Author's Accepted Manuscript

Hydrophobic Associated Polymer Based Silica

Nanoparticles Composite with Core-shell
Structure as a Filtrate Reducer for Drilling
Fluid at Utra-high Temperature
Hui Mao, Zhengsong Qiu, Zhonghou Shen,
Weian Huang

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Reference:

S0920-4105(15)00102-3
http://dx.doi.org/10.1016/j.petrol.2015.03.003
PETROL2984

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Journal of Petroleum Science and Engineering

Received date: 9 December 2014

Accepted date: 3 March 2015
Cite this article as: Hui Mao, Zhengsong Qiu, Zhonghou Shen, Weian Huang,
Hydrophobic Associated Polymer Based Silica Nanoparticles Composite with
Core-shell Structure as a Filtrate Reducer for Drilling Fluid at Utra-high
Temperature, Journal of Petroleum Science and Engineering, http://dx.doi.org/
10.1016/j.petrol.2015.03.003
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Hydrophobic Associated Polymer Based Silica Nanoparticles Composite with Core-shell

Structure as a Filtrate Reducer for Drilling Fluid at Utra-high Temperature
Hui Mao*1, Zhengsong Qiu, Zhonghou Shen, Weian Huang
School of Petroleum Engineering, China University of Petroleum (East China), Qingdao Shandong, 266580,
China;

ABSTRACT
Nano or micro-nano based materials have attracted a strong interest due to its attractive properties and they
have great potential for developing intelligent drilling fluid in petroleum industry. In this article, a novel hydrophobic
associated polymer based silica nanoparticles composite with core-shell structure which was mainly used for
developing intelligent drilling fluid additive for drilling ultra-deep well under ultra-high temperature, ultra-high
pressure and salinity, was prepared with Acrylamide, 2-Acrylamide-2-methylpro pane sulfonic acid, Maleic anhydride, Styrene and silica nanoparticles via inverse micro emulsion polymerization and sol-gel preparation, and
was characterized by particle size distribution, SEM, TEM ESEM and the influence law of comprehensive performance of water based drilling fluid and its mechanism influenced by novel hydrophobic associated polymer
based silica nanoparticles composite were studied too. Micro-model drilling fluid flooding and drilling fluid displacement experiment of core column were adopted to assess the plugging stability of micro-pores and micro-cracks and effect on wellbore stability. The experimental data showed that, the composite as a micro-nano
drilling fluid additive, possessed excellent properties such as thermal stability, rheology, fluid loss and lubricity.
Especially, it could plug the formation effectively and improve the pressure bearing capability of formation significantly.
KEYWORDS: Polymers; Drilling fluids; Composite materials; Microstructure; Thermal properties; Ultra-high
temperature

1. Introduction
As we all know that drilling fluid in the drilling process of oil and gas well drilling engineering can be seen as
the equivalent to the blood in the human body [1]. Drilling fluid is a typical coarse dispersion colloidal suspension

* Corresponding author at: College of Petroleum Engineering, China University of Petroleum (East China), Qingdao Shadong, 266580, China; Tel:+86 18561917201. E-mail addresses: maohui01@163.com.

system that contains a fluid phase, a solid phase and a chemical phase and commonly used water-based drilling
fluid is a dirty mixture of water, bentonite, viscosity increaser, fluid loss reducer, lubricants, often referred to as
mud [1,2] . Drilling fluid has many important functions and corresponding necessary properties. The principal
functions are to: (1) remove the cuttings away from under the bit and transport the cuttings from the bottom to the
surface; (2) form a thin, low-permeability filter cake which seals pores and other openings in formation penetrated
by the bit; (3) maintain a stable wellbore; (4) cool and lubricate the bit and the drill string; (5) bring information
back to the surface; (6) reduce friction between the drilling string and the side of the hole [3,4] and so on. Polymer
is a very important kind of drilling fluid additives with strong hydrophilicity and larger hydrodynamic volume after
hydration which can control the drilling fluid rheology and auxiliary drop filtration effectively. Synthetic polymer
chemistry has a significant contribution to oil and gas drilling engineering in high temperature and high pressure
applications [5-8]. Synthetic polymers were successfully formulated for deflocculating [9,10], fluid-loss-control
[11-15], viscosity increaser [16], adsorbent [17] and gel inhibition [18-19] at high temperature according its specific

characteristics and were proved to have a wide utility. With the increase of well depth thermal stability becomes
an important performance characteristics of polymers under ultra-high temperature and ultra-high pressure applications. But field application shows that it is often impossible to fulfill certain functional tasks that are essential
in challenging drilling and production environments using conventional macro type fluid additives due to their
inadequate physical, mechanical, chemical, thermal and environmental characteristics [20]. Therefore, the petroleum industry is looking for physically small, multi-functional, biologically degradable, thermally stable, environmentally friendly, novel polymers or natural products for designing intelligent drilling fluids to use virtually in all
areas of petroleum exploration and exploitation [21-23]. The intelligent drilling fluid can meet the borehole stability,
environment-friendly, reservoir protection at the same time, and can identify the different complex circumstances
down hole automatically while drilling and self-change its function to ensure the drilling engineering smoothly.
Fortunately, with the rapid development of nanotechnology, micro-nano materials make drilling fluid with multiple
functions simultaneously become possible and using micro-nano materials to prepare the high-performance intelligent drilling fluid has a greater potential [24-28]. According to the experimental results of Amanullah and Arfaj,
the newly developed nano based drilling fluid or micro-nano based drilling fluid produces suitable high and low
end rheological properties including gelling characteristics and thus expected to fulfill its functional task during
drilling and after cessation of drilling [20]. It is known that ultra-high temperature, high pressure (uHTHP)

drilling fluids and ultra-high temperature, low-pore pressure (uHTLP) drilling fluids are still quite a challenge
to drilling engineering. When bottomhole temperatures exceed 200
2

, the design and formulation of drilling

fluids can present a host of problems. Drilling fluids destabilize under such extreme conditions, possibly
causing wellbore instability, well control problems, and ultimately loss of the well. For example, drilling buried
hill hydrocarbon reservoir in offshore oilfield around Bohai Sea Bay Basin, China has often resulted in failure
to reach desires objectives. Bottom hole temperatures up to 220

