Applied Clay Science 161 (2018) 427–435

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Applied Clay Science

journal homepage: www.elsevier.com/locate/clay

Research paper

Magnesium aluminum silicate nanoparticles as a high-performance T

rheological modifier in water-based drilling fluids
⁎
Kai Wanga,b, Guancheng Jianga,b, , Fan Liua,b, Lili Yanga,b, Xiaoxiao Nia,b, Jinxi Wanga,b
a
College of Petroleum Engineering, China University of Petroleum (Beijing), 18 Fuxue Road, Changping, Beijing 102249, People's Republic of China
b
State Key Laboratory of Petroleum Resources and Prospecting, Ministry of Education (MOE) Key Laboratory of Petroleum Engineering, China University of Petroleum
(Beijing), 18 Fuxue Road, Changping, Beijing 102249, People's Republic of China

A R T I C LE I N FO A B S T R A C T

Keywords: Horizontal well operations are playing an important role in extraction of oil and gas in recent years. However,
Nano-sized layered material cuttings sediments occurred frequently in the long horizontal section, causing friction increases and drill pipe
Water-based drilling fluids sticking. This study demonstrated a nano-sized layered material, i.e. magnesium aluminum silicate (MAS), as a
Rheological modifier high-performance rheological modifier in water-based drilling fluids (WBDs) to avoid the sedimentation of
Horizontal wells
suspended cuttings. A series of rheological tests indicated that low-concentration MAS suspensions exhibited
Carrying cuttings
better shear-thinning performance, higher gel strength, and quicker recovery ability of gel structure, which are
the key factors for effectively carrying cuttings, than the commonly used high-concentration sodium bentonite
(Na-BT) suspensions. The particle size distribution analyses revealed that the MAS maintained smaller particle
size (d50 = 50.70 nm) than that of Na-BT (d50 = 9.99 μm), when dispersed in water. Furthermore, the results of
transmission electron microscopy analysis demonstrated that nano-sized MAS formed much denser network
structures than larger micron-sized Na-BT. In addition, scanning electron microscopy analysis indicated that
MAS suspensions maintained much smoother filtrate cakes than Na-BT suspensions and effectively filled the tiny
pore of filter paper with 80 nm pore size to mimic fine-grained formations. Moreover, after hot rolling at 150 °C
and 120 °C, the pure MAS suspensions and WBDs containing MAS maintained better rheological and filtration
properties, inferring excellent thermal stability of MAS. These results suggest that the MAS is expected to become
a high-performance rheological modifier in WBDs for horizontal well drilling, by maintaining excellent rheo-
logical properties, exhibiting good thermal stability, forming smoother filtrate cakes and reducing the friction
and torque.

1. Introduction
Horizontal wells, together with multi-branch horizontal wells,
cluster wells and extended reach wells are regarded as the advanced
well style to extract oil and gas in recent years. These wells not only
significantly improve the outflow areas of oil and gas to enhance the
production greatly, but also save operating costs and reduce the number
of wellsites (Baba Hamed and Belhadri, 2009; Li et al., 2016b, 2017b;
Wang et al., 2014; Zhou et al., 2016). Nevertheless, cuttings sedi-
mentation and the formation of a “cuttings bed” can develop in the long
horizontal section of horizontal wells, causing an increase of friction
and pipe sticking problems (Egenti, 2014). Drilling fluids are essential
for oil and gas drilling exploration, which can transport cuttings from
well bottom to ground surface, support the wall of the well, ensure well
stability, balance formation pressure, cool and lubricate drilling
equipment, and help break rocks (Kelessidis et al., 2011; Li et al., 2015;
Yang et al., 2017a). The primary function of drilling fluids is suspending
and carrying cuttings. However, it is difficult to effectively transport
cuttings from the horizontal section of horizontal wells to ground sur-
face using common drilling fluids. Therefore, it is necessary to develop
high-performance drilling fluids with excellent rheological properties in
order to reduce or eliminate the problem of cuttings sedimentation in
horizontal wells. Drilling fluids are categorized according to composi-
tion, and mainly include water-based drilling fluids (WBDs), oil-based
drilling fluids (OBDs), and synthetic drilling fluids (SBDs). WBDs are
considered as the environmentally friendly, low-cost, and preferred
drilling fluids, compared with OBDs and SBDs (Kelessidis et al., 2013;
Zakaria et al., 2012).
Sodium bentonite (Na-BT) as a common rheological modifier is
widely used with WBDs (Song et al., 2016), because the Na-BT can
disperse, swell, and exfoliate easily in water. The resulting dispersion
constructs a characteristic “house of cards” structure (Yang et al.,

⁎
Corresponding author at: College of Petroleum Engineering, China University of Petroleum (Beijing), 18 Fuxue Road, Changping, Beijing 102249, People's Republic of China.
E-mail address: m15600263100_1@163.com (G. Jiang).

https://doi.org/10.1016/j.clay.2018.05.012
Received 12 March 2018; Received in revised form 11 May 2018; Accepted 11 May 2018
Available online 26 May 2018
0169-1317/ © 2018 Elsevier B.V. All rights reserved.
K. Wang et al. Applied Clay Science 161 (2018) 427–435

2017b) and possesses the ability to suspend cuttings and weighting Table 1
materials. In addition, the Na-BT forms a relatively thin and compact chemical and mineral compositions of the MAS and Na-BT (wt%).
filter cake to protect the wall of the well and block the penetration of Chemical SiO2 Na2O Al2O3 MgO CaO Fe2O3 SO3 K2O P2O5 TiO2
fluids into formations (Shakib et al., 2016). Generally, high amounts of
Na-BT are required for WBDs to obtain adequate suspending and car- Na-BT 62.49 4.44 19.09 3.67 3.17 4.62 0.44 0.88 0.17 0.76
MAS 63.99 4.32 0.43 28.83 0.24 0.04 0.64 0.01 0.02 0.02
rying capacities to effectively transport cuttings. However, WBDs with a
high concentration of Na-BT may generate thick filter cakes and in-
crease the plastic viscosity, which can cause pipe sticking and formation Mineral Montmorillonite Kaolinite Calcite Dolomite Feldspar Quartz
damage problems and ultimately result in a decrease of drilling effi-
ciency (Li et al., 2015). Thus, a variety of natural or synthetic polymers Na-BT 78.7 1.6 9.5 3.2 2.6 4.4
are introduced into WBDs to improve the function of low-concentration MAS 94.8 - 5.2 - - -

