Carbon 174 (2021) 581e593

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Carbon
journal homepage: www.elsevier.com/locate/carbon

Research Article

High concentration graphene nanoplatelet dispersions in water

stabilized by graphene oxide
Sreemannarayana Mypati , Andrew Sellathurai , Marianna Kontopoulou ,
Aristides Docoslis , Dominik P.J. Barz *
Graphene Integrated Functional Technologies (GIFT), Department of Chemical Engineering, Queen’s University, Kingston, ON, K7L 3N6, Canada

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

Article history: The preparation of aqueous graphene nanoplatelet (GNP) dispersions is a challenging task due to their
Received 21 October 2020 tendency to agglomerate. In contrast, graphene oxide (GO), an oxidized form of GNP, has amphiphilic
Received in revised form characteristics which allow it to disperse in an aqueous milieu without the addition of a surfactant.
18 December 2020
Therefore, we utilize GO as a dispersing agent to prepare highly-concentrated aqueous GNP dispersions,
Accepted 23 December 2020
which can be used for various applications. The nature of the dispersed phase is investigated by various
Available online 29 December 2020
material characterization methods. Furthermore, we measure the zeta potentials of the dispersed phased
as well as the contact angles of dispersions on different substrates. The latter data are used in the
Keywords:
Graphene nanoplatelets
extended DerjaguineLandaueVerweyeOverbeek theory to gain insight into the interactions that
Graphene oxide determine dispersion stability. We find that the stability of such dispersions mainly depends on the pH
Dispersion stability value as well as the ratio of GO and GNP concentrations. The rheology of the dispersions is investigated
Rheology and different nematic phases are identified. Finally, highly-concentrated dispersions are used for printing
Liquid crystals of graphene films on a flexible substrate. After reduction of the minor GO fraction, the films have a high
Printing conductivity of more than 4500 S m
1.
© 2020 Elsevier Ltd. All rights reserved.

1. Introduction times, without the use of harmful organic solvents and/or

Graphene is an allotrope of carbon comprising of single layer sp2
hybridized carbon atoms that are arranged in a two-dimensional
(2D) hexagonal lattice [1,2]. This 2D structure results in unique
material properties, such as high surface area, electron mobility [3],
thermal conductivity [4], optical properties [5], and flexibility [6].
Few or multi layer graphene, also known as graphene nanoplatelets
(GNP), can be made from thermal or mechanical exfoliation of
graphite, cf. Refs. [7,8]. This approach offers better economical
competitiveness while maintaining product characteristics close to
single layer graphene. Consequently, GNP has a variety of promising
applications in energy storage devices [9,10], optical sensors [11],
and polymer nano-composites [12,13], just to name a few. However,
for implementation on an industrial scale, several other challenges
have to be overcome such as the formulation of highly-
concentrated dispersions which can be used for material printing.
Ideally, these dispersions should be stable over longer processing
* Corresponding author.
E-mail address: dominik.barz@queensu.ca (D.P.J. Barz).
dispersing agents that have to be removed after processing.
The addition of graphene to liquids has many potential tech-
nological applications. Examples include, but are not limited to,
functional fluids with enhanced thermal conductivity or lubricity
[14,15], polymer composites with improved mechanical and elec-
trical properties [16], graphene hydrogels for energy storage de-
vices [17e19], as well as highly-concentrated graphene inks for
printed electronics [20,21]. Different processes have different re-
quirements; therefore, various dispersions with a wide range of
solid concentrations and a variety of solvents must be formulated.
An overarching criterion is dispersion stability without any
noticeable aggregation over a desired duration. However, aromatic
carbon rings, as illustrated in Fig. S1 of the Supporting Information
(SI), make the graphene surface hydrophobic. Thus, GNP particles
are prone to agglomeration in polar solvents due to van der Waals
attraction and/or p-p stacking.
Stable GNP dispersions can be obtained in organic solvents
[22e24], or polar media like water through covalent and non-
covalent functionalization of graphene sheets [25,26]. Another
method is the addition of dispersing agents (surfactants), which are
often complex in nature [27e30]. All these strategies have

