Applied Clay Science 127–128 (2016) 70–77

Contents lists available at ScienceDirect

Applied Clay Science

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

Research paper

Polyethyleneimine as shale inhibitor in drilling fluid

Jiang Guancheng, Qi Yourong, An Yuxiu ⁎, Huang Xianbin, Ren Yanjun
a
State Key Laboratory of Petroleum Resources and Prospecting, China University of Petroleum, (Beijing), Changping District, Beijing 102249, China
b
MOE Key Laboratory of Petroleum Engineering, China University of Petroleum, (Beijing), Changping District, Beijing 102249, China

a r t i c l e i n f o a b s t r a c t

Article history: In this paper, the inhibition property of polyethyleneimine (PEI) in drilling fluid was studied. The inhibition prop-
Received 22 December 2015 erty was evaluated by linear swell test and roll recovery. The addition of PEI70000 resulted in the lowest swelling
Received in revised form 11 April 2016 height, compared with the others inhibitor. Especially PEI was environmental and friendly. The inhibition mech-
Accepted 12 April 2016
anism was investigated by Fourier transform infrared spectroscopy, X-ray diffraction, X-ray photoelectron spec-
Available online xxxx
troscopy, Scanning electron microscopy, Zeta potential and Surface area analyzer. The negative charge in the
Keywords:
surface of montmorillonite (Mt) was neutralized by the positive charge of PEI. PEI was adsorbed in the surface
Polyethyleneimine of Mt and intercalated into the interlayer of Mt, which reduced the hydration repulsion of diffuse electric double
Shale inhibition layer and leaded to inhibit the hydration of clay. Hydrogen bonding between amino groups in PEI and hydroxyl in
Hydration swelling the surface of Mt can be formed in the process. The coordination of electrostatic interaction and hydrogen bond-
Adsorption ing presented water molecules from the interlayer space of Mt, which resulted from the adsorption and interca-
Clay particle lation of PEI in the surface and interlayer space of Mt. There was an amount of nitrogen in the backbone and side
of PEI, leading to more positive ion than chitosan quaternary ammonium salt (HTCC). The more positive ion re-
sulted in the stronger force between inhibitor and clay due to the protonation of nitrogen in water. The molecular
weight of PEI has great influence on inhibition property. The larger molecular weight of PEI performed the better
inhibition property except for PEI1800. Indicating the molecular weight of PEI was not the sole factor to control the
inhibition property. What was more, the larger molecular weight of PEI leaded to the worse water-solubility.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction though the existence of overpressure may be major factors in causing

wellbore instability (Riley et al., 2012; Díaz-Pérez et al., 2007; Paikaray
Wellbore instability problems of shale are frustrated drilling engi- et al., 2008). The charged nature of clay minerals and the hydrophilic
neers as these rocks make up over 75% of drilled formation (Rajnauth, enables them to swell and take part in cation exchange reactions. Clay
2012). N 90% of wellbore instability problems are caused by problematic mineral such as Mt results in an increase in swelling and osmotic pres-
shale (Al-Bazali, 2011). It is one of the most significant technical prob- sure of shale through hydration of the clay and cation exchange
lems in petroleum exploration and a major source of lost time and rev- (Balaban et al., 2015). Inhibiting the hydration of clay is an effective
enue. Shale reservoirs have distinctive features compared with way to control wellbore instability (Bunger et al., 2014). Oil based
traditional reservoirs (Josh et al., 2012). Shale is organic rich and com- fluid is the preferred system in these shale formations (Shivhare and
prised of consolidated clay mineral, natural fractures and nanopores Kuru, 2014). The clay is unhydrated in oil based fluid, but it exists in
predominantly. Shale instability manifests itself in a number of different the fatal environment issues (Patel et al., 2007). Oil based fluid is not
ways, leading to a variety of different problems (Bybee, 2009; Rahman biodegradable and harm for health and environment. Due to potential
et al., 2000; Yu et al., 2003; Chen et al., 2003; Mohiuddin et al., 2007). detrimental effect of non-environment friendly oil based fluid, Environ-
For example, the wellbore may collapse, enlarge holes. Cuttings from ment Protection Agency and other regulatory bodies are imposing in-
drilling shale may disperse and disintegrate when encounter drilling creasingly stringent regulations on the use and disposal of non-
fluid, or agglomerate around the drill bit. These problems result in environment friendly oil based drilling fluid. It has been desirable to
wellbore instability. drill with water based fluid, but water based fluid exists in issues as
Clay mineral composition is considered as a major causal factor in well (Chenevert and Pernot, 1998; Ji et al., 2012; Patel and Gomez,
shale instability (Van Oort, 2003). The nature of the clay mineral re- 2013). When water-sensitive shale formation is exposed to convention-
mains as the most cited primary causes of wellbore instability, even al drilling fluid, shale has an immediate tendency to take up water from
the drilling fluid and swell and disperse rapidly, leading to wellbore in-
⁎ Corresponding author at: State Key Laboratory of Petroleum Resources and
stability issues such as bit-balling, disintegration of cuttings, borehole
Prospecting, China University of Petroleum, (Beijing), Changping District, Beijing wash-out, high torque and drag, and stuck pipe. The drilling fluid indus-
102249, China. try was searching for inhibitive water based drilling fluid all the time.

