SPE 157031

Application of Nanotechnology in Drilling Fluids

Katherine Price Hoelscher, Guido De Stefano, Meghan Riley, Steve Young, M-I SWACO

Copyright 2012, Society of Petroleum Engineers

This paper was prepared for presentation at the SPE International Oilfield Nanotechnology Conference held in Noordwijk, The Netherlands, 1214 June 2012.

This paper was selected for presentation by an SPE program committee following review of information contained in an abstract submitted by the author(s). Contents of the paper have not been
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Abstract
The potential to confidently apply water-based drilling fluids in unconventional shale formations has been studied using
engineered nanoparticles to minimize shale permeability through physically plugging the nanometer-sized pores. This paper
discusses the development of nanoparticle technology and testing protocols developed using Marcellus and Mancos as shale
candidates. In addition, new methods to better understand the plugging mechanism are currently under evaluation.
Nanoparticles in this study are specifically designed to physically plug the nanometer-sized shale pores, thereby reducing pressure
transmission in the shale. Silica nanoparticles are commericially available and can be engineered to meet all specifications needed
for the purpose. The particle size can vary between 5 and 100 nanometers (nm) and. The right sizes of nanoaprticles can be
selected and in combination with a correct fluid loss package can minimize the fluid rock interaction. Surface treatment on the
nanosilcia particle has been discovered to have a major influence on the final performance. It was revealed that appropariately
sized nanoparticles with surface treatments compatible with ions present in drilling and formation fluids is required for effective
plugging.
Marcellus and Mancos shales were used in the development phase due to their wide industry interest and geological similarity.
The authors examined an in-house method, still under development, using the Shale Membrane Test that is intended to provide
quantitative plugging and filter cake measurements using various shale samples.

Introduction
Nanotechnology has come to the forefront of research in the past decade with numerous applications in a variety of industries.
There are hundreds of nanotechnology based products available, most of which are in healthcare, defense and coating
industries. Their products are primarily based on materials composed of nanoparticles to enhance durability or repelling
properties, drug delivery and electronics. The oilfield provides ample opportunities for these materials to be applied.
An investigation into using nanoparticles as a drilling fluid additive to enhance wellbore stability has been successful. The
nanomaterial works by virtually shutting off water movement between the formation and wellbore. In shale formations with
nanodarcy (nd) permeability, such as the Marcellus, the usual drilling fluid method of relying on a filter cake to reduce fluid
loss (or leak off) cannot be used because a filtercake may not form due to the extrememly low permeability shale (Figure 1).
The solution for this problem is to engineer a nanoparticle which will be added to the drilling fluid to plug the pores of the
shale and shut off water loss. The particle design considerations and testing are described herein.

Figure 1: The thickness of a filter cake

is dependent on the fluid loss or leak off
into the formation. In low permeability
shale formations, virtually no filter cake
forms in the wellbore.
2 SPE 157031

