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Procedia Engineering 148 (2016) 49 – 56

4th International Conference on Process Engineering and Advanced Materials

Rheological Behaviour of Graphene Nano-Sheets in Hydrogenated

Oil-Based Drilling Fluid
Chai Yee Hoa, Suzana Yusupb,*, Chok Vui Soonc, Mohamad Taufiq Arpinc
a
Biomass Processing Lab, Center of Biomass and Biofuels Research, MOR Green Technology, Chemical Engineering Department, Universiti
Teknologi PETRONAS, 31750, Perak, Malaysia
b
Associate Professor, Biomass Processing Lab, Center of Biomass and Biofuels Research, MOR Green Technology, Chemical Engineering
Department, Universiti Teknologi PETRONAS, 31750, Perak, Malaysia
c
Platinum Green Chemicals Sdn. Bhd. LOT15-19 & PT 1409, Senawang Industrial Estate, Batu 4, Jalan Tampin, 70450, Seremban Negeri
Sembilan Darul Khusus, Malaysia

Abstract

An experimental investigation has been carried out to investigate the rheological effect of hydrogenated oil-based drilling fluid
when dispersed with graphene nano-sheets. The rheological aspects that were investigated were viscosity and shear stress of the
fluid respectively. The weight concentration of graphene sheets carried out in this experimental investigation were 25 ppm, 50
ppm and 100 ppm respectively. Graphene nano-sheets were dispersed via hydrodynamic cavitation dispersion and ultrasonic bath
for three (3) hours each. From the analysis, the graphene-oil based drilling fluid exhibit higher viscosity as compared to the
hydrogenated oil-based drilling fluid over the shear rate range of 0 – 140 s-1. Interestingly, the graphene-oil based fluid is a
Bingham fluid but behaves similar to a Newtonian fluid as it possesses zero shear stress. Temperature dependence of the studied
nanofluid was carried out at 30oC, 40oC and 50oC respectively to observe the relationship between the additions of nanoparticles
into the hydrogenated oil-based drilling fluid as compared to the base fluid. Two rheological models (Bingham model and Power
Law model) were fitted to predict the behavior of graphene-oil based drilling fluid with respect to temperature and shear rate.

©©2016
2016The
TheAuthors. Published
Authors. by Elsevier
Published Ltd. Ltd.
by Elsevier This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of ICPEAM 2016.
Peer-review under responsibility of the organizing committee of ICPEAM 2016
Keywords: graphene-nanosheet; hydrodynamic cavitation; hydrogenated oil; drilling fluid

* Corresponding author. Tel.: +605-368-7642; fax: +605-365-176.

E-mail address: drsuzana_yusuf@petronas.com.my

1877-7058 © 2016 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY-NC-ND license
(http://creativecommons.org/licenses/by-nc-nd/4.0/).
Peer-review under responsibility of the organizing committee of ICPEAM 2016
doi:10.1016/j.proeng.2016.06.490
50 Chai Yee Ho et al. / Procedia Engineering 148 (2016) 49 – 56