, however, the pressures requiring drilling

fluid weights just to 1.04-1.1 g/cm3 equivalent, which belongs to the typical ultra-high temperature and
low-pore pressure reservoir, place severe limitations on the performance of drilling fluids and often contribute in failure to reach the desired drilling objectives. Polymers as viscosifying agent and filtrate reducer that
control rheological properties and fluid loss create major challenges for drilling fluid performance and stabil-

are reached. Additionally, the gelation of drilling fluids containing low

ity when temperatures over 200

solids content and high fluid loss can become difficult to control under ultra-high temperature conditions.
Both of these issues are compounded when the ultra-high temperature is coupled with a requirement for low
fluid density. However, hydrophobic associated polymer with excellent temperature resistance ability, salt resistance ability and anti-pollution capacity, is expected to be used in deep and ultra-deep well drilling. While silica
nanoparticles with high surface energy, rigidity, dimensional stability and thermal stability, the use of nano fillers
for polymer matrix may be combined rigidity, dimensional stability and thermal stability of inorganic material with
toughness, processability and joint performance of polymer together to get polymer based nano-composites with
excellent properties. But the surface modification of inorganic materials such as silica nanoparticles, requires the
presence of functional groups on the surface of the particles capable of either being involved in polymerization
reaction or reacting with terminal groups of preformed polymers [29-31]. Several strategies have been reported
for grafting polymer chains to silica particles [32-35]. In this paper, a novel hydrophobic associated polymer based
nano-silica composite with core-shell structure, mainly used for developing intelligent drilling fluid additive for
drilling ultra-deep well under ultra-high temperature, ultra-high pressure and salinity, was prepared with Acrylamide (Am), 2-Acrylamide-2-methylpro pane sulfonic acid (AMPS), Maleic anhydride (MA), Styrene (St) and nano-silica via inverse micro emulsion polymerization and sol-gel preparation.
2. Experimental
2.1 Materials
Silica nanoparticles (AEROSIL 200, Germany) with an average particle size (Dp) of 12 nm and a specific
surface area of 200 m2/g, were used as received. Acrylamide (AM), Styrene (ST), and Maleic Anhydride (MA)
were purchased from Sinopharm Chemical Reagent Co. Ltd. and used without further purification. Tetraethyl orthosilicate (TEOS), 2-Acrylamide-2-methylpro panesulfonic acid (AMPS) was purchased from Aladdin Industrial
3

Corporation and used without further purification. Potassium persulfate (K2S2O8), sodium hydrogen sulfite
(NaHSO3), Span 80, and OP-10 were all purchased from Sinopharm Chemical Reagent Co. Ltd. and used without
further purification and with a purity>99 wt.%. Deionized water was used throughout the experiments.

Figure 1 Schematic representation of SDFL preparation.

2.2 Preparation of SDFL
Figure 1 shows the synthesis mechanism of SDFL. The polymerization of the novel polymer based nano-silica composite with core-shell structure (coded as SDFL) was divided into two steps. Firstly, the block hydrophobic

associated

polymer

P(AM-NaAMPS-MA-b-St)

was

prepared

by

Acrylamide

(AM),

2-Acrylamide-2-methylpro pane sulfonic acid (AMPS), Maleic anhydride (MA) and Styrene (St) via inverse micro
emulsion polymerization. In brief, 0.06 mol AMPS and 0.01 mol MA were dissolved into 120 mL deionized water,

, 0.1 mol AM and 0.02 mol St were added with deio-

and adjusted pH value to 7 by adding 2 mol/L NaOH at 50

nized water to control the total concentration at 15 wt.%. 3 g span-80 and 1 g OP-10 were also added. Then the
mixture was loaded into a reaction flask. After the above steps, this mixed solution was stirred in high speed and

and deoxygenated

protected by nitrogen for 30min. 0.07 g K2S2O8 was added dropwise and heated up to 90
with nitrogen for 4-5 h, then cooled the reactor to 60

. Secondly, the polymer based nano-silica composite was

prepared via sol-gel preparation. Adding a certain amount of tetraethyl orthosilicate (TEOS) and Silica nanoparticles into the reaction flask react 2-3 h. Finally, the composite was obtained by filtering, washing and drying.
2.3 Characterization

The molecular structure of composite materials was characterized by Infrared spectra (IR) were recorded
using a Nicolet 6700 FT-IR spectrometer (NEXUS, USA).Thermo gravimetric analysis (TGA) of the SDFL was
performed on a SDT Q600 instrument (TA Instruments, USA). The sample was heated at a rate of 5

/min under

N2 flow (100 mL/min). The particle size distribution and specific surface area of micro-nano composites were
determined by ultra-high speed intelligent laser diffraction particle size analyzer delivers (Malvern Mastersizer
3000, Britain). Scanning electron microscopy (SEM, Hitachi S4800, Japan), transmission electron microscopy
(TEM, Hitachi JEM-2100UHR, Japan) and environmental scanning electron microscope (ESEM, Quanta 450, FEI)
were used to study the morphology, structure and in situ surface topography of wet samples of the composite.
The viscosity of the drilling fluid was tested with six-speed rotational viscometer (ZNN-D6, Qingdao). The rheological and filtration test procedure were executed by the American Petroleum Institute drilling fluid indoor test
criteria [36].
2.4 Drilling fluid preparation and property test
The fresh water-based drilling fluid was made up by water, bentonite and Na2CO3 (400:16:0.8 ratio by weight),
and then pre-hydrated for 24h. The saturated NaCl-based drilling fluid was prepared by adding saturated NaCl
into fresh water-based drilling fluid, and then pre-hydrated for 24h.
In this study, the synthetic composite materials were added into the fresh water based slurry at 4 wt.% by
stiring in high speed for 20min and maintaining at indoor environment for 24h, or there was another way that colling the composite materials after hot rolled aging for 16h under the set temperature and then stirred in high
speed for 20min to get the same objective. According to drilling fluid test program SY/T56211993 to test the
drilling fluid rheological parameter. The reading value of viscometer () at different rotational speed (600 r/min
and 300 r/min) was respectively measured by the six-speed rotational viscometer. The equation (1) ~ (3) were
used to calculating the apparent viscosity (AV), plastic viscosity (PV) and yield value (YP) [1].

AV = 600 / 2

(1)

PV = 600 - 300

(2)

YP = 0.511(300 PV )

(3)

2.5 Shale inhibition performance test

2.5.1 Shale hot-roiling recovery experiment
A 50g air drying shale sample (size diameter 6~10 mesh) was weighed and added in aging gar containing
350 mL deionized water or drilling fluid. Loading this system into a roller furnace and rolling at 77
5

for 16 h. The

sample in the jar should be washed with water on a 40 mesh sifter and dried for 4 h at 105

in a drying oven.

Then shale weight ( m ) was recorded after the temperature dropped to room temperature. The shale rolling recovery rate ( R ) was calculated using the equation (4):
(4)

R = m / 50

Where R is the shale rolling recovery rate (%); m is the shale weight after rolling at 77

for 16 h (mm).

The bigger the shale recovery rate is, the better the inhibition performance of the test liquid.
2.5.2 Shale swelling experiment
The shale samples were pulverized to make all powder through 100 mesh sieve, and dried to constant weight
at 105

, and then cooled to room temperature. Compacting the powder at certain pressure (4MPa) and mea-

suring the initial height

H1

(mm) of the compacted sample. Then, the sample was placed in a shale expansion

instrument to make a direct contact with the test liquid and to determine the linear expansive capacity over a
specified period. The ending linear height

H2

(mm) of the compacted sample was recorded to calculate the

shale linear swelling rate (P). The shale linear swelling rate (P) was calculated using the equation (5):

P=

Where

H 2 H1
100%
H1

(5)

P is the shale linear swelling rate (%); H1 and H 2 are the initial height and the ending linear

height of the compacted sample, respectively (mm).