https://doi.org/10.1016/j.carbon.2020.12.068
0008-6223/© 2020 Elsevier Ltd. All rights reserved.
S. Mypati, A. Sellathurai, M. Kontopoulou et al.
considerable drawbacks. On the one hand, the processing of organic
solvents is potentially hazardous and harmful for the user and the
environment. On the other hand, surface functionalization and
surfactants can negatively impact the mechanical and electrical
properties of the product and have to be removed after processing.
Hence, stable aqueous GNP dispersions, formulated without com-
plex chemical reagents and/or processes, are highly desirable.
Unlike GNP, graphene oxide (GO) - the oxidized derivative of
graphene, is readily dispersible in water because of hydrophilic
oxygen groups located on the basal plane and the edges, cf.
Fig. S1 in the SI. A literature review reveals that GO sheets can be
dispersed over a wide range of pH values (2.5e10), concentra-
tions (as high as 25 mg ml
1) and ionic strength (up to 100 mM)
[31,32]. Furthermore, GO has amphiphilic characteristics like a
surfactant and, therefore, was used to disperse carbon nanotubes
in aqueous media [33e35]. Kazi et al. [36] and He et al. [37] also
employed GO as a dispersing agent in aqueous GNP dispersions;
however, only extremely low GNP concentrations
(0.1e0.8 mg ml
1) were formulated. Recently, Li et al. fabricated
free standing films as supercapacitor electrodes from mixtures of
GO and GNP in a ratio of 1:1 [38]. However, many processes, such
as coating, printing or the manufacturing of e-textiles require
high GNP concentrations (5 mg ml
1 to 50 mg ml
1) and low GO
concentrations to achieve significant thermal and electrical
conductivities [20,39,40].
Likewise, knowledge of the rheology is important for printing,
dispensing, or extruding processes as different viscosity ranges
(0.01e1000 Pa s) are required depending on the technology [41].
Thin films, fibers or hydrogels that are fabricated from low con-
centration dispersions generally consist of randomly ordered
sheets having a negative impact on the electrical, mechanical and
optical properties. At high solid concentrations, an ordering of the
sheets is observed, which is beneficial for many applications [42].
However, the rheological behavior of highly-concentrated dis-
persions is distinctly different compared to dispersions containing
low solid concentrations. When an anisotropic 2D material like
GO is dispersed in an isotropic solvent like water, liquid crystal
(LC) phases can form under suitable conditions [43]. Liquid crys-
tals are free-flowing materials which have an ordered structure
(in flow direction) similar to a crystalline solid [44]. Generally, GO
dispersions are considered as a lyotropic LC, meaning that the
properties of the LC depend on the concentration of amphiphilic
or anisotropic particles [44e46]. Generally, phases of GO disper-
sions can be categorized as isotropic liquids, nematic liquids as
well as arrested forms, such as glass or gels. The LC phases depend
on several factors like sheet aspect ratio, pH value, and total solids
concentration. For instance, Jalili et al. showed that at a constant
GO concentration of 2.5 mg ml
1, the order in the nematic phase
decreased with decreasing (lateral) sheet size and eventually
vanished below 700 nm [47]. Tkacz et al. demonstrated a pH-
dependent LC phase for two sheet sizes. For GO dispersions with
a pH value larger than the pKa value of carboxylic acid, the phases
for 300 nm and 550 nm size are isotropic and nematic, respec-
tively [48]. Kim et al. observed a nematic phase formation for a
sheet size of 700 nm and above a GO concentration of 7.5 mg ml
1
[49]. Hence, the remarkable rheological, optical and dielectric
properties of GO can be attributed to the existence of these phases
[44,50].
As mentioned above, there is some very limited work which
uses GO to stabilize very low concentrations of GNP. Such diluted
concentrations have limited relevance for technological applica-
tions. In this work, we formulate and thoroughly characterize
novel highly-concentrated aqueous GNP dispersions that can be
used for a many processes including but not limited to printing,
coating, graphene hydrogel synthesis, or fluid functionalization.
582
Carbon 174 (2021) 581e593
We use relatively small quantities of GO as a dispersant because it
has the advantage that, unlike other surfactants, its reduced form
has similar properties as GNP. Another original contribution of
this work is the application of the extended-Derjaguin-Landau-
Verwey-Overbeek (XDLVO) theory to obtain insights into disper-
sion stability. Likewise, there is no study which investigates the
rheology and LC phases of GO/GNP dispersions which is our
motivation to pursue it. This article continues with a section on
the experimental materials and methods. Then, we briefly review
some theory of colloidal stability before we present the experi-
mental results and discussion. As an application, we print films of
the GO/GNP dispersions on a flexible substrate and demonstrate
their excellent electrical conductivity. Finally, the article is sum-
marized with some concluding remarks.
2. Experimental methods and materials
In this section, we specify the materials and the characterization
methods used to characterize the dispersions and the printed films.
2.1. Materials and chemicals
The GO is purchased from a commercial manufacturer (Gra-
phenea Inc., Cambridge, MA, USA) as 4 mg ml
1 aqueous
surfactant-free (stock) solution. The GNP is prepared by thermo-
mechanical exfoliation (TME) of graphite flakes (
325 mesh, pu-
rity >99%, Sigma-Aldrich Canada Company, Oakville, ON, Canada)
as described in Ref. [51]. The TME process is conducted in a Ther-
moFisher PolyLab QC Unit connected to an electrically heated
Haake Rheomix 600 QC intensive batch mixer (ThermoFisher Sci-
entific, Waltham, MA, USA). Hydrochloric acid (37 wt% in water)
and sodium hydroxide pellets (Reagent grade, Sigma-Aldrich Can-
ada Company, Oakville, ON, Canada) are used to adjust the pH value
of the dispersions. Deionized (DI) water (RiOs-DI®3, EMD Milipore
Corporation, MA, USA) with a resistivity of 18 MU cm is used
throughout this work.
2.2. Preparation of compound dispersions
For the preparation of the dispersions, the GO stock solution is
diluted to obtain the desired concentrations. The diluted stock so-
lution is then sonicated (FB11203, Fisherbrand®, Toronto, ON,
Canada) in a water bath for 1 h. During the sonication, GNP is slowly
added to the GO dispersion up to the desired weight percentage. All
dispersions are prepared in scintillation glass vials with a volume of
20 ml. The stability of the dispersion is evaluated by visual in-
spection of the vials; images are taken immediately after sonicat-
ion, and after 3, 12 and 24 h.
2.3. Characterization methods
The pH of the dispersions is measured with a pH electrode
(Fisherbrand™ accumet™ AP125, Ottawa, ON, Canada). The con-
ductivity of the dispersions is measured with a conductivity probe
(Sevenmulti™, Mettler Toledo, ON, Canada). The thickness of the
GO, GNP and GO/GNP sheets is measured using atomic force mi-
croscopy (AFM) (MFP3D, Asylum Research, Santa Barbara, CA). The
lateral dimensions are measured by scanning electron microscopy
(SEM) (FEI-MLA Quanta 650 FEG-ESEM, ThermoFisher Scientific,
Hillsoboro, Oregon, USA). The samples for SEM and AFM are pre-