http://dx.doi.org/10.1016/j.clay.2016.04.013
0169-1317/© 2016 Elsevier B.V. All rights reserved.
 J. Guancheng et al. / Applied Clay Science 127–128 (2016) 70–77 71

Many approaches have been taken over the years, including inorganic 2. Materials and methods
salts (Huadi et al., 2010), such as KCl, CaCl2, NH4Cl, modified gilsonites
and asphalts (Davis and Tooman, 1989), functionally cationic poly qua- 2.1. Materials
ternary amines polymers (Patel, 2009), amphoteric polyamino acids
(Gholizadeh-Doonechaly et al., 2009; Xiong et al., 2012; Zhong et al., Polyethleneimine was purchased from Aladdin Inc. Chitosan quater-
2011) and nonionic polymer (Brady et al., 1998; Guo et al., 2006; nary ammonium salt (HTCC) (Mn 54,000 Da, Quaternary salt graft de-
Zhang et al., 2013), cationic polymers (Rosa et al., 2005). However, gree 60–80%, Purity ≥ 95%) was purchased from Jiaxing Kerui
these approaches have some disadvantages, for example, short effec- Biological Technology Co., Ltd. Polyether amine was obtained from oil
tiveness, worse inhibiting capability, toxicity, low heat and salinity tol- field. Montmorillonite (Mt) which was sodium bentonite was pur-
erance, worse compatibility. Even if some issues have been solved, but chased from Weifang Huawei Company. Shale was obtained from oil
the hydration of water-sensitive shale is not completely controlled field. The other experimental chemicals were purchased from domestic
(Ramirez et al., 2007). High performance water based mud (HPWBM) reagent company. All the chemical materials were used without further
newly developed water based fluid comprised a unique polymeric purification.
amine which is polyether ended with amine group; nevertheless it is
poor heat tolerance duo to the hydrolysis reaction of the polyether. It
is urgent need of researching the effective and environment friendly 2.2. Methods
shale inhibitor. Clay particle is electronegative (Bonini et al., 2009),
and it is obviously that the effective shale inhibitor is electro positivity 2.2.1. Linear swell tests
based on fundamental laws of electricity which the opposite charges at- The expansion heights of inhibitors solutions with time were deter-
tract each other. Positive groups enter into interlayer space and prevent mined by CPZ-2dual channel linear swell meter (Tongchun, Qingdao). A
clay particle from swelling and dispersing. Electro positivity is an essen- filter paper was put on the bottom of pressure tank, then 5 g Mt was
tial characteristic as excellent shale inhibitor. Atom with lone pair elec- poured into pressure tank. The pressure tank bears 10 MPa pressure
trons is liable to form hydrogen bonds between hydrogen atom and for 5 min by hydraulic press. A series of concentration of
these typical atoms of oxygen atom, nitrogen atom and sulphur atom. polyethyleneimine solutions were prepared. Then the solutions were
Hydrogen bond is the main driving force of preventing clay particle poured into pressure tank and the value is recorded zero.
from swelling and dispersing (Tang et al., 2014), and these clay particle
have a number of hydrogen atoms and oxygen atoms with lone pair
electrons, and atoms with lone pair electron are another essential char- 2.2.2. Rolling recovery tests
acteristic as shale inhibitor. The debris of shale between 6 mesh and 10 mesh were prepared.
Polyethyleneimine (PEI) is water soluble polymer with an The concentration of inhibitor solution is fixed on 2 wt%. 300 ml
amount of cation groups (Poghosyan et al., 2015; Foundas et al., solution and 20 g shale debris were poured into digestion tank.
2015; Neville et al., 2013). Their solutions are alkaline (Rajagopalan Then the digestion tanks were put into the BGRL-5 roller furnace
et al., 2015). Meanwhile, there are a number of nitrogen atoms (Tongchun, Qingdao) and rolled at 120°C for 16 h. After cooled into
which form hydrogen bond. What is more important, PEI was room temperature took away upper suspension, then 200 ml
environmental and friendly (Wang et al., 2015a and b). In fact, deionized water was added. This procedure was repeated for three
polyethyleneimine has been widely applied in bioengineering (Liu times. Precipitate was dried at 100 °C for 48 h. The dried precipitate
et al., 2015; Zhu et al., 2015), waste water treatment industry was sieved thought 40 mesh and weighted. The Calculated rolling
(Adewunmi et al., 2015), oil treatment industry (Wang et al., 2015a recovery as the following formula: Recovery = W2 / W1. Shale debris
and b), sensor (Li et al., 2015), coating industry (Sunintaboon et al., denoted by W1 and after hot rolled denoted by W2.
2009), catalyst (Park and Kim, 2015; Zakharova et al., 2009),
membrane (Fang et al., 2015). Polyethyleneimine is synthesized by
ring opening polymerization of ethyleneimine. There are a series of 2.2.3. Preparation of Mt/PEI hybrids and purification of PEI
products which are classified by molecular weight and structure. In 300 ml 2 wt% of PEI solution was prepared. Then 9 g Mt was
this work, the evaluation of the inhibiting property classified by added into PEI solution to make Mt/PEI dispersion, following fierce
different molecular weight was studied and the inhibition stirred for 30 min at 8000 rpm. Then the dispersion endured at
mechanism was explored vis a variety of characterization methods. 120 °C for 16 h to balance the adsorption and hydration between
The application of polyethleneimine is provided in drilling fluid. Mt and PEI. The dispersion was carried out centrifugal treatment
The study of inhibition properties of PEI as shale inhibitor was at 10,000 rpm for 15 min. The precipitate was washed several
invested. PEI exhibited high performance as an outstanding shale times by deionized water until the upper liquid was clearly. Finally
inhibitor according to shale linear swelling and rolling recovery. the precipitate was dried at 100°C for 24 h. Then be grinded into
The mechanism of PEI vis Mt was observed (Fig. 1). powder for XRD, XPS and FT-IR.

