ONGC SUMMER TRAINING REPORT

IOGPT, PANVEL, NAVI MUMBAI

NANO PARTICLE BASED STIMULATION

Prepared By:
Sumit Kumar
Dept. of Petroleum Engineering
DIT UNIVERSITY, Dehradun

1
 Acknowledgement:

I express my sincere gratitude to Mr. Tej Pal DGM (Production) for

providing me such a great opportunity of training at ONGC Ltd,
IOGPT, PANVEL. I am also grateful to Mr. Sajith S EE
(Production), for assigning me this Project.

It was a great learning experience at ONGC, Panvel. I am happy to carry

treasure of knowledge which will be useful for my future.

CERTIFICATION

2
It is hereby certified that Mr. Sumit Kumar of B.Tech. Petroleum
Engineering, DIT University, has successfully completed his training in
Production Department, IOGPT, Oil & Natural Gas Corporation Limited
Panvel, Navi Mumbai under my guidance during period from 13 st June
2017 to 7th July 2017 & 8th Aug 2017 to 18th Aug 2017. His conduct
during the training was satisfactory.

SAJITH S,
EE(P)
IOGPT, Panvel

Preface

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Theory of any subject is important but without its practical
knowledge it becomes useless,  particularly for technical
students. A technical student cannot become a perfect engineer
or technologist without practical understanding of their branch,
hence training provides a golden opportunity for all technical
students to interact with the working environment. The principal
necessity of in-plant training is to get details about unit operation and
unit process which are carried out in chemical industries and to
know more about the equipment’s used in these industries. The in-
plant training program is very advantageous for the technical
students who have a vivid idea about the industries. This training
helps to understand the basic concept of the industry.
During this period the students becomes aware of the problems
faced in the plant and are also aware of the industrial atmosphere
and also with the industrial people.

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 Table of Content

S.NO. CONTENT PAGE NO.

1. Brief overview 6
2. General introduction to nanoparticle 9
3 Definitions of nanoparticles and 10
nanomaterials by various organizations
4. Classification of nanoparticles 11
5. Characteristics of metallic nanoparticles 12
6. Applications of nanotechnology in oil 13
and gas industry
7. Nanotechnology and gas industry 13
8. Nanotechnology and oil industry 14

9. Nanotechnology and exploration 15

10. Possibilities of nanotechnology in the 16
petroleum industry
11. Well stimulation 17
12. Nanoparticle based stimulation 21
13. Viscoelastic surfactant with nanoparticle 22
14. Comparison with other polymer based 23
stimulation techniques
15. Experimental studies 24
16. Experimental studies 27
17. Effectiveness of nanoparticles mixed 28
VES stimulation
18. Conclusions 40
19. References 42

5
 Brief overview of ONGC

Oil and Natural Gas Corporation Limited (ONGC) was set up as a

commission on August 14, 1956. The company became a corporate on
June 23, 1993. It is a global energy holding company. The Company is
engaged in the exploration, development and production of crude oil and
natural gas. The Company's segments include Exploration & Production
(E&P), and Refining. The Company's geographical segments include
operations in two categories: In India, which includes Onshore and
Offshore, and Outside India. The Company's business spread include
various areas, such as oil field services, transportation of the oil and
natural gas, and production of value-added products, such as Liquefied
Petroleum Gas (LPG), Naphtha, Refining, Petrochemicals, Power,
unconventional and alternate sources of energy. The Company's
subsidiaries include ONGC Videsh Limited (OVL), Mangalore Refinery
and Petrochemicals Limited (MRPL) and ONGC Mangalore
Petrochemicals Limited. The Company's oil and gas reserves are located
internationally at Russia, Colombia, Vietnam, Brazil and Venezuela.

6
History:

During the pre-independence period (1947-1960), the Assam Oil

Company in the northeastern and Attock Oil Company in northwestern
part of the undivided India were the only oil companies producing oil in
the country, with minimal exploration input. The major part of Indian
sedimentary basins was deemed to be unfit for development of oil and
gas resources.

After independence, the national Government realized the importance oil

and gas for rapid industrial development and its strategic role in defense.
Consequently, while framing the Industrial Policy Statement of 1948,
the development of petroleum industry in the country was considered to
be of utmost necessity.
Until 1955, private oil companies mainly carried out exploration of
hydrocarbon resources of India. In Assam, the Assam Oil Company was
producing oil at Digboi (discovered in 1889) and the Oil India Ltd. (a
50% joint venture between Government of India and Burmah Oil
Company) was engaged in developing two newly discovered large fields
Naharkatiya and Moran in Assam. In West Bengal, the Indo-Stanvac
Petroleum project (a joint venture between Government of India and
Standard Vacuum Oil Company of USA) was engaged in exploration
work. The vast sedimentary tract in other parts of India and adjoining
offshore remained largely unexplored.
After 1960 ONGC has been instrumental in transforming the country's
limited upstream sector into a large viable playing field, with its
activities spread throughout India and significantly in overseas
territories. In the inland areas, ONGC not only found new resources in

7
Assam but also established new oil province in Cambay basin (Gujarat),
while adding new petroliferous areas in the Assam-Arakan Fold Belt and
East coast basins (both inland and offshore).
After 1990 the liberalized economic policy, adopted by the Government
of India in July 1991, sought to deregulate and de-license the core
sectors (including petroleum sector) with partial disinvestments of
government equity in Public Sector Undertakings and other measures.
As a consequence thereof, ONGC was re-organized as a limited
Company under the Company's Act, 1956 in February 1994.