The bigger the shale linear swelling rate is, the better the inhibition performance of the test liquid.
2.6 Drilling fluid displacement experiment
The schematic of the artificial core flooding apparatus used in the drilling fluid displacement experiment is
shown in Figure 2. Table 1 shows the core parameters. The diameter and length of the artificial core were 2.5 and
7.41 cm, respectively. There were two artificial core models for different experiments. Table 1 lists some key parameters of s artificial core models. A back-pressure regulator (BPR) with accuracy less than 0.001 MPa was
used to control the pressure right downstream of the artificial core. Details of the artificial core flooding apparatus
and other apparatus used in this experiments can be found elsewhere [37,38].
The steps are as follows: (1) Weigh the fractured artificial core and then vacuumize for 12 h. (2) Pump the
deionized water into the vacuum equipment and control the pressure at 10 MPa for 12 h so that water can be fully
saturated; (3) Weigh the core after it was saturated with water and calculate the core porosity. The core porosity
6

( ) was calculated as equation (5); (4) Put the core into the gripper, control the confining pressure of 3.5MPa and
then fresh water-based drilling fluid, SDFL based drilling fluid and deionized water were used for displacement
experiment. (5) Record the exit pressure and entrance pressure by digital collection system. The differential
pressure of exit pressure and entrance pressure represent the plugging effect for different drilling fluid. The resistance factor and the residual resistance factor were calculated using the equation (6) and (7):

= ( M 2 M1 ) /

Where

(5)

Res = Pp / Pw

(6)

Rres = Ps / Pw

(7)

is core porosity (%); M 1 and M 2 are the mass of the core before and after it was saturated,

respectively (g);

is the density of deionized water (g/cm );

sidual resistance factor, respectively; Pp ,

Ps

and

and

Res

Rres

are the resistance factor and re-

are the plugging flooding pressure, subsequent water

Pw

flooding pressure and fresh water-based mud flooding pressure, respectively (MPa).

Figure 2 Schematic of the artificial core flooding apparatus

Table 1 Core parameters
parameters

Core 1

Core 2

length (cm)

7.41

7.41

radius (cm)

2.5

2.5

15

15

32

34

initial permeability (10-3 m2)

-3

permeability after fracturing(10 m )

7

dry weight (g)

66.97

67.56

wet weight (g)

74.79

75.12

2.7 Micro-model test

The glass-etched micro-model used in this drilling fluid displacement experiment was made by etching a two
dimensional network of micro-pores and micro-throats, which was patterned from the pore structure of a core
obtained from Yuguo oil filed in Turpan-Hami Basin by a photochemical method. The size of the micro-model was
80 mm 80 mm 6 mm, and the depth of the channel was about 0.040 mm, and the width was about 0.05 mm,
respectively. A Nikon Model L110 digital camera was used to record images and videos within the micro-model.
Details of the artificial core flooding apparatus and other apparatus used in this experiments can be found elsewhere [39]. The schematic of the microscopic drilling fluid displacement experimental apparatus is shown in Figure 3.
The micro-model tests were conducted to investigate the microscopic drilling fluid displacement mechanisms
and the plugging ability of micro-pores and micro-cracks and wellbore stability of different displacement methods.
The steps are as follows: (1) the micro-model was evacuated and the back pressure was controlled in 1.5 MPa; (2)
the micro-model was saturated with the deionized water at 0.02 mL/min; (3) The test fluid was injected with a back
pressure of 1.5 MPa; (4) the deionized water was injected at 0.02 mL/min after the test fluid drive; (5) record images and videos within the micro-model by digital camera.

Figure 3 Schematic of the microscopic drilling fluid displacement experimental apparatus

3. Results and discussion
3.1 Optimum synthesis conditions of SDFL
According to the free radical copolymerization principle, factors affecting on the polymerization reaction
include pH, temperature (

), the mass fraction of initiator (%), reaction monomer concentration (%) and mo8

nomer molar ratio. The orthogonal test was designed of 5 factors and 4 levels. Factors and levels of orthogonal
test were showed in the Table 2.
Table 2 The factors and the level of orthogonal test

level

pH

temperature
(

mass fraction

reaction monomer

of initiator

concentration

(%)

(%)

[C]

[D]

monomer molar ratio

AM:AMPS:MA:ST:SiO2

[A]

[B]

[E]

40

0.1

10

5:3:1:1:1

50

0.2

15

5:3.25:0.75:1:1

60

0.3

20

5:2.75:1.25:1:1

70

0.4

25

5:2.5:1.5:1:1

The orthogonal test table of synthesis of SDFL was showed in Table 3. Sixteen kinds of micro-nano filtration reducing agent composites were synthetized according to design conditions. The rheological characteristic
at room temperature and HTHP filter loss at 180

of sixteen kinds micro-nano filtration were determined re-

spectively. The test drilling fluid formulation was fresh water base mud + synthetic micro-nano filtration (1%) +
Na2SO3 (0.5%). In drilling engineering, in order to break rock effectively at high shear rate and suspend cuttings
effectively at low shear rate, the required yield point to plastic viscosity ratio (0/P) of drilling fluid is high, which
shows the strength of drilling fluid shear diluted characteristics. The bigger the yield point to plastic viscosity
ratio of drilling fluid is, the better the drilling fluid thixotropy. Because the results of orthogonal test were related
to the optimization of rheology and HTHP filtration effect, so when the fluid loss reducing capacity and regulating rheological ability of the synthetic polymer / nanoparticles micro-nano filtration were deposed, 0/p and
FLHTHP should be standardized firstly, thus, denoted 0/p and FLHTHP by X and Y, and then the same weight was
given to the two evaluation indexes, H is a comprehensive evaluation index, and H=X-Y. The bigger the H is,
the better the rheology, and the more ideal fluid loss effect.
Table 3 The orthogonal test results of SDFL
p

mPas

Pa

E1

18

0.28

D2

E2

21

C3

D3

E3

25

C4

D4

E4

38

No.

