coatings

Article
Monitoring Aging Effects in Graphite Bisulfates by Means of
Raman Spectroscopy
Carlo Camerlingo 1, *,† , Marcella Salvatore 2,3 and Gianfranco Carotenuto 4

1 CNR-SPIN, Institute for Superconductors, Innovative Materials and Devices, S.S. Napoli, Via Campi Flegrei
34, 80078 Pozzuoli, Italy
2 Dipartimento di Fisica “Ettore Pancini”, Università degli Studi di Napoli Federico II, Complesso Universitario
Monte S. Angelo, Via Cinthia, 80126 Napoli, Italy; marcella.salvatore@unina.it
3 Centro Servizi Metrologici e Tecnologici Avanzati (CeSMA), University of Naples “Federico II”,
Complesso Universitario San Giovanni, Corso Nicolangelo Protopisani, 80146 Naples, Italy
4 CNR-IPCB, Institute for Polymers, Composites and Biomaterials, P.le E. Fermi, 1, 80055 Portici, Italy;
gianfranco.carotenuto@cnr.it
* Correspondence: carlo.camerlingo@cnr.it
† Retired since 1 August 2023.

Abstract: Graphite bisulfate (GBS) compounds consist of graphite layers intercalated by HSO4− ions
and H2 SO4 molecules. Owing to electrostatic interactions with the graphene plane, HSO4− ions cause
point defects in the graphite’s crystalline structure, while H2 SO4 molecules are free to move via
diffusion in the spaces between the adjacent graphite sheets and segregate to form linear defects.
In the present work, we report the results of our investigation using Raman spectroscopy on the
temporal evolution of such defects on selected GBS samples over 84 months. Two characteristic
lengths correlated with the average distance between defects have been estimated and their evolution
with aging was investigated. The results show a decrease in the density of point-like defects after
aging, regardless of the pristine structural configuration of the GBS samples, revealing a structural
instability. This study can provide significant information for the technological development of
industrial processes aimed to produce expanded graphite based on GBS precursors, where the aging
of GBS is known to influence the efficiency and quality.

Keywords: graphite bisulfate; graphite intercalation; aging effects

Citation: Camerlingo, C.; Salvatore,
M.; Carotenuto, G. Monitoring Aging
Effects in Graphite Bisulfates by
Means of Raman Spectroscopy.
1. Introduction
Coatings 2024, 14, 101. https://
doi.org/10.3390/coatings14010101 Sealing components (e.g., gaskets, o-rings), resistant to high temperatures, chem-
ically inert and thermally conductive, are mostly made of pure graphite. Frequently,
Academic Editor: Dimitrios Tasis
these mechanical components have a very complex shape (e.g., engine gasket units) and
Received: 7 December 2023 consequently their manufacturing is difficult. The method typically used to fabricate
Revised: 5 January 2024 these pure-graphite components with a complex geometry is based on compacting by
Accepted: 11 January 2024 pressing a special type of highly porous and disordered graphite filament known as ‘ex-
Published: 12 January 2024 panded graphite’, which is prepared from the graphite bisulfate compound (C48 H206 O28 S7 ).
Graphite bisulfate represents the most important of the available graphite intercalation
compounds (GICs). It was prepared for the first time by Brodie in the 1855 by oxidiz-
ing graphite flakes with concentrated nitric acid (HNO3 , 65% in water) in the presence
Copyright: © 2024 by the authors. of sulfuric acid (H2 SO4 ) [1]. The chemical process developed by Brodie included both
Licensee MDPI, Basel, Switzerland.
an oxidating reaction of the graphite crystal by HNO3 and the insertion of sulfuric acid
This article is an open access article
molecules (H2 SO4 ) uniformly among the graphite crystal sheets. However, since nitric acid
distributed under the terms and
oxidizes graphite to graphite cations (graphonium ions), HSO4− ions are also as a result
conditions of the Creative Commons
inserted into the crystal in order to balance the positive charges generated in the graphite
Attribution (CC BY) license (https://
crystal. Therefore, graphite bisulfate has both an ionic nature and a covalent nature, which
creativecommons.org/licenses/by/
are the two possible classes of intercalation compounds. The presence of a strong oxidizer
4.0/).