Na-BT suspensions, supplying optimal rheological and filtration control
properties.
Natural polymers, such as xanthan gum, starch, polyanionic cellu-
lose (PAC), and carboxymethyl cellulose (CMC) are environmentally
friendly and can modify the rheological and filtration control properties
in WBDs efficiently (Ismail et al., 2016; Li et al., 2016a; Song et al.,
2016). However, these natural polymers do not maintain their prop-
erties in WBDs under high temperatures due to thermal degradation
(Dias et al., 2015; William et al., 2014; Yan et al., 2013). To overcome
the drawback, many polymers with higher thermal stability were syn-
thesized. Yan et al. synthesized an amphiphilic comb-like terpolymer,
which enhanced greatly the rheological and filtration control properties
in low-solid WBDs under a high temperature of 150 °C (Yan et al.,
2013). Liu et al. demonstrated that the amphoteric polyacrylamide
derivate increased the viscosity of Na-BT dispersions as well as reduced
the filtration volume under high calcium contaminations after 150 °C
hot rolling (Liu et al., 2016). Zhang et al. synthesized a quadripolymer
viscosifier, which maintained good rheological and filtration control
properties in clay-free WBDs at 90 °C (Zhang et al., 2017).
However, most of the synthetic polymers require complex pre-
paration procedures and may contain remaining toxic chemicals, which
are not environmentally friendly and thus restrict the application of
synthetic polymers in WBDs. Therefore, it is necessary to look for other
new materials, which can maintain the excellent rheological perfor-
mance to reduce or eliminate the problem of cuttings sedimentation as
well as producing smooth and thin filtrate cakes to lower the friction, as
the high-performance additive in WBDs for horizontal wells.
Additionally, the new material needs to maintain performance at high
temperatures, and be harmless to the environment. Our previous work
showed that Laponite nanoparticles can greatly improve the rheological
properties, filtrate cake quality, and nano-crack plugging performance
in WBDs; however, a high temperature or concentration is needed to
generate the excellent rheological properties (Liu et al., 2017).
Magnesium aluminum silicate (MAS) is a mixture of natural smec-
tite clays, mainly including montmorillonites and saponites
(Khunawattanakul et al., 2008; Lopezgalindo et al., 2007). MAS can
also be synthesized artificially. The MAS possesses a similar layer
structure as bentonite and belongs to the group of (2:1) phyllosilicates,
with layers composed of two silicon‑oxygen tetrahedral sheets either
side of a magnesium‑oxygen or aluminum‑oxygen octahedral sheet.
When the MAS is dispersed in water, negative charges are on the layer
surface and positive charges are on the edge of the layer, which is the
same as the bentonite. Moreover, it is noteworthy that the MAS sus-
pension exhibits excellent viscoelasticity and thixotropy
(Kanjanakawinkul et al., 2013; Pongjanyakul and Puttipipatkhachorn,
2009). Therefore, MAS has been extensively applied in various fields,
such as paints, pesticides, pharmaceutics, and cosmetics, to suspend
and stabilize medicines and pigments (Li et al., 2017a; Pongjanyakul
et al., 2005; Pongjanyakul and Suksri, 2010). These applications inspire
us to utilize the MAS in drilling fluids to generate high gel strengths,
which should facilitate effective suspension and transport of cuttings in
horizontal wells.
Although the MAS is used in various fields, there are few studies
about the application of the MAS as a rheological modifier in drilling
fluids. In this study, we investigated the rheological and filtration
“-”: no presence of the item.
control properties of the MAS, and comprehensive comparison studies
were performed with the commonly used Na-BT. The purpose of this
work was to develop novel, safe and high-performance materials for
WBDs, and to form low-solid and environmentally friendly WBDs,
which would reduce or eliminate the tendency for sedimentation of
cuttings in long horizontal well drilling.
2. Experimental part
2.1. Materials
Bentonite (sodium form) was purchased from Sigma-Aldrich Inc.
(America). Magnesium aluminum silicate (MAS) was purchased from
Sheng Xin Chemical Technology Co., Ltd. (Guangzhou, China). Barite
and polyanionic cellulose with low viscosity (PAC-LV) were kindly
provided by Shida Bocheng Technology Co., Ltd. (Beijing, China). The
chemical and mineral compositions of the MAS and Na-BT were de-
terminated by X-ray fluorescence (XRF) and X-ray diffraction (XRD)
(Chambi-Peralta et al., 2018), as shown in Table 1.
2.2. Preparation of the MAS and Na-BT suspensions
MAS powders were dispersed in deionized water with a vigorous stir
at 5000 rpm for 30 min. Then, the MAS suspension was stored in a
sealed bottle at 25 °C for 24 h. The MAS suspensions at concentrations
of 1.0 wt%, 1.5 wt% and 2.0 wt% were prepared, respectively. The
preparation procedures of Na-BT suspensions were identical to the MAS
suspension, but the concentrations of Na-BT suspensions were 4 wt%,
6 wt%, and 8 wt%. To simulate the high temperature of well bottom,
the hot rolling experiments were used to study the effect of high tem-
peratures on drilling fluids. Therefore, hot rolling experiments were
performed on the MAS and Na-BT suspensions. After the Na-BT and
MAS powders were dispersed in deionized water with the vigorous stir
at 5000 rpm for 30 min, these suspensions were placed into sealed
stainless steel aging cells (Fann Instrument Company, America). Then,
the aging cells were rolled at 150 °C for 16 h in a roller oven (Model
802P, Fann Instrument Company, America).
2.3. Rheological tests
Rheological tests of the Na-BT and MAS suspensions were conducted
by a HAAKE rheometer (Thermo Electron Corporation, Germany)
equipped with a cone-plate model at 25 °C. In addition, the gap between
the cone rotor and the plate is 53 μm, and the diameter of cone rotor is
35 mm, containing a cone angle of 1.0°. All tests begin with a pre-
shearing procedure (3 min, γ̇ = 3000 s − 1) and rest for 10 min to avoid
artificial errors causing by sample positioning. The apparent viscosity
was measured under a shear rate from 1000 s−1 to 0.1 s−1.
The frequency dependences of elastic modulus (G′) and viscous
modulus (G″) were measured by the oscillation frequency sweep,
choosing the strain (γ) in linear viscoelastic range, and the frequency
ranged from 0.01 to 10 Hz.

