Multiwalled carbon nanotubes and graphene

oxide as nano-additives in water-based

drilling fluid for enhanced fluid-loss-control &
gel strength
Cite as: AIP Conference Proceedings 2151, 020001 (2019); https://doi.org/10.1063/1.5124631
Published Online: 29 August 2019

Abdul Azeem Mohamed Mohideen, Mohamed Shuaib Mohamed Saheed, and Norani Muti Mohamed

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AIP Conference Proceedings 2151, 020001 (2019); https://doi.org/10.1063/1.5124631 2151, 020001

© 2019 Author(s).
 Multiwalled Carbon Nanotubes and Graphene Oxide as
nano-additives in Water-Based Drilling Fluid for Enhanced
Fluid-Loss-Control & Gel Strength

Abdul Azeem Mohamed Mohideen1 Mohamed Shuaib Mohamed Saheed1, 2 and

Norani Muti Mohamed 1, 2,*

1
Department of Fundamental and Applied Sciences,
Universiti Teknologi PETRONAS, 32610 Seri Iskandar, Perak Darul Ridzuan
2
Centre of Innovative Nanostructures & Nanodevices (COINN),
Universiti Teknologi PETRONAS, 32610 Seri Iskandar, Perak Darul Ridzuan.

Corresponding author: noranimuti_mohamed@utp.edu.my*

Abstract. Water-based drilling fluid (WBDF) with low permeability and tangible gel strength is highly preferable in
drilling industry to have uninterrupted drilling operations. Hence, it is crucial to sustain certain rheological properties of
WBDF such as viscosity, gel strength and fluid-loss. Recent studies have identified various nano-additives with the ability
to enhance the specific rheological properties of WBDF. In this paper, the enhancement of fluid loss control and gel strength
of WBDF were studied using various combination of nano-additives multiwalled carbon nanotubes (MWCNT) and
graphene oxide (GO). The synthesized MWCNT improved the gel strength independently without enhancing the fluid loss
control of WBDF as the result of its hydrophobic characteristics. GO impressively enhanced the fluid loss control of WBDF
with or without the presence of MWCNT but does not contribute significantly in terms of gel strength.

INTRODUCTION
Water-based drilling fluid is a reliable, ecosystem friendly liquid used in most drilling operations worldwide. The
main functions of drilling fluids include providing hydrostatic pressure to prevent formation fluids from contaminating
the hydrocarbon in the wellbore, keeping the drill bit cool and clean during drilling, carrying out drill cuttings, and
suspending the drill cuttings while drilling is paused and when the drilling assembly is brought in and out of the hole
[1]. Well-dispersed and durable nano-additives will reduce fluid loss (FL), filtrate thickness (FT), and enhance gel
strength (GS) of WBDF. Effective control over fluid loss depends on the addition of fluid loss additives at correct
volume to ensure the clay solids dispersed homogeneously. Fluid-loss control additive may also act as thinners, or
viscosifiers under certain circumstances, and react unfavorably with other additives in the drilling fluid. The
characteristics of nano-additives was studied thoroughly to understand how these nano-additives enhance the fluid
loss control of drilling fluid and ensure cost-efficient drilling operation with minimal impact to the environment.
Significant amount of research [2,3] has been conducted on enhancing the rheological properties of WBDF using
various organic and inorganic materials to substitute expensive clay-based additive. Nanoparticle-based additives
exhibit better fluid loss control with thinner filter cakes to ensure efficient drilling operation with minimal cost as
reported by D. V. Kosynkin et al [4–8]. Recently, GO and MWCNT were reported [9,8,10–11] to improve fluid loss
control and gel strength of WBDF separately.

NANOSCIENCE AND NANOTECHNOLOGY

AIP Conf. Proc. 2151, 020001-1–020001-6; https://doi.org/10.1063/1.5124631
Published by AIP Publishing. 978-0-7354-1896-7/$30.00

020001-1
 Fluid loss is the loss of drilling fluid into the formation via fractures occurs naturally or induced by drilling [13]
which reduce productivity by blocking hydrocarbon exit flow paths or causing formation collapse [6, 7, 10]. The
acceptable range for fluid loss reported to be within 7.2 – 15 mL over 30 minutes [5, 11]. Lately, various nano-
additives developed to enhance the fluid loss control of drilling fluids. Graphene oxide (GO) is one of the commonly
obtained from an aqueous dispersion of graphite oxide [18] and creates a robust tile-like interlocking of the flakes
with better filtration up to 6.1 mL compared to standard suspension (∼12 g/L) of clays and polymers used in the oil
industry gave an average fluid loss of 7.2 mL [18]. MWCTNs and nano silica showed a reasonable reduction of filtrate
volume.

