AADE-11-NTCE-3

Flow Behavior of Nanoparticle Stabilized Drilling Fluids and Effect of High Temperature Aging
Sushant Agarwal1,2, Phuoc Tran1, Yee Soong1, Donald Martello1, Rakesh K. Gupta1,2
1

US DOE, National Energy Technology Laboratory, P.O. Box 10940, Pittsburgh, PA 15236; 2 Department of Chemical Engineering, West Virginia University, P.O. Box 6102, Morgantown, WV 26506
Copyright 2011, AADE
This paper was prepared for presentation at the 2011 AADE National Technical Conference and Exhibition held at the Hilton Houston North Hotel, Houston, Texas, April 12-14, 2011. This conference was
sponsored by the American Association of Drilling Engineers. The information presented in this paper does not reflect any position, claim or endorsement made or implied by the American Association of
Drilling Engineers, their officers or members. Questions concerning the content of this paper should be directed to the individual(s) listed as author(s) of this work.

Abstract
Nanoclay and nanosilica were used to stabilize invert
emulsion model drilling fluids for HTHP application. Though
each nanomaterial can stabilize the emulsion by itself, best
properties were obtained when both were used. Yield stress
and plastic viscosity were found to be dependent on
composition and the hydrophobic/hydrophilic nature of the
nanoparticles. Adding barite results in loss of yield stress,
however, it can be regained by increasing the nanosilica
content. Aging at 225oC (437oF) for 96 hrs showed that the
nanoparticle stabilized emulsions remain stable with only
small changes in rheological properties.
Introduction
Drilling fluids serve many purposes in a drilling operation;
these include the removal of cuttings, lubricating the drill bits,
maintaining the stability of the hole and preventing the inflowoutflow of fluids between borehole and the shale formation
[1]. Many different kinds of drilling fluids can be formulated
to serve the drilling needs which require careful balancing of
often contradictory requirements. Depending on the
characteristics of the base fluid, the drilling fluids are
classified as water-based (brines or muds), oil-based (oildispersions or invert-emulsions) or gaseous fluids (foams,
aerated muds or aphrons). Water-based fluids or muds (WBM)
are the most common. However, they are suitable only for
relatively low temperature and pressure drilling operations.
For high temperature and high pressure (HTHP) drilling
operations, the requirements for the drilling fluids are more
severe, and usually oil-based fluids or muds (OBM) are
employed. According to the US Department of Energy Deep
Trek program [2], a HTHP drilling operation is defined as one
where the bore hole static temperature (BHST) exceeds 177oC
(350oF) and the pressure is in excess of 25,000 psi. However,
as the depth of the drilling wells keeps increasing, more severe
drilling conditions can be expected which may exceed 315oC
(600oF) temperature and 40,000 psi pressure [3]. In such
extreme conditions, oil-based drilling fluids are preferred
because of their better stability [1, 4, 5]. However, at HTHP
conditions, drilling fluids are also likely to experience
gelation, degradation of weighting materials and the
breakdown of polymeric additives which act as viscosifiers,
surfactants and fluid-loss additives [6]. Note that the thermal

degradation of polymeric additives leads to loss in rheological

properties which can cause serious operational problems such
as barite sag. OBMs, in particular, are more susceptible to
barite sag [5] at HTHP conditions. Thus, developing OBMs
for HTHP operations which maintain their rheological
properties remains a desirable task.
In OBMs, the solid phase contains viscosifiers and weight
materials in addition to drill solids. Organophilic clays are
common viscosifiers, while barite is a common weighting
material; the former helps to control the viscosity while the
latter allows for adjustment of the density. At HTHP
conditions, however, the polymeric components of drilling
fluids are likely to experience thermal degradation [6] which
results in breakdown of the emulsion and fluid phase
separation. This can cause serious operational problems,
including the undesirable phenomenon of barite sag [5]. Thus,
developing OBMs which maintain their morphology and
rheological properties during HTHP operations is a desirable
task. This is the objective of the research described here, and it
requires the utilization of non-polymeric additives such as
nanoparticles.
Nanoparticles can be used to stabilize water-in-oil
emulsions in place of polymeric surfactants. Similar to
surfactants, nanoparticles and microparticles can also be
hydrophobic, hydrophilic or amphiphilic. They can exhibit a
large free energy of adsorption and attach themselves to the
oil-water interface, especially for particles of intermediate
wettability [7]. Also, relatively hydrophilic particles tend to
form oil-in-water emulsions, while the use of relatively
hydrophobic particles results in water-in-oil emulsions. The
degree of hydrophobicity or hydrophilicity can be determined
by making a measurement of ow, the contact angle that the
particle makes with the interface. In quantitative terms, G,
the energy required to remove a particle of radius R from an
oil-water interface of tension ow into oil is given by:

