applied

sciences
Article
Zwitterionic Polymer P(AM-DMC-AMPS) as a
Low-Molecular-Weight Encapsulator in Deepwater
Drilling Fluid
Xin Zhao 1,2, *, Zhengsong Qiu 1,2 , Yongjun Zhang 3 , Hanyi Zhong 1,2 , Weian Huang 1,2
and Zhichuan Tang 1
1 School of Petroleum Engineering, China University of Petroleum, Qingdao 266580, China;
qiuzs@upc.edu.cn (Z.Q.); zhonghanyi@126.com (H.Z.); masterhuang1997@163.com (W.H.);
teamo_tzc@163.com (Z.T.)
2 National Engineering Laboratory for Testing and Detection Technology of Subsea Equipments,
Qingdao 266580, China
3 Tianjin Ruiyang Offshore Engineering Company Limited, Tianjin 300450, China;
zhangyongjun_upc@163.com
* Correspondence: zhaoxin@upc.edu.cn; Tel.: +86-532-8698-3576

Academic Editor: Peter Van Puyvelde

Received: 9 April 2017; Accepted: 31 May 2017; Published: 8 June 2017

Featured Application: This work aims to simultaneously realize good encapsulation performance
and low-temperature rheological property for deepwater drilling fluid. It is expected to be used
in deepwater oil and gas drilling operations.

Abstract: In deepwater oil and gas drilling, the high-molecular-weight encapsulator aggravates the
thickening of the drilling fluid at low temperatures. Therefore, it is hard to manage the downhole
pressure, and drilling fluid loss occurs. In this paper, a zwitterionic polymer P(AM-DMC-AMPS)
which was the terpolymer of acrylamide, methacrylatoethyl trimethyl ammonium chloride, and
2-acrylamido-2-methylpropane sulfonic acid, was developed as a low-molecular-weight encapsulator.
It was characterized by Fourier transform infrared spectrum analysis, nuclear magnetic resonance,
and gel permeation chromatography. Moreover, the low-temperature rheology, shale inhibition
and filtration properties of water-based drilling fluids (WBDFs) containing different encapsulators
were experimentally investigated and compared. The results showed that the molecular weight of
P(AM-DMC-AMPS) was about 260,000, much lower than that of the conventional encapsulators.
In the deepwater drilling temperature range 4–75 ◦ C, WBDF containing P(AM-DMC-AMPS) had
lower and more stable rheological property because of its short molecular chains. The high shale
recovery rate and low swelling rate indicated its strong shale inhibition performance, owing to
its adsorption on the clay surface and the wrapping effect through both hydrogen bonding and
electrostatic interaction. It also improved the filtration property of WBDF, and was compatible with
other WBDF components. This product is expected to simultaneously realize the good encapsulation
performance and low-temperature rheological property for deepwater drilling fluid.

Keywords: low-molecular-weight encapsulator; deepwater drilling fluid; low-temperature rheological

property; shale inhibition; filtration property; zwitterionic polymer

1. Introduction
Offshore deepwater regions are rich in oil, natural gas and gas hydrate resources. The drilling
fluid is called the blood of drilling engineering [1], and it is extremely important for deepwater drilling
operations. Shale in deepwater is water sensitive, so it is prone to hydration on exposure to filtrates of

Appl. Sci. 2017, 7, 594; doi:10.3390/app7060594 www.mdpi.com/journal/applsci

Appl. Sci. 2017, 7, 594 2 of 16

water-based drilling fluid (WBDF), thus causing wellbore instability [2–5]. Serious thickening of the
drilling fluid occurs in deepwater drilling when it is cooled down by the low-temperature environment
(approximately 4 ◦ C) [6–8], leading to operation troubles.
Salt/polymer WBDF was initially used in deepwater drilling operations in the Gulf of Mexico
in the early 1990s [9]. The partially hydrolyzed polyacrylamide (PHPA) was used to inhibit the
hydration of shales to maintain the integrity of cuttings as well as the wellbore stability. As the
drilling operations moved into deeper water regions, the wellbore instability in water-sensitive shale
formation and thickening of drilling fluid caused by the high-molecular-weight polymer PHPA made
this WBDF unsatisfactory for deepwater drilling operations. Synthetic-based drilling fluid (SBDF) has
the advantages of high penetration rate, wellbore stability, etc. However, field applications show that
it is an extraordinary challenge in managing the downhole pressure, because the elevated rheology
of drilling fluid at a low temperature leads to a high equivalent circulating density (ECD). Since the
safe density window between the fracture pressure and pore pressure in deepwater drilling is very
narrow, the substantial increase in ECD exceeds the safe density limit, resulting in loss circulation of
drilling fluid [6,10,11]. The frequent lost circulation significantly reduced or eliminated the economic
benefits. Moreover, there are environmental concerns on the use of SBDF for some regions. Therefore,
WBDF is favored in consideration of environmental protection and costs, but the shale inhibition
and low-temperature rheology problems related to the high-molecular-weight encapsulator are still
big concerns.
In recent years, a high performance WBDF has been developed [5,12,13], and it performs
better than traditional WBDFs (water-based drilling fluids) in deepwater drilling. Owing to the
development of a novel hydration inhibitor along with the use of encapsulator, the novel WBDF
can achieve comparable shale inhibition to SBDF. Generally, the encapsulators for WBDF were
the high-molecular-weight amide polymers, such as PHPA, polyacrylamide (PAM), and particular
zwitterionic polymer [3,14–19]. They can form multi-point adsorption on the surface of clay particles
on the wellbore by hydrogen bonding interaction of –CONH2 and other adsorption groups, and bridge
the surrounding clay particles together and wrap them, thus preventing the dispersion and exfoliation
of clay particles [13]. At the same time, the encapsulator can also maintain the integrity of drill
cuttings in drilling fluid, enabling them to be easily removed by solid control equipment. Therefore,
the high-molecular-weight (usually above 2,000,000) polymer is required to effectively bridge and
wrap the clay particles [17]. However, the long molecular chains of these polymers result in high
friction, and the curly molecular chains are prone to form grid structure through intertwining, and
thus the WBDF thickens [20]. Particularly in deepwater drilling, the polymer molecular chains
curl up and entangle with each other at a low temperature. Due to this, the viscosity and gel
strength of WBDF substantially increase, so the ECD apparently increases, resulting in lost circulation.
In addition, the viscous drilling fluid due to the presence of high-molecular-weight encapsulator at
a low temperature usually adheres to the vibration screen and unable to get through the sieve, thus
leading to drilling fluid leakage [21]. Since deepwater drilling is a high-risk and high-investment
operation with a daily expense of approximately $1,000,000, problems such as lost circulation and
leakage of drilling fluid lead to huge economic loss, and increase security risks. The ideal deepwater
drilling fluid should have both excellent shale hydration inhibition and low-temperature rheological
properties. Therefore, at present, it is essential to solve the contradiction that the encapsulator with
high-molecular-weight causes thickening of drilling fluid at a low temperature, while that with
low-molecular-weight provides poor encapsulation performance. Experimental study showed that,
when the molecular weight of conventional encapsulator was lower than 2,000,000, the encapsulation
effect was not satisfactory [22]. As currently reported, in consideration of both the encapsulation
and low-temperature rheological properties, the low-molecular-weight encapsulator product was
developed and its molecular weight was about 900,000 [21,23]. Field applications showed that it
mitigated the thickening of WBDF at low temperatures to some extent. However, at present, the
rheology-related problem has not been completely solved and lost circulation of drilling fluid occurs
Appl. Sci. 2017, 7, 594 3 of 16

frequently in deepwater drilling operations. Moreover, it should be noted that the latest encapsulator is
a cationic polymer, which can neutralize the negative charge on clay surface and increase the stability of
shale. However, there are concerns about the compatibility of cationic polymer with other components
of WBDF, because sometimes serious flocculation of the drilling fluid occurs when cationic polymer is
added [24,25]. Therefore, the molecular structure and molecular weight of the encapsulator need to be
further optimized.
In this paper, to simultaneously realize the good encapsulation performance, low-temperature
rheological property and compatibility of drilling fluid, a zwitterionic polymer P(AM-DMC-AMPS)
with low-molecular-weight for deepwater drilling was developed. It was synthesized using acrylamide
(AM), methacrylatoethyl trimethyl ammonium chloride (DMC), and 2-acrylamido-2-methylpropane
sulfonic acid (AMPS) as the monomers, and was named SDCap as a commercial product for potential
application in the future. Its feasibility on deepwater drilling was investigated through experimental
evaluations of the low-temperature rheological property, shale inhibition and filtration property.