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K. Wang et al. Applied Clay Science 161 (2018) 427–435

Fig. 1. Apparent viscosity under different shear rates of MAS and Na-BT suspensions before (a) and after (b) hot rolling at 150 °C.

In the creep-recovery experiment, the creep stage was conducted at common rheological parameters of WBDs according to the American
a fixed shear stress (0.1 Pa) for 10 min first, and then recovery lasted for Petroleum Institute (API) guidelines. The stable dial readings were re-
10 min at zero shear stress, during which the creep compliance (Jc) and corded at rotations of 600 rpm (θ600), 300 rpm (θ300), 6 rpm (θ6), and
recovery compliance (JR) were measured accordingly. 3 rpm (θ3). The apparent viscosity (AV), plastic viscosity (PV), and yield
The alternate strain sweep experiment was performed to measure point (YP) were calculated by the following equations:
the G′ as a function of the alternate strain. The alternate strain sweep (1)
AV = 0.5 θ600
procedure was from 0.1% strain to 100% strain lasting 3 min respec-
tively, and repeated 3 times, with a fixed frequency of 2 Hz for the PV = θ600 − θ300 (2)
entire process.
YP = 0.51(θ300 − PV) (3)

2.4. Filtration testing The initial gel strength (Gel10 s) and 10 min gel strength (Gel10 min)
were recorded as the half of maximum dial reading at θ3 after standing
The filtration tests of the MAS and Na-BT suspensions stored at 25 °C undisturbed for 10 s and 10 min, respectively. The filtration volume
or hot-rolled at 150 °C were performed using a filter press (Fann (FLAPI) of WBDs was measured as the above filtration testing, using the
Instrument Company) according to the American Petroleum Institute API filter paper.
(API) fluids test guideline. All filtration tests were performed at 25 °C
under a 0.69 MPa pressure supplied by nitrogen. The filter paper used 3. Results and discussion
was Teflon filter paper (Minglie Membrane Corporation, Shanghai,
China) with 80 nm pore size instead of the API filter paper with 2.7μm 3.1. The shear-thinning performance of the MAS and Na-BT suspensions
pore size. The filtration volume (FLAPI) was recorded at 2.5, 5, 7.5, 10,
15, 20, 25, and 30 min, respectively. Generally, drilling fluids are non-Newtonian fluids with the shear-
thinning performance, which exhibit high viscosity at the annular space
2.5. Microstructural analysis (low shear rates), benefiting for carrying and suspending cuttings and
weighting materials, but low viscosity at the drilling bit (high shear
The filtrate cakes obtained were dried in a vacuum oven at 50 °C rates) with the benefit of hydraulic breaking rocks (He et al., 2018). As
before observation. The dried filtrate cakes were coated with Au and shown in Fig. 1, all suspensions displayed a typical non-Newtonian
observed by a SU8010 scanning electron microscopy (SEM) to study the pseudoplastic fluid (Eq. (4)). In Table 2, the apparent viscosity and
surface morphology of the filtrate cakes at a 5 kV accelerating voltage. shear rate were fitted using the Eq. (4) with a high R2.
The micro-morphology of the Na-BT and MAS particles suspended in μa = Kγ n − 1 (4)
water was observed by a F20 transmission electron microscopy (TEM)
from FEI Corporation (America) at 20 kV accelerating voltage. The Na- where μa is the apparent viscosity (mPa∙s), K is the flow consistency
BT and MAS suspensions were separately diluted to 0.1 wt% by deio- coefficient, γ is the shear rate (s−1), and n is the flow behavior index.
nized water. Then, the 0.1 wt% suspension experienced an ultrasonic The K and n are also displayed in Table 2. For the pseudoplastic fluid, a
dispersing process for 30 min, and was dripped onto a carbon film. After larger K indicates a higher viscosity at low shear rates, and a smaller n
the carbon was dried at 25 °C, the TEM measurement was conducted indicates higher shear-thinning performance. As shown in Table 2, the
immediately. low-concentration MAS suspensions were comparable with high-con-
The particle size distribution of the Na-BT in water was measured by centration Na-BT suspensions displaying a smaller n and a larger K. In
a Mastersizer 2000 analyzer (Malvern Instruments Ltd., UK). The par-
ticle size distribution of the MAS in water was measured by a Zetasizer Table 2
Nano ZS analyzer (Malvern Instruments Ltd., UK), because the MAS Pseudoplastic fluid fitting results of MAS and Na-BT suspensions.
particles were smaller than the micrometer scale. The zeta potential of Before hot rolling After 150 °C hot rolling
the Na-BT and MAS suspensions was also measured by the Zetasizer
n 2
K (Pa∙s ) n R K (Pa∙sn) n R2
Nano ZS analyzer (Malvern Instruments Ltd., UK). All suspensions were
given ultrasonic treatment for 30 min at 25 °C to make particles disperse 4% Na-BT 0.17 0.30 0.923 1.04 0.22 0.968
homogeneously in water, before measurements. 6% Na-BT 1.97 0.09 0.980 10.57 0.07 0.977
8% Na-BT 7.10 0.03 0.989 81.99 0.02 0.994
1% MAS 0.56 0.23 0.991 2.11 0.18 0.996
2.6. Rheological and filtration measurements of WBDs
1.5% MAS 2.11 0.13 0.997 8.58 0.10 0.999
2% MAS 7.27 0.05 0.998 18.61 0.09 0.999
A Fann model 35-A rotational viscometer was used to measure the