Coatings 2024, 14, 101. https://doi.org/10.3390/coatings14010101 https://www.mdpi.com/journal/coatings

Coatings 2024, 14, 101 2 of 11

(HNO3 ) has a key role in this chemical process, because the oxidized edges of the graphite
crystals, rich in large oxygen-containing species like carboxyl (-COOH), formyl (-CHO),
and hydroxyl (-OH) groups, allow the molecular/ionic molecules (H2 SO4 and HSO4− ) to
permeate in the crystal, with formation of graphite/H2 SO4 /HSO4− solid solutions. Ni-
tric acid can be replaced by other types of strong oxidizers like potassium permanganate
(KMnO4 ), potassium dichromate (KCr2 O7 ), oxygen peroxide (H2 O2 ), sodium perchloride
(NaClO3 ), sodium periodate (NaIO4 ), etc.; however, the expanding capability and the
stability of the achieved graphite bisulfate products are generally much lower than the
product obtained by HNO3 oxidation. Expanded graphite, processable by compacting with
pressing, is obtained via thermal treatment (thermal shock) of graphite bisulfate. During
this thermal treatment, H2 SO4 molecules present in the graphite crystal react with the
nearest carbon atoms of graphite sheets, producing a gaseous mixture of carbon dioxide,
sulfur dioxide, and moisture that, when violently released from the layered structure of
the graphite crystal, causes significant expansion. In particular, the intercalating agent
and graphite react according to the following scheme: C + 2H2 SO4 = CO2 + 2SO2 + 2H2 O.
Obviously, a low percentage of lattice defects (vacancies) randomly distributed in the
graphite sheets is simultaneously generated by this chemical reaction. Expanded graphite
is very useful as a precursor of many other industrial products derived from graphite
like graphite nanoplatelets, graphene oxide (GO), few-layer graphene (semi-graphene),
single-layer graphene, graphene aerogels, thermally reduced graphene (TRG), chemically
reduced graphene (CRG), etc. Most of these materials are prepared by exfoliation of the
expanded graphite filaments by using sono-acoustic energy (ultrasound). In particular, a
high-intensity sonication treatment is applied to expanded graphite dispersed in a liquid
medium (e.g., acetone). The resulting graphite nanocrystal thickness depends on the degree
of intercalation, which is usually expressed by a ‘staging’ index (i.e., number of graphite lay-
ers contained between two intercalated layers; for example, in a stage I compound, a single
layer of graphene regularly alternates with intercalated species). The staging index depends
on the quality of the graphite bisulfate and therefore on the sulfuric acid concentration and
the type of oxidizing agent involved in the reactive system; however, it also depends on the
aging time. Indeed, freshly prepared stage I graphite bisulfate has a very strong ability to
expand by the effect of a thermal shock, but such a phenomenon reduces in intensity with
the aging of this chemical product. An investigation of the graphite bisulfate aging process
could provide significant information for the technological development of industrial pro-
cesses based on this type of compound, since its ability to expand is strongly influenced
by the time elapsed since its preparation. Indeed, GBS compounds and most GICs are not
stable in air, water, or organic media [2,3]. The configuration assumed by intercalation
substances and the defects induced in the graphene layers influence the free energies of
formation of the lamellar structure [4] and, consequently, the process of expansion.
The aging effects on HNO3 intercalation graphite have been investigated before by
E. J. Samuelsen et al. [5]. They observed a change in staging, the disappearance of the
intermediate crystalline phase, and the growth of a new ordered phase over a period
of 5 months. These changes are related to the thermal settling of the graphite crystals
and defect configuration changes. A study of aging effects over a longer time could give
interesting information from a basic and applicative point of view. As far as we know, no
similar works are present in the literature. This lack of information motivates us to monitor
the aging effects in GBS for considerably longer times. In the present paper, we report the
results of our investigation on aging effects in GBS for a time period of 84 months. For this
purpose, we fabricated GBS by reacting graphite flakes with an oxidizing agent/sulfuric
acid mixture, as described in detail in ref. [6]. Seven different oxidizing agent/sulfuric
acid mixtures have been used. The graphite bisulfate samples were periodically monitored
by micro-Raman spectroscopy over a period of 84 months. Raman spectroscopy provides
an efficient method to characterize graphene and graphite-based materials [6–11]. Indeed,
information on defect configurations can be inferred from a Raman spectral analysis [12,13].
In GBS compounds, HSO4− ions cause point defects in the graphite crystalline structure.
Coatings 2024, 14, 101 3 of 11