2. Materials and Methods

2.1. Materials
AM was purchased from Jinan Jinrihe Chemical Co., Ltd. (Jinan, China); AMPS was purchased
from Zhengzhou Dingshengxin Chemicals (Zhengzhou, China); DMC was purchased from Jinan
Duoxin Co., Ltd. (Jinan, China). Sodium hydrogen sulfite, ammonium persulfate and mercaptoacetic
acid were purchased from Sinopharm Chemicals (Shanghai, China), and all these materials were
analytically pure. All the drilling fluid additives used for preparing the testing WBDFs were provided
by China Oilfield Services (Sanhe, China) and Shida Chuangxin technology Co., Ltd. (Dongying,
China); sodium bentonite with a cation exchange capacity of 74 mmol/g was purchased from Boyou
Bentonite Group Co. Ltd. (Weifang, China), and it consisted of 57.6% montmorillonite, 32% quartz,
8% potassium feldspar, 0.6% kaolinite, 1.2% illite, and 0.6% chlorite. Drilling fluid bentonite was
purchased from Weifang Huawei Bentonite Group Co., Ltd. (Weifang, China), following the American
Petroleum Institute (API) standard. For the shale recovery rate tests, the shale sample #1 was obtained
from the deepwater wells in the South China Sea, and it consisted of 23% clay, 45% quartz, 13% calcite,
10% anorthose, 4% dolomite, 4% halite, and 1% gypsum; the shale sample #2 was obtained from wells
in Bohai Bay, and it consisted of 25% clay, 43% quartz, 20% anorthose, 9% potassium feldspar, 2%
dolomite, and 1% calcite.

2.2. Preparation of SDCap

The aqueous solution polymerization method [26] was used to prepare the SDCap. Under a
stirring conditions, AM, AMPS and DMC with a mole ratio of 6:1:3 were added into a four-necked
flask, wherein the solvent was deionized water. The mole ratio of the three monomers was determined
by experimental investigations on the effects of monomer ratio on the molecular weight, cationic
degree and the inhibition performance of the product. As the mole fraction of DMC increased, the
molecular weight of the product decreased, whereas the cationic degree increased. As the mole fraction
of AM increased, the molecular weight of the product increased, whereas the cationic degree decreased.
The orthogonal tests showed that, when the monomer molar ratio was 6:1:3, the shale inhibition
performance of the product was the best. A total concentration of the monomers was maintained to be
15%, and oxygen was removed by purging the flask with nitrogen. The temperature was increased to
60 ◦ C, while 0.1% mixture of sodium bisulfite and ammonium persulfate was added as the initiator
with continuous introduction of nitrogen. After 2 h reaction time, the reaction was terminated by the
addition of mercaptoacetic acid. Then, a target product was obtained after extracted with acetone.
The molecular structure was shown in Figure 1.
Appl. Sci. 2017, 7, 594 4 of 16
Appl. Sci. 2017, 7, 594 4 of 16

Figure 1. Molecular structure of SDCap (commercial name of P(AM-DMC-AMPS)).

Figure 1. Molecular structure of SDCap (commercial name of P(AM-DMC-AMPS)).

2.3. Characterization and

2.3. Characterization and Performance
Performance Evaluation
Evaluation

2.3.1. Characterization of the Product

2.3.1 Characterization of the Product
The Fourier transformation infrared (FT-IR) spectra of SDCap were recorded by a NEXUS
The Fourier transformation infrared (FT-IR) spectra of SDCap were recorded by a NEXUS FT-IR
FT-IR spectrometer (Thermo Nicolet Corporation, Denver, CO, USA), scanning from 4000 cm−1
spectrometer
− 1
(Thermo Nicolet Corporation, Denver, CO, USA), scanning from 4000 cm−1 to 400
to 400 cm .The nuclear magnetic resonance (NMR) spectra were recorded by a Bruker AVANCE
cm−1.The nuclear magnetic resonance (NMR) spectra were recorded by a Bruker AVANCE III 400
III 400 MHz spectrometer (Bruker BioSpin, Rheinstetten, Germany) using D2 O as the solvent [27].
MHz spectrometer (Bruker BioSpin, Rheinstetten, Germany) using D2O as the solvent [27]. Gel
Gel Permeation Chromatography (Malvern 270 max GPC, Malvern Instruments, Malvern, UK) was
Permeation Chromatography (Malvern 270 max GPC, Malvern Instruments, Malvern, UK) was used
used to determine
to determine the molecular
the molecular weight
weight of SDCap
of SDCap [28]. [28].
2.3.2. Shale Inhibition Performance
2.3.2. Shale Inhibition Performance
Shale recovery rate test has been designed to simulate the exposure of shale samples to the drilling
Shale recovery rate test has been designed to simulate the exposure of shale samples to the
fluid in the wellbore. The hydration dispersion of shale samples in water and drilling fluid could be
drilling fluid in the wellbore. The hydration dispersion of shale samples in water and drilling fluid
evaluated, reflecting the inhibition effect of drilling fluid on the dispersion of clay particles. Mass
could be evaluated, reflecting the inhibition effect of drilling fluid on the dispersion of clay particles.
of 40 g shale samples, which were screened with a 10-mesh and 280 mL test fluid, was added into
Mass of 40 g shale samples, which were screened with a 10-mesh and 280 mL test fluid, was added
the oven cell. After hot rolling for 16 h, the solution containing shale samples were screened with a
into the oven cell. After hot rolling for 16 h, the solution containing shale samples were screened
40-mesh sieve. The remaining shale samples were dried at 105 ◦ C for 4 h, and then weighed, and the
with a 40-mesh sieve. The remaining shale samples were dried at 105 °C for 4 h, and then weighed,
recovery rate was determined [14,16].
and the recovery rate was determined [14,16].
The linear swelling test has been designed to evaluate the swelling rate of shale in drilling
The linear swelling test has been designed to evaluate the swelling rate of shale in drilling fluid.
fluid. The tests were conducted using a NP-2 swelling instrument (Haitongda, Qingdao, China)
The tests were conducted using a NP-2 swelling instrument (Haitongda, Qingdao, China) to
to measure the linear swelling rate of the core sample after immersed in pure water and drilling
measure the linear swelling rate of the core sample after immersed in pure water and drilling fluid
fluid [29,30]. Bentonite which was crushed and sifted through a 100-mesh screen, was used to prepare
[29,30]. Bentonite which was crushed and sifted through a 100-mesh screen, was used to prepare the
the core sample.
core sample.
2.3.3. Rheological Property
2.3.3. Rheological Property
The rheological properties of different WBDFs were measured at 4, 25, 50 and 75 ◦ C, using a
ZNN-D6The rheological properties ofQingdao,
viscometer (Haitongda, different China)
WBDFswithwere
themeasured at 4, 25, 50standard
API recommended and 75 °C, using a
procedure.
ZNN-D6 viscometer (Haitongda, Qingdao, China) with the API recommended standard procedure.
The apparent viscosity (AV), plastic viscosity (PV) and yield point (YP) were calculated using the
The apparent
following viscosity
equations [31].(AV), plastic viscosity (PV) and yield point (YP) were calculated using the
following equations [31]. AV = 0.5 × θ600 (mPa·s) (1)
AV = 0.5 × θ600 (mPa·s)
PV = θ600 − θ300 (mPa·s)
(1)
(2)