Fig. 1. Scheme of inhibiting mechanism of PEI with Mt.

72 J. Guancheng et al. / Applied Clay Science 127–128 (2016) 70–77

2.2.4. Structure characterization techniques

2.2.4.1. Fourier transforms infrared spectroscopy (FT-IR) measurements.

FT-IR spectral analysis of Mt/PEI hybrid was recorded by Magna-IR
560 spectrometer. 2 mg sample and 200 mg KBr were prepared and
fully blended. The mixture be poured into the mold and endured at
50 MPa pressure by hydraulic press.

2.2.4.2. X-ray diffraction (XRD) measurements. Mt and Mt/PEI hybrid

spectra analysis of XRD were recorded by a D8 Advance Diffractometer.
2 g sample was prepared. The sample was poured into the mold and
compacted by glass sheet. 2θ angle was scanned between 0.5° and 10°.
Bragg's equation was used to analyze the basal spacing. Bragg's equation
was 2dsinθ = nλ (λ = 1.5406 nm, n = 1).
Fig. 2. Linear swelling curves of Mt in PEI solution with different molecular weight PEI. The
2.2.4.3. X-ray photoelectron spectroscopy (XPS) measurements. XPS analy- concentration of PEI solution was 4 wt%.
sis of Mt and Mt/PEI hybrid were measured by ESCALAB 250 X-ray pho-
toelectron spectrometer. 2 g sample was prepared. The sample was
poured into the mold and endured at 10 MPa pressure for 10 s by hy- the end of the tests. The concentration of PEI solution was fixed 4 wt%.
draulic press. The compacted samples were dried at 80 °C for 24 h. Spec- The swelling height of Mt in PEI70000 solution was 1.41 mm after 16 h
tra scans of C, N, O, Si, Mg and Al were carried out. and the reduction rate was 76.2%, comparing to the swelling height in
water. In PEI600, PEI1800 and PEI10000 solution the swelling heights of
2.2.4.4. Scanning electron microscopy (SEM). SEM analysis was per- Mt were 2.25 mm, 3.19 mm and1.87 mm, following the reduction
formed by a Quanta 200F scanning electron microscope. 10 ml PEI solu- rates of 62.0%, 46.1% and 68.4%. PEI solution was effective to inhibit
tions were prepared. Then every 10 mg Mt was poured into PEI solution. swelling of Mt. The swelling heights reduced with the increase of molec-
The mixed solutions were dispersed by ultrasonicator at room temper- ular weight except for PEI1800, exhibiting there was another factor to
ature for 10 min, Then the solutions be put for 24 h. 1 drop of solution control the inhibition of PEI except for molecular weight. PEI was classi-
was added to filter cake. The filter cakes were dried at 80 °C for 6 h. fied by molecular weight and structure. Maybe the structure of PEI1800
The dried samples were adhered to adhesive tapes, and then metal was different from the other PEI. The detailed interpretation needed fur-
sprayed for 2 min. ther to study. The interaction between PEI and Mt great contributed to
the inhibition capability of PEI solution. PEI was water-soluble polymer
2.2.4.5. Zeta potential measurements. The dispersions were performed by with an amount of cation groups. Mt was sheet silicate mineral with an
Zetasizer Nano ZS instrument. A series of 0.1 wt% Mt dispersions were amount of negative charge in the side of the sheet. PET was adsorbed in
prepared and dispersed by ultrasonicator at room temperature for the side of Mt through attraction between cation charge and negative
20 min. Different amounts of PEI were added in Mt aqueous dispersion charge. Meanwhile there were a few of nitrogen atoms and hydrogen
to make a series of Mt/PEI dispersions. atoms in PEI backbone and side, and was easy to form hydrogen bond
with hydrogen and oxygen in Mt. The lower molecular weight of PEI
2.2.4.6. Surface area analyzer BET. Shale be crushed and sieved between 6 has the bigger free space and increases the chance in touch with Mt.
mesh and 10mesh. 10 g shale was put into 2 wt% PEI solution and 10 g The swelling heights of Mt reduced with the addition of PEI. The change
was poured into water for 10 h. Then the shale was dried at 100 °C for of swelling height was not linear correlation with concentration of PEI.
24 h. BET analysis was performed by Quadrasorb–SI surface area analyz- The molecular motion of PEI great contributed to inhibition capability.
er equipment. However, the concentration was still a major factor to control the inhi-
bition capability. The addition of PEI reduced the swell of Mt. The
3. Results and discussion inhibiting degree of PEI solution strengthened with the increase of mo-
lecular weight in the same concentration except for PEI1800 solution. The
3.1. Inhibition evaluation result was the same as mentioned above. There were more than two
factors to control the degree of inhibition. Concentration and molecular
Based on evaluation procedure of shale inhibitor in drilling fluid, the weight were two major factors. The swelling heights of Mt in different
most frequent methods to evaluate the performance of inhibition were inhibitor solution were showed (Fig. 4). KCl and polyether amino
linear swell test and roll recovery test. The linear swelling test revealed were widely applied in oil field as inhibitor. The diameter of K+ was fair-
the swelling property of clay mineral with relation to wellbore instabil- ly with interlamellar spacing of Mt, and the K+ entered into the interla-
ity. The rolling recovery test was designed to simulate the change of mellar of Mt, preventing the water from invading. The polyether amino
shale caused by inhibitor. Herein the two methods are combined to es- was the polymer with the polyether in the backbone and the amino in
timate inhibition property of PEI solution, from which we can make a the end group. The polymether amino considered as the best perfor-
clearly judgment on the prospect of PEI as an excellent shale inhibitor. mance inhibitor in recently years was adsorbed in the surface of Mt
through ether group and amino group. HTCC was water-soluble chito-
3.1.1. Linear swell tests san quaternary ammonium salt with the amount of quaternary ammo-
The linear swelling heights of pristine Mt in water and PEI solution nium groups in the side. The detailed inhibition was studied in earlier
with different molecular weight were exhibited (Fig. 2). The swelling work (An et al., 2015). The concentration of inhibitor was fixed 4 wt%.
curves of all samples showed a similar tendency with strong increase The swelling heights of Mt in KCl, polyether amino, HTCC and PEI70000
in first 2 h and slower grow after 2 h, which was the typical behavior solution were 2.92 mm, 2.35 mm, 1.98 mm and 1.41 mm. The corre-
of Mt in aqueous solution. But there was a great different between in sponding reduction rates were 50.7%, 60.3%, 66.6% and 76.2%. PEI solu-
water and PEI solution. It continued to swell in water until 16 h and tion exhibited high performance as inhibitor to inhibit the swelling of
the swelling heights of PEI solution were nearly stable after 10 h Mt. Compared with polyether amino, the larger amount of positive ion
(Fig. 3). The swelling heights of Mt in PEI solution in any time were in HTCC resulted in the high performance to inhibit the swelling of Mt
slower than in water, leading to the significant decrease of swelling at (An et al., 2015). The inhibiting of KCl was evident weaker than other
 J. Guancheng et al. / Applied Clay Science 127–128 (2016) 70–77 73

