 8, 2875–2879.
Deurbergue, A., Oberlin, A., Oh, J.H., Rouzaud, J.-N., 1987. Graphitization of Korean
anthracites as studied by transmission electron microscopy and X-ray diffraction.
International Journal of Coal Geology 8, 375–393.
Duber, S., Rouzaud, J.-N., Bény, C., Dumas, D., 1993. Graphitization of anthracites. 21st
Biennal Carbon Conference, Extended Abstracts, p. 316.
226 S. Rodrigues et al. / International Journal of Coal Geology 85 (2011) 219–226
Duber, S., Pusz, S., Kwiecinska, B.K., Rouzaud, J.-N., 2000. On the optically biaxial
character and heterogeneity of anthracites. International Journal of Coal Geology
44, 227–250.
Evans, E.L., Jenkins, J.L., Thomas, J.M., 1972. Direct electron microscopic studies of
graphitic regions in heat-treated coals and coals extracts. Carbon 10, 637–642.
Ferrari, A.C., 2007. Raman spectroscopy of grapheme and graphite: disorder, electron-
photon coupling, doping and nonadiabatic effects. Solid State Communications 143,
47–57.
Franklin, R.E., 1951. Crystallite growth in graphitizing and non-graphitizing carbons.
Proceedings of the Royal Society London A 209, 196–218.
Garcia, A.B., Cameán, I., Pinilla, J.L., Suelves, I., Lázaro, M.J., Moliner, R., 2010. The
graphitization of carbon nanofibers produced by catalytic decomposition of
methane: synergetic effect of the inherent Ni and Si. Fuel 89, 2160–2162.
González, D., Montes-Moran, M.A., Suárez-Ruiz, I., García, A.B., 2004. Structural
characterization of graphite materials prepared from anthracites of different
characteristics: a comparative analysis. Energy & Fuels 18, 365–370.
González, D., Montes-Moran, M.A., García, A.B., 2005. Influence of inherent coal mineral
matter on the structural characteristics of graphite materials prepared from
anthracites. Energy & Fuels 19, 263–269.
Hishiyama, H., Irumano, H., Kaburagi, Y., 2001. Structure, Raman scattering, and
transport properties of boron-doped graphite. Physical Review B 63, 245406.
Katagiri, G., Ishida, H., Ishitani, A., 1988. Raman spectra of graphite edge planes. Carbon
26, 565–571.
Kilby, W.E., 1988. Recognition of vitrinite with non-uniaxial negative reflectance
characteristics. International Journal of Coal Geology 9, 267–285.
Kilby, W.E., 1991. Vitrinite reflectance measurement — some technique enhancements
and relationships. International Journal of Coal Geology 19, 201–218.
Kwiecinska, B., Petersen, H.I., 2004. Graphite, semi-graphite, natural coke, and natural
char classification — ICCP system. International Journal of Coal Geology 57, 99–116.
Kwiecinska, B., Murchison, D.G., Scott, E., 1977. Optical properties of graphite. Journal of
Microscopy 109, 289–302.
Laggoun-Defarge, F., Lallier-Verges, E., Suárez-Ruiz, I., Cohaut, N., Jiménez Bautista, A.,
Landais, P., Prado, J.G., 1994. Evolution of vitrinite ultrafine structure during
artificial thermal maturation. In: Mukhopadhyay, P.K., Dow, W.G. (Eds.), Vitrinite
Reflectance as a Maturity Parameter, Applications and Limitations: ACS Symposium
Series, 570, pp. 194–205.
Larouche, N., Stansfield, B.L., 2010. Classifying nanostructured carbons using graphitic
indices derived from Raman spectra. Carbon 48, 620–629.
Lee, Y.-J., 2004. The second order Raman spectroscopy in carbon crystallinity. Journal of
Nuclear Materials 325, 174–179.
Lespade, P., Marchand, A., Couzi, M., Cruege, F., 1984. Caractérisation de matériaux
carbones par microspetrometrie Raman. Carbon 22, 375–385.