G = R 2 ow (1 + cos ow )

(1)
and this quantity takes on its maximum value when ow is 90.
Thus, for angles which have values slightly less than or
slightly greater than this value, colloidal particles are
essentially irreversibly adsorbed at the interface.
Since microparticles and nanoparticles of various shapes,
sizes and surface characteristics are commercially available,

Agarwal, Tran, Soong, Martello and Gupta

these can be employed for imparting stability to invert

emulsions used as drilling fluids. Indeed, hydrophobic
nanosilica [8-10] and organically-modified bentonite clay [11,
12] have both been used to stabilize water-in-oil emulsions. In
the present work, however, we examine the effect of using a
combination of hydrophobic nanosilica and organicallymodified nanoclay on the rheology of invert emulsions.
Materials
Poly 1-decene, an olefin oil, was used as continuous phase
for invert emulsions. It was purchased from Sigma-Aldrich
and had a viscosity of 0.8 poise, density of 833 kg/m3 and
boiling point of 316oC. The dispersed phase was deionized
water. Organically-modified nanoclays were obtained from
Southern Clay Products. These are montmorillonite based
clays which have been modified by various organic cations by
means of a cation exchange reaction to make them
hydrophobic for easy dispersion in non-polar media.
Depending on the nature of the organic treatment, these clays
can have varying degree of hydrophobicity. The nanoclays
used in this work, in increasing order of hydrophobicity, were:
Cloisite 30B, Cloisite 25A, Cloisite 20A and Cloisite 15A.
Hydrophobic nanosilica particles were Aerosil R104 (12
nm), Aerosil R106 (7 nm), Aerosil R974 (12nm) and Aerosil
R972 (16 nm) and they were provided by Evonik-Degussa.
According to manufacturer, Aerosil R104 and R106 are
treated with octamethylcyclotetrasiloxane, whereas R 974 and
972 are treated with dimethyl dichlorosilane to make the
particles hydrophobic. For purposes of comparison,
Witcomul 3158, an oil soluble sulfonate emulsifier for invert
emulsion drilling fluids, was obtained from Akzo-Nobel.
Excalibar brand API-grade Barite supplied by Van Horn, Metz
& Co., Inc. of Pittsburgh was used as the weighing agent. It
had a specific gravity of 4.2 and a median size of 15
micrometers.
Experimental Methods
Invert emulsions were prepared by emulsifying water in
nanoparticle containing oil. For this, a calculated amount of
nanoclay was first dispersed in 70 ml of oil and ultrasonicated
for 20 seconds using a high intensity 750 watt power
ultrasonic horn and then left overnight for dispersion to take
place. After this, the required amount of nanosilica was added,
and the mixture was ultrasonicated again for 20 seconds. The
dispersion was now allowed to rest for at least 24 hours. To
prepare the emulsion, 30 ml of deionized water was added
slowly to the oil dispersion while homogenizing at 24,000 rpm
for 2 minutes by high speed stirring with an IKA Ultra Turrax
rotor-stator mixer. Water must be added slowly rather than in
bulk as all the water may not emulsify, and a portion of it may
form a separate phase. Upon emulsification, a white gel-like
emulsion was obtained. This was left to rest for 24 hrs for
equilibration and to allow time for water to hydrate the
nanoclay before making any measurements. It should be noted
that the nanoparticle content reported here is on the basis of oil
content and not the total amount of emulsion. For surfactant
containing emulsions, the surfactant was added in place of
nanosilica particles to the nanoclay-oil dispersion and then

AADE-11-NTCE-3

water was emulsified as described above.

