C Journal of

Carbon Research

Article
Thermogravimetric Analysis (TGA) of Graphene Materials:
Effect of Particle Size of Graphene, Graphene Oxide and
Graphite on Thermal Parameters
Farzaneh Farivar 1,2,† , Pei Lay Yap 1,2,† , Ramesh Udayashankar Karunagaran 1,2 and Dusan Losic 1,2, *

1 School of Chemical Engineering and Advanced Materials, The University of Adelaide,

Adelaide, SA 5005, Australia; [email protected] (F.F.);
[email protected] (P.L.Y.); [email protected] (R.U.K.)
2 ARC Hub for Graphene Enabled Industry Transformation, The University of Adelaide,
Adelaide, SA 5005, Australia
* Correspondence: [email protected]
† These authors contributed equally to this work.

Abstract: Thermogravimetric analysis (TGA) has been recognized as a simple and reliable analytical
tool for characterization of industrially manufactured graphene powders. Thermal properties of
graphene are dependent on many parameters such as particle size, number of layers, defects and
presence of oxygen groups to improve the reliability of this method for quality control of graphene
materials, therefore it is important to explore the influence of these parameters. This paper presents
a comprehensive TGA study to determine the influence of different particle size of the three key
materials including graphene, graphene oxide and graphite on their thermal parameters such as





 carbon decomposition range and its temperature of maximum mass change rate (Tmax ). Results
showed that Tmax values derived from the TGA-DTG carbon combustion peaks of these materials
Citation: Farivar, F.; Yap, P.L.;
Karunagaran, R.U.; Losic, D.
increasing from GO (558–616 ◦ C), to graphene (659–713 ◦ C) and followed by graphite (841–949 ◦ C)
Thermogravimetric Analysis (TGA) The Tmax values derived from their respective DTG carbon combustion peaks increased as their
of Graphene Materials: Effect of particle size increased (28.6–120.2 µm for GO, 7.6–73.4 for graphene and 24.2–148.8 µm for graphite).
Particle Size of Graphene, Graphene The linear relationship between the Tmax values and the particle size of graphene and their key
Oxide and Graphite on Thermal impurities (graphite and GO) confirmed in this study endows the use of TGA technique with more
Parameters. C 2021, 7, 41. https:// confidence to evaluate bulk graphene-related materials (GRMs) at low-cost, rapid, reliable and simple
doi.org/10.3390/c7020041 diagnostic tool for improved quality control of industrially manufactured GRMs including detection
of “fake” graphene.
Academic Editor: Gil Goncalves

Keywords: graphene; graphene oxide; graphite; thermogravimetric analysis

Received: 25 March 2021
Accepted: 26 April 2021
Published: 27 April 2021

1. Introduction
Publisher’s Note: MDPI stays neutral
with regard to jurisdictional claims in
Graphene, a two-dimensional (2D) carbon material with a single layer of sp2 carbon
published maps and institutional affil- arranged in a hexagonal lattice, has been described as the material of 21st century and a
iations. new disruptive technology as a result of the combination of its unique properties since its
discovery in 2004 [1]. A wide range of graphene applications have been demonstrated in
recent years ranging from lightweight composites, functional coatings, adsorbents, elec-
tronics, energy storage and etc. [2–5]. Translations of these applications from academia
Copyright: © 2021 by the authors.
to industry is rapidly increasing in recent years, underpinning fast growing and new
Licensee MDPI, Basel, Switzerland.
emerging graphene industry that apply graphene across many sectors. Manufacturing
This article is an open access article
and supplying high quality graphene materials with known properties for these industrial
distributed under the terms and applications is one of the key obstacles for the growth of this industry. In recent years,
conditions of the Creative Commons many graphene manufacturing processes have been developed and hundred companies
Attribution (CC BY) license (https:// worldwide have been established for the industrial production of graphene materials in the
creativecommons.org/licenses/by/ forms of powders, pastes or dispersions, which are now available in the market [5,6]. Un-
4.0/). fortunately, recent comprehensive quality evaluation studies revealed unexpected findings