After the conversion of business of the erstwhile Oil & Natural Gas
Commission to that of Oil & Natural Gas Corporation Limited in 1993,
the Government disinvested 2 per cent of its shares through competitive
bidding. Subsequently, ONGC expanded its equity by another 2 per cent
by offering shares to its employees.

VISION AND MISSION:

To be world class oil and Gas Company integrated in energy business
with dominant Indian leadership and global presence.

8
GENERAL INTRODUCTION TO NANOPARTICLES:
Nanotechnology is the science that deals with matter at the scale of 1
billionth of a meter (i.e., 1-9 m = 1 nm), and is also the study of
manipulating matter at the atomic and molecular scale. A nanoparticle is
the most fundamental component in the fabrication of a nanostructure,
and is far smaller than the world of everyday objects that are described
by Newton ’ s laws of motion, but bigger than an atom or a simple
molecule that are governed by quantum mechanics. The United States
instituted the National Nanotechnology Initiative (NNI) back in 2000,
which was soon followed (2001) by a plethora of projects in
nanotechnology in nearly most of the U.S.Departments and Agencies.
About 20 Research Centers were subsequently funded by the Nationa1
Science Foundation ( NSF ), an agency responsible solely to the
President of the United States and whose mandate is to fund the best of
fundamental science and technology projects. NSF was the lead U.S.
agency to carry forward the NNI. The word “nanotechnology” soon
caught the attention of various media (TV networks, the internet, etc.)
and the imagination and fascination of the community at large. In
general, the size of a nanoparticle spans the range between 1 and 100
nm. Metallic nanoparticles have different physical and chemical
properties from bulk metals (e.g., lower melting points, higher specific
surface areas, specific optical properties, mechanical strengths, and
specific magnetizations), properties that might prove attractive in
various industrial applications. However, how a nanoparticle is viewed
and is defined depends very much on the specific application. In this
regard, Table 1.1 summarizes the definition of nanoparticles and
nanomaterials by various organizations. Of particular importance, the
optical property is one of the fundamental attractions and a characteristic
of a nanoparticle. For example, a 20-nm gold nanoparticle has a
characteristic wine red color. A silver nanoparticle is yellowish gray.
Platinum and palladium nanoparticles are black. Not surprisingly, the
9
optical characteristics of nanoparticles have been used from time
immemorial in sculptures and paintings even before the 4th century AD.
Definitions of nanoparticles and nanomaterials by various
organizations:
International Organization for Standardization ( ISO ), American Society
of Testing and Materials ( ASTM ), National Institute of Occupational
Safety and Health ( NIOSH ), Scientific Committee on Consumer
Products ( SCCP ), British Standards Institution ( BSI ), and
Bundesanstalt für Arbeitsschutz und Arbeitsmedizin ( BAuA ).

Organization Nanoparticle Nanomaterial

1. ISO A particle spanning 1–100 nm –
(diameter)

2. ASTM An ultrafine particle whose –

length in 2 or 3 places is 1–100
nm
3. NIOSH A particle with diameter –
between 1 and 100 nm, or a
fiber spanning the range 1–100
nm.
4. SCCP At least one side is in the Material for which at
least one side or internal
nanoscale range.
structure is in the
nanoscale
5. BSI All the fields or diameters are in Material for which at
the nanoscale range. least one side or internal
structure is in the
nanoscale
6. BAuA All the fields or diameters are in Material consisting of a
the nanoscale range. nanostructure or a
nanosubstance

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CLASSIFICATION OF NANOPARTICLES:
Nanoparticles are broadly classified in to three classifications:
1. One dimension nanoparticles
One dimensional system (thin film or manufactured surfaces) has been
used for decades. Thin films (sizes 1–100 nm) or monolayer is now
common place in the field of solar cells offering, different technological
applications, such as chemical and biological sensors, information
storage systems, magneto-optic and optical device, fiber-optic systems.
2. Two dimension nanoparticles
Carbon nanotubes
3. Three dimension nanoparticles
Dendrimers, Quantum Dots, Fullerenes (Carbon 60),