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K. Wang et al. Applied Clay Science 161 (2018) 427–435

addition, with increasing concentrations, the K was enhanced and n

declined for both MAS and Na-BT suspensions. These results indicated
that the low-concentration MAS suspension exhibited better shear-
thinning performance than a high-concentration Na-BT suspension. The
viscosity and shear-thinning performance of the Na-BT and MAS sus-
pensions were improved after hot rolling at 150 °C. However, the 8 wt%
Na-BT suspension lost flowability and showed excessively high viscosity
after hot rolling at 150 °C, as visually shown in Fig. 3, which should be
avoided for drilling fluids. Nonetheless, a low-concentration MAS sus-
pension (1 wt%, 1.5 wt%, and 2 wt%) still exhibited good shear-thin-
ning performance and suitable viscosity after hot rolling at 150 °C.
Moreover, the maximum solid content of MAS suspensions is only 2 wt
Fig. 3. Gel states of Na-BT and MAS suspensions before and after hot rolling at
%, belonging to the low-solid drilling fluids, which was beneficial for
150 °C. (a, b Na-BT suspensions with concentrations of 4 wt% and 8 wt%, re-
high drilling rates (Li et al., 2018).
spectively, were inverted after standing for 24 h at 25 °C; c, d MAS suspensions
with concentrations of 1 wt% and 2 wt%, respectively, were inverted after
3.2. Gel strength of the MAS and Na-BT suspensions standing for 3 h at 25 °C; a1-d1 suspensions were those of samples a-d after
shaking for 5 s; samples a2-d2 were those of samples a-d after hot rolling at
It is necessary to maintain relatively high gel strength for the WBDs 150 °C for 16 h; the orange color was dyed by biological stain).
to suspend and carry cuttings in long distance horizontal wells.
Furthermore, the high drilling efficiency can be obtained by reducing suspensions exhibited higher G′compared with high-concentration Na-
the circulating pressure loss in WBDs circulation. The elastic modulus BT suspensions, which were advantageous for suspending and carrying
(G′) was used to reflect the gel strength of the suspensions. In addition, cuttings. The low G″ of MAS suspensions would help reduce the circu-
the viscous modulus (G″), also known as loss modulus, was used to lating pressure loss, and improve drilling efficiency. After hot rolling at
reflect the circulating pressure loss of the suspensions. The frequency 150 °C, the G′ of MAS suspensions were properly improved, and the G″
dependences of both G′ and G″ of the Na-BT and MAS suspensions are of MAS suspensions were slightly increased. Unfortunately, the G′ and
presented in Fig. 2. The G′ and G″ of both Na-BT and MAS suspensions G″ of the 8 wt% Na-BT suspension dramatically increased after hot
improved with increasing concentration. Before hot rolling, the G′ of rolling at 150 °C, and the sample was not able to flow (Fig. 3b2).
the Na-BT and MAS suspensions exhibited a limited frequency depen- Moreover, after hot rolling at 150 °C, the G′ of the 4 wt% Na-BT sus-
dence, showing the typical gel feature. The low-concentration MAS pension were improved but still maintained lower values, which would
suspensions maintained a similar or even higher G′ compared with not carry cuttings effectively.
high-concentration Na-BT suspensions. In Fig. 2c, the G″ of MAS sus- As shown in Fig. 3, both gel state and shear-thinning behavior of Na-
pensions were close to those of high-concentration Na-BT suspensions BT and MAS suspensions were visually observed. After standing for 3 h
and maintained low values. Therefore, the low-concentration MAS

Fig. 2. Evolution of the elastic (G′) and viscous (G″) moduli with oscillation frequency for Na-BT and MAS suspensions before (a;c) and after (b;d) hot rolling at
150 °C.

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K. Wang et al.
Fig. 4. Variation of the G′ with alternate strain for Na-BT and MAS suspensions
before (a) and after (b) hot rolling at 150 °C.
at 25 °C, the 2 wt% MAS suspension formed a gel, which still held on to
the bottle bottom after inversion, and returned to liquid state im-
mediately after shaking for several seconds, displaying high gel strength
and good shear-thinning performance. However, the 4 wt% and 8 wt%
Na-BT suspensions could not form a gel as 2 wt% MAS suspension even
after standing for 24 h at 25 °C, and the 8 wt% Na-BT suspension could
not flow after hot rolling at 150 °C for 16 h. Thus, the low-concentration
MAS suspensions were more suitable than high-concentration MAS
suspensions to maintain high gel strength in WBDs.
3.3. Recovery performance of the gel structure
In circulation process of WBDs, the WBDs flow through the drilling
bit nozzle to the annular space and experience a rapid change from the
high strain to low strain. Therefore, a quick recovery of the gel structure
under the extreme condition is very important for WBDs to suspend and
Fig. 5. Creep-recovery curves of Na-BT and MAS suspensions.
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Applied Clay Science 161 (2018) 427–435
carry cuttings. Fig. 4 shows the resulting G′ of the Na-BT and MAS
suspensions of alternate low (0.1%) and high (100%) strain. At a high
(100%) oscillatory strain, the G′ of all suspensions nearly maintained a
constant below 0.2 Pa, which indicated a thorough disruption of the gel
structure. Then, at a low (0.1%) oscillatory strain, the G′ increased
gradually, which indicated that the gel structure started recovering
(Appel et al., 2015; Gaharwar et al., 2014). The faster recovery per-
formance means that the G′ needs shorter time to reach relative con-
stant values at low strain. Particularly, the G′ of the 4 wt% Na-BT sus-
pension declined first and then increased at the recovery stage (0.1%
oscillatory strain), which could be due to the inertial effects of the
rheometer on the recovery of the weak gel structure. Before hot rolling,
the recovery performance of the gel structure improved with increasing
concentration for both Na-BT and MAS suspensions, and low-con-
centration MAS suspensions exhibited faster gel structure recovery
performance than high-concentration Na-BT suspensions. After hot
rolling at 150 °C, the recovery performance of MAS suspensions became
better, while the recovery performance of Na-BT suspensions were
worse. The G′ of Na-BT suspensions could not reach relative constant
values at low strain. After three cycles of low and high oscillatory
strain, the MAS suspensions still exhibited excellent recovery proper-
ties. These results revealed that low-concentration MAS suspensions
maintained better recovery performance than high-concentration Na-
BT suspensions, especially after hot rolling at 150 °C. Therefore, the
immediate recovery of the MAS gel structure would be more beneficial
for carrying cuttings in drilling high temperature deep wells.
3.4. Creep and recovery behavior
The creep-recovery experiments give an indication about the gel
structure properties of the Na-BT and MAS suspensions at a fixed shear
stress. The compliance is the ratio of the strain to the constant stress.
The high creep compliance (Jc) represents a weak gel structure whereas
the low Jc indicates a strong gel structure. The compliance of a gel
structure is composed of elastic recovery component and viscous irre-
versible component in the linear viscoelastic range (Morariu et al.,
2014; Sozer, 2009). The elastic recovery percentage (ER) was calcu-
lated with the following equation:
Jmax − J∞
ER = × 100%
Jmax (5)
where Jmax represents the maximum Jc in the creep period, J∞ re-
presents the final recovery result at the longest time in the recovery
period.
The creep-recovery curves of the Na-BT and MAS suspensions are
shown in Fig. 5a, b, and the Jmax, J∞ and elastic recovery percentage
(ER) are displayed in Table 3. The Jmax of both MAS and Na-BT sus-
pensions decreased with increasing concentrations, and low-con-
centration MAS suspensions showed lower Jmax than that of high-
K. Wang et al. Applied Clay Science 161 (2018) 427–435