C 2021, 7, 41. https://doi.org/10.3390/c7020041 https://www.mdpi.com/journal/carbon

C 2021, 7, 41 2 of 12

that a large percentage of these industrially-produced graphene materials in the market

are not as per declared as single or few layer graphene, but rather a mixture of graphene,
graphitic and other carbonaceous materials [7–9]. The properties and the quality of these
graphene materials are far from the properties of single or few layered graphene defined by
the International Organization for Standardization (ISO) [10–12]. These surprising results
triggered considerable concerns for down-stream graphene end-users with a potential
grave impact on the future of and the growing of multi- million dollars graphene industry
and its associated industries, which intend to use this outstanding material. The main
concerns are the presence of nanographite (>10 graphene layers) or unexfoliated graphitic
particles, highly defective graphene, graphene oxide (GO) and impurities from the produc-
tion process, which could be overlooked by currently used characterization techniques that
focus on single particle analysis. For these reasons, the standardization of graphene and
reliable quality control for industrially- produced graphene materials, has now become
one of the most critical prerequisites for the growing graphene industry, where the fight
against “fake graphene” in the market is one of the top priorities.
Most of the recommended advanced characterization techniques within the current
ISO graphene measurement standards being developed, including SEM, TEM, AFM and
Raman spectroscopy are localized characterization methods, which are able to probe
the properties of graphene materials only for a very small area, such as single graphene
particles [10,11,13–15]. These methods are more appropriate for chemical vapour deposition
(CVD) graphene layers, but are limited for characterization of graphene powders, which
are lacking the representative measure of their key properties at larger bulk quantities.
These techniques also require skilled technical personnel, can be time-consuming and not
affordable for typical graphene manufacturers, which are usually small start-up companies.
Thus, quality control of produced graphene powders is typically performed externally
by academic institutions using a limited amount of samples (µg) and localised testing
of very few selected graphene particles, which are then used to make the claims of the
properties of the product produced at large scale. This level of testing is unable to provide
an understanding of the properties of graphene powders when produced in industrial-scale
batches (kg or tonne). Ultimately, this leads to a supply chain that lose the credibility on
the properties claimed by the graphene manufacturers.
Hence, there is a significant demand to develop and implement a more representable,
reliable, simple, and low-cost analytical methods that provides information of bulk prop-
erties for industrially produced graphene materials. Several analytical methods such
as thermogravimetric analysis (TGA), X-ray diffraction (XRD), surface area (Brunauer–
Emmett–Teller, BET nitrogen adsorption/desorption method), particle size distribution
(PSD), Fourier-transform infrared (FTIR) spectroscopy and pH titration can meet these
requirements [11,13–15]. They could provide valuable information about the properties
of graphene powders such as the crystal and graphitic structure, surface area, chemical
composition, impurities and functional groups. Among them, TGA, a routinely used
analytical technique in the industry for characterization of the thermal properties and
impurities of minerals, polymers and carbon materials, is very promising, but has not been
explored for the quality control of graphene materials [16–19].
In our recent study, we demonstrate how TGA method can be used as a valuable
quality control and analytical tool for the qualitative and quantitative analysis of manu-
factured raw graphene powders and be used as a simple and reliable method to combat
with the “fake graphene” [20]. This study revealed the influence of structural and chemical
composition properties of graphene materials such as number of layers, particle size, de-
fects and level of oxygen on TGA/DTG parameters which requires more clarification to
make TGA a more reliable method for qualitative and quantitative analysis of graphene
materials that can be used as a simple method for the identification of fake graphene.
One of the key objectives in the present work is to explore and establish the correlation
between key TGA/DTG features and the particle size of GRMs (summarized in Scheme 1),
which has not been previously reported. Herein, we systematically investigate the effect of
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the particle size of selected GRMs including graphite (Gft), graphene (Gr) and graphene
oxide (GO) on their TGA and DTG properties with focus on the thermal decomposition of
carbon including their DTG peak range and Tmax derived from their respective DTG carbon
combustion peaks. Three materials including graphite, graphene and GO are prepared
and characterized by HRTEM, FESEM, XPS, Raman, XRD and FTIR to determine their key
characteristics such as number of layers, defects, chemical composition and crystallinity.
Their particle size is determined by two comparative methods including SEM and laser
diffraction (LD) techniques, followed by TGA characterization to establish the relationship
between the Tmax values derived from the TGA- DTG peaks of the carbon combustion re-
gion with different particle size. Outcomes from this study provide important information
about the influence of the particles size of these materials and will help gaining confidence
in TGA method for characterization of graphene materials as a quick method for detecting
“fake graphene” with large contents of graphitic particles. The established and standard-
ized TGA method will be a valuable, low-cost and simple characterization tool that can be
effectively and practically used as a diagnostic tool for industrially manufactured GRMs.