A1

B1

C1

D1

A1

B2

C2

A1

B3

A1

B4

0/p

FLHTHP

25

0.42

0.40

0.017

0.33

23

0.63

0.30

0.325

8.5

0.34

20.8

0.67

0.19

0.477

0.18

35.5

0.00

0.93

-0.925

mL

A2

B1

C2

D3

E4

22

0.27

33

0.38

0.80

-0.425

A2

B2

C1

D4

E3

26

0.19

26.2

0.04

0.46

-0.418

A2

B3

C4

D1

E2

45

9.2

0.20

21

0.08

0.20

-0.117

A2

B4

C3

D2

E1

31

13

0.42

17

1.00

0.00

1.000

A3

B1

C3

D4

E2

36

12

0.33

18.2

0.63

0.06

0.565

10

A3

B2

C4

D3

E1

33.5

11

0.33

22.5

0.63

0.28

0.350

11

A3

B3

C1

D2

E4

24.5

0.29

34

0.46

0.85

-0.392

12

A3

B4

C2

D1

E3

28

0.29

37

0.46

1.00

-0.542

13

A4

B1

C2

D2

E3

19

0.26

27

0.33

0.50

-0.167

14

A4

B2

C1

D1

E4

21

0.19

34.5

0.04

0.88

-0.833

15

A4

B3

C4

D4

E1

23.5

0.30

20.2

0.50

0.16

0.340

16

A4

B4

C3

D3

E2

31.5

0.19

25.8

0.04

0.44

-0.398

K1

-0.027

-0.002

-0.407

-0.369

0.427

K2

0.010

-0.144

-0.202

0.192

0.094

K3

-0.005

0.077

0.411

0.001

-0.163

K4

-0.265

-0.216

-0.088

-0.110

-0.644

0.275

0.293

0.818

0.560

1.070

A2

B3

C3

D2

E1

Optimal
Level

As can be seen the orthogonal analysis range results from Table 3, influence factors sequence of comprehensive effect of polymerization reaction product is that monomer molar ratio > initiator mass fraction >
reacting monomer concentration > temperature > pH value. From the mean analysis results ,the optimum
synthesis condition is A2, B3, C3, D2, E1, While pH value is 7, temperature is 60

, the initiator mass fraction

is 0.3 % (w/w), monomer concentration is 15 % (w/v), the monomer molar ratio of AM:AMPS:MA:ST:SiO2 is
5:3:1:1:1.
3.2 Micro-morphology characterization
3.2.1 FT-IR analysis
As can be seen the infrared spectra test results from Figure 4, the product is with the primary / secondary
amides C=O bond stretching vibration nearby 1669.77 cm-1, -NH2 stretching vibration nearby 3346.64 cm-1 ,
-1

C=O bond stretching vibration in AMPS nearby 1206.65 cm , Asymmetric stretching vibration of S=O bond
nearby 1185.35 cm-1, symmetric stretching vibration of -CH3 nearby 2870.3 cm-1. The characteristic absorption
peaks of the benzene ring were 1615.83 cm-1 and 1455.25 cm-1. C-H bending vibration at benzene ring was
10

667.99 cm-1. The stretch vibration absorption spectra of the two carbonyls (C=O) on anhydride (1860 ~ 1800
-1

-1

cm and1800 ~ 1740 cm ) was not existent in the spectrum, that showed maleic anhydride in the product had
been hydrolyzed into carboxyl [40]. The absorption peaks of stretching vibration of -OH on -COOH were
2927.13 cm-1 and 2951.76 cm-1. The absorption peak of stretching vibration of -C-O on -COOH was 1402 cm-1,
-1

for absorption peak, the absorption peak of stretching vibration of Si-O-C bond was 1068.41 cm . Stretching
-1

-1

vibration peak of vinyl C=C didnt not appear 1000 cm ~ 900 cm interval. It Indicated that the polymerization
was complete, there was no residual monomer. The FTIR results showed that, molecular chains were with to
all the comonomer links.
100
90
80

Transmittance (%)

70
60
50
40
30
20
10
0
4000

3500

3000

2500

2000

1500

1000

500

-1

wavelength (cm )

Figure 4 FTIR spectra of the of SDFL

3.2.2 Molecular weight distribution analysis
The relative molecular weight of SDFL was measured by the gel permeation chromatography (GPC, SFD,
German), using polystyrene as standard sample, phosphate buffer solution as mobile phase, and the column
was SHODEX (K-806M chloroform system, Styrene and Divinylbenzene copolymer as packing). The test results are the molecular weight (Mw) equaled 7.36895 105, number average molecular weight (Mn) equaled
3.32174 105, and the dispersion index is 2.2184.
3.2.3 TEM observation
Figure 5 shows the TEM image of SDFL in dilute aqueous solution, from which we can see that the composite particle size was about 300nm, and the particles well dispersed in aqueous solution indicating that the
hydrophobic associating polymers had been successfully coated on the surface of inorganic silica nanoparticles and a micro-nano composite with core-shell structure had formed.

11

Figure 5 TEM image of SDFL in dilute aqueous solution

3.2.4 SEM observation
The solid fresh sectional SEM image of SDFL in Figure 6 shows that composite morphology was particulate and the particles between each other was connected through the polymer matrix, and particle size distribution was in the range of 280-320nm.

Figure 6 The solid fresh sectional SEM image of SDFL

3.2.5 Particle size distribution
The particle size distribution curve and specific surface area of SDFL in dilute aqueous solution was
shown in Figure 7 and Table 4. One can see that the median particle size D(50) of this composite material was
285nm, D(10) was 0.185nm, D (90) was 0.422nm and the range of particle size distribution was narrow and
therefore, it had a very large surface area, reaching to 22370 m2/kg. The diameter test results were consistent
with the SEM and TEM characterization results, further verified that the product synthesis achieved the design
objective.

Table 4 The results of diameter distribution and specific surface area of Polymer/Nano-silica
Analysis Items

Results

Scattering Model

Mie

Unit

12

Analysis Items

Results

Unit

Concentration

0.0010%

Dispersant

Water

Consistency

0.257

Particle Absorption

0.100

Specific Surface Area

22370

m /kg

Weighted Residual

11.72%

Span

0.835

Particle Refractive Index

1.572

D(10)

0.185

Dispersant Refractive Index

1.330

D(50)

0.284

Shading Degree

7.09%

D(90)

0.422

D[3,2]

0.268

D[4,3]

0.295

3.2.6 Thermal analysis

Figure 7 shows the TGA curves for the block hydrophobic associated polymer P(AM-NaAMPS-MA-b-St)
based silica nanoparticles composite. The composite exhibited four stages of the decomposition. The first

. The second degradation stage occurred in the range of 290 320 . The third decomposition stage began at 320 and ended at 420
440 .The fourth stage became smooth at temperatures higher than 440 C. Here, the first stage corres-

decomposition stage began at room temperature and ended at 120

ponded to the decomposition of water and other volatile substances in SDFL, the second stage corresponded
to the decomposition of amide and carboxyl groups, the third stage to the degradation of sulfonic groups, and
the fourth stage to the decomposition of the polymer backbone. In the range of room temperature to 500

total weight loss rate was 60% showed that the SDFL itself has a good characteristics of temperature resistance.
100
90
80
70

TG (%)

60
50
40
30
20
10
0
0

50

100 150 200 250 300 350 400 450 500 550 600 650

Temperatue ( )

Figure 7 TGA curve for the SDFL

3.3 Rheological properties
Table 5 shows the effect of SDFL concentration on the rheological characteristic and filtrate volume cha-

racteristic of the fresh water based drilling fluid (Formulation A) after aging under 230 . It can be seen that the
filtrate volume decreased with the increase of the SDFL concentration after the aging test. When the SDFL
13

concentration was high enough (e.g., 0.5% for water based drilling fluid), the filtrate properties changed slowly.
This illustrated that SDFL was a very efficient fluidloss reducer. Whats more, the apparent viscosity (AV),
plastic viscosity (PV), yield point (YP) increased with the increase of the SDFL concentration after the aging
test, which means the strength of drilling fluid shear diluted characteristics became better and the drilling fluid
thixotropy changed well and this was good for breaking rock effectively at high shear rate and suspending cuttings effectively at low shear rate.