pared by spray coating and air drying of a 0.05 mg ml
1 dispersion
in ethanol on a silicon wafer. The functional groups and carbon to
oxygen ratio of the GO, GNP and GO/GNP powdered samples are
quantified using X-ray photoelectron spectroscopy (XPS) mea-
surements (AXIS Supra, Kratos Analytical Ltd., Manchester, UK). The
S. Mypati, A. Sellathurai, M. Kontopoulou et al.
XPS survey scan analysis is carried out with an analysis area of
300  700 mm and a pass energy of 160 eV, while the high-
resolution C1s scans are carried out with a pass energy of 20 eV.
X-ray diffraction (XRD) and Raman spectroscopy are two widely
used non-destructive techniques to provide insights into the crys-
tallographic structure, inter-layer distance and the structural de-
fects of graphene-based materials [52,53]. The crystallinity and d-
spacing investigations are performed with a XRD instrument
(XSPert Pro, Philips Analytical B.V., Almelo, The Netherlands) using
Co Ka radiation. The diffraction patterns are analyzed using the
X’Pert Highscore Pro software. The results are converted to Cu Ka
radiation for the sake of better comparison with literature data. To
obtain insights into the structural defects and disorder of the
sheets, Raman spectra are measured with a Raman spectrometer
(LabRAM, HORIBA Scientific, NJ, USA) equipped with a 632.8 nm
He/Ne laser and an Olympus BX-41 microscope system. All spectra
are collected over a 20 s exposure time and repeated for 3 times. To
investigate the various functional groups on the surface of GO and
GNP, Fourier transform infrared (FTIR) spectroscopy (IFS85, Bruker
Scientific LLC, MA, USA) is employed in KBr mode at a resolution of
about 1 cm
1. For conducting the XRD, FTIR and Raman measure-
ments, powder samples are prepared by drying the aqueous dis-
persions at 40 C in an oven.
The zeta potential of the dispersed sheets at 25  C is measured
based on electrophoretic light scattering using a Zetasizer (Nano ZS,
Malvern, U.K.). The rheological characterization of the dispersions
is conducted with a rheometer (Twindrive™ MCR702, Anton Paar
Canada Inc., QC, Canada). Steady shear measurements are recorded
using a concentric cylinder geometry (cup diameter: 18.07 mm, bob
diameter: 16.66 mm, bob length: 24.92 mm) at increasing shear
rates from 0.01 to 10 s
1. Contact angles are measured using the
sessile drop method with a digital goniometer (OCA 15 EC, Data-
Physics Instruments GmbH, Filderstadt, Germany). XDVLO theory
calculations are performed with MATLAB (Version: R2018a, Math-
work, Inc, Natick, MA, USA). The statistical analysis of the disper-
sion stability data is conducted using Minitab (Version: Minitab 17,
Minitab, LLC, PA, USA).
2.4. Printing of dispersions
Printing of the dispersions is performed with a material
dispenser which consists of an automated XYZ stage (DPNT0549,
Precision Valve Automation (PVA), Cohoes, NY, USA), equipped
with a micro dispensing valve FCM 100 [54]. The experiments are
conducted by dispensing the dispersions through a 250 mm (inner
diameter) dispensing nozzle onto a flexible transparent substrate
(HP LaserJet Transparency Films, HP. Inc. ON, Canada). The thick-
ness of the printed film is obtained using a surface profiler con-
sisting of a digital microscope and a dynamic range sensor laser
with a wavelength of 650 nm (MVP-400, DRS 500, Optical Gaging
Products (OGP), Rochester NY, USA). The sheet resistance of the
printed films is measured based on the van der Pauw method [55]
using a four-point probe station (S-1160, Signatone Corporation,
Gilroy, CA, USA).
3. Theory
In this section, we discuss the interactions between GO and GNP
sheets dispersed in water and briefly review the XDVLO theory.
3.1. Sheet interactions
When 2D materials like GNP or GO are dispersed in an aqueous
electrolyte, the p-conjugated carbon atoms can form different non-
covalent bonds and attract each other, or, due to electrical charges
583
Carbon 174 (2021) 581e593
present on the surface, they repel each other. The non-covalent
bonds include p-p, cation-p and anion-p interactions with the
poly-aromatic compounds or graphite-based materials [25]. When
GO and GNP sheets are jointly dispersed in an aqueous media, the
following sheet interactions are possible: (i) GO - GO, (ii) GNP - GNP
and (iii) GO - GNP. These interactions depend on the pH value, ratio
of concentrations, as well as the lateral dimensions of the sheets
[56]. Furthermore, the stability of a p-p bond, or of a repulsion,
depends on the sheet orientation. The possible orientations
include, but are not limited to, face-face centered, face-face parallel
offset as well as edge to face T-shaped interactions. The literature
concerned with aromatic compounds shows that the parallel offset
interactions are more stable compared to face-face centered or T-
shaped interactions [57].
Fig. 1a) and b) show the electrostatic repulsion between two
GO sheets and the p-p attraction between two GNP sheets in a
parallel offset orientation, respectively. When a GO and a GNP
sheet interact, the sp2 hybridized carbons of the GO’s basal plane
attract the GNP through p-p interaction. In this regard, Fig. 1c)
illustrates the face-face centered and parallel offset interaction
while Fig. 1d) shows a T-shaped interaction. The p-p interaction
triggers the adsorption of the GO sheet on the GNP sheet surface
and they form a ‘‘compound sheet’’. Therefore, we name the dis-
persions accordingly as compound (GO/GNP) dispersions. Here,
we assume that interactions of compound sheets can be described
as linear superposition of a GO and GNP sheet. Such a compound
sheet has an (overall) negative charge from the adsorbed GO,
which counteracts the influence of the van der Waals attraction as
indicated in Fig. 1e) [37]. In addition, the exfoliation of GNP gen-
erates defects on the sheet edges, consisting of unfilled carbons
(cf. Fig. S1 in the SI). Such active edge carbons can act as favorable
sites for oxidation if they come in contact with atmospheric ox-
ygen, inducing the formation of hydrophilic groups on the edges
[58]. These groups can repel the oxygen functional groups of
either a GO or a compound sheet.
3.2. Extended DLVO theory
The colloidal stability of GO sheets were already studied based
on the DLVO theory [59]. In the classical DLVO theory, the total
interaction energy between two infinite surfaces in contact with a
liquid is estimated by the sum of the attractive van der Waals and
the repulsive electrostatic energies. In addition, van Oss et al.
proposed in the XDVLO theory the addition of the Lewis acid-base
(polar) interactions for high energy surfaces in contact with
aqueous media [60]. We employ the XDVLO theory to gain insight
into the stability of a compound dispersion. Hence, correlations are
needed to calculate the van der Waals (vdW) and the electrostatic
double layer (EL) interaction energies, as well as the Lewis acid-
base (AB) interactions.
First, we calculate the van der Waals interaction energy between
two parallel, thin and infinite GO and GNP sheets (indexed i ¼ 1, 2).
Here, we consider that all the possible sheet interactions, as already
mentioned in the previous section, can be linearly superimposed.
Thus, the van der Waals attraction energy per unit surface area can
be calculated according to Refs. [59,61].
!
A 1 1 1 1
WvdW ¼
þ