Scheme 1. Representative TGA-DTG graphs and the Tmax values of graphene, GO, and graphite,
which are used as foundation to explore the influence of particle size.
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2. Materials and Methods

2.1. Materials and Sample Preparation
Graphite used in this study was in the form of graphite flakes provided by a local
graphite mine company (Uley, Eyre Peninsula, SA, Australia). Prior to TGA measure-
ment, graphite flakes were crushed and sieved to different flake sizes including ≤25 µm,
25–53 µm, 53–100 µm and 100–150 µm. Commercial graphene materials provided by
undisclosed company with different particle size (7 to 74 µm) were processed using tip
sonication technique [21]. For the preparation of GO samples, non-sieved graphite powder,
powder sieved at ≤25 µm and 25–53 µm were reacted with oxidising agents to form GO
through improved Hummer’s method according to our published work previously [22].
More details about the samples are tabulated in Table S1. To minimize the discrepancy arise
from other factors such as oxygen level, morphology, level of defects and thickness, the
three main carbon materials studied in this work were processed from their corresponding
parent material using the same preparation method. For instance, all the GO prepared
using the same graphite flakes which were sieved to different size before undergoing the
same oxidation and exfoliation process.

2.2. Characterization Techniques

2.2.1. Thermogravimetric Analysis
TGA analyses of prepared samples (~5 mg) were performed using a Mettler Toledo
TGA/DSC 2 with heating rate at 10 ◦ C/min in air condition at flow rate of 60 mL/min.
Collected TGA data demonstrated typical mass loss with regards to temperature and their
corresponding first derivative (DTG) graphs provided information on mass loss rate versus
temperature. TGA-DTG plots have been popularly applied to determine the composition of
water, volatile compounds, combustible carbon and impurities in graphene and its related
materials. In this study, we focused on the thermal parameter (temperature of maximum
mass change rate, Tmax ) by fitting the TGA-DTG curves using Origin software. Tmax of the
final mass loss step related to the carbon combustion can be determined from the maximum
peak position in the negative region of the DTG curve (Scheme 1).

2.2.2. Scanning and Transmission Electron Microscopy (SEM and TEM)

Lateral size and morphology of the representative carbon materials were determined
using scanning electron microscope (FE-SEM, Quanta 450 FEG, FEI, USA; and SEM, Hitachi
SU1510, Japan) at an operating voltage of 10–30 kV and a transmission electron microscope
(TEM) at 120 kV (TEM, FEI Tecnai G2 Spirit, FEI, USA; Philips CM200, Japan at 200 kV).
For SEM imaging, samples were dispersed in ethanol (GO and Gft) and isopropanol (Gr)
by gentle sonication and drop casted on a carbon tape, followed by coating the sample
with ca 5 nm of Pt coating. For TEM imaging, the dispersed samples were drop-casted on a
lacey carbon film on Cu grid. For SEM, at least images of 50 particles were obtained (at
3 different spots) and at for TEM least 20 particles (at 3 different spots) for each of the tested
sample. The lateral size (LxW) of each particle was measured from obtained images with
the average of the two values was presented for their average lateral size. One image is
selected to show the representative particle size for each material.