Table 5 The effects of drilling fluid properties in different SDFL solution

AV

PV

YP

FLAPI

FLHTHP

mPas

mPas

Pa

mL

mL

Formulation A

0.14

26

52

Formulation A + 0.1% SDFL

12

10

0.20

18

46

Formulation A + 0.2% SDFL

16

13

0.23

15

37

Formulation A + 0.3% SDFL

21.5

16

5.5

0.34

11.6

26

Formulation A + 0.4% SDFL

27.5

20

7.5

0.38

9.2

24

Formulation A + 0.5% SDFL

32

21

11

0.52

5.4

21.5

Formulation A + 1.0% SDFL

46

30

16

0.53

4.8

18

Formula

YP/PV

Table 6 lists the influence of SDFL on apparent viscosity(AV), plastic viscosity(PV), yield point(YP), filtration loss(FLAPI) , HTHP filtration loss(FLHTHP) and Lubrication coefficient of the fresh water-based drilling fluid
(Formulation A) and saturated NaCl-based drilling fluid (Formulation B) after aging under 230

. As indicated in

Table.1, after adding SDFL, drilling fluids displayed a largely increase in AV, PV, YP, and a significant decrease
in FL and lubrication coefficient. The drilling fluid systems set temperature stability, salt tolerance, perfect
rheological properties, good lubricity, and fluid loss control properties in one, and the function of drilling fluids
showed significant pluralism. The excellent properties of micro-nano-based drilling fluid were due to the unique
molecular design of SDFL which polymer matrix with high degree branching structure had big steric hindrance
and micro-cross-linked structure which combined rigidity and thermal stability of nano-silica with characteristics
of hydrophobic associating polymers together. The polymer matrix could provide viscosity at high temperature
and the micro-nanoparticles could cause that the entropy of SDFL has a much higher contribution to the specific heat than that of conventional drilling fluid agents, thereby, when the micro-nanoparticles were circulated

14

into the bottom, more heat could be absorbed to improve the performance of the other systems of drilling fluids.
Besides, Si-OH at the surface of the composite could react with Si-OH at the surface of clay by polycondensation

and produce strong chemical adsorption which resulted in thickening hydration membrane and increas-

ing hydration membrane repulsive force at high temperature and high pressure [41]. Thus, the flocculation
among clay particles at high temperature and high pressure was prevented effectively to keep a reasonable
particle distribution in drilling fluid and form a thin-dense mud cake. Meanwhile, the ultrafine spherical micro-nano particles may form an ultrathin bed similar to the spherical bearing type surface between the pipe and
the wellbore and thereby can let easy sliding of the drill string along the spherical bearing surface.

Table 6 The effect of SDFL on rheological properties, filtration behaviors and lubrication properties of different
drilling fluids formulations after thermal aging tests under 230

/16h.

Properties
Drilling fluid combination

AV

PV

YP

FLAPI

FLHTHP

Lubrication

(mPas)

(mPas)

(Pa)

(mL)

(mL)

coefficient

Formulation A

7.5

6.0

1.5

27.0

51.8

0.426

Formulation A + 0.5%SDFL

32

21

11

5.4

21.5

0.028

Formulation B

5.0

4.0

1.0

32.0

63.5

0.438

Formulation B + 0.8%SDFL

26.0

21.0

5.0

8.2

22.0

0.057

3.4 Filtrate properties

Figures 8 and 9 show the effect of SDFL concentrations on the API filtrate volume of freshwater based

drilling fluid and salt-water drilling fluid before and after aging under 230 , respectively. It can be seen that the
API filtrate volume decreased significantly with the increase of the SDFL concentration before or after the aging
test under ultra-high temperature. The API filtrate volume after the aging test was larger than that before the
aging test, meaning that the elevated temperature could raise permeability of the filter cake and spoil a part of
the mud gel structure [13]. However, if aged at elevated ultra-high temperatures of 230C, even if some clay
aggregation occurred in drilling fluid system, the residual clay network was kept, thus the API filtrate volumes of
fresh water based drilling fluid and salt-water based drilling fluid were still smaller than 5 mL and 15 mL, respectively. When the novel hydrophobic associated polymer based nano-silica composite with core-shell
structure concentration was high enough (e.g., 1.0% for fresh water based drilling fluid and 1.2% for salt-water

15

based drilling fluid), the API filtrate properties changed very slowly. And this illustrated that SDFL was a very
efficient fluid loss reducer.
35

30
before thermal aging test
after thermal aging test

FL (mL)

25

20

15

10

5
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

FLR Concentration (%)

Figure 8 The effect of SDFL concentration on the filtrate volume of fresh-water drilling fluid (before and after
the aging test).
100
90
80

before thermal aging test

after thermal aging test

70

FL (mL)

60
50
40
30
20
10
0
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

0.8

0.9

1.0

1.1

1.2

1.3

FLR Concentration (%)

Figure 9 The effect of SDFL concentration on the filtrate volume of salt-water drilling fluid (before and after the
aging test).
3.5 Temperature resistant capacity
Filtration properties and rheology characteristics test results of SDFL in fresh water based drilling fluid
aging after 16 h at different temperature was shown in Table 7. From Table 7, one can see that 1% SDFL
concentration could make the drilling fluid filtrate loss decreased obviously, especially the HTHP filtrate volume,
and the HTHP filtrate volume was only 16 mL after aging at 220

/16 h. At the same time, the rheological

property of drilling fluid system was improved due to the increase of yield point to plastic viscosity ratio. High
HTHP filtration and high temperature rheological property showed that SDFL had excellent thermal stability
which could resist temperature up to 220

in the drilling fluid system.

Table 7 The variation results of drilling fluid properties in different temperature