; (1)
12p l2 ðl þ t1 þ t2 Þ2 ðl þ t1 Þ2 ðl þ t2 Þ2
where t is the thickness of a sheet and l is the separation distance.
The Hamaker constant can be approximated as
S. Mypati, A. Sellathurai, M. Kontopoulou et al. Carbon 174 (2021) 581e593

Fig. 1. Possible sheet interactions in the compound (GO/GNP) dispersion: a) GO-GO electrostatic repulsion; b) GNP - GNP p-p interactions; c) GO - GNP face-face centered and offset
p-p interactions; d) GO - GNP edge to face interaction; and e) Electrostatic repulsion and p-p interactions between compound sheets. (A colour version of this figure can be viewed
online.)

2  2   3    1
2
3hne 4 n1
n23 n22
n23 2 exp eJ0
þ 13
1
Az pffiffiffi         5 6k T 3 kB T
8 2 n2 þ n2 1=2 n2 þ n2 1=2 n2 þ n2 1=2 þ n2 þ n2 1=2 Jeff ¼ B    1 (5)
1 3 2 3 1 3 2 3 e 2
2 exp eJ0 1
(2) 3 kB T
þ 3 þ1

Here, h is the Planck constant and n1 ¼ 1.88 [62], n2 ¼ 2.37 [63], and The surface potential is not readily available since it cannot be
n3 ¼ 1.33 are the refractive indices in the visible regime of GO, GNP directly or indirectly measured. Nevertheless, the zeta potential,
and water, respectively. The main absorption frequency in the UV which is the electrical potential located at the interface of Stern and
pffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi diffuse double layer, can be inferred from measurement of elec-
region ne ¼ n1 3=ðn2 þ 2Þ is calculated based on the absorption
frequency of a Bohr atom n1 ¼ 3.3 1015 s
1 and the average trokinetic phenomena such as electrophoresis [65,66] or streaming
refractive index n ¼ 2:12 of the GO and GNP sheets dispersed in an potential/current [67]. The respective equations for the (implicit)
aqueous medium. calculation of the surface potential from the measured zeta po-
Next, the electrostatic double layer interaction energy is calcu- tential are given in the SI.
lated. Here, we follow the methodology outlined in Ref. [64]. Ac- Lastly, the acid-base interaction energy is determined according
cording to the linear superposition approximation, the area specific to Ref. [68] as
electrostatic interaction energy between the two sheets can be
written as  
l
l
0
WAB ¼ WAB ,exp 0 (6)
l
 
εr ε0
l
WEL ðlÞ ¼ 2 Jeff ;1 Jeff ;2 exp (3) Where, l0 ¼ 0:157 nm represents the minimum separation distance
lD lD between the sheets [68], l is the correlation length between solvent
0 is the free en-
Here, εr is the relative dielectric constant of the liquid, ε0 is the molecules which is 0.6 nm for water [69], and WAB
qffiffiffiffiffiffiffiffiffiffi
dielectric permittivity in a vacuum and lD ¼ εε0 RT
is the Debye ergy component at l0 . We calculate this parameter based on the van
2F 2 I
Oss-Chaudhury-Good model [70] according to
length. The calculation of lD requires the universal gas constant R,
solvent temperature T, Faraday constant F and the ionic strength I ¼
1
P 2 qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 þ 
 qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi
 þ 

2 i zi ci which summarizes the influence of the concentration ci 0
¼
2 g1
gþ g1
g
g2
gþ g2
g

WAB 3 3 þ 3 3
and valency zi of all ionic species in the solution. The effective qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi


potential Jeff depends on the nature of the electrolytes; in the gþ þ

1
g2 g1
g
2 (7)
experiments, we use a 1-1 (NaOH) and a 2-1 (H2 SO4 ) electrolyte.
For an arbitrary surface potential J0 , the effective potential in a Here g1 ; g2 ; and g3 are the respective surface energies for GO,
symmetric z-z electrolyte can be written as GNP, and water, where "þ" denotes the electron acceptor and "-"
the electron donor constituents. The nonpolar and polar surface
energy components of GO and GNP are given in Table S1 in the SI.
 
4kB T z eJ The surface energy components of the solvent ewater at different
Jeff ¼ tanh i 0 (4)
zi e 4kB T pH valuese are determined by the contact angle measurements
(given in Fig. S2 in the SI) on three substrates (polytetrafluoro-
where e denotes the elementary charge. For an asymmetric 2-1 ethylene, glass, and silica wafer) with known surface energy com-
electrolyte, it is ponents. We use the correlation according to Ref. [69].
584
S. Mypati, A. Sellathurai, M. Kontopoulou et al.
qffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffi qffiffiffiffiffiffiffiffiffiffiffiffi 
ð1 þ cosqÞgL ¼ 2 gLWS g3
LW þ gþ S g3 þ