YPPV
= =0.5 × (θ300
θ600 − (mPa·s)
− θ300 PV) (Pa) (3)
(2)

2.3.4. Filtration Tests YP = 0.5 × (θ300 − PV) (Pa) (3)

The API filtrate volume of the WBDF was measured by a ZNS-2A filtration apparatus (Haitongda,
Qingdao, China) at 4 ◦ C and 0.7 MPa [32]. The high temperature and high pressure filtrate volume
Appl. Sci. 2017, 7, 594 5 of 16

was measured by a GGS 42-1 HTHP filtration apparatus (Haitongda, Qingdao, China) at 150 ◦ C and
3.5 MPa [27]. The surface morphology of filter cake formed by WBDF in API filtration tests was
scanned using a S-4800 scaning electron microscope (Hitachi, Tokyo, Japan) [33,34].

2.4. Inhibition Mechanism Analysis

2.4.1. Analysis of the Particle Size

The particle size distribution of clay particles was measured using a Bettersize 2000 laser particle
size analyzer (Dandong Bettersize instruments, Dandong, China) to study the influence of SDCap on
the size distribution of clay particles [35].

2.4.2. Analysis of Zeta Potential

The surface charges of clay suspensions in the presence of different concentration of SDCap were
measured using the zeta potential analyzer (Nano Brook Omni, Brook Heaven, NY, USA).

2.4.3. Adsorption of SDCap on Bentonite

Mass of 2 g sodium bentonite was added into the conical flask, and then 50 mL aqueous solution
containing SDCap was added. The pH was adjusted to 8.5. The suspension was agitated at 200 r/min
for 24 h, and then was separated by centrifugal elutriation. The concentration of SDCap in the
supernatant was measured, and the adsorbance was calculated as follows [36,37].

A = (C0 − C)V/m (4)

where A is the adsorbance, mg·g−1 ; V is the solution volume, mL; M is the mass of adsorbed bentonite,
mg; C0 is the initial SDCap concentration, mg/L; and C is the concentration after absorption, mg/L.

3. Results and Discussions

3.1. Characterization of SDCap

The infrared spectrum results are shown in Figure 2. The –NH2 stretch vibration absorption peak
and characteristic absorption peak appeared at 3416.3 cm−1 and 622.4 cm−1 , respectively, while the
C=O characteristic absorption peak in amide groups appeared at 1665.9 cm−1 , indicating that the
AM chain segments existed in the product. The –COO absorption peak appeared at 1724.4 cm−1 ,
while the –CH–N+ (CH3 )3 methylene bending vibration absorption peak and quaternary ammonium
group absorption peak appeared at 1449.7 cm−1 and 950.7 cm−1 respectively, indicating that the DMC
chain segments existed in the product. The –SO3 – absorption peak and vibration absorption peak
appeared at 1192.2 cm−1 and 1042.5 cm−1 , respectively, indicating that the product contained AMPS
chain segments. The methyl and methylene asymmetric absorption peak appeared at 2942.9 cm−1 .
No C=C absorption peak was observed within 1635–1620 cm−1 , indicating that the three monomers
were sufficiently copolymerized. The analysis was further confirmed in Figure 3, which showed the
nuclear magnetic resonance spectrum (NMR) of SDCap. There was no absorption peak in the range of
6–7 ppm, indicating that there was no C=C in the product and the three monomers were completely
polymerized. The structure was characterized by NMR analysis, as shown in Figure 3.
The results of gel permeation chromatography test showed that the number-average molecular
weight and weight-average molecular weight of SDCap were about 260,000 and 380,000, respectively.
The molecular weight was much lower than that of the conventional encapsulator (over 2,000,000).
Appl. Sci. 2017, 7, 594 6 of 16
Appl.Sci.
Appl. Sci.2017,
2017,7,7,594
594 66of
of16
16

Figure
Figure 2.
Figure2. Analysis of
2.Analysis of SDCap
SDCap Infrared
Infrared spectrum.
Infraredspectrum.
spectrum.

Figure3.
Figure 3.Analysis
Analysisof
ofSDCap
SDCapnuclear
nuclearmagnetic
magneticresonance
resonancespectrum.
spectrum.
Figure 3. Analysis of SDCap nuclear magnetic resonance spectrum.

3.2. Rheological
3.2. Rheological Properties
Properties ofof Water-Based
Water-Based Drilling
Drilling Fluids
Fluids with
with SDCap
SDCap under
under Deepwater
Deepwater Drilling
Drilling
3.2. Rheological Properties of Water-Based Drilling Fluids with SDCap under Deepwater Drilling Temperature
Temperature
Temperature
WBDFs are multicomponent systems, so each component has to be compatible with others,
WBDFs are
WBDFs are multicomponent
multicomponent systems,systems, so so each
each component
component has has toto be
be compatible
compatible withwith others,
others,
otherwise the WBDF system would not be stable during drilling operations [38]. In order to evaluate
otherwise the
otherwise theWBDF
WBDFsystem
systemwould
would notnotbebe stable
stableduring
during drilling
drilling operations
operations [38].
[38].In
In order
order toto evaluate
evaluate
the properties of SDCap in drilling fluid under field application conditions, two typical WBDFs were
theproperties
the propertiesofofSDCap
SDCapin indrilling
drillingfluid
fluidunder
underfield
fieldapplication
applicationconditions,
conditions,two twotypical
typicalWBDFs
WBDFswere were
selected as the basic test fluids. WBDF-1 was a typical glycol/polymer WBDF, and WBDF-2 was a
selected as
selected as the
the basic
basic test
test fluids.
fluids. WBDF-1
WBDF-1 was was aa typical
typical glycol/polymer
glycol/polymer WBDF, WBDF, and and WBDF-2
WBDF-2 was was aa
typical KCl/PHPA WBDF. Both WBDFs have been widely used in onshore and offshore drilling [13,39],
typical KCl/PHPA
typical KCl/PHPA WBDF. WBDF. Both Both WBDFs
WBDFs have have been
been widely
widely used
used in in onshore
onshore andand offshore
offshore drilling
drilling
and the formulas are shown in Table 1. In consideration of gas hydrate inhibition in deepwater drilling
[13,39], and
[13,39], and the
the formulas
formulas are are shown
shown in in Table
Table 1.1. In
In consideration
consideration of of gas
gas hydrate
hydrate inhibition
inhibition inin
operations, at least a mass fraction of 10% NaCl was added in the WBDFs. Therefore, good salt
deepwater drilling
deepwater drilling operations,
operations, at at least
least aa mass
mass fraction
fraction of of 10%
10% NaCl
NaCl waswas added
added in in the
the WBDFs.
WBDFs.
resistance was also required for SDCap. It is noticed that the encapsulators in WBDF-1 and WBDF-2
Therefore, good
Therefore, good salt
salt resistance
resistance waswas also
also required
required forfor SDCap.
SDCap. ItIt is
is noticed
noticed that
that the
the encapsulators
encapsulators in in
were FA-367 and PHPA, respectively. FA-367 was a widely used zwitterionic encapsulator, and PHPA
WBDF-1 and
WBDF-1 and WBDF-2
WBDF-2 were were FA-367
FA-367 andand PHPA,
PHPA, respectively.
respectively. FA-367
FA-367 waswas aa widely
widely used
used zwitterionic
zwitterionic
was the representative of conventional encapsulator. In order to compare the properties of SDCap
encapsulator, and
encapsulator, and PHPA
PHPA was was the
the representative
representative of of conventional
conventional encapsulator.
encapsulator. In In order
order to
to compare
compare
with FA-367 and PHPA, the 0.3% FA-367 in WBDF-1 was replaced by 0.45% SDCap (WBDF-3), and
the properties
the properties of
ofSDCap
SDCapwithwith FA-367
FA-367and and PHPA,
PHPA,the the0.3%
0.3% FA-367
FA-367in in WBDF-1
WBDF-1was wasreplaced
replacedby by 0.45%
0.45%
the 0.25% PHPA in WBDF-2 was replaced by 0.375% SDCap (WBDF-4). The concentration of SDCap
SDCap (WBDF-3),
SDCap (WBDF-3), and and the
the 0.25%
0.25% PHPA
PHPA in in WBDF-2
WBDF-2 was was replaced
replaced by by 0.375%
0.375% SDCap
SDCap (WBDF-4).
(WBDF-4). The The
in WBDF-3 and WBDF-4 was 1.5 times of that of FA-367 and PHPA because the molecular weight
concentration of
concentration of SDCap
SDCap in in WBDF-3
WBDF-3 and and WBDF-4
WBDF-4 was was 1.5
1.5 times
times of
of that
that of
of FA-367
FA-367 andand PHPA
PHPA because
because
the molecular
the molecular weight
weight of of SDCap
SDCap was was farfar smaller
smaller thanthan that
that of
of FA-367
FA-367 andand PHPA,
PHPA, and and higher
higher
Appl. Sci. 2017, 7, 594 7 of 16