Drilling fluid combination

experimental
16

AV

PV

YP

FLAPI

FLHTHP

conditions

/16h
210/16h
220/16h
230/16h

fresh water based drilling fluid

200

fresh water based drilling fluid + 1% SDFL

fresh water based drilling fluid + 1% SDFL
fresh water based drilling fluid + 1% SDFL

mPas

mPas

Pa

mL

mL

7.5

1.5

27

51.8

31

23

7.3

20.5

42

31

11

5.4

16

46

30

16

4.8

18

3.6 Salt resistant capacity

From Figure 10, the apparent viscosity of partially hydrolyzed polyacrylamide (HPAM) aqueous solution
decreased with the increase of Ca2+ concentration, and showed typical characteristics of polyelectrolyte. This is
because ionic charge of high molecular polymer was shielded by the ion charge of external electrolyte under
the influence of the external ion which resulting in polymer molecular chain convergence curl and polymer hydrodynamic radius reduced. So its water solution apparent viscosity decreased. The apparent viscosity of the
solution of dioxide multiple hydrophobically associating copolymer introduced inorganic silica nanoparticles
2+

decreased first and then increased with Ca

concentration increased, and the apparent viscosity was higher

than that of HPAM in aqueous solution. This is because the novel synthetic polymers not only introduced inorganic silica nanoparticles and anionic sulfonate groups extremely insensitive to salt, but also introduced a
little bit of hydrophobic group (PSt) in hydrophilic macro chain [42]. Due to the high charge density of sulfonic
acid groups in AMPS and strong hydration, it is conducive to improve the water solubility behavior of the copolymer. Meanwhile, the two bond and three strongly electronegative O atoms in molecule shared a negative
charge which made the sulfonic acid group stable [41], so it is insensitive to the cation in the drilling fluid sys2+

tem .On the other hand, with the increase of Ca

concentration, the ion shielding effect of on apparent viscos-

ity declined, but the solvent polarity enhanced with the increase of content of inorganic salt ions .Thus it is more
conducive to the association of hydrophobic associating polymer hydrophobic chain. The hydrodynamic radius
of polymer molecular became larger and the solution apparent viscosity increased slowly when the ion shielding effect ended.

17

30.0
27.5

HPAM
FLR-1

25.0
22.5

AV (mPa.s)

20.0
17.5
15.0
12.5
10.0
7.5
5.0
2.5
0.0
0.0

0.1

0.2

0.3

0.4

0.5

0.6

0.7

Concentration of salt (wt.%)

Figure 10 The apparent viscosity of 0.5% polymer aqueous solution under different concentration of CaCl2
3.7 Hydrophobic associating property
From Figure 11, at the same concentration (1%) of SDFL, the plastic viscosity (PV) and yield point(YP) of
SDFL aqueous solution were first increase, then the change trend of decrease with the increase of the content
of styrene link in molecular chain. But the API filtrate volume showed the tendency of first decrease, and then
increase. This is because when the styrene content is low, the association of the hydrophobic block segment is
based on intramolecular association which led molecular chain curling up and small hydrodynamics radius of
molecular chain. Thus the copolymer solution viscosity is smaller. When styrene content increases, the hydrophobic block link becomes longer, the hydrophobic association between big macromolecular chain enhances, hydrodynamic radius becomes bigger, and viscosity increases gradually. When the hydrophobic block
segment content continues to increase, styrene hydrophobic block its association trend becomes large, while
the association between the macromolecular chain is weakened. Therefore, the solution viscosity decreases
with the increase of the content of styrene link.
35.0
32.5
PV(mPas)
YP(Pa)
API(mL)

30.0
27.5
25.0
22.5
20.0
17.5
15.0
12.5
10.0
7.5
5.0
2.5
0.0
0.0

0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

St (mol.%)

Figure 11 The properties results of SDFL solution at different styrene content

3.8 Micro-crosslink structure property

18

The ESEM images of the 0.3% SDFL in aqueous solution and 1.0% NaCl solution were shown in Figure
12. We can see that, the aqueous solution and 1.0% NaCl solution both emerged micro crosslinking properties
after silica nanoparticles introduced into the polymer, but the network structure of SDFL in aqueous solution
was stronger and the grid structure was closer. This is determined by the unique molecular conformation of
hydrophobic associating polymer connecting silica nanoparticles as shown in Figure 13. Therefore, the unique
molecular structure of the polymer based silica nanoparticles and its micro crosslinking form in solution could
keep the drilling liquid viscosity effectively, and a small amount of SDFL added to water-based drilling fluids
could greatly increases the viscosity of the drilling fluid, which served to reduce the amount of fluid filtration.

(a) 0.3% SDFL in aqueous solution

(b) 0.3% SDFL in 1.0% NaCl solution

Figure 12 ESEM images of 0.3%SDFL in aqueous solution and 1.0% NaCl solution
NH2
O=C

OH
SiO2

HO
O
O= C

NaO3S

C=O

O
HO

NH

SO3Na

C =O

O= C

O=C

NH

OH

O
C =O

C=O
NH2

Figure 13 Schematic diagram of molecular structure of SDFL

3.9 Particle size distribution of drilling fluids
In order to study the influence of particle size distribution of fresh water based drilling fluid after adding
SDFL, particle size distribution instrument (Baxter Bettersize2000 laser, Dandong China) was used to analyze
the effect of particle size distribution by adding 0.3% SDFL in fresh water based drilling fluid after aging 16 h

19

under 230

. The drilling fluid system was fresh water based drilling fluid + 0.3% SDFL + 0.1% FA367 + 3%

SMPC + 2% SPNH, and the experimental results as shown in Figure 14.

Figure 14 The effects of particle size distribution of different drilling fluids

From Figure 14, we can see that the fresh water based drilling fluid without SDFL was with small of fine
particles, high proportion of coarse particles and smaller mean particle size after aging test. But after adding
0.5%SDFL, the proportion of fine particles and mean particle size increased obviously. The drilling fluid system
by fine particle in high temperature aging after a marked increase in of the particle size, mean particle size
increased bigger, particle size distribution more reasonable gradation, which can form the mud cake more
dense in the borehole, the filtrate volume reducing, and more conducive to the wellbore stability. In summary,
particle size distribution gradation became more reasonable, and mud cake could be denser in the borehole,
which would reduce the filtrate volume more effective and be more conducive to the wellbore stability.
3.10 Inhibition properties
Selecting the complex formation shale samples at 2768 meters deep of Yuguo oil filed G9-2 well in Turpan-Hami Basin to compare the inhabitation of different inhibitors concluding inorganic salt KCl, cationic NW-1
and SDFL. Shale inhibition evaluation results as shown in Figure 15.

20

100

shale rolling recovery rate (%)

94

shale rolling recovery rate

shale swelling rate

90
80

71
70
60

55.2

50
40
30
20

24
15.6
9.6

10

9.8
2.3

0
Water

5%KCl

0.5%NW-1

0.5%NPC

Figure 15 The shale inhibition results of SDFL

From Figure 15 we can see, the shale rolling recovery rate in deionized water was only 24%, shale swelling rate was as high as 15.6%, indicating that these shale samples had strong hydration swelling and dispersion ability. At the same time we could find SDFL had a better shale inhibition effect than KCl and NW-1 obviously. When the mass fraction of SDFL is 0.3%, the shale recovery rate is as high as 94%, which increased
3.92 times than that of samples in deionized water. However, the shale swelling rate is only 2.3%, decreased
6.78 times than samples in deionized water, indicating that SDFL has excellent inhibiting capacity to shale
hydration dispersion and swelling. This is because the SDFL was with small particle size, large specific surface
area, high surface energy which made it has high surface chemical activity and increased interaction capacity
between SDFL and clay mineral. Therefore, SDFL particles tend to be adsorbed on the surface of clay particles
and form a layer of film to prevent water molecules into clay particle clearance, which can effectively inhibit the
clay minerals hydration dispersion, swelling and reduce the water sensitive of reservoir.
3.11 Lubricating property
The curve of extreme pressure lubricating coefficient of fresh water based drilling fluid influenced by SDFL
after aging 16 h under 230

was shown as Figure 16. From Figure 16, we can see that extreme pressure

lubrication coefficient of the fresh water based drilling fluid decreases gradually with the SDFL amount increased. When the mass fraction of SDFL is 0.5%, the reduction rate of extreme pressure lubricating coefficient of the fresh water based drilling fluid could reach to 93.4%, which indicated that SDFL polymer based
silica nanoparticles composite could increase the drilling fluid system lubrication effectively.

