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Graduate Studies The Vault: Electronic Theses and Dissertations

2013-09-16

Nanoparticle-based Drilling Fluids with Improved

Characteristics

Zakaria, Mohammad Ferdous

Zakaria, M. F. (2013). Nanoparticle-based Drilling Fluids with Improved Characteristics

(Unpublished doctoral thesis). University of Calgary, Calgary, AB. doi:10.11575/PRISM/27055
http://hdl.handle.net/11023/977
doctoral thesis

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 UNIVERSITY OF CALGARY

Nanoparticle-based Drilling Fluids with Improved Characteristics

by

Mohammad Ferdous Zakaria

A THESIS

SUBMITTED TO THE FACULTY OF GRADUATE STUDIES

IN PARTIAL FULFILMENT OF THE REQUIREMENTS FOR THE

DEGREE OF DOCTOR OF PHILOSOPHY

DEPARTMENT OF CHEMICAL AND PETROLEUM ENGINEERING

CALGARY, ALBERTA

SEPTEMBER, 2013

© Mohammad Ferdous Zakaria 2013

 Abstract

The success of well-drilling operations is heavily dependent on the drilling fluid. Drilling
fluids cool down and lubricate the drill bit, remove cuttings, prevent formation damage,
suspend cuttings and also cake off the permeable formation, thus retarding the passage
of fluid into the formation. During the drilling through induced and natural fractures, huge
drilling fluid losses lead to the higher operational expenses. That is why, it is vital to
design the drilling fluid, so that it may minimize the mud invasion in to formation and
prevent lost circulation. Typical micro or macro sized lost circulation materials (LCM)
show limited success, especially in formations dominated by micro and nano pores, due
to their relatively large sizes. The objective of this thesis was to investigate the
performance improvement by the usage of NPs (nanoparticles) as lost circulation
additives in the drilling fluid. In the current work, a new class of nanoparticles (NPs)
based lost circulation materials has been developed. Two different approaches of NPs
formation, and addition, to water based and invert-emulsion drilling fluid have been
tested. All NPs were prepared in-house either within the invert-emulsion drilling fluid; in-
situ, or within an aqueous phase; ex-situ, which was eventually blended with the drilling
fluid. The laboratory measurements included measuring mud weight, pH, lubricity
viscosity, gel strength, standard API LTLP filter test and high temperature and high
pressure (HTHP) test. In this work we evaluated fluid loss performance of a wide range
of NPs preferably selected from metal hydroxides, e.g. iron hydroxide, metal
carbonates, e.g. calcium carbonate and metal sulfate and sulfide e.g barium sulphate
and ferrous sulfide respectively.

The use of improved NP-based invert emulsion drilling fluid showed an excellent fluid
loss control, rheological properties together with a good lubricity profile. This thesis
reports an experimental and theoretical study on filtration properties of invert emulsion
drilling fluids under static conditions. Under API standard filtration test at LTLP and
HTHP, more than 70% reduction in fluid loss was achieved in the presence of 1-5 wt%
NPs.

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The results have also shown that the filter cake developed during the NP-based drilling
fluid filtration was thin (thickness less than 1 mm), which implies high potential for
reducing the differential pressure sticking problem, formation damage and torque and
drag problems while drilling. Moreover, at the level of NPs added, no impact on drilling
fluid apparent viscosity, and the fluid maintained its stability for more than 4 weeks.
Other NPs prepared by in-situ and ex-situ method also showed an excellent fluid loss
control. Results of the modeling showed that NP-based drilling fluid didn’t follow the
Darcy equation at the initiation of filtration and therefore the initial region was found flat
and nanoparticles reduced the premeability instantly. It was also shown that
nanoparticles transport in filtration was predominantly influenced by the Brownian
diffusion. Compare with the drilling fluid alone and drilling fluid with LCM, increasing
shear rate did not increase the same extent of shear stress in case of NP-base fluid
(both ex-situ and in-situ prepared), which can be attributed to the fact that smaller
particles were dispersed more effectively than the larger bulk particles and provided
bridging between clay particles due to their larger surface area. Tailor made NPs with
specific characteristics is thus expected to play a promising role in solving the
circulation loss and other technical challenges faced with commercial drilling fluid during
oil and gas drilling operation.

iii
 Acknowledgements

All kinds of praise and all thanks belong to ALLAH, the One, the Lord of the Universe,
the Creator, the Most Gracious and the Most Merciful.
I would like to express my deepest sense of appreciation, gratitude and
indebtedness to my respected supervisor Dr. Maen Husein and co-supervisor Dr. Geir
Hareland for the opportunity of being part of their research team. Thanks Prof. Husein
and Prof.Hareland, it has been a great honor for me to be associated with your team. I
greatly appreciate your continuous support, excellent supervision and encouragement
throughout this work. I would also like to thank my defense committee members Dr.
Roberto Aguilera, Dr. Brij Maini, Dr. Ronald J. Spencer and Dr. T. Nguyen for their time
and providing their constructive criticism of my work.
It is also a pleasure for me to express again my sincere appreciation and
profound regards to Dr. Maen Husein and Dr. Geir Hareland for providing the guidelines
to efficiently conduct all the laboratory experiments, constructive suggestions and
criticism throughout the period of research work. I am also thankful to Dr. Husein in the
final preparation of the manuscript. I am grateful to Ms.Patricia Teichrob for editing my
thesis and all kinds of support during my research works.
I would also like to extend my sincere thanks to the current and past members of
the Nanotechnology for Energy & Environment (NTEE) research team; Salman Al-
khaldi, Belal Abu Tarboush, Ahmad Al-As'ad, Alex Borisov, Nashaat Nassar, Zied Ouled
Ameur, Amr Abdelrazek Elgeuoshy Meghawry Abdrabo and everyone in the Real-Time
Drilling Engineering Research Group for their support, brilliant ideas and
encouragement.
I wish to thank all the staff of the Chemical Engineering department for their
valuable support. Special acknowledgement to Bernie Then and Ms.Paige Deitsch for
providing a convenient entourage to conduct the laboratory experiments.
I would like to thank team members of nFluids Inc; David Edmonds and Jeremy
Krol for their constructive criticism and support in our current research. And I also would
like to extend my appreciation to my colleagues at Ineos Oligomers and my family friend

iv
Dr.Soumaine Dehkissia for their unconditional support in various ways which have
inspired me this far.
This research was financially supported by a grant from the Natural Science and
Engineering Research Council of Canada (NSERC), Talisman Energy Inc and Pason
Systems. This support is gratefully acknowledged. Finally, my acknowledgments go to
Queen Elizabeth II Graduate (Doctoral) Scholarships for financial support.
And last but not the least, I profoundly acknowledge gratefulness to my beloved
parents and wife who have provided constant encouragement.

v
 Dedication

This works is dedicated to:

My lovely supportive parents, brothers and sisters

My beloved wife, Asma Sharmin

And my wonderful daughter Subah Maknun

With love and appreciation

vi
 Table of Contents

Abstract ................................................................................................................. ii
Acknowledgements .............................................................................................. iv
Dedication ............................................................................................................ vi
Table of Contents ................................................................................................ vii
List of Tables ......................................................................................................... x
List of Figures ...................................................................................................... xii
List of Symbols, Abbreviations and Nomenclature .............................................. xv

CHAPTER ONE: INTRODUCTION .......................................................................1

1.1 Problem statement and significance of the research ...................................1
1.2 Research Objectives....................................................................................4
1.3 Organization of the Thesis ...........................................................................7

CHAPTER TWO: LITERATURE REVIEW ............................................................9

2.1 Introduction ..................................................................................................9
2.2 Drilling fluid Classification ..........................................................................10
2.3 Functions of Drilling Fluids.........................................................................11
2.4 Drilling fluid related challenges ..................................................................12
2.5 Clay Chemistry used in drilling fluids .........................................................16
2.6 Nanoparticles.............................................................................................20
2.6.1 Nanoparticle synthesis.....................................................................24
2.7 Nanoparticle-based drilling fluids ...............................................................26
2.8 General characteristics of drilling fluid filtration ..........................................36
2.9 Filtration mechanism..................................................................................42

CHAPTER THREE: EXPERIMENTAL METHODS..............................................48

3.1 Drilling Fluid Samples ................................................................................48
3.2 NPs and NP-based drilling fluid formation .................................................49
3.2.1 Ex-situ preparation of NPs ...............................................................50
3.2.1.1 Fe(OH)3 NPs .........................................................................51
3.2.1.2 CaCO3 NPs ...........................................................................51
3.2.1.3 FeS NPs ................................................................................52
3.2.1.4 BaSO4 NPs ............................................................................52
3.2.2 In-situ preparation ............................................................................53
3.2.2.1 Fe(OH)3 NPs .........................................................................53
3.2.2.2 CaCO3 NPs ..........................................................................54
3.2.2.3 FeS NPs ................................................................................55
3.2.2.4 BaSO4 NPs ............................................................................56
3.3 Characterization methods and techniques.................................................56
3.3.1 Particle characterization ..................................................................56
3.3.2 Toxicity evaluation ...........................................................................57
3.3.4 Emulsified water droplet measurement............................................58
3.3.5 Drilling fluid characterization ............................................................58

vii
CHAPTER FOUR: RESULTS AND DISCUSSION ..............................................63
4.1 Fe(OH)3 Nanoparticles (NPs) Characterization .........................................63
4.1.1 X-ray diffraction analysis..................................................................64
4.1.2 Water droplet size distribution .........................................................66
4.1.3 Size distribution of ex-situ prepared Fe(OH)3 NPs ..........................67
4.1.4 Determination of particle size of in-situ prepared Fe(OH)3 NPs .......68
4.2 Drilling fluid Characterization .....................................................................70
4.2.1 Stability of NP-based Fluid ..............................................................70
4.2.2 LTLP Filtration .................................................................................71
4.2.2.1 Commercial NPs....................................................................72
4.2.2.2 In-house prepared Fe(OH)3 NPs ..........................................73
4.2.3 Filtrate Characterization...................................................................78
4.2.4 HTHP Filtration ................................................................................79
4.2.5 Effect of high shear on fluid loss control ..........................................83
4.2.6 Effect of presence of organophillic clays on fluid loss ......................85
4.2.7 Effect of Oil: Water ratio on fluid loss ...............................................86
4.2.8 Rheology behavior of NP-based fluid ..............................................87
4.2.9 Drilling fluid density and pH .............................................................93
4.2.10 Drilling fluid lubricity .......................................................................93
4.2.11 Preparation and performance evaluation of Fe(OH) 3 NPs in invert
emulsion drilling fluids provided by different suppliers .......................97
4.2.12 Performance of Fe(OH)3 NPs in water based mud (WBM) ..........100
4.2.13 Toxicity evaluation Fe(OH)3 samples ...........................................102
4.3 CaCO3 Nanoparticles (NPs) Characterization ........................................103
4.3.1 X-ray diffraction analysis................................................................103
4.3.2 Size distribution of ex-situ prepared CaCO3 ..................................104
4.3.3 Determination of particle size of in-situ prepared CaCO3 ..............106
4.3.4 LTLP Filtration of in-house prepared CaCO3 NPs ..........................112
4.3.5 HTHP Filtration of in-house prepared CaCO3 NPs ........................116
4.3.6 Drilling fluid density and pH ...........................................................117
4.3.7 Rheology behavior of NP-based fluid ............................................118
4.4 Invert emulsion drilling fluid API fluid loss characterization using other
NPs .........................................................................................................121
4.5 Summary of the API fluid loss study of different NPs in Invert emulsion..122

CHAPTER FIVE: MODELLING .........................................................................126

5.1 LTLP API filtration model using Darcy’s law ............................................126
5.2 NP based fluid transport using Stoke-Einstein equation ..........................140
5.3 Rheology model of NP-based fluid .........................................................145

CHAPTER SIX: CONCLUSIONS‎, CONTRIBUTIONS TO KNOWLEDGE‎AND

RECOMMENDATIONS .............................................................................149
6.1 Conclusions .............................................................................................149
6.2 Original contributions to knowledge .........................................................154
6.3 Recommendations for future research.....................................................154

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REFERENCES ..................................................................................................157

APPENDIX A: CLASSIFICATION OF LOST-CIRCULATION ZONES…………172

APPENDIX B: LOST CIRCULATION MATERIALS SIZE SELECTION
METHODS …………………………………………………………..173
APPENDIX C: DIFFUSION COEFFICIENT AND PECLET NUMBER…………174

ix
 List of Tables

Table 2.1: Comparative cost analysis study of NP-based drilling mud ................33
Table 3.1: Compositions of the invert emulsion and water based muds
employed in this work .........................................................................48
Table 4.1: API LTLP loss of drilling fluid in the presence and abscense
of 1 wt% commercial Fe2O3 NPs. NPs were thoroughly mixed with
the invert emulsion drilling fluid. No LCMs added to both samples ....73
Table 4.2: Comparative study of API LTLP fluid loss of drilling fluids with
1.6 wt% conventional Gilsonite LCM, and 1 wt% in-situ and ex-situ
prepared NPs ....................................................................................74
Table 4.3: API LTLP fluid loss comparing drilling fluid and drilling fluid with
Gilsonite LCM as base cases with drilling fluid samples containing
the in-house prepared Fe(OH)3 NPs only ..........................................78
Table 4.4: ICP results of the filtrate collected following API LTLP to determine
the Ca and Fe content .......................................................................79
Table 4.5: HTHP filtration property of different drilling fluid samples ..................81
Table 4.6: Effect of temperature and pressure on mud cake thickness ..............82
Table 4.7: HTHP Fluid loss of different drilling fluid samples using
engineered NPs only .........................................................................82
Table 4.8: Effect of shearing effect on LTLP fluid loss control ............................84
Table 4.9: Effect of organophillic clays on LTLP fluid loss control ......................85
Table 4.10:Effect of Oil: Water ratio on Fluid loss Control when using LCM .......87
Table 4.11:Effect of Oil: Water ratio on Fluid loss Control when using NPs ........87
Table 4.12:Density and pH measurements of drilling fluid samples with
LCM and Fe(OH)3 NPs ......................................................................93
Table 4.13:Co-efficient of friction (CoF) of drilling mud samples .........................94
Table 4.14:Coefficient of friction (CoF) and % torque reduction in the
presence and absence of NaCl salt in the invert emulsion
drilling fluid ........................................................................................96
Table 4.15:Effect of ex situ and in situ prepared Fe(OH) 3 NPs on the
performance of three different invert emulsion samples of drilling
fluids provided by three different suppliers. Concentration of NPs
1 wt%, composition of invert emulsion: (90:10) oil:water (v/v) ...........98
Table 4.16:API LTLP WBM fluid loss with and without NPs ..............................100
Table 4.17:Microtox bioassay of Fe(OH)3 NPs ..................................................102
Table 4.18:API LTLP fluid loss comparing invert emulsion drilling fluid
as base cases with invert emulsion drilling fluid samples
containing the in-house prepared CaCO3 NPs using
reaction-2 (R2) ................................................................................114
Table 4.19:API LTLP fluid loss comparing water based drilling fluid as
base cases with water based drilling fluid samples containing
the in-house prepared CaCO3 NPs by reaction-2 (R2) ....................114

x
Table 4.20:API LTLP fluid loss comparing invert emulsion drilling fluid as
base cases with invert emulsion drilling fluid samples containing
the in-house prepared CaCO3 NPs using reaction-5 (R5) ...............115
Table 4.21:HTHP fluid loss comparing invert emulsion drilling fluid as base
cases with invert emulsion drilling fluid samples containing the
in-house prepared CaCO3 NPs using reaction-2 (R2) .....................117
Table 4.22:HTHP fluid loss comparing invert emulsion drilling fluid as
base cases with invert emulsion drilling fluid samples containing
the in-house prepared CaCO3 NPs using reaction-5 (R5) ...............117
Table 4.23:Density and pH measurements of drilling fluid samples
with CaCO3 NPs ..............................................................................118
Table 4.24:Co-efficient of friction of invert emulsion drilling fluid samples.........121
Table 4.25:API LTLP Fluid loss using BaSO4 and FeS NPs based invert
emulsion ..........................................................................................122
Table 5.1: Permeability reduction of mud cake in the presence and
absence of NPs. (R2) and (R5) refer to the raction used to
prepare the CaCO3 NPs per Section 3.2 .........................................133
Table 5.2: Experimental and Bingham Plastic viscosity and Yield point ............148
Table B.1: Lost circulation materials selection methods ....................................173
Table C.1: Effect of particle sizes of DF (dp =2-200 μm in DF) on Peclet
number which is a control sample of Fe(OH) 3 NP-based fluid .........174
Table C.2: Effect of Fe(OH)3 NPs size in DF ranges from 0.001-0.3 μm
(1-300 nm) on Peclet number ..........................................................174
Table C.3:Effect of particle sizes of DF (dp =2-200 μm in DF) on Peclet
number which is a control sample of CaCO3 NP-based fluid ...........175
Table C.4:Effect of CaCO3 NPs size in DF ranges from 0.001-0.3 μm
(1-300 nm) on Peclet number ...........................................................175

xi
 List of Figures

Figure 1.1: Schematics showing a) fluid loss control using NPs along with
LCM, mechanism of pore throat blocking by b) plugging and
sealing, c) bridging and mud flow restriction by NPs only, and
d) fluid loss using conventional LCM ..................................................3
Figure 2.1: Drilling mud circulation down the drill pipe ......................................... 9
Figure 2.2: Drilled fines and fluid particles invasion into the formation ...............14
Figure 2.3: Drilling fluid loss into the formation ...................................................15
Figure 2.4: Basic units of clay minerals and the silica and alumina sheets ........ 16
Figure 2.5: Schematic representation of Montmorillonite clay (bentonite)
Structure ............................................................................................17
Figure 2.6: Schematic representation of the fixed and diffused double layer
near a clay surface ...........................................................................19
Figure 2.7: Particle size scale ............................................................................ 20
Figure 2.8: Pore throat sizes in rocks ................................................................. 21
Figure 2.9: Surface area to volume ratio of same volume of materials............... 21
Figure 2.10: Schematic representation of NPs in invert emulsion fluid ............... 25
Figure 2.11: A characteristic filtration plot of drilling fluid during drilling .............38
Figure 2.12: Three Types of Filtration Curves .................................................... 39
Figure 2.13: Bridging effects with varying particles diameter in pore throat ....... 42
Figure 2.14: Overview of Filtration mechanisms ................................................45
Figure 2.15: Effect of particle diameter on collision probability ........................... 46
Figure 2.16: NPs plugging probability during drilling ..........................................47
Figure 3.1: Schematic representation of the ex-situ method for NP-based
drilling fluid preparation ...................................................................50
Figure 3.2: Schematic representation of in-situ NP-based drilling fluid ..............53
Figure 3.3: Schematic of In-situ prepared CaCO3 NPs-based drilling fluid
using CO2 ........................................................................................55
Figure 3.4: Drilling fluid loss apparatus for a) LTLP and b) HTHP tests ............ 59
Figure 3.5: Fann Model 35A viscometer for measuring viscosity .......................60
Figure 3.6: OFITE drilling fluid lubricity tester .....................................................62
Figure 4.1: X-ray diffraction pattern for the ex-situ prepared iron-based NPs. ...64
Figure 4.2: X-ray diffraction pattern of ex-situ prepared Fe(OH)3 NPs
collected on the filter paper ..............................................................65
Figure 4.3: Particle size distribution histogram of water droplet obtained
from a water-in-oil emulsion by dispersing water into base-oil
with the aid of primary emulsifier ....................................................66
Figure 4.4 : TEM photographs and corresponding particle size distribution
histograms of ex-situ prepared Fe(OH)3 NPs in the range between
a) 1-120 nm and b) 1-30 nm ............................................................ 68
Figure 4.5: SEM Images at 48x magnification of mud cakes following API
LTLP filtration tests a) without NPs, b) with in-situ NPs (90/10
oil/water invert emulsion mud and 1 wt% Fe(OH)3 NPs) .................69
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Figure 4.6: Elements contained in mud cake a) without NPs, b) with Fe(OH)3
NPs as per EDX analysis .................................................................70
Figure 4.7: Photos comparing NP-based and original invert emulsion drilling
fluids (Invert emulsion (90 vol. oil/10 vol. water); 1 wt% Fe(OH)3
in-situ prepared NPs).......................................................................71
Figure 4.8: Mud cake of drilling fluid with commercial NPs and without NPs ... 73
Figure 4.9: Mud Cakes with thickness of a) DF only, b) DF+LCM,
c) DF +LCM with 1 wt % ex-situ NPs, and d) DF+LCM with
1 wt % in-situ NPs ...........................................................................77
Figure 4.10: Mud Cakes of a) DF only, b) DF+LCM, c) DF with 1wt % ex-situ
NPs and d) DF with 1wt % in-situ NPs ........................................... 78
Figure 4.11: Filter cakes obtained following API HTHP tests on invert emulsion
drilling fluids with and without Fe(OH)3 NPs and Gilsonite LCMs ...82
Figure 4.12: Mud cakes obtained following API HTHP tests on invert emulsion
drilling fluids with in-house prepared NPs only ............................... 83
Figure 4.13: Quality of unblended and blended mud cake ................................. 85
Figure 4.14: Rheological behavior of drilling fluid containing a) LCM together
with in-house prepared 1 wt% Fe(OH)3 NPs, b) 1 wt% Fe(OH)3
NPs no LCMs. ................................................................................89
Figure 4.15: Gel strength behavior of drilling fluid a) with LCM and NPs
together ex-situ and in- situ method b) in the absence of LCM,
with NPs only ex-situ and insitu method ........................................91
Figure 4.16: Shelf life of drilling fluid samples in terms of rheology behavior ......92
Figure 4.17: Aging effect of drilling fluid samples in terms of gel strength
Behavior ......................................................................................... 92
Figure 4.18: Apparent viscosity at 600 rpm of 3 invert emulsion drilling fluids
provided by different supplies in the presence and absence of
1 wt% Fe(OH)3 NPs. Composition of invert emulsion: (90:10) oil:
water (v/v)........................................................................................99
Figure 4.19: X-ray diffraction pattern of ex-situ prepared CaCO3 NPs starting
from the aqueous precursor salts ..................................................104
Figure 4.20 : TEM photographs of ex-situ CaCO3 NPs at two different
magnifications .............................................................................105
Figure 4.21 : Particle size distributions of ex-situ prepared CaCO3 NPs ...........105
Figure 4.22 : SEM images of mud cake a&b) without NPs ;c&d) in-situ
CaCO3 NPs (R2); and e&f) in-situ CaCO3 NPs (R5) ...................107
Figure 4.23 : Elements containing mud cake a) without NPs,b) with
In-situ NPs (R2) and c) with in-situ NPs (R5) from EDX data ......109
Figure 4.24 : Available pore openings (nm) in mud cake of DF without
NPs...............................................................................................110
Figure 4.25: Particle size distribution of in-situ CaCO3 NPs, prepared by
reactions (R2) and (R5), in the mud cake ....................................110