These defects are localized; indeed, they cannot move from the lattice positions where they
originate. Differently, H2 SO4 molecules are free to move by diffusion in the space between
the adjacent graphite crystallographic planes and segregate mostly at the crystal edges to
maximize all physical interactions, allowing the formation of a network of linear defects in
the graphite matrix structure [4,14].

2. Materials and Methods

Graphite bisulfates were synthesized from graphite flakes by using seven different ox-
idizing agent/sulfuric acid mixtures: nitric acid, potassium nitrate, potassium dichromate,
potassium permanganate, sodium periodate, sodium chlorate, and hydrogen peroxide (see
the list in Table 1). The reactions were performed under thermostatic conditions, using a
9:1 parts by volume H2 SO4 /oxidizing agent ratio with a reaction time of 1 h. Constant
quantities of graphite flakes (2 g, Aldrich, >100 mesh) and sulfuric acid (40 mL) and molar
amounts of oxidizing agent were used. Preparation details are reported in ref. [6]. The
samples were periodically characterized by micro-Raman spectroscopy over a time period
of 84 months. Visible Raman spectroscopy was used employing a 17 mW He-Ne laser
source (wavelength 632.8 nm). The apparatus was a Jobin-Yvon system from Horiba ISA,
with a Triax 180 monochromator equipped with a liquid-nitrogen-cooled charge-coupled
detector. The grating of 1800 grooves/mm allows for a final spectral resolution of 4 cm−1 .
The spectra were recorded in air at room temperature with an acquisition time of 120 s. A
100× optical objective was used to collect the signal in an area size of ca. 2 µm. Spectral
data were analyzed numerically using the best-fitting routine in GRAMS/AI (2001, Thermo
Electron, Waltham, MA, USA) to model the spectra by an overlap of Lorentzian functions.
This allowed us to determine the main vibrational modes occurring in the Raman sig-
nal and to estimate their parameters, namely the centers, widths, and intensities of the
spectral peaks.

Table 1. Raman spectroscopy data of GBS compounds measured before aging (0 months).

Eg Band (cm−1 ) 2D Band (cm−1 )

Sample Oxidizing Agent
G Mode Gb Mode 2D1 2D2
A HNO3 1581 1602 2646 2681
B NaClO3 1580 1603 2637 2681
C NaIO4 1585 1608 2659 2681
D KMnO4 1580 – 2634 2680
E K2 Cr2 O7 1580 1599 2644 2681
F H 2 O2 1580 – 2642 2681
G KNO3 1579 1596 2644 2681
graphite flakes – 1582 – 2641 2681

3. Results
The Raman spectrum of GBS sample A (HNO3 ) is reported in Figure 1 and is compared
with the Raman spectrum of pristine graphite. The spectrum of graphite is dominated by
a strong peak at 1582 cm−1 , which is related to the Eg degenerated vibrational modes of
carbon atoms (G mode). The occurrence of intercalation layers in the graphite modifies
this peak and splits it into two modes, which are assigned to displacements of carbon
atoms belonging to internal layers of stacking regions and to stacking boundary layers,
respectively. The G mode related to interior layer phonons is centered at ca. 1580 cm−1 ,
similar to graphite, while the position of the Gb mode due to boundary layer phonons
is at a higher wavenumber, depending on the stacking order [10,11]. The split of the G
peak is clearly shown in Figure 1a. Two modes occur at 1602 cm−1 and 1581 cm−1 in
the spectrum of A (HNO3 ) (i), while a single peak centered at 1582 cm−1 is observed
Coatings 2024, 14, 101 4 of 11

