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Synthesis, Characterization, and Performance of Graphene Oxide and Phos-

phorylated Graphene Oxide as Additive in Water-Based Drilling Fluids

Eny Kusrini, Felix Oktavianto, Anwar Usman, Dias Puspitaning Mawarni,

Muhammad Idrus Alhamid

PII: S0169-4332(19)33822-X
DOI: https://doi.org/10.1016/j.apsusc.2019.145005
Reference: APSUSC 145005

To appear in: Applied Surface Science

Received Date: 24 January 2019

Revised Date: 5 December 2019
Accepted Date: 6 December 2019

Please cite this article as: E. Kusrini, F. Oktavianto, A. Usman, D. Puspitaning Mawarni, M. Idrus Alhamid,
Synthesis, Characterization, and Performance of Graphene Oxide and Phosphorylated Graphene Oxide as
Additive in Water-Based Drilling Fluids, Applied Surface Science (2019), doi: https://doi.org/10.1016/j.apsusc.
2019.145005

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 Synthesis, Characterization, and Performance of Graphene Oxide and Phosphorylated

Graphene Oxide as Additive in Water-Based Drilling Fluids

Eny Kusrini1,*, Felix Oktavianto1, Anwar Usman2, Dias Puspitaning Mawarni3, Muhammad

Idrus Alhamid4

1
Department of Chemical Engineering, Faculty of Engineering, Universitas Indonesia,

Kampus Baru-UI Depok, 16424, Indonesia

2
Department of Chemistry, Faculty of Sciences, Universiti Brunei Darrusalam, Negara Brunei

Darussalam
3
Faculty of Medical, Veteran National Development University of Jakarta, 16514, Indonesia
4
Department of Mechanical Engineering, Faculty of Engineering, Universitas Indonesia,

Depok 16424, Indonesia

Corresponding author’s e-mail address: ekusrini@che.ui.ac.id, Tel.: +62-21-7863516 ext.

*

204, Fax: +62-21-7863515.

 Abstract

Graphene oxide (GO) and phosphorylated graphene oxide (PGO) have been synthesized from
graphite electrode waste (GrW) or spent pot lining (SPL) from industrial aluminum wastes. The
graphite waste was successfully recovered from the industrial aluminum wastes by alkaline and
acid leaching method. The GO was then synthesized according to modified Hummers method
in room temperature. The addition of oxygen into graphite structure was indicated by the
formation of new vibrational bands at 3344, 1727, and 1069 cm-1 in the infrared (IR) spectrum,
and the increase of oxygen content was confirmed by energy dispersive X-ray (EDX). The
formation of single or few layers of graphene is confirmed through X-ray diffraction (XRD)
analysis which show a down shift of 2θ peak and longer interlayer distance. Additional
phosphate group to graphene oxide in functionalization process, in order to enhance the
dispersion of graphene in water, was confirmed by scanning electron microscopy-energy
dispersive X-ray (SEM-EDX). The effect of heat treatment on phosphorylated graphene oxide
(PGO) was investigated by calcination at different temperatures (200–500ºC). The Fourier
transform infrared (FTIR) spectroscopy and EDX results indicated that heat treatment
decreased the oxygen containing group in PGO. An addition of GO as additive in water-based
drilling fluids resulted in better rheology properties (plastic viscosity (PV) reduced from 10 to
7 cp and yield point (YP) increased from 11 to 15 lbs/100 ft2), an increase in fluid loss control
performance (filtrate volume decreased from 6 mL to 3.6 mL and filter cake thickness reduced
from 1.06 to 0.33 mm), and an increase in lubricity ability (lubricity coefficient reduced from
0.158 to 0.119). In the alkaline environment, the bentonite particles are negatively charged, and
GO may also turn to be negatively charged. The repulsive static interaction might reduce the
plasticity. The zeta potential of the GO and PGO was measured to be -38.90 and -41.23 mV,
indicating that both are not easily agglomerated. The additional PGO as additive in water-based
drilling fluids showed a negative impact due to significant pH decreased of drilling fluid.