g
S g3
þ
(8)
where the subscripts S and superscript LW denote the solid sub-
strate and nonpolar Lifshitz-van der Waals components, respec-
tively. The resulting values are given in Table S1 in the SI.
4. Results and discussion
In this section, we first characterize the utilized GO and GNP
sheets using various analytical methods. Then, we study the sta-
bility of the compound dispersions by experiment and theory.
Finally, we investigate the rheology of the dispersions and, to
demonstrate an application, print a conductive film on a flexible
substrate.
4.1. Characterization of dispersing agent and dispersed phase
We first investigate the stability of pure aqueous GO dispersions
and then the stability of pure aqueous GNP dispersions. It turns out
that GO dispersions in a concentration range of 0.25e15 mg ml
1
are stable for at least 24 h. In contrast, the GNP dispersions
aggregate and settle relatively quickly, even at a very low concen-
tration of 0.05 mg ml
1. Fig. 2a) shows the photographs of a
0.5 mg ml
1 GO dispersion and a 0.05 mg ml
1 GNP dispersion. The
GO is well dispersed due to the presence of the oxygen functional
groups on the sheet surface and edges which induce electrostatic
repulsion. The GNP sheets aggregate due to the van der Waals
attraction and p-p interaction [22,37]; we observe the sedimen-
tation of the larger aggregates.
The thickness, sheet size and inter layer spacing of the sheets
can be determined by SEM, AFM and XRD measurements. The SEM
images and the sheet size distribution histograms of the GO and
GNP are shown in Figs. S3a) and b) of the SI. The GO sheets have
irregular shape and the majority of the sheets have a characteristic
Fig. 2. Characterization of a GO and a GNP dispersion at respective concentrations of 0.5 mg ml
1 and 0.05 mg ml
1: a) Digital images; AFM images with line profiles of b) GO and c)
GNP; d) Powder X-ray diffraction patterns; e) Raman spectra f) FTIR spectra. (A colour version of this figure can be viewed online.)
585
Carbon 174 (2021) 581e593
lateral size between 200 and 600 nm. The GNP flakes have also an
irregular shape compared and the vast majority has a lateral
dimension between 250 nm and 750 nm. Fig. 2b) and c) show the
AFM images and line profiles of air-dried GO and GNP dispersions
coated on a silicon wafer, respectively. The GO profile indicates the
presence of few-layers sheets, with the majority of sheets having a
thickness of around 2 nm. The GNP profile shows a thickness of
around 2.5 nm. Fig. 2d) displays the XRD spectra of the GNP and GO
samples. The GNP diffraction pattern shows a strong diffraction
peak at 2q ¼ 26.4 . This is a characteristic of a crystalline graphite
(002) plane with an inter layer spacing of 0.34 nm [71]. In the GO
diffraction pattern, the (002) plane is located at 2q ¼ 10.69 , which
corresponds to an inter layer spacing of 0.84 nm. The increase in
inter layer spacing is due to the presence of the oxygen functional
groups at edges and surface. From the AFM and XRD information,
we calculate the number of stacked layers following the procedure
in Ref. [72]. We arrive in around 1e2 and 5e6 layers for a GO and
GNP sheet, respectively.
The quality of GO and GNP sheets can be evaluated by the
Raman spectra given in Fig. 2e). In a typical spectrum of carbon
based materials, we can observe the G band (1577 cm
1) caused by
the in-plane vibration of the sp2 C]C bonds. The D (1335 cm
1) and
D (1610 cm
1) defect induced bands are observed due to the out of
plane ring breathing of sp2 carbons and the edge defects from the
exfoliation [73]. The double resonant 2D band (2678 cm
1) is
characteristic to graphene; its shape and intensity can be used to
determine layer thickness. Here, it is around 4e5 layers for GNP
deduced from the deconvolution of the 2D band. The result is very
close to the AFM/XRD results. The calculated ID/IG ratios of GO and
GNP are 1.05 and 0.38, respectively. The high intensity ratio of D
and G bands (ID/IG) reveal large quantity of defects in the GO due to
the oxygen functional groups on its surface.
The GO and GNP samples are also analyzed based on the FTIR
spectra given in Fig. 2f). The GO spectrum reveals the presence of
various oxygen functional groups. The characteristic absorption
S. Mypati, A. Sellathurai, M. Kontopoulou et al.
bands appeared at 3432, 1721, 1630, 1380, 1153, and 1070 cm
1
which correspond to the stretching vibrations of the OeH bond
from phenolic or carboxylic groups, C]O stretching of carboxylic
group, C]O stretching of carbonyl groups, OeH deformation, CeO
stretching of epoxy groups and CeO stretching of alkoxy groups,
respectively [31]. In contrast, only one sharp band at 1576 cm
1 is
observed in the GNP spectrum. It is related to the C]C sp2 hy-
bridized carbons and indicates that the GNP has only a negligible
amount of oxygen surface groups. Thus, the defects observed in the
Raman spectra are likely related to the edges. Furthermore, the
powdered samples are analyzed using XPS measurements; results
are given in Fig. S4 in the SI. The GO survey spectrum shows a
carbon to oxygen C/O ratio of 2.08 for the GO. The high resolution
C1s spectrum reveals the presence of various functional groups
consisting of mainly eOH and eO. The GNP features a C/O ratio of
20.6 with mainly eOH and eO functional groups.
4.2. Stability of the compound dispersions
To investigate the stability of the compound dispersions, we
prepare 16 samples with varying concentrations of GO and GNP.
Their composition along with selected properties are shown in
Table S2 of the SI. The sheet size and thickness of the compound
sheets are provided in SI. The SEM and AFM data reveal a thickness
of around 4 nm and lateral dimension of the sheets show a wide
range with the majority larger than 800 nm. The average lateral
dimension of the compound sheets is around 1500 nm. The thick-
ness of the compound sheets corresponds more or less to the
combined thickness of a GO and a GNP sheet. This is an indication
for the adsorption of GO onto GNP. Digital images of the dispersions
are taken at 0, 3, 12 and 24 h to evaluate the stability. Fig. 3a) shows
nine different samples after 24 h. First of all, we cannot find any
indication that the compound sheets separate because no yellowish
GO layer is observed. This strong adsorption can be explained by
the strong p-p interaction of the p-conjugated sp2 hybridized
carbons present for both GO and GNP. We choose two sets of air
dried compound dispersions and characterize them with Raman
spectroscopy and XRD. Fig. S5a) in the SI shows the results of the
Raman spectroscopy. These results indicate that the compound
sheets at higher concentrations of GNP have more layers than at
lower GNP concentrations, despite the constant ratio of GO to GNP.
Fig. 3. a) Digital images of aqueous compound dispersions at various concentrations after 24 h; b) Contour map of the (transient) dispersion stability as a function of the GO and
GNP concentrations (square dots represent the experimental value). (A colour version of this figure can be viewed online.)
586
Carbon 174 (2021) 581e593
It is possible that GNP/GO/GNP sheets are formed since the distance
between sheets decreases at higher solid concentrations. Further-
more, the XRD patterns, given in Fig. S5b) and Fig. S6 in the SI, show
the (001) and (002) peaks corresponding to GO sheet and crystal-
line graphite plane, respectively. We also observe a minor shift in
the (002) peak towards lower diffraction angles for all compound