Table 3
Compliance values and elastic recovery percentage of Na-BT and MAS suspensions.
Samples 4% Na-BT 6% Na-BT 8% Na-BT 1% MAS 1.5% MAS 2% MAS

−1
Jmax (Pa ) 9546.341 0.553 0.310 0.818 0.114 0.044
J∞ (Pa−1) 9545.253 0.550 0.299 0.627 0.095 0.035
ER (%) 0.01 0.54 3.55 23.35 16.67 20.45

Fig. 6. API filtration test and SEM results of the filtrate cakes. [a FLAPI of Na-BT and MAS suspensions; b SEM of 80-nm pore-sized Teflon filter paper; c-f SEM of
filtrate cakes of Na-BT and MAS suspensions (c 4% Na-BT, d 6% Na-BT, e 2% MAS, f 3% MAS)].

concentration Na-BT suspensions. Meanwhile, the strength of gel
structure reflected by the Jmax were similar to results of the G′. There-
fore, the low-concentration MAS suspensions exhibited the stronger gel
structure than high-concentration Na-BT suspensions, which supplied
better suspending capacity than high-concentration Na-BT suspensions.
Moreover, in recovery period, the MAS suspensions showed much
higher elastic recovery than high-concentration Na-BT suspensions
(Table 3). These results revealed that the viscous irreversible flow
component of MAS suspensions was much lower than that of high-
concentration Na-BT suspensions. The lower viscous irreversible flow is

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K. Wang et al. Applied Clay Science 161 (2018) 427–435

lower filtrate volume than high-concentration Na-BT suspensions. In

Fig. 6e,f, the SEM image of filtrate cakes of 2 wt% and 3 wt% MAS
suspensions showed a much smoother surface morphology, compared
with the filtrate cake surface of 4 wt% and 6 wt% Na-BT suspensions,
which were much rougher, as shown in Fig. 6c, d. The MAS suspension
maintained a smoother filtrate cake and a lower filtrate volume than
high-concentration Na-BT suspensions. These results demonstrated that
the low-concentration MAS suspensions can plug the nano-pore (about
80 nm) better and form a smoother filtrate cake than high-concentra-
tion Na-BT suspensions before and after hot rolling tests. Therefore, the
MAS is advantageous for reducing the friction and torque and pre-
venting the penetration of fluids into nano-pores compared with Na-BT.

3.6. Microstructural analysis

The low-concentration MAS suspension exhibited better rheological

Fig. 7. Difference of microstructure between Na-BT and MAS suspensions. (a
particle size distribution and zeta potential of Na-BT and MAS suspensions; b
TEM of 4% Na-BT suspension; c TEM of 1% MAS suspension).
advantageous for reducing pumping energy requirement and increasing
drilling efficiency.
3.5. Filtration control property analysis
Apart from the rheology, the filtration control property is also very
important to ensure a successful drilling operation for WBDs. The low
filtrate volume of WBDs penetrates into the formation, which can de-
crease the risk of wellbore instability. Simultaneously, a compact and
smooth filtrate cake is able to reduce the friction between drill pipes
and the borehole markedly, and prevent drill pipes from sticking.
Therefore, the excellent filtrate control property includes the low fil-
trate volume as well as the smooth and compact filtrate cake for WBDs.
In the developed API filtration test, the 80-nm pore-sized Teflon filter
paper was used to mimic the tiny pore of formations. Additionally, the
nano-pore structure of the Teflon filter paper is illustrated in Fig. 6b. As
shown in Fig. 6a, the filtrate volume of the Na-BT and MAS suspensions
decreased with increasing concentration before and after hot rolling
tests. The low-concentration MAS suspensions maintained similar or
even lower filtrate volume than high-concentration Na-BT suspensions.
After hot rolling at 150 °C, both filtrate volumes of the Na-BT and MAS
suspensions increased, whereas the MAS suspensions still maintained
properties, such as the better shear-thinning performance, higher gel
strength, quicker recovery of gel structure and lower viscous irrever-
sible flow, as well as filtration control properties, including smoother
filtrate cakes and lower filtrate volume, compared with the high-con-
centration Na-BT suspension. However, there is nearly no difference
between the Na-BT and MAS on the crystal structure and chemical
composition (Table 1). To explain the above results, the particle size
distribution, zeta potential analyses and TEM analysis were used to
compare samples and to illustrate factors influencing the rheology and
filtration differences between the Na-BT and MAS suspensions. As
shown in Fig. 6a, the particle size of the MAS (d50 = 50.70 nm) was
much smaller than that of Na-BT (d50 = 9.99 μm). Therefore, for a
given mass of sample the MAS would possess more particles than the
Na-BT, and consequently more individual layers than Na-BT. When the
MAS or Na-BT dispersed in water, the layers formed specific structures
by electrostatic interaction. The zeta potential of the MAS and Na-BT
was −28.6 and − 26.8 mV, respectively, indicating similar electrostatic
interaction. Accordingly, the low-concentration MAS suspension
maintained higher gel strength compared with the high-concentration
Na-BT suspension, because MAS possessed the larger quantity of layers,
which could generate the stronger gel structure in water. As shown in
Fig. 7b, c, the Na-BT layers were fewer than MAS layers, and the greater
number of smaller MAS layers arranged closely and formed much
denser network structures than the larger Na-BT layers. In fact, many
researchers have focused on the influence of clay particle size on the
rheology of clay suspensions (Hauser and Reed, 1937; Michot et al.,
2009; Michot et al., 2004; Paineau et al., 2011). According to the study
of Hauser et al., montmorillonite (Wyoming bentonite) with a smaller
particle size was easier to gel in water at lower concentrations (Hauser
and Reed, 1937). Moreover, the relationship between the clay particle
size and the sol-gel transition of clay suspensions was researched, which
revealed the mechanism that the suspension with larger particles gelled
at higher concentrations (Paineau et al., 2011). Therefore, in this work,
the Na-BT with larger particle size formed gel structures at higher
concentrations, while the MAS with smaller particle size formed gels at