Appl. Sci. 2017, 7, 594 7 of 16

of SDCap was far smaller than that of FA-367 and PHPA, and higher concentration of SDCap was
required to maintain
concentration the desired
of SDCap encapsulation
was required property.
to maintain WBDF-5
the desired was a WBDF
encapsulation containing
property. WBDF-5SDCap
was
optimized
a WBDFin containing
our laboratory, and optimized
SDCap it was expected to have
in our more satisfactory
laboratory, and it waslow-temperature rheological
expected to have more
property as well
satisfactory as other properties.
low-temperature The rheological
rheological property asproperties of these
well as other five WBDFs
properties. The are shown in
rheological
Figure 4.
properties of these five WBDFs are shown in Figure 4.

(a)

(b)

(c)
Figure 4. Rheological properties of WBDFs at the temperature range 4–75 °C: (a) changes in AV
Figure 4. Rheological properties of WBDFs at the temperature range 4–75 ◦ C: (a) changes in AV
(apparent viscosity) as a function of temperature; (b) changes in PV (plastic viscosity) as a function
(apparent viscosity) as a function of temperature; (b) changes in PV (plastic viscosity) as a function of
of temperature; and (c) changes in YP (yield point) as a function of temperature.
temperature; and (c) changes in YP (yield point) as a function of temperature.
Appl. Sci. 2017, 7, 594 8 of 16

Table 1. Composition of the WBDFs (water-based drilling fluids).

Mass Fraction/%
Component Function
WBDF-1 WBDF-2 WBDF-3 WBDF-4 WBDF-5
bentonite filtrate reducer and viscosifier 4.0 4.0 4.0 4.0 2.0
PHPA encapsulator 0.25
FA-367 encapsulator 0.3
SDCap encapsulator 0.45 0.375 0.35
XC viscosifier 0.1 0.1 0.15
PAC-LV filtrate reducer 0.5 0.6 0.5 0.6
CMC-LV filtrate reducer 0.5
starch filtrate reducer 1.0 1.0
SMP filtrate reducer 4.0 4.0 4.5
polyamine shale inhibitor 2.0
Polyglycol shale inhibitor 3.0 3.0
KCl shale inhibitor 3.0 4.0 3.0 4.0 4.0
NaCl hydrate inhibitor 10.0 10.0 10.0 10.0 20.0

The results showed that, for all tested WBDFs, the rheological parameters obviously increased
as the temperature reduced. Particularly, when the temperature was reduced from 25 to 4 ◦ C, the
increase in rheological parameter was more apparently, which was indicated by the more sharp slope
of the rheology-temperature curve from 25 to 4 ◦ C. This low temperature interval is just the essential
difference between deepwater drilling and onshore or offshore drilling, and it causes significant
thickening of the drilling fluids. Therefore, we have to pay special attention to the rheological
properties at 25–4 ◦ C .The ratios of rheological parameters at 4 ◦ C and 25 ◦ C were used to describe
the thickening of the drilling fluid at a low temperature. The AV represents the total viscosity of the
drilling fluid and is the sum of PV and YP. PV represents the viscosity resulting from internal friction,
while YP represents the viscosity generated by formations of grid structures among clay particles and
high molecular polymers.
For WBDF-1, the AV at 4 ◦ C was 52 mPa·s. The AV(4 ◦ C)/AV(25 ◦ C) ratio was 1.55; PV(4 ◦ C)/
PV(25 ◦ C) ratio was 1.57; and the YP(4 ◦ C)/YP(25 ◦ C) ratio was 1.52. When 0.3% FA-367 was replaced
by 0.45% SDCap, the AV of the drilling fluid (WBDF-3) was reduced by 22.1% (from 52 mPa·s to
40.5 mPa·s). For WBDF-3, the AV(4 ◦ C)/AV(25 ◦ C) ratio was 1.45; PV(4 ◦ C)/PV(25 ◦ C) ratio was 1.45;
and the YP(4 ◦ C)/YP(25 ◦ C) ratio was 1.44. All ratios of rheological parameters at 4 ◦ C and 25 ◦ C were
reduced, indicating the thickening of the drilling fluid at a low temperature was mitigated using SDCap
instead of FA-367. For WBDF-2, the AV at 4 ◦ C was up to 83 mPa·s. The AV(4 ◦ C)/AV(25 ◦ C) ratio
was 1.69; PV(4 ◦ C)/PV(25 ◦ C) ratio was 1.71; and the YP(4 ◦ C)/YP(25 ◦ C) ratio was 1.64. When 0.25%
PHPA was replaced by 0.375% SDCap, the AV of the drilling fluid (WBDF-4) was reduced by 31.3%
(from 83 mPa·s to 57 mPa·s). For WBDF-4, the AV(4 ◦ C)/AV(25 ◦ C) ratio was 1.54; PV(4 ◦ C)/PV(25 ◦ C)
ratio was 1.56; and the YP(4 ◦ C)/YP(25 ◦ C) ratio was 1.50. Therefore, using SDCap instead of PHPA
also mitigated the thickening effect of the drilling fluid at a low temperature.
For WBDF-5 which was expected to be a drilling fluid with better rheological property, the AV, PV
and YP at 4 ◦ C were 32 mPa·s, 22 mPa·s, and 10 Pa, respectively, and were all lower than that of other
four WBDFs. The AV(4 ◦ C)/AV(25 ◦ C) ratio was 1.33; PV(4 ◦ C)/PV(25 ◦ C) ratio was 1.38; and the
YP(4 ◦ C)/YP(25 ◦ C) ratio was 1.25. In comparison, the AVs of the two conventional WBDFs (WBDF-1
and WBDF-2) were 52 mPa·s and 83 mPa·s. The AV of WBDF-5 was only 61% and 39% of that of the
conventional WBDFs, respectively. The AV(4 ◦ C)/AV(25 ◦ C) ratios of the two conventional WBDFs
were 1.55 and 1.69, respectively; the PV(4 ◦ C)/PV(25 ◦ C) ratios were 1.57 and 1.71, respectively; and
the YP(4 ◦ C)/YP(25 ◦ C) ratios were 1.52 and 1.64, respectively. Therefore, all the ratios of rheological
parameters at 4 ◦ C and 25 ◦ C for WBDF-5 were much lower than that of the conventional WBDFs,
indicating this optimized WBDF had better low-temperature rheology. Moreover, the curves of AV, PV
and YP with temperature in Figure 4 were more stable in the temperature range 4–75 ◦ C, indicating
Appl. Sci. 2017, 7, 594 9 of 16
Appl. Sci. 2017, 7, 594 9 of 16