in the spectrum of graphite flakes (ii). A list of the position of these modes is reported
in Table 1 for GBS compounds that were produced with different oxidizing agents. In
the case of samples D (KMnO4 ), F (H2 O2 ), and G (KNO3 ), the split of the Eg mode is
negligible, and the signal can be modeled by a single peak centered at about 1581 cm−1 .
The thermogravimetric analysis (TGA) reported in ref. [6] has confirmed a relatively low
intercalation degree for these GBS compounds as the weight loss percentages during TGA
are lower than 10% while values were estimated in the 17%–52% range for the weight
loss percentages of the remaining GBS compounds. In the case of sample A (HNO3 ), the
measured weight loss was 17%. The D mode located at about 1334 cm−1 originates from
edge or discontinuities in the carbon lattice, where translational symmetry is broken, and
it is usually associated with structural defects occurring in the graphite [8,15]. This mode
is relatively weak in the flakes of pure graphite (spectrum (ii) in Figure 1a) but becomes
more intense in the GBS spectrum (spectrum (i) in Figure 1a) because of the bounding
surface increase and an expected larger number of defects. The second order of this mode
(2D band) is observable in the high wavenumber region of the Raman spectrum at about
2640 cm−1 . The D and 2D modes are dispersive bands, and hence, their actual position
and intensity depend on the laser excitation energy [8]. In Figure 1b, the broad bands
assigned to 2D modes of the sample A (KNO3 ) (i) and graphite flakes (ii) are shown. The
spectrum of graphite flakes (ii) is characterized by two main peaks (2D1 and 2D2 ) centered
at 2641 cm−1 and 2681 cm−1 , respectively. Two further weaker components occur at 2611
cm−1 and 2710 cm−1 . These features are consistent with the Raman response of graphite,
where a double resonance process involving a link between phonons and the electronic
band structure is expected. Indeed, the four components of the 2D band are related to
a splitting of the graphite electron bands [8]. The position of the 2D1 mode in the GBS
spectrum (spectrum (i) in Figure 1b) is 2646 cm−1 , slightly higher than in the graphite flake
spectrum, and its relative intensity concerning the 2D2 mode increases, thus indicating a
change in the electronic structure related to a modified stacking configuration, in agreement
with the behavior exhibited by multilayer graphene [8]. A list of the 2D1 and 2D2 mode
positions in GBS compounds produced with different oxidizing agents is reported in Table
1. The position of the 2D2 modes does not change, while the centers of the 2D1 mode
vary in the range of 2637–2659 cm−1 depending on the fabrication process. Aging of
the samples implies some changes in the Raman spectroscopy response due to structural
readjustments of intercalation components inside the stacked layered structure of GBS
compounds. The Raman spectra of sample A (KNO3 ) over time are reported in Figure 2
for the spectral ranges of 1200–1800 cm−1 (Figure 2a) and 2500–2775 cm−1 (Figure 2b).
Raman acquisitions were performed on a pristine sample after 3, 12, 14, 20, 30, 61, and 84
months, as indicated in Figure 2. The split of the G band is clearly visible in almost all
spectra, with component modes centered at 1602 cm−1 and 1581 cm−1 (Figure 2a). Their
relative intensity changes with aging. Indeed, the intensity of the mode assigned to the
vibration of bounding layer atoms (at 1602 cm−1 ) initially increases with respect to the
peak at 1581 cm−1 , reaching a maximum in the spectrum measured after 20 months of
aging, gradually decreasing afterwards. A less regular dependence on the intensity of the
D mode is observed, but a clear decrease in the intensity is visible in the last two spectra,
for aging times longer than 61 months. In the higher region of the spectrum (Figure 2b),
the spectra are characterized by two main peaks, which are centered at 2641 cm−1 and
2681 cm−1 . Starting from the spectrum collected after 30 months of aging, a gradually
broadening of the modes occurs and their energy is lowered, particularly relevant for
the 2D1 peak initially centered at 2641 cm−1 , which moves to 2636 cm−1 . In general, the
effects of aging on the Raman responses are qualitatively similar in all the GBS compounds
considered. However, in the case of sample B (NaClO3 ), the intensity of the D mode is
higher and the peaks are broader than in the other samples (see Figure S1). The dependence
of the area ratio of the G and Gb peaks and of the area ratio of the D and G modes is
reported in Figure S2a and S2b, respectively. The Gb mode component increases in the first
aging period and reaches a maximum after about 14–20 months, after which it decreases
Coatings 2024, 14, 101 5 of 11