1. Introduction

Drilling fluids are one of the more important components in any drilling operations as it provides lubrication,
cooling down of drilling bits and removal of solid fragments from the wellbore. Researchers had widely proven that
the thermal conductivity properties of nanofluids are superior to the base fluid and the same concept is applicable to
nanofluid as drilling fluids. Researchers are predicting that nanofluids will not only be exclusive towards heat
transfer applications but also towards the drilling applications as well [1-2]. Nanoparticles can be regarded as
substitutes for costly additives in drilling fluid formulations [3] to achieve the desired properties of drilling fluid.
Nasser et al. [18] obtained lower mud friction and better fluid loss control when mud formulations are dispersed
with nano-graphite powder. Taha and Lee [19] concluded that drilling muds containing graphene improve drilling
bit’s life span by more than 75%.
However, it is equally important to focus on the rheological aspect of drilling fluids, inclusive of nanofluids, in
any drilling operations. An ideal drilling fluid should suspend solid fragments at static conditions while
contemporaneously able to flow when minimum shear stress is applied.
Graphene consist of a single layer of carbon atoms which are tightly packed in hexagonal geometry in 2-D lattice
[4]. It has an exceptional thickness at 0.34 nm with sp 2 bonding between carbon-carbon atoms. It is widely known
that graphene has a high range of thermal conductivity, ranging from 3,000 W.m -1K-1 up to 5,000 W.m-1K-1 [5],
which makes it a suitable material for heat transfer applications. The mechanical properties of graphene can be
measured up to 1 TPa with intrinsic fracture strength of 130 GPa [4] with enhanced mechanical performances.
The dispersion of nanofluids are categorised into two: one-step method and two-step methods [6,12]. Two-step
methods are usually more economical for the production of large quantity of nanofluids [7]. Two-step method
utilizes physical agitation to disperse nanoparticles in dry powder form into its respective base fluid to produce
nanofluids. This method usually consists of ultrasonication, high-shear mixing, homogenization and ball milling
methods [7]. However, a novel method of combination of hydrodynamic cavitation dispersion and ultrasonication
were used to homogenize and produce nanofluids in this study.
Hydrodynamic cavitation is a process where gas bubbles within liquid grow and collapse under pressure variation
through a constricted channel at high velocity [8]. The collapse of bubble is termed implosion, where the bubble
imploded outwards while causing cavitation effects. Cavitation is regarded as one of the unwanted phenomenon
process in any process industry due to its damaging behaviour which causes erosion at the wall surface of pipes.
However, the high implosion energy released in hydrodynamic cavitation dispersions are able to break down large
agglomerates into smaller sizes to further improve the stability of nanofluids.

2. Experimental

2.1. Materials

Graphene nano-sheets and hydgorenated oil-based drilling fluid were procured from Platinum Green Chemicals
Sdn. Bhd., Malaysia. An example of transmission electron microscope (TEM) image is shown in Fig. 1 was taken
using Zeiss Libra 200FE Microscope at 200,000x magnification. From Fig. 1(a)., a flat plane geometry is observed
which shows a monolayer of carbon atoms packed tightly in a 2-D lattice. The darker image denotes the presence of
superimposition of the top layer graphene sheet against the lower graphene sheet.
Fig. 1(b) shows the result from Fourier Transform Infrared (FTIR) spectroscopy analysis of graphene
nano-sheets. It is observed that the peak at 3434 cm-1 shows the presence of –OH functional group. A short peak is
seen at 2921 cm-1 which shows sp3 bonding between carbon and hydrogen atoms. The presence of alkynes at 2296
cm-1 is indicated with a weak peak denoting little or no change in dipole moment. A medium peak is seen at 1632
cm-1 which proves the existence of double bonds between carbon atoms. At 1411 cm-1, a C-C in-ring aromatics is
determined which exhibits possible presence of hetereocyclic compound as there are presence of nitrogen atoms due
to C-N stretching at 1091 cm-1. The presence of nitrogen atoms may be derived during the preparation and
exfoliation of graphene nano-sheets using nitric acid [9].
Hydrogenated oil contains alkanes between C15 – C18 which are both linear and branched. It has a density of
780 kg/m3 at 15oC, with boiling point limits at 300 oC and flashes at 90oC. The hydrogenated oil does not possessed
any oxidizing properties and is insoluble in water.
 Chai Yee Ho et al. / Procedia Engineering 148 (2016) 49 – 56 51

a b

Fig. 1. TEM image of graphene nano-sheets at (a) 200,000x magnification and (b) FTIR spectra of graphene-nanosheets

Fig. 2. Graphene-oil nanofluid at 25 ppm, 50 ppm and 100 ppm (from left to right)