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CHARACTERISTICS OF METALLIC NANOPARTICLES:
Nowadays there are various uses of nanoparticles in different industry
but as a petroleum engineer we talk here about metallic nanoparticles.
The various characteristics of different nanoparticles relative to bulk
metals are summarized below:
Optical function: The surface absorption plasmon of Au and Ag can
express various colors by changing the size of the particle, the form or
shape of the particle, and the rate of condensation. A new paint that has
the durability of an inorganic pigment and the vivid color of an organic
substrate can be made. Nanoparticles smaller than the wavelength of
light can be used to make high penetration conductivity materials (there
is little absorption, dispersion, and reflection).
Catalyst function: Reaction efficiencies can be enhanced since the
specific surface area of such nanoparticles is large compared with
existing particles; to the extent that the surface terrace is regular at the
atomic level, a hyperactive catalyst with high selectivity can be made:
for example, Au nanoparticles.
Thermal function: When the particle diameter is small (less than 10
nm), the melting point is also lower than a bulk metal. Electronic wiring
can be made with nanoparticles that have a low boiling point, for
example, a polymer.
Electrical function: Since superconductivity transition temperature
rises so that particle diameter is small (less than 1 nm), it can be used to
make high temperature superconductivity material.
Mechanical function: Since the mechanical characteristics improve,
mechanical strength can be sharply raised by mixing the nanoparticles
with metals or ceramics.

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Magnetic function: The attractive force of a magnetic metal increases
on reduction of the particle diameter, such that soft-magnetic materials
can be made in the form of an alloy of nanoparticles. Moreover, a
permanent magnet can be made if the nanoparticles are smaller than the
magnetic domain made to magnetize.

APPLICATIONS OF NANOTECHNOLOGY IN OIL AND GAS

INDUSTRY
Nanotechnology is poised to impact dramatically on all sectors of
industry. Nanotechnology could be used to enhance the possibilities of
developing conventional and stranded gas resources. Nanotechnology
can be used to improve the drilling process and oil and gas production
by making it easier to separate oil and gas in the reservoir.
Nanotechnology can make the industry considerably greener. There are
numerous areas in which nanotechnology can contribute to more-
efficient, less-expensive, and more-environmentally sound technologies
than those that are readily available.

NANOTECHNOLOGY AND GAS INDUSTRY:

Nanotechnology could be used to enhance the possibilities of developing
unconventional and stranded gas resources. Near-term challenges focus
on liquefied-natural-gas (LNG) infrastructure and efficiency, LNG
quality, and developing gas-to-liquids (GTL) technology. Midterm
challenges include developing super pipelines; constructing floating
GTL platforms; production, regasification, and storage issues; and
compressed-natural-gas transport. Long-term issues to be addressed are
production of methane hydrates and gas by wire—producing electricity
at the location of the gas source and carrying the electricity by wire to
market rather than the gas to market by pipeline. Nanotechnology can
address the problems associated with accessing stranded natural-gas
13
resources by developing nanocatalysts and nanoscale membranes for
GTL production and creating nanostructured materials for compressed-
natural-gas transport or long-distance electricity transmission.

NANOTECHNOLOGY AND OIL INDUSTRY:

The oil industry needs strong, stable materials in virtually all of its
processes. By building up such substances on a nanoscale, it could
produce equipment that is lighter, more resistant, and stronger. GP Nano
Technology Group Ltd. in Hong Kong was one of the first to develop
silicon carbide, a ceramic powder, in nano size. It yields exceptionally
hard materials. The company is now investigating other composites and
believes that nanocrystalline substances can contribute to harder, more
wear-resistant and more durable drilling equipment. Nanotubes have
many potential applications within the oil industry. For instance,
nanotubes could be used to create lighter, stronger, and more corrosion-
resistant structural materials in platforms for offshore drilling.
Nanotechnology could help improve oil and gas production by making it
easier to separate oil and gas in the reservoir—for instance, through
improved understanding of processes at the molecular level. There are
many other potential clean energy sources that could be enhanced
through the use of nanotechnology. The practical application of
nanotechnology in the oil sector is, fortunately, less frightening. It opens
interesting prospects for improved oil recovery, not least through better
understanding of processes at the interface between liquids and solids.
The aim is to understand how oil and water can be separated more
effectively. Nanotechnology could be applied to improved oil recovery
in the form of tailoring surfactants. These can then be added to the
reservoir in a more controlled way than with existing substances, thereby
releasing more oil. It could also help develop new metering techniques
with tiny sensors to provide improved information about the reservoir.