samples. This increase in inter-layer spacing might be attributed to
the expansion of layers due to the absorption of water in the
aqueous dispersions [74].
Fig. 3a) also reveals that for constant GO to GNP ratio and
increasing GNP concentration, the duration of dispersion stability
increases. This trend is observed for a constant GNP concentration
and increasing GO to GNP ratio as well. The dispersions prepared
with a GO to GNP ratio of 0.15 (S3, S6, S9) are completely stable over
24 h. However, dispersions are also stable when the GO to GNP ratio
is 0.1 and the GNP concentration is above 10 mg ml
1 . We prepare
a contour plot for time-dependent stability as a function of the GO
and GNP concentration by employing a regression analysis. The
resulting 2nd-order polynomial has a coefficient of determination
of R2 ¼ 0.95 and is given in the SI. This equation can be utilized to
predict the stability duration with a good accuracy in order to
determine the maximum processing time. Fig. 3b) shows a stability
map based on the regression where the experimental values are
plotted as square dots. We realize the strong influence of the GO
concentration. To formulate a 5 mg ml
1 GNP dispersion which is
stable for at least 20 h, around 1.3 mg ml
1 of GO is required. If the
GNP concentration is 25 mg ml
1, only around 1.8 mg ml
1 of GO
needs to be added. As a rule of thumb, we can say that the GO to
GNP ratio should be always higher than 0.1 to formulate stable
compound dispersions. However, it should noted that the stability
depends on the surface energy of the GO stemming from the
functional groups. The C/O ratio, which depends on manufacturing
process, is therefore an important parameter of the dispersion
stability. As mentioned above, the C/O ratio of the GO and GNP in
this work is 2.08 and 20.6, respectively. We also perform XPS
analysis of the GO/GNP sample 7; results are given in Fig. S7 of the
SI. It turns out the C/O ratio of the compound sheet corresponds to
7.9. This value is in between the GO and GNP and indicates
increased presence of functional groups on a compound sheet
compared to pure GNP.
S. Mypati, A. Sellathurai, M. Kontopoulou et al.
4.2.1. XDVLO interactions
To acquire data for the electrostatic part of the XDVLO in-
teractions, we measure the zeta potentials of dispersions consisting
of 0.25 mg ml
1 GO and varying GNP concentrations ranging from
0 to 1.25 mg ml
1. Furthermore, we vary the pH value of the
samples and measurements are performed at the intrinsic pH value
(pH z 4.7) as well as in an acidic (pH ¼ 1.9) and an alkaline
(pH ¼ 9.5) milieu. Fig. 4a) shows the results of the zeta potential
measurements. For all GNP concentrations, the magnitude of the
zeta potential increases with increasing pH value. This increase is
related to the de-protonation of the carboxylic groups on the GO
surface in an alkaline milieu. The influence of the GNP concentra-
tion is, given the standard deviations of the experiments, not very
pronounced. This verifies that the surface charge of a compound
sheet mainly arises from the (adsorbed) GO. We use the results of
the zeta potential measurements to compute the respective surface
potentials as given in the SI. We also need the ionic strength and the
Debye length for the XDVLO interactions. We compute them solely
based on the pH value of the dispersions since no other electrolytes
are added. The parameters are given in Table S3 in the SI.
Fig. 4b) shows the total XDVLO interaction energy of dispersions
with 0.25 mg ml
1 GO and varying GNP content at their intrinsic pH
value. We observe that all dispersions have a positive interaction
energy and, therefore, are stable over a wide range of distances. The
adsorption of GO on the GNP surfaces results in an overall
negatively-charged compound sheet. This electrical charge de-
creases the van der Waals attraction between the GNP surfaces of
the compounds and contributes to the dispersion stability. The
minor energy increase for the higher GNP concentration is related
to the minor increase in zeta potential, as previously discussed, and
also to the slight difference in the intrinsic pH values. In Fig. 4c), we
compare the XDVLO interaction energies for dispersions with
Fig. 4. a) Zeta potential vs pH value at varying concentrations of GNP and a constant GO concentration; Interaction energy vs the separation distance: b) XDVLO interactions at
varying GNP concentration and intrinsic pH value; c) XDVLO interactions at constant GO and GNP concentrations but varying pH; d) Comparison of XDVLO and DLVO interactions at
constant GO and GNP concentrations and pH ¼ 1.9. The inset shows a magnification to highlight the secondary minima. (A colour version of this figure can be viewed online.)
587
Carbon 174 (2021) 581e593
0.25 mg ml
1 GO and 1.25 mg ml
1 GNP but different pH values.
The alkaline dispersion at pH ¼ 9.5 features a much larger energy
barrier compared to the dispersion in an acidic milieu. One the one
hand, we have highest surface (zeta) potential at high pH values
which is responsible for strong electrostatic repulsion. On the other
hand, we observe that the width of the (positive) energy barriers
are proportional to the Debye length. At acidic pH, the ionic
strength is high which diminishes the screening (Debye) length of
the electrostatic interactions and, thus, facilitates agglomeration of
the sheets. To investigate the effect of translational and rotational
diffusion on the stability of the dispersions, the interaction energy
between compound sheets are calculated in thermal energy units
kB T. For the cases of two compound sheets interacting face-to-face
(Fig. 1c)), or edge-to-face (Fig. 1d)) at room temperature, the
repulsion barriers are calculated to be on the order of magnitude of
103 kB T and 10 kB T, respectively. That is, they are significantly
higher than the sheet’s thermal energy. The thermal energy cal-
culations are performed by multiplying the area specific repulsion
energy barrier (J m
2) of Fig. 4b) by the surface area of interaction
between two sheets. The latter are approximated as square-shaped
objects with an edge of 700 nm and thickness of 5 nm.
To infer the influence of acid-base (polar) interactions on the
stability, we compare the XDVLO and DLVO interaction energies in
Fig. 4d) for a pH value of 1.9. We also provide the single van der
Waals and Lewis acid-base interaction energies for the sake of an
improved understanding. We notice that both curves feature a
similar shape but the DLVO plot has a much larger energy barrier
than the XDVLO plot. This can be explained when we inspect the
acid-base and van der Waals interactions. Below a separation dis-
tance of roughly 10 nm, they become considerably negative and
diminish the positive electrostatic interactions. The physicochem-
ical mechanism behind this is the increase in the number of
S. Mypati, A. Sellathurai, M. Kontopoulou et al.
hydrogen bonds due to the protonation of carboxylate to carboxylic
groups, which also lowers the surface charge and contributes to the
reduced stability in an acidic milieu. Furthermore, we observe that
XDVLO and DLVO interactions feature a secondary minima, as
demonstrated in the inset of Fig. 4d). This feature has important
consequences because shaking the dispersion can break the ag-
gregates and therefore re-disperse a settled dispersion [75].
To summarize, the theoretical considerations from the XDVLO
theory show that the electrostatic repulsion overcomes the