The solids and fluid loss polymers control the final thickness of the filter cake development [6, 8]. The filter cake
thickness directly correlated to the differential torque needed to rotate the drill string which affects the drilling time
and cost. The drilling efficiency decreases exponentially when filtrate thickness increases. Conventional mud filtrate
additives such as PAC, CMC and PHPA are in macro sizes and cannot plug the nanopore throat of the wall of the
wellbore [19]. Pristine graphene monolayer has a theoretical Connolly surface area of 2,965 m2/g and has been shown
to form a membrane impermeable even to helium gas [18]. The thickness of the GO flakes could also result in much
thinner filter cakes than those obtained using clay-based materials [18]. The combination of large-flake GO and
powdered GO in a 3:1 ratio performed best in the API tests, leaving a filter cake ∼20 μm thick compared to standard
suspension (∼12 g/L) of clays and polymers used in the oil industry develop filter cake ∼280 μm thick [18].

The gel strength (GS) is another important drilling fluid properties because it demonstrates the ability of the
drilling mud to suspend drill solid and weighing material when circulation is paused. GS of the drilling mud are the
internal structures which strengthen during static[7]. The GS of the mud with higher plastic viscosity (PV) increases
the equivalent circulating density (ECD), surge, and swab pressures and also reduces the rate of penetration (ROP)
with chances of differential sticking and finally reduces the efficiency of the drilling process. The variation of gel
strength in WBDF generally caused by bacteria, drill solids, salt, chemical contamination such as lime, gypsum,
cement, and anhydride, acid gases such as carbon dioxide (CO2) and hydrogen sulphide (H2S) [20]. Among primary
drilling fluids nano-additives, MWCNT found better material for improving gel strength; it may be due to its high
surface area and nanotube structure [19]. MWCNT exhibits reasonable GS 3.8/3.3 Pa-s with better fluid loss control
[19]. Acceptable range for initial gel strength is within 3.5 – 4.5 Pa-s and 10-minutes gel strength is 5.5 – 8.5 Pa-s
[19].

EXPERIMENTAL SECTION

Materials

Fe2O3/Al2O3, the catalyst for nucleation of MWCNT, hydrogen, argon, ethylene (C2H4), dispersed GO in H2O (4
mg/ml) and BaSO4 were acquired commercially. Scomi Oil Sdn Bhd provided API 13-A standard xanthan gum (XG)
and soda ash.

Synthesis of nano-additive
MWCNT sample was synthesized using a vertical bed (OVF-1200-3) with the experimental setup as reported by
Shukrullah et al [21]. This reactor is composed of a quartz tube and a vertical heating zone with the temperature
controlled by digital temperature controller. The flows of gases to the mixer are controlled using flow meters. Initially,
Fe2O3/Al2O3 catalyst was placed in high temperature zone of the quartz tube, where CNTs grow as the result of the
catalytic decomposition of the ethylene over metal catalyst. In the growth of CNTs, argon gas (200 sccm) was purged
initially into the system and the temperature was raised to 700°C at the ramping rate of 10°C per minute. At this point,
ethylene and hydrogen gases were added to the process at the flow rate of 100 and 200 sccm, respectively. After an
hour of reaction, the supply of gases was stopped, and the reactor was cooled down to room temperature in argon
ambient condition. The final product was then collected and stored in dust and moisture free environment.

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 Characterization of nano-additive

Synthesized MWCNT was characterized using a set of analytical and quantitative tools. Field Emission Scanning
Electron Microscope, FESEM (Zeiss Supra55 VP) was used to measure the length, outer diameter and the surface
morphology of the grown nanotubes whilst X-ray diffraction spectroscope (XRD) utilized for the determination of
CNT in the synthesized nano-additive. The physicochemical properties of GO were evaluated by Fourier-transform
infrared spectroscopy (FTIR). The rheological investigation of WBDF focused on fluid loss (FL), filtrate thickness
(FT), and gel strength (GS) properties at low pressure and low temperature (LPLT).

Formulation of WBDF

Xanthan gum (XG) is a rheological modifier commonly used in WBDF for increased viscosity and better
dispersion stability. Water was viscosified with XG and weighted with barite selected as the base mud for the MWCNT
nano-additive studied for this research. WBDF was prepared by adding 2 g of XG into water while stirring to prevent
agglomeration. After adding XG the solution was stirred for 20 minutes, followed by an addition of a small amount
of soda ash to ensure the pH of water maintained within the range of 9-10. [18] Next, the nano-additives (MWCNT)
were added gradually while stirring for 10 minutes and finally barite particles were added as the weighing agent while
stirring the mixture for another 15 minutes. It is observed that XG usage adversely at pH less than 8.5 as it affects the
emulsion/suspension stabilizer function of XG and cause the viscosity of enhanced.

Rheological and API Filter-Loss Test

Flow properties of drilling fluids such as plastic viscosity (PV), yield point (YP), 10-seconds gel strength (10 s
GS), and 10-min gel strength (10 min GS) were determined by using FANN 35 Viscometer. The cup of the viscometer
was filled with mud sample and placed onto the FANN Rheometer. The plumb bob was suspended inside the cylinder
and immersed in the mud sample which was rotated by the outer cylinder with the plumb bob sheared at 300 rpm
(θ300) & 600 rpm (θ600) for each sample. The deflection of the plumb bob is a measure of the viscosity of the drilling
fluid at that shear rate. After the mud has remained static for some time (10 secs) the rotor was set at a low speed (3
rpm), and the deflection noted. This is reported as the initial, or 10 second gel (θ10sec). The same procedure was
repeated after the mud remained static for 10 minutes to determine the 10-minute gel (θ10min). Both gels were
measured in the same units as Yield Point (Pa s). Gel strength usually appears on the mud report as two figures (e.g.
17/25). The first being the initial gel, and the second the 10-minute gel.