Fig. 3. Linear swelling curves of MT in different molecular weight of PEI solutions with different PEI concentrations: a) 600; b) 1800; c) 10,000; d) 70,000.

inhibitors in the same concentration. KCl was inorganic substance with property improved with the increase of molecular weight. It was further
different interaction mechanism with Mt, and the durability of inhibi- exhibited PEI inhibited the hydration of shale apparently. The result was
tion was shorter than the polymer inhibitors. There was an amount of the same as mention above (Fig. 2) except for PEI1800. In the study of lin-
nitrogen atoms in the backbone and in the side of PEI, leading to the ear swell test, the molecular entered into interlayer space of Mt, which
more positive ion than HTCC due to the protonation of nitrogen in was relation to molecular structure. But in the study of rolling recovery
water. As mentioned above, the more positive ion resulted in the stron- test, PEI was coated and twined in the shale, which was barely relation
ger force between inhibitor and Mt. The large amount positive ion con- to molecular structure. Comparing to the other inhibitors, the addition
tributed to the high performance of PEI solution as inhibitor. of PEI resulted in the highest rolling recovery (Fig. 6). In the same con-
dition, the rolling recovery of KCI was 19.89%. The rate of polyether
3.1.2. Rolling recovery tests amino was 57.68%. And the PEI solution was contributed to 65.75%.
The rolling recovery tests exhibited the change of shale in inhibitors The larger amount of positive ion of PEI was considered as the major fac-
solution. The shale was hydrated in water. The hydration resulted in the tor due to highest rolling recovery.
weight decrease of shale. The change of weight was characterized the
inhibition capability of inhibitors. The rolling recovery was linear rela- 3.2. Inhibition mechanism analysis
tion with change of weight. The higher rolling recovery was the better
inhibition capability of inhibitor. The rolling recovery of shale in differ- 3.2.1. Infrared spectroscopy
ent PEI solution was showed (Fig. 5). The value of rate were 56.25%, The infrared spectra of Mt and Mt/PEI hybrids were showed (Fig. 7).
53.25%, 62.55% and 65.75%, comparing to 9.33% in water. In the addition In FT-IR pattern of pristine Mt, a typical characteristic of Mt group was
of PEI, the rolling recovery increased significantly. And the inhibition

Fig. 4. Linear swelling curves of Mt in different inhibitors solutions. The concentration of Fig. 5. Rolling recovery of PEI with different molecular weight. The concentration of PEI
inhibitors solutions were 4 wt%. was 2 wt%.
74 J. Guancheng et al. / Applied Clay Science 127–128 (2016) 70–77