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NANOTECHNOLOGY AND EXPLORATION:
In high-temperature/high-pressure conditions, old electrical sensors and
other measuring tools often are not reliable. But researchers currently are
developing a set of reliable and economical sensors from optical fibers
for measuring temperature and pressure, oil-flow rate, and acoustic
waves in oil wells. These new sensors are small in size, work safely in
the presence of electromagnetic fields, are able to work in high
temperatures and pressures, and can be changed at a sensible cost
without interfering in the procedure of oil exploration. Changing and
displacing old sensors in oil wells is very costly. But this technology
could, with its accurate and reliable measurements, make a great
improvement in oil exploration. In the future, the industry may be using
nanoscale sensors for probing properties deep in the reservoir, allowing
us to unravel the complex nature of the rock/fluid interactions and their
effects on multiphase flow and providing the ability to design a suitable
exploitation plan for the asset. Another area of significant challenge lies
in the upgrading of bitumen and heavy crude oil. Because of their high
density and viscosity, it is difficult to handle and transport them to
locations where they could be converted into valuable products.
Significant resources and intense research activities have been devoted
to develop processes and specifically designed catalysts for on-site field
upgrading combined with hydrogen/methane production. These
processes would incorporate a minimized and controlled carbon
rejection, in conjunction with a catalytically enhanced hydrogen
generation performed on the rejected carbon from the upgrading process.
This central activity will be complemented with an effort to integrate the
research for ultradispersed catalytic formulas for the in-situ upgrading of
bitumen as well as for hydrogen generation from coal/coke or petroleum
pitch. The former requires research on specifically designed adsorbents
and catalysts to be introduced into the reservoir porous media in
nanosized form. The latter requires extensive research on both catalytic
active phases and process setup as well as adopting different catalytic
15
forms for effective contact with the gasifying materials. This research
has the potential to generate significant technology to convert bitumen
and heavy-oil reserves into products cost-effectively.

POSSIBILITIES OF NANOTECHNOLOGY IN THE

PETROLEUM INDUSTRY:
• Nanotechnology-enhanced materials that provide strength and
endurance to increase performance and reliability in drilling, tubular
goods, and rotating parts.
• Improved elastomers, critical to deep drilling and to improve drilling in
high-temperature/high-pressure environments.
• Designer properties to enhance hydro-phobic or hydrophilic behavior,
to enhance materials for waterflood applications.
• Nanoparticulate wetting carried out using molecular dynamics, which
shows promise in solvents for heterogeneous surfaces and porous solids.
• Lightweight, rugged materials that reduce weight requirements on
offshore platforms, and more-reliable and more-energy-efficient
transportation vessels.
• Nanosensors for improved temperature and pressure ratings in deep
wells and hostile environments.
• New imaging and computational techniques to allow better discovery,
sizing, and characterization of reservoirs.
• Nanosensors deployed in the pore space by means of “nanodust” to
provide data on reservoir characterization, fluid-flow monitoring, and
fluid-type recognition.
• Small drill-hole evaluation instruments to reduce drilling costs and to
provide greater environmental sensitivity because of less drill waste.

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WELL STIMULATION:
Well stimulation is a well intervention performed on an oil or gas well to
increase production by improving the flow of hydrocarbons from the
drainage area into the well bore.
In other words well stimulation is a well-treatment technologies for
increasing the rate of oil flow from the reservoir to the well. Well
stimulation is used for situations where the natural reservoir flow
characteristics are not favorable and need to be improved for effective
oil recovery.
There are mainly three commonly used well stimulation methods:
1. Hydraulic fracturing,
2. Acid fracturing, and
3. Matrix acidizing.

Fig: Well stimulation

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Hydraulic fracturing
The design of a hydraulic fracture is a function of reservoir flow and
mechanical characteristics. Reservoirs that have relatively better flow
characteristics (within the range of these characteristics where well
stimulation is needed) and are relatively weak mechanically tend to
require less intensive fracturing, which leads to a relatively smaller
volume of fracture fluid used. Reservoirs that have relatively poor flow
characteristics and are relatively strong mechanically tend to require
more intensive fracturing, which leads to a relatively larger volume of
fracture fluid used.

Fig: Hydraulic fracking

Acid fracturing:
Acid fracturing is commonly limited in application to carbonate
reservoirs, i.e., those rich in limestone and dolomite. This is significant
because California’s oil resources are primarily found in silica-rich rock
rather than carbonate rock.

18
 Fig: Acid fracturing

Matrix acidizing:
Matrix acidizing for silica-rich reservoirs typically has a very limited
penetration distance from the well into the reservoir. Therefore matrix
acidizing in silica-rich rock has a limited effect on larger-scale reservoir
flow characteristics, with the possible exception of reservoirs where
natural fracture flow paths are effective in which acidizing may open up
natural fractures by dissolving plugging material.

19
 Fig: Matrix acidizing

The term stimulation with respect to petroleum production refers to a

range of activities used to increase the production of oil from petroleum
reservoirs (a body of rock containing oil in pore spaces or natural
fractures) by increasing the permeability of the materials through which
oil flows to the well.
There are two distinct situations that lead to the use of stimulation
technologies:
1. Damage induced by well drilling and construction, and
2. Through oil production operations
Damage may occur in the form of blockage of perforations in the well
casing by scale formation (mineral precipitation) or sand production
from the reservoir into the well. Damage can also occur to the rock in
the immediate vicinity of the well as a result of mechanical disturbances
and chemical interaction with the fluids (drilling mud) used during the
drilling of the well bore. Mechanical damage in the form of crushing and
20
compaction of the rock may occur as a result of creating the perforations
through the casing, a process carried out by literally shooting a projectile
through the steel casing to punch holes to connect the well to the
reservoir. Techniques to correct these adverse impacts of well
construction by clearing blockages in the well, or restoring the
permeability of the rock, are termed well stimulation.
The term stimulation also refers to the use of techniques to enhance the
natural permeability of the undisturbed rock containing the reservoir to
the point that it can provide economic rates of oil production. In this
event, stimulation technologies may be applied that increase reservoir
permeability sufficiently to allow enhanced rates of oil production. This
stimulation is also on occasion termed well stimulation, but is perhaps
more precisely called reservoir stimulation.