Keywords: Additive; Functionalized graphene structure; Graphite waste; Modified Hummers

method; Phosphorylated graphene oxide; Water-based drilling fluids

1. Introduction

Aluminum (Al) industry continues to grow rapidly year by year with the production rate
of 5% per year, and it was predicted to reach 68 million tons in 2020 [1]. Such an increasing in
Al production prompts an increase in the use of graphite electrode in electrolysis of Al2O3. The
electrolytic cell lining should be replaced every 3–5 years, and the spent pot lining (SPL) or
graphite cathode (GrW) become solid waste of Al industry. This waste contains hazardous
materials such as fluoride and cyanide, which are soluble in water and can cause serious health
and environmental problems. Direct landfill method is the most conventional and widely
practiced, therefore discharged SPL causes surrounding environment issues.
The main content of SPL is carbon in the form of graphite (85%) [2], which can be actually
utilized as raw material to produce graphene-related materials. Graphene is well known as
an allotrope of two-dimensional planar sheets of sp2-bonded carbon atoms, and it has
extraordinary mechanical, electrical, thermal, and physical properties [3]. Owing to the
interesting properties, graphene has been widely studied and potentially utilized in various
applications. The utilizations of graphene into final applications face many problems, mainly
because of high production cost, low yield, and low quality. To overcome these problems,
chemical oxidation of graphite followed by its reduction has become the most potential and
economical route to produce graphene. In this sense, Hummers method is the most popular, but
this method has few issues of safety aspects as it involves reactions at high temperatures,
and NOX gas is produced.
In order to utilize graphene, its dispersion is an important issue, since it is usually applied
using solvent-assisted techniques, such as layer by layer assembly, spin-coating, and filtration
[4]. Graphene is only well dispersed in some uncommon organic solvent such as N-
methylpyrrolidone (NMP), dimethyl sulfoxide (DMSO), and dimethylformamide (DMF) [5],
while dispersion of graphene in common solvent can only be achieved by long sonication time
[6]. To achieve well dispersed graphene, chemical modifications on its surface can be applied.
Although, graphene oxides show great dispersibility in water, but the oxygen containing groups
cause significant decrease in their electrical properties [4]. To overcome this problem, other
functional groups have been introduced on the graphene structure. The functionalization of
graphene can be performed by covalent and non-covalent modification techniques, and in both
cases the surface modification is followed by reduction to obtain functionalized graphene [4, 7-
9].
 One of fascinating applications of graphene is its utilization as additive in water-based
drilling fluid. Thermal stability, reduced fluid loss, and lubricating capabilities are the main
advantages of additional graphene to the drilling fluid [10]. In this sense, graphene could
penetrate microscopic holes of metal and then crystallize at high pressure to form a protective
layer to increase lubrication, improving penetration rates during drilling. As an American
Petroleum Institute (API) standard filtration test on water-based drilling fluid, graphene oxide
concentration of about 0.2 (w/w.%) should result in lower filtrate volume and thinner filter cake
compared to standard suspensions of clay and polymers used in the petroleum industry [11].
The graphene oxide mixture should also have better shear thinning and thermal stability at
higher temperatures compared to clay-based additives [12].
In this study, SPL is used as raw material to synthesize graphene-based compounds, and
possibility of the synthesized graphene oxide (GO) to be utilized as drilling fluid additive is
also investigated. The GO was then chemically modified by introducing phosphate group is on
the graphene surface in order to achieve its good dispersion of the modified GO in water [12].
Here, in order to minimize defect to the synthesized graphene structure, thermal reduction has
been selected, instead of chemical reduction. It should be noted that the thermal reduction could
also suppress the use of reagents and solvents, which may produce new type of wastes and new
environmental problems. The phosphorylated graphene oxide (PGO) was found to have good
thermal and electrical properties and high cation exchange capacity. Possibility of this graphene
family member related substance to be utilized as drilling fluid additive to increase drilling fluid
performance also investigated.

2. Experimental
2.1 Materials
SPL was obtained from aluminum industry (Inalum Co., Indonesia) and it was used as the
raw material. Sulfuric acid (H2SO4 95-97%) for analysis, potassium permanganate (KMnO4)
crystals, hydrochloric acid (HCl 37%), sodium hydroxide (NaOH) pellets, ortho-phosphoric
acid 85% for analysis (H3PO4 85%) were purchased from Merck (Darmstadt, Germany) and
they were used without any further purification.

2.2 Purification of SPL

Two steps of leaching techniques were used to recover graphite from SPL according to the
procedure reported by Shi et al. [13]. In brevity, SPL was crushed and screened to uniform 200
mesh-sized particles. SPL powder was then reacted with 2.5M NaOH for 3 h at 90ºC with ratio
of 6 mL NaOH to 1 g SPL. Precipitate was then separated from liquid, washed with
demineralized water, and dried at 60ºC for about 12 h. The obtained solid was then further
reacted with 9.7 M HCl at 90ºC for 3 h. Precipitate was separated from liquid, washed with
water, and dried in oven at 60ºC.