Fig. 6. Rolling recovery of inhibitors. The concentration of inhibitor was 2 wt%.

presented. Some of the major functional group peaks were showed as Fig. 8. X-ray diffraction patterns of Mt/PEI hybrids with dry sample. The molecular weight
follow: stretching band of O\\H (3622 cm−1), physisorbed water of PEI was representing in bottom right corner of PEI.
stretching band (3446 cm−1), water deformation band (1637 cm−1),
stretching band of Si\\O (1037 cm−1), vibration bands of Al\\Al\\OH thickness and 0.2 nm of hydrogen bond length were subtracted,
(914 cm−1), vibration band of Al\\O and Si\\O (796 cm−1). exhibiting the space of monolayer PEI. The monolayer structure of PEI
the spectrums of Mt/PEI hybrid, some relatively strong and weak was observed in interlayer. The hydrogen bond was formed between
peaks assigned to PEI were observed. The stretching bands of N\\H N atom and H atom of PEI and H atom and O atom in the surface of
(2856 cm− 1 and 2869 cm− 1), which indicated the incorporation of Mt. The expansion of d(100) spacing was slight different due to different
PEI in Mt. Comparing to pristine Mt, the peak of stretching band of molecular weight and structure of PEI. The expansion of d(100) spacing
physisorbed water was blue shift 25 cm−1, exhibiting the incorporation had barely relation to molecular weight. In the study of the linear swell-
of PEI with water in Mt. Si\\O stretching band (1037 cm−1) was blue ing, the swelling height was relative with molecular weight as men-
shift 2 cm−1, indicating the hydrogen band be formed between Si\\O tioned above. The expansion of d(100) spacing was not the sole factor
and N\\H. The vibration bands of Al\\O and Si\\O (500–1000 cm−1) to control the swelling of Mt. The adsorption in the surface of Mt was
were shift different degree. The hydrogen band between Mt and PEI considered as major factor to control the swelling of Mt, and it was ac-
was formed. PEI was adsorbed in the surface of Mt through hydrogen cording with the data mentioned above.
band and entered into the interlayer space of Mt through the coopera-
tion of ionic band and hydrogen band.
3.2.3. X-ray photoelectron spectroscopy
3.2.2. X-ray diffraction Mt and Mt/PEI were characterized by X-ray photoelectron spectros-
XRD patterns of pristine Mt and Mt/PEI hybrids were presented copy (XPS) and their compositions were reflected in the XPS surveys
(Fig. 8). In XRD pattern of pristine Mt, a typical characterization of (Fig. 9). Quantitative analysis indicated that Mt has a high content of ox-
monolayer hydration interlayer d(001) spacing was displayed. In the ad- ygen atoms (57.33%) and silicon atoms (17.63%), and small amounts of
dition of PEI, XRD patterns of Mt were modified due to the interlayer ad- carbon (15.38%) and aluminum (8.05%), and nitrogen (0.78%) and mag-
sorption of PEI in the surface of Mt. The 2 wt% addition of PEI with nesium (0.83%) residues. Mt/PEI was composed of O, C, Si, Mg, Al and N
different molecular weight, the d(001) spacing of Mt increased from atoms, and the spectrum of Mt/PEI shows an N 1 s peak at 399.7 eV, in-
1.26 nm to 1.41 nm, 1.42 nm, 1.42 nm and 1.39 nm. The interlayer dicating the successful modified of PEI moieties. The amounts of silicon,
space contributed by PEI was about 0.15 nm after 0.96 nm of layer aluminum, magnesium and oxygen decreased, but the content of

Fig. 7. FT-IR spectra of Mt and Mt/PEI hybrids. PEI with different molecular weight was Fig. 9. X-ray diffraction patterns of Mt/PEI hybrids with dry sample. The molecular weight
represented. of PEI was representing in bottom right corner of PEI.
 J. Guancheng et al. / Applied Clay Science 127–128 (2016) 70–77 75

Fig. 10. SEM images of a) pristine Mt and b)–e) Mt/PEI hybrid with 2 wt% PEI loading. b) PEI600; c) PEI1800; d) PEI10000; e) PEI70000.