xiii
Figure 4.27: Rheological behavior of invert emulsion drilling in presence and
absence of 4 wt% in-house prepared CaCO3 NPs. No LCMs
added ...........................................................................................119
Figure 4.28: Gel strength behavior of invert emulsion drilling fluid in presence
and absence of 4 wt% in-house prepared CaCO3 NPs.
No LCMs added ...........................................................................119
Figure 4.29: LPLT fluid loss behavior of different ex-situ NPs in invert
emulsion drilling fluid .....................................................................123
Figure 4.30: LPLT fluid loss behavior of different in-situ NPs in invert
emulsion drilling fluid ....................................................................123
Figure 4.31: Different NPs and NPs-containing drilling fluid stability
Evaluation..................................................................................... 125
Figure 4.32: NPs-containing drilling fluid filter cakes (thickness <1 mm) ...........125
Figure 5.1: Filtrate volume variation with square root of time in the
presence and absence of in-situ and ex-situ prepared
Fe(OH)3 NPs .................................................................................131
Figure 5.2: Filtrate volume variation with square root of time in the presence
and absence of in-situ and ex-situ prepared CaCO3 NPs ............131
Figure 5.3: Mud cake permeability variation with time in the presence and
absence of in-situ and ex-situ prepared Fe(OH)3 NPs...................132
Figure 5.4: Mud cake permeability variation with time in the presence and
absence of in-situ and ex-situ prepared CaCO3 NPs.................... 133
Figure 5.5: Comparison of permeate (filtrate) flux with time in the presence
and absence of in-situ and ex-situ prepared Fe(OH)3 NPs........... 136
Figure 5.6: Comparison of permeate (filtrate) flux with time in the presence
and absence of in-situ and ex-situ prepared CaCO3 NPs..............136
Figure 5.7: Variation of Mud cake thickness with time for NP-based fluid .......140
Figure 5.8: Effect of particle sizes of DF (dp =2-200 μm in DF) on Peclet
Number..........................................................................................144
Figure 5.9: Effect of Fe(OH)3 and CaCO3 NPs size in DF ranges from
0.001-0.3 μm (1- 300 nm) on Peclet number .................................144
Figure 5.10: Bingham Plastic model for Fe(OH)3 NP-based drilling fluid ..........146
Figure 5.11: Bingham Plastic model for CaCO3 NP-based drilling fluid
(R5) and (R2) refer to the reaction used to prepare the particles
as detailed in section 3.2 ............................................................. 146

xiv
 List of Symbols, Abbreviations and Nomenclature

Symbol Definition

A
Definition cross sectional area of the filter cake under static filtration,cm2
Ar Hamaker constant which has values generally in order of Jouls
CNP Concentration of nanoparticles,molarity
DBM Brownian diffusion coefficient, cm2/sec
DNP diffusion co-efficient of nanoparticles,cm2/sec
Evdw Van der Waals potential energy, Jouls
J total flux, moles/cm2-s
JDiffusion diffusion flux of NPs, moles/cm2-s
Jadvection advection flux, moles/cm2-s
M Molarity, (mol/L)
N rotor speed (rpm)
Pe Peclet number
Qc volumes of the filter (cm3) cake at a given time, (cm3/min)
Qf volume of filtrate in (cm3) at a given time,(cm3/min)
R radius of the particle,cm
S filter effective surface area = 62.06 cm2
T absolute temperature,K
U characteristic velocity of flow,cm/sec
Vt sedimentation velocity of particles in dilute suspension,cm/sec
V volume of permeate or filtrate in mL
Yp yield point (lbf/100ft2)
ac collector radius or collector characteristics length,cm
ap particle radius,cm
dg diameters of the grains,cm
dp diameters of the particles,cm
dNP nanoparticles diameter,cm
h distance between the particles (nm)
hmc thickness of the mud cake at a given time, cm
k permeability in darcies
kB Boltzman constant= 1.38X10-23 J/K

xv
 r ratio between the volume of the filter cake at a given time to the volume of
t time in sec
the fluid filtrated in the filter press
∆P differential pressure in atmospheres ,(atm)
Shear stress,Pa
Yield stress,Pa
Shear rate ,sec-1
µ dynamic viscosity of the liquid,cP
density of the particles,g/cm3
density of liquid, g/cm3
collision probability
φ porosity of medium
μp plastic viscosity (cP)
 viscometer dial reading (o)
ϴ600 dial readings at 600 rpm
ϴ300 dial readings at 300 rpm
Abbreviation
AADE The American Association of Drilling Engineers
Abbreviation
AEUB ALBERTA ENERGY AND UTILITIES BOARD
API American Petroleum Institute
DF Drilling Fluids
EDX Energy dispersive X-ray
HTHP High Temperature and High Pressure
IF-WS2 Inorganic fullerene-like disulfide tungsten
LCMs Lost circulation materials
LC50 Lethal concentration used as an indicator of the toxicity of a compound
LTLP Low Temperature and Low Pressure
NPs Nanoparticles
OBM Oil based mud
SEM Scanning electron microscopy
TEM Transmission Electron microscopy
WBM Water based mud
XRD X-ray diffraction analysis
nm nanometer

xvi
 Chapter One: Introduction

1.1 Problem statement and significance of the research

The success of any well-drilling operation depends on many factors and one of the most
important is the drilling fluid. Drilling fluids, a.k.a. drilling mud, are circulated from the
surface into the drill string and subsequently introduced to the bottom of the borehole as
fluid spray out of drill bit nozzles and back to surface via the annulus between the drill
string and the well hole. Drilling fluids cool down and lubricate the drill bit, remove
cuttings from the hole, prevent formation damage, suspend cuttings and weighting
materials when circulation is stopped, and cake off the permeable formation by
retarding the passage of fluid into the formation (ASME, 2005). However drilling
operations face great technical challenges with drilling fluid loss being the most notable
of them. Drilling fluid loss is defined as the partial or complete loss of fluid during drilling.
Loss of fluid, in turn, impacts the cost of drilling. The cost of the drilling fluid system
often represents one of the single peak capital expenditure in drilling a new well and can
bump up swiftly when drilling deep holes, complex formations or in remote locations
(Abdo and Haneef, 2010). According to a recent in-house estimate, fluid losses during
drilling costs the industry around $800 million per year. Regardless of the real number
of the economic impact in this segment, it represents a very large portion of the total
non-productive expense for drilling a well and therefore fluid loss/circulation loss issues
have intensified than past. Provided that the overall economics prove to be favorable, a
more efficient route needs to be addressed during drilling by eliminating losses of fluid
or at least controlling them to the extent that drilling can continue uninterrupted (Fraser
et al., 2003). Therefore, drilling fluids are typically formulated with loss circulation
materials (LCMs). The primary function of LCM is to plug the zone of loss in the
formation, away from the borehole face so that subsequent operation will not suffer
additional fluids losses. LCM forms a barrier which limits the amount of drilling fluid
penetrating the formation and prevents loss (Chenevert and Sharma, 2009). Most of the
new lost circulation materials have been developed in the past 10 years (McLean et al.,

1
2010). However, using these existing lost circulation materials are not found so effective
to serve their primary goals of curing fluid loss. Current experience shows that it is often
impossible to reduce fluid loss successfully with these micro and macro type fluid loss
additives due to their physio-chemical and mechanical characteristics, e.g. size, surface
charge, solvation and mechanical resistance etc., thus raising the economic
consequences of non-productive drilling time (Chenevert and Sharma, 2009; Fraser et
al., 2003). For example, LCM with diameters in the range of 0.1-100 µm may play an
important role when the cause of fluid loss occurs in 0.1 µm-1 mm porous formation. In
practice, however, the size of pore opening in shales that may cause fluid loss varies in
the range of 10 nm-0.1 µm. Therefore, nanoparticles (NPs) as a loss circulation material
could fulfill the specific requirements by virtue of their size domain, hydrodynamic
properties and interaction potential with the formation (Amanullah et al., 2011; Srivatsa,
2010; Abdo and Haneef, 2010). Alternatively, NPs can help bridging empty gaps
between macro LCMs, and therefore, providing an effective seal to formation with larger
pore throat size. The plugging of pore throats by the use of nanoparticles is a new
approach for controlling fluid penetration into shales and could significantly reduce
wellbore instability problems (Sensoy,2009). Pore space is defined as a collection of
channels through which fluid can flow. The effective width of such a channel varies
along its length. Pore bodies are wide portions and pore openings or pore throats are
the relatively narrow portions that separate these pore bodies (Nimmo,2004).

NPs thus could be a promising option for the development of drilling fluids to provide the
effective sealing, filling and cementing properties resulting in the reduction of porosity,
permeability of the wellbore formations and thereby prevent the loss of fluid. This is not
viewed as formation damage, since these particles can be used during the drilling
operation far from reservoir formation. These particles are ultrafine in nature and
possess very high specific surface area of interactions. By adding small quantities of
NPs in drilling fluid ensuring mixing at the molecular level, wrapping and
interpenetrating network structures to achieve this new class fluid. By forming a thin, low
permeability filter cake which seals pores and other openings in the formations

2
penetrated by the drill bit as shown in Figure 1.1, NP-based drilling fluid could also
prevent unwanted influxes of formation fluids into the borehole from permeable rocks
penetrated during drilling. Kanj et al. (2009) suggested that small particles of high
concentrations might bridge across the pore throat. Again smaller particles aggregate
around larger ones to fill the tinier spaces and hence effectively plug the pore opening
spaces. In water-based drilling fluids, NPs of mixed metal hydroxides (MMH) have
already been used to replace polymers as viscosity modifying agents (Agarwal et al.,
2009). NPs of MMH work as a bridging material, which promotes aggregation between
the platelets of bentonite/montmorillonite clay to form a gel structure. Particle size and
surface characteristics of NPs can also be easily manipulated in water-in-oil emulsions
in a similar fashion to those formed in (w/o) microemulsions (Husein and Nassar,
2007a&b).

b)
a)
Mud flow

- --
c)
No/- Partial fluid loss using NPs

d) Legend
Mud flow

LCM
- - ----- ------ ------ ------
Nanoparticles

------- - Fluid

-
--- loss------
without using
------ NPs
------

------ ------ ------

Figure 1.1: Schematics showing a) fluid loss control using NPs along with LCM,
- -- -- -- sealing, c) bridging and mud
mechanism of pore throat blocking by b) plugging and
flow restriction by NPs only, and d) fluid loss using conventional LCM.
-

------- -

-
3

-
In light of the aforementioned functional properties of NPs, our approach consisted of
developing tailor made NP-based drilling fluid which would best interact with the rest of
the drilling fluid components as well as the formation and reduce fluid loss during
drilling, meanwhile optimize the functionality of the drilling fluid over a wide range of
conditions; including temperature, pressure, drilling environment and formation.
Moreover, the proposed NP-based fluid would reduce the total solids and/or chemical
additives to the typical drilling fluid leading to an overall lower fluid cost (Amanullah et
al., 2011; Abdo and Haneef, 2010; Mokhatab et al., 2006).

1.2 Research Objectives

This research investigates the role of in-house prepared dispersed NPs in reducing
drilling fluid loss and the impact their existence might have on drilling fluid
characteristics; including viscosity, density, pH and lubricity. The hypothesis is that
dispersed NPs in drilling fluids are better able to conceal pores as a result of a fine
balance between particle dispersion and deposition onto micro and nanopores. As
shown in Figure1.1, the NPs will selectively deposit over fine pores or will conceal gaps
between already deposited clay particles. Such research will be the key to unlocking the
problems of inter channel pore clogging of formation (keeps away the migration of
drilled fines entering the pores), reduce fluid loss and improve the productivity of the
wells. In order to meet the challenge of improving the properties of drilling fluid, this
research has been undertaken with several parallel developments of NPs. These well-
dispersed NPs employed in fluid formulation are unique and have high surface energy,
which can readily attach with other additives and create a barrier to lower the fluid loss
in an efficient manner. All this needs to be achieved without introducing fundamental
property change in the drilling fluid. The overall goals of this research are therefore, to
develop a method for in-house preparation of NPs, which can be easily mixed and
stabilized in water as well as invert emulsion based drilling fluids, and to evaluate the
performance of the final product. Low aromatic hydrotreated oil was selected, since
such a base oil makes the invert emulsion fluid more environmentally friendly.
Accordingly, the objectives of this research are summarized as follows:

4
1) In-house synthesis and characterization of NPs and the preparation of stable NP-
based drilling fluids.
2) Study the impact of the presence of the NPs on drilling fluid loss using API low-
temperature-low-pressure (LTLP) test as well as the high-temperature-high-pressure
(HTHP) test. Both oil-based and water-based drilling fluids were tested.
3) Detail the effect of NPs on drilling fluid properties; including viscosity, density, pH
and lubricity.
4) Investigate how the behavior of NPs in the drilling fluid is affected by other
components of the drilling mud.
5) Investigate the possibility of eliminating other loss circulation material (LCM)
additives as a result of NPs addition, which may lead to an overall drilling fluid price
reduction.

The project has been divided into four main phases:

Phase one: In-house, in-situ and ex-situ, preparation of the dispersed Fe(OH)3(s) NPs
in the drilling fluid and their characterization:

1. NPs of Fe(OH)3(s) were successfully prepared in-house. Two schemes were

used. Ex-situ scheme, where the NPs were prepared by aqueous reactions of the
precursor salts and the product NPs mixed with the drilling fluid. In-situ scheme,
where the aqueous precursors were directly added to the drilling fluids, and the
NPs nucleated within the drilling fluid.
2. Characterization of the ex-situ prepared particles, which included particle
identification using X-ray diffraction (XRD), and determination of particle size
distribution using transmission electron microscopy (TEM).
3. Characterization of the in-situ prepared particles followed their collection on the
filter cake; including particle identification using energy-dispersive X-ray
spectroscopy (EDX), and determination of particle size distribution using
scanning electron microscope (SEM).

5
 4. Study the fluid loss of NP-based drilling fluid following API low temperature and
low pressure (LTLP) and high temperature and high pressure (HTHP) filter press
protocols. Also, determining the thickness of the resultant filter cake, since thin
filter cake prevents stuck pipe during drilling.
5. Characterize the NP-based drilling fluid in terms of its viscosity, density, pH and
lubricity.

Phase two: In-house, in-situ and ex-situ, preparation of CaCO3(s) NPs in the drilling
fluid and their characterization:

1. NPs of CaCO3(s) were prepared in drilling fluid. Three schemes were used in this
case. Ex-situ scheme, where the NPs were prepared by aqueous reactions of the
precursor salts and the product NPs mixed with the drilling fluid. Two schemes of
in-situ preparation of the CaCO3(s) NPs were adopted. In one scheme the
aqueous precursor salts were directly added to the drilling fluid, and the NPs
nucleated in the drilling fluid, while in the other scheme an aqueous calcium salt
was added to the drilling fluid followed by CO 2(g) bubbling. This scheme of in-situ
preparation of the CaCO3(s) particles helps creating the particles in the drilling
fluid while in the formation, and therefore, prevents any changes to the nature of
particles during drilling.
2. Characterization of the ex-situ prepared particles included particle identification
using X-ray diffraction (XRD), and particle size determination using transmission
electron microscopy (TEM).
3. Characterization of the in-situ prepared particles followed after their collection on
the filter cake; including particle identification using energy-dispersive X-ray
spectroscopy (EDX), and determination of particle size distribution using
scanning electron microscope (SEM).
4. Study the fluid loss of NP-based drilling fluid following API low pressure and low
temperature (LTLP) and high pressure and high temperature (HTHP) filter press
protocols. Also, determining the thickness of the resultant filter cake, since thin
filter cake prevents stuck pipe during drilling.

6
 5. Characterize the NP-based drilling fluid in terms of its viscosity, density, pH and
lubricity.

Phase three: In-house, in-situ and ex-situ, preparation of BaSO4(s) and FeS(s) NPs in
the drilling fluid by two methods and characterize their LTLP fluid loss property only.

1. NPs of BaSO4(s) and FeS(s) were successfully prepared in-house. Two schemes
were used. Ex-situ scheme, where the NPs were prepared by aqueous reactions
of the precursor salts and the product NPs mixed with the drilling fluid. In-situ
scheme, where the aqueous precursors were directly added to the drilling fluids,
and the NPs nucleated within the drilling fluid.
2. Study only the fluid loss of NP-based drilling fluid following API low pressure and
low temperature (LTLP) protocol.

Phase four: This phase involves developing a mathematical model to describe fluid
loss and cake growth using NPs as a lost circulation material.

1.3 Organization of the Thesis

This thesis is organized into six chapters. The first chapter presents a brief scope of the
research and its significance. General overview of lost circulation material used in
drilling fluid and challenges faced while drilling is introduced. Introduction of NPs as new
lost circulation materials and its potential application in fluid loss reduction are
explained.

Chapter two presents an extensive literature review on drilling fluids, nanoparticles

(NPs), NP-based drilling fluid, filtration mechanism and governing equation used in
filtration process.

In Chapter three, experimental methods used for in-house NPs preparation (ex-situ and
in-situ) is explained together with methods used to characterize the NPs and the NP-
based drilling fluids.

7
Results obtained from the experimental works are discussed and analyzed in detail in
Chapter four. NP-based fluids are compared with the base fluid in terms of fluid loss at
LTLP and HTHP conditions, density, viscosity and lubricity. TEM and XRD analyses
reveal the ex-situ prepared NPs characterization, whereas SEM images of mud cake
unveiled the characteristics of in-situ prepared NPs.

Chapter five deals with modeling of NP-based fluid filtration performance through
porous media (API filter paper) at LTLP condition. The cake thickness growth model at
30-min time period are proposed. Also Bingham plastic model are used to describe the
rheological behavior of NP based fluid.

Chapter six presents the conclusion drawn from the work, original contributions to
knowledge and recommendation for future research to extend this study.

8
 Chapter Two: Literature Review

This chapter reviews the drilling fluid general functions and their related challenges, clay
chemistry, nanoparticles properties and previous experimental studies of drilling fluid
properties using lost circulation materials and nanoparticles with particular reference to
those which are directly relevant to the subject under investigation.

2.1 Introduction

Drilling fluids are composed of a number of liquids and gaseous fluids and mixtures of
fluids and solids (Vasii,2008). A drilling fluid is typically used in a drilling operation in
which that fluid is circulated or pumped from the surface, down the drill string and is
subsequently introduced to the bottom of the bore hole as it squirts out of nozzles on
the drill bit and back to the surface via the annulus as shown in Figure 2.1.

Figure 2.1: Drilling mud circulation down the drill pipe (courtesy of Payson Petroleum,
reprinted by permission).

9
Large pumps are used to circulate the mud on a drilling rig. They pick up the mud from
the mud tank and force it into and down the drill string and to the bit. Typical pressure at
the exit of these pumps can be as high as 7,500 psi (52,000 kPa) (Dyke and
Baker,1998). At the bit the mud jet out of the bit nozzles to move cuttings away from the
bit. The mud then moves back up the hole to the surface. The mud picks up cutting
made by the bit and carries them as it returns to the surface. The mud and cuttings
return to the surface in the annulus between the outside of the drill string and the inside
hole. At the surface, the mud and cuttings leave the well through a side outlet with a
pipe called the mud return line. At the end of the flow line, mud and cuttings fall on to a
vibrating screen (or sieve) named as shale shakers which is the device on the rig for
removing drilled solids from the mud. A wire-cloth screen vibrates while the drilling fluid
flows on top of it. The liquid phase of the mud and solids smaller than the 200 wire
mesh (< 74 μm) pass through the screen and go back to the pits while larger solids are
retained on the screen and eventually discarded (ASME, 2005; AADE,1999;
Chilingarian and Vorabutr, 1983).