Filtrate volume & thickness was determined by FANN LPLT Filter Press. The cup of the LPLT filter press was
arranged properly with filtrate paper and rubber gasket before filling 2/3 of cup filled with mud sample. The fluid
from a mud sample was then forced through a filter under specified temperature and pressure. LPLT filter press test
conducted by applying 100 psi of differential pressure at room temperature. A graduated cylinder used as test tube,
collected the dripping water from the filter press. The volume of dripping water measured for every 5 minutes interval
till 30 minutes and recorded as mL/30 minutes. The thickness of the solid residue remained on the filter paper known
as filter cake or mud cake was measured in millimeters using digital Vernier caliper.

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 RESULT & DISCUSSION

Characterization of GO

FESEM image in Figure 1 (a) shows the crippled flat sheet morphology of GO, implying thin GO with large
surface area to provide better filtration with thin filter cake. The FTIR of GO is presented in Figure 1 (b). Some of the
major absorption peaks are located at 3400, 1715, 1580, 1250, and 1063 cm-1, attributed to the stretching vibrations
of O–H, C=O (–COOH), C=C, C–O (alkoxy) and C–O (epoxy), respectively. It indicates a typical chemical structure
of GO.

(a) (b)

FIGURE 1. (a) FESEM analysis on surface morphology of GO at 2KX magnification & (b) FTIR analysis of GO

Characterization of MWCNT

Figure 2 (a) shows the morphology of the synthesized MWCNT, which appear as tabular, rope like shape
predicted to have large surface area coverage to provide better gel strength (GS) for WBDF. Synthesized MWCNT
have almost 95% of carbon content with low impurities. The XRD of MWCNT is presented in Figure 2 (b) where the
most significant Bragg peaks of MWCNT appeared with Miller indices at the angle of 25o, 43o, & 45o. The presence
of catalysts (Fe & Al) in the CNT sample is indicated by (*).

(a) (b)

FIGURE 2. (a) Morphology of MWCNT with typical diameter of 30 nm observed at 100KX magnification and (b) XRD pattern
of synthesized MWCNT (diameter ~ 30 nm)

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 Effect of MWCNT and GO on rheology and fluid loss properties of WBDF

Nano-additives effects on rheology and fluid loss are described by their parameters which is presented in Table
1. GO aqueous dispersion has significantly increase the plastic viscosity (PV), but with no obvious changes to the
yield point (YP) and gel strength (GS). The increase in PV is believed to be due to the well dispersed GO particles in
water, giving higher density of GO particles in water exceeded that of micron sized XG particles even though at very
low concentration. However, small addition of GO in WBDF leads to dramatic decrease in FL & FT. Even though
MWCNT do not affect the FL or FT of WBDF at different concentration levels due the hydrophobicity where
nanotubes tend to be suspended in WBDF like a milling bead to homogenize the drilling fluid mixture with nano
additives, thus it improves the gel strength (GS). However, the mud density and pH remained constant indicating that
the concentration of nano-additive used is very small almost < 0.05% and these nano-additives are very stable,
chemically inert without causing any chemical reaction with other components in WBDF such as XG, soda ash and
barite.

TABLE 1. Effect of nano-additives on rheology and fluid loss of WBDF

CONCLUSION

MWCNT exhibits better gel strength compared to GO. Hence, MWCNT have been selected to combine with
GO to develop an additive with better fluid loss, thin filter cake and high gel strength. Nanomaterials with relatively
larger surface area and thinner diameter such as GO able to reduce the fluid loss (FL) from 20mLto 15 mL and filtrate
thickness (FT) from 0.3mm to 0.1mm of WBDF with 0.02% of GO nano-additive. Lower FL & thinner FT can be
achieved by increasing the concentration of GO up to 0.1%. MWCNT nano-additive excellently enhanced the gel
strength (GS) of WBDF without affecting the performance of GO. Nano-additives such as MWCNT & GO is more
economically feasible because it only requires small concentration of additive to significantly improve the drilling
fluid’s performance. Besides fluid-loss control and gel strength, incorporation of MWCNT & GO based nano-
additives could potentially further improve the lubricity, viscosity, thermal stability and other known rheological
properties as reported by A.R. Ismail et al[7].

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 ACKNOWLEDGEMENT

The authors wish to extend their gratitude and appreciations to the management of the Yayasan Universiti
Teknologi Petronas (YUTP) for financial support to carry out this research through Centre of Innovative
Nanostructures and Nanodevices (COINN) Grant Scheme (YUTP 0153 AA-A99).

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