Table 4
The formulations and rheological and filtration properties of WBDs.
Formulation Water (g) Na-BT (g) MAS (g) PAC-LV (g) Barite (g) ρ (g·cm−3)

WBDs-Ma 300 0 3 1.5 180 1.4

WBDs-Bb 300 12 0 1.5 180 1.4
Properties AV (mPa·s) PV (mPa·s) YP (Pa) Gel10 s/10 min (Pa/Pa) θ6/θ3 FLAPI (mL)
WBDs-M 31 16 15 13/28 16/15 5.0
WBDs-M (HRc) 25 14 11 10/26 13/12 5.2
WBDs-B 44 33 11 5/12 9/8 6.0
WBDs-B (HR) 28 24 4 2/4 4/3 6.6

a
WBDs-M: MAS-based WBDs.
b
WBDs-B: Na-BT-based WBDs.
c
HR: WBDs after hot rolling at 120 °C for 16 h.

433
K. Wang et al.
a lower concentration.
Moreover, when the layers moved in water, the smaller layers ex-
perienced lower friction and resistance than the larger layers.
Furthermore, the smaller layers maintained the higher specific surface
energy compared with the larger layers. Therefore, when the gel
structure (network structures) of the smaller layers was disrupted, more
layers were exposed in suspensions increasing the surface energy. To
lower the higher surface energy, the small layers had to recombine a
network structure quickly (Andrey Shalkevich et al., 2007). Moreover,
the lower friction of smaller layers facilitated the quicker recovery of
the gel structure. Thus, the MAS suspension maintained the quicker
recovery property and better shear-thinning performance compared
with Na-BT suspension. Besides, low viscous irreversible flow and G″ of
the MAS suspension were attributed to the low solid content of MAS
suspensions and the lower friction of smaller MAS layers.
The smaller particle size of the MAS was also the reason for the low
filtrate volume and smooth filtrate cake. The nano-pores of the filter
paper were not effectively plugged by the large micron-sized Na-BT
particles, which could not penetrate into the nano-pores. Compared
with the Na-BT, the nano-sized MAS particles were small enough to
penetrate into the nano-pores and formed compact filtrate cakes to
prevent fluids passing through the nano-pores. Therefore, the MAS
suspension maintained low filtrate volume through the 80-nm pore-
sized Teflon filter paper. Consequently, the MAS would be more sui-
table than the Na-BT for coating shale formations containing numerous
of nano-sized pores. Furthermore, the small MAS particles filled the
nano-pores to accumulate a thinner and smoother filtrate cake than the
larger Na-BT particles, because the smaller particles move more easily
(orientation, rotation, etc.), inducing a more orderly and compact ac-
cumulation than the larger particles.
3.7. Application in WBDs
The application of the MAS in WBDs was investigated in the la-
boratory and compared with Na-BT. To maintain a lower filtration
volume in WBDs, the common fluid loss reducer (PAC-LV) was used.
Moreover, barite was used as weighting material to prepare the WBDs
with a density of 1.4 g·cm−3. The formulations of WBDs based on the
MAS and Na-BT are shown in Table 4.
To suspend the same quantity of barite, the WBDs-M only contained
1 wt% MAS, while the WBDs-B contained 4 wt% Na-BT. After hot
rolling at 120 °C, the rheological properties of WBDs-B declined more
compared with those of WBDs-M, which indicated that the WBDs-M
exhibited better thermal stability than WBDs-B. Furthermore, the
WBDs-M maintained a lower plastic viscosity (PV) than WBDs-B, and a
lower PV could reduce the circulating pressure loss and increase drilling
efficiency. Meanwhile, the high YP, Gel10 s/10 min, θ6 and θ3 are ad-
vantageous for suspending the barite and cuttings in WBDs (He et al.,
2018). Moreover, the WBDs-M exhibited the higher YP, Gel10 s/10 min,
θ6 and θ3 compared with WBDs-B, especially after hot rolling at 120 °C
for 16 h, which indicated that the WBDs-M maintained a better property
to carry barite and cuttings than WBDs-B. In addition, the FLAPI of
WBDs-M was lower than that of WBDs-B before and after hot rolling.
Theses results demonstrated that the MAS possessed good compatibility
with other additives in WBDs, and the WBDs-M maintained better
rheological and filtration properties than WBDs-B. The excellent rheo-
logical properties and thermal stability of WBDs-M indicated that the
WBDs-M was more suitable for carrying cuttings and decreasing the
circulating pressure loss in horizontal wells.
4. Conclusion
The MAS, a nano-sized layered material, delivers improved rheo-
logical properties and much smoother filtrate cakes, compared with Na-
BT, and therefore offers advantages for WBDs used with drilling hor-
izontal wells, through more effective suspension and return of cuttings,
434
Applied Clay Science 161 (2018) 427–435
reduced friction and torque, and improved drilling efficiency. The low-
concentration MAS suspension showed excellent rheological properties,
such as better shear-thinning performance, higher gel strength, quicker
recovery of gel structure and lower viscous irreversible flow, compared
with the high-concentration Na-BT suspension. Particularly, the 2 wt%