Marques, M., Suárez-Ruiz, I., Flores, D., Guedes, A., Rodrigues, S., 2009. Correlation
between optical, chemical and micro-structural parameters of high-rank coals and
graphite. International Journal of Coal Geology 77, 377–382.
Nemanich, R.J., Solin, S.A., 1979. First- and second-order Raman scattering from finite-
size crystals of graphite. Physical Reviews B 20, 392–401.
Oberlin, A., Terriere, G., 1975. Graphitization studies of anthracites by high resolution
electron microscopy. Carbon 13, 367–376.
Pappano, P.J., Schobert, H.H., 2009. Effect of natural mineral inclusions on the
graphitizability of a Pennsylvania anthracite. Energy & Fuels 23, 422–428.
Pierson, H.O., 1993. Handbook of carbon, graphite diamonds and fullerenes. Noyes, Park
Ridge, NJ. 400 pp.
Pinto de Jesus, A., 2003. Evolução sedimentar e tectónica da Bacia Carbonífera do Douro
(Estefaniano C inferior, NW de Portugal). Cadernos Laboratorio Xeolóxico de Laxe
28, 107–125.
Pusz, S., Duber, S., Kwiecinska, B., 2002. The study of textural and structural transforma-
tions of carbonized anthracites. Fuel Processing Technology 77 (78), 173–180.
Pusz, S., Kwiecinska, B., Duber, S., 2003. Textural transformation of thermally treated
anthracites. International Journal of Coal Geology 54, 115–123.
Sadezky, A., Muckenhuber, H., Grothe, H., Niessner, R., Pöschl, U., 2005. Raman
microspectroscopy of soot and related carbonaceous materials: spectral analysis
and structural information. Carbon 43, 1731–1742.
Sato, Y., Kamo, M., Setaka, N., 1978. Raman spectra of carbons at 2600–3300 cm− 1
region. Carbon 16, 279–280.
Sheng, C., 2007. Char structure characterized by Raman spectroscopy and its
correlations with combustion reativity. Fuel 86, 2316–2324.
Suárez-Ruiz, I., García, A.B., 2007. Optical parameters as a tool to study the
microstructural evolution of carbonized anthracites during high-temperature
treatment. Energy & Fuels 21, 2935–2941.
Suárez-Ruiz, I., Flores, D., Marques, M.M., Martinez-Tarazona, M.R., Pis, J., Rubiera, F.,
2006. Geochemistry, mineralogy and technological properties of coals from Rio
Maior (Portugal) and Peñarroya (Spain) basins. International Journal of Coal
Geology 67, 171–190.
Tan, P.H., Dimovski, S., Gogotsi, Y., 2004. Raman scattering of non-planar graphite:
arched edges, polyhedral crystals, whiskers and cones. Philosophical Transaction of
the Royal Society London A 362, 2289–2310.
Ting, F.T.C., 1981. Uniaxial and biaxial vitrinite reflectance models and their
relationship to paleotectonics. In: Brooks, J. (Ed.), Organic Maturation Studies
and Fossil Fuel Exploration. Academic Press, London, pp. 379–392.
Tuinstra, F., Koenig, J.L., 1970. Raman spectrum of graphite. Journal of Chemical Physics
53, 1126–1130.
Vidano, R.P., Fischbach, D.B., Willis, L.J., Loehr, T.M., 1981. Observation of Raman band
shifting with excitation wavelength for carbons and graphites. Solid State
Communications 39, 341–344.
Wang, Y., Alsmeyer, D.C., McCreery, R.L., 1990. Raman spectroscopy of carbon
materials: structural basis of observed spectra. Chemistry of Materials 2, 557–563.
Zaida, A., Bar-Ziv, E., Radovic, L.R., Lee, Y.-J., 2007. Further development of Raman
microprobe spectroscopy for characterization of char reativity. Proceedings of the
Combustion Institute 31, 1881–1887.