attraction of the van der Waals and the acid-base interactions.
However, the electrostatic interactions depend strongly on the pH
value of the solution and the sheets tend to agglomerate in an acidic
milieu. We apply this knowledge in a limited experiment. We use
sample S3, which is stable at an intrinsic pH value of 3.62, and
lower the pH value to 2. As shown Fig. S8a) in the SI, the dispersion
becomes unstable in the acidic milieu. Likewise, sample S2 is un-
stable at an intrinsic pH of 3.77 and becomes stable when the pH is
increased to 10 as shown in Fig. S8b). It should be noted that the
XDVLO calculations presented herein are deemed sufficient to
provide a semi-quantitative explanation of the observed phenom-
ena. Sheet-Sheet interactions can be predicted with higher accu-
racy by employing more sophisticated approaches, such as
excluded volume potential calculations and considering the dis-
tance of closest approach between composite sheets [76e78]. Such
calculations, however, are non-trivial, especially for irregularly
shaped objects, and require the use of methods of statistical me-
chanics and intense computational effort that are outside the scope
of the present work.
4.3. Rheology of the compound dispersions
In practical applications, such as printing, dispensing or spray
coating, external stresses act on the dispersions changing their
rheology and may make them unsuitable for the process. There is a
collection of literature which contributes towards the under-
standing of the rheology of pure GO dispersions having concen-
trations up to 40 mg ml
1 [43,44,48,50]. The orientational
behaviour of GO domains at low shear rates showed a twist-
tumbling orientation and at high shear rates, the GO domains
were disrupted to smaller domains and achieved a more aligned
orientation [79]. A similar phenomenon was also observed in rod-
like liquid crystalline polymers (LCPs) [80]. In our study, we
expand this knowledge and investigate the rheology of the
Fig. 5. a) Viscosity vs shear rate of aqueous compound dispersions with varying total solid concentration and GO to GNP ratio (in brackets). Symbols are experimental data while
lines are results from regression to eq. (9); b) Viscosity at a shear rate of 0.01 s
1 as a function of GO and GNP concentration. Square symbol represent experimental data. (A colour
version of this figure can be viewed online.)
588
Carbon 174 (2021) 581e593
compound dispersions having high GNP and low GO concentra-
tions by measuring the steady-shear flow behavior. Fig. 5a) shows
the viscosity of compound dispersions with various total solid
concentrations and GO to GNP ratios as a function of the shear rate.
LCPs typically display three distinct regions: A shear-thinning re-
gion at very low shear rates, followed by a plateau region, and a
second shear thinning region at high shear rates [80]. In the present
case, the plateau and second shear thinning regions are evident for
all compositions. The shear rate dependence is attributed to the
orientation of the sheets. At lower shear rates, the sheets are rather
randomly-distributed. At higher shear rates, the sheets align in the
applied shear direction [79e81]. A more detailed inspection of
Fig. 5a) reveals that there is no simple correlation between viscosity
at a given shear rate and the total solid concentration. For example,
the dispersions with total solid concentrations of 5.75 mg ml
1 and
10.5 mg ml
1 have very similar viscosities. In contrast, the disper-
sions with 10.75 mg ml
1 and 11 mg ml
1 solid content have one
order of magnitude higher viscosity than the 10.5 mg ml
1
dispersion. It is obvious that there is a rather complex influence of
the composition. It is assumed that the GO in the compound dis-
persions form a larger 3D network in water via hydrogen bonds
which leads to an increase of the viscosity. A similar behavior is
observed for pure GO dispersions [50,82].
We analyze the rheological data at a shear rate of 0.01 s
1 by
performing a 4th-order polynomial regression, given in the SI, to
obtain a correlation between viscosity and concentrations. We
arrive in an excellent R2 value of 0.98. The regression can be used to
obtain the viscosity at a given concentration of GO and GNP in order
to choose suitable parameters for the processing of the compound
dispersions. Analysis of the coefficients confirms that there is a
higher influence of the GO concentration compared to the GNP
concentration on the viscosity. Fig. 5b) shows a contour plot of the
viscosity as a function of the GO and GNP concentrations based on
the regression. The complex influence of the composition on the
viscosity, as well as the dominant influence of the GO content, is
obvious. On a simplified level, we can say that even dispersions
with a very high total solid concentration have relatively low vis-
cosities as long as the GO content is below around 1 mg ml
1. The
viscosity increases significantly with further addition of GO as we
demonstrate in Fig. S9 in the SI.
4.3.1. Identification of the liquid crystal phases
The concentration, sheet size (aspect ratio) and solvent pH value
S. Mypati, A. Sellathurai, M. Kontopoulou et al.
influence not only the nature of the dispersion, but also the phase
behaviour and the formation of LC phases. In our study, the (stock)
ð1
nÞ
GO dispersions, having a 4 mg ml
1 concentration, are first soni-
cated for 1 h. Subsequent AFM and SEM measurements reveal that
the majority of these GO sheets have a lateral size between 200 and
600 nm. Because of this rather small sheet size, a LC phase for-
mation at the intrinsic pH value is unlikely [43,49]. Further SEM and
AFM analysis show that the vast majority of the GNP flakes have a
lateral size between 250 and 750 nm. As mentioned above, in our
work compound sheets are formed due to the adsorption of GO on
the GNP through p-p stacking. As can be seen in Fig. S7 in the SI, the
compound sheets are typically larger than a single GO or GNP sheet.
The average lateral sheet size of a compound sheet is around
1400 nm and we can observe LC phases in respective dispersions
depending on the total solid concentration. Fig. 6 illustrates the
three different scenarios, depending on the composition, that are
possible when an isotropic GO solution is mixed with an unstable
GNP dispersion: (i) Sedimentation of the compound sheets. (ii) The
dispersion is stabilized without (isotropic) structural ordering of
the sheets. (iii) The dispersion is stabilized with (nematic) struc-
tural ordering of the sheets. Dispersions with structural ordering
are beneficial for many applications. For instance, a low viscosity
nematic dispersions can be used for spray coating or printing ap-
plications while a highly-viscous nematic liquid or gel can be used
for wet spinning to form graphene fibers or hydrogels. The pro-
duced fibers or films can achieve high mechanical strength and
electrical conductivity due to the micro-structural ordering
(alignment) of sheets [42]. Therefore, analyzing the rheological
data with respect to the total solid content is a useful character-
ization of the dispersion phases. For the sake of convenience, we
calculate the total volume percentage f of our dispersions by
approximating the density of GO and GNP with that of graphene
(2267 mg cm
3) and arrive in a range of f z 0.25e1.27.
To quantify the rheology, the Carreau-Yasuda equation
Fig. 6. Possible phase phenomena in compound dispersions. (A colour version of this figure can be viewed online.)
589
Carbon 174 (2021) 581e593
   