NANO PARTICLE BASED STIMULATION:

Therefore we know the importance of stimulation in petroleum industry,
and we have many techniques to stimulate our well.
But still we need some special techniques to stimulate our well
effectively and efficiently. On the way of searching new techniques we
have many option but when we use nanoparticle in our stimulation
techniques to complete our stimulation then this techniques is known as
nanoparticle based stimulation.
For stimulating any well or reservoir we normally use acid stimulation
techniques.
ACID STIMULATION TECHNIQUES:
 Viscoelastic surfactant fluids/foamed acid
 Matrix acid job
 Closed fracture acid, etc.

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Viscoelastic surfactant fluids/foamed acid:
In the process of well stimulation we fracture many type of formation
with variety of fluids such as high concentration crosslinkers, linear gels,
and polyacrylamide, silkwaters, althouh these fluids are echonomical,
they can result in severe damage during the stimulation and do not offer
advantage of all inclusive system.
But the viscoelastic foamed have widespread application in oil and gas
fields. It is particularly beneficial in low pressure wells. The foamed acid
system is requires one acid resistant viscosifying agent and one foaming
agent. Viscoelastic surfactant (VES) is an excellent viscosifying agent in
aqueous fluids. Apart from the viscosifying property, VES is also good
foaming agent in aqueous solutions.
VES foamed acid has been customized by using a VES as foaming as
well as viscosifying agent. VFA increases the effective volume of acid
and reactive surface area by 2-3 times, which increase the overall acid
exposure in the reservoir.

VISCOELASTIC SURFACTANT WITH NANO PARTICLE:

The problem with VES fluids is that they are expensive and used for
fracture-packing temperatures upto about 200degree F. VES fluids do
not form a filter cake on the formation face because the viscosity of VES
fluids is based on the arrangement of low molecular weight surfactants
and not high molecular weight polymer like guar and hydroxypropyl
guar. Therefore they leak into the reservoir matrix. Because of poor
efficiency of VES fluids, the permeability of reservoir is generally less
than 400 md and more total fluid volume is required for a given
treatment. In addition, a larger amount of fluid leaks off into the
reservoir matrix, which needs to remove after treatment.
To overcome these drawbacks of VES, we can load VES micelles with
nanoparticles. Previous study shows that rheology of cationic wormlike
22
with liked charged nanoparticles. The formation of micelle-nanoparticles
junctions act as physical cross-links between micelles and these
junctions help to have significant viscosity and elasticity in dilute and
semidilute wormlike micelles. The rheological data of nanoparticle
pseudocrosslinked wormlike micelles in brine shows that the
addition of nanoparticles increased the surfactant micellar fluid’s
zero shear rate viscosity more than 100 times. The formation of
more thermally stable micelles will lead to 20 to 100% less use of
VES at higher temperatures.

COMPARISON WITH OTHER POLYMER BASED

STIMULATION TECHNIQUES:
Polymer based fluids have been used as completion and fracturing fluids
in oil industry for stimulate the oil and gas wells from decade. The
problem with these types of fluid is that they leave a polymer residue in
formation. This is a negative impact on fracture permeability and causes
of skin damage.
But when we use VES as it solve all these type of problem because of its
rheological properties. And the VES with additives of nano particle have
high thermal stability and viscosity in comparision to VES without nano
particle additives.
The main advantage of VES is its not create any type of formation
damage because it is compatible with a wide range of completion brines,
CaCl2, CaBr2, KCl, and NH4C and crude oils salt with a hydrophobic
part trigger rapid micellar growth because of their strong binding to the
micelles.

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Atomic force microscopy (AFM) images of the measured calcite surface: (a) before; (b) after
nano-modification

MATERIAL AND CHEMICAL REQUIRED:

Amidoamine oxide surfactant
MgO and ZnO(nanoparticles)
CaBr2 and CaCl2 brine solutions

EXPERIMENTAL WORKS:
Synthesis of zno nanoparticles using solid state reaction method:
 0.2M of Zinc acetate dihydrate in methanol was first ground for
by mortar pestle for 10 min and then mixed with 0.02M of
NaOH.
 After the above mixture was ground for 30 min, the product was
washed many times with deionized water.
 After that the product was again washed with methanol to
remove the by-products.
 The final product was then filtered using micron filter paper and
dried into solid powder at 80ºC for 15 min on hot plate.
 After that the powder was annealed at 400ºC for 30 min.
 Collect sample at different temperature and duration.
24
 Fig – filteration of precipitate

Fig-conversion of precipitate into solid powder via drying on hot

plate.