2.2 Drilling fluid Classification

Drilling fluids are typically classified according to their base material into water-based
muds and oil-based muds. In water-based muds (WBM), water is the continuous phase
and solid particles are suspended in water or brine. Oil-based muds (OBM) are exactly
the opposite. Oil is the continuous phase and solid particles are suspended in oil, water
or brine is emulsified in the oil by surfactants (ASME, 2005; Srivatsa, 2010). Oil based
drilling fluids have definite advantages when compared to water based fluids. These
include maintaining stable rheology and filtration control for extended periods of time
and increased lubricity. In addition, oil base drilling fluids can be used to drill through
most troublesome shale formations due to their inherent inhibitive nature and
temperature stability (Mas et al.,1999). The filtrate from a water based mud may cause
clays in the formation to swell and disperse, which can cause severe damage to well
productivity. Many instances are on record where a formation of proved productivity has
been exposed to water or water based mud and consequently production was greatly

10
decreased or in some cases completely lost (Sharma and Jiao, 1992; Tovar et al., 1994;
Argiller et al., 1999). A study has shown that drilling fluid loss costs the oil and gas
industry over $800 million per year (Fraser et al., 2003). An attempt has therefore been
made to develop an invert emulsion drilling fluid (water-in-oil) which would mitigate the
problem. Oil alone does not have the ability to form a filter cake on the wall of the bore
hole but mud additives are used to restrict the loss of fluid into permeable formations.
The filter cake or sheath is water impermeable and substantially oil impermeable so that
virtually none of the fluid base oil or the water in the fluid is lost into the formation. Even
though the filtrate is small amount of oil, fluid which may penetrate the filter cake does
not substantially affect formation permeability (Baker 1995; 2006). Therefore this oil
based system has been directed towards modification by obtaining satisfactory
suspending particles and forming thin filter cake characteristics. These have resulted in
the development of the emulsification of water or water based mud in the oil. The use of
invert emulsion oil mud has greatly increased over the past few years due to the
demands of drilling deeper and more difficult wells.

2.3 Functions of Drilling Fluids

A properly designed and maintained drilling fluid system performs the essential
functions. A drilling fluid is used to carry out the following functions (ASME, 2005;
Chilingarian and Vorabutr, 1983):

a. Removal of Cuttings. Drilled cuttings are removed that results in a cleaner hole.
The ability of a mud to carry cuttings to the surface depends partly on the
characteristics of the mud and partly on the circulating rate in the annulus. When
the pump capacity is too low to provide adequate annular velocity for cuttings
removal, increasing the mud viscosity particularly the yield point may result in a
cleaner hole.
b. Suspension of Cuttings. Good drilling fluids have thixotropic properties that
caused the solids particles, being carried to the surface, to be held in suspension
when circulation is stopped.

11
 c. Control Formation Pressure. It is a very important function of drilling fluid
because it is the first line of defense against possible blowouts.
d. Caking off Permeable Formations. A good drilling fluid provides filtration
properties that retard the passage of fluid into the formation. In many cases it
may be necessary to add fluid loss control additives to reduce the fluid loss.
Ideally the muds form a thin tough filter cake across the permeable formations.
This keeps the hole in stable condition. It also minimizes the quantities of mud
and filtrate entering the formation.
e. Cooling and Lubrication. During drilling operations, both the drill string and the bit
develop heat through friction. Drilling mud helps to cool the drill string and also
provides lubrication by reducing friction between drill string and borehole walls.
Thus the lubricity of the mud is important. The cooling function depends upon the
thermal conductivity of the mud.
f. Reduce Formation Damage. Formation damage is very much tied to the filtration
properties of the mud. Damage from filtrate invasion depends on the quantity of
filtrate entering the formation.
g. Minimize Corrosion. In water based mud corrosion is controlled by alkalinity or by
addition of corrosion inhibitors. It has been found that in muds containing oil as
the continuous phase, little or no corrosion occurs.

2.4 Drilling fluid related challenges

Many drilling problems are due to conditions or situations that occur after drilling begins
and for which the drilling fluid was not designed. Zamora et al. (2000) discussed 10
mud-related concerns. Failure to adequately address these concerns can lead to
excessive well costs, unscheduled trouble time, unnecessary high-risk activities, and
poor performance. Some of these problems can be solved by adding materials to the
drilling fluids to adjust their properties. The top 5 mud related problems are found
directly relevant to the subject under investigation and described as follows:

12
a. Borehole instability. Borehole instability is common problems in shale section.
Any formation can collapse if the mud weight is not appropriate to control it. To
minimize its borehole instability, proper mud characteristics (mud viscosity, drag
and torque reduction and fluid loss) are important.
b. Stuck pipe. During drilling oil and gas wells, drill string consisting of pipes and
collars are used to drill the formation. Filtrates invade permeable zones and filter
cakes are deposited on the wall of holes. A portion of the drill string is then
embedded in the mud cake on the walls of the borehole. When the drill string is
no longer free to move up, down or rotate, the drill pipe is supposed to stuck.
This problem is generally caused by the drill pipe sticking to the mud cake on the
wall of the wellbore due to filtrate loss in the wall of the well and the formation of
a thick filter cake or due to the cuttings backing into the wellbore as drilling fluid
circulation is stopped. The pull force to free the pipe is a function to the
differential pressure, co-efficient of friction and the total contact area of the pipe
on the hole wall. The co-efficient of friction (CoF) is one of the important functions
of drilling fluid. An oil-based drilling fluid has co-efficient of friction (CoF) of 0.10
or less (metal to metal) (Chang et al.,2011). In comparison, water has a CoF of
0.34 and the CoF of water-base drilling fluids typically ranges between 0.2 and
0.5 (Chang et al., 2011). It is known that presence of ordinary materials in drilling
mud can cause increased viscosity and mud weight (Dickerson and Rayborn,
1992). This high mud weight can cause damage to sub-surface formations,
plugging of production zones, hole erosion, decreased penetration rate, pipe
failures, stuck pipe and lost circulation (Amoco, 1996; BHI, 1998; Reid et al.,
2000; Njobuenwu and Nna, 2005). So in order to decrease probability of stuck
pipe it is necessary to design new materials which do not increase viscosity and
mud weight (Paiaman and Al-Anazi, 2008). To minimize differential sticking,
maintaining proper mud characteristics (fluid loss, mud density, lubricity, low solid
in mud) is very important.

13
c. Salt section hole enlargement. Salt sections may be eroded by the drilling fluid,
which causes hole enlargement. To avoid this problem, salt saturated mud
system is prepared for drilling through the salt bed.
d. Formation damage. Formation damage is generally a reduction in permeability
near the wellbore with porosity reduction. This represents a positive skin effect.
Almost every field operation is a potential source of damage to well productivity.
Diagnosis of formation damage problems has led to the conclusion that formation
damage is usually associated with either the movement and bridging of fine
solids in the producing horizons and the penetration of drilling fluid particles into
formation which cause pore plugging of the porous media. The fine solids may be
introduced from wellbore fluids or generated in situ by the interaction of invading
fluids with rock minerals or formation fluids. There are a number of ways that
drilling fluid filtrate might interact with the formation to cause permeability
damage. Some of these have been investigated in published papers (Al-Hitti et
al.,2005; Zamura et al.,2000; Chilingarian and Vorabutr,1983). Figure 2.2 shows
the blockage of the reservoir-rock pore spaces caused by the fine solids in the
mud filtrate or solids dislodged by the filtrate within the rock matrix.

Figure 2.2: Drilled fines and fluid particles invasion into the formation
(Zwager, 2007).

14
In addition to pore throat blockage, the formation damage also can be happened due to
clay-particle swelling or dispersion, scale and precipitation, emulsion blockage and
water blockage (Peng, 1990).

e. Lost circulation. Lost circulation means the uncontrolled flow of substantial

amount of drilling mud to an encountered formation. This can be a partial lost,
some returns to surface or a complete loss with no returns to the surface. Lost
circulation can occur in several types of formation, including highly permeable
formations, fractured formations and cavernous zones (Chilingarian and
Vorabutr, 1983). Different lost circulation zones are described in Appendix A.
Lost circulation occurs when hydrostatic pressure of mud exceeds the breaking
strength of the formation and that creates cracks along which the fluid will flow.
Fluid will flow in large fracture greater than 100 microns. In practice, the size of
pore opening of shales that can cause lost circulation is in the range of 10 nm-0.1
microns (Sensoy et al.,2009). Overbalance pressures in excess of about 7000
kPa (1000 psi) are generally considered to be severe and may cause serious
losses of filtrate and associated solids to the formation (Bennion et al.,1997).
Figure 2.3 shows the fluid loss during drilling.

Figure 2.3: Drilling fluid loss into the formation (courtesy of nFluids Inc, reprinted by
permission).
15
 Lost circulation materials can be added to mud to bridge or deposit a material where
the drilling fluid being lost to the formation. To minimize lost circulation, proper mud
design (usage of suitable lost circulation materials, maintan proper mud weight,
maintain adequate hole cleaning) is necessary. In addition, the appropriate size
distribution of bridging materials to create an effective sealing of impermeable filter
cake which deposits very rapidly on the face of the formation and thereby inhibiting
continual losses of drilled fluid (Al-Hitti et al., 2005).

2.5 Clay Chemistry used in drilling fluids

Clays are naturally occurring materials mainly composed of hydrous aluminum silicates
and typically formed over long periods of time by chemical weathering of rocks that
contain silicate (Deriszadeh, 2012). The colloid chemistry of clays to drilling fluid design
is of value at the present and will continue to be so in the future (Browning and
Perricone,1963). Clays are usually microscopic in size (typically < 2 µm) and also occur
as submicroscopic particles. Pauling (1930) studied the crystalline structure of clays. It
is also pointed out by Grim (1953) that most of the clay minerals have two structural
units that are the building blocks of their atomic lattices. Silica tetrahedron is the first
unit and alumina octahedral coordination which is the second unit as shown in Figure
2.4. These basic sheets are stacked together to form different clay minerals.

Figure 2.4: Basic units of clay minerals and the silica and alumina sheets (Mitchell and
Soga, 2005).

16
Clays are the major constituents of shale and due to their special characteristics they
play a crucial role in the mechanical and chemical properties of shale (Santamarina et
al., 2002). Clays are also the major constituent in drilling fluid and provide the fluid a
distinctive character. The properties exhibited by a particular drilling fluid largely depend
on the origin and characteristics of the clay component present in the fluid (Maduka,
2010). Three types of clays are used in drilling fluid formulation: montmorillonite
(smectite), kaolinites and illites. Among them montmorillonite, which is also known as
bentonite, is the most commonly used clay because of its superior ability to swell
uniformly in fresh water upon shear application resulting in a more homogeneous clay-
water mixture (Chilingarian and Vorabutr, 1983). Montmorillonite clay has the formula
[(A)0.3 (Al1.3,Mg0.7) (Si4)O10.(OH)2.xH2O] where A is an exchangeable cation, K+, Na+, or
0.5 Ca2+. Figure 2.5 displays the structure of Montmorillonite clay minerals according to
Grim (1962). According to literature, (Santamarina et al., 2002; Mitchell and Soga,
2005), bentonite has a high specific surface area of 800 m2/g. The diameter of bentonite
platelets could vary between 2000 to 20000 A° with a thickness of about 10 A° bentonite
platelets are bonded together by weak Van der Waals bonds. Therefore it may allow
water to enter the space between the platelets (Deriszadeh, 2012).

Figure 2.5: Schematic representation of Montmorillonite clay (bentonite) structure

(Grim,1962).

17
Browning and Perricone (1963) showed the effect of pH on clay surface. pH values
increment from 10.5 to 11 in the absence of deflocculates rapidly increased the system
resistance to shear with time indicating an increased tendency of surface area of the
clay suspension. The more stable clays system can be introduced by maintaining
proper pH. Chilingarian (1952) found that hydroxyl ion (OH-) adsorb on bentonite clay
platelets increased the total negative charges on the clay sheets causing repulsion of
nearby platelets (dispersed state). Figure 2.6 represents the ion exchange behavior of
clay surface. A double layer occurs when counter ions are attracted to the charged
surface of a particle and form a layer. The ions are held in place by Coulombic forces.
A diffuse layer occurs when the electrostatic attraction between the ions in solution and
the colloidal surface is counteracted by diffusion where the charge on the particle is
neutralized by a swarm of ions. The net negative charge of the clay surface has the
capacity to attract cations or positive charge molecules. With cation exchange may
result in a well dispersed mud system and simply as a result of neutralization of
negative charges on clay platelets. In such cases, plastic viscosity with decreasing
internal friction and gel strength reduction may occur. Highly charged cations can
impact greater attraction of clay platelets allowing lower fluid loss and form a filter cake
having very low permeability. Cations held by clays can be replaced by other cations.
This means they are exchangeable. Hanshaw (1963) showed that the order of cation
exchange selectively is dependent upon whether clay is dispersed or compacted. In
fact, the negative charge on particles is compensated by attraction of cations on the
surface. In the case of bentonite high concentration of cations would also occur inside
the particles as the spacing between platelets of each particle could vary due to this
presence of weak van der Waals forces among the adjacent platelets in each particle. A
small fraction of cations on the surface of particles develop the inner compact layer
commonly referred to as the immobile Stern layer (Mitchell and Soga 2005; Deriszadeh,
2012). In fact, some researchers concentrated on the fluid and ionic flows through micro
pores and the interparticle space of the clays (Mitchell and Greenberg, 1973; Moyne
and Murad, 2002; Smith, 2005; Sherwood, 1994).

18
Figure 2.6: Schematic representation of the fixed and diffused double layer near a clay
surface (Dampier, 2004).

The drilling fluid is a colloidal clay system though its consistency is critical. It must be
fluid enough to be pumped and thick enough to keep the cuttings suspended. In order to
prevent the loss of fluid, it is necessary to minimize the amount of fluid entering the
porous formations. The colloidal clay in drilling mud contributes to the filter cake building
up against the wellbore. When a suspension of a finely divided precipitate is filtered, the
filtration is slow because the particles pack tightly on the filter. The filter cake deposited
by a coarser precipitate of larger particles is less dense and more porous. The
characteristics of the filter cake formed depend on the degree of peptization or
flocculation of the suspension (Zakaria et al.,2012). Stable (peptized) suspensions form
dense, compact sediments while flocculated suspensions form more voluminous
sediments. The filter cake formed from a stable suspension will be dense and relatively
impenetrable in comparison to that formed from a flocculated suspension. Thus a stable
suspension has more effective plastering characteristics (Baker, 2006; Schmidt et al.,
1987). Chemical changes in clay minerals use certain additives in order to modify the
properties of drilling fluid. These additives could result in a safe and speedy drilling with
a maximum productive capacity after completion of a well.

19
2.6 Nanoparticles

Nanoparticles are defined as particulate dispersions or solid particles with a size in the
range of 1-100 nm (Nabhani and Emami,2012; Zakaria et al.,2011). Using nanoparticles
in drilling fluid provide a new era in drilling industry. Amanullah and Al-Tahini (2010)
defined nano fluids as any fluids (drilling fluids, drill-in-fluids, etc.) used in the
exploitation of oil and gas that contain at least one additive with particle size in the
range of 1-100 nm. They also classified nano fluids as simple nano fluids and advanced
nano fluids. Simple nano fluids contain nano particles of only one dimension, whereas
advanced nano fluids are ones with multiple nanosize additives. Commonly used drilling
fluid additives such as bentonite and barite in the conventional drilling fluids have much
larger particle diameters, ranging between 100 nm to more than 100 microns (Srivatsa,
2010; Abrams, 1977; Cai et al., 2012). Figure 2.7 shows a scale of typical particle size
ranges. There have been several methods for the selection of the lost circulation
materials, which are based on the size for the purpose of keeping mud loss at minimum
and given in Appendix B.

Figure 2.7: Particle size scale (adapted from Abrams (1977) and Sensoy et al., (2009)).

In general pore-throat sizes (diameters) are greater than 2 μm in conventional reservoir

rocks, range from about 0.03 to 2 µm in tight-gas sandstones, and range from 0.005 to
0.1 μm in shales (Nelson, 2009). Figure 2.7 shows the pore size connection for
sandstone, tight sand and shales according to Rezaee et al.(2012). Al-Bazali et al.
(2005) also reported average pore throat sizes of variety of shales in the range from 10
to 30 nm. Even though, loss in shale formations is not a big problem, nanoparticles can

20
be ideal additives to minimize fluid seeping into such a sensitive formation (Chenevert
and Sharma, 2009).

Figure 2.8: Pore throat sizes in rocks (adapted from Rezaee et al., (2012)).

According to Smalley and Yakobson (1998), the laws that govern nanoscale material
behave)ior are completely different than the laws governing the macro and micro-scale
behavior. Nanoparticles possess very large surface area per volume as shown in Figure
2.9.

Figure 2.9: Surface area to volume ratio of same volume of materials (Amanullah and
Al-Tahini, 2009).

21
These particles are smaller than micro particles requiring a very low additive
concentration and hence provide superior fluid properties at low concentrations of the
additives (Amanullah and Al-abdullatif, 2010).This causes a very large potential for
interaction with other matter as a function of volume. These enormous surface areas to
volume dramatically increase the interaction of the nanoparticles with the matrix or
surrounding fluid (Monteiro and Quintero,2012). This property of nanoparticles‎ provide
them increased interaction with reactive shale to eliminate shale-drilling mud
interactions and the associated bore hole problems (Amanullah et al., 2011). In addition,
due to large surface area per volume, it is expected that less proportion of nanoparticles‎
need to be employed relative to micron-sized additives conventionally used to achieve a
similar effect. As nano based fluids require small volumes, it significantly decreases
drilling time and increases the productivity index of the drilling activity by increasing the
rate of penetration (ROP). The main application of nanoparticles would be to control the
spurt and fluid loss into the formation and hence control formation damage (Husein et
al.,2012a; Amanullah et al., 2011). The nanoparticles can form a thin and impermeable
mud-cake. Due to its high surface to volume ratio the particles in the mud cake matrix
can easily be removed by traditional cleaning systems during completion stages. Thus,
the nanoparticles can be used as rheology modifiers, fluid loss additives and shale
inhibitors at very small concentrations (Zakaria et al., 2012; Amanullah et al., 2011;
Amanullah and Al-abdullatif, 2010). Research showed that the thermal conductivity and
the convection heat transfer coefficient of the fluid can be largely enhanced by the
suspended nanoparticles (Xuan et al., 2003; Choi et al., 2001). These features make
the nanofluid very attractive in cooling or lubricating application in many industries
including manufacturing, transportation, energy and electronics, etc. Hence, the
enhanced thermal conductivity of drilling fluid will provide efficient cooling of drill bit
leading to an increase in operating life cycle of a drill bit. Micro and macro sized
particles used in drilling fluid accelerate the wear and tear of the surface and subsurface
equipment. Conversely nanoparticles due to its extreme tiny size, the wear and tear of
down hole equipment due to abrasive action is negligible because less kinetic energy

22
impacts by nanoparticles. It is explained by the role of kinetic energy or dynamic action
(sedimentation speed) of nanoparticles on the bit. Particles in suspension in liquid
medium are subjected to three kinds of forces: a) gravitational forces the particles to fall
down, b) viscosity of the liquid decreases the speed of their displacement and c)
Archimedes force is opposed to gravitation forces in this case. By applying fundamental
relation of dynamics, the expression of the steady sedimentation speed of a particle is
can be approximated by Stokes law:

Vt = ( ) (E 2.1)

From the equation E 2.1, it is noticed that the speed varies in proportion to the square of
the radius of the particle. Particles with larger radius will sediment much faster than
smaller ones. Hence, comparing with the larger sized particles (micro or macro
additives) nanosized particles, the kinetic energy will be much less due to its low
sedimentation speed. Therefore Amanullah et al.(2011) reported that nanoparticles
could not harm the downhole tools during the dynamic operation.

Nanoparticles could improve the electrical conductivity of drilling fluids by forming

electrically conductive filter cake that highly improves real time high resolution logs
(Monteiro and Quintero,2012). Due to low requirement of nano additive in mud
formulation, nanobased fluid could be the fluid of choice in conducting the drilling
operation in sensitive environments. The wettability of a formation can be changed by
nanoparticles. The use of nanoparticles to change rock wettability and its subsequent
effect on oil recovery has been reported by several authors (Qinfeng et al., 2010; Ju et
al., 2006). From experimental results, it is expected that some nanoparticles application
in EOR will maximize recovery and boost hydrocarbon production. In a parallel research
to this one, Nwaoji et al.(2013) and Nwaoji (2012) found nanoparticles with LCM blend
bridge the formation, act as an excellent propping and sealing properties of the
fracturing fluid and increased the core fracture breakdown pressure (fbp) resulting in
strengthening wellbores in shale formations.