2.2. Nanofluid Preparation

The dispersion of graphene nano-sheets into hydrogenated oil-based fluid was done by two-step methods via
combination of hydrodynamic cavitation (HC) dispersion and bath ultrasonication technique.
A pilot scale hydrodynamic cavitation unit was set up for hydrodynamic cavitation dispersion for the production
of nanofluid A variable frequency drive (VFD) pump, which has the range of 0 – 50 Hz frequency, is used to control
the inlet flow pressure at the orifice.
Sonication of the nanofluid samples were carried out using Bath Ultrasonic Branson 8510E-DTH at 320 W
power with a frequency of 40 kHz to homogenize the samples.
The batch volumes for each sample run required 1.5 L of hydrogenated oil-based fluid to reach the minimum
volume requirement to prevent pump from “dry-running”. The mass concentrations of graphene nano-sheets were
weighed 25 ppm, 50 ppm and 100 ppm. Graphene nano-sheets and hydrogenated based oil were pre-stirred for 15
minutes with VELP Scientifica Digital Overhead Stirrer – DLS for sample pre-homogenization. The pre-stirred
samples were transferred to the HC unit for three (3) hours of hydrodynamic cavitation process at 10 bar at 1.5 L
min-1. The homogenized samples were transferred to ultrasonic bath for three (3) hours of sonication to further
homogenize graphene-oil fluid samples. The prepared nanofluid samples are as shown in Figure 2.
52 Chai Yee Ho et al. / Procedia Engineering 148 (2016) 49 – 56

2.3. Rheology Analysis

Viscosities of the nanofluids were measured using Malvern Bohlin Gemini II Rheometer, which was connected
to a PC controlled Peltier plate temperature controller to vary the temperature of the nanofluid samples from 30 oC to
50oC. The spindle attached to the rheometer is lowered down to the pre-set gap at 30 um above the sample via a
torsion bar that is suspended on an air bearing. The sample resistance twisting the torsion bar allows the system to
detect the stiffness of the bar, which translated the torque measured to shear stress data.
The spindle selected in this study is a cone-and-plate stainless steel spindle with 2o angle and 40 mm diameter.
The data collection of the rheometer includes viscosity, shear stress, shear rate, RPM, temperature, and time. All
measurements have a delay time and integration time of 10 seconds to record the data under steady state conditions.
The estimated percentage deviation in the rheometer measurement ranges up to 3%.

3. Models

Bingham Plastic model and Power Law model were selected as both models are viscosity dependant on shear rate
that depicts non-Newtonian behavior of the fluid. The accountability of both models are taken into consideration in
this study due as drilling fluids are generally described with classic rheological models such as Bingham plastic
model and Power Law model.

3.1. Bingham Plastic Model

Materials which exhibit “infinite” viscosity until adequate stress is applied to initiate flow are known as Bingham
plastic fluids [10]. Bingham model is highly dependent on the parameters shear stress ( ) and the shear rate ( ) of
the liquid samples, which gives a directly proportional re lationship between both parameters. Bingham plastic
fluids are described based on Bingham plastic viscosity (u) and yield stress ( ) [11]. The resulting proportionate
relationship between shear stress and shear rate is known as “plastic viscosity”. The model is described as follow:

W W 0  uy (1)

The Bingham Plastic model is suitable for model-fitting for fluids with concentrated suspensions and colloidal
systems.

3.2. Power Law Model

Fluids which follows power law models are classified into types: shear-thinning and shear-thickening under
increasing shear rates. Liquid samples which increases or decreases exponentially usually follows the Power Law.
The Power Law model are described bed by two parameters, consistency coefficient (K) and flow behavior index
(n). The Power Law model can be described as follows:

V K. J n (2)

Where taking logarithms on both sides gives,

log V log K  n log J (3)

As magnitude of n < 1, the fluid is known as shear-thinning and when n > 1, it has shear-thickening behaviour.
The applicability of Power Law model is suitable over the shear rate range of 10 1 to 104 s-1 [11] which falls in the
scope in this study.
 Chai Yee Ho et al. / Procedia Engineering 148 (2016) 49 – 56 53

4. Results and Discussions

In this study, the rheology analysis was performed over the range of shear rate of 0 – 140 s-1 to measure the
viscosity and shear stress of the samples. The viscosity of the samples were compared against the base fluid over the
same set of shear range at different temperature and concentrations. The shear stress of the samples were determined
to ascertain the nature of the fluid by comparing with the rheological behavior models with the experimental data.