temperature under the deepwater drilling conditions, thus reducing the risk of rheology-related
problems.
that its rheological properties were more independent on temperature under the deepwater drilling
conditions, thus reducing the risk of rheology-related problems.
3.3. Shale Inhibition Properties of Water-Based Drilling Fluid with SDCap
3.3. Shale Inhibition Properties of Water-Based Drilling Fluid with SDCap
3.3.1. Inhibition on Shale Hydration Dispersion
3.3.1. Inhibition on Shale Hydration Dispersion
The shale recovery rate test can reflect the encapsulation effect of encapsulators on clay
The shale
particles. A highrecovery
recovery rate testimplies
rate can reflect the encapsulation
the strong effectproperty
shale inhibition of encapsulators
of drillingonfluid.
clay particles.
Figure 5
A high recovery rate implies the strong shale inhibition property of drilling fluid.
shows the results of shale recovery rate tests with the five WBDFs. The recovery rates of shales from Figure 5 shows the
results
the Southof shale
Chinarecovery
Sea (shalerate#1)tests
andwith the Bay
Bohai five (shale
WBDFs. #2)The
wererecovery ratesand
only 4.2% of shales
15.7% from
in purethe water,
South
China Sea (shale
respectively, #1) andthat
indicating Bohai theBay (shale
shales were#2) highly
were only 4.2%
prone to and 15.7% in
hydration pure water,
dispersion andrespectively,
were hard
indicating that the shales
recover, particularly forwere highly prone
deepwater wells.toTherefore,
hydrationwellbore
dispersion and were occurred
instability hard recover, particularly
easily, and the
for deepwater
rheological andwells. Therefore,
filtration wellbore
properties instability
of drilling occurred
fluid easily,
were also and thedue
impacted rheological and filtration
to the dispersed clay
properties
particles. Theof drilling
WBDFs fluid were also
significantly impacted
increased the due to therate.
recovery dispersed
For shaleclay
#1 particles. The WBDFs
from deepwater wells,
significantly
the recoveryincreased
rates were the 75.4%,
recovery rate. For
68.2%, shaleand
77.5%, #1 from
72.0%deepwater
for WBDF-1,wells,WBDF-2,
the recovery rates were
WBDF-3, and
75.4%,
WBDF-4, 68.2%, 77.5%, andFor
respectively. 72.0% for WBDF-1,
shale WBDF-2,rates
#2, the recovery WBDF-3,
wereand WBDF-4,
83.5%, 79.3%,respectively.
87.9%, and For83.8%,
shale
#2, the recovery
respectively. Forrates were 83.5%,
WBDF-5, 79.3%, 87.9%,
the recovery andshale
rates for 83.8%,
#1respectively.
and shale #2 For WBDF-5,
were 82.2%the and recovery
89.3%,
rates for shaleindicating
respectively, #1 and shale its#2strong
were 82.2%
shale and 89.3%, property.
inhibition respectively,
The indicating its strongthat
results showed shale inhibition
SDCap was
property.
compatible The results
with the showed
WBDFs,that andSDCap was compatible
the recovery rate waswith the WBDFs,
increased whenand usingtheSDCap
recovery rate was
instead of
increased when using SDCap instead of conventional encapsulator in WBDFs.
conventional encapsulator in WBDFs. Therefore, it could effectively inhibit the hydration dispersion Therefore, it could
effectively
of shales. inhibit the hydration dispersion of shales.

Figure 5.
Figure 5. Shale
Shale recovery rates for
recovery rates for different
different WBDFs.
WBDFs.

3.3.2. Shale Swelling Tests

3.3.2. Shale Swelling Tests
The encapsulator can adsorb on the clay particles on the wellbore surface, and the water
The encapsulator can adsorb on the clay particles on the wellbore surface, and the water molecules
molecules entering inside the wellbore rocks can be slowed down. Therefore, the encapsulator also
entering inside the wellbore rocks can be slowed down. Therefore, the encapsulator also has a certain
has a certain capability of inhibiting the swelling of shale. Due to this reason, the shale swelling tests
capability of inhibiting the swelling of shale. Due to this reason, the shale swelling tests were also
were also conducted to evaluate the inhibition property of the encapsulators, and the results were
conducted to evaluate the inhibition property of the encapsulators, and the results were shown in
shown in Figure 6. It was found that the swelling rate of clay sample in pure water within 8 h was up
Figure 6. It was found that the swelling rate of clay sample in pure water within 8 h was up to 40.8%,
to 40.8%, indicating that the clay sample was highly prone to hydration swelling. In comparison, the
indicating that the clay sample was highly prone to hydration swelling. In comparison, the swelling
swelling rate were 8.8%, 7.3%, 8.3%, 8.0% and 7.7% for WBDF-1, WBDF-2, WBDF-3, WBDF-4, and
rate were 8.8%, 7.3%, 8.3%, 8.0% and 7.7% for WBDF-1, WBDF-2, WBDF-3, WBDF-4, and WBDF-5,
WBDF-5, respectively, indicating all the WBDFs could effectively inhibit the swelling of clay, and
respectively, indicating all the WBDFs could effectively inhibit the swelling of clay, and their inhibition
their inhibition effects were very similar.
effects were very similar.
Based on the results of shale inhibition tests and rheological property tests, the WBDF with
Based on the results of shale inhibition tests and rheological property tests, the WBDF with SDCap
SDCap had strong shale inhibition property, and had much better low-temperature rheological
had strong shale inhibition property, and had much better low-temperature rheological property than
property than WBDFs with FA-367 and PHPA, even the concentration of SDCap was 1.5 times of
WBDFs with FA-367 and PHPA, even the concentration of SDCap was 1.5 times of that of FA-367 and
that of FA-367 and PHPA. Therefore, using SDCap as the encapsulator in deepwater drilling fluid
PHPA. Therefore, using SDCap as the encapsulator in deepwater drilling fluid can both improve the
can both improve the low-temperature rheological property and shale inhibition property. In
Appl. Sci. 2017, 7, 594 10 of 16
Appl. Sci. 2017, 7, 594 10 of 16
Appl. Sci. 2017, 7, 594 10 of 16
addition, SDCaprheological
low-temperature has good property
salt resistance performance
and shale indicatedInby
inhibition property. its stable
addition, properties
SDCap in salt
has good the
presence
addition, of
resistance 10–20%has
SDCap NaCl.
performance good salt by
indicated resistance
its stableperformance
properties in indicated by of
the presence its10–20%
stable NaCl.
properties in the
presence of 10–20% NaCl.