2.2.3. Raman Spectroscopy

Raman spectrometer (LabRAM HR Evolution, Horiba Jvon Yvon Technology, Japan)
with a 532 nm laser (mpc3000) was used to understand the vibrational characteristics and
distinguish the carbon materials tested in this work. The Raman spectra were collected
at 500 to 3000 cm−1 with an integration time of 10 s for three accumulations using a
100× objective lens and laser spot was 721.16 nm. Raman spectra were obtained from at
least from 5 different particles and their 3 spots (center and edge). One representative
Raman graph is presented.
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2.2.4. FTIR Spectroscopy

Functional groups present in the carbon samples were confirmed using FTIR spectrom-
eter (Nicolet 6700, Thermo Fisher) with the spectra collected in the range of 500–4000 cm−1 .

2.2.5. Powder X-ray Diffraction (XRD)

Powder X-ray diffractometer (600 Miniflex, Rigaku, Japan) equipped with a Cu X-ray
tube (λ = 1.54 Å, 40 kV and 15 mA) was run at with 10◦ min-1 scan speed in the range of
2θ = 5 to 80◦ to determine the interlayer spacing of the examined carbon materials.

2.2.6. X-ray Photoelectron Spectroscopy (XPS)

X-ray Photoelectron Spectroscopy (XPS, AXIS Ultra DLD, Kratos, UK) equipped with
a monochromatic Al Kα radiation source (hv = 1486.7 eV) was applied to identify the
presence of impurities and the chemical composition of the materials at 225 W, 15 kV and
15 mA. XPS survey spectra were measured at 0.5 eV step size over −10 to 1100 eV at
160 eV pass energy with peak fitting analysis performed using Casa XPSTM software. The
core-level XPS spectra were calibrated to the adventitious carbon at 284.8 eV.

2.2.7. Particle Size Distribution (PSD) by Laser Diffraction (LD)

Particle size distribution (PSD) of the samples was determined using the principle of
laser light diffraction (LD) on a Mastersizer 2000 (Malvern Instruments, Malvern, UK) with
refractive index and absorption set at 2.42 and 1, respectively, using water as the dispersant.
Sample (fine powder) was gradually added into a tank containing water until obscuration
(~5%) was achieved and all the measurements were carried out without ultrasonication to
preserve the primitive size of the carbonaceous particles. PSD graphs were plotted based
upon the median particle size by volume, d(50)v , with three measurements collected for
each sample.

3. Results and Discussion

3.1. Structural and Chemical Characterization of GO, Graphene and Graphite
The lateral size and morphology of prepared GO, graphene and graphite materials
with different particle size used in this TGA study were verified by combination of FESEM
and PSD/LD characterizations. FESEM analysis was used in this work to reflect the actual
particle size and shape of GRMs with limitations of selected number of imaged particles,
which do not represent whole bulk powder samples. For that reason, complementary
PSD/LD method was applied to measure the particle size in dispersion despite that this
method assumes the measured 2D sheets as spherical particles.
Typical FESEM images of selected single particle to represent the average particle size
of GO, graphene and graphite samples are summarized in Figure 1, Figure S1 and Table 1.
FESEM images of GO exhibited highly wrinkled GO sheets with their lateral size in two
lateral dimensions recorded (Table 1) prepared after extensive oxidation and exfoliation
process. Representative image of graphene samples with different particle size captured
by SEM illustrated the isolated graphene sheets with varied lateral size obtained. The
thickness of prepared graphene layers was confirmed in the range of 3–7 layers (Figure S2),
suggesting <10 layers of Few Layer Graphene (FLG) grade was used throughout this work.
Typical SEM images of individual graphite particles sieved with different sieves fractions
were presented in Figure 1k–n.
Comparative particle size measurements of these samples using LD method with
their PSD curves are also presented in Figure 1d,j,o. Note that the particle size was
expressed in median particle size by volume, d(50)v , where the particle size by volume
distribution can be defined as the relative proportion of volume occupied by particles
with different size denoted by the peak of the curve [23,24]. The tested GO, Gr and Gft
samples demonstrated a monodisperse population particle pattern with d(50)v recorded at
28–121 µm for GO, 7–74 µm for Gr and 24–150 µm for graphite, respectively. In this study,
the measured particle size from SEM technique was found to be in good agreement with the
C 2021, 7, 41 6 of 12