carbon atoms and nitrogen increased. The adsorption of PEI moieties zeta potential of Mt dispersion. The zeta potential of Mt was reversed
was in the surface of Mt successfully. due to the addition of 0.1 wt% PEI solution. With the addition of PEI so-
lution, the zeta potential of Mt waved between −8eV and 8 eV, indicat-
3.2.4. Scanning electron microscopy ing the colloidal of Mt become to agglomerate. The positive in the
The scanning electron microscope (SEM) images were showed backbone and side bone of PEI neutralized the negative in Mt, leading
(Fig. 10). The images revealed different association modes of pristine to the instable of Mt colloidal. PEI was adsorbed in the surface of Mt
Mt and Mt/PEI solution after rolled 150 °C for 16 h. The filter cakes meanwhile was desorbed. The balance was formed between adsorption
were made as the standard of API. The pristine Mt was serious hydrated and desorption, leading to the hydration repulsion of double electrostat-
and swelled (Fig. 10a). But Mt/PEI hybrids were mild hydrated and the ic layer and dispersion of the clay.
clay particle were bigger (Fig. 10b–e). In the addition of PEI resulted in
the hydration of the clay particle sharply reduced. The size of the clay 3.2.6. Surface area analysis
particle increased obviously, compared with the size of the clay particle BET specific surface area test showed the surface area, pore volume,
without PEI. PEI exhibited an excellent inhibiting the hydration of the pore width for water were 13.98 cm2/g, 0.002838 cm3/g and 5.60 nm
clay. (Table 1). The surface area of shale with treatment of PEI decreased.
The reduction rate of surface area with different PEI solution was
3.2.5. Zeta potential 30.4%, 20.8%, 31.9% and 32.9%, indicating the stronger interaction be-
The zeta potential evaluation of Mt and Mt/PEI solution were pre- tween PEI and shale. The pore volume of shale after treated by PEI
sented (Fig. 11). The negative surface charge was formed by the isomor- was sharply declined. PEI were adsorbed in the surface of shale stable
phous substitution in the octahedral layer (Frost and Rintoul, 1996). The and almost entered into the nanopores of shale. Compared to pristine
addition of positive charge in the interlayer space broke charge balance. shale, the increasing of pore width maybe resulted from other factor.
The typical zeta potential of Mt was −10.3 mV and presented the favor- The hole opening and surface defect in the PEI solution can resulted in
able dispersion in water. In the addition of PEI resulted in decrease of the increasing of pore width.

3.2.7. Probable inhibition mechanism

The experimental and the mechanism analysis of the inhibition
property of PEI were studied. The PEI solution was in touch with Mt dis-
persion, and the negative charge was neutralized by the positive charge
in PEI through the coordination of electrostatic attraction and hydrogen
bonding, and then PEI was adsorbed in the surface of Mt. The hydroxyl
and amino groups as adsorption groups were adsorbed in the surface
and the interlayer of Mt, leading to the weakness and even the collapse
of the diffuse double layer, further resulting in the aggregation of Mt

Table. 1
BET analysis of natural shale in water and PEI solution.

Samples Surface area (cm2/g) Pore volume(cm3/g) Pore width(nm)

Water 13.98 0.002838 5.60

PEI600 9.73 0.000311 8.44
PEI1800 11.07 0.000179 8.07
PEI10000 9.52 0.000222 8.23
PEI70000 9.38 0.000294 8.01
Fig. 11. Zeta potential of MT particles in PEI solutions with different molecular weight.
76 J. Guancheng et al. / Applied Clay Science 127–128 (2016) 70–77