The morphology of the emulsion, i.e., the dispersed phase
size and size distribution was characterized with the use of an
optical microscope fitted with a digital camera. ScionImage
software was used to capture and analyze the images. A
standard grating was used to calibrate the images. As the
emulsions were quite concentrated to observe directly, they
were diluted with additional oil for the microscopy work. A
droplet of the diluted emulsion was placed on a slide and then
covered with a cover slip before observing in the microscope.
To make the weighted fluids of specific gravity 1.3 or 1.5,
required amounts of washed and dried barite were added to the
invert emulsions while stirring with the high speed
homogenizer for two minutes.
Rheology measurements were carried out to determine
yield stress and the plastic viscosity of these model drilling
fluids with the help of a Carri-Med CSL100 stress controlled
rheometer fitted with parallel plate fixtures. The diameter of
each plate was 4 cm, while the gap was set at 1 mm for all the
experiments. Before making measurements, all the samples
were pre-sheared for 1 hour at 850 s-1 to impart a common
shear history. This was followed by 10 minutes of rest. Then
stress ramp up and ramp down experiments were performed to
obtain flow curves from which the yield stress and plastic
viscosity could be calculated. All rheology measurements
were carried out at 25oC.
High temperature aging of the model drilling fluids was
carried out at 225oC using a 500 ml Fann aging cell. The cell
was pressurized to 500 psi by nitrogen gas to prevent the
evaporation of water contained in the drilling fluid. The
pressurized cell was placed in a pre-heated oven for static
aging for 96 hrs. The aged drilling fluids were depressurized
once the contents of the cell had cooled to room temperature.
The aged emulsion was degassed in a vacuum chamber before
being examined for rheology and morphology properties as
described earlier.
Results and Discussion
Drilling fluids should exhibit a gel structure with apparent
yield stress so as to prevent the settling of suspended solids,
such as hole-cuttings and barite particles, should the flow be
stopped for any reason. However, the gel structure should
disintegrate quickly once the flow is restarted. In other words,
a drilling should have a high viscosity at low shear rates to
keep solids in suspension but a low viscosity at high shear
rates in order that pumping costs not become excessive during
an actual drilling operation. Such behavior is obtained by
adding polymeric additives and clay particles that form a long
range three dimensional network that breaks down on
applying a shear stress but quickly re-builds on the cessation
of flow.
Several simple models are available (see, for example,
Gupta, 2000 [13]) to represent yield stress fluids which
include the Bingham plastic, Casson and Herschel-Bulkley
models. Although none of these models fits the experimental
data perfectly, the Casson equation was found to be the best
amongst the available equations for the drilling fluids

AADE-11-NTCE-3

Flow Behavior of Nanoparticle Stabilized Drilling Fluids and Effect of High Temperature Aging

described in this work. This is a two-constant equation that

gives the shear stress in terms of the shear rate & as:

( )

1/ 2

= ( 0 )

1/ 2

+ ( & )

1/ 2

(2)

in which 0 and are the Casson model yield stress and

plastic viscosity respectively.
Invert emulsions were prepared with nanoclay and
nanosilica as emulsion stabilizers. It was found that though
both nanoclay and nanosilica can stabilize the emulsions, the
nanosilica was more effective in this regards, and it had large
effect on the droplet size. In addition, it was found that the
most stable emulsion was obtained when both nanoclay and
nanosilica were used in combination. Figure 1 shows flow
curves for invert emulsions prepared with nanoclay and
nanosilica. It can be seen that the largest increase in the yield
stress and viscosity is obtained when both nanoclay and
nanosilica are used together. This kind of effect is also
observed in the morphology of the emulsions.

to the surfactant stabilized emulsion.

Table 1. Yield stress and plastic viscosity for nanostabilized and surfactant stabilized emulsions (30%v
water)
Composition

Yield stress
(dynes/cm2)

2wt% nanoclay
1%v R104 nanosilica
2wt% nanoclay + 1%v
nanosilica
2wt% nanoclay +
polymeric surfactant

3.6
27.6
54.2

Plastic
viscosity
(poise)
2.33
1.8
2.26

44.7

1.82

100000
2w t% nanoclay + 1%v
nanosilica R104 (12nm)

viscosity (Poise)

10000

1%v Aerosil R104

(a)

2w t% (0.84%v)
Cloisite20A nanoclay

1000

100

10

(b)

1
1

10

100

1000

10000

shear stress (dynes/cm )

Figure 1. Effect of nanoclay and nanosilica on flow

behavior of invert emulsions containing 30%v water.
Figure 2 shows the morphology of these emulsions which
reveals that large droplets are obtained for the emulsions that
only contain nanoclay, but the droplet size is much smaller for
emulsions containing hydrophobic nanosilica, and it is also
comparable to emulsion prepared with a polymeric surfactant.
Table 1 shows yield stress and plastic viscosity values for
these emulsions. It is clear that there is a synergistic effect of
nanoclay and nanosilica on the yield stress. It should also be
noted that the nano-stabilized fluid has comparable properties