2.3 Synthesis of graphene oxide (GO)

The obtained graphite (Gr) after the purification steps was then oxidized using modified
Hummers method [14]. Here, graphite was dissolved in sulfuric acid-phosphoric acid (H2SO4-
H3PO4) mixture under continuous stirring. Potassium permanganate (KMnO4) was added
slowly while temperature of the mixture was maintained under 60ºC, forming dark greenish
solution. The mixture was then continuously stirred at room temperature for 72 h. Weight ratio
of reactants was varied to be KMnO4:graphite = 6:1, KMnO4:H2SO4-H3PO4 = 1:20, and
H2SO4:H3PO4 = 9:1.
After 72 h, the reaction was stopped by adding an excess of cold water and hydrogen
peroxide (35 v/v%) until the yellowish-brown solution was formed. Graphite oxide was then
separated from solution by centrifugation at 8000 rpm for 10 min. Then, the obtained precipitate
was repetitively washed with 2 M HCl and water several times until pH of the mixture reached
4–5. Sonication then was applied for 15 min in order to ensure exfoliation of graphite oxide to
form graphene oxide (GO).

2.4 Functionalization of GO and heat treatment of PGO

At this stage, GO was reacted with H3PO4 85% at 50ºC for 12 h. Ratio of H3PO4 to GO
was varied to be within 70–90 mL to 1 g. Dark greenish solution was formed at this step. After
the reaction finished, washing process with water was done several times until pH of mixture
reached 4–5. Drying process was done by heating the mixture at 70ºC until water content was
not detected, giving the dried crude product of PGO. Hereafter, it was recalled as PGO 70 (ratio
H3PO4 = 70 mL/ g GO) and PGO 90 (ratio H3PO4 = 90 mL/ g GO). The PGO was then heated
in furnace at different temperatures; 200, 400, and 500ºC, for 1 h to eliminate oxygen containing
groups and other volatile compounds. The effect of the heat treatment was confirmed through
characterization.

2.5 Drilling fluid performance test

In this step, GO, PGO 70, and PGO 90 were added to water-based drilling fluid
formulation. The performance of the drilling fluid was tested according to the API standard,
which involved rheology properties, fluid loss, and lubricity. Dosage of 2.4 lb/barrel graphene
family member substance is used for the tests. In prior to the tests, drilling fluid was rolled at
high temperature (135ºC or 275 F) to simulate real operation condition and to observe
possibility of GO and PGO applications at high temperature operation. The formulation of
drilling fluid used in this study was according to the formulation used in an actual wellbore in
Indonesia, as presented in Table 1. Weight of water as based drilling fluid is 319 g. The mixer
setting was set in low speed mode.

2.6 Characterization technique

The structures of the purified GO and PGO were confirmed through Fourier transform
infrared (FTIR) spectroscopy, X-ray diffraction (XRD), and scanning electron microscopy-
energy dispersive X-ray (SEM-EDX). FTIR spectrum was recorded using Thermo Scientific
Nicolet Is5, XRD analysis was performed using PANalytical Empyrean, and SEM-EDX was
measured using JEOL JSM-6510.

3. Results and Discussion

3.1 Purification of graphite waste (GrW)

The impurities contained in SPL include Na3AlF6, NaF, CaF2, Al2O3 and NaAl11O17 [15].
Similarly, based on the XRD analysis, graphite cathode (GrW) used in this study contained
graphite (carbon) of 85%, Villiaumite (NaF) of 6%, cryolite (Na3(AlF6) of 3% and calcium
fluoride (CaF2) of 4% and Valleriite (Mg.68Al.32(OH)2) (Fe1.07Cu.93S2).6553) of 2% [2]. The
use of cryolite (Na3AlF6) in aluminum production process combined with high temperature of
operation for long time caused electrolyte to penetrate and underwent redox reactions in
graphite cathode. All these impurities in graphite waste should be removed during leaching
process of SPL, before it can be used as precursor for synthetic process of graphene derivatives.
In this study, the purification was based on leaching process which converted insoluble
impurities into soluble substances, thus they can be separated from graphite through
precipitation process. The purification process consisted of two steps of leaching with NaOH
and HCl, respectively. Reactions that took place during this step have been proposed by Shi et
al. as follows [13]:

Reaction with NaOH:

𝑁𝑎3 𝐴𝑙𝐹6 + 4 𝑁𝑎𝑂𝐻 → 𝑁𝑎𝐴𝑙(𝑂𝐻)4 + 6 𝑁𝑎𝐹 (1)
 𝐴𝑙2 𝑂3 + 𝑁𝑎𝑂𝐻 + 3 𝐻2 𝑂 → 2 𝑁𝑎𝐴𝑙(𝑂𝐻)4 (2)
Reaction with HCl:
𝑁𝑎𝐴𝑙11 𝑂17 + 34 𝐻𝐶𝑙 → 𝑁𝑎𝐶𝑙 + 11 𝐴𝑙𝐶𝑙3 + 17 𝐻2 𝑂 (3)
𝐶𝑎𝐹2 + 2 𝐻𝐶𝑙 → 𝐶𝑎𝐶𝑙2 + 2 𝐻𝐹 (4)
Metallic layer is formed after the reaction with NaOH took place, and this layer can be separated
from precipitate. The graphite obtained from this purification step (Gr) is in the form of black
powder, as shown in Figure 1.

3.2 Synthesis of GO

In this study, GO was synthesized at room temperature according to Hummers method with
slight modifications [13]. This method has a main advantage in safety aspect, as the oxidation
reaction took place at room temperature, eliminating any potential of unwanted explosive
reaction due to high temperature. Moreover, this method does not need any temperature control,
which makes this synthesis method more practical and low probability of failure. With this
method, Mn2O7, which was produced from reaction between KMnO4 and H2SO4, acted as
oxidizing agent. The reaction is suggested to be as follows:
𝐾𝑀𝑛𝑂4 + 3𝐻2 𝑆𝑂4 → 𝐾 + + 𝑀𝑛𝑂3+ + 𝐻3 𝑂+ + 3𝐻𝑆𝑂4− (5)
𝑀𝑛𝑂3+ + 𝑀𝑛𝑂4− → 𝑀𝑛2 𝑂7 (6)
The oxidation process can be observed visually through the change in colour of the mixture
during synthesis. In the early phase, the colour of reaction mixture is dark green from KMnO4,
and it becomes red-brownish originated from Mn2O7 as reaction progressed. Along the
synthesis of GO, exfoliation also took place during washing and sonication step, and GO was
successfully synthesized.

3.3 Functionalization of GO
Phosphoric acid is used as phosphate group source in this functionalization step. The
electrophile properties of GO make it suitable precursor to produce chemically modified
graphene. Oxygen containing groups of GO is reactive and can be further modified with other
functional groups. After reaction with phosphoric acid, homogeneous dark greenish solution of
PGO was obtained. This PGO visually showed good dispersiblity in water and formed stable
solution, which took longer time to settle because of highly hydrophilic phosphate group.
Phosphorus species was attached to carbon lattice through C–O–P bond resulted in PGO
structure, as shown in Figure 2.

3.4 Heat treatment of PGO

 Heat treatment of the obtained PGO was applied to eliminate volatile compounds and other
oxygen containing groups. The PGO was heated at 200, 400, and 500ºC, because these
temperatures are higher than oxygen group critical temperature but lower than phosphorus
species critical temperature (720ºC) [16]. The existence of oxygen containing groups in GO
could modify the graphene properties, especially its thermal and electrical properties. Thus, in
this work, oxygen containing groups are supposed to be completely eliminated from the
graphene. After the heat treatment, very fine particles of PGO were produced and significant
increase in volume was observed, indicating that further exfoliation process took place. Mass
reduction of heat treated PGO indicated the elimination of some oxygen containing groups from
the PGO structure. The PGO was heated at 200, 400, and 500ºC, respectively, then they were
named as PGO (200), PGO (400), PGO (500).

3.5 Characterizations

3.5.1 FTIR studies

Figure 3 shows FTIR spectra of purified graphite (Gr), GO, and PGO, along with graphite
waste (GrW). It is clearly observed that most of peaks and noises which previously existed in
graphite waste (GrW) disappeared in purified graphite (Gr) after leaching process. This
indicates that most of impurities in Gr have been successfully removed from GrW. As compared
to Gr, the FTIR spectrum of GO shows new peaks at 3344, 1726, 1627, and 1073 cm-1 related
to  (O-H),  (C=O),  (C=C), and  (C–O) stretching mode, respectively, which are the main
functional groups existed in GO structure (see Figure 3). These peaks are similar observed with
the FTIR result of GO with absorption peaks at 3397, 1730 and 1624 cm-1 are assigned to  (O-
H),  (C=O),  (C=C), respectively, that has been reported by Liu et al. [17].