measurements from LD method that validates the applicability of LD technique to probe

the particle size of GRMs although there is a controversy on the reliability and accuracy
of the particle size measurement arise from indirect particle sizing techniques including
dynamic light scattering (DLS) and LD for GRMs [24,25]. For instance, a well-defined
correlation between TEM-measured nanosheet length and DLS-measured hydrodynamic
radius to estimate the lateral size of 2D nanosheets (graphene, MoS2 and WS2 ) was reported
by M. Lotya et al. [26]. Nevertheless, DLS method may not be accurately applied to
determine the nanosheet size in view of its high relative error (40%) in this study [26]. In
contrast, LD method was found to offer high accuracy and comparable PSD data with SEM
technique for GO particles with only maximum deviation of 7–9% recorded despite that
this method is claimed to be limited for spherical particles and underestimates the presence
of particles with small size [25]. Similar to our work, this recent study strongly supports the
applicability of LD technique to provide the PSD information of bulk GRMs considering
the low cost, simple, rapid and high throughput of LD technique. For the purpose of this
study, PSD from LD technique is mainly applied to demonstrate the trend of the particle
size of GRMs apart from exploring the dependence of their particle size on the TGA-DTG
features despite that it is not a commonly used technique to determine the particle size
of GRMs. The particle size of the GRMs studied in this work is compared between direct
(SEM) and indirect (LD) particle sizing techniques (Table 1, Figure 1 and Figure S1). Note
that the PSD curves produced using LD technique are highly reproducible with nearly zero
standard deviation recorded for all the three repeated LD measurements as depicted in
Figure S3. This strongly suggests the high reproducibility of applying this particle sizing
technique to determine the particle size of GRMs.

Figure 1. Representative FESEM images with PSD/LD plot of (a–d) GO 1–3, (e–j) Gr 1–5 and (k–o) Gft 1–4. Direct imaging
technique (FESEM) was adopted to represent the size of GRM particles based on the 2D lateral dimensions as indicated by
the orange solid line; Typical LD-particle size distribution (PSD/LD) plots based on median particle size by volume, d(50)v
where the peak of the curve determined from their graphene, GO and graphite dispersions.

Figure 2a showed the characteristic Raman peaks of GO, graphene and graphite.
The ratio of the peak intensity of the D to G bands (ID /IG ) at around 1350 cm−1 and
1580 cm−1 , respectively, indicates the level of disorder or defect present in the carbon
materials (Figure 2a) [28]. As expected, all the GO samples in these studies are highly
defective with ID /IG ratio recorded between 0.87–0.91, indicating that these samples have
C 2021, 7, 41 7 of 12

undertaken rigorous exfoliation and oxidation process. Meanwhile, graphene samples

exhibited ID /IG ratio of 0.19–0.33, suggesting that these graphene materials experienced
mild level of defects compared to graphite that could be resulting from the exfoliation
process [29]. Of all the carbon materials, graphite samples appeared to be the least defective
materials with ID /IG ratio of <0.1, which could be explained by less materials processing
stages involved except for physical sieving process step. Our Raman spectroscopy find-
ings are in good agreement with the thickness outcome determined by HRTEM analysis
(Figure S2), confirming that the graphene studied in this work is FLG as evidenced by
a distinguished and symmetric 2D band at about 2700 cm−1 detected for the graphene
sample; while a broader and asymmetric 2D peak alongside with a shoulder peak observed
at around 2720 cm−1 for graphite sample [30].

Table 1. Measurement results for comparative PSD/LD and SEM particle size characterization of the series of GO, graphene
and graphite used in this study. Average lateral size measurements were performed following ISO/TS 21356-1:2021 [27]
using in ate least 20–50 particles taken from SEM and TEM images at least 3 different spots. Results from PSD/LD
measurements are presented as an average plus stdev are based on 3 LD measurements.