MAS suspension maintained better rheological properties than the 8 wt
% Na-BT suspension before and after hot rolling at 150 °C, showing the
potential of the MAS for the low-solid and high-temperature WBDs. In
addition, the MAS suspension maintained low filtrate volume and much
smoother filtrate cake for plugging nano-pores. Furthermore, the MAS-
containing WBDs showed excellent rheological properties and thermal
stability after hot rolling at 120 °C. In order to assess the practical
feasibility for the use of MAS as a drilling fluid modifier, the cost/
benefit ratio should be evaluated. On the one hand the cost of MAS is
currently about 6–8 times the cost of Na-BT, but on the other a lower
quantity of MAS is needed to attain much better performance of the
drilling fluid. The application of the MAS in WBDs could substantially
reduce the use of the Na-BT and polymer viscosifiers, which would be
highly beneficial for developing low-solid and environmentally friendly
WBDs in horizontal well drilling.
Acknowledgements
This study was supported by the Funds for National Major Projects
(Grants 2017ZX05009-003, 2016ZX05020-004, and 2016ZX05040-
005), the National Natural Science Foundation of China (Grants
51521063 and 51474231).
Conflicts of interest
All authors declare that no conflict of interest exists in this work.
References
Appel, E.A., Tibbitt, M.W., Webber, M.J., Mattix, B.A., Veiseh, O., Langer, R., 2015. Self-
assembled hydrogels utilizing polymer-nanoparticle interactions. Nat. Commun. 6,
6295.
Baba Hamed, S., Belhadri, M., 2009. Rheological properties of biopolymers drilling fluids.
J. Pet. Sci. Eng. 67, 84–90.
Chambi-Peralta, M.M., Vieira Coelho, A.C., Machado de Souza Carvalho, F., Toffoli, S.M.,
2018. Effects of exchanged cation, acid treatment and high shear mechanical treat-
ment on the swelling and the particle size distribution of vermiculite. Appl. Clay Sci.
155, 1–7.
Dias, F.T.G., Souza, R.R., Lucas, E.F., 2015. Influence of modified starches composition on
their performance as fluid loss additives in invert-emulsion drilling fluids. Fuel 140,
711–716.
Egenti, N.B., 2014. Understanding Drill-cuttings Transportation in Deviated and
Horizontal Wells. Nigeria Annual International Conference and Exhibition, Lagos,
Nigeria; SPE Paper No. 172835.
Gaharwar, A.K., Avery, R.K., Assmann, A., Paul, A., McKinley, G.H., Khademhosseini, A.,
Olsen, B.D., 2014. Shear-thinning nanocomposite hydrogels for the treatment of
hemorrhage. ACS Nano 8, 9833–9842.
Hauser, E.A., Reed, C.E., 1937. The thixotropic behavior and structure of bentonite. J.
Phys. Chem. 41, 911–934.
He, Y., Jiang, G., Deng, Z., Liu, F., Peng, S., Ni, X., Shi, Y., Cui, W., 2018. Polyhydroxy
gemini surfactant as a mechano-responsive rheology modifier for inverted emulsion
drilling fluid. RSC Adv. 8, 342–353.
Ismail, A.R., Aftab, A., Ibupoto, Z.H., Zolkifile, N., 2016. The novel approach for the
enhancement of rheological properties of water-based drilling fluids by using multi-
walled carbon nanotube, nanosilica and glass beads. J. Pet. Sci. Eng. 139, 264–275.
Kanjanakawinkul, W., Rades, T., Puttipipatkhachorn, S., Pongjanyakul, T., 2013.
Nicotine-magnesium aluminum silicate microparticle surface modified with chitosan
for mucosal delivery. Mater. Sci. Eng. C Mater. Biol. Appl. 33, 1727–1736.
Kelessidis, V.C., Poulakakis, E., Chatzistamou, V., 2011. Use of Carbopol 980 and car-
boxymethyl cellulose polymers as rheology modifiers of sodium-bentonite water
dispersions. Appl. Clay Sci. 54, 63–69.
Kelessidis, V.C., Zografou, M., Chatzistamou, V., 2013. Optimization of Drilling Fluid
Rheological and Fluid Loss Properties Utilizing PHPA Polymer. Middle East Oil and
Gas Show and Conference, Manama, Bahrain; SPE Paper No. 164351.
Khunawattanakul, W., Puttipipatkhachorn, S., Rades, T., Pongjanyakul, T., 2008.
Chitosan–magnesium aluminum silicate composite dispersions: characterization of
rheology, flocculate size and zeta potential. Int. J. Pharm. 351, 227–235.
Li, M.-C., Wu, Q., Song, K., Qing, Y., Wu, Y., 2015. Cellulose nanoparticles as modifiers for
rheology and fluid loss in bentonite water-based fluids. ACS Appl. Mater. Interfaces 7,
5006–5016.
K. Wang et al.
Li, M.-C., Wu, Q., Song, K., De Hoop, C.F., Lee, S., Qing, Y., Wu, Y., 2016a. Cellulose
nanocrystals and polyanionic cellulose as additives in bentonite water-based drilling
fluids: rheological modeling and filtration mechanisms. Ind. Eng. Chem. Res. 55,
133–143.
Li, X., Gao, D., Zhou, Y., Zhang, H., 2016b. A model for extended-reach limit analysis in
offshore horizontal drilling based on formation fracture pressure. J. Pet. Sci. Eng.
146, 400–408.
Li, B.X., Wang, W.C., Zhang, X.P., Zhang, D.X., Mu, W., Liu, F., 2017a. Integrating uni-
form design and response surface methodology to optimize thiacloprid suspension.
Sci. Rep. 7, 46018.