25
SYNTHESIS OF MGO NANOPARTICLES:
 All the starting chemicals used in the present work were of
analytical grade. 1M of MgCl2.6H2O solution was prepared in 100
ml of de-ionized water.
 Then NH4OH solution was poured to the above solution at 100°C
and the resulting mixture was constantly stirrered to at room
temperature (25°C) for 2 hrs by using magnetic stirrer.
 There after the solution is kept for ageing for 24 hrs.
 After the reaction, the resulting white precipitates were filtered and
washed with de-ionized water and then ethanol (Merck) for several
times to remove the by-products or impurities.
 The filtered cake was dried in air at 100°C for 4hr.
 The synthesized samples were calcined at different temperature
and for different time duration in air to obtain MgO nanoparticles.

Fig- dried in air at 100°C for 4hr.

EXPERIMENTAL STUDIES:

26
The viscosity and elasticity were measured by using amidoamine oxide
surfactant, and approximately 30 -nm MgO and ZnO nanoparticles in
CaBr2 and CaCl2 brine solutions in this study. A HP/HT viscometer was
used to generate the rheological data at different temperatures and 300 –
psi. Apparent fluid viscosity was measured by using 4 -vol% VES in
14.2 -ppg CaBr2 brine at 275°F and at 10 s -1. The 30 -nm MgO particles
were added to the VES fluid as a 6 -pptg (pound per 1000 gallon) slurry
in monopropylene glycol (MPG) at a ratio of 2.5 -ml MPG per 1 g of
particles. The MPG and nanoparticles were mixed together for 3 minutes
and then added to fluid to evenly disperse particles in fluid. This helped
with particle dispersion within the fluid rather than staying as clumps.
Then, 4 -mL VES was added to this fluid and mixed in the stirrer at least
30 min. Once the particles were added to the fluid, they were tested
within the hour. Testing error could have occurred if the samples were
more than 1 or 2 hours old since the particles could have interacted and
agglomerated once in the brine. The same procedure was applied to 4
-vol% VES in 14.2 -ppg CaBr2 brine with 6 -pptg 30 -nm ZnO
nanoparticles and without nanoparticles. Apparent viscosity was
measured by decreasing surfactant concentration to 2 -vol% VES.
Shear rate sweep (100 to 1 s-1) was performed for the 4 -vol% VES in
14.2 -ppg CaBr2 brine from 100 to 250°F with and without
nanoparticles. The sample was first heated to 100°F and waited to shear
at 100°F at 100 s-1 for 30 minutes, and then a shear rate sweep was run.
The same fluid was heated to 150°F and the same procedure was applied
until 250°F. To determine the effect of salinity, apparent fluid viscosity
was measured by using 4 -vol% VES in 13 -ppg CaBr2brine at 275°F
and at 10 s-1. The 13 -ppg CaBr2 brine solution was prepared by
diluting from 14.2 -ppg CaBr2. The same procedure was applied to 4
-vol% VES in 13 -ppg CaBr2 brine with and without nanoparticles. To
investigate the effect of type of salts on the viscosity of VES micelles,
apparent fluid viscosity was measured by using 4 -vol% VES in 11.6
-ppg CaCl2 brine at 180°F and at 10 s-1. The 10.8 -ppg CaCl2 brine was

27
prepared by diluting from 11.6 -ppg CaCl2 and the viscosity tests were
conducted at 200°F with and without nanoparticles.
Elasticity was measured in an HP/HT viscometer by using 4 vol% VES
in 14.2 ppg CaBr2 brines with and without MgO nanoparticles at 75 and
275°F. To break the VES micelles, a fish oil was used as an internal
breaker, and apparent fluid viscosity was measured by using 4 vol%
VES in 14.2 ppg CaBr2 brine at 275°F and 10 s-1.

EFFECTIVENESS OF NANOPARTICLES MIXED VES

STIMULATION:
Effect of Nanoparticles on the Rheological Properties of VES Fluids.
The rheology of the amidoamine oxide surfactant in CaBr2 and CaCl2
brine solutions with and without nanoparticles were investigated in this
study. The results from viscometer testing of the surfactant micellar
fluids with and without nanoparticles are shown in Fig. 1.a. VES
micelles are not stable at high temperatures and thermally turn into
spherical structures. The data indicates that the addition of nanoparticles
increased the viscosity and maintained, viscosity at high temperatures.
Viscoelasticity in the fluid arises from two separate mechanisms. The
first is the entanglement of micelles, and the second is the micelle-
particle junctions themselves, which effectively join two or more
micelles, creating additional viscoelasticity. Fig. 1.b indicates the
viscosities of VES fluids with and without nanoparticles at a temperature
of 275°F and shear rate of 10 s-1. With the addition of 6 pptg 30 nm
MgO nanoparticles, the VES fluid system can maintain its viscosity at
approximately 100 cp at 275°F. However, without nanoparticles, the
viscosity decreases. In addition, MgO nanoparticles in 2 vol% VES fluid
provide higher viscosity than ZnO nanoparticles in that fluid. Fig. 2
shows the comparison between 2 vol% VES micelles and 4 vol% VES
with and without nanoparticles at 275°F and a shear rate of 10 s-1. An
increase in the VES concentration leads to increase in the amount of