GO Graphene Graphite
GO1 GO2 GO3 * Gr1 Gr2 Gr3 Gr4 Gr5 * Gft1 Gft2 Gft3 Gft4 *
25– 25– 53– 100–
Sieve fraction/µm <25 un-sieved N.A. <25
53 53 100 150
23.5 46.4 44.9 130.6
Average lateral size, 7.0 ± 15.9 28.3 49.4 52.8 ± 11.3 158.8
± ± 73.4 ± 40.4 ± ±
SEM ± stdev (µm) 2.8 ± 3.7 ± 0.5 ± 6.0 3.4 ± 2.1 ± 20.2
10.6 21.2 37.0 13.7
28.6 45.7 13.2 36.8 60.3 24.2 60.0 104.0 148.8
Average d(50) from 120.2 ± 7.6 ± 73.4 ±
± ± ± ± ± ± ± ± ±
LD ± stdev (µm) 0.032 0.028 0.100
0.010 0.077 0.018 0.043 0.060 0.099 0.028 0.056 0.006

Structural properties of the carbon materials were studied using powder XRD tech-
nique as presented in Figure 2b. Pristine graphite sample showed a strong and well-defined
peak appeared at 2θ = 26.6◦ , while this peak also found at the same position but with a
weaker and lower intensity in graphene parent sample. Upon the intercalation of oxygen
groups using strong oxidizing agents, a massive peak shift was detected from 2θ = 26.6◦ to
10.8◦ in GO samples, confirming an increased interlayer spacing between the graphene lay-
ers due to insertion of oxygen functional groups such as epoxide, hydroxyl and carboxylic
groups [22,31]. Similarly, all their respective counterpart materials exhibited the same XRD
pattern (Figure S4).
FTIR analysis of the carbon materials (Figure 2c) further corroborated the XRD results
with the characteristic transmittance bands for oxygen functional groups including C=O
(1720 cm−1 ), -OH (3000–3500 cm−1 ) and C-O-C (1228 cm−1 and 1048 cm−1 ) found in
GO. Nearly a flat line with no obvious peak was detected for both Gft and Gr, suggest-
ing no significant amount of oxygen functional groups was found in these two carbon
materials [22,32].
XPS analysis further substantiated the discussed characterization outcomes with the
elemental quantification performed on the parent graphene and its associated materials
determined from their survey scans. Based on the curve fitting analysis, relatively high
carbon content can be observed for Gft (94.2 atomic %) and Gr (97.7 atomic %) compared to
GO (68.1 atomic % C). As expected, GO has the highest oxygen content (31.9 atomic % O),
followed by Gft (5.2 atomic % O) and Gr (2.4 atomic % O).

3.2. Elucidating the Impact of Particle Size of GO, Graphene and Graphite on Their
TGA Characteristics
Prepared GO, graphene (Gr) and graphite (Gft) samples with different particle size
were subjected to thermal decomposition up to 1000 ◦ C in the air atmosphere to probe
their particle size dependence thermal characteristics. Representative TGA graphs are
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presented in Figure 3, showing TGA graphs on the top and their corresponding first
derivative thermogravimetry DTG graphs on the bottom with their respective Tmax values.
An example demonstrating the plot of TGA-DTG curves with the derivation of thermal
parameters can be found in Figure S5. These graphs representing the thermal pattern
of GO, Gr and Gft clearly showed that all these materials were completely burnt in the
air atmosphere before 1000 ◦ C, leaving no residue behind that suggests their high purity.
Subsequent DTG graphs generated from TGA curves demonstrated three distinguished
DTG peaks corresponding to three mass loss events (GO) as well as a typical DTG peak
that can be related to only a single mass loss step occurred during the thermal degradation
for both Gr and Gft.

Figure 2. (a) Raman spectra, (b) XRD diffractograms with a right inset showing comparative intensity of Gr and Gft,
(c) FTIR spectra and (d) XPS survey plots with an inset of atomic composition of parent GO, Gr and Gft materials.