Fig. 3. Viscosity comparison of 25 ppm, 50 ppm and 100 ppm graphene-oil nanofluid and hydrogenated oil at 30oC

This study investigates viscosity parameter at the higher shear rate ranging from 20 s-1 to 140 s-1. Fig. 3 shows
viscosity of graphene-oil based drilling fluid at 30oC increases with increasing graphene nanoparticle concentration.
Similar observations are also observed by other researchers [13-15]. A sharp viscosity hike for 25 ppm
concentration at 120 s-1 can be attributed to possible “jamming” of nanoparticles at the bottom of cone-and-plate
spindle. Addition of 25 ppm of graphene nano-sheets increases the viscosity averagely by 16% while 50 ppm and
100 ppm concentration yields 39% and 50% viscosity increment respectively. The higher the particle loadings, the
greater the viscosity of the fluid. Similar trend was also observed by several other researchers in their work [5,16-
17].
a b

Fig. 4. Graphical results of viscosity against shear rate at (a) 30oC, (b) 40oC, and (c) 50oC of graphene-oil nanofluid and hydrogenated oil.
54 Chai Yee Ho et al. / Procedia Engineering 148 (2016) 49 – 56

Fig. 4(a) – 4(c) shows viscosity decreases exponentially to base fluid’s viscosity at increasing shear rate
regardless of concentration. The initial shear rate from the range of 0.01 s -1 to 0.1 s-1 can be extensively ignored as
shearing is relatively static when compared to higher shear rates which resulted in inconsistencies in initial viscosity
measurements. However, the viscosity trend continues to decrease exponentially at increasing shear rates until it
reaches a base viscosity similar to the base fluid’s viscosity. An example of base viscosity between graphene-oil
nanofluid and hydrogenated oil-based fluid at higher shear rate is shown in Fig. 3.
The addition of graphene nano-sheets at various concentrations into hydrogenated oil does not alter the fluid’s
behaviour as shown in Fig. 5. However, the addition of graphene nano-sheets greatly increases the shear stress at
higher shear rates by approximately 50% at higher shear rates.

Fig. 5. Comparison of shear stress at 25 ppm, 50 ppm and 100 ppm concentration graphene-oil nanofluid and hydrogenated oil at 30oC

At lower shear rates, the experimental data fits well into both rheological models, Bingham plastic model and
Power Law model. However, the Power Law model deviated mostly from the experimental data at higher shear rate
as illustrated in Fig. 6 – 8. This can be attributed to the exponential, n, which contributes to the exponential shear
stress increase at higher shear rate. The n obtained in the calculations is n > to achieve exponential increase of shear
stress which demonstrates graphene-oil fluid as a shear-thickening fluid. As mentioned, the agglomerations of
graphene nano-sheets during rheological analysis can contribute to the shear—thickening behaviour of the fluid.

Fig. 6. Comparison of experimental data and rheological models at 30 oC

 Chai Yee Ho et al. / Procedia Engineering 148 (2016) 49 – 56 55

Fig. 7. Comparison of experimental data and rheological models at 40 oC

Fig. 8. Comparison of experimental data and rheological models at 50oC

5. Conclusions

Based on the work carried out in this research, it can be concluded that even the addition of graphene nano-sheets
at very low nanoparticle loadings can contribute to a maximum increase of viscosity by 50% despite a very low
increase in magnitude. The rheological behaviour of graphene-oil based fluid remains similar to the base fluid with
respect to the nanoparticle concentrations. Bingham model data fitted closely to the experimental data at all shear
rate range while Power Law deviates further at higher shear rate. The slight thickening of graphene-oil based fluid
can be attributed to the agglomeration of graphene nano-sheets when subjected to rheology test. Utilization of
graphene nano-sheets can perform well at other drilling fluid properties such as better fluid loss control, friction and
improvement of drilling bit life span despite a very minor trade off in terms of viscosity.
56 Chai Yee Ho et al. / Procedia Engineering 148 (2016) 49 – 56

6. Recommendations

The current work can be further analyzed in details by investigating nanoparticle size after hydrodynamic
cavitation dispersion process and how it affects the rheological behavior of graphene-oil based fluid. Possible
agglomerations which lead to slight shear thickening during rheological analysis can also be studied on how the
nanoparticle suspension samples subjected under high shear rate rotation behave as it is closely related to the drilling
process.

Acknowledgements

The authors would like to gratefully acknowledge the materials provided by Platinum Green Chemicals Sdn.
Bhd. as well as the hydrodynamic cavitation unit used for preparation of nanofluids in this work.

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