(c)
Figure 2. Water droplet distribution in oil stabilized
with (a) 2wt% Cloisite 20A nanoclay, (b) 2wt% nanoclay
and 1%v Aerosil R104 nanosilica and (c) 2wt% nanoclay
and 0.77gm/100ml polymeric surfactant (10xdiluted, Scale
bar = 50 m).
Next we investigated the effect of the relative
hydrophobic/hydrophilic nature of the nanoclay on the
rheological properties of the invert emulsions. To see the

Agarwal, Tran, Soong, Martello and Gupta

effect of nanoclay hydrophobicity, invert emulsions containing

4%v nanoclay and 0.5%v nanosilica were prepared. The
nanosilica was Aerosil R104 in all emulsions and nanoclays
used were Cloisite 30B, 25A and 15A. These clays have been
organically modified in such a way that their ease of
dispersion in a non-polar medium is as follows 15A > 25A >
30B. Figure 3 shows flow curves for these fluids while the
corresponding flow parameters are given in Table 2.
Table 2. Effect of nanoclay type on yield stress and
plastic viscosity of emulsions (4%v nanoclay + 0.5%v
nanosilica)
Nanoclay type
Yield stress
Plastic viscosity
(dynes/cm2)
(poise)
Cloisite 30B
8.1
2.58
Cloisite 25A
12.1
3.05
Cloisite 15A
100.9
3.10

AADE-11-NTCE-3

Table 3. Effect of nanosilica type on yield stress and

plastic viscosity of emulsions (1%v nanosilica)
Nanosilica type
Yield stress
Plastic viscosity
(dynes/cm2)
(poise)
Aerosil R974 (12nm)
43.2
1.7
Aerosil R104 (12nm)
27.6
1.8
Both, Aerosil R104 and R974, have the same nanoparticle
size of 12 nm but R974 is less hydrophobic than R104 which
means that R974 has more number of hydroxyl sites on the
particle surface to form hydrogen bonds to build a long-range
gel structure. Therefore, R974 is more effective in developing
a yield stress.
100000

1%v Aerosil R974

Cloisite 30B

1000

Viscosity (poise)

Cloisite 25A

Cloisite 15A

100

viscosity (Poise)

10000

1%v Aerosil R104

1000

100

10

1
1

10

10

100

1000

10000
2

shear stress (dynes/cm )

Figure 4. Effect of nanosilica type on emulsion properties.

1
1

10

100

1000

10000

shear stress (dynes/cm )

Figure 3. Flow curves showing the effect of nanoclay type

on emulsion flow behavior.
Figure 3 and Table 2 show that the ease of dispersion of
nanoclay has a very significant effect on the yield stress and
the viscosity of these emulsions. This can be expected as the
better exfoliation of the nanoclays results in better dispersion
of nanoplatelets in the oil which helps in forming a gel
network. It also helps in stabilizing emulsion droplets as it is
easier for the nanoplatelets to approach the water-oil interface
than in the form of large aggregates.
To
investigate
the
effect
of
nanosilica
hydrophilic/hydrophobic characteristics, invert emulsions
stabilized by only 1%v nanosilica were prepared. Figure 4
shows flow curves for Aerosil R104 and R974, and Table 3
shows corresponding yield stress and plastic viscosity values.

Effect of Adding Barite

Barite is added to the drilling fluids to increase their
specific gravity so that the required amount of hydrostatic
pressure can be maintained in the drilling hole to prevent the
blow up. API grade barite was added to these nano-stabilized
emulsions to obtain fluids of specific gravity 1.3 and 1.5. The
unweighted emulsion contained 30%v water which was
stabilized by 2wt% Cloisite 20A nanoclay and 1%v Aerosil
R104. The specific gravity of this emulsion was 0.9. Figure 5
shows flow curves for barite containing drilling fluids, and
Table 4 gives yield stress and plastic viscosity values. It is
seen that when barite is added to the emulsion, its yield stress
decreases significantly while the plastic viscosity is remains
essentially the same. This could due to the fact that the gel
structure formed by nanoclay and nanosilica is disrupted by
large-sized microparticles of barite. To see if the gel structure
can be attained again, the nanosilica content was increased to
2%v. As can be seen from Figure 5 and Table 4, yield stress
increases as a result, indicating that the gel structure has