23
2.6.1 Nanoparticle synthesis

Selection of nanoparticles is dependent on its properties and particle size. There are
different methods for nanoparticles synthesis which are categorized as dry and wet
methods. Dry methods consist of jet and ball milling, micronizer whereas wet synthesis
consist of solvent evaporation, chemical precipitation, spray drying and emulsion
method (Midoux et al., 1999). Husein and Nassar (2008) reported five main techniques
for preparation of nanoparticles; namely: (i) chemical co-precipitation, (ii)
electrochemical, (iii) sonochemical, (iv) sol-gel processing and (v) microemulsions.
Engineered nanoparticles are designed and manufactured with specific properties or
compositions (e.g., shape, size, surface properties, and chemistry). All these techniques
require the presence of a stabilizing agent to prevent aggregation of the resultant
nanoparticles. Among them, water-in-oil, (w/o), microemulsions serve as an excellent
media for the preparation of wide variety of colloidal nanoparticles. (w/o)
Microemulsions typically provide easy control over nanoparticles size and shape and
produce highly homogeneous nanoparticles due to their ability to mix reactants
efficiently at the molecular level (Husein and Nassar, 2008). Nanoparticles get stabilized
in (w/o) microemulsions by means of steric stabilization which is provided by the
adsorbed surfactant molecules on the surface of the nanoparticles (Nassar and Husein,
2007a; 2007b). The surrounding surfactant layer limits their growth and protects them
from aggregation, and hence, maintains their colloidal stability. Stability of colloidal
particles is dictated by the net between the repulsive and the attractive forces which
emerge as the particles approach one another due to Brownian motion and/or other
external forces. When repulsive forces dominate, stable colloidal suspension is
maintained, while net attractive forces lead to particle aggregation and precipitation.
Van der Waals force is an attractive type interaction and is inversely proportional to the
sixth power of the distance between the surfaces of the particles (Husein and Nassar,
2008; Nassar and Husein 2007a,b; Kostansek, 2003). (w/o) Microemulsions are
thermodynamically stable systems and are different in nature than the kinetically stable
invert emulsions typically used in drilling operations. Entropy of dispersion is very
important parameter for the formation of microemulsion systems. Entropy of dispersion

24
contributes to very effective mixing of water pools and, hence very high rate of
intermicellar exchange dynamics compared to invert emulsion systems. This high rate is
indispensable for formation of nanoparticles in (w/o) microemulsions (Husein and
Nassar, 2008). In-situ formation of nanoparticles in invert emulsions, on the other hand,
relies heavily on effective mixing and shearing. This research attempted to adopt (w/o)
microemulsion technique to prepare nanoparticles in invert emulsion drilling fluids with
this fact in mind. Figure 2.10 shows the NPs preparation in an invert emulsion drilling
fluid following chemical co-precipitation method. By adding small quantities of
nanoparticles, or preparing them in-situ, in drilling fluid ensuring mixing at the molecular
level, wrapping and interpenetrating network achieve this new class fluid that could be
used in down hole drilling. The nanoparticles will be tightly held in the water pools,
surrounded by surfactant layers that limit their growth and protect them from
aggregation. A number of investigations were performed using nanoparticles in drilling
fluid to ‎improve the functional characteristics described earlier (Cai et al.,2012; Monteiro
and Quintero,2012; Tour et ‎al.,2011; Manea, 2011; Srivatsa, 2010; Abdo and Haneef,
2010; Chenevert and Sharma, 2009; Sensoy, 2009; Agarwal et al., 2009; Roddy et
al.,2009; Paiaman and Al-Anazi,2008; Sayyadnezad et al.,2008; Jimenez et al.,2003),
but none, had in fact adopted in-situ preparation technique, and most used commercial
nanoparticles.‎

Figure 2.10: Schematic representation of NPs in invert emulsion fluid.

25
2.7 Nanoparticle-based drilling fluids

The spurt loss is considered one of the sources of solid particles and particulate
invasion into the formation. Beeson and Wright (1952) observed that spurt losses
ranging from 2.3 to 7 mL may take place in the formation having permeability in the
range of 7 to 469 md. Muds producing soft and thick cakes increase the potential of
differential sticking and formation damage. This highlights the importance of mud design
to produce clear filtrate with virtually no spurt, low filtrate volume and well-dispersed and
tightly packed thin mud cake. It is often impossible to fulfill certain functional tasks using
conventional macro and micro type mud additives. According to Amanullah and Al-
Tahini (2009), due to the scope of manufacturing of tailored made nanoparticles with
custom made functional behavior, ionic nature, physical shape and sizes and charge
density/volume opened the door to the development of a new generation fluid for drilling
which is expected to play a leading role in overcoming technical challenges associated
with the conventional macro and micro particles based drilling fluid. In order to increase
the penetration rate in deep drilling systems and prevent fluid loss researchers are
working on developing a new nano-particle-based drilling fluid and additives that can
improve the efficiency, extend the life of drilling fluids, control fluid loss and less
susceptible to degradation under high temperature and pressure (HTHP) operations.
Recent experiments have demonstrated that nano fluids have attractive properties for
applications in heat transfer, drag reduction, binding ability for sand consolidation, gel
formation, wettability alteration, and corrosive control (Mokhatab, 2006; Krishnamoorti,
2006).

Amanullah et al. (2011) disclosed a WBM with less than 1 wt% NPs, resulting in no mud
spurt loss. High potential for reducing differential pressure sticking problems while
drilling, reduce torque and drag problems in deviated, horizontal extended reach and
multi-lateral drilling operations. Tiny concentration of less than 1% w/w of nanomaterial
plays an important role in increasing rate of penetration. But more interestingly,
Amanullah et al. (2011) formulated their “nano-based drilling fluids” by mixing
nanoparticles with the base fluid, i.e. water. They did not use a real drilling fluid

26
formulated by industry. Therefore, they were in need for very active stabilizers to
maintain the nanoparticles dispersed. The polymeric viscosifier and surfactant additives
used are costly, i.e. not practical. Moreover, industrial drilling fluids contain many
additives that may compromise the stability of their drilling fluids and render them
ineffective. For all practical purposes their “drilling fluids” are model drilling fluids which
have no industrial applications. Also, looking at the fluid loss experimental results, it is
clear that fluid loss reduction for a period of 30 min was not improved at all or became
negative compared to the bentonite based mud (without nanoparticles as a control
sample). Calcium‎carbonate is a well-known weighting material in drilling fluid. Reducing
solid, i.e. clay, content by introducing CaCO 3 is not a new idea. Their claim regarding
increasing ROP, decreasing formation damage and decreasing the coefficient of friction
are indirectly related to NPs addition. They only improved the rheological behavior of
fluid in terms of stability and gel strength. Srivatsa and Ziaja (2012) disclosed a WBM
with viscoelastic surfactant and 10 wt % NPs. It also tests higher amounts of 20 wt%
and 30 wt% NPs. 10 wt% is considered as the minimum concentration needed for fluid
loss and address differential sticking problems. The authors used model “drilling fluids”
formulated by adding different proportions of surfactants, polymers and/or
nanoparticles. No actual nano-based drilling mud was used. A large amount of
surfactant and polymers were used in fluid formulation. With the addition of NPs at
different concentration resulted at 20-40 % fluid loss reduction. Due to the large amount
of NPs with surfactant-polymer blend could make the drilling fluid practically undesirable
in terms of drilling cost and other functional activities. Water based mud in real
application do not mix with large amount of surfactant and polymers. Polymer-surfactant
blend suppress the NPs fluid mud cake with a desirable thickness so that differential
sticking problem can be eliminated. No experimental results and mechanism proved the
lubricity nature of their commercial silica NPs used in their works. Aston et al. (2002)
disclosed NPs at a concentration of 0.7 to 1.4 wt% and discussed preventing differential
sticking and formation damage avoidance as well as fluid loss reduction. Three
components were required for fluid loss control – emulsified brine, fine solids, and fluid
loss control chemical such as Gilsonite, asphalt or synthetic polymer. High

27
concentrations of fluid loss additives were not required since they did not improve fluid
loss control. The study focused on the effect of every component of an OBM on fluid
loss, and in fact formulated the fluids using the base oil and added one component at a
time. Once the solid particles were tested, they were not in suspension, Illite provided
loss prevention but it was in the micro-domain.

The use of engineered nanoparticles increases the intra-granular strength and reduces
permeability and porosity of formation. Oil-based muds offer a good solution to shale
instability problems. Nevertheless, development of water-based mud is also needed for
environmentally sensitive areas where nanoparticles might be effective in plugging pore
throat openings and stabilizing the wellbore. Sensoy (2009) disclosed a WBM with
nanoparticles. It states that 5 wt% NPs is not as effective as 10 wt% which is
considered the minimum needed for fluid loss. Reduced fluid penetration into Atoka
shale up to 98% compared to sea water. NPs were between 5 to 20 nm in size. No
actual nano-based drilling fluids were used. The author used dispersion of nanoparticles
in water. Permeability reduction was taken longer time with higher amount of silica NPs.
Extra additives were required to disperse the silica NPs in drilling fluid. Tests were not
covered for invert emulsion mud and HTHP conditions. The application of this fluid
pertains to nanopore throat reduction rather than considering the overall fluid loss. We
anticipate that this approach could damage the formation by forming internal plugging
into the formation and in this manner could significantly increase wellbore instability
problems. As it took longer time to reduce permeability means the penetration of drilling
fluid particles or NPs passes from the hole into the formation. Therefore we can
conclude that spurt loss is higher in this case before pore plugging occurred. Similarly
Chenevert and Sharma (2009) investigated permeability reduction of shale formations
using specific nanoparticles in the water based drilling fluids. By identifying the pore
throat radii of shale samples, the investigators were able to select fine particles that
would fit into the pore throats during the drilling process and create a non-permeable
shale surface. They formulated their water based mud with silica, iron, aluminum,
titanium or other metal oxides and hydroxides nanoparticles having size range of 1-500

28
nm and also composed of a surface active agent (alkyl amines, alkyl sulphates, alkyl
sulphates containing aromatic rings, Polyethylene glycol (PEG), Polypropylene glycol
(PPG) etc) . The minimum concentration required to reduce the fluid penetration was 10
wt% NPs. It was observed that addition of 10 wt% of silica NPs reduced fluid
penetration by 72% in 36 h for Atoka Shale and 50% in 23 h for GOM Shale. It was also
observed that high concentration of nanoparticles (41 wt%) completely plugged the pore
throats by 2 h for Atoka Shale. Thus, these fluids based on nano fluids can be used
effectively in horizontal and directional shale drilling as nanoparticles can easily
penetrate into the shale and hence drastically reduce the shale-drilling mud interactions
and stabilize the wellbore. It was also found by Huang and Crews (2008) that
nanocrystals with hydraulic fracture proppant reduced fines migration without disturbing
productivity. The NPs asscociate with VES (viscoelastic surfactant) micelles through
surface adsorption and surface-charge attraction to stabilize fluid viscosity at high
temperatures and produced a pseudofilter cake of viscous VES fluid on porous media
that reduced the rate of fluid loss significantly and improved fluid efficiency for hydraulic
fracturing.

Ying,(2012) disclosed the use of precipitated sub-micron barite as a weighting agent

in ‎drilling fluid. The precipitated barite showed less sag than conventional weighting
agents which led to a ‎decrease in pipe sticking. The precipitated barite was used in
amounts from 20-99.9% by volume and ‎did not lead to an unwanted increase in
viscosity. They also reported the use of polymers, which might bridge the particles and
produce thin mud cake as per literature. Thin mud cake leads to a ‎decrease in pipe
sticking. So, no clear distinction between the roles of the submicron particles or the
polymer in reducing pipe sticking problems was made in Ying,(2012) work.‎ Ballard and
Massam (2012) investigated precipitated submicron barite as a weighting agent in a
drilling fluid. The ‎precipitated weighting agents showed less sag than conventional
weighting agents. Preferred ‎precipitated agents are calcium carbonate, barium sulfate,
iron oxide, magnesium carbonate and a wide ‎variety of others. The precipitated
weighting agents have a particles sizes varying between 20 and 90 nm. They also

29
disclosed that precipitated barium sulfate can be made by mixing barium chloride
and ‎sodium sulfate. Their works mainly focused on optimizing the viscosity of a drilling
fluid and avoiding high viscosities while achieving high densities, an attribute especially
needed for high pressure drilling. Further, unlike the methods developed in this study,
the precipitated weighting agent is prepared ex-situ, where a coating material
(dispersant) ‎surrounds it, and is then added as a solid powder to the drilling fluid.‎

Paiaman and Al-Anazi (2008) suggested to reduce the thickness of mud cake utilizing
carbon black nanoparticles in drilling fluid. Carbon black NPs having specific Gravity=
1.9-2.1, initial diameter about 30 nm which after aggregation increased to 150-500 nm
was used in the works. The presence of carbon black particles reduced the thickness of
the mud cakes and increased the thermal stability up to 3000 °F (1649 °C). Results
have shown that adding 2 % by volume of carbon black to water based drilling mud
decreased mud cake thickness, mud viscosity and yield point which led to less
permeability and stuck pipe problems. Results also showed that thickness reduction
was found better at high temperature and pressure.

Griffo and Keshavan (2007) disclosed a drilling bit grease that comprises from 0.1-10
wt% at least one nanomaterial. The ‎grease is comprised of a common base stock such
as synthetic oil, petroleum oil, and mineral oil or ‎a combination thereof. Soaps, urea,
fine silica, fine clays and silica gel may be used as thickeners. ‎Preferred lubricating
nanoparticles include molybdenum disulfide, graphite, carbon black, lead oxide, ‎zinc
nanoparticles ranges from 0.5-50 nm.‎ In their works it was found that addition of
thickeners were necessary along with NPs. Although the invention did not claim that
lubricity was based on NPs only; most of the metals considered in their works were
heavy metals, which have a big environmental impact (e.g. lead). Uses of nanoparticles
in drilling fluid will also expand its area of application in fracturing fluid additive, cement
slurry additives, completion fluid additive. Nanoparticles increase the mechanical
strength of the fluid. Roddy et al. (2009) observed that addition of nano-silica having a
particle size in the range of about 1 nm to about 100 nm and present in an amount in

30
the range of about 1% to about 25% by weight to the cement slurry (comprised of
cement, water) reduced the cement setting time and increased the mechanical strength
of the resulting cement explains the fact that light nanomaterials can take overall load.
Some nanoparticles may carry magnetic property which can change the density of fluid
when necessary. Jimenez et al. (2003) made an effort to prepare nanoparticles treated
drilling fluid which was responsive to the change density state required to control
subsurface pressures, preserve and protect the drilled hole. The nanoparticles were
sized between 0.5 and 200 nm and formed into clusters having average size of between
0.1 µm and 500 µm. The clusters were formed by incorporating the nanoparticles into a
matrix of glass or ceramic. Group VIII metals Cd, Au and their alloys were found to
provide an excellent result in adjusting fluid density in a reversible manner. They have
shown that 90% of the supermagnetic nanoparticles from the treated drilling fluid from
the downhole location again recovered to a magnetic field at the surface resulting in the
adjustment of drilling fluid density within a short period of time and circulated the
magnetic nanoparticles to the surface level for reusing them in the drilling fluid. From
the study it is shown that viscosity could also change with the addition of nanoparticles.
Javora and Qu (2009) used an aqueous based well treatment fluid containing an
additive having a median particle size of the calcium carbonate nanoparticles less than
or equal to 1 µm as viscosifying additive. The amount of calcium carbonate
nanoparticles used in drilling fluid was approximately 20 wt%. The nanoparticles used in
well treatment fluid were capable of being suspended in the fluid without the aid of a
polymeric viscosifying agent. Nanoparticles suspended in a well treatment fluid even at
high temperature, e.g. 350 °F, typically exhibit sag no greater than about 8%. It was
observed from the study that addition of nanoparticles altered the viscosity of the fluid.
Using nanoparticles, Huang and Crews (2008) reduced the leak off viscoelastic
surfactant simulation fluids at high temperature for completion applications. They also
discovered that, micellar fluids such as surfactants can have wall building
characteristics when small concentrations of nanoparticles are added. The
nanoparticles pseudo-crosslink the elongated micelles in a manner similar to cross-
linking Polymers. They further investigated the pseudo-crosslink characteristics of the

31
worm like micelles in surfactant systems and concluded that nanoparticles first
associate with end caps which are energetically unfavorable and then this becomes
junctions for worm like micelles, which enhance the wall building characteristics of the
fluid system, improve thermal stability and also improve the viscosity of the fluids. Berret
(2004) investigated the interaction of nanoparticles with co-polymers and observed the
formation of “super-micellar” aggregates. Nanoparticles which have a hydroxyl group
(-OH) on the surface and causes nanoparticles to be agglomerated. This agglomeration
causes poor dispersions and addition of surfactants reduces this problem. Asphaltic
materials are also used as additive to bind the metal oxides at high temperature tend to
decrease the fluid loss. McGlothlin and Baggett (1972) invented an invert emulsion
drilling fluid employing manganese oxide with asphalt constituents. Addition of MnO 2 the
fluid loss reduction was approximately 66 % than the control sample at 300°F with
substantially no breakdown of the emulsion. The amount of metal oxide or oxides
employed were from about 1 to about 10 wt%. Miller (1971) improved plastering
properties and reduced fluid loss properties at extreme conditions of borehole
temperature and pressure using asphalt material as a filler or plaster at high
temperature. He formulated the oil based drilling fluid containing a small amount of a
secondary weighting material inert to the fluid and having particle size of no more than 3
µm. Suitable inert materials for the secondary weight phase were the iron oxides and
titanium oxides. Each sample was tested for fluid loss by maintaining the fluid in a high-
temperature, high pressure filter press at 300°F and 500 psi for 30 min. The
investigations showed that iron oxides having size 3 μm had 12 % less fluid loss, TiO2
particles having 0.18 μm had 36 % and 0.19 μm showed 12 % less fluid loss than the
control samples. The investigation again showed that addition of TiO2 with fine barium
sulphate lower the fluid loss 38% than the control samples. Ravi et al. (2011) made an
effort to introduce a lost circulation composition into a lost circulation zone to reduce the
loss of fluid into the formation. The lost circulation composition comprised of portland
cement in an amount of about 10% to about 20 % by weight of the lost circulation
composition, nano-silica in an amount of about 0.5 % to about 4 % by weight of the lost
circulation composition, the nano-silica having a particle size of about 1 nm to about 100

32
nm, amorphous silica in an amount of about 5 % to about 10 % by weight of the lost
circulation composition, synthetic clay in an amount of about 0.5 % to about 2 % by
weight of the lost circulation composition, sub-micron sized calcium carbonate in an
amount of about 15 % to about 50 % by weight of the hydraulic cement and water in an
amount of about 60 % to about 75 % by weight of the lost circulation composition. It was
investigated that lost circulation compositions rapidly developed static gel strength and
remained pumpable for at least about 1 day. The sample was observed to gel while
static but returned to liquid upon application of shear. Thus mixed nanocomponents
with cement could reduce the setting time for mud cake formation and development of
gel strength. The retention of nanoparticles from concentrated dispersions in
sedimentary rocks has recently been investigated by Rodriguez et al. (2009). They
mentioned that NPs retention by the porous medium had consistent competition
between adsorption (vander Waals attraction between nanoparticles and solid surface)
and desorption (Brownian motion and hydrodynamic drag). Tour et al. (2011) used
drilling fluid including chemically converted nanoplatelet graphenes with functional
groups. The graphene comprised about 0.001% to about 10 vol.% . The functionalized
chemically-converted graphene sheets were about 1.8 nm to about 2.2 nm in thickness.
Whatman 50 allowed some graphene oxide to pass through the filter. Filtration rates
varied from 0.10 mL/min to 0.28 mL/min for graphene oxide and chemically converted
graphene solution on whatman 50 filter paper. Surface charge plays an important role
on the transport of nanoparticles and trapped in porous media. Poulton and Raisweel
(2005) reported that the natural spherical iron oxides nanoparticles (10-20 nm) in
sediments tend to aggregate at the edges of clay grains due to their surface charge
characteristics. Kosynkin et al. (2012) showed that using graphene oxide (GO) with a
concentration of 0.2 % (w/w) by carbon content exhibited 15.27 % fluid loss reduction in
water based drilling fluid compare to the water based control drilling fluid sample. GO
preparation technique was not user friendly. During spurt loss, NPs pass through the
filter cake which could damage the formation due to internal pore blockage by their NPs.
Saboori et al. (2012) also investigated mud cake thickness and water loss using CMC
nanoparticles having particle size distribution 27 nm to 930 nm with average size of 47

33
nm in water based mud. NPs were prepared by ball milling method. It was found that
existance of naoparticles caused the amounts of water loss and mud cake thickness to
decrease. Compare with the micron-sized CMC (10 gm) used in control samples, nano
CMC (10 gm) can decrease only 7 % fluid loss. Manea (2011) investigated nanoscale
polymer additives in water based mud to measure the fluid loss. 2.5 wt% nano Xanthan
gum and 3 wt% nanopolymer together in mud reduced 29 % water loss whereas mud
treated with NaOH and addition of 2.5 wt% nano Xanthan gum and 3 wt% nanopolymer
together reduced fluid loss by 48% led to the conclusion that in an alkali medium, the
efficiency of Xanthan gum was enhanced. On the other hand, increasing the sodium
hydoxide concentration in the mud also increase the pH of the mud which could lead to
the undesirable mud viscosity reported by Irawan et al. (2010). Deep water drilling has
been emerging as an important drilling activity to all oil and gas companies in order to
increase the daily production of crude oil. Drilling in deep water wells normally
associated with high temperature high pressure (HTHP) condition. HTHP wells are
generally considered to be those which encounter bottom hole temperatures in excess
of 350 °F (177 °C) and more than 500 Psi pressure. A research program initiated by
Tran et al. (2007) to develop nano particles based drilling fluids to perform in high
temperature drilling. Under their study, they assumed the benefits of using drag-
reducing polymer additives with nanoparticles could improve the drilling penetration
rate, lubrication, and cooling the drill bit.

Hydrogen sulphide which is corrosive, toxic and dangerous gas largely produced in gas
and petroleum industries. It can diffuse into the drilling fluid from formations during oil
and gas wells drilling. Investigations are being carried out to remove hydrogen sulphide
from this drilling fluid to reduce the environmental pollution, protect the health of drilling
personnel and prevent corrosion of pipelines and equipments. Sayyadnejad et al.
(2008) showed that utilizing zinc oxide (ZnO) nanoparticles synthesized by spray
pyrolysis method in water based drilling mud removed hydrogen sulphide completely
within 15 min where as bulk zinc oxide removed 2.5% of hydrogen sulphide in as long
as 90 min under the same operating conditions. The results obtained in this research

34
showed that ZnO nanoparticles in the range about 14-25 nm size, 44-56 m2/g specific
surface area used as an effective scavenger for removing hydrogen sulphide (H2S) from
drilling mud.
Since HTHP/environmentally sensitive/remote areas drilling are inherently
expensive, the choice of drilling fluids and its continuous phase require careful
evaluation to successfully handle the environmental challenges. Drilling fluids
formulated with low aromatic oil (contain less than 1% of aromatic fractions) are 5 to 14
times less toxic than diesel based fluid under the EPA criteria. LC 50 currently has a limit
of 30,000 ppm for the suspended particulate phase of the whole mud (Sáchez et al.,
1999). Research concerning the toxicity of NPs is still in its infant stages. However a
study was investigated by García et al. (2011) showed that iron oxide NPs exhibit low or
no toxicity at low concentration (0.67 mg/mL) and reported LC 50 = 2.3 x 10-4 mg/mL
which would be special interest to use it in drilling fluid.