h g_ ¼ h g_ /0 1 þ ðlg_ Þa a
(9)
is employed [50], where hðg_ /0Þ and g_ are the zero shear viscosity
and shear rate, respectively. The shear thinning exponent n pro-
vides information on the non-Newtonian behavior. Strong gel like
characteristics are present if n approaches 0. The Yasuda parameter
a is a non-dimensional constant which reflects the curvature in the
Newtonian plateau and l is a relaxation time. A regression of the
Carreau-Yasuda model to the experimental data in Fig. 5a) gives
excellent R2 values of around 0.98. Regression parameters are
provided in Table S4 in the SI. The shear thinning exponent n is zero
for dispersions with total concentrations of 15 mg ml
1 and higher.
Moreover, we realize that for a compound dispersion the zero shear
viscosity and relaxation time are strongly related to the GO con-
centration. This is because the GO contributes more to the
hydrogen bonding and the orientation of the sheets which
considerably impacts the rheology.
Fig. 7a) shows the viscosity vs the total volume percentage f at
0, 0.01 and 0.1 s
1 shear rates. We find that all curves show a very
similar trend. The influence of the shear rate is solely manifested as
a shift on the y-axis where lower shear rates results in higher vis-
cosities. The viscosity of an LCP system shows a complex de-
pendency on the concentration, resulting in different phases, such
as isotropic, viscous nematic liquid, nematic gel, etc. [43,49,50]. The
viscosity goes through a sharp maximum, which is associated with
the transition from the isotropic to the anisotropic phase [80]. This
trend is clearly followed in the phase diagram shown in Fig. 7a). The
decrease in viscosity at concentrations beyond a critical volume
percentage of f z 0.37 is attributed to a transition from the
isotropic to a biphasic/nematic phase. In this regime, the presence
of aligned domains results in a decrease in the viscosity with
concentration, as the anisotropic dispersions become shear thin-
ning at a lower shear rate than the isotropic ones [80]. At
S. Mypati, A. Sellathurai, M. Kontopoulou et al.
Fig. 7. a) Non-monotonic relation between shear viscosity vs total solid volume percentage; b) Zero shear viscosity vs total solid volume percentage for three different GO to GNP
ratios (lines are guides to the eye). (A colour version of this figure can be viewed online.)
concentrations of f above 0.47, the viscosity increases once more,
indicating the transition to a LC system [83].
A further increase in concentration results in a second local
viscosity maximum, and a subsequent plateau, beyond which the
viscosity continues to increase. This plateau has not been reported
before, and may be due to the complex dependence of the zero
shear viscosity at different GO to GNP ratios. Fig. 7b) shows the
influence of f on the zero shear viscosity for three different GO to
GNP ratios. For a constant GO to GNP ratio, the zero shear viscosity
increases with increasing f. For a constant f, we observe that the
zero shear viscosity increases with increasing GO content. Beyond
f z 0.69 the viscosity increases steadily, corresponding to high
viscous nematic, and possibly the onset of the formation of nematic
gels at high concentrations [50].
4.4. Micro-dispensing on flexible substrate
As mentioned in Section 1, highly-concentrated GNP dispersions
are required for a multitude of applications. To exemplify this, we
print a 1 cm2 film on a flexible substrate; i.e., a cellulose acetate
transparent sheet. We use a dispersion of 15 mg ml
1 GNP stabi-
lized with 1.5 mg ml
1 GO (weight ratio of 0.1), which corresponds
to sample S8 in this study. The printed films are dried in an oven at
90  C for 60 min. The films are subsequently treated with 100 mM
ascorbic acid for another 60 min at 95  C. This step converts the
minor GO fraction to rGO in order to improve the film conductivity.
We measure the film conductivity before and after the reduction
Fig. 8. a) Conductivity of reduced and un-reduced printed film before and after bending test; Digital images of reduced printed letters (Queen’s) used as a connecting wire for
glowing the LEDs in b) flat and c) bend modes. (A colour version of this figure can be viewed online.)
590
Carbon 174 (2021) 581e593
process to obtain insights into its efficiency. We also measure the
conductivity before and after bending the flexible substrate for 50
times; the results are given in Fig. 8a). The thickness of all printed
films is relatively similar and is about 3e4 mm measured using a
laser-equipped gauging instrument. The non-reduced film without
any bending features a conductivity of 255 S m
1. After bending, the
conductivity decreases to 165 S m
1. The reduced film without any
bending has a conductivity of 4531 S m
1. After bending the
reduced film for 50 times, the conductivity decreases to 615 S m
1.
The electrical conductivity of the un-bended films is comparable or
even higher than conductivities of films prepared by others using
printing or vacuum filtration; cf. Refs. [37,84e86]. The bending
losses are 86% and 35% for the reduced and the unreduced film,
respectively. We realize that the influence of the bending is more
significant when the GO content in the film is reduced. Still, the
conductivity of the film made from our compound dispersion is,
even after bending, almost 20% higher than a printed and reduced
film which was made from a 10 mg ml
1 GO dispersion and without
any bending [21].
As shown in Fig. 8b), we print the lettering of our institution
(Queen’s) and treat it with the GO reduction process. The printed
and reduced lettering is used as a connecting wire to operate a
series of LEDs connected to a 12 V power source in order to
demonstrate the applicability of our dispersions for printed elec-
tronics and other comparable technologies. The printed lettering is
also subjected to a bending test for 50 times. No (obvious)
morphological changes are observed on the printed sheet and its
S. Mypati, A. Sellathurai, M. Kontopoulou et al.
ability to conduct the current to power the LED is maintained, as
shown in Fig. 8c), which confirms the very good adhesion of the
film on the substrate.
5. Concluding remarks
In this study, we successfully prepare highly-concentrated sta-
ble aqueous GNP dispersions where we use GO as a dispersant. The
GO and the GNP sheets form compounds having features of either
material. First, several compound dispersions with different ratios
and concentrations of GO and GNP are tested for their stability over
24 h. The results clarify that the stability is correlated to the con-
centration ratio of GO to GNP in the dispersion. The knowledge
obtained from this test is used to construct a contour map which
gives the stability duration of a dispersion at a given GO and GNP
concentration. The XDLVO theory is employed to infer the stability
mechanisms and to describe the influence of the pH value on the
stability. We find that dispersions are always stable at their intrinsic
pH when the GO to GNP ratio is 0.15 or more. Unstable dispersions
become stable when the pH value is shifted to an alkaline milieu,
which increases the electrostatic repulsion between the compound
sheets.
Next, the rheology of the dispersions is studied at various GO
and GNP concentrations. The results reveal that all dispersions
show a shear thinning behavior. Further, we employ the Carreau-
Yasuda model to identify the liquid crystal phases and packing or-
der of the compound dispersions. The results show the formation of
nematic liquid and nematic gel phases depend on the total volume
percentage of the sheets in the dispersion.
Finally, we demonstrate the applicability of the dispersions by
printing films on a flexible substrate. The printed films show
reasonable conductivity which may be sufficient for certain appli-
cations. High film conductivities are demonstrated after a simple
reduction step which converts the minor GO fraction in the film.
Bending tests reveal that the films maintain a good conductivity
even after multiple bending cycles. The utilization of the compound
dispersions has several advantages. The inks can be printed without
addition of viscosifiers since the viscosity can be adjusted by the
composition. The printed films show sufficient adhesion on the
substrate without any addition of binders or surface pre-treatment.
The films made from compound dispersions can be used for an
array of applications, such as current collectors in wearable elec-
tronics or as an electrode material for various electrochemical
devices.
Possible further studies include dynamic shear tests in order to
obtain insights into the transition from liquid to gel regimes.
Likewise, adhesion of printed dispersions onto other (flexible)
substrates should be investigated. Here, improvements are possible
by modifying the dispersion with polymer binders and adhesion
promoters. Though, their utilization may have a negative impact on
the conductivity of the films.
CRediT authorship contribution statement
Sreemannarayana Mypati: Conceptualization, Methodology,
Formal analysis, Investigation, Writing - original draft, Writing -
review & editing. Andrew Sellathurai: Investigation, Formal anal-
ysis, Visualization. Marianna Kontopoulou: Supervision, Re-
sources, Writing - review & editing. Aristides Docoslis:
Supervision, Resources, Writing - review & editing. Dominik P.J.
Barz: Conceptualization, Methodology, Supervision, Resources,
Writing - original draft, Writing - review & editing, Funding
acquisition.
591
Carbon 174 (2021) 581e593
Declaration of competing interest
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this paper.
Acknowledgements
The authors gratefully acknowledge financial support from the
Natural Sciences and Engineering Research Council of Canada
(NSERC), MITACS, Queen’s Faculty of Engineering and Applied Sci-
ence Dean’s Research Award, as well as an Ontario Early Researcher
Award for D.P.J.B. We thank Grafoid Inc. for providing access to the
scanning electron microscope and Surface Western for performing
the XPS measurements.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.carbon.2020.12.068.
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