Li, X., Gao, D., Zhou, Y., Zhang, H., Yang, Y., 2017b. Study on the prediction model of the
open-hole extended-reach limit in horizontal drilling considering the effects of cut-
tings. J. Nat. Gas Sci. Eng. 40, 159–167.
Li, M.-C., Wu, Q., Song, K., French, A.D., Mei, C., Lei, T., 2018. pH-responsive water-based
drilling fluids containing bentonite and chitin nanocrystals. ACS Sustain. Chem. Eng.
6, 3783–3795.
Liu, F., Jiang, G., Peng, S., He, Y., Wang, J., 2016. Amphoteric polymer as an anti-calcium
contamination fluid-loss additive in water-based drilling fluids. Energy Fuel 30,
7221–7228.
Liu, F., Jiang, G.-C., Wang, K., Wang, J., 2017. Laponite nanoparticle as a multi-functional
additive in water-based drilling fluids. J. Mater. Sci. 52, 12266–12278.
Lopezgalindo, A., Viseras, C., Cerezo, P., 2007. Compositional, technical and safety spe-
cifications of clays to be used as pharmaceutical and cosmetic products. Appl. Clay
Sci. 36, 51–63.
Michot, L.J., Bihannic, I., Porsch, K., Maddi, S., Baravian, C., Mougel, J., Levitz, P., 2004.
Phase diagrams of Wyoming Na-montmorillonite clay. Influence of particle aniso-
tropy. Langmuir 20, 10829–10837.
Michot, L.J., Baravian, C., Bihannic, I., Maddi, S., Moyne, C., Duval, J.r.m.F.L, Levitz, P.,
Davidson, P., 2009. Sol-gel and isotropic/nematic transitions in aqueous suspensions
of natural nontronite clay. Influence of particle anisotropy. 2. Gel structure and
mechanical properties. Langmuir 25, 127–139.
Morariu, S., Bercea, M., Sacarescu, L., 2014. Tailoring of clay/poly(ethylene oxide) hy-
drogel properties by chitosan incorporation. Ind. Eng. Chem. Res. 53, 13690–13698.
Paineau, E., Michot, L.J., Bihannic, I., Baravian, C., 2011. Aqueous suspensions of natural
swelling clay minerals. 2. Rheological characterization. Langmuir 27, 7806–7819.
Pongjanyakul, T., Puttipipatkhachorn, S., 2009. Polymer-magnesium aluminum silicate
composite dispersions for improved physical stability of acetaminophen suspensions.
AAPS PharmSciTech 10, 346–354.
Pongjanyakul, T., Suksri, H., 2010. Nicotine-loaded sodium alginate–magnesium
435
Applied Clay Science 161 (2018) 427–435
aluminum silicate (SA–MAS) films: Importance of SA–MAS ratio. Carbohydr. Polym.
80, 1018–1027.
Pongjanyakul, T., Priprem, A., Puttipipatkhachorn, S., 2005. Influence of magnesium
aluminium silicate on rheological, release and permeation characteristics of diclo-
fenac sodium aqueous gels in-vitro. J. Pharm. Pharmacol. 57, 429–434.
Shakib, J.T., Kanani, V., Pourafshary, P., 2016. Nano-clays as additives for controlling
filtration properties of water–bentonite suspensions. J. Pet. Sci. Eng. 138, 257–264.
Shalkevich, Andrey, Stradner, Anna, Kumar Bhat, Suresh, Muller, Franc¸ois,
Schurtenberger, P., 2007. Cluster, glass, and gel formation and viscoelastic phase
separation in aqueous clay suspensions. Langmuir 23, 3570–3580.
Song, K., Wu, Q., Li, M.-C., Wojtanowicz, A.K., Dong, L., Zhang, X., Ren, S., Lei, T., 2016.
Performance of low solid bentonite drilling fluids modified by cellulose nano-
particles. J. Nat. Gas Sci. Eng. 34, 1403–1411.
Sozer, N., 2009. Rheological properties of rice pasta dough supplemented with proteins
and gums. Food Hydrocoll. 23, 849–855.
Wang, Q., Chen, X., Jha, A.N., Rogers, H., 2014. Natural gas from shale formation – the
evolution, evidences and challenges of shale gas revolution in United States. Renew.
Sust. Energ. Rev. 30, 1–28.
William, J.K.M., Ponmani, S., Samuel, R., Nagarajan, R., Sangwai, J.S., 2014. Effect of
CuO and ZnO nanofluids in xanthan gum on thermal, electrical and high pressure
rheology of water-based drilling fluids. J. Pet. Sci. Eng. 117, 15–27.
Yan, L., Wang, C., Xu, B., Sun, J., Yue, W., Yang, Z., 2013. Preparation of a novel am-
phiphilic comb-like terpolymer as viscosifying additive in low-solid drilling fluid.
Mater. Lett. 105, 232–235.
Yang, L., Jiang, G., Shi, Y., Lin, X., Yang, X., 2017a. Application of ionic liquid to a high-
performance calcium-resistant additive for filtration control of bentonite/water-
based drilling fluids. J. Mater. Sci. 52, 6362–6375.
Yang, L., Jiang, G., Shi, Y., Yang, X., 2017b. Application of ionic liquid and polymeric
ionic liquid as shale hydration inhibitors. Energy Fuel 31, 4308–4317.
Zakaria, M., Husein, M.M., Harland, G., 2012. Novel Nanoparticle-based Drilling Fluid
with Improved Characteristics. International Oilfield Nanotechnology Conference
and Exhibition, Noordwijk, The Netherlands; SPE Paper No. 156992.
Zhang, X., Jiang, G., Xuan, Y., Wang, L., Huang, X., 2017. Associating copolymer acry-
lamide/diallyldimethylammonium chloride/butyl acrylate/2-acrylamido-2-methyl-
propanesulfonic acid as a Tackifier in clay-free and water-based drilling fluids.
Energy Fuel 31, 4655–4662.
Zhou, F., Xia, T., Wang, X., Zhang, Y., Sun, Y., Liu, J., 2016. Recent developments in coal
mine methane extraction and utilization in China: a review. J. Nat. Gas Sci. Eng. 31,
437–458.