Background
Activity in unconventional shale gas plays has dramatically increased due to advances in technology throughout the multiple
stages of drilling and production. Oil-based drilling fluids are used primarily due to their drilling performance and low
reactivity with the shale formation while maintaining wellbore stability, however environmental agencies, from EPA to local
authorities, are ensuring that the operators in the gas plays regulate their drilling operation by adhering to certain protocols and
activities. Synthetic-based mud could be targeted next. Our goal is to compete with oil-based systems using an innovative
water-based fluid. Unfortunately, current water-based systems have a lower rate of penetration (ROP) and can cause wellbore
instability due to interactions with the shale formations. Saturated salt systems can bring some advantages, but requirements
for the waste disposal increase the environmental footprint and cost of each well due to the conductivity of the solids. These
can be 2-4% of the total cost of the project, leading us to develop a straight forward, simple, cost-conscience design which
precludes the use of chloride based material and provide shale stability to low-reactive shales. Improvements in drilling
performance and reduction of salt use could significantly reduce waste expenses and increase the use of water-based fluids in
shale formations.
The hurdle to maintaining wellbore stability in shale formations is to control the water interaction with the rock. The water enters
the shale through pores, which vary in size from around 3 to 100 nanometers (Sensoy 2009) inducing fractures thereby reducing
the stability of the wellbore. By effectively plugging the exposed pores of the rock and not allowing water to enter wellbore
stability is retained. One conventional bridging theory is referred to as the one-third rule of filtration (Abrahms theory) where the
material used to plug a pore is required to be roughly one third to one seventh of the size of median pore opening. There are other
theories with varying size requirements for the plugging material, however, none are perfect. An ideal plugging material will also
accommodate the variability in pores within the formation.
The current approach to wellbore stabilization exploits chemical interactions with the shale formation. Synthetic or oil-based
fluids are a simple approach to remedy the invasion of water into the formation, but are costly or have environmental concerns.
When the current water-based fluids are used, a high salt content in the fluid reduces the amount of cation exchange between
the drilling fluid and formation. Amine chemistry is also used to maintain stability in chemically reactive formations, but this
is not the case for unconventional shale with low CEC values and low swellable clay content. A new approach to wellbore
stability was taken with nanoparticles that do not rely on these mechanisms.
To better understand wellbore stability in shales and their behavior in fluids, internal studies on wax preserved Marcellus shale
cores demonstrate how shales swell and fracture. Samples were submerged in freshwater or a sodium chloride solution (109
ppb) at 150F for twelve days. Images of the shale were taken prior to being submerged, six and twelve days after exposure to
the fluids. Figure 2 is of the shale core results for the freshwater exposure with fractures visible to the eye after six days. The
sodium chloride sample had a similar result. Upon further investigation of the fractures, it was found ther samples had
comparable fracture widths of 5-45 m. Intersecting fractures were common and the fractures were always parallel to the
bedding plane, as shown in Figure 2. Even with a high salt content in the fluid or with synthetic oil, the shale is subject to
form fractures, leading to a decrease in wellbore stability.

0 days 6 days 12 days

Figure 2: A preserved Marcellus shale core sample submerged in freshwater at 150F. The presence of fractures can be seen in
the sample over twelve days (top). Magnified portions of shale core samples submerged in freshwater (bottom left) and a NaCl
solution (109 ppb, bottom right). Both samples have fractures with similar widths. The scale bars are 500 m.
SPE 157031 3

An innovative material or approach is needed. Nanoparticles have the potential to bring about such a change that provides
wellbore stability in shale formations and improves our environmental footprint by not using toxic chemicals or chlorides in
the drilling fluid. Nanoparticles would be used to physically plug the shale pores instead of chemical inhibition to impede
water flow between the wellbore and formation, thus eliminating swelling of the shale and reducing the formation of fractures.
Many design considerations for the nanoparticles have been addressed with the nanoparticles of choice being composed of
silica. Their chemistry is well established and can be inert to avoid reactions with the drilling and formation fluids. The
nanoparticles have flexibility with the chemistry of their coating, which is necessary to avoid agglomeration and maintain
dispersion in these fluids. The size of the nanoparticle required can be obtained in order to meet the requirements of the shale
formation of interest once the pore throat size has been evaluated. They are commercially viable with a number of suppliers to
choose from. Our study has been designed to stabilize the Marcellus shale in the northeastern United States because of
increased industry interest in the area. The Marcellus shale is not as reactive as others, with a relatively low cation exchange
capacity (CEC) of 3 meq/100 g, but it is still prone to fracture and have wellbore stability issues, as seen in Figure 2. The
permeability of the Marcellus shale is at the nanodarcy level.

Nanoparticle Screening and Characterization

Numerous commercially available silica nanoparticles have been screened from a variety of suppliers. The first screening test
requires stability in various salt solutions that are present in drilling and formation fluids, as well as temperature stability. The
range of salts includes calcium, sodium and potassium cations, along with carbonates, hydroxides and chloride anions. Figure
4 shows how two candidates behaved when they were exposed to NaCl or NaOH solutions. Table 1 illustrates how samples
from the varying size and surface treatments from the same supplier behaved in these tests. If a comparison between the 20
nanometer samples with three different treatments is made, it is clear that the size is not the only parameter that is important
for effective plugging leading to low fluid loss. It is also noteworthy to compare samples with similar surface treatments with
different diameters as seen with treatment D. Finding the appropriate combination of diameter and surface treatment is key to
successful plugging.