The cost of nanobased drilling fluid may make them economically feasible. Srivatsa
(2010) reported the cost of a typical oil based drilling fluid containing silica NPs was
costly. A comparative cost between commercial silica NPs used by Srivatsa (2010) and
NPs prepared in ex-situ/in-situ method by Husein et al. (2012) shown in the following
table:
Table 2.1: Comparative cost analysis study of NP-based drilling mud (Srivatsa, 2010).

Cost/unit Cost/component
Component Volume
($) ($)
Diesel Oil 0.8 bbl 42 33.6
Emulsifier 6 lbs 1.5 9.0
Water 0.14 bbl NA NA
Gel 5 lbs 1.20 6.0
Calcium Chloride 20 lbs 0.20 4.0
Lime 3 lbs 0.10 0.30
Total Cost (1bbl) 52.9
NP (silica) at 10 wt% conc. Srivatsa (2010) 35 lbs 2.5 87.5
In-situ/ex-situ NPs 1 wt% Fe(OH)3 conc.
4.8 lbs NA 12.78
prepared by Husein et al. (2012a)

35
From the above table, total cost of the 1bbl diesel based mud is $52.90. Addition of
commercial NPs (10 wt%) contributed to $140.4/bbl, whereas in-situ/ex-situ NPs based
mud overall cost would be $65.71/bbl. So based on the literature in-situ/ex-situ NPs
costs are less expensive and more cost effective in terms of drilling cost per well. In
respect to filtration control of drilling fluid suggests that there should be a proper
criterion of particle size distribution. Experimental works presented by different
researchers in literature showed the single size of NPs used in mud formulation and
reached hardly near to the objectives. Whereas we suggest the cost effective in house
ex-situ and in-situ prepared NPs having wide range of particle size distribution could be
successful to handle the different permeabilities and porosities of the formation.
Nonetheless we can conclude that the addition of NPs to drilling fluid has a positive
effect on fluid properties. In this work we evaluate fluid loss performance along with
other characteristics of drilling fluid after blend of custom prepared engineered NPs in
drilling fluid. From earlier literature review a wide range of NPs are preferably selected
from metal hydroxides, e.g. iron hydroxide, metal carbonates, e.g. calcium carbonate
and metal sulfate and sulfide e.g barium sulphate and ferrous sulfide respectively.

2.8 General characteristics of drilling fluid filtration

The invasion of filtrate occurs once filtration starts during drilling. It is well known that
there is a mud spurt at the start of a filtration process before filtration begins. In the
drilling well, mud spurt may be much larger when filtration takes place against the more
permeable rocks. In fact they can be infinite (i.e. circulation is lost) unless the mud
contains particles of the size required to bridge the pores of the rock, and thus establish
a base on which the filter cake can form. Only particles of a certain size relative to the
pore size can bridge these pores. Particles lager than the pore openings cannot enter
the pore, and are swept away by the mud stream. Particles considerably smaller than
the opening, on the other hand, invade the formation unhindered. Intermediate particles
of a certain critical size stick at bottle-necks in the flow channels, and form a bridge just
inside the surface pores. Once a primary bridge is established, successively smaller
particles, down to the fine colloids, are trapped, and thereafter only filtrate invades the

36
formation. The mud spurt period is very brief, a matter of a second or two. Krueger
(1963) produced a typical curve for cumulative filtration volume versus time as shown in
Figure 2.11. Equilibrium conditions are reached after about 6 to 10 h and fluid loss rate
becomes constant as indicated by the straight line portion of the curve. The first portion
of the curve is the dynamic fluid loss rate through equilibrium dynamic mud cake laid
down on newly exposed formation. The second portion of the curve represents the
duration when circulation was stopped and the static mud cake allowed to build up on
top of the dynamic cake. The third portion of the curve represents the period when the
circulation is resumed and equilibrium dynamic fluid loss rate is established. During T0
and T1 time period, deposition of particles occurs and is characterized by filtration
through a cake of constant thickness. Outmans (1963) suggested that during this
period, the rates of particle deposition and cake compaction must be equal. During T 2
and T3, filtration rate, cake thickness and permeability are constant. The next phase of
the curve corresponds to the period of static filtration (T3 to T4) which occurs when
circulation is stopped. During this time filter cake thickness will start to increase. This
static filtrate affects the subsequent drilling operation. Therefore it is necessary to
predict the static fluid loss in which the filter cake forms upon a previously deposited
dynamic filter cake. It is logically thought that the lower the mud cake permeability, the
thinner the mud cake and the lesser the volume of filtrate from muds. The primarily
concern is to control the static filtration rate/loss in order to overcome drilling and
completion difficulties associated with filter cake growth to great thickness during long
period of static filtration, which is often the case during swabbing, fishing and trips.
Thick filter cakes restrict the easy passage of downhole tools and allow excessive
amount of filtrate to move into the formation, creating a potential cause of caving and a
long term formation damage problem as a result of fluid invasion (Maduka, 2009). In the
third phase (T4 to T6) of Figure 2.11, a new dynamic equilibrium filtration rate is achieved
and total resistance to filtration increases due to cake depositing in the static phase.
This theory was proposed by Ferguson and Klotz (1954) and also confirmed by Peng
(1990).

37
Figure 2.11: A characteristic filtration plot of drilling fluid during drilling (Krueger, 1963).

Darley (1965) reported that initial filtration rates depended on the concentration of solids
and particle size distribution in the mud. It was suggested that there was a critical size
range for bridging in the surface pores. Once the pores are bridged by appropriate size
particles, successively smaller ones are trapped, and a filter cake is established.
Schremp and Johnson (1952) described the drilling mud filtration process into two
steps: (1) bridging of openings in the filter medium, and (2) filtration of fluid throughout
the filter cake that developed on the filter medium as the filtration continues. Gates and
Bowie (1942) discussed the relationship between particles size distribution and filtration
properties. They showed that the best filtration control properties of the muds were
composed of approximately 65 wt% colloids, 30 wt% silt and 5 wt% sand, whereas the
poorest filtration control muds were composed of 1 wt% colloids, 94 wt% silt and 5 wt%
sand. And increasing temperature increased the filtration rates of the fluids tested.
Barkman and Davidson (1972) showed three characteristic shapes of the filtration curve
as shown in Figure 2.12.

38
 Figure 2.12: Three Types of Filtration Curves (Barkman and Davidson, 1972).

They concluded that the shape of the curves depended on the sizes of the suspended
solids and filter medium. Figure 2.12a results when the suspended particles are larger
than the pores of the filter medium and no invasion takes place. The intercept of the
straight line at time zero becomes negative. Figure 2.12b occurs when the suspended
solids are much smaller than the pores of the medium and invasion takes place at the
early part of the experiment. Therefore a positive intercepts is apparent. In Figure 2.12c
S-shaped curve, which is not common, occurs when several filtration mechanisms
(plugging mechanisms, pore throat blockage and pore filling) operate simultaneously. It
is evident that filtration curves mostly depend on the particle/pore-throat size ratio,
filtration velocity and mechanism of capture of particles (Pang and Sharma,1997).
Jones and Babson (1935) investigated the filtration properties in artificial formation
prepared from the unconsolidated sand at pressures upto 4000 psi and temperatures
upto 275°F under dynamic conditions. They found that filtration flow rates attained a
constant value at the end of about 2 h. Regardless of the nature of mud or temperature,

39
variation in pressures above 500 psi had very little effect on the filtrate flow rate or on
the mud cake thickness. It was found that the fluid loss increased rapidly with reduced
apparent viscosity for weak thixotropic mud but unaffected for strong or moderately
strong thixotropic muds. Byck (1940) investigated the effect of formation permeability on
the filtration characteristics of drilling fluids. It was shown that the filtration rate was
dependent on the permeability of the cake as long as it was several orders of magnitude
lower than the permeability of the formation. Willams and Cannon (1938) performed
static filtration tests at pressures ranging from 30-1500 psi for a wide range of drilling
fluid and concluded that cake resistance increased by the addition of bentonite and rate
of filtration could be varied by adding weighting materials. Larsen (1938) reported the
following relationships drilling fluid filtration experiments at pressures ranging from 25-
8000 psi and temperatures in the range of 60-250°F.

Fluid loss α t1/2 (E 2.2)

Fluid loss α (E 2.3)

Fluid loss α Cake thickness (E 2.4)

It was also found that fluid loss increased by calcium ion flocculation of the mud.
Flocculation of muds causes the particles to associate in the form of a loose, open
network causing considerable increase in permeability. Conversely, deflocculation of a
mud by the addition of a thinning agent causes a decrease in cake permeability.
Moreover, most thinners are sodium salts, and at high concentration, the sodium ion
may displace the polyvalent cations in the base exchange positions on the clay, thereby
dispersing the clay aggregates, and further reducing cake permeability. Thus, the
electrochemical conditions prevailing in a mud are a major factor in determining the
permeability of its filter cake (Maduka, 2010).

Fordham et al. (1988) proposed two fundamental models for dynamic filtration of a
drilling fluid. One of them is convection diffusion balance model based on the fluid loss
control between the convective transport of mud particles towards the filtration surface

40
by the filtration flux and the diffusion of particles away from the surface. Another one is
particle adhesion model which suggests that particle permanently stick at the cake
surface depends on both the filtration rate and the colloidal interactions between
particles. Once stuck, particles are unable to migrate away from the surface. Milligan
and Weintritt (1961) reported the effects of elevated temperature on filtration of drilling
fluids. They concluded that at an elevated temperature, muds might undergo irreversible
reactions or changes in composition. The increase in temperature reduces the viscosity
of the filtrate, and therefore, cumulative filtrate volume increases proportionally. Many
organic filtration control agents start to degrade significantly at temperatures above
100°C. Chemical degradation of one or more components used in mud can affect filtrate
properties. Electrochemical equilibria which govern the degree of flocculation and
aggregation, altering the permeability of the filter cake due to an elevated temperature
(Maduka, 2010).

The static filtration equation for mud filtrate through a mud cake is described by Darcy’s
law. In 1856, Henry Darcy published the following equation to describe the flow of fluid
through porous medium (Chelton, 1967):

dQf kAP
 (E 2.5)
dt hmc

Larsen (1938) found that if a mud was filtered through paper at constant temperature
and pressure, fluid loss Qf was proportional to square root of time √t . Although this
finding is not strictly true for all muds, but close enough for practical purposes. Carman
(1938) extensively studied the cake filtration and concluded that Darcy’s law is
applicable for mud filtration. It is shown that drilling fluid loss behavior with time has
been estimated from the experimentally derived data by using Darcy law in the literature
(Maduka, 2010; Kumar, 2010; Hoff et al., 2005).

41
In current study, API static filtration equation is described at Chapter 5 as a part of
sequential filtration for realistic drilling condition for predicting the drilling fluid loss
control by nanoparticles.

2.9 Filtration mechanism

Particles in suspension in a liquid medium are subjected to three kinds of forces: a)

gravitation forces, b) drag forces and c) Archimedes force (Martin and Ohmae, 2008).
Filtration occurs when fluid-containing particles are captured flowing through a porous
medium. Particles are deposited due to the different mechanisms as described by
Zamani (2010); Farajzadeh (2004) and deZwart (2007).

Particles transport by interception. This particle transport mechanism becomes

important when particles are larger in size. Interception occurs when particles following
a streamline hits the surface of a grain and attach to it. Particles having equal density of
the fluid follow the streamline in porous media at low velocities. When the particle is
retained by a previously deposited particle, it is referred to as bridging. Figure 2.13
shows the bridging of the particles in a pore throat with varying particles diameter. It
shows the bridging effect that occurs when two or more particles arrive at the same
moment to pass through or when one particle is already attached to the grain and
another particle wants to pass through.

Figure 2.13: Bridging effects with varying particles diameter in pore throat (de Zwart
(2007), Farajzadeh (2004)).

42
Happel (1958) used the following relationship to calculate the probability of collision.

= (E2.6)

As is the porosity dependent parameter and express as

= (E2.7)
where, z= 2-3p+3p5-2p6 and p = (1-φ) 1/3 ; where φ is the porosity of medium.

Particles transport by Impaction. When the density of particle is larger than that of the
fluid, inertia deviate the approaching particles from the stream line and attach them to
the surface of a grain. This mechanism is responsible for collecting larger particles. The
inertial effect is characterized by the dimensionless Stokes number (Tien,1989 ; Ives,
1970) as

Nst= (E 2.8)

Particles transport by Sedimentation. When the density of particles is different than the
density of the fluid, the fluid velocity will be different than the particles velocity. The
expression of steady state sedimentation velocity of particles in dilute suspension, V t
are given in E 2.1. Particles with large radius will sediment much faster than the small
ones and less kinetic energy will be impacted by small particles.

Particles transport by Diffusion. Small particles experience to random Brownian motion

that increases the collision frequency between particles and grains. The collision
probability due to diffusion is equal to

= 0.9 ( ) (E2.9)

43
Diffusion is important for small particles (dp<1 μm) and is usually neglected for larger
particles. Ives (1970) found that the Brownian motion is dominant in transporting the
submicron size particles but for the particles with greater than 1 μm in diameter, the
viscous drag of the fluid restricts this movement and the mean free path of the particle is
at most one of two particle diameter and therefore the mechanism is neglected. At a
short distance, below 50 nm, two particles attract themselves due to van der Waals
forces and it is expressed by the following relation:

Evdw = - (E2.10)

Van der Waals forces become more significant when h is below 10 nm. It is often used
to describe the intermolecular interactions. For a better stability of a suspension, the
Brownian motion is certainly most interesting. For mass transfer of nanoparticles in the
presence of surface interaction forces over the filter grain dg, the Brownian diffusion
coefficient can be defined by the Stoke-Einstein equation:

(E2.11)

Pe = (E2.12)

where Pe is the Peclet number (ratio of the convective motion of fluid to the movement
due to Brownian diffusion).

Particles transport by straining. When fluid containing particles approaches a pore

throat, particles which are too small to pass through, get stuck there. This phenomenon
is called straining or size exclusion (Farajzadeh,2004). It is determined by the ratio of
porous media (pore throat) diameter to the particle diameter. When this ratio is less than
10 (too small) cake will build up on the surface of the media (Farajzadeh, 2004). If the
concentration of particles is too high, they can also make a surface cake. In such cases,

44
many particles may reach the pore opening at a time and cram in it by aching action
(Zamani, 2010).

Particles transport by Electrical forces. Oppositely charged particles are attracted to a

charged fiber as shown in Figure 2.14. This collection mechanism is not limited to a
certain particle size and electrostatic charges may influence particle deposition.

van der Waals attraction forces and double layer repulsion forces are also significant for
the capture and detachment of the particles. They determine whether a particle will stick
to the grain or not. In other words, if the sum of the hydrodynamic and electrostatic
forces is attractive, a particle will be retained and if the sum is repulsive particles will not
adhere to the grain (Farajzadeh, 2004). All of the above mechanisms are summarized in
Figure 2.14. As NPs (dp<< 1µm) are used in the current work, it is believed that diffusion
is the most dominant mechanism as per Figure 2.15.

Electrostatic attraction - +

Figure 2.14: Overview of Filtration mechanisms (adapted from Wilcox et al., 2010).

45
 Figure 2.14: Effect of particle diameter on collision probability (Farajzadeh, 2004).

Generally, three possible mechanisms may contribute to dispersed NPs deposition from
invert emulsion drilling fluid. Brownian diffusion, steric stabilization, and van der Waals
attraction forces. Double layer repulsion forces enhance particle stability in water based
muds.

a) NPs from the drilling fluid may physically plug or bridge across the flow paths in
the porous formation upon the first filter cake is formed by clay particles. NPs
plugging probability during drilling is shown in Figure 2.16. The movement or
transport of NPs by diffusion mechanism is believed to occur during fluid flow
through porous medium.
b) Chemical interaction between the fluid containing NPs and the formation rock
and drilling fluid may precipitate NPs or other semisolids that plug the pore
spaces. Adin et al. (1979) concluded that chemical interactions greatly affect the

46
 attachment of particles on the surface. Raveendran (1993) found that water
molecules strongly bind with certain clays and minerals by the strong hydrogen-
bonding surface groups such as hydrated ions or hydroxyl (-OH) groups. Van der
waals attraction forces and electrical double layer repulsions can present in the
NPs based system depending on whether the surfaces have respectively unlike
and like potentials.
c) NPs with surfactant act as pseudo-solid and due to hydrophilic and hydrophobic
surface of surfactant effectively suspend NPs in the fluid system and create
stable drilling fluid through steric stabilization which potentially improves the lost
circulation.

Figure 2.16: NPs plugging mechanism during drilling (courtesy of nFluids Inc,
reprinted by permission).

47
 Chapter Three: Experimental Methods

This chapter describes the experimental procedures involved in the synthesis of the
different nanoparticles (NPs), preparation of the NP-based drilling fluid, and the
methods and instruments used to characterize the resultant NPs and the performance
of the product fluid. The particles were characterized using TEM, SEM with EDX and
ICP. The drilling fluid, on the other hand, was characterized using Fann mud balance for
density and Fann viscometer for viscosity and the gel strength measurements. The NP-
based drilling fluid lubricity was measured by Ofite lubricity tester and its filtration
properties were evaluated using API low temperature low pressure (LTLP) and high
temperature high pressure (HTHP) tests. Finally, the resultant mud cake was
characterized using SEM and EDX images and its thickness was measured by digital
caliper.

3.1 Drilling Fluid Samples

The invert emulsion muds used in this study were supplied by several Calgary based
drilling fluid companies, while the water-based mud was prepared in-house. Primarily,
two mixes of the invert emulsion drilling fluids were tested; namely 90 oil:10 water (V/V)
and 80 oil:20 water (V/V). The compositions of the invert emulsion and water-based
muds are shown in Table 3.1.

Table 3.1: Compositions of the invert emulsion and water based muds employed in this
work.

Invert Emulsion Mud Water based Mud

Oil: water (V/V) =90:10 or 80:20 Water= 500 mL

Base Oil= Low-aromatic oil Bentonite Clays= 10 g
Brine = 30% Calcium Chloride Surfactant = 0.5 g
Organophillic Clays =15 kg/m3 Xanthan= 1.5 g
Primary Emulsifier= 10 L/m3
Secondary Emulsifier = 5 L/m3

48
The loss circulation material (LCM) content of the drilling fluid, mainly Gilsonite, was
fixed at 1.6 wt% in the invert emulsion mud as recommended by one company. In some
experiments, nonetheless, no LCM was added in order to provide a bench mark to
evaluate NPs as sole loss prevention agents. The experiments mostly cover invert
emulsion based mud characterization, although a number of filtration tests of water
based mud were also performed. The in-house technique for the synthesis of the NPs
developed in this work is a chemo-mechanical process. The unique process has
enabled finely dispersed NPs formation in water-in-oil based drilling fluids as well as
water-based drilling fluids. The severity of the drilling process, nevertheless, may induce
particle agglomeration. However, the surfactants existing in a typical drilling fluid act as
stabilizers and limit agglomeration through steric hindrance (Husein and Nassar, 2008).

The method developed in this work is versatile and different types of precipitates of NPs
were prepared; including Fe(OH) 3, CaCO3, FeS and BaSO4. Complete investigation
was, nevertheless, focused on the performance of Fe(OH) 3 and CaCO3 NPs. The
method above uses two different approaches to prepare the NPs; namely in-situ and ex-
situ. The two terms essentially refer to whether the “birth place” of the NPs is inside or
outside the drilling fluid. The NPs concentration was varied between 1 wt% and 5 wt%
for both in-situ and ex-situ prepared particles.

3.2 NPs and NP-based drilling fluid formation

The choice of Fe(OH)3 NPs was based on the fact that the precursors are inexpensive,
and the product NPs are good scavengers for H 2S that may evolve during drilling
(Husein et al., 2012a; Zakaria et al., 2012;Husein et al., 2010; Nassar et al., 2010).
Hydrogen sulfide is a very toxic and corrosive gas and may easily diffuse into the drilling
fluid from formation during drilling oil and gas wells (Sayyadnejad, 2008). Moreover,
H2S may evolve during completion when acid wash is used to remove metal salts scale
(Nasr-EI-Din et al., 2000). Similar to previous studies (Abdo and Haneef, 2010; Cai et
al., 2012; Srivatsa, 2010; Sensoy, 2009; Manea, 2011; Agarwal et al., 2009; Jimenez et
al., 2003; Paiaman and Al-Anazi, 2008; Roddy et al., 2009; Sayyadnejad et al., 2008),

49
and in order to establish the advantage of the in-house preparation method developed
in this study, commercial NPs were employed at an early stage. Fe2O3 NPs (Nano
structured and amorphous materials Inc, Texas, USA) were used to provide bench
marking. Fe2O3 is a thermally degraded form of iron oxide hydroxide (Balek and Šubrt,
1995). On the other hand, CaCO3 (fine/coarse) is a conventional lost circulation
materials used as a bridging agent and/or weighting material in oil based as well as
water based drilling fluids. The choice of nano CaCO3 in drilling fluid was due to its wide
range of applications in drilling fluid property manipulation from mud weight to fluid loss
control. Apart from those nanomaterials, fluid loss studies were also carried using FeS
and BaSO4. There is a synergy between Fe(OH) 3 NPs and FeS NPs, as the latter is the
final product of the reaction between Fe(OH) 3 NPs with H2S during drilling (Husein et al.,
2010; Nassar et al., 2010). Moreover, both FeS and BaSO 4 (barite) are widely used as
weighting materials in drilling fluids (Chilingarian and Vorabutr, 1983; Moore and
Cannon,1936). They provide the high density needed to balance drilling operations.