28
micelle-to-micelle overlap and the viscosity of the fluid. As the
concentration of the surfactant is increased, more surfactant will adsorb
on the surface of the particles and steric repulsive forces will increase in
the system. This may affect the behavior of the system in two ways:
reducing the size and strength of the aggregates and contributing to
partial stability in the system, which causes a decrease in the viscosity.
Fig. 3 indicates that these micro- and nanoparticles give nearly identical
results and help maintain the viscosity at 275°F. The nanometer MgO
particles would stay within the VES that flows into the subterranean
formation during a treatment. These MgO nanoparticles may be used to
stabilize the VES fluid instead of MgO microparticles for fluid-loss
control treatments. The results from viscometer testing of the surfactant
micellar fluids with and without nanoparticles at different shear rates
and temperatures are shown in Fig. 4-5. This fluid contains 14.2 ppg
CaBr2 brine and 4 vol% VES at temperatures from 100 to 250°F and the
shear rate from 100 to 1 s-1, with 6 pptg MgO or ZnO nanoparticles.
The low shear rate measurements were conducted after the fluids were
static for 30 minutes at 100, 150, 200, and 250°F respectively. The
addition of approximately 30 nm size particles to VES micellar fluids
has increased the viscosity of VES micelles. Low shear rate tests proved
about two-fold increase in fluid viscosity by the addition of
nanoparticles. The increase by the addition of MgO nanoparticles is
higher than that by the addition of ZnO nanoparticles. In Fig. 6, when
the concentration of CaBr2 is decreased from 14.2 ppg to 13 ppg, the
loading of nanoparticles to VES micelles maintains the viscosity at 200
cp, but without nanoparticles the viscosity is less than 100 cp at 275°F.
The decrease in the amount of salt causes a reduction in the curvature
energy of the surfactant molecules in the end caps. This results in a
decrease in micelle length, and the viscosity. The viscosities of 2 and 4
vol% VES in 10.8 ppg CaCl2 brine with and without nanoparticles at
200°F and a shear rate of 10 s-1 have been shown in Figs. 7 and 8. The
addition of approximately 30 nm MgO particles stabilizes the VES

29
micelles, and VES micelles without nanoparticles have a 200 cp
viscosity but the viscosity appears to decrease over time. For 4 vol%
VES micelles, the viscosity without nanoparticles is a bit higher than
that with either MgO or ZnO nanoparticles within 4 hours. These figures
show that MgO particle/surfactant interaction generates a stronger
network that causes increase in the viscosity more than ZnO
particle/surfactant interaction. According to the Hofmeister series, the
relative influence of ions on the physical behavior of colloidal systems
ranks as; Br- > Cl-. The larger anions increase the adsorption of
surfactants. Therefore, CaBr2 seems more effective to interact with VES
than CaCl2 brine solutions. Fig. 9 depicts the viscosity of 4 vol% VES
in 11.6 ppg CaCl2 brine with and without nanoparticles as a function of
time. The VES micelles have some stability with and without
nanoparticles. However, the addition of ZnO or MgO nanoparticles to
VES micelles may reduce viscosity to lower levels than VES micelles
without nanoparticles. Luo et al., (2012) have suggested that the
decrease in viscosity at high salt concentration may be because of the
formation of branched wormlike micelles. The crosslinks in the micelle
network can slide along the micelles and therefore serve as stress release
points. This branched micelle network will show lower viscosity than
that of the entangled linear micelles. The nanoparticles at these
conditions slightly promote the branching process. The viscosities of 4
vol% VES in 14.2 ppg CaCl2 brine with different particle concentration
at 275°F and a shear rate of 10 s-1 have been shown in Fig. 10. The
addition of nanoparticles should cause an increase in nonlinear viscosity
with increasing particle concentration, and a decrease in the viscosity
exponent in the overlap regime. However, the viscosity of VES micelles
at different concentrations gives approximately identical results except
VES micelles with 0.5 pptg MgO nanoparticles, so this is independent of
particle concentration. Elasticity measurements were conducted with
oscillatory testing in the HP/HT viscometer. The results from the
measurements are seen in Figs. 11-14. Storage and loss modulus of 4 vol