After phosphorylation process, a new peak at wavelength 980 cm-1 observed which related
to P–O bond [18] and intense peak at wavelength 1226 cm-1 due to P=O bond in accordance
with structure of PGO (see Figure 2(c)). The FTIR spectrum of PGO 70 resembles that of PGO
90. However, the heat treatment of PGO apparently caused reduction or elimination in most of
oxygen containing groups, as it can be seen from PGO (200), PGO (400), PGO (500) which
show decreased in FTIR intensity related to oxygen group such as OH, C=O, C–O. Higher
temperature caused elimination of more oxygen containing groups. It can be clearly seen that
almost all of peaks related to oxygen containing groups have been significantly reduced, but
peaks related to P–O bond (980 and 1226 cm-1) remained due to high thermal stability of P–O
bond.

3.5.2 XRD studies

XRD patterns of Gr, GO, and PGO are shown in Figure 4. XRD pattern of Gr shows sharp
peak at 2θ value = 26.44º with 0.336 nm interlayer separation which indicates high crystallinity
and well-ordered layer stacking of graphite. This result confirmed the precipitate purified from
SPL to be graphite. The XRD pattern of GO showed spectral shift at 2θ = 9.48º and increasing
in interlayer space to 0.932 nm, which is similar to the results reported in the synthesized GO
[13]. The existence of oxygen groups in GO is known to weaken van der Waals interaction
between lattice layers in the graphite structure, leading to an increase in interlayer distance and
exfoliation of graphite layer. It is noticed that XRD peaks of GO were wider compared those
of Gr, indicating more amorphous structure of GO due to the exfoliation process.
Phosphorylation of GO caused further exfoliation process resulted in more amorphous structure
which can be seen from XRD pattern of PGO, where its interlayer space (10.68 nm) is slightly
increased compared with that of GO. Interestingly, heat treatment on PGO at 200ºC does not
cause significant change in PGO crystal structure, suggesting that most of oxygen containing
groups are not decomposed upon heating at this temperature for 1 h. However, XRD patterns
of PGO synthesized at higher temperature (PGO-400 and PGO-500) show a peak shift to 24.65º
and lower interlayer distance (3.61 nm) is observed due to the elimination of oxygen containing
groups from the carbon graphene lattice.

Layer distance of PGO-400 is similar to that of purified graphite (Gr) but the crystallinity
is less, implying that graphene layer is further exfoliated and randomly arranged. Pressure is
generated between layers when oxygen containing groups are decomposed from PGO structure.
Heat treated PGO-90 (PGO-90 (400) and PGO-90 (500)) are more amorphous, especially in
PGO-90 (400) shows no diffraction peak. Thus, PGO-90 (400) is fully exfoliated or fully
amorphous structure upon heat treatment. From this result, it can be seen that during calcination
further exfoliation took place and resulted in fewer layer of graphene.

From XRD peaks, average number of layers in graphite and graphene-related compounds
can be calculated using Debye-Scherrer equation [19], 𝑡 = 0.89𝜆⁄𝛽 cos 𝜃. In this sense,
stacking height and lateral size of crystallites were calculated by Debye-Scherrer equation, and
they can be used to estimate the graphene structure. The calculation results are presented in
Table 2. It was found that oxidation process significantly reduced the number of layers of the
synthesized GO.

For comparison purposes, commercial additives such as Soltex [20] and Duraton were also
characterized by XRD. Soltex is a sulfonated asphalt that made from the sulfonation method
[21]. Based on the XRD patterns, Soltex and duration are amorphous. Soltex has peaks at 2 of
19.98, 32.28, 32.89 and 48.75, while Duraton has peaks at 2 of 12.39, 20.86, 24.84, 26.63
and 38.33 (see Figure 5a and b). Soltex can enhance filter cake properties in both water and
oil-based muds. Soltex also can be used as stabilizer shale formation and increase lubricity and
control high temperature high pressure (HTHP) fluids loss in water and oil-based muds [21]. In
addition, it can be stably used in drilling application until temperature of 260C or 500 F [21].
In our studies, we only conducted the simulation drilling fluids at 275 F and water-based mud.