3.2.1 Ex-situ preparation of NPs

In the ex-situ method the NPs are formed literally ‘out of place’ meaning the NPs
formation reactions take place outside the drilling fluid. NPs are formed from their
precursors in reaction vials at a standard condition. A general ex-situ NP-based fluid
preparation sequence is shown in Figure 3.1.

Aqueous Aqueous precursor-2 Drilling Fluid

precursor-1
NPs
Slurry
Reaction & mixing NPs mixing with drilling Drilling fluid
at room temp fluid followed by high with desired
(25 °C and 200 rpm) shear action NPs
(2500 rpm @ 30 min)

Figure 3.1: Schematic representation of the ex-situ method for NP-based drilling fluid
preparation.

50
3.2.1.1 Fe(OH)3 NPs
Ferric hydroxide NPs were prepared by first solubilizing a specific amount of anhydrous
iron (III) chloride powder (laboratory grade, Fisher Scientific Company, Toronto, ON,
Canada) in 2 mL deionized water to give final concentration of 2.5 M followed by
addition of a stoichiometric amount of NaOH(s) pellets (Fisher Scientific Company,
Toronto, ON, Canada) under 200 rpm of mixing and 25 oC. The color of the aqueous
solution turned reddish brown signaling the formation of precipitate of Fe(OH) 3(s) as per
reaction (R1).

FeCl3(aq) + 3NaOH(aq)  Fe(OH)3(s) + 3NaCl(aq) (R1)

Part of the particles was recovered for characterization and the rest was mixed with the
invert emulsion drilling fluid in a slurry form. The fluids were mixed/sheared at 2500 rpm
to unifromly disperse the slurry using Hamilton beach mixer.

Similar to invert emulsion drilling fluid, ex-situ Fe(OH)3 NPs were also prepared in
the water based drilling fluid and tested only for LTLP fluid loss performance.

3.2.1.2 CaCO3 NPs

Calcium carbonate NPs were prepared by first solubilizing a specific amount of
anhydrous sodium carbonate powder (99% ACS reagent, Sigma-Aldrich Fine Chemical,
Toronto, ON, Canada) in 5 mL deionized water to give a final concentration of 2.26 M
followed by addition of 1 mL of 7.6 M stoichiometric amount of aqueous calcium nitrate
(99.5%, VWR, USA) under 200 rpm of mixing at 25 oC. The color of the aqueous
solution turned white signaling the formation of precipitate of CaCO 3(s) as per reaction
(R2). Part of the particles was recovered for characterization and the rest was mixed as
a slurry with 500 mL invert emulsion drilling fluid. The fluids were mixed/sheared at
2500 rpm to unifromly disperse the slurry ‎using Hamilton beach mixer.

Ca(NO3)2(aq) + Na2CO3(aq)  CaCO3 (s) + 2 NaNO3 (aq) (R2)

51
 Similar to invert emulsion drilling fluid, ex-situ CaCO3 NPs were also prepared in
the water based drilling fluid and tested only for LTLP fluid loss performance.

3.2.1.3 FeS NPs

Iron (II) Sulfide NPs were prepared by solubilizing a specific amount of aqueous sodium
sulfide (laboratory grade, Fisher Scientific Company, Toronto, ON, Canada) with
aqueous iron (II) chloride (laboratory grade, Fisher Scientific Company, Toronto, ON,
Canada). First, a specific amount of aqueous iron (II) chloride was solubilized in 1 mL
deionized water to give a final concentration of 3.4 M followed by the addition of 4 mL of
0.9 M stoichiometric amount of aqueous sodium sulfide and mixing at 200 rpm and
25oC. The color of the aqueous solution turned black signaling the formation of
precipitate of FeS(s) as per reaction (R3). Finally, the product was mixed with the drilling
fluid as a slurry using Hamilton beach mixer and sheared at 2500 rpm.

Na2S(aq) + FeCl2(aq)  FeS(s) + 2 NaCl (aq) (R3)

3.2.1.4 BaSO4 NPs

Ex-situ preparation of barium sulfate NPs followed the same procedure as above. A
specific amount of aqueous barium chloride (Sigma-Aldrich, Toronto, ON, Canada) was
reacted with aqueous sodium sulfate (VWR, Calgary, Canada) under 200 rpm of mixing
at 25oC. First, a specific amount of aqueous barium chloride was solubilized in 3 mL
deionized water to give a final concentration of 1.14 M followed by the addition of 3 mL
of 1.14 M stoichiometric amount of aqueous sodium sulfate. The color of the aqueous
solution turned white signaling the formation of BaSO 4(s) as per reaction (R4). Finally,
the product slurry was mixed with the drilling fluid using the Hamilton beach mixer and
sheared at 2500 rpm to achieve a homogenous mixture.

Na2SO4(aq) + BaCl2(aq)  BaSO4(s) + 2 NaCl (aq) (R4)

52
 3.2.2 In-situ preparation
The term in-situ NPs is used to mean that NPs were created in place. NPs were formed
from their precursors by reactions in the drilling fluid. Formation of NPs in this manner
minimizes particles aggregation and allowing easier handling than ex-situ prepared
NPs. A general in-situ NP-based fluid preparation scheme is shown in Figure 3.2. The
in-situ NPs preparation was used to prepare NP-based drilling fluid in invert emulsion as
well as water based muds.

Aqueous precursor -2 with

drilling fluid
Aqueous precursor -1
with drilling fluid Reaction, mixing and high shear action
with drilling fluid at room temperature Drilling fluid with
(25 °C, 200 rpm and 2500 rpm @30 min) desired NPs

Figure 3.2: Schematic representation of in-situ NP-based drilling fluid.

3.2.2.1 Fe(OH)3 NPs

In invert emulsion drilling fluid, this scheme of NPs synthesis followed the two
microemulsion method as per Husein and Nassar (2008). A 1 mL of 5 M FeCl3(aq) was
added to 250 mL of the drilling fluid and mixed at 200 rpm for 24 h. In a separate vial, 1
mL of 16 M NaOH(aq) (stoichiometric amount) was added to 250 mL of the drilling fluid
and mixed at 200 rpm for 24 h. The two vials were mixed and left overnight at 200 rpm
and 25oC. Two control samples were prepared, one containing the FeCl3(aq) in the
drilling fluid and another containing the NaOH (aq) in the drilling fluid, and the samples
were left to mix overnight at 200 rpm and 25 oC. Finally, and in order to achieve a
uniform mixture of the fluid was sheared using Hamilton beach mixer at 2500 rpm. It is
worth noting that no phase separation was observed in the experimental as well as the
control samples, even after a period of 4 weeks.

Similar to invert emulsion drilling fluid, in-situ Fe(OH)3 NPs were also prepared in
the water based drilling fluid and tested only for LTLP fluid loss performance.

53
3.2.2.2 CaCO3 NPs
Calcium Carbonate NPs were prepared in-situ in invert emulsion drilling fluids using two
different methods as per the reaction R2 and R5. The first method followed exactly
Fe(OH)3 NPs preparation presented in Figure 3.2. A 5 mL of 2.2 M sodium carbonate
was added to 250 mL of the drilling fluid and in a separate vial 1 mL of 7.6 M aqueous
calcium nitrate was added to 250 mL of the drilling fluid. The samples were left to mix
overnight at 200 rpm and 25oC. Finally, fluids were sheared at 2500 rpm again by the
Hamilton beach mixer before testing.
Similar to invert emulsion drilling fluid, in-situ CaCO3 NPs were also prepared in
the water based drilling fluid using the first method and tested only for LTLP fluid loss
performance.
The second method of in-situ synthesis of calcium carbonate NPs in invert
emulsion drilling fluid employed reaction (R5). Carbon dioxide, CO2 (99.9% purity,
Praxair, Edmonton) and Ca(OH)2 (92 % Purity, Canamara United Supply, Calgary) were
used as the precursors. First, 3 g Ca(OH)2 was added to 6 mL of water and then mixed
overnight at 200 rpm and 25 oC. The calcium hydroxide solution was added to 500 mL
invert emulsion drilling fluid and sheared at 2500 rpm using a Hamilton beach mixer for
30 min. Carbon dioxide, CO2, gas was allowed into the drilling fluid sample through a
sparger for 10-20 min until pH changed to neutral. The pH of the invert emulsion drilling
fluid was roughly estimated using a pH paper. The mechanism leading to CaCO3 NPs
formation included CO2 transport to the water pools through the organic phase, reaction
in the water pools, Brownian collisions leading to material exchange, nucleation of
CaCO3, particle growth and may be aggregation due to Brownian collisions
(Bandyopadhyaya et al., 2001). Finally, to ensure uniform dispersion of the NPs ‎ a
Hamilton beach mixer was used at 2500 rpm. Figure 3.3 is a schematic representation
of the experimental procedure used to form the NPs as per reaction (R5). This approach
has serves within borehole NPs preparation, which may reduce particle aggregation
upon shearing drilling fluid through the drill bit. It may also help controlling CO2
emissions and converting it into value added product.

54
 Ca(OH)2 (aq) + CO2(g)  CaCO3 (s) + H2O (R5)

Reaction pathways as per Soony et al. (2002) involves the following steps.

CO2(g) CO2(aq) (R6)

CO2(aq) + H2O H2CO3 ; pH= 4 (R7)

H2CO3 H+ + HCO3- (R8)

HCO3- H+ + CO3 2- (R9)

Ca2++CO3 2- CaCO3 ; pH= 8 (R10)

Figure 3.3: Schematic of In-situ prepared CaCO3 NPs-based drilling fluid using CO2.

3.2.2.3 FeS NPs

In-situ Iron (II) Sulfide NPs were prepared by the method presented in Figure 3.2, and
only invert emulsion was employed here. First, 1 mL of 3.4 M aqueous iron (II) chloride

55
was added to 250 mL of the drilling fluid and in a separate vial 4 mL of 0.9 M aqueous
sodium sulfide was added to 250 mL of the drilling fluid. The samples were left to mix
overnight at 200 rpm and 25 oC. Finally, to ensure good dispersion product NPs, the
invert emulsion mud was sheared at 2500 rpm by a Hamilton beach mixer for 30 min.

3.2.2.4 BaSO4 NPs

In-situ preparation of barium sulfate NPs followed the same procedure as above, and
again, only invert emulsion muds were employed. First, 3 mL of 1.14 M aqueous barium
chloride was added to 250 mL of the drilling fluid and in a separate vial 3 mL of 1.14 M
aqueous sodium sulfate was added to 250 mL of the drilling fluid. The samples were left
to mix overnight at 200 rpm and 25 oC. Finally, to ensure good dispersion ‎product NPs,
the invert emulsion mud was sheared at ‎2500 rpm by a Hamilton beach mixer for 30
min. ‎

3.3 Characterization methods and techniques

3.3.1 Particle characterization
The ex-situ prepared NPs were characterized using X-ray diffraction patterns and
transmission electron microscopy, whereas the in-situ prepared NPs were characterized
as part of the mud cake following deposition on the filter paper using energy dispersive
X-ray spectroscopy.
The ex-situ prepared NPs were collected by centrifuging the aqueous colloidal
suspension at 5000 rpm for 30 min to recover the NPs followed by washing several
times with deionized water. The particles were left to dry at room temperature for 24 h.
The dried particles were ground using a pestle and mortar before been introduced to
Ultima III and Ultima IV Multipurpose Diffraction system. Ultima III operating at 40 KV
and 44 mA and Ultima IV operating at 40 KV and 40 mA use Cu Kα and Co Kβ radiation
respectively (Rigaku Corporation, USA) with a θ–2θ goniometer. Each scan used a 2°
step size from 0 to 90° for Ultima III and 5 to 90° for Ultima IV with a counting time of
2 ‎s/step. The structure was identified by comparing the diffractograms with spectra in
the JADE ‎program, Materials Data XRD Pattern Processing Identification &

56
Quantification. Ultima III and Ultima IV were used for Fe(OH)3 and CaCO3 based NPs
structure identification respectively. The particle size distribution was determined using
transmission electron microscopy, TEM. A small amount of the powder used for XRD
analysis was dispersed in 5 mL of methanol using sonication and one drop of the
methanol dispersion was deposited on a copper grid covered with carbon film, and was
left to evaporate for 24 h. In order to avoid possible aggregation upon methanol
evaporation, only a thin layer was deposited on the copper grid. The grid was then
introduced to a Philips Tecni (FEI USA Inc., Hillsboro, OR) TEM equipped with 200 kV
Field Emission Gun and Gatan ‎Imaging Filter (GIF) with a slow scan CCD camera. ‎
The in-situ prepared NPs, on the other hand, were characterized following their
collection on the filter cake. Filter cake of drilling fluid was dried at room temperature
(~25o C) for 4 days. The samples were then mounted and gold vapor applied to the
surface of the dried filter cake to create an electrically conductive layer necessary for
SEM photographs. In addition, an electrically conductive carbon particle suspension
was used to glue the filter cake sample to pedestal. Oil based mud needed more time to
achieve good gold coat, whereas water based mud took less time. Scanning electron
microscopy (SEM) analysis was performed on a FEI ESME XL30 (Philips XL30 ESEM,
USA). The instrument uses 20 kV acceleration voltage, WD= 10 mm with secondary
and backscattered electron signal. The images were taken under high vacuum mode
and recorded with a slow scan camera. Elemental analysis of the mud cakes was
performed with the energy-dispersive X-ray spectrometry (EDX) attached to the SEM.

3.3.2 Toxicity evaluation

The assessment of the environmental effects requires an evaluation of the NPs
ecotoxicity. The Microtox bioassay was used to assess the toxicity of the Fe(OH)3 NPs
only. Samples were analyzed using Microtox method (EC50 % at 15 min) in an external
lab (Kaizen Lab, Calgary, Canada). The effective concentration, EC50, is defined as the
concentration that produces a 50% light reduction (García et al., 2011) and was
measured after 15 min contact time. The test system measured the light output of the
luminescent bacteria of the NPs sample and compared it to the light output of a control

57
sample containing no NPs. A difference in light output between the sample with NPs
and the control was attributed to the effect of the NPs on the organisms. Microtox is a
qualitative test of toxicity and the protocol of testing is shown as follows (Kaizen Lab,
Calgary, Canada).

Aqueous extraction of solid samples

Create dilution

Determine EC50 (15°C,15 min)

Pass : EC50 ≥ 75%; Non-toxic

Fail : EC50< 75%; Toxic

3.3.4 Emulsified water droplet measurement

Water-in-oil invert emulsions with primary emulsifier were prepared using 10 v/v%
water, which is the same as the drilling fluid, except for the fact that solids were not
added. The water droplet diameters of the invert emulsion were measured using
Morphologi G3 microscope (Malvern Instruments Inc, USA).

3.3.5 Drilling fluid characterization

The filtration properties of the different drilling fluids involved in this study were
measured according to API 30-min test (API RP 13B-2,2012; API RP 13B-1,2003).
Data were collected using a standard FANN filter press (Fann Model 300 LTLP, Fann
Instrument Company, USA) and filter paper (pore size 2.7 µm, Fann Instrument
Company, USA). The low temperature low pressure (LTLP) test was conducted
according to the following procedure. A volume of 500 mL of the drilling fluid was
poured into the filter press cup and 100±5 psi of pressure was applied through CO 2
supply cylinder at room temperature of 25oC. The cumulative volume of permeate was

58
reported after 7.5 min and 30 min from the graduated cylinder reading. Three replicates
were prepared for every sample and 95% confidence intervals are reported in the
results. The smoothness of the final filter cake was reported through visual observation,
while the thickness was measured using a digital caliper (0-6˝ TTC Electronic digital
calipers model # T3506, Canada). The concentration of the NPs in permeate was
correlated to iron and calcium concentration measured by an inductively coupled
plasma (ICP) (IRIS Intrepid IIXDL, Thermo Instruments Canada Inc., Canada). A
portable 175-mL Ofite high temperature high pressure (HTHP) filter press (OFI Testing
Equipment Inc, USA) and filter paper (pore size 2-5 µm, specially hardened for filter
presses, Fann Instrument Company, USA) was used to study the filtration
characteristics of the mud at differential pressure of 500 psi and temperatures of 177°C
(350oF). Fann LTLP and Ofite HTHP filter presses are shown in Figure 3.4.

a) b)

Figure 3.4: Drilling fluid loss apparatus for a) LTLP and b) HTHP tests.

It should be noted that the area of the filter paper used in the HTHP filter press is one-
half the area of the standard filter press. Therefore, the volume of filtrate collected in 30-
min is typically reported as double. Commercial invert emulsion drilling fluid without NPs
and LCM (Gilsonite) and with 1.6 wt% LCM only were considered as baseline drilling
fluids for comparative evaluation of API and filtration experiments. Invert emulsion

59
drilling fluids containing NPs and 1.6 wt% LCM or NPs only were considered as the
nano-based drilling fluids of study.
Fann Model 140 mud balance (Fann Instrument Company, USA) was used to
measure the mud density. During the measurement care was taken in order to eliminate
any errors due to air entrapment. The pH measurements were performed using pH
papers (0-14) (VWR international, Calgary, Canada). Several readings were collected in
order to ensure precision, despite the limitations of pH determination using pH paper,
since a pH meter could not be inserted in the mud. In addition, and in order to provide
more reliability for the method, hydrated lime, similar to the one used in drilling fluid,
was dissolved in water at the same concentration as the water in the drilling fluid, and
its pH was measured using pH meter (Model: AccumetAB15+,Fisher Scientific, Toronto,
Canada ) and pH papers.

A rotational Fann 35A viscometer (Fann Instrument Company, USA) was used to
measure the rheological properties of the drilling fluid at six different speeds as shown
in Figure 3.5.

Figure 3.5: Fann Model 35A viscometer for measuring viscosity.

A volume of approximately 350 mL of the fluid was poured into the viscometer cup, and
the mud was sheared at a constant rate in between an inner bob and outer rating
sleeve. The system was left to rotate at a certain rpm until reaching the steady state
reading for 5 min. The readings were collected at 600, 300, 200, 100, 6 and 3 rpm.
These experiments were conducted at room temperature. The dimensions of bob and

60
rotor were chosen such that the dial reading on the viscometer is equivalent to apparent
viscosity in centipoises at rotor speed of 300 rpm. The apparent viscosities for all rotor
speeds were calculated using equation (E3.1) below (Fann 35 viscometer manual,
2008):
 
Apparent/ Effective viscosity, μa = 300   (E3.1)
N
where N is the rotor speed (rpm) and  is the viscometer dial reading (o). The shear rate
can be calculated as per equation (E3.2) (Fann 35 viscometer manual,2008).

Shear rate, sec-1 = 1.7023N (E3.2)

The plastic viscosity and yield point are found using the following equations (Fann 35
viscometer manual, 2008):
Plastic viscosity, μp = ϴ600 - ϴ300 (E3.3)
Yield point, Yp = ϴ300 - μp (E3.4)
where μp plastic viscosity (cP), Yp yield point (lbf/100ft2), ϴ600 and ϴ300 are the dial
readings at 600 and 300 rpm, respectively.

Gel strength of the drilling fluid was measured at lower shear rate after the drilling mud
is static for a certain period of time. The readings at 3 rpm were taken after 10 sec and
10 min following stirring the drilling fluid at 600 rpm for 5 min. The first reading noted
after the mud is in a static condition for 10 sec is called 10 sec gel strength. The second
gel strength noted after 10 min is called 10 min gel strength. Gel strength is usually
expressed in pressure unit lbf/100ft2. The difference between the initial gel strength and
those taken after a 10 min test period were used to define how thick the mud would be
during round trips.
Lubricity test is designed to simulate the speed of rotation of the drill pipe and the
pressure the pipe bears against the wall of the bore hole (OFITE lubricity test manual,
2011). It also predicts the wear rates of mechanical parts in known fluid systems.
Lubricity property of the NP-based drilling fluid was evaluated by OFITE Lubricity Tester
(Part no: 111-00, serial: 07-09, Houston, USA) at 150 inch-pounds of torque which are

61
applied to two hardened steel surfaces, a block and ring rotating at 60 rpm rotational
speed as shown in Figure 3.6.

Figure 3.6: OFITE drilling fluid lubricity tester.

The test sample is completely immersed between the ring and block. The apparatus
runs for 5 min in order to coat the metal test pieces with the sample fluid. The torque
adjustment handle is then turned until 150 inch-pounds of torque have been applied to
the test block. The machine again runs a 5 min stabilization period. A friction coefficient
reading is then taken. Additional readings are taken every 5 min until three consecutive
readings agree within ±2 units. The drilling fluid lubricity coefficient can be calculated
using the following equation as given in the Ofite manual (Ofite lubricity tester manual,
2011).
lb force to turn the ring Meter Reading
Coefficient of friction = = (E3.5)
lb torque load applied 100
Coefficient of Friction (CoF) is used to quantify how readily two surfaces slide in the
presence of a lubricant or oil. It is a key factor which directly affects the torque and drag.
The lower the value of the coefficient of friction, the higher the lubricity, or vice-versa.
The torque reduction at a given load can be calculated using the following equation.
(AL  BL )
Percent torque reduction at given load = x 100 (E3.6)
AL
where AL = Torque meter reading of untreated mud (inch-pounds)
BL = Torque meter reading of treated mud (inch-pounds)

62
 Chapter Four: Results and Discussion

Initially the experimental analysis was performed on the base drilling fluid, mostly invert
emulsion containing all ingredients, e.g. organophilic clays, primary and secondary
emulsifiers, brine, etc. except for the lost circulation materials (LCMs), to understand the
nature of the fluid loss, and later with drilling fluid containing conventional LCMs, i.e.
Gilsonite. The next step was to test these fluid systems in the presence of in-house
prepared nanoparticles (NPs), and commercial Fe2O3 NPs. Concentrations between 1-4
wt% NPs were used depending on the stability of the NPs in the drilling fluid (Husein et
al., 2012 a&b; Zakaria et al., 2012). Needless to say that low concentrations were
targeted to study large-scale application. Results pertaining to the detailed preparation
and performance of Fe(OH)3 NPs are presented first. Then, the preparation and
performance of CaCO3 NPs were considered in details, due to the wide application of
CaCO3 particles in drilling fluids (Manea, 2012; Simon et al., 2010; Whitfill at al., 2003).
Finally the preparation and performance of BaSO4 and FeS NPs were considered in
order to prove the applicability of the in-house preparation method developed in this
work to other NPs. It should be noted also that BaSO4 and FeS are widely used as
weighting material in drilling fluids (Scott and Robinson, 2010; Moore and Cannon,
1936). In all cases the NP-based fluids were compared with the corresponding control
DF samples. The use of NPs to increase the mud density, while minimizing sagging was
demonstrated by other groups (Amanullah et al., 2011). Therefore, the characteristics of
NP-based DF were evaluated by measuring mud weight, pH, viscosity, gel strength, API
LTLP and HTHP filter tests and lubricity as described in Chapter 3.