Figure 6. Swelling rates of samples in different WBDFs.

Figure 6.
Figure 6. Swelling
Swelling rates
rates of
of samples
samples in
in different
differentWBDFs.
WBDFs.
3.3.3. Shale Inhibition Mechanism of SDCap with Low-Molecular-Weight
3.3.3. Shale
3.3.3. Shale Inhibition
Inhibition Mechanism
Mechanism of of SDCap
SDCap with with Low-Molecular-Weight
Low-Molecular-Weight
Adsorption of SDCap on sodium bentonite:
Adsorption
Adsorption of SDCap
of SDCap on sodium
on sodium bentonite:
The adsorption isotherm of bentonite:
SDCap is illustrated in Figure 7. It was found that SDCap could
effective
The get adsorbed
adsorption onto
isotherm the
of clay
SDCap surface.
The adsorption isotherm of SDCap is illustrated
is As the
illustrated in concentration
in Figure
Figure 7.7. It wasoffound
It was SDCap
found thatincreased,
that SDCap
SDCap could the
could
adsorbance
effective
effectiveget increased
getadsorbed
adsorbed significantly.
onto the clay
onto The
the surface. absorption
As the As
clay surface. capacity
concentration is the primary
of SDCapof
the concentration reason
increased, for
SDCap the the inhibition
adsorbance
increased, the
performance
increased
adsorbance of SDCap.significantly.
significantly.
increased During
The drilling,
absorption when the
Thecapacity
absorption drilling
is the primary
capacity fluid containing
isreason
the for theSDCap
primary interact
inhibition
reason with clay
performance
for the inhibition
particles
of SDCap.onDuring
performance wellbore
of SDCap. or During
in drilling
drilling, cuttings,
whendrilling,
the drilling
when through
fluid both the
containing
the drilling hydrogen
fluidSDCap
containing bonding
interact between
with
SDCap the amide
clay particles
interact with on
clay
group
wellbore and
particles or clay,
onin and the
drillingor
wellbore electrostatic
cuttings, through
in drilling interaction
boththrough
cuttings, between
the hydrogen cationic
both thebonding
hydrogen group
betweenand
bonding clay,
thebetweenSDCap
amide group can
and
the amidebe
adsorbed
clay,
groupandand onclay,
the the surface
electrostatic of clay particles
and theinteraction
electrostaticbetween andcationic
interactiondoesbetween
not fall cationic
group off
andeasily.
clay,groupTherefore,
SDCap it adsorbed
canclay,
and be inhibits
SDCapthe onclay
canthe
be
hydration
surface
adsorbed dispersion,
of clay
on theparticles
surfacethus
and maintaining
of does
clay not the
fall offand
particles wellbore
easily.
does stability
Therefore,
not fall off and
it inhibits keeping
easily. the the integrity
clay hydration
Therefore, of drill
dispersion,
it inhibits the clay
cuttings.
thus maintaining
hydration the wellbore
dispersion, stability andthe
thus maintaining keeping the integrity
wellbore stability of anddrill cuttings.
keeping the integrity of drill
cuttings.

Figure 7.
Figure 7. Variations of adsorbance
Variations of adsorbance of
of SDCap
SDCap on
on clay
clay particles
particles as
as aa function
function of
of concentration.
concentration.
Figure 7. Variations of adsorbance of SDCap on clay particles as a function of concentration.
Analysis on clay particle size distribution:
Analysis on clay particle size distribution:
Analysis on 8clay
Figure particle
shows size distribution:
the variations of distributions of the bentonite particle size in the presence of
Figure 8 shows the variations of distributions of the bentonite particle size in the presence of
different concentration
Figure 8 shows theof ofvariations
SDCap. After adding SDCap,
of distributions of the the size of bentonite
bentonite particles obviously
different concentration SDCap. After adding SDCap, the size ofparticle sizeparticles
bentonite in the presence
obviouslyof
increased. D of bentonite
different concentration
50 suspension
of SDCap. without
After SDCap
addingSDCap
SDCap,was 11.1
the μm,
size while
of while that
bentonite of suspension
particles with
obviously
increased. D50 of bentonite suspension without was 11.1 µm, that of suspension with
0.5% SDCap
increased. D50was 131.3 μm,suspension
of bentonite indicating without
the addition
SDCapof was
0.5%11.1
SDCapμm, increased
while thatthe D50 of bentonite
of suspension with
suspensions
0.5% SDCap by wasmore than
131.3 μm,10indicating
times. This
thedemonstrated that the
addition of 0.5% dispersed
SDCap bentonite
increased the D50particles were
of bentonite
suspensions by more than 10 times. This demonstrated that the dispersed bentonite particles were
Appl. Sci. 2017, 7, 594 11 of 16

0.5% SDCap was 131.3 µm, indicating the addition of 0.5% SDCap increased the D50 of bentonite
suspensions
Appl. Sci.
Appl. by 7,
Sci. 2017,
2017, more
594 than 10 times. This demonstrated that the dispersed bentonite particles
7, 594 11 of
11 16were
of 16
Appl. Sci. 2017, 7, 594 11 of 16
wrapped together by SDCap, and were not easily dispersed in the drilling fluid. The results also
wrapped together
wrapped together by
by SDCap,
SDCap, and
and were
were not
not easily
easily dispersed
dispersed in
in the
the drilling
drilling fluid.
fluid. The
The results
results also
also
reflected the strong adsorption capacity of SDCap.
wrapped the
reflected together
strongby SDCap, and
adsorption wereofnot
capacity easily dispersed in the drilling fluid. The results also
SDCap.
reflected the strong adsorption capacity of SDCap.
reflected the strong
Zeta potential analysis: adsorption capacity of SDCap.
Zeta potential
Zeta potential analysis:
analysis:
The
Zeta results
potentialof zeta potential tests in Figure 9 showed that the addition of SDCap did not
analysis:
The results
The results of zeta
zeta potential
potential tests
tests in Figure
Figure 99 showed
showed that
that the
the addition
addition of of SDCap did did not
significantly impact of the surface charges ofinclay for it was a zwitterionic polymerSDCap with both notcationic
The results
significantly of zeta
impact the potential
surface tests of
charges in clay
Figurefor 9 was
it showed
a that the addition
zwitterionic polymer of SDCap
with both did not
cationic
significantly
and anionic groups impact the
(sulfonicsurface charges
acid groups). of clay for it was a zwitterionic polymer with both cationic
significantly
and impact
anionic groups
groups the surface
(sulfonic acidcharges ofThe
groups). claycationic
The cationic
groups
for it was
groups
helped polymer
a zwitterionic SDCap get
helped SDCap
SDCap get with adsorbed
both onto
get adsorbed
adsorbed
onto the
cationic
the
and anionic (sulfonic acid groups). The cationic groups helped onto the
surface of
surfaceclay
and anionic
of particles
groups
clay by
particles electrostatic
(sulfonic
by adsorption,
acid groups).
electrostatic while
The cationic
adsorption, the
groups
while effect
the helped
effect of
ofelectrical
SDCap neutralization
getneutralization
electrical adsorbed ontowas was
the not
surface of clay particles by electrostatic adsorption, while the effect of electrical neutralization was
apparent,
surface
not thus
apparent, avoiding
of claythus the
particles excessive
by electrostatic
avoiding electrical
the excessive
excessiveadsorption,neutralization or
while the effect
electrical neutralization
neutralization even
or of electrical
electrical
even reversal
neutralization
electrical caused
was by
reversal caused
caused
not apparent, thus avoiding the electrical or even electrical reversal
cationic
by
by polymer
notcationic
apparent,
cationic which
polymer
polymer resulted
thus avoiding
which
which inexcessive
the
resulted
resultedserious flocculation
electrical
in serious
in serious flocculation
flocculationof drilling
neutralization
of drilling
of drillingfluid
or even
fluid
fluid(shown
(shown
(shown in
electrical
in Figure
inreversal 10).
caused
Figure 10).
Figure 10).
by cationic polymer which resulted in serious flocculation of drilling fluid (shown in Figure 10).