3.5.3 SEM-EDX studies

As shown in Figure 6(a), SEM images of GrW showed some small pieces of objects on the
surface of graphite structure which can be considered to be impurities. After purification
process, large area of graphite plane was observed and showed fewer objects on plane surface
(Figure 6(b)). SEM image of GO shows disorganized arrangement of layer caused by
exfoliation and folding of graphene layer, and some transparent area also observed which
indicates fewer layer of GO compared to graphite (Figure 6(c)). Introduction of phosphor to
GO structure caused reduction in pore size of PGO (see Figure 6(d)). Heat treatment of PGO
(Figures 6(e) and (f)) caused further exfoliation process resulted in more transparent layer of
graphene especially in PGO-70 (400). The zeta potential of the GO and PGO was measured to
be -38.90 and -41.23 mV, indicating that both are not easily agglomerated [22]. These surface
zeta potential are quite similar with GO (-34.3±2.2 mV) and polydopamine-GO (-37.1 ±1.1
mV) with previously observed by Liu et al. [17].

EDX result of GrW indicated the presence of many impurities, such as F, Al, Na, Ca, which
were originated from substances used during production process of aluminum. This finding is
quite similar with the waste cathode carbon block from waste aluminum cathode [23]. The Gr
showed significant reduction in impurities content (Table 3) which indicated that purification
process has been done effectively, eliminating those elements from GrW.
After oxidation of Gr, high content of oxygen is observed, indicating that highly oxidized
GO is successfully synthesized in this work. Addition of phosphor through functionalization
process with H3PO4 also can be observed in the EDX results (Table 3). Moreover, heat
treatment of PGO caused reduction of oxygen content and increased in carbon and phosphor
contents. This result suggests that during calcination process, the oxygen groups are partially
eliminated. Higher calcination temperature resulted in further elimination of oxygen containing
groups, which can be seen that PGO 70 (400) has a lower content of oxygen compared to PGO
70 (200).

3.6 Performance Application as Additive in Water-Based Drilling Fluids

The mixer was set in low speed mode (see Figure 7). Figure 8 shows the illustration of GO
or PGO as drilling fluid additive, where arbecel PAC LV is carboxymethyl celullose, and unibar
is barite. The data of drilling performance tests are summarized in Table 4. The tests were done
after drilling fluid was heated in rolling oven at temperature 275 F. The results indicated that
the addition of GO particles to drilling fluid formulation increased the performance of the
drilling fluid. Although the detailed mechanism of the improvement of water-based drilling
fluid upon the addition of GO is still an open question, but the changes in rheology, fluid loss,
plastic viscosity (PV), increased in yield point (YP) and gel strength of the fluid demonstrated
the applicability of the GO as additive in water-based drilling fluids [24]. From rheological
properties, addition of GO led to a decrease in PV, increased in YP and gel strength compared
to the blank (see Table 4). As we know that PV is a function of the solid particles concentration,
size and shape and the viscosity of the fluids phase of drilling fluid [25, 26]. The addition of
GO, PGO 70 and PGO 90 (3.050%) reduces the plastic viscosity in fluids. This is because the
size of decrease, thus reducing their size resulting in less friction and easy resistance to flow. It
can be rationalized that highly negative charge of GO in drilling fluid will neutralize positive
charge of bentonite clay, resulting in lower liquid viscosity which, in turn, causes lower PV
value even though addition of GO will increase solid content of drilling fluid. The lower PV
value has a positive impact in drilling operation to avoid high pressure drop along drilling string
that can decrease fluid circulation and fluid ability to lift cutting.

Increasing the yield point (YP) because of the decrease in viscosity and increase the
internal force of the fluid. The surface area of nanomaterials such as GO and PGO increase,
thus their surface energy increase. Thereby, the particle is attraction and the particles grow up
and adhere together to decrease the surface energy, thus increase in YP. Increasing the YP will
enhance the ability of fluids to clean the drilling cutting from reservoir well and decrease the
torque of the drill string and also decrease the adhere drill string. This value is slightly lower
than addition of commercial products. Interaction between well-dispersed GO particles resulted
in higher gel strength value because of the attraction force between particles [26]. Our results
are comparable with the GO-ZnO nanocomposite that reported as additive on drilling fluids and
its potential for removal of H2S in oil reservoir in laboratory scale [26]. The increase in the
rheology properties such as plastic viscosity (5 – 28%), YP (25-42%) and gel strength (25-33%)
decreases the filtration rate. Increasing the YP, gel strength and shear rate can increase drilling
mud performance, thus it is preferred to carry the drilling cutting, reducing the drilling string
torque and avoid adhere of the drill string [26].