21

100

0.45

90

0.40

80

0.35

70

0.30

60

0.25

lubricating coefficient
reduction rate of lubricating coefficient

50

0.20

40

0.15

30

0.10

20

0.05

10

0.00

reduction rate of lubricating coefficient (%)

lubricating coefficient

0.50

0
0.0

0.1

0.2
0.3
concentration of FLR-1 (%)

0.4

0.5

Figure 16 The effects of extreme pressure lubricating coefficient of water based drilling fluid by SDFL concentration
In the extended reach well and horizontal well drilling engineering, rock cuttings carrying at horizontal
section and cuttings bed formation avoiding are serious challenges faced by drilling fluid. Taking the advantage
of the characteristics of silica nanoparticles such as larger surface area, higher surface energy, ultrafine size
and rigid, combining with the unique properties of polymer, SDFL polymer based silica nanoparticles material
adding to the drilling liquid could quickly form a weak gel system which was conducive to clean cuttings bed
and carrying cuttings. On the other hand, micro nano particles dispersed in drilling fluid would adsorb on the
metal and clay surface quickly and effectively, due to the rigidity, dimensional stability and thermal stability of
inorganic silica nanoparticles, a spherical surface lubricating film similar to a ball bearing could be formed between drilling string and borehole by the existence of SDFL composite micro nano materials. The lubricating
film formed on the friction surface was relatively stable and of high intensity, which would significantly reduce
the friction between drilling string and borehole during oil and gas drilling process and was benefit to the sliding
between drill stem and well bore. Whats more, rotary torque and tripping resistance was decreased, bit balling
was weakened and a thin and dense mud cake was formed, as shown in figure 17.

22

(a)

(b)

Figure 17 SEM images of mud cake surface morphology, (a) SEM image of the fresh water based mud cake
surface morphology after natural air drying, (b) SEM image of the SDFL based mud cake surface morphology
after natural air drying

23

3.12 Plugging ability

In order to study the plugging ability of micro-pores and micro-cracks and wellbore stability by SDFL,
drilling fluid displacement experiment of core column was carried after fracture-making and the displacement
experiment results as shown in Figure 18 and Table 8. From Figure 19 and Table 8 we can see that, the displacement pressure at both ends of core column by fresh water-based drilling fluid flooding was 0.1 MPa, while
the displacement pressure by SDFL based drilling fluid flooding was 3.2 MPa with 2.7 MPa water drive pressure, and the resistance factor of 32, the residual resistance factor of 27, indicating that the polymer based
silica nanoparticles could well plug micro-pores and micro-cracks. Because silica nanoparticles have the peculiarities such as small particle size, high rigidity, good thermal stability, not easy to crush and hydrate, the
micro-nanoparticles cross-linked and bridged together under the action of molecular chain of polymer matrix
could instantly plug the micro-pore and micro-cracks matched with its own size and form an isolation layer
while the formation was continuously drilled. Simultaneously, bridge and crosslink actions between micro-nanoparticles with different sizes had the ability to plug the micro-pores, micro-crack lager than its own size
by self-assembly in drilling fluids, as shown in Figure 19 (a). Thus through these bridge and filling actions, a
thin, firm and dense multi-level network structure could form in a short time earlier at the new drilled formation,
as shown in Figure 19 (b). Moreover, the extension of polymer matrix nonpolar part of SDFL made the polar
molecules, such as water difficult to pass through the film which was formed by nonpolar molecules. So the
mud cake was thin-dense which could reduce the filtration loss and improve the pressure bearing capability of
formation significantly. It is also beneficial to reservoir protection and wellbore stability.
0.5
fresh water based drilling fluid
FLR-1 based drilling fluid
deionized water

3.5

3.5

3.0

3.0

2.5

2.5

2.0

2.0

1.5

1.5

1.0

1.0

0.5

0.5

0.0
12

0.0

P2-P1(MPa)

0.3

0.2

P2-P1(MPa)

0.4

0.1

0.0
0

10

Injection volume

Figure 18 The results of drilling fluid displacement experiment of core column

24

Table 8 Resistance factor and residual resistance factor data

program

parameters

fresh water-based mud flooding pressure

(MPa)

0.1

plugging flooding pressure (MPa)

3.2

subsequent water flooding pressure (MPa)

2.5

resistance factor

32

residual resistance factor

27

(a)

(b)

Figure 19 Plugging mechanisms of micro-pores and micro-cracks by SDFL (a) Self-assembly morphology of
SDFL in dilute aqueous solution; (b) thin and dense mud cake.
To investigate the plugging mechanisms of micro-pores and micro-cracks and wellbore stability mechanisms after different drilling fluid drive, two flooding tests were conducted in micro-models. A micro-model
test of SDFL based drilling fluid drive was first conducted; micro-model images at a certain pressure are shown
in Figure 20 (b), (d) and (e). And then a micro-model test of fresh water based drilling fluid drive was conducted;
micro-model images at a certain pressure are shown in Figure 20 (c) and (f). Figure 20 (a) was the micro-model
image before flood drive. The red arrow indicates the direction of drilling fluid displacement experiment of micro-model test. From Figure 20 (b) and (c), we can see that there were two plugging states during the drilling
fluid drive process. The fresh water based drilling fluid had a poor plugging ability when it was driven at a certain pressure. The fresh water based drilling fluid got into the micro pores and micro cracks along the displacement direction and finally passed through the micro-model, and the micro pores and micro cracks was
saturated by fresh water based drilling fluid. However, the SDFL based drilling fluid had a good plugging ability.
The displacement that SDFL based drilling fluid got into the micro pores and micro cracks along the dis25

placement direction was one-fourth

fourth of the micro-model.
micro model. From Figure 20 (d) and (e), we can see that there are
about two plugging patterns (see the part marked
marked by black lines and red lines) at higher magnification env
environment, and one of the plugging patterns is accord with ideal packing theory as shown in Figure 21 (a), and
another is accord with bridging packing theory as shown in Figure 21 (b). Reservoir protection drilling fluid must
according to the pores and throats size add a continuous sequence particle size distribution of temporary
plugging particles to plug the various sizes of formation pores and cracks effectively, as well as plugging pores
are formed
ormed between the temporary particles. And only forming a reasonable continuous sequence particle size
distribution can ensure a thin and dense mud cake formed. The conventional drilling fluid treating agent or
drilling fluid system with a less distribution
distribution of micro nano particle could not satisfy the micron pores and fra
fractures. Compared with the above, the novel hydrophobic associated polymer based silica nanoparticles co
composite with core-shell
shell structure just could plug the micron pore and fracture.