in intensity. The behavior shown by different samples can be ascribed to a relocation of

the defects inside the graphene layers with aging, which affects the Raman response of
the material. As inferred in Figures 2 and S2, the D and 2D mode intensities have a non-
monotonic dependence on the aging time, indicating a reduction in the punctual defects in
graphene layers after an initial increase in their density during the first 30 months. This
process also influences the strain of the graphene layers inside and, more significantly, at
the boundary of the stacking regions of the GBS, as inferred from the time dependence of
the relative intensity of the G and Gb modes. A relaxation of the graphene lattice is inferred
after aging, which can be ascribed to a segregation of moving intercalating components at
the graphite grain boundaries.

Figure 1. Raman spectrum of GBS A (HNO3 ) (i) and of graphite flakes (ii) in the wavenumber range
of 1100–1800 cm−1 (a) and 2450–2750 cm−1 (b), respectively. Red lines represent the experimental
data and the black lines represents the modes which have been determined by the fit of the signal
with an overlap of Lorentzian peaks. The spectroscopy data refer to pristine samples.

The influence of aging on the Raman spectroscopy response of GBS compounds can
be related to the configuration of defects in the samples and their modification occurring
over time due to thermal relaxation mechanisms. Similarly to graphene, two kinds of
lattice defects can occur in the graphite intercalation layers: point-like defects generated by
lattice vacancies or chemical effects and extended defects, which are related to edge effects,
appearing as strain, dislocations, or discontinuities at crystal grain borders [16].
Instead, the neutral molecules of the intercalant H2 SO4 can indeed move by thermal
diffusion in the spaces between the adjacent graphite stacks and segregate to maximize
all physical interactions. This allows the formation of aggregates that electrostatically
interact with external layers of the graphite stacking structures, locally deforming them
and inducing linear-like defects. The observed splitting of the Eg band in the two G and Gb
modes depends on the extent of the influence of these defects on the Raman response.
The defects induce disorder in the system that can be accounted for by two character-
istic lengths, LD and La , which are correlated with the average distance between defects.
The parameter LD is related to point-like defects, while La takes into account the extended
defects at the grain borders. L. G. Cançado et al. proposed a method to distinguish the
contributions of the two kinds of defects in graphene via Raman spectroscopy and estimate
LD and La from the AD /AG ratio of the peak areas of the D and G modes and the ΓG
Coatings 2024, 14, 101 6 of 11

peak width of the EG mode [13]. The AD /AG ratio gives an indication of the relevance
of point-like defects in the graphene layers because the Raman D mode is related to light
scattering events enabled by defects and is not allowed in defect-free graphene.

Figure 2. Sample A (HNO3 ): dependence of the Raman spectrum on the aging time in the spectral
ranges of 1200–1800 cm−1 (a) and 2500–2800 cm−1 (b), respectively.

Depending on the light excitation energy E L , the AD /AG ratio and ΓG values are
correlated, because both are a function of LD and La .
Indeed, ΓG is given by:

−lξ
ΓG ( L D , L a ) = ΓG (∞) + CΓ e ph (1)

where ξ is the phonon localization length, l ph is the phonon coherence length, ΓG (∞) is
the peak width of the material without defects, and CΓ is a constant. The AD /AG ratio is
calculated as:
2 2
 
πr πr
− S − S
AD 4
CS0D 1 − e L2  + 4C1D lS ( La −2 lS ) e L2
AG EL = +
D D
S La
(2)
πr2 r2
h i − S  ( L a −2lS )