Figure
Figure
Figure 8. Clay
8. Clay
8. Clay particle
particle size
size
particle distributionin
distribution
size distribution in the
in the presence
the presence of
presence ofofdifferent
different
differentconcentration of SDCap.
concentration
concentration of SDCap.
of SDCap.
Figure 8. Clay particle size distribution in the presence of different concentration of SDCap.

Figure 9. Variations of zeta potential as a function of concentration of SDCap.

Figure 9. Variations
Figure 9. Variations ofof zetapotential
zeta potential as
as a
a function
functionofofconcentration
concentrationof SDCap.
of SDCap.
Figure 9. Variations of zeta potential as a function of concentration of SDCap.

Figure 10.
Figure 10. Flocculation
Flocculation of
of 4%
4% bentonite
bentonite suspension
suspension caused
caused by
by addition
addition of
of cationic
cationic polymer
polymer
Figure 10. Flocculation of 4% bentonite suspension caused by addition of cationic polymer
encapsulator.
encapsulator.
Figure 10. Flocculation of 4% bentonite suspension caused by addition of cationic polymer encapsulator.
encapsulator.
Appl. Sci. 2017, 7, 594 12 of 16
Appl. Sci. 2017, 7, 594 12 of 16

3.4. Filtration
3.4. Filtration Properties
Properties of
of Water-Based
Water-Based Drilling
Drilling Fluid
Fluid with
with SDCap
SDCap
Figure 11
Figure 11shows
showsthethe results
results of APIof API and HTHP
and HTHP filtration
filtration tests oftests of different
different WBDFs. WBDFs. In API
In API filtration
filtration tests, the filtrate volume was 6.6 mL for WBDF-1, while
tests, the filtrate volume was 6.6 mL for WBDF-1, while that of WBDF-3 was 5.7 mL, indicating that of WBDF-3 was 5.7 mL,
indicating
that that theproperty
the filtration filtrationofproperty
WBDF was of WBDF was improved
improved by using
by using 0.45% 0.45%instead
SDCap SDCapof instead of 0.3%
0.3% FA-367.
FA-367. The filtrate volume was reduced from 3.7 mL to 3.5 mL when
The filtrate volume was reduced from 3.7 mL to 3.5 mL when 0.25% PHPA was replaced by 0.375% 0.25% PHPA was replaced by
0.375% SDCap (WBDF-2 and SBDF-4). The filtrate volume of the optimized
SDCap (WBDF-2 and SBDF-4). The filtrate volume of the optimized WBDF-5 was 4.8 mL. In general, WBDF-5 was 4.8 mL. In
general,
the the API
API filtrate filtratelower
volume volume thanlower
5 mLthan
could 5 mL
meetcould meet the requirement
the requirement of drillingof drilling operations.
operations. In HTHP
filtration tests, the filtrate volumes were apparently larger than that in API filtrationAPI
In HTHP filtration tests, the filtrate volumes were apparently larger than that in testsfiltration tests
for the high
for the high temperature
temperature and high pressure and high pressure
influence theinfluence
quality ofthe thequality of the
filter cake andfilter cake and
promote thepromote
invasionthe of
invasion of drilling fluid filtrates into the wellbore. The HTHP filtrate
drilling fluid filtrates into the wellbore. The HTHP filtrate volume of WBDF-1 was up to 24.2 mL. volume of WBDF-1 was up to
24.2 mL. The WBDF-3 still had lower HTHP filtrate volume than
The WBDF-3 still had lower HTHP filtrate volume than WBDF-1, indicating that the addition of SDCap WBDF-1, indicating that the
addition
also of SDCap
improved also improved
the filtration property the filtration
of WBDF under property of WBDF The
HTHP condition. under HTHP HTHP condition.
filtrate volumesThe of
HTHP filtrate volumes of WBDF-2 and WBDF-4 were very
WBDF-2 and WBDF-4 were very similar. The HTHP filtrate volume of WBDF-5 was 15.8 mL, similar. The HTHP filtrate volume
whichof
WBDF-5 was 15.8 mL, which
was the smallest among these five WBDFs. was the smallest among these five WBDFs.

Figure 11. Filtration

Figure 11. Filtration volumes
volumes with
with different
different WBDFs.
WBDFs.

In order
In order to to further
further investigate
investigate the the effect
effect of
of SDCap
SDCap on the the filtration
filtration property of WBDF, WBDF, the the
micro-structureofofthe
micro-structure thefilter
filtercake
cakewhich
which was
was formed
formed byby drilling
drilling fluid
fluid on onthethe surface
surface of filter
of filter paperpaper
in thein
the filtration
API API filtration testsinvestigated
tests was was investigated using SEMusinganalysis,
SEM analysis,
as shown as in
shown
Figurein12.Figure
In order 12. to
Ineliminate
order to
eliminate
the influence the ofinfluence of otheron
other additives additives on the characterization
the characterization of the structure,of the4% structure,
bentonite4% bentonite
suspension
suspensiononly
containing containing only encapsulator
encapsulator was investigated. was investigated.
The filtrateThe volumefiltratein volume
the API in the APItests
filtration filtration
was
tests was also measured. The SEM photos clearly showed the
also measured. The SEM photos clearly showed the micro-structures of the filter cakes formed by micro-structures of the filter cakes
formed by
different testdifferent
fluids. For test 4%fluids. For 4%suspension
bentonite bentonite suspension without encapsulator,
without encapsulator, it could not itform could not filter
a fine form
a fineand
cake, filterthecake,
surfaceandofthe thesurface
filter cakeof the
wasfilter
verycake
coarse. wasThere
verywerecoarse.lotsThere
of poreswereand lots of pores
fractures in and
the
fractures in the filter cake, as shown in Figure 12a,b. Therefore, the filtrates
filter cake, as shown in Figure 12a,b. Therefore, the filtrates of the drilling fluid easily invade inside of the drilling fluid easily
invade
the rockinside
formation the inrock formation
wellbore, in wellbore,
resulting resulting
in hydration in hydration
swelling and dispersionswelling and dispersion
of shales. The filtrate of
shales. The
volume of the filtrate volume of
API filtration thecould
tests API filtration
confirm the testsanalysis
could confirm
for all the thetest
analysis for all
fluid was the test
leaking andfluid
the
was leaking
filtrate volume and wasthelarge
filtrate
thanvolume
200 mL, was large than
indicating the200 mL,
very indicating
poor quality the very
of the poor
filter cake.quality of the
Therefore,
filter cake.
filtrate reducersTherefore,
have tofiltrate
be used. reducers
The filter have
caketoformed
be used.by 4%Thebentonite
filter cake formed by
suspension with 4% bentonite
0.3% PHPA
was better than that formed by bentonite suspension, but it was still not satisfactory, as shownnot
suspension with 0.3% PHPA was better than that formed by bentonite suspension, but it was still in
satisfactory,
Figure 12c,d.as shown
Owing tointheFigure 12c,d. Owing
absorption of PHPA toon
theclay
absorption
particlesofinPHPA on clay
the filter cake,particles
the filterincake
the filter
was
cake, the
tighter withfilter cake wassurface
smoother tighterthanwiththatsmoother
formed surface
by 4%than that formed
bentonite suspensionby 4%without
bentonite suspension
encapsulator.
without encapsulator. However, there were still lots of pores and
However, there were still lots of pores and fractures, and the flocculation could be observed which fractures, and the flocculation
could be
would observed
result in unevenwhich wouldofresult
surface filterin uneven
cake. The surface of filter cake.
filtrate volume was up Thetofiltrate
64.0 mL. volume was up to
In comparison,
a64.0
tightmL.
filterIncakecomparison,
with smooth a tight
surface filter
was cake
formed with
by 4% smooth surface
bentonite was formed
suspension by 4%
containing 0.3%bentonite
SDCap,
suspension containing 0.3% SDCap, as shown in Figure 12e,f, and the
as shown in Figure 12e,f, and the filter volume was 29.6 mL. Very tight filter cake surface was observed, filter volume was 29.6 mL.
Very tight filter cake surface was observed, even in the SEM photo with 5000-fold magnification. The
molecular chain was short and the adsorption capacity was strong, so clay particles with adsorbed
Appl. Sci. 2017, 7, 594 13 of 16