For API fluid loss test, GO showed good performance compared to additive commercial
product resulted in lower value of filtrate volume and significant reduction of cake thickness
(almost 70% reduction compared to additive commercial product). Small particle sizes in
suspension system, low layer thickness of GO caused by exfoliation, and good dispersible of
GO are the main reasons of superior performance of GO as fluid loss control. Moreover,
addition of GO also gives better lubricity result of drilling fluid. Figure 9 shows the comparison
between GO and PGO as drilling fluid additive resulting in significant reduction of cake
thickness.

Addition of GO into the drilling fluid resulted in decreasing of the pH value from 8.36 to 7.78,
but it is still adequate for drilling application. Meanwhile, addition the PGO 70 and PGO 90
into drilling fluid, the pH is drop until 3.67 and 3.36, respectively, which is detrimental to
drilling fluid properties maintenance. PGO caused significant decreased in pH value of overall
mud system (less than pH 4), resulting in low drilling fluid performance. The low pH causes
unfavourable condition for other substances used in drilling fluid formulation, especially
polymer substance which can be degraded in low pH condition. Highly acidic property of PGO
is caused by hydrolysis of polyphosphate structure in PGO to orthophosphate while rolled in
high temperature during testing procedure. Thus, this result indicates that PGO is not suitable
to be used at high temperature operation in drilling application up to 275 F.

A drilling fluid formulation have been investigated by many researchers to obtain the optimal
and the best drilling mud formulation. This is needed to fulfill the minimum cost for drilling of
well. Generally, cost for drilling is usually constant if they did not have any problem in well
and or instability in well [20]. In order to develop the drilling fluid system, each component and
mixing technology are required to obtain the best of mud formulation. The price a commercial
additive such as Soltex is about 108 USD for 25 kg [20]. Herein, the feasibility of GO as an
additive in water-based drilling fluid is still of interest, and it has been previously
demonstrated that control of equivalent circulation density (ECD) of GO is very important for
such an application. If ECD of GO is too high, it causes loss of circulation, and vice versa if it
is too low, it causes kick. Based on the ECD simulation, graphene is more suitable for high
pressure wells, meanwhile GO is more suitable for low pressure wells [27].

4. CONCLUSION

In this study, graphene oxide (GO) and phosphorylated graphene oxide (PGO) have been
successfully synthesized from SPL of aluminum industrial waste. The chemical structures of
GO and PGO were confirmed through FTIR, SEM-EDX, and XRD characterizations. Heat
treatment of PGO caused reduction in oxygen content and further exfoliation process. An
addition of GO into drilling fluid led to an increase in the performance of water-based drilling
fluid, as indicated by better rheological properties (a reduce in plastic viscosity from 10 to 7 cp
and an increase in yield point from 11 to 15 lbs/100 ft2), the decrease in fluid loss (6 to 3.6 mL),
thinner filter cake (1.06 mm to 0.325 mm), and better lubricity parameter (lubricity coefficient
decreased from 0.158 to 0.119) compared to base formulation. Meanwhile, an addition of PGO
into drilling fluid caused lower drilling fluid performance, because of degradation of
polyphosphate to orthophosphate at high temperature. Thus, due to its low pH addition of PGO
is unfavourable for other substances used in formulation of drilling fluid.

Acknowledgments

The authors greatly acknowledge the Ministry of Research, Technology and Higher Education

of the Republic of Indonesia for research grant award through PTUPT grant, No. NKB-

1732/UN2.R3.1/HKP.05.00/2019. Also we appreciate to Dwi Aprillia Wulandari, S.Si., M.Si.

from Universitas Indonesia for her support in providing the Figures.

Declarations

Author contribution statement

Eny Kusrini: Conception, experimental design, manuscript composition and wrote the paper.

Felix Oktavianto: Performed the experiments

Anwar Usman and Muhammad Idrus Alhamid: contributed reagents, materials, analysis tools

and interpreted the data.

Dias Puspitaning Mawarni: Contributed for preparing of figures

Competing interest statement

The authors declare no conflict of interest.