Solid

Figure 3: Nanoparticle stability study. The left image is of silica nanoparticles unaffected by a sodium chloride solution.
The right sample solidified after exposure to sodium hydroxide.
.
Size Fluid Loss 25% 25% NaOH
Treatment KCl Na2CO3 K2CO3 NaCl KCO2H
(nm) 100 nm (mL) CaCl2 NaOH pH 11
5 A 50 ok ok ok ok ok ok ok ok
20 A 50 solid solid solid ok ok solid solid ok
5 B 50 ok ok ok ok ok ok ok ok
75 C 50 ok solid ok precipitate precipitate ok ok ok
20 C 50 ok solid ok precipitate precipitate ok ok ok
20 D 4 ok solid ok ok ok ok ok ok
75 D 23 ok solid ok ok ok ok ok ok

Table 1: Performance of silica nanoparticles with varying surface treatments and sizes when subjected to salt solutions. The
salts were selected because of their presence in drilling or formation fluids.

Successful candidates were then subjected to a modified API fluid loss test using a hydrophilic filter membrane with 100 nm
pores, the smallest commercially available. The volume of fluid loss at 100 psi was measured and the values are displayed is
in Figure 3. The samples were color coded by their diameter. The ten to thirty nanometer diameter nanoparticles had the
lowest amount of fluid loss overall. This behavior follows the one-third rule of filtration theory using the 100 nm membranes.
4 SPE 157031

Fluid Loss with 100 nm Filter Membrane

5 nm 10-30 nm 40-50 nm 70-100 nm
60
50 50 50 50 50 50 50 50
50
Fluid Loss (mL)

40

30 23
20 17
14 14 14 16 16
12 9
10 8
10 4 4 4 4
0
Sample
Figure 4: Modified API fluid loss using 100 nm filter membranes results for various nanoparticle samples. The samples are
grouped according to their diameter with the fluid loss volumes above each bar. The 10-30 nm particles yielded the lowest
overall fluid loss.

Samples of the desired size and surface treatment were analyzed with cryo-transmission electron microscopy (TEM) at Rice
University in Houston, Texas. The TEM has the ability to image single atomic layers and determine crystal structures by
using a beam of focused electrons instead of light to image the sample. It has the power to magnify much higher than a light or
the scanning electron microscope (SEM). The samples were vitrified, or instantaneously frozen, for analysis in a cryo-TEM.
The images give more insight as to the coatings on the silica nanoparticles and confirmation of their size (Figure 5). X-ray
photospectrometry (XPS) analysis of the nanoparticles resulted in finding primarily silicon and oxygen present, but no
significant signals for other elements. We could ascertain using XPS and cryo-TEM that there are no major contaminants,
particularly heavy metals in the samples.

Figure 5: Cryo-TEM images of two nanoparticle samples. Both have roughly the same diameter, but have different surface
treatments.

Test Results

Shale Permeability Apparatus

An in-house method to produce quantitative plugging and filter cake measurements is currently being developed and tested in
collaboration with the University of Texas in Austin. The apparatus is called the Shale Membrane Tester or SMT. The findings
of this study were used to better understand the plugging mechanism of shale pores without taking into consideration any
modifications of the rock itself. The design places a shale core in a cell with differential pressure applied above and below the
sample. Figure 6 is a diagram of the current design.
SPE 157031 5

As fluid flows across the top of the shale surface, the changes in pressures and temperature are monitored. The speed at which
the top and bottom pressures equilibrate by fluid moving through the shale can be calculated back to permeability with the
following equation:

where: k = shales permeability, t = test time, A = cross sectional area of shale sample, C = compressibility of the testing
solutions, L = thickness of shale sample, Po = initial pore pressure, Pm = top pressure, Pt = bottom pressure, = fluid viscosity
and V = bottom reservoir volume. The slower the change in the bottom pressure, the less permeable the shale sample. Core
samples with small fractures have a measured permeability in the millidarcy to darcy range. Tight shale samples with
nanometer sized pores yield permeabilities in the nanodarcies could be physically plugged with nanoparticles. The SMT has
the ability to detect and measure the changes in these extremely low permeabilities. A typical test to assess the ability of a
fluid to plug the pores of a shale sample is as follows:

1) The shale is slowly pressurized with brine above and below until the pressure change has stabilized.
2) The sample is then exposed to another fluid (brine or drilling fluid) and the pressure change monitored.
3) The drilling fluid containing the nanoparticles is then flowed over the sample and the pressure allowed to equilibrate.
4) A final brine solution is introduced to the sample to assess the plugging ability of the nanomaterial.

P
4
Out to Waste BP Flow Direction
R

Flow Direction
O-ring
Nitrogen
P P Cylinder
Injection 2 3
Pump
Recess for shale sample
Main Cell
with Shale

P Pressure
1 Gauge

Figure 6: Test equipment schematic for the Shale Membrane Tester (left) and closer view of the main cell with the shale
sample (right).

The pressures and temperatures are recorded throughout the experiment. Initial experiments were completed with sodium
chloride brine (aw 0.75) with a water activity equal to the water activity of the shale followed by neat aqueous nanoparticle
solutions. It was found that an active nanoparticle concentration of 10 wt% was needed to significantly reduce the shale
permeability. A drilling fluid with 10 wt% of the nano-additive was too high due to logistics and costs. Further optimization
was necessary.
Different sizes and coatings were analyzed and it was determined that the treatment is key to the success of their plugging
ability due to good dispersion in the solution. Large agglomerates formed in untreated silica samples and did not aid in
reducing the fluid loss, which agrees with the screening test we performed.
6 SPE 157031

Nanoparticle Performance
After further optimization, the critical nanoparticle concentration had been reduced to 3 wt% after utilizing the screening tests
mentioned above along with coupling the nanoparticle solution with a water-based drilling fluid formulation with no salt or
amine added. Figure 7 shows the dramatic difference in the permeability of the shale between the solutions. The starting
permeability of the shale sample was 0.153 nd for this shale sample. The water-based drilling fluid with the nanoparticles was
then flushed over the shale sample which reduced the permeability of the sample to 0.0042 nd, over a 98% reduction in the
permeability. Brine was then flushed back over the sample to assess how the nanoparticles plugging ability behaved after the
mud was not present. The permeability remained low (0.013 nd) even after 15 hours of exposure. The test has been repeated
on other shale samples with similar results. These findings confirm that the silica nanoparticles can physically plug shale at
low loading levels in a water-based drilling fluid while being environmentally friendly and and cost effective.

Figure 7: SMT results of the driving (top, black) pressure and the bottom pressure (red and blue) in the main cell. The shale
sample was first exposed to brine then the drilling fluid containing nanoparticles was added. There was a reduction in
permeability greater than 98%. The reduced permeability was maintained after the drilling fluid was removed and brine was
flowed over the sample after extended time.
Future Work and Conclusions

The silica nanoparticles can be further optimized and will be investigated in our upcoming work. The next round of
experiments will address testing fractured shale samples which will assess the ability of the drilling fluid and nanoparticles to
stop fluid movement in an already fractured formation. We are also exploring adding functional groups to the silica
nanoparticle coating to improve performance. The groups are expected to associate with the shale surface and anchor the
nanoparticles to the formation. The results may reduce the nanoparticle concentration required to shut off water movement in
the shale and thus reduce cost and increase efficacy.
Properly engineered nanoparticles have the ability to successfully drill shale formations using water-based drilling fluids with
confidence due to advances in nanotechnology research. We can move forward knowing that the environmental impact is
lower than our current systems, government regulations will be satisfied and the overall savings due to maintaining the
wellbore stability will be huge.

Acknowledgements

The authors would like to thank Professors M.E. Chenevert and M. M. Sharma and their group members from the University
of Texas for their work on the SMT apparatus.

References
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SPE 157031 7

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