−π S
( L a +r S ) ( L a − lS ) L2 ( L a −2lS ) L2
2πC0D
A lc L2D
1 + 4lS L2a
e D + 2C1D
A lc L2
1− e lc e D
a

where C0D 1D 0D 1D
S , CS , C A , and CS are constants, lc is the electron coherence length, and rS
and ls are the sizes of point and extended defects, respectively. We extended this approach
to the intercalated graphite samples, considering the G mode of the Raman response
(1581 cm−1 peak) in the analysis, which is related to carbon interlayers. We used the
parameter values adopted in ref. [13] to model the AD /AG ratio’s dependence on ΓG
(ΓG (∞) = cm−1 l ph = 16 nm; lc = 4.1 nm; lS = 2 nm; le = 3.7 nm; and rS = 2.2 nm).
Similarly, a small value of between ξ = La and ξ = 10 LD was assumed for the phonon
localization length, depending on the kind of defect which is dominant out of point-like
and extended defects. The experimental values of the AD /AG (E L )4 ratio vs. ΓG are reported
in Figure 3, where E L = 1.96 eV is the photon energy of the laser excitation beam. The
data refer to sample A (HNO3 ) which was characterized by Raman spectroscopy before
Coatings 2024, 14, 101 7 of 11

aging (black circles in Figure 3) and after 84 months of aging (red circles in Figure 3).
The Raman acquisitions were performed at different positions of the GBS surface. In
Figure 3, the spread of AD /AG (E L )4 ratio values is relatively large, and no significant
variation between the initial and aged state is noticed. In fact, the average values are
AD /AG (E L )4 = 34.5 ± 12.7 eV4 for the pristine sample and AD /AG (E L )4 = 27.9 ± 12.8 eV4
for the aged one. These data were compared with the AD /AG (E L )4 dependence on ΓG
calculated via Equations (1) and (2). A good match with the experimental data can be
obtained by setting La = 28 nm and LD = 13.3 nm for the pristine state and La = 43 nm and
LD =14.8 nm after aging. The curves in Figure 3 refer to the model-predicted dependence
for values of LD = 13.3 nm (black curve) and LD = 14.8 nm (red curve) and variable
La values. This suggests an increase in the Raman scattering homogeneity due to larger
sizes and more relaxed grains. This feature is compatible with a segregation of mobile
intercalating components to the grain boundaries and an increase in the regularity of the
stacked boundary layers. A similar behavior was observed in the remaining samples. In
Figure 4, the average values of AD /AG (E L )4 and ΓG data are reported, referring to GBS
compounds produced with NaClO3 (sample B, black dots), NaIO3 (sample C, red dots),
KMnO4 (sample D, blue dots), and H2 O2 (sample F, green dots). Full dots refer to pristine
samples, while data collected after the aging are plotted with empty circles. As a reference,
the trend predicted by the model for the dependence of AD /AG (E L )4 on ΓG (Equation (2))
is reported in Figure 4 for fixed LD values of 11.4 nm (black line), 18 nm (red line), and
30 nm (blue line) and a variable La . In Figure 4, a larger variation with aging is observed in
sample B. Both the AD /AG (E L )4 ratios and ΓG decrease with aging as in the case of sample
A (Figure 3). These spectroscopy data are compatible with a relatively high density of point
defects because they can be modeled by relatively low LD parameters. The values of LD
and La were estimated by a numerical fit of the data with Equation (2). A moderate increase
in LD from 11 ± 1 nm to 13 ± 1 nm is demonstrated with aging. The change in ΓG values,
and consequently in La , is more relevant, reflecting a relaxation of the graphite grains. In
such a case, both point-like and linear defects weakly evolve towards a clean configuration.
The defect density in sample C is lower than in sample B and a larger LD of 17 ± 1 nm was
estimated in the initial state. In this case, aging weakly influences the defect configuration,
even if a trend towards a decrease in the defect density is inferred, mainly concerning LD
and point-like defects. Samples D and F are characterized by a low density of defects, but a
significant increase in LD is exhibited after aging also in these cases.