The key mass loss events of GO can be explained based on their decomposition
temperatures: <100 ◦ C for water elimination, 100–360 ◦ C due to the removal of oxygen
functional groups and 360–1000 ◦ C can be linked to the oxidative pyrolysis of carbon
framework [33]. It is worth mentioning that the first and second DTG peaks, representing
the loss of water and oxygen functional groups events, did not vary significantly with
different sieved size of GO samples. Similar to the third mass loss step of GO, the only
DTG peak found in graphene and graphite samples can be ascribed to the combustion of
carbon in the air condition. These DTG peaks appeared to change noticeably when varied
size of carbonaceous materials were analyzed, which is the focus of our present study that
C 2021, 7, 41 9 of 12

will further unveil in the next sections. As depicted in the DTG graphs (bottom row of
Figure 3a–c), their carbon combustion temperature was distinctly marked in terms of the
temperature of maximum mass change rate (Tmax ) with GO experienced the earliest carbon
combustion (Tmax = 550–616 ◦ C), followed by graphene (Tmax = 650–713 ◦ C) and graphite
(Tmax = 840–950 ◦ C). The distinguished Tmax can be attributed to the maximum of the
external heat energy required to overcome the strong bonding within their carbon lattice
structure. The observed lower Tmax in GO indicated that less heat energy is required to
overcome weaker non-graphitic sp3 hybridized carbon with a high density of defects after
the rigorous oxidation reaction compared with graphene and graphite. GO also has high
level of oxygen groups, which is an additional reason for lower level of energy for their
decomposition. Graphene has higher Tmax because it needs larger amount of heat energy
to break down the sp2 hybridized carbon atoms ordered by covalent bonds in a hexagonal
carbon framework. Graphite, the most thermodynamically stable carbon materials studied
in this work, demands even more heat energy due to its strongest 3D carbon network,
consisting of a large number of graphene stacked layers held by additional van der Waals
forces [21]. From these studies, it is obvious that Tmax can be regarded as a key parameter
that can be used for their identification and specifically for detection of presence of GO and
graphite impurities in graphene materials as summarized in Table S2.

Figure 3. Plots of TGA (top row)-DTG (bottom row) for an array of carbonaceous materials with varied sizes: (a) GO,
(b) grapheme * and (c) graphite * samples, showing the Tmax values derived from their respective DTG peaks in the carbon
combustion region. * Inset illustrates closed-up image of rising Tmax values as particle size of GRMs increased. Plots of
Tmax values vs the median particle size, d(50)v , determined by PSD/LD technique of (d) GO, (e) Gr and (f) Gft samples.

The obtained Tmax values of GO, graphene and graphite were plotted as a function of
median particle size obtained from PSD/LD measurement and presented in Figure 3d–f.
As explicated in the previous section, the substantial rising Tmax trend visualized on the
three types of tested carbonaceous materials with GO series exhibited the lowest Tmax
range (550–616 ◦ C), followed by 650–713 ◦ C for Gr samples and Gft batches recorded the
C 2021, 7, 41 10 of 12

highest Tmax range (840–950 ◦ C) can be linked to their respective carbon building blocks
involved in the bonding and structural framework. Regarding the influence of particle
size, it was discovered that with the increase of the particle size, the Tmax representing
the carbon combustion region shifted to the right, resulting a higher Tmax values for all
the characterized materials. Taking GO as example, as the particle size increases from
28.6 µm, to 45.7 µm and 120.2 µm in GO 1–3, the Tmax values in the DTG plot of its carbon
combustion region (third mass loss step) in GO gradually shifted from 558.7 ◦ C to 579.7 ◦ C
to 615.7 ◦ C (Figure 3d). In the case of Gr samples, PSD analysis showed that the measured
particle size 7.6 µm, 13.2 µm, 36.8 µm, 60.3 µm and 73.4 µm can be well-correlated to their
growing Tmax values, 659.0 ◦ C, 677.7 ◦ C, 689.7 ◦ C, 702.8 ◦ C and 713.0 ◦ C, respectively
(Figure 3e). Similarly, as the particle size of tested graphite samples increased from 24.2 µm,
60.0 µm, 104.0 µm to 148.8 µm, an increasing of Tmax values of 841.3 ◦ C, 886.2 ◦ C, 922.2 ◦ C
and 948.3 ◦ C trend can be observed as evidenced in Figure 3f. A key message from this
study is that there is a significant difference in the Tmax value between graphene and its
key impurities including GO and graphite and their particle size do not overlap with the
Tmax value of graphene as presented in Figure 4. Hence, there is no potential error resulting
from this TGA-DTG method to identify these impurities in industrial graphene materials
regardless of their particle size.