4.1 Fe(OH)3 Nanoparticles (NPs) Characterization

The structure of the ex-situ prepared Fe(OH)3(s) NPs was determined using X-ray
diffraction (XRD) patterns, whereas its particle size distribution was evaluated using
TEM photographs. Detailed particle characterization is provided herein.

63
4.1.1 X-ray diffraction analysis
The X-ray diffraction pattern of the ex-situ prepared NPs shown in Figure 4.1 indicates
no evidence of strong distinct peaks which would be expected from a crystalline
material. This said, the most likely product as suggested by the figure is Fe(OH)3(s). The
peak maximum around 2θ= 35° can be attributed to the presence of aggregates
dispersed in an amorphous phase (Zakaria et al., 2012). Streat et al. (2008) has also
prepared ferric hydroxide using ferric chloride and stoichiometric quantity of sodium
hydroxide in deionized water and reported the same XRD pattern.

Figure 4.1: X-ray diffraction pattern for the ex-situ prepared iron-based NPs.

Reaction pH might affect the final nature of the iron oxide/hydroxide product. The
optimum pH for the precipitation of Fe(OH) 3(s) is found 5 (Zakaria et al., 2012). Liu et al.
(2005) reported the same initial pH level of the precipitated amorphous Fe(OH)3
prepared from aqueous FeCl 3 and NaOH precursors. Phase transformation of Fe(OH)3
gel to α-Fe2O3 particles was impacted by the pH range. In a different study, Cai et al.
(2001) found that at room temperature the reaction pH affected the crystallinity of iron
oxide material. They reported narrow and distinct peaks for 1.5≤ pH< 4. At pH= 4 there
were two broad and less intense peaks similar to the ones appearing in Figure 4.1
suggesting poor crystallinity. At pH≥ 6, crystallinity was re-gained. It is to be noted that
64
amorphous iron (III) hydroxide can transform into α-Fe2O3, β-FeOOH or α-FeOOH with
the change in reaction temperature (Nassar and Husein, 2007a). The X-ray diffraction
pattern of a filter cake collected following LTLP test of a drilling fluid containing ex-situ
prepared Fe(OH)3 NPs and organophilic clays is shown in Figure 4.2. The pattern in
Figure 4.2 suggests that Fe(OH)3 NPs acted as intercalating agents and had entered
into the crystallite layers of bentonite clay. It is believed that such a structure of
nanometal-clay composite could improve drilling fluid properties; including loss
prevention and wellbore strengthening. In addition, this structure suggests good
compatibility, dispersion and communication between the NPs and the rest of the drilling
fluid constituents, which ultimately could offer better functionality than regular bentonite
clays. NPs embedded randomly on the surface of clay particles promote gelation of the
bentonite particles (Baird and Walz, 2006; Lee et al., 2010). Similar observation was
also reported by Fernandez et al. (2010) using acrylamide polymer with bentonite clays.
An important outcome of good gelation is inhibition of clay swelling as reported by Mei
et al. (2011).

Figure 4.2: X-ray diffraction pattern of ex-situ prepared Fe(OH)3 NPs collected on the
filter paper.

65
4.1.2 Water droplet size distribution
Emulsion samples were prepared by mixing water with the similar type base oil (low
aromatic oil) and the primary emulsifiers used in the drilling fluids formulation but no
solids, i.e. bentonite, were used. The water droplets were observed in the oil phase by a
microscope. It was clear that 10/90 (V water/V oil) contained droplets size from 1-30 µm
with mean droplet diameter at 20 µm as shown in Figure 4.3. Water-in-oil (w/o)
microemulsions have been demonstrated as a very versatile and reproducible method
that allows control over nanoparticle size and yields particles with a narrow size
distribution (Lopez-Quintela, 2003), by virtue of their nanometer scale water pools. In
principle, invert emulsion drilling fluid can be employed in a similar manner to prepare
NPs. However, knowing the fact that invert emulsions typically contains much larger
water pools, as shown in Figure 4.3, mixing becomes a very important parameter. In
studies by Anisa and Nour (2010) and Fjelde (2007), it was shown that stirring speed
largely affects the droplet size distribution in (w/o) emulsions. Higher shearing and
duration of stirring lead to a very tiny droplets, which can act as nanoreactors. In this
works, the NPs were stirred at 200 rpm during preparation and sheared in the drilling
fluid at 2500 rpm, which enabled them to accommodate into the water pools effectively.

Figure 4.3: Particle size distribution histogram of water droplet obtained from a water-
in-oil emulsion by dispersing water into base-oil with the aid of a primary emulsifier.

66
As can be seen in Figure 4.3, most of the droplets were 11-20 µm in diameter. It should
be noted, nevertheless, that the detection limit of the instrument used was down to 0.5
μm in size. Therefore, Figure 4.3 should be considered with caution. Similar experiment
has been performed by Fjelde (2007) for 25/75 and 5/95 (V water/V oil) emulsions in the
presence of primary and secondary surfactants and water droplet sizes between 3-50
μm were reported for both mixes at different temperatures. Generally, the water droplets
in an emulsion may vary in size from less than 1 μm to more than 1000 μm (kokal,
2006). Typically in oil based drilling fluids, macroemulsion, which may have droplet
sizes in the range from 0.1-100 μm (Kokal, 2006; Bumajdad et al., 2011), are used.
Generally microemulsions consist of nano-sized water pools dispersed within the
bulk organic phase which act as nanoreactors for the chemical reduction of the metallic
precursors and metallic nanoparticle preparation (Kitchens,2004). Size of the particles
can be controlled by surfactant/co-surfactant type, concentration of the reagents and
water/surfactant molar ratio (Zielińska-Jurek et al.,2012). The total concentration of
metal ions under the present experiment is so small that the influence of water droplet
size has no great influence on the nanoparticles formation and growth. Moreover, the
primary and secondary surfactant rich ‎stabilized invert emulsion fluid limit particle
growth and agglomeration of metal ‎particles in water pools and renders particle sizes in
the nm scale (Husein and Nassar, 2008). ‎

4.1.3 Size distribution of ex-situ prepared Fe(OH)3 NPs

The TEM photographs and the corresponding particle size distribution histogram for the
ex-situ prepared Fe(OH)3 are shown in Figure 4.4. The histogram shows a spread in the
size distribution with most of the population falling in the range between 1-30 nm. The
photograph confirms that there is good degree of agglomeration, which must have
resulted from the high degree of collision between the precipitated particles while
shearing, especially since no surfactants were added to the aqueous phase.

67
a) TEM Photographs Particle Sizes from 1 to 120 nm b) Particle Sizes from 1 to 30 nm

100 nm

Particle size (nm)

Figure 4.4: TEM photographs and corresponding particle size distribution histograms of
the ex-situ prepared Fe(OH)3 NPs in the range between a) 1-120 nm and b) 1-30 nm.

Dispersing the ex-situ prepared NPs by ultrasonication in methanol for 10 min before
deposition on the TEM grid did not seem to eliminate aggregation, despite the fact that
the NPs were not found to exhibit magnetic properties. Therefore, it is concluded that
this agglomeration at room temperature is not due to magnetic attraction, but rather due
to the high surface energy of the particles (Bumajdad et al., 2011). Once mixed with the
drilling fluid, the surfactant rich stabilized invert emulsion, or water-based muds, limits
the aggregation of the ex-situ prepared particles, especially since the concentration of
NPs in the drilling fluid is kept very low, < 5 wt%. On the other hand, in-situ prepared
NPs are expected to be very well dispersed by virtue of the surfactant component of the
drilling fluid mix.
The wide size distribution of particles has prompted an investigation on the
filtration characteristics of LCM-free NP-based drilling fluid. The results of this
investigation are detailed below.

4.1.4 Determination of particle size of in-situ prepared Fe(OH)3 NPs

When NPs are prepared in-situ within invert emulsion drilling fluids, it is not easy to
separate the particles for characterization. Alternatively, these particles could be
characterized following their collection on the mud cake. SEM images of the mud cake

68
without and with NPs are shown in Figure 4.5a,b, respectively. The observed
morphologies of the two samples have some distinct features. The mud cake with NPs
was fully intact and displayed a very smooth surface with no visible cracks at even 48
times magnification. It is worth noting that the cake surface was covered with Fe(OH)3
particles, as was visually confirmed from the reddish brown color of the surface. The
texture of the mud cake in the absence of NPs was rough and full of cracks. It is,
therefore, plausible to believe that the voids and gap of pores were effectively filled with
NPs, and NPs acted as an effective filling agent. This said, one should also keep in
mind the effective intercalation between Fe(OH)3 NPs and the organophilic clays
reported earlier. These observations are very important for the explanation of fluid loss
prevention and lubricity reported in this study as well as wellbore strengthening reported
in a recent study, which employed the same method and NPs developed in this study
(Nwaoji et al.,2013; Nwaoji,2012). Lastly, effective adsorption/deposition of Fe(OH) 3
NPs on the organophillic clays forming the ‎cake may also contribute to a surface
chemical reactivity, which can provide further sealing. Lai et ‎al. (2000) reported that
Cu2+ ions were effectively adsorbed onto iron oxide-coated ‎sand. Finally, it is important
to note that mud cakes tested were LCM free.

a) b)

Crack

Figure 4.5: SEM Images at 48x magnification of mud cakes collected following API
LTLP filtration tests a) without NPs, b) with 1 wt% in-situ NPs (90/10(v/v) oil/water invert
emulsion mud, no LCMs).

69
The elemental distribution mapping of EDX for the sample of mud cake without NPs and
mud cake with NPs are depicted in Figure 4.6. Through elemental analysis it was
determined that 0.7 wt% of iron ion was found on the mud cake. Results indicated that
iron ions could trap into the micropores and mesopores of the cake-containing clays. It
can be also attributed to diffusion of adsorbed metal species from the surface into the
nanopores, which are the least accessible sites of adsorption. This is believed to
contribute to effective sealing while filtering.

Figure 4.6: Elements contained in mud cake a) without NPs, b) with Fe(OH)3 NPs as
per EDX analysis.

4.2 Drilling fluid Characterization

4.2.1 Stability of NP-based Fluid
Visual observation was used to assess the stability of the NP-based fluids. Stability
against agglomeration and sagging relates here to the ‘shelf life’ of the NP-based fluid.
Figure 4.7 shows photos of samples representing the original drilling fluid (90 vol. oil/10
vol. water) invert emulsion samples without and with in-situ prepared Fe(OH)3 NPs. The
photos show no sign of sagging or aggregation even after 4 weeks of setting at room
temperature and confirm that, at the concentration of the added NPs, no agglomeration
or sagging takes place. Therefore, no extra additives were required to stabilize the NP-
base drilling fluid. The stability of an invert emulsion system containing dispersed
particles can be attributed to a steric effect conferred by adsorbed materials, mostly

70
surfactant molecules, onto the particles (Husein and Nassar, 2008; Nassar and Husein,
2007a). Careful evaluation of the system stability as a result of NPs addition showed
that no sagging was experienced for the different NPs considered in this work; including
Fe(OH)3, CaCO3, BaSO4 and FeS, up to 5 wt% and stable samples are obtained for
several weeks. This applies to both, in-situ prepared NPs and NPs prepared ex-situ and
then mixed with the drilling fluid.

a) b)

NP-based Fluid Original Drilling Fluid

NP-based Fluid Original Drilling Fluid

Figure 4.7: Photos comparing NP-based and original invert emulsion drilling fluids
(Invert emulsion (90 vol. oil/10 vol. water); 1 wt% Fe(OH) 3 in-situ prepared NPs).

NPs that grow or agglomerate to sizes beyond the stabilization capacity of invert
emulsion fluid might settle under gravity, which was not apparent in the above photos.
This suggests that the mixing provided during the preparation of in-situ and ex-situ NPs
as well as during mixing of ex-situ prepared NPs with the drilling mud was sufficient to
provide dispersion at a molecular level, which, in turn, leads to the formation of very
small particles that are well dispersed and stabilized in the rest of the fluid. As stated
earlier, adsorption of emulsifiers on the surface of these particles helps further
stabilizing them within the fluid. A qualitative assessment of the stability of the
nanobased fluid was done by checking its rheology behavior after 1 month which is
detailed in the rheology section.

4.2.2 LTLP Filtration

Filtration property is dependent upon the amount and physical state of colloidal
materials used in the mud. When mud containing sufficient colloidal material is used,

71
fluid loss can be minimized as these materials will deposit and contribute to cake
formation, which increases resistance for fluid permeation. This resistance is highly
dependent on the structure and integrity of the filter cake. Details on the integrity and
structure of the cake were provided earlier. On the other hand, the spurt loss of the
drilling fluid is considered as one of the sources of solid particles and particulate
invasion to the formation, which can cause serious formation damage as a result of
internal mud cake formation in the vicinity of the wellbore (Amanullah et al., 2011; Al-
Hitti et al, 2005; Peng, 1990). Internal pore throat blockage may create a flow barrier
which reduces oil and gas flow. Moreover, higher particle flocculation in drilling fluid
leads to a thicker mud cake which increases the probability of differential sticking and
stuck pipe problems (Amanullah et al., 2011). This highlights the importance of using
low concentration of dispersed NPs in fluid design with virtually no spurt loss, low filtrate
volume and good quality filter cake.

4.2.2.1 Commercial NPs

At first, commercial iron oxide NPs were introduced into the commercial invert emulsion
drilling fluid as per literature procedure (Agarwal et al.,2009; Amanullah et al., 2011;
Srivatsa, 2010; Abdo and Haneef,2010), which involved mixing at 2500 rpm for 30 min.
This experiment served as bench marking. The performance towards fluid loss
prevention was very poor as can be seen in Table 4.1. It is to be noted that the original
drilling fluid (DF) was completely LCM free. A large amount of small ‘fish eyes’ (lumps of
agglomerated commercial NPs) on the NP-based mud cake was clearly seen, as shown
in Figure 4.8. It appears that, even under the high shear mixing used to prepare the in-
house NPs, commercial NPs did not seem to effectively disperse into the drilling fluid.
This, in a way, limited their interaction with the clays and resulted in a poorly structured
filter cake. The mud cake in the absence of NPs was provided for comparison. The
thickness of the mud cake developed upon filtering commercial NP-based drilling fluid
was 0.76 mm, whereas the one obtained from filtering the invert emulsion mud was 0.31
mm.

72
Table 4.1: API LTLP loss of drilling fluid in the presence and abscense of 1 wt%
commercial Fe2O3 NPs. NPs were thoroughly mixed with the invert emulsion drilling
fluid. No LCMs added to both samples.

Commercial LPLT Fluid Loss (mL) Fluid Loss

Samples Time
NPs Used Reduction
Types (min) DF with
(20-40 nm) DF %
1 wt% NPs
90:10 (v/v) 7.5 1.7±0.6 1.7±0.6 0
Fe2O3/FeOOH
Oil: Water 30 4.5±0.6 4.2±0.6 6.67

fish eyes

Commercial NP-based mud Mud cake without NPs

cake

Figure 4.8: Mud cake of drilling fluid with commercial NPs and without NPs.

4.2.2.2 In-house prepared Fe(OH)3 NPs

Following the hypothesis outlined earlier; in-house prepared NPs may better
interact ‎with the drilling fluid, especially the in-situ formed ones, in-house prepared
Fe(OH)3‎ NPs were formulated inside, or added to, the drilling fluid. In-house ‎Fe(OH)3‎
NPs at 1 wt% and size varying from 1-120 nm had better plugging performance
than ‎commercial Fe2O3 NPs and will be detailed in the fluid loss experiments. ‘Fish
eyes’, which ‎appeared in the mud cake containing the commercial NPs, were minimized
in the presence ‎of the in-house; both ex-situ and in-situ, formulated NPs as can be seen

73
in Figure 4.9 and 4.10. Moreover, NaCl, which is a by-product of the Fe(OH)3 formation
reaction, is commonly used as ‎a bridging solid to prevent clay swelling and clay
dispersion, which, in turn, lead to the ‎minimiiinm clay related formation damage (Mohan
et al., 1993; Crowe ,1990). ‎
Generally, the characteristics of the resultant filter cake depended on the degree
of peptization or ‎flocculation of the suspension. Stable (peptized) suspensions form
dense and ‎compact sediments, while flocculated suspensions form more voluminous
sediments ‎and particles are associated in the form of a loose, open network (Smith and
Hartman, 1987). Filter cake ‎formed from stable dispersion of NPs is relatively
impenetrable, and hence, creates more resistance to flow in comparison to that formed
from flocculated commercial NPs. This might explain why in-house prepared NPs
showed better performance. ‎In-house prepared NPs are better dispersed in the drilling
mud. Therefore, they effectively adsorbed into the pore space of clay platelets and
formed well dispersed plastering effect on the filter paper. This implies lower penetration
of drilling fluid into the formation and, hence lesser damage to the formation. In-house
prepared NPs progressively built up on the surface of the filter cake and acted as a shut
off valve. Effective mud cake resulted in much lower fluid loss as can be clearly seen in
Table 4.2.

Table 4.2: Comparative study of API LTLP fluid loss of drilling fluids with 1.6 wt%
conventional Gilsonite LCM, and 1 wt% in-situ and ex-situ prepared NPs.

Time LTLP Fluid Loss (mL)

Samples
Types (min) DF DF +LCM DF+LCM with 1 DF+LCM with 1
wt% ex-situ NPs wt% in-situ NPs
90:10 (v/v) 7.5 2.0±0.2 1.4±0.2 0.2±0.2 0
Oil: Water 30 3.96±0.2 3.6±0.1 (9%*) 1.1±0.1 (72%*) 0.5±0.2 (87%*)
Cake thickness, mm 0.31 0.76 0.52 0.44
*Fluid loss reduction, %.

Original drilling fluid (DF) without NPs and LCM and drilling fluid with 1.6 wt% LCM were
considered as a baseline for comparative evaluation of fluid loss property of the ex-situ

74
and in-situ prepared nanobased fluid. Based on the original DF, fluid loss over a period
of 30 min decreased by 9% for the drilling fluid containing 1.6 wt% LCM only, while it
decreased by 70% for the drilling fluid containing 1 wt% ex-situ prepared Fe(OH)3 NPs
and by more than 80% for the drilling fluid containing the in-situ prepared Fe(OH)3 NPs.
Both ex-situ and in-situ drilling fluid samples contained 1.6 wt% Gilsonite LCM. In-situ
prepared NPs, which, as stated earlier, immediately adsorb onto ‎neighbouring clay
platelets when squeezed through the filter cake by virtue of their ‎high dispersion, fill the
pores and the gaps of clay network and, hence tremendously ‎lower the fluid loss
compare to the ex-situ prepared NPs. On the other hand, for the ‎typical LCM, particles
larger than pore opening cannot enter the pore at first and ‎might be swept away by the
mud stream, of course under dynamic drilling.
During spurt loss period (t< 7.5 min), mud particles attempt to flow with the
filtrate ‎through the filter paper. The emulsion droplets provide sufficient surface area for
the ‎water-containing NPs to spread on the mud cake. This may have resulted in NPs
bridging across pore ‎throats to form the external mud cake immediately, and thus
lowering the spurt loss. ‎Iron oxides/hydroxides have affinity for negative charges
(Follett, 1965), while the edges of the betonite clay are negatively charged (Xu et al.,
2005; Lai et al., 2000; Follett, 1965). This ‎may explain the high particle-clay interaction
during filtration (Xu et al., 2005; ‎Lai et al., 2000; Follett, 1965). Fluid loss control of
drilling muds using similar approach was not ‎reported in the literature. Most of the
literature on NP-based drilling muds considered ‎water based muds employing
commercial NPs, and loss reduction of 40% was reported for 1-30 wt% NPs (Amanullah
et al., 2011; Srivatsa, 2010; Cai et al., ‎2011). Using similar explanation to Aston et al.
(2002), NPs probably acted at the ‎interfacial region between the emulsion droplets and
the oil phase when pressure is ‎applied during filtration and made the region viscous.
This phenomenon could slow ‎down the flow of oil through the cake and thereby lower
the fluid loss. Moreover, there ‎could be an additional effect from NPs acting as bridging
agents between long chain hydrocarbons, including those of LCM molecules, in the
invert emulsion drilling fluids.‎

75
 The above results are particularly important when drilling in shale formations.
Even though shales have macro to nano pores, shales are very sensitive ‎to water loss
since they tend to swell easily (Chenevert and Sharma,2009). Conventional LCMs will
not be able ‎to block the nanopores due to their micron sizes. Therefore, smaller
particles, i.e. NPs, ‎are needed to better fit the nanopores.‎
In order to prevent drilling and completion problems, mud cake quality and build
up characteristics are also very important. Figure 4.9 includes photographs of the mud
cake formed in the presence and absence of NPs. Compared with LCM based cake, the
NP-based drilling fluid produced thin mud cake less than 1 mm. The NP-based DF
deposited a fine thin layer of iron (III) hydroxide NPs on the cake surface. Addition of
NPs did not cause an increase in the thickness of the mud cake, especially since small
concentrations of NPs were used in fluid formulation and these NPs are believed to be
located on the top of the clays and eventually filled the gap or holes in the clay platelets.
The NPs are subsequently captured within the clay layers. This multiple layer structure
provides much better sealing, prevents further flow through the pores, and subsequently
lower clay deposit and thinner filter cake. During filtration clays provided disordered
stacking and displayed the highest permeability. NPs reduced this roughness of clay
surface by the thickness of the deposit. It could be associated with dispersion ability of
nanoparticles to be well-distributed more effectively on the surface of bentonite clays or
‘intercalation’ of NPs in clay layers provided lower permeability. This eventually
decreases the volume of the cake leads to a minimum amount of fluid in the pores.
Moreover small concentrations of NPs were used in fluid formulation. On the
other hand, large sized LCM could not lodge in the porous space of the cake and the
cake exhibited sufficient porosity to permit continued flow through it as filtration
proceeds. This, in turn, led to more clay depositing onto the cake and particles
accumulation. Moreover, Figure 4.9 c-d shows that a layer of NPs was the last to
deposit on the cake surface leading to crack-free and smooth surface. Thin filter cake
suggests a high potential for reducing the differential pressure sticking problem while
drilling.