AADE-11-NTCE-3

Flow Behavior of Nanoparticle Stabilized Drilling Fluids and Effect of High Temperature Aging

formed again. Thus, even for weighted drilling fluids,

properties can be changed by adjusting nanoparticle
concentration.
Table 4. Yield stress and plastic viscosity for barite
containing emulsions (30%v water).
Plastic
Composition
Yield stress
(dynes/cm2) viscosity
(poise)
2wt% Nanoclay + 1%v nanosilica
54.1
2.3
2%v nanoslica
346.0
2.3
Barite 1.3 + 2wt% Nanoclay +
29.0
2.2
1%v nanosilica
Barite 1.5 + 2wt% Nanoclay +
44.0
2.1
1%v nanosilica
Barite 1.3 + 2wt% Nanoclay +
332.0
1.8
2%v nanosilica

decrease in yield stress value which indicates a loss of gel

structure. To see if any changes in the morphology also occur
due to aging, emulsions were characterized by microscopy.
Figure 7a and 7b show that on aging the water droplet size has
increased possibly due to coalescence. However, if the aged
drilling fluid is again homogenized by high speed stirring, an
emulsion with fine droplets is obtained again as seen in Figure
7c. This also results in an increase in yield stress values as
shown in Figure 6 and Table 5. It should be noted that when
emulsion stabilized by a polymer surfactant was aged, it
degraded severely with oil and water phases separating which
could not be emulsified again. Thus, we can conclude that
nanoparticles are quite effective in maintaining emulsion
stability when exposed to high temperatures.

100000

Fresh emulsion
aged at 225 deg C, 96 hrs

10000

Re-homogenized, aged at
225 degC, 96 hrs

unw eighted emulsion

viscosity (poise)

1000000
2%v nanosilica
Barite 1.3

100000
viscosity (poise)

Barite 1.5

10000

Barite 1.3+2w t%nanoclay+

2%v nanosilica

1000

100

1000

10
100

10

10
1

100

1000

10000
2

10

100

1000

10000

shear stress (dynes/cm )

shear stress (dynes/cm )

Figure 6. Flow curves for aged drilling fluids.

Figure 5. Effect of adding barite on the fluid properties.

Effect of Aging
The main objective of this work is to replace polymeric
surfactants with nanoparticles which are more stable at high
temperatures. Thus, to see if nanoparticles can maintain
effectiveness in preserving rheological properties of invert
emulsions, static aging of these model drilling fluid emulsions
was carried out using a Fann aging cell. Fresh emulsion (30%v
water, 2wt% Cloisite 20A and 1%v Aerosil R104) was loaded
in the aging cell and the cell was pressurized to 500 psi by N2
at room temperature. Then the cell was placed in the oven at
225oC (437oF) for 96 hrs. After which the cell was cooled
down and the aged drilling fluid was analyzed. Figure 6 shows
the rheology curve for aged drilling fluid compared with the
fresh drilling fluid and Table 5 shows yield stress and plastic
viscosity values. One can see that after aging there is a

Table 5. Flow properties of aged emulsions.

emulsions
Yield stress
Plastic viscosity
(dynes/cm2)
(poise)
Fresh emulsion
54.2
2.26
After aging,
20.4
2.49
225oC, 96 hrs
After aging and
41.8
2.64
homogenization

Agarwal, Tran, Soong, Martello and Gupta

(a)

AADE-11-NTCE-3

On aging at 225oC for 96 hrs, there is some loss in

yield stress but emulsion remains stable. Rehomogenizing the emulsion results in recovery of
yield stress.

Acknowledgments
This technical effort was performed in support of the
National Energy Technology Laboratorys on-going research
in Nanofluids for oil and gas deep hole drilling under the
URS activity number 4.640.920.002.
(b)

(c)

Figure 7. Effect of aging on water droplet distribution in

oil stabilized with 2wt% nanoclay and 1%v Aerosil R104
nanosilica (a) fresh, (b) aged at 225oC, 96 hrs and (c) aged and
re-homogenized. (5x dilution, Scale bar = 50 m)
Conclusions
Model oil-based invert emulsions were prepared using
nanosilica and nanoclays as emulsion stabilizers in place of
polymeric surfactants. Rheological properties were measured
to see the effect of nanoparticles, added barite and aging at
225oC for 96 hrs. The results showed the following:
Stable invert emulsions can be obtained by using
organically modified nanoclay and hydrophobic
nanosilica.
Best stability and flow properties are obtained when
both nanoclay and nanosilica are used together.
Nanoclay that disperses easily in oil phase shows
better gel formation capacity.
Relative hydrophilic and hydrophobic nature of
nanosilica also has significant effect on gel forming
behavior.
On adding barite, there is a decrease in yield stress
value, however it can be regained by increasing
nanosilica content.

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