Figure 3. Effects of the aging on the area ratio of D and G modes (AD /AG (E L )4 ) (E L = 1.96 eV)
and the width of G peak (ΓG ) of sample A (HNO3 ). Red circles refer to data collected at
84 months after the data reported with black circles. The curves were calculated using the model
of L. G. Cançado et al. [13] for LD = 13.3 nm (black curve) and LD = 14.8 nm (red curve), and a
variable La .
Coatings 2024, 14, 101 8 of 11

Figure 4. Effects of aging on the area ratio of D and G modes (AD /AG E L ) and the width of G peak
(Γ G ). The data refer to GBS compounds produced with different oxidation agents, namely NaClO3
(sample B, black dots), NaIO4 (sample C, red dots), KMnO4 (sample D, blue dots), and H2 O2 (sample
F, green dots). Full dots refer to data collected at 84 months after the data reported with empty circles.
As a reference, the trend predicted by the model for the dependence of AD /AG (E L )4 on Γ G (Equation
(2)) is reported in the figure for a fixed LD of 11.4 nm (black line), 18 nm (red line), and 30 nm (blue
line) and a variable La .

Samples E (K2 Cr2 O7 ) and G (KNO3 ) are not shown in Figure 4, but their behavior
is similar to that of samples D and F, with a relatively high LD value correlated with a
relatively low density of point defects. A list of the estimated La and LD parameters before
and after aging is reported in Table 2. A list of experimental AD /AG (E L )4 and ΓG values
far all the GBS compounds investigated is reported in Table S1 in the Supplementary
Materials. In general, La does not change significantly or slightly increases with aging but,
in the case of sample F, La decreases from 78.0 nm to 57.3 nm, indicating a relocation of
extended defects.

Table 2. Aging and defect characterization.

LD (nm) La (nm)
Sample Oxidizing Agent
Pristine After Aging Pristine After Aging
A HNO3 14 ± 1 15 ± 1 28 ± 2 43 ± 1
B NaClO3 11 ± 1 13 ± 1 16± 1 37 ± 1
C NaIO4 17 ± 1 19 ± 1 24 ± 1 26 ± 1
D KMnO4 26 ± 1 52 ± 4 63 ± 1 58 ± 2
E K2 Cr2 O7 22 ± 2 33 ± 4 >80 >80
F H 2 O2 22 ± 7 53 ± 8 78 ± 1 57 ± 2
G KNO3 59 ± 13 >80 46 ± 2 >80

4. Discussion
In GBS compounds, localized point-like defects in the graphite crystalline structure
can be generated by HSO4− ions which interact electrostatically with graphene layers, while
H2 SO4 molecules form a network of linear defects in the graphite matrix structure. Neutral
Coatings 2024, 14, 101 9 of 11

molecules can indeed move via diffusion in the spaces between the adjacent graphite
crystallographic planes and segregate to maximize all physical interactions. As the oxidized
and intercalated graphite crystals are separated from the liquid reaction medium where
they were generated (i.e., H2 SO4 +HNO3 65%), they become unstable systems. Such crystal
instability causes a progressive segregation of the mobile intercalating molecules (H2 SO4 ) at
the boundaries of the crystal and therefore on the external crystal surface. The intercalated
graphite crystal has a polycrystalline nature; indeed, the structure of an intercalated crystal
can be described as a system of small crystallites separated by defective regions that are
centered on the intercalating molecules. However, this polycrystal is not a static but a
dynamic system. As a result of the strong π − π interactions acting between adjacent
graphite sheets, these crystalline regions tend to grow slowly over time by squeezing out
the mobile intercalating molecules that, as a consequence, accumulate and/or segregate.
Over time, most of these mobile intercalating molecules migrate inside the crystal up to
the crystal boundary, where they accumulate and then are released outside the crystal.
However, only neutral molecules like H2 SO4 can move inside the crystal; indeed, ionic
intercalating molecules (H2 SO4− ) are stably positioned close to the positive charges in
the sheets. During the sulfuric acid segregation process, a small percentage of mobile
intercalating molecules does not reach the crystal boundary to escape, and is trapped in
the crystal between two adjacent crystallites, producing linear defects because all sheet
deformations produced by the intercalating molecule propagate to the full graphene sheet
and defects in the crystal always are linear. In this work, we have estimated the defect
configuration of graphene layers of GBS by applying the model proposed by L. G. Cançado
et al. [13] for graphene. This model allowed us to distinguish between point-like and linear
defect changes occurring with aging in GBS. As far as we know, this is the first time that
this model has been applied to the analysis of GBS, even if Raman spectroscopy is widely
used for characterizing graphene and graphene oxides. Previously, aging effects have
been investigated in GBS by X-ray diffractometry [5]. Changes in the GBS crystallographic
phases have been reported with aging, indicating a relocation of the intercalant molecules
that interact with graphene layers. In general, we found a decrease in the density of
localized point-like defects with aging, regardless of the pristine structural configuration
of the samples. Indeed, GBS compounds fabricated using different oxidizing agents have
been considered in this study. Larger relative increases in the LD characteristic length
for point-like defects have been observed in samples D (KMnO4 ), E (K2 Cr2 O7 ), F (H2 O2 ),
and G (KNO3 ), which exhibit LD values larger than 20 nm in the pristine state. Aging
did not affect the extended defect configuration, and the La characteristic length did not
change significantly over time, except in the case of sample F (H2 O2 ), which exhibits a
small decrease in La with aging.