Appl. Sci. 2017, 7, 594 13 of 16

even in the SEM photo with 5000-fold magnification. The molecular chain was short and the adsorption
capacity was strong, so clay particles with adsorbed SDCap molecules were evenly dispersed on the
SDCap molecules were evenly dispersed on the surface of wellbore without apparent flocculation,
surface of wellbore without apparent flocculation, forming tight filter cake. Therefore, the addition of
forming tight filter cake. Therefore, the addition of SDCap improved the filtration property of
SDCap improved the filtration property of WBDF, thus mitigating the wellbore instability problems
WBDF, thus mitigating the wellbore instability problems caused by the invasion of drilling fluid
caused by the invasion of drilling fluid filtrates.
filtrates.

Figure 12. SEM photos of filter cakes formed by different test fluids. (a) 4% bentonite suspension
Figure 12.magnification);
(400-fold SEM photos of(b) filter
4% cakes formed
bentonite by different
suspension test fluids.
(3500-fold (a) 4% bentonite
magnification); (c) 4%suspension
bentonite
(400-fold magnification);
suspension with 0.3% PHPA (b) (400-fold
4% bentonite suspension(d)(3500-fold
magnification); magnification);
4% bentonite (c) 4%
suspension with bentonite
0.3% PHPA
suspension with 0.3% PHPA (400-fold magnification); (d) 4% bentonite suspension with 0.3%
(4000-fold magnification); (e) 4% bentonite suspension with 0.3% SDCap (400-fold magnification); PHPA
(4000-fold magnification); (e) 4% bentonite suspension with 0.3% SDCap
(f) 4% bentonite suspension with 0.3% SDCap (5000-fold magnification). (400-fold magnification); (f)
4% bentonite suspension with 0.3% SDCap (5000-fold magnification).
4. Conclusions
4. Conclusions
Zwitterionic polymer P(AM-DMC-AMPS) named SDCap was developed as a low-molecular-weight
Zwitterionic polymer P(AM-DMC-AMPS) named SDCap was developed as a
encapsulator for deepwater drilling fluid. The number-average and weight-average molecular weight
low-molecular-weight encapsulator for deepwater drilling fluid. The number-average and
of SDCap were about 260,000 and 380,000, respectively, much lower than that of the conventional
weight-average molecular weight of SDCap were about 260,000 and 380,000, respectively, much
encapsulator. In the deepwater drilling temperature range 4–75 ◦ C, the WBDF containing SDCap
lower than that of the conventional encapsulator. In the deepwater drilling temperature range 4–75
had lower and more stable rheological property than that containing conventional encapsulators
°C, the WBDF containing SDCap had lower and more stable rheological property than that
PHPA and PA-367, because of its short molecular chains. The shale recovery rate of WBDF containing
containing conventional encapsulators PHPA and PA-367, because of its short molecular chains. The
SDCap was higher than that of WBDFs containing conventional encapsulator, and the swelling rate
shale recovery rate of WBDF containing SDCap was higher than that of WBDFs containing
of these WBDFs were similar, indicating the strong shale inhibition performance of SDCap although
conventional encapsulator, and the swelling rate of these WBDFs were similar, indicating the strong
its molecular weight was low. In addition, SDCap improved the filtration property of WBDF by
shale inhibition performance of SDCap although its molecular weight was low. In addition, SDCap
forming tight filter cake, and was completely compatible with other components in WBDFs for it was
improved the filtration property of WBDF by forming tight filter cake, and was completely
a zwitterionic polymer with low-molecular-weight. The strong shale inhibition property of SDCap
compatible with other components in WBDFs for it was a zwitterionic polymer with
owes to its adsorption on the surface of clay particle and wrapping effect through both hydrogen
low-molecular-weight. The strong shale inhibition property of SDCap owes to its adsorption on the
bonding and electrostatic interaction. An optimized WBDF containing SDCap was also presented and
surface of clay particle and wrapping effect through both hydrogen bonding and electrostatic
interaction. An optimized WBDF containing SDCap was also presented and it performed better than
other WBDFs. It was concluded that using SDCap instead of conventional encapsulators can
maintain the wellbore stability and keep the integrity of drill cuttings by inhibiting shale dispersion,
Appl. Sci. 2017, 7, 594 14 of 16

it performed better than other WBDFs. It was concluded that using SDCap instead of conventional
encapsulators can maintain the wellbore stability and keep the integrity of drill cuttings by inhibiting
shale dispersion, and prevent the drilling fluid from lost circulation and adhesion on the vibrating
screen caused by the severe thickening at a low temperature.

Acknowledgments: This work was supported by the National Basic Research Program of China (2015CB251205),
the National Natural Science Foundation of China (51374233 and 51474236), and the Postdoctoral Innovative
Project Foundation of Shandong Province (No. 201602027).
Author Contributions: Xin Zhao, Zhengsong Qiu and Yongjun Zhang conceived and designed the experiments;
Yongjun Zhang synthesized the encapsulator; Xin Zhao, Yongjun Zhang and Zhichuan Tang performed the
evaluation experiments; Xin Zhao, Hanyi Zhong and Weian Huang analyzed the data; and Xin Zhao wrote
the paper.
Conflicts of Interest: The authors declare no conflict of interest.

Abbreviations
AM acrylamide
AMPS 2-acrylamido-2-methylpropane sulfonic acid
DMC methacrylatoethyl trimethyl ammonium chloride
PHPA partially hydrolyzed polyacrylamide
FA-367 Commercial zwitterionic encapsulator
WBDF water-based drilling fluid
API American Petroleum Institute
FT-IR Fourier transformation infrared
NMR nuclear magnetic resonance
SEM Scanning electron microscopy
AV apparent viscosity, mPa·s
PV plastic viscosity, mPa·s
YP yield point, Pa
θ600 600 r·min−1 reading in the viscometer
θ300 300 r·min−1 reading in the viscometer
HTHP high temperature and high pressure

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