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 (b)
(a)

Figure 1. Metallic layer is formed after the reaction with NaOH took place (a) and the purified

graphite (Gr) is in the form of black powder (b)

 (a) (b) (c)

Figure 2. Structure of (a) graphene oxide (GO), (b) phosphorylated graphene oxide (PGO), and

(c) heat treated PGO

Figure 3. FTIR spectra of graphite waste (GrW), purified graphite (Gr), GO, PGO and
heated PGO at 400 and 500C
 Gr

GO
Intensity

PGO70
PGO 70 (400)

PGO70
PGO 70(200)
(500)
Intensity

PGO
PGO70
PGO 90(400)
70 (400)

10 20 30 40 50 60 70
PGO70
90(500)
(400)
80
PGO
2 theta
Intensity

PGO
PGO90
90 (500)

10 20 30 40 50 60 70 (400)
PGO 90 80
2 theta

PGO 90 (500)

10 20 30 40 50 60 70 80
2 theta

Figure 4. XRD patterns of Gr, GO, PGO and heat treatment of PGO in 200, 400 and 500ºC
 a
350
300
Intensity (a.u.)

250
200
150
100
50
0
0 5 10 15 20 25 30 35 40 45 50 55 60 65
2θ ()

b
450
400
350
Intensity (a.u.)

300
250
200
150
100
50
0
0 5 10 15 20 25 30 35 40 45 50 55 60 65
2θ ()

Figure 5. XRD patterns of commercial additive for drilling fluids for a) Soltex (sodium asphalt

sulfonate) and b) Duraton

 (a) (b) (c)

(d) (e) (f)

Figure. 6. SEM images with 25.000 magnification for (a) GrW; (b) Gr; (c) GO; (d) PGO-70; (e)

PGO-70 (200); (f) PGO-70 (400)

Figure 7. The mixer setting was set in low speed mode.
Figure 8. Illustration of GO or PGO as drilling fluid additive, where arbecel PAC LV is
carboxymethyl celullosa, and unibar is barite
Figure 9 Comparison GO and PGO as drilling fluid additive resulted significant reduction of

cake thickness, where arbecel PAC LV is carboxymethyl celullosa (CMC)

Highlights
 GO and PGO have been synthesized from graphite electrode waste
 Effect of heat treatment on PGO was investigated by calcination at different
temperatures
 GO as additive in water-based drilling fluids resulted in better rheology properties
 GO increase in fluid loss control performance and an increase in lubricity ability
 PGO as additive showed a negative impact because significant pH decreased of
drilling fluid
Table 1. Water-based drilling fluid formulation

Component Dosage (g) Percentage (%) Time (min) Speed mode

Bentonite 6 7.624 5 Low
KOH 0.6 0.762 3 Low
KCl (97%) 34 43.202 10 Low
Diazo vispol 1.7 2.160 5 Low
Carboxymethyl celullosa 4 5.083 5 Low
Unistarch 4 5.083 5 Low
Additive 2.4 3.050 5 Low
Barite 26 33.036 5 Low

Table 2. Estimation of layer number for Gr, GO, and PGO

2θ FWHM (rad) d (nm) t (nm) n

Gr 26.44 0.0048 0.336 29.495 88

GO 9.48 0.0171 0.932 8.041 9

PGO 70 8.27 0.0361 1.069 3.804 4

PGO 90 8.41 0.0357 1.021 3.847 4

Table 3. EDX elemental analysis of GrW, Gr, GO, PGO and and heat treatment of PGO in 200
and 400ºC
Element Material

GrW Gr GO PGO 70 PGO 70 (200) PGO 70 (400)

C 72.97 88.15 51.23 48.69 54.5 58.59

O 9.58 6.46 47.26 44.39 36.56 31.16

P - - - 5.83 6.86 8.22

Al 3.31 0.69 0.29 0.33 0.22 0.52

F 9.35 0.47 - - - -

Na 4.1 1.08 - - - -

Cu 1.73 2.26 0.81 0.76 0.54 0.51

Ca 0.69 0 - - - -

Cl 0 0.89 0.41 - 0.32 -

Table. 4. Comparison data of commercial, GO, and PGO as additive in water-based drilling

fluids

Mud properties Results at 275F

Unit Blank Commercial GO PGO 70 PGO 90
PV Cps 10 17 7 2 1
YP lbs/100 ft2 11 19 15 2 2
Gel Strength 10" lbs/100 ft2 3 7 7 2 2
Gel Strength 10' lbs/100 ft2 3 5 8 2 2
LSR YP lbs/100 ft2 0 3 3 1 1
pH 8.36 9.2 7.78 3.67 3.36
Volume filtrate ml/30" 6 4.5 3.6 > 50 > 50
Mud Cake API Mm 1.06 1.18 0.325 1.24 1.135
Lubricity - 0.158 0.089 0.119 0.137 0.137