dispersion. Then PEI intercalated the interlayer space of Mt. On the ac- Díaz-Pérez, A., Cortés-Monroy, I., Roegiers, J.C., 2007. The role of water/clay interaction in
the shale characterization. J. Pet. Sci. Eng. 58, 83–98.
count of the high amount side bone of PEI, it was easy to inter into the Fang, X., Li, J., Li, X., Sun, X., Shen, J., Han, W., Wang, L., 2015. Polyethyleneimine, an effec-
interlayer of Mt, leading to strengthen of driving force between PEI tive additive for polyethersulfone ultrafiltration membrane with enhanced perme-
and Mt. The larger amount of positive ion assigned to PEI was major fac- ability and selectivity. J. Membr. Sci. 476, 216–223.
Foundas, M., Britcher, L.J., Fornasiero, D., Morris, G.E., 2015. Effects of polyethyleneimine–
tor to contribute the high performance as inhibitor. phosphonate–carboxylic copolymers on the dispersion of boehmite particles. Colloids
Surf. A Physicochem. Eng. Asp. 466, 10–17.
4. Conclusions Frost, R.L.; Rintoul, L., Rintoul., 1996. Lattice vibrations of montmorillonite: an FT Raman
and X-ray diffraction study. Appl. Clay Sci. 11, 171–183.
Gholizadeh-Doonechaly, N., Tahmasbi, K., Davani, E., 2009. Development of high-
In summary, the adsorption of PEI in the surface and the performance water-based mud formulation based on amine derivatives. Soc. Pet.
intercalation of interlayer of Mt was major factor to inhibit the Eng., 121228
Guo, J., Yan, J., Fan, W., Zhang, H., 2006. Applications of strongly inhibitive silicate-based
hydration of Mt, and the interaction between the positive ions in drilling fluids in troublesome shale formations in Sudan. J. Pet. Sci. Eng. 50, 195–203.
the PEI and the negative ions in Mt was another major factor to Huadi, F., Aldea, C., MacKereth, B.M., Mukhlis, T., 2010. Successful KCl free highly inhibi-
inhibit the hydration of Mt. The inhibition mechanism of PEI exhibit- tive and cost effective WBM applications, Offshore East Kalimantan, Indonesia. Soc.
Pet. Eng., 132690
ed us the method of development of excellent performance shale in- Ji, L., Guo, Q., Friedheim, J.E., Zhang, R., Chenevert, M.E., Sharma, M.M., 2012. Laboratory
hibitor in water drilling fluid and the guidance of chance of evaluation and analysis of physical shale inhibition of an innovative water-based dril-
operational parameters to achieve best performance in water drilling ling fluid with nanoparticles for drilling unconventional shales. Soc. Pet. Eng., 158895
Josh, M., Esteban, L., Delle Piane, C., Sarout, J., Dewhurst, D.N., Clennell, M.B., 2012.
fluid. In the study of the linear swelling tests, the addition of PEI
Laboratory characterisation of shale properties. J. Pet. Sci. Eng. 88–89, 107–124.
showed highest performance as shale inhibitor. And the rolling re- Li, K., Jiang, J., Tian, S., Yan, F., Chen, X., 2015. Polyethyleneimine-nano silica compos-
covery showed the accordance conclusion. The synthetic evaluation ites: a low-cost and promising adsorbent for CO2 capture. J. Mater. Chem. A 3,
2166–2175.
of linear swelling test and rolling recovery test, the PEI exhibited
Liu, J., Liu, G., Liu, W., Wang, Y., 2015. Turn-on fluorescence sensor for the detection of
the best inhibition property. The larger amount of positive ion heparin based on rhodamine B-modified polyethyleneimine–graphene oxide com-
assigned to PEI was major factor to contribute the high performance plex. Biosens. Bioelectron. 64, 300–305.
as inhibitor. The molecular weight of PEI has great influence on the Mohiuddin, M.A., Khan, K., Abdulraheem, A., Al-Majed, A., Awal, M.R., 2007. Analysis of
wellbore instability in vertical, directional, and horizontal wells using field data.
inhibition. The larger molecular weight of PEI was the better J. Pet. Sci. Eng. 55, 83–92.
inhibition. But the molecular weight was not sole factor to control Neville, F., Murphy, T., Wanless, E.J., 2013. The formation of polyethyleneimine–
inhibition property. The larger molecular weight leads to the worse trimethoxymethylsilane organic–inorganic hybrid particles. Colloids Surf. A
Physicochem. Eng. Asp. 431, 42–50.
water-solubility and increased cost. Meanwhile it still exist some Paikaray, S., Banerjee, S., Mukherji, S., 2008. Surface characteristics of shales and implica-
problems. PEI is more expensive than HTCC and polyether amino, tion on metal sorption. Environ. Chem. Lett. 6, 91–94.
and the reduce of cost is the key issue. On the other side, the Park, J., Kim, S., 2015. Electrochemical analysis of polyethyleneimine-conductive carbon
black supports for pt–pd electrocatalysts. J. Nanosci. Nanotechnol. 15,
compatibility with the other agents used in the drilling fluid needs 1610–1613.
further research. The next work is in progress. Patel, A.D., 2009. Design and development of quaternary amine compounds: shale inhibi-
tion with improved environmental profile. Soc. Pet. Eng., 121737
Patel, A., Gomez, S.L., 2013. Shale inhibition: what works? Soc. Pet. Eng., 164108
Acknowledgements Patel, A., Stamatakis, S., Young, S., Friedheim, J., 2007. Advances in inhibitive water-based
drilling fluids—can they replace oil-based muds? Soc. Pet. Eng., 106476
We would like to thank for the financial support from National Poghosyan, A.H., Arsenyan, L.H., Antonyan, L.A., Shahinyan, A.A., Koetz, J., 2015. Molecular
dynamics simulations of branched polyethyleneimine in water-in-heptanol micelles
Natural Science Foundation of China (51474231), Foundation for stabilized by zwitterionic surfactants. Colloids Surf. A Physicochem. Eng. Asp. 479,
innovative Research Groups of the Natural Science Foundation of 18–24.
China (51221003 and 51521063) and New method and technology Rahman, M.K., Naseby, D., Rahman, S.S., 2000. Borehole collapse analysis incorporating
time-dependent pore pressure due to mud penetration in shales. J. Pet. Sci. Eng. 28,
Foundation of China National Petroleum Corporation (2014A-4212) 13–31.
for this work. Rajagopalan, B., Oh, E.S., Chung, J.S., 2015. The effect of diethylenetriamine on the
solvothermal reactions of polyethyleneimine-graphene oxide/lithium titanate nano-
composites for lithium battery anode. J. Power Sources 275, 702–711.
References Rajnauth, J.J., 2012. Is it time to focus on unconventional resources? Soc. Pet. Eng., 158654
Ramirez, M.A., Benaissa, S., Ragnes, G., Almaraz, A.A., 2007. Aluminum-based hpwbm suc-
Adewunmi, A.A., Ismail, S., Sultan, A.S., 2015. Study on strength and gelation time of poly- cessfully replaces oil-based mud to drill exploratory well in the Magellan Strait,
acrylamide/polyethyleneimine composite gels reinforced with coal fly ash for water Argentina. Soc. Pet. Eng., 108213
shut-off treatment. J. Appl. Polym. Sci. 132 n/a-n/a. Riley, M., Young, S., Stamatakis, E., Guo, Q., Ji, L., De Stefano, G., Price, K., Friedheim, J.,
Al-Bazali, T.M., 2011. The consequences of using concentrated salt solutions for mitigating 2012. Wellbore stability in unconventional shales - the design of a nano-particle
wellbore instability in shales. J. Pet. Sci. Eng. 80, 94–101. fluid. Soc. Pet. Eng., 153729
An, Y., Jiang, G., Ren, Y., Zhang, L., Qi, Y., Ge, Q., 2015. An environmental friendly and bio- Rosa, R.S., Rosa, A., Farias, S.B., Garcia, M.H., Coelho, A.D.S., 2005. A new inhibitive water-
degradable shale inhibitor based on chitosan quaternary ammonium salt. J. Pet. Sci. based fluid: a completely cationic system. Soc. Pet. Eng., 94523
Eng. 135, 253–260. Shivhare, S., Kuru, E., 2014. A study of the pore-blocking ability and formation damage
Balaban, R.d.C., Vidal, E.L.F., Borges, M.R., 2015. Design of experiments to evaluate characteristics of oil-based colloidal gas aphron drilling fluids. J. Pet. Sci. Eng. 122,
clay swelling inhibition by different combinations of organic compounds and in- 257–265.
organic salts for application in water base drilling fluids. Appl. Clay Sci. 105–106, Sunintaboon, P., Duangphet, S., Tangboriboonrat, P., 2009. Polyethyleneimine-
124–130. functionalized poly(methyl methacrylate) colloidal nanoparticles for directly coating
Bonini, M., Debernardi, D., Barla, M., Barla, G., 2009. The mechanical behaviour of clay natural rubber sheet. Colloids Surf. A Physicochem. Eng. Asp. 350, 114–120.
shales and implications on the design of tunnels. Rock Mech. Rock. Eng. 42, Tang, X., Zhang, J., Wang, X., Yu, B., Ding, W., Xiong, J., Yang, Y., Wang, L., Yang, C., 2014.
361–388. Shale characteristics in the southeastern Ordos Basin, China: Implications for hydro-
Brady, M.E., Craster, B., Getliff, J.M., Reid, P.I., 1998. Highly inhibitive, low-salinity glycol carbon accumulation conditions and the potential of continental shales. Int. J. Coal
water-base drilling fluid for shale drilling in environmentally sensitive locations. Geol. 32–46.
Soc. Pet. Eng., 46618 Van Oort, E., 2003. On the physical and chemical stability of shales. J. Pet. Sci. Eng. 38,
Bunger, A.P., Sarout, J., Kear, J., Delle Piane, C., Detournay, E., Josh, M., Dewhurst, D.N., 213–235.
2014. Experimental chemoporoelastic characterization of shale using millimeter- Wang, C., Bao, X., Ding, X., Ding, Y., Abbad, S., Wang, Y., Li, M., Su, Y., Wang, W., Zhou, J.,
scale specimens. J. Pet. Sci. Eng. 118, 40–51. 2015a. A multifunctional self-dissociative polyethyleneimine derivative coating poly-
Bybee, K., 2009. Wellbore-stability performance of water-based-mud additives. Soc. Pet. mer for enhancing the gene transfection efficiency of DNA/polyethyleneimine
Eng., 0909-0078 polyplexes in vitro and in vivo. Polym. Chem. 6, 780–796.
Chen, G., Chenevert, M.E., Sharma, M.M., Yu, M., 2003. A study of wellbore stability in Wang, C., Fang, S., Duan, M., Xiong, Y., Ma, Y., Chen, W., 2015b. Synthesis and evaluation of
shales including poroelastic, chemical, and thermal effects. J. Pet. Sci. Eng. 38, demulsifiers with polyethyleneimine as accepter for treating crude oil emulsions.
167–176. Polym. Adv. Technol. 26, 442–448.
Chenevert, M.E., Pernot, V., 1998. Control of shale swelling pressures using inhibitive Xiong, K.; Ma, P.; Yong, F.; Qian, F.; Yang, R.; Meng, Y., Meng, 2012. Application of alumi-
water-base muds. Soc. Pet. Eng. 49263. num & amino drilling fluid in drilling encountering massive coal. Soc. Pet. Eng.
Davis II, N., Tooman, C.E., 1989. New laboratory tests evaluate the effectiveness of gilson- 155897.
ite resin as a borehole stabilizer. Soc. Pet. Eng. 17203.
 J. Guancheng et al. / Applied Clay Science 127–128 (2016) 70–77 77