76
 a) b) c) d)

Thickness= 0.31mm Thickness= 0.76 mm Thickness= 0.52 mm Thickness= 0.44mm

Figure 4.9: Mud Cakes with thickness of a) DF only, b) DF+LCM, c) DF +LCM with 1
wt% ex-situ NPs, and d) DF+LCM with 1 wt% in-situ NPs.

Because the fluid loss performance is improved dramatically with the Fe(OH) 3 ‎NPs
additives, it raises the question as to whether conventional LCMs are still needed
to ‎control the fluid loss, especially in light of the fact that NPs displayed a relatively wide
size distribution, at least the ‎reported ex-situ prepared ones. These measurements
suggest that a wide size range of NPs can be used as substitutes for ‎conventional
LCMs in the mud, e.g. Gilsonite. The hypothesis ‎was larger size NPs would contribute
to blocking large formation pores and help ‎bridging large voids, and once a primary
bridge is established, successively NPs, down ‎to few nm, are trapped and thereafter
stop the filtrate from invading the formation. ‎The filtration properties of a drilling fluid
with NPs only also consider the wall/cake building ability of the NPs with the solid
components of drilling fluid such as clays. The results of the API low temperature low
pressure LTLP experiments are shown in Table 4.3. An interesting observation was that
a wide range of NPs size distribution gave the lower filtrate volume than the Gilsonite
LCM. A reasonably low fluid loss value and thin mud cake with a thickness of less than
1 mm significantly improved the performance of the NP-based drilling fluid. These
results are summarized in Figure 4.10.

77
Table 4.3: API LTLP fluid loss comparing drilling fluid and drilling fluid with Gilsonite
LCM as base cases with drilling fluid samples containing the in-house prepared
Fe(OH)3 NPs only with no LCM.
Samples Time LTLP Fluid Loss (mL)
Types
(min) DF DF +LCM DF with 1 wt% DF with 1 wt%
ex-situ NPs in-situ NPs
90:10 (v/v) 7.5 2.0±0.2 1.4±0.2 0.15±0.1 0
Oil: Water 30 3.96±0.2 3.6±0.1 (9%*) 1.25±0.2 (68%*) 0.9±0.2 (77%*)
*Fluid loss reduction, %.

a) b) c) d)

Figure 4.10: Mud Cakes of a) DF only, b) DF+LCM, c) DF with 1 wt % ex-situ NPs and
d) DF with 1 wt % in-situ NPs.

4.2.3 Filtrate Characterization

Loss of fluid from invert emulsion drilling muds usually allows oil and chemicals into the
formation. In order to provide a measure of how much NPs seeped through the filter
cake during API LTLP filtration, the concentrations of iron and calcium in the filtrate
were determined using inductively coupled plasma (ICP). In the total filtrate volume, the
Fe(OH)3 NP-based fluid reduced the calcium content 500 times relative to the drilling
mud alone. It should be noted that typically the aqueous phase of the invert emulsion
drilling fluids contain calcium hydroxide in order to control alkalinity (Chilingarian and
Vorabutr, 1983). On the other hand, no iron was found in the original drilling fluid or the
NP-based drilling fluid, as shown in Table 4.4. The results can be attributed to the fact
that clays are negatively charged and adsorbed species with high affinity to negative
charges such as iron oxide/hydroxide (Xu et al., 2005; Lai et al., 2000; Follett, 1965), as
discussed earlier. Therefore, NPs provided bridges between the clay particles reducing

78
the area available for the fluid seepage and hence forcing Ca 2+ ions to adsorb onto the
negatively charged clays.

Table 4.4: ICP results of the filtrate collected following API LTLP to determine the Ca
and Fe content.

Filtrate Samples of mg (In total volumes)

Drilling fluid (DF)
Ca Content Fe Content
Without NPs 478 Nil

With 1 wt % in-situ NPs 0.87 Nil

Those NPs interact with the formation and eventually plug the pore either internally
or ‎externally, preferably. If, on the other hand, it blocks the pore channel,
formation ‎damage may occur and oil and gas production will be interrupted. ICP results,
together ‎with the fact that filter cakes were thin, suggest only external plugging took
place.
+ 2+
In clays, often Na or Ca , are too large to be accommodated in the interior of the
lattice and therefore may be easily exchanged by other cations when available in
solution (Deriszadeh,2012). NPs either ex-situ or in-situ could exchange cations with
clays and locate on the exterior surface and near the pore openings are kinetically more
accessible than the interior pore wall. Therefore NPs bridge across pore throats to form
the external mud cake immediately.

4.2.4 HTHP Filtration

The HTHP API filtration test simulates drilling in deep formation, where both the
temperature and the pressure of formation and the drilling fluid may reach high values.
High temperatures may alter the size, identity and surface morphology of the Fe(OH) 3
NPs (Agarwal et al., 2009; Balek and Šubrt, 1995). This may ultimately lead to reducing
the NPs effectiveness. Generally, nanoparticle aggregation and the formation of large
irregular particles can be captured by visual analysis of the filter cake. The results
79
shown in Table 4.5 and Figure 4.11 provide details on fluid loss reduction and sealing
potential of the filter cake for invert emulsion muds. Based on the original DF, fluid loss
over a period of 30 min decreased by 24% for the drilling fluid containing 1.6 wt% LCM
only, while it decreased by 53% for the drilling fluid containing 1 wt% ex-situ prepared
Fe(OH)3 NPs and 61% for the drilling fluid containing the in-situ prepared Fe(OH)3 NPs.
In this experiment, both ex-situ and in-situ NP-based drilling fluids contained 1.6 wt%
Gilsonite LCM. The better dispersed in-situ prepared NPs exhibited lower mud cake
thickness than ex-situ prepared NPs as shown in Figure 4.11.
Generally, the higher loss of the drilling mud with and without NPs or LCMs when
compared with low temperatures is attributed to the lower viscosity of the fluid at 177 oC.
Cake thickness is proportional to filtration loss (ASME, 2005). As the mud is not being
circulated, the filter cake grows undisturbed with the filtrate rate. Table 4.6 shows fluid
loss reduction and mud cake thickness under API HTHP conditions. As temperature and
pressure go up, lower mud cake thickness in presence of Fe(OH)3 NPs is obtained.
Similar observations were reported by Javeri et al.(2011) and Paiaman and Al-
Anazi,(2008). It is true that in the absence of NPs and LCMs filter cake displayed low
thickness, but it should be noted that the filter cake was not effective towards filtrate
reduction. NPs increase the tortuous flow path and travel time of the fluid to pass
through the filter cake and lower the fluid loss.
In the presence of NPs filtration rate became slow probably due to the high level
of interaction between ‎the NPs, Gilsonite and clays, which led to effective bridging even
at high temperature. ‎In addition, and as noted by Aston et al. (2002), water droplets with
sizes≥ 5.5 μm tend ‎to bridge the 3 μm pores on the filter paper. At the high
temperatures encountered in this ‎experiment, water pools may coalesce to form larger
droplets. At the low concentration ‎of NPs it is more likely that the particles interacted
with the rest of the mud constituent ‎rather than merely aggregating. Moreover,
temperature affects clays by changing the orientation of the adsorbed water pools in the
clay matrix. The rigid bonding of water may decrease dispersion of the clay and form a
more porous filter cake which allows a greater filtrate flow at high temperature (Fisk and
Jamison, 1989).

80
Table 4.5: HTHP filtration property of different drilling fluid samples.
Samples Time HTHP Fluid Loss (mL)
Types
(min) DF DF +LCM DF with 1 wt% DF with 1 wt%
ex-situ NPs in-situ NPs
90:10 (v/v) 7.5 9±0.1 6.2±0.2 2±0.2 0
Oil: Water 30 19±0.1 14.4±0.1 9±0.1 (53%*) 7.5±0.2 (61%*)
Cake thickness, mm 1.7 (24%*)
7.3 2.7 1.3
*Fluid loss reduction,%

LCM+NPs LCM No LCM or

LCM+NPs NPs
(In-situ) (Ex-situ) Filter cake
Filter cake Filter cake
Filter cake

Thickness= 1.3 mm Thickness= 2.7 mm Thickness= 7.3 mm Thickness= 1.7 mm

Figure 4.11: Filter cakes obtained following API HTHP tests on invert emulsion drilling
fluids with and without Fe(OH)3 NPs and Gilsonite LCMs.

81
Table 4.6: Effect of operating conditions of API filtration test on mud cake thickness with
and without Fe(OH)3 NPs and Gilsonite LCMs.
Temperature Mud cake thickness (mm)
and Pressure DF DF +LCM DF with 1 wt% DF with 1 wt% in-
ex-situ NPs+LCM situ NPs+LCM
25 °C,100 Psi 0.31 0.76 (2.5*) 0.52 (1.7*) 0.44 (1.4*)
177 °C,500 Psi 1.7 7.3 (4.3*) 2.7(1.6*) 1.3 (0.8*)
*Thickness improvement, x times compared to DF

In a similar manner, one run with NPs in the absence of the Gilsonite LCM was
performed. The results are shown in Table 4.7. The data on fluid loss at 30 min show
that in the absence of LCMs, the NPs are performing better. Based on the original DF,
fluid loss over a period of 30 min decreased by 79% for the drilling fluid containing 1
wt% ex-situ prepared Fe(OH)3 NPs, while it decreased by 86% for the drilling fluid
containing 1 wt% in-situ prepared Fe(OH)3 NPs. This observation can be attributed to
the fact in the absence of LCMs there seems to be higher interaction between the NPs
and the clays, which resulted in better sealing and more effective filter cake.

Table 4.7: HTHP fluid loss of different drilling fluid samples in the presence and
absence of Fe(OH)3NPs. No LCMs were added. Cake Thickness at 30 min.
Samples Time HTHP Fluid Loss (mL)
Types
(min) DF DF with 1 wt% DF with 1 wt% in-
ex-situ NPs situ NPs
90:10 (v/v) 7.5 9±0.1 0 0
Oil: Water 30 19±0.1 4±0.1 (79%*) 2.7±0.2 (86%*)
Cake thickness, mm 1.7 2.1 1.1

*Fluid loss reduction, %.

82
 In-situ NPs NP-free DF Ex-situ NPs
Mud cake Mud cake Mud cake

Thickness Thickness Thickness

1.1 mm 1.7 mm 2.1 mm

Figure 4.12: Mud cakes obtained following API HTHP tests on invert emulsion
drilling fluids with in-house prepared NPs only. No LCMs added.

LCMs seem to consume NPs, which would otherwise interact with the mud cake to a
better extent than the interaction of the NP-LCM combination. The better dispersed in-
situ prepared NPs exhibited lower mud cake thickness than ex-situ prepared NPs as
shown in Figure 4.12. When subjected to high temperatures, NPs are likely to maintain
stability and dispersion in the water-in-oil ‎emulsions. Agarwal et al. (2009) used nano
CuO with 23-37 nm diameters and nano ‎alumina with 40-50 nm diameters in invert
emulsion drilling fluids and showed that ‎drilling fluids maintain their stability even at
175oC. It appears that when NPs are mixed with drilling fluid, clay suspensions may
bind with NPs ‎resulting space-filled structure. A sol-gel formation may be induced,
which finally ‎blocks fluid flow through the filter media, upon filtration. Addition of in-
house prepared Fe(OH)3 NPs, increases the ionic ‎strength of the fluid, due to the
formation of NaCl by-product, which causes stronger interaction with the clays during
HTHP filtration (Agarwal et al., 2009). As discussed earlier, the elimination ‎of spurt loss
observed in these experiments may reduce formation damage, and thin mud cakes
could ‎possibly reduce stuck pipe problems (Chilingarian and Vorabutr, 1983).

4.2.5 Effect of high shear on fluid loss control

High degree of mixing and shearing of the drilling fluid is essential to form NP-based
drilling fluid using the in-house preparation technique, as described earlier. This step is
important whether the particles are prepared in-situ or ex-situ. Shearing device may

83
significantly increase the dispersed phase fraction and dampens coalescence by
breaking agglomerated particles (Amanullah, 2011). Hamilton beach three blade high
speed mixer was used in addition to vigorous agitation of fluid during preparation. This
inexpensive equipment is used mostly in food processing. High-shear mixers provide
rapid micro-mixing and emulsification. Providing no blending displayed higher fluid loss
when compared with blending at 2500 rpm using Hemilton beach blender for same DF
with and without 1 wt% in-situ Fe(OH)3 NPs, as shown in Table 4.8. Figure 4.13 shows
that the mud cake collected following the filtration of unblended drilling fluid is full of
precipitates, agglomerates and ‘fish eyes’ as highlighted by the circles, while the one
collected from a blended sample is much more smooth and does not show
agglomerate. Very high mixing rates result in smaller particles in the mud as it serves
formation of very small water pools, in the case of in-situ prepared NPs, and minimizing
particle aggregation during the formation. Same effect was also observed during the
addition of ex-situ prepared NPs. It was found by Altun and Serpen (2005) that
variations in the mixing speed have important effects on fluid loss property and higher
mixing speeds yielded lower filtration loss. In a similar study, Newman et al. (2010)
showed that properties of drilling fluid were significantly affected when mechanical
mixing is applied. It was also understood that to obtain smaller droplets of uniform size
in water-in-oil emulsion, energy must be applied in the form of shear.

Table 4.8: Effect of shearing effect on LTLP fluid loss control in the presence and
absence of NPs.
LTLP Fluid Loss (mL/30 min)
Samples
Types Unblended DF 2500 rpm Blending 2500 rpm Blending 1 wt%
(No NPs) DF (No NPs) in-situ NPs +DF

90:10 (v/v) 1.25±0.2

Oil: Water 8±0.1 3.96±0.2

84
 Blended NP-based Mud cake

Figure 4.13: Quality of unblended and blended mud cake.

4.2.6 Effect of presence of organophillic clays on fluid loss

Table 4.9 shows the effect of varying the composition of organophillic clays from 12 to
15 kg/m3 in the presence and absence of 1 wt% Fe(OH) 3 NPs.

Table 4.9: Effect of organophillic clays on LTLP fluid loss control.

Samples Amount of organophillic LTLP Fluid Loss (mL/30 min)
Types clays used in DF
DF without NPs DF+ with 1 wt%
in-situ Fe(OH)3
90:10 (v/v) 12 kg/m3 4.9±0.1 NPs
2.3±0.1
Oil: Water 15 kg/m3 3.96±0.2 1.25±0.2

As evident from the table, increasing clays concentration improves loss prevention. It
should be noted that clay content cannot be indefinitely increased. Solids content of the
drilling fluid is one of factors that causes formation damage and decreases rate of
penetration ROP (Newman et al., 2009). Solids are added to fulfill the functional tasks
of the mud such as increasing mud density, viscosity and fluid loss control. The higher
the amount of total solid in the drilling fluid the lower the rate of penetration, which in
turn increases rig days and reduces productivity index. Unlike the Gilsonite LCM,

85
increasing the content of clays in presence of NPs increased fluid loss prevention, since
more clays are available to form the mud cake. NPs would still be performing their role
as bridging particles and will have higher surface to communicate with in the presence
of more clays.
A major outcome of the current study is that low NPs concentration can
significantly reduce fluid loss. In events were high solid concentration is not desirable,
for example due to the need to keep fluid density to a minimum, NPs can replace clay
additive. Addition of low concentrations of NPs did not have any effect on the mud
density, as will be detailed later.

4.2.7 Effect of Oil: Water ratio on fluid loss

Filtration behavior of emulsified oil is strongly influenced by oil/water ratio, additive
chemistry and concentration (Aston et al., 2002). Two formulations; namely 90:10 (v/v)
and 80:20 (v/v) oil: water mixes, were tested in the presence and absence of in-house
prepared NPs. This experiment is particularly relevant to in-house prepared NPs, since
aqueous precursors are added. The results shown in Table 4.10 reflect a decrease in
filtrate volume in the presence of Gilsonite LCMs and Fe(OH)3 NPs. Table 4.11 shows
the same trend in presence of NPs and absence of LCMs.
Increasing the water content from 10 to 20 percent by volume caused the fluid
loss to decrease 26% and 25% for drilling fluid control samples and drilling fluid
containing Gilsonite LCM, respectively. Addition of NPs, again, decreases the fluid loss
to 44% and 10% for ex-situ and in-situ method, respectively, due to the changed water
content from 10 to 20 percent by volume. The reduction of fluid loss was dramatic in the
case of ex-situ prepared NPs. This may suggest that extra water pools were originally
needed to disperse better the particles. In-situ prepared NPs are more readily dispersed
in the 10 percent water content. Therefore, in 20 percent water content, the fluid loss
reduction was not varied too much. Higher water content may increase collision among
water pools, which, in turn, may lead to more particle agglomeration (Husein and
Nassar, 2010). This, in a way, decreases the effectiveness of the NPs. Nevertheless,
one should not ignore the lower interaction between the organophilic clays constituting

86
the filter cake and the drilling fluid as the water content increases. Filtration rates
through hydrophobic membranes results in much lower permeate flux (Deriszadeh et
al., 2010). Aston et al. (2002) found the ‎similar trends and proposed major savings can
be attained by decreasing the oil to water ratio, while attaining more loss prevention.

Table 4.10: Effect of Oil: Water ratio on Fluid loss control in presence and absence of
LCM and in-house prepared Fe(OH)3 NPs.

LTLP Fluid Loss (mL)

Samples Time
DF DF+ LCM DF+LCM+ 1 wt% DF+LCM+ 1 wt%
Types (min)
ex-situ NPs in-situ NPs
90:10 (v/v) 7.5 2.0±0.2 1.4±0.2 0.2±0.2 0
Oil: Water 30 3.96±0.2 3.6±0.1 1.10±0.1 0.5±0.2
80:20 (v/v) 7.5 1.0±0.2 1.0±0.2 0 0
Oil: Water
30 2.9±0.1 2.7±0.2 0.62±0.1 0.45±0.1

Table 4.11: Effect of Oil: Water ratio on fluid loss control in presence and absence of
in-house prepared NPs. No LCMs added.

LTLP Fluid Loss (mL)

Samples Time
DF DF with 1 wt% DF with 1 wt%
Types (min)
ex-situ NPs in-situ NPs

90:10 (v/v) 7.5 2.0±0.2 0.15±0.1 0

Oil: Water 30 3.96±0.2 1.25±0.2 0.9±0.2
80:20 (v/v) 7.5 1.0±0.2 0 0
Oil: Water 30 2.9±0.1 0.8±0.1 0.5±0.2

4.2.8 Rheology behavior of NP-based fluid

Drilling fluid with good pumpability exhibit lower viscosity at high shear rate and higher
viscosity at lower shear rate. This property of drilling mud is used widely where high
viscosities are required during tripping operation and low viscosities during drilling
operation to clean the cuttings from the bottom of the hole (Chenevert and Sharma,
2009; Fraser et al., 2003). The plot of apparent viscosity and shear rate as shown in
Figure 4.14 resembles the non-linearity of the curves at low shear rates and approach

87
linearity at high shear rates. The fact that addition of NPs created a slight change in the
rheology supports the theory that NPs behavior is governed by NPs grain boundary and
surface area/unit mass (Amanullah et al., 2011; Srivatsa, 2010). Although the addition
of small concentration of NPs is not sufficient to cause a significant rheology changes in
the system compared to the drilling fluid and drilling fluid with LCM only, particle size,
nature of particle surface, surfactants, pH value and particle interaction forces may play
significant role in altering the viscosity (Agarwal et al.,2009). The minor effect of NPs on
viscosity is attributed to the low concentrations employed in this study. Abu Tarboush
and Husein (2012) noted that NPs may increase the viscosity of heavy oil by bridging
between asphaltene molecules and aggregates.
The results are also highly dependent on the hydroxyl group (OH-) on the surface
of the NPs may lead to NPs agglomeration in an organic solution leading to a higher
mass of selective physisorption of organic clay suspension on the NP-free surface,
which may reduce the fluid viscosity slightly (Srivatsa, 2010). A small amount of NPs
exhibit stable rheological properties. Fluid with high viscosity