Figure 4. Summary of TGA-DTG graphs for GO, graphene and graphite with different particle size
showing non-overlapped Tmax values and the ability of TGA-DTG method to distinguish GO and
graphitic impurities from graphene for their quality control.

The correlation analysis performed on Tmax vs particle size graphs (Figure 3d–f)
showed that high coefficients of determination (adjusted R2 values > 0.9) based on the
Tmax values in all the three samples as tabulated in Table S3. Regardless of the type of
carbon materials, this finding strongly suggests that the Tmax values derived from the
DTG peak in the carbon combustion region can be linearly correlated to the particle size
of the carbon materials studied. The observed steadily increasing linear trend can be
explained by the large surface area of these materials that needs more heat energy for their
thermal decomposition. As supported by W. Jiang et al. and M. Shtein et al., carbonaceous
C 2021, 7, 41 11 of 12

particles with smaller size possess higher amount of edge sites per mass unit, this means
that smaller carbon particles are more reactive and susceptible towards combustion process
compared to particles with larger size [14,19]. This also implies that carbon materials
with larger particle size tend to shift their Tmax to higher temperature because of slower
combustion kinetics in air, which is also evidenced in our studies [19]. Our comprehensive
evaluation over different types of carbonaceous materials clearly showed that particle size
of carbonaceous materials can be linearly correlated to the Tmax values derived from their
corresponding DTG peaks in the carbon combustion region, which is in good agreement
with the reported literature [14,19].

4. Conclusions
In summary, in this study, we presented the influence of particle size of GO, graphene
and graphite with the aim to establish correlation of key TGA-DTG thermal parameter
(Tmax ) that can be used for qualitative determination of bulk graphene powders and their
impurities such as graphite and GO particles. The Tmax values derived from the DTG
peak of the carbon combustion region exhibited a direct and linear relationship with the
particle size of the carbonaceous materials regardless of the type of carbonaceous materials
(graphene, GO and graphite) as confirmed by their respective high R-squared values
(R2 > 0.91) achieved in their linear regression analyses. A significant difference in the Tmax
value can be identified between graphene and its key impurities (GO and graphite) and
their particle size, where their Tmax values do not overlap with the Tmax value of graphene
that rules out the possibility to have erroneous results due to deviation from particle size
to identify these impurities in industrial graphene materials using the TGA-DTG approach.
This study shows the potential of TGA analysis to be used as a low-cost screening tool
for the quality control and characterization of manufactured graphene materials and their
products at an industrial scale, which has been overlooked previously.

Supplementary Materials: The following are available online at https://www.mdpi.com/article/10

.3390/c7020041/s1.
Author Contributions: Conceptualization, D.L., F.F. and P.L.Y.; Methodology, F.F. and P.L.Y.; Formal
analysis, F.F., P.L.Y. and R.U.K.; Investigation, F.F. and P.L.Y.; Writing—Original Draft Preparation,
F.F., P.L.Y. and D.L.; Writing—Review & Editing, D.L. and P.L.Y.; Resources, D.L.; Supervision, D.L.;
Project Administration, D.L.; Funding acquisition, D.L. All authors have read and agreed to the
published version of the manuscript.
Funding: This research was funded by the ARC Research Hub for Graphene Enabled Industry
Transformation (IH150100003).
Institutional Review Board Statement: Not applicable.
Data Availability Statement: All obtained Data are available at The University of Adelaide Data
Storage system.
Acknowledgments: The authors thank the Australian Microscopy and Microanalysis Research
Facility (AMMRF) for the facilities access and technical support of TEM (Ashley Slattery); and XPS
(Chris Bassell) at the Microscopy Australia Facilities (NCRIS scheme) situated at the University of
South Australia.
Conflicts of Interest: The authors declare no conflict of interests.

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