5. Conclusions
Knowledge of the effects of aging on the structural properties of graphite intercalation
compounds is an important requirement for industrial processes of expanded graphite
production and in general for GBS applications. In this work, we have investigated the
effect of aging on graphite bisulfate compounds over 84 months, a period considerably
longer than the ones considered in similar works. In particular, Raman spectroscopy
allowed us to monitor the changes occurring in the defect configuration of the graphene
layers and the stacking regions of the GBS due to the interaction between graphene layers
and intercalant ions and molecules. To achieve this, we have extended the approach used
for graphene characterization to the analysis of the spectroscopic data of GBS. To the
best of our knowledge, this is the first time that an investigation of this type has been
performed. This study allowed us to distinguish between point-like and linear defect
changes occurring with aging. In general, we found a decrease in the density of localized
point-like defects with aging, regardless of the pristine structural configuration of the
samples. In the case of samples with a relatively high density of point-defects, a slight
decrease in the density of linear defects was inferred, concurrent with a segregation of
Coatings 2024, 14, 101 10 of 11

mobile intercalating components to the grain boundaries and an increase in the regularity
of the stacked boundary layers. In general, the proposed approach provides a convenient
method for GBS and GIC characterization, not only for aging effect estimations, but also
for controlling the processes of GBS, GIC, and expanded graphite fabrication.

Supplementary Materials: The following supporting information can be downloaded at https:

//www.mdpi.com/article/10.3390/coatings14010101/s1: Figure S1: Effect of aging on the Raman
response of the graphite bisulphate prepared with NaClO3 as oxidizing component (sample B
(NaClO3 )). The Raman spectra have been collected on a fresh prepared sample (0) and after 3, 12, 14,
29, 30, 61, and 84 months of aging, respectively. Figure S2: Effect of aging on the Raman response of
the graphite bisulphates prepared with HNO3 (sample A, black dots and line) and NaClO3 (sample B,
red dots and line) as oxidizing component. The time dependence of the AGb /AG area ratio of the Gb
and G mode peaks (a) and of the ratio of the D and G mode peaks (b) are reported. Table S1: Effects
of the aging on the AD /AG area ratio of D and G Raman modes and the width of G peak (ΓG ). Data
refer to GBS produced with different oxidation agents and have been used to estimate La and LD
parameters reported in Table 2. EL = 1.96 eV is photon energy of the excitation laser.
Author Contributions: Conceptualization and methodology, C.C., M.S. and G.C.; investigation, C.C.
and M.S.; writing—review and editing, C.C., M.S. and G.C. All authors have read and agreed to the
published version of the manuscript.
Funding: This research received no external funding.
Data Availability Statement: Data are contained within the article.
Conflicts of Interest: The authors declare no conflicts of interest.

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