(a)

(b)

(c)

(d)

(e)

(f)

Figure 20 Microscopic images for SDFL based drilling fluid flooding and fresh water based drilling fluid
flooding: (a) the micro-model
model image before flood drive; (b)SDFL based drilling fluid drive; (c) fresh water based
drilling fluid drive; (d) the boundary of the micro-model
micro
after based drilling fluid flooding;; (e) the center section
of the micro-model after SDFLbased
based drilling fluid flooding;
flooding; (f) the center section of the micro
micro-model after fresh
water based drilling fluid flooding.

26

Figure 21 Schematic of the two plugging mechanisms,

aplugging mechanism of ideal packing theory, b

plugging mechanism of bridging packing theory

4 Working mechanism

(1) Keep the liquid phase viscosity effectively under high-temperature and high-pressure environment
Firstly, due to the higher branched degree structures of the AMPS and larger steric hindrance, the main
chain rigidity increased which played a certain role to raise the temperature resistance of the copolymer. Secondly, the existence of styrene hydrophobic chain in synthetic SDFL filtrate loss reducer molecules in the hydrophobic chain made the solvent hydrophobic association, and the process was endothermic, high temperature was benefit to the association between copolymer molecules which lead to viscosity increased. Thirdly,
high specific surface area of micro nano particles could lead to more contributions to the specific heat given by
entropy of the SDFL than that of conventional drilling fluid. Therefore, SDFL has a much higher specific heat
than the conventional drilling fluid loss agent. When drilling fluid circulated with micro nano particles into the
bottom, more heat could be absorbed than conventional drilling fluid additives which improved performance of
drilling fluid system of other additives to a certain extent. Thereby it could increase the drilling fluid system
temperature resistance. At last, rigidity and thermal stability of silica could combine with the properties of hydrophobic associating copolymers by introducing inorganic silica nanoparticles. The copolymer was with micro
crosslinking structure and significant thermal stability. Thus, the unique molecular structure of the polymer

27

based silica nanoparticles and its micro crosslinking form in solution could keep the drilling liquid viscosity effectively at high temperature and high pressure so that it could play a role in reducing the amount of fluid loss.

(2) Prevent coalescence of the clay particles at a high temperature

The micro nano filtrate loss reducer SDFL molecules contained strong hydrate group such as sulfonic acid
group, carboxy group and acylamino group which could produce strong adsorption with clay mineral particles.
It has good heat resistance, can effectively keep the adsorption sites under high temperature, and thicker water
film can be formed after treatment agent absorbed at the particles appearance which could reduce the content
of free water and enhance the thermal stability of drilling fluid. Secondly, Si-OH in SDFL molecules could act
condensation with Si-OH on the surface of clay mineral and form firm chemical adsorption [15,41], as shown in
Figure 22. This adsorption increased the treatment agent adsorption at the clay appearance under high temperature high pressure condition which made the water film at clay particle surface thicker and membrane hydration repulsion larger, thus effectively preventing the coalescence between the clay particles under high
temperature and high pressure and maintaining reasonable particle size distribution which could form close
mud cake and reduce loss.
Si

Si

Si

O
O
O
O

Si

Si

Si

Si

Si

OH
Al

Al

Al

Al

Al

O
OH

Si

Si

O
O

SiO2

C=O

NH
O
O

Si
O

NH
O

O
O

Si

OH

Si

Al

Al

Al

Al

Al

Al

Si

Si

Si

Si

O
O
O
O

O
O

C =O

O= C
O=C

Si

NaO3S

O
O
OH

HO

NaO3S

Al

Si

Si

O
O
O
O

Si

Si

O
O
O
O

Si

Si

O
O

Figure 22 Schematic diagram of the interaction of clay and SDFL

(3) Improve mud cake quality

Because silica nanoparticles has the characteristics of small size, high rigid strength, excellent thermal
stability, not easy to crush and not to hydrate, when the new formation is being drilled, micro nano particles in
SDFL could crosslink and bridge together under the polymer matrix molecular chain which could block the
28

matched micro pore and micro cracks instantly and form an isolation layer. At the same time, through the autonomous assembling of micro nanoparticles SDFL in aqueous solution bridging and cross-linking effect between different micro nanoparticles in SDFL, also could plug the micro pores and micro cracks larger than its
volume. So firmly and dense multistage network structure was formed in a relatively short period of time by the
bridging and crosslinking effect at the new open formation. Secondly, as the extension of the non-polar part of
SDFL molecules, other polar molecules like water molecule was very hard to go through the membrane composed of nonpolar molecules, thus thick and dense mud cake was formed [43] and pressure bearing capacity
of formation was effectively improved, thereby filtration was reduced under the high temperature and high
pressure.
5. Conclusions
A novel hydrophobic associated polymer based silica nanoparticles composite with core-shell structure
which was mainly used for developing smart drilling fluid additive for drilling ultra-deep well under ultra-high
temperature, ultra-high pressure and salinity, was prepared with Acrylamide, 2-Acrylamide-2-methylpro pane
sulfonic acid, Maleic anhydride, Styrene and silica nanoparticles via inverse micro emulsion polymerization and
sol-gel preparation. Its particle distribution ranged from 280-320 nm with micro-cross-linked property in
aqueous solution and the new synthesized filtrate reducer has a more ideal filtrate reduction property, thermal

/16h was only 20.5

stability, rheology, and lubricity, especially HTHP filtrate reduction. HTHP filter loss of 200

mL. Besides, it could improve the rheological properties of drilling fluid system and also has a better saline-alkaline tolerance. the experiment results of micro-model drilling fluid flooding and drilling fluid displacement experiment of core column showed that the composite as a micro-nano drilling fluid additive, it could plug
the formation effectively and improve the pressure bearing capability of formation significantly, isolate the interaction between the drilling fluid and the formation fluid made it beneficial to stabilize the borehole and protect
the reservoir. And the excellent performance of the composite acting on drilling fluid roots in both combining the
rigidity, thermal stability and dimensional stability of silica nanoparticles with characteristics of hydrophobic
associated polymer together and the molecular structure design concept of micro-cross-linked structure.
Acknowledgments
This work is supported by Natural Science Foundation of China (Project Nos. 51474235, 51474236), the
National Science and Technology Major Project of China (No.2011ZX05021-004), Postdoctoral Innovative
Project Foundation of Shandong Province (No.201303060), Science and Technology Major Project of CNPC
(No.2014E38-2) and Fundamental Research Funds for the Central Universities (No. 15CX06019A).
29

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Highlights

Micro-nano material has great potential for developing intelligent drilling fluid.

Drilling fluid possessed excellent properties after adding micro-nano composites.

Wellbore plugging capacity was studied upon core displacement experiment.

The polymers coated on the surface of nano-silica formed core-shell structure.

The composites can improve the pressure bearing ability of formation significantly.

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