30
% VES in 14.2 ppg CaBr2 at 75°F are plotted as a function of time in
Fig. 11. The dominant factor is storage modulus at room temperature
and loss modulus is dominant at high temperature as seen in Fig. 12.
When the nanoparticles are added to the system at room temperature and
275°F, the loss modulus becomes the dominant factor, and the curve
shows a maximum and then a decrease as seen in Figs. 13-14. At a
critical frequency, the response of the dispersion changes from viscous
to elastic behavior. The moduli for the samples containing 4 vol% VES
are strongly frequency dependent. The storage modulus G` depicts the
energy storage in the structure of the VES fluid and is related to strength
of the flocculated network. The decrease in the value of the G` means
the weakening of the network structure resulted from the formation of
micelle-like spherical aggregates on the surface of the particles.
Therefore, viscous forces will dissipate most of the energy and the
amount of energy stored may be negligible. The dominance of loss
modulus indicated that the micelles were strongly networked. The
application of internal breaker at 275°F is shown in Figs. 15-16. The
fluid system used was 4 vol% VES in 14.2 ppg CaBr2 brine with MgO
nanoparticles and 1.5 gptg internal breaker. The fish oil was used as an
internal breaker. The breaker systems will turn wormlike VES micelles
into non-viscous, more spherical micelles by generating VES breaking
compounds over time. The apparent viscosity as a function of time data
shows that the viscosity reduces rapidly with higher breaker loadings.
When the internal breakers break the VES micelles that generate
pseudo-filter cake, the filter cake will collapse into broken VES fluid
with nanoparticles.

31
32
Fig. 1-the apperent viscosity of VES at concentrations of 4% (a) and
2% (b) shows that nanoparticles maintain the fluid viscosity over
time at 275o F.

Fig. 2- When the surfactant concentration increases from 2 to 4

vol% VES, the viscosity of the fluid increases.

33
Fig. 3—The addition of micro- or nanoparticles to VES fluid
maintains the viscosity at high temperatures and gives identical
results.

Fig. 4. When the temperature increases from 100 to 250°F and

shear rate changes from 100 to 1 s -1, the viscosity increases with the
addition of nanoparticles

34
Fig. 5—The comparison of VES fluid system with MgO and ZnO
nanoparticles at temperatures from 100 to 250°F and shear rates
from 100 to 1 s-1.

Fig. 6—When the salt concentration decreases, the VES micelles

have viscosity stability at high temperatures.

35
Fig. 7—MgO nanoparticles increase the viscosity more than ZnO
nanoparticles.

Fig. 8— The viscosity of VES micelles depends on the type of the salt
solutions and the concentration of surfactants.

36
Fig. 9—The addition of MgO nanoparticles stabilizes the viscosity of
VES micelles at 180°F.

Fig. 10- The addition of different concentrations (2-8 pptg) of MgO

nanoparticles gives identical results at 275°F.

37
Fig. 11— Storage modulus (G') is the dominant factor for the VES
fluid system without nanoparticles at room temperature.

Fig. 12- Loss modulus is the dominant factor for VES fluid system
without nanoparticles at 275°F.

38
Fig. 13- Loss modulus (G") is the dominant factor when the
nanoparticles are added to VES fluid system at room temperature.

Fig.14- Loss modulus is the dominant factor when the

nanoparticles are added to VES fluid system at 275°F.

39
Fig. 15—The breaking of VES micelles with 1.5 gptg internal
breaker at 275°F.

Fig. 16- The breaking of VES micelles with 3 gptg internal breaker
at 275°F.
40
Conclusions:
The results presented in this work indicate that a considerable
strengthening of micellar entanglements and an increase in viscosity of
VES fluid can be induced by adding of small amounts of nanoparticles,
as follows;
1) The addition of approximately 30-nm MgO or ZnO particles to VES
micellar fluids has increased the viscosity at moderate, low, and ultralow
fluid shear rates. Low shear rate tests proved about two-fold increase in
fluid viscosity by the addition of nanoparticles.
2) Micro- and nanoparticles have potential to improve viscosity of VES
fluids; similarly, but nanoparticles may be the better choice for fluid loss
control. The MgO nanoparticles would stay within the VES that flows
into the subterranean formation during a treatment. The viscosity of VES
micelles at different concentrations has approximately identical results
except VES micelles with 0.5 pptg MgO nanoparticles, so this is
independent of particle concentration.
3) When the salt concentration is decreased from 14.2 to 13 ppg, the
VES micelles with nanoparticles has some viscosity stability. The
increase in the amount of salt causes an increase in the curvature energy
of the surfactant molecules in the end caps, and the viscosity of VES
micelles. However, the addition of large amounts of salt causes the
decrease in the viscosity of VES micelles generated both by the
entanglement of the wormlike micelles and by the electrostatic forces
between micelles.
4) For VES micellar systems without nanoparticles, the dominant factor
is storage modulus at room temperature and loss modulus becomes
dominant at high temperature. When the nanoparticles are added to the
system at 275°F, the loss modulus becomes the dominant factor.
5) The apparent viscosity of 4 vol% VES in 14.2 ppg CaBr2 brine with

41
MgO nanoparticles reduces rapidly with the loading of 1.5 gptg internal
breaker. The breaker systems turn wormlike VES micelles into spherical
micelles.

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