Yu, M., Chenevert, M.E., Sharma, M.M., 2003. Chemical–mechanical wellbore instability Zhang, S., Qiu, Z., Huang, W., Cao, J., Luo, X., 2013. Characterization of a novel aluminum-
model for shales: accounting for solute diffusion. J. Pet. Sci. Eng. 38, 131–143. based shale stabilizer. J. Pet. Sci. Eng. 103, 36–40.
Zakharova, L.Y., Syakaev, V.V., Voronin, M.A., Valeeva, F.V., Ibragimova, A.R., Ablakova, Y.R., Zhong, H., Qiu, Z., Huang, W., Cao, J., 2011. Shale inhibitive properties of polyether di-
Kazakova, E.K., Latypov, S.K., Konovalov, A.I., 2009. NMR and spectrophotometry amine in water-based drilling fluid. J. Pet. Sci. Eng. 78, 510–515.
study of the supramolecular catalytic system based on polyethyleneimine and am- Zhu, D., Li, X., Liao, X., Shi, B., 2015. Polyethyleneimine-grafted collagen fiber as a carrier
phiphilic sulfonatomethylated calix[4]resorcinarene. J. Phys. Chem. C 113, for cell immobilization. J. Ind. Microbiol. Biotechnol. 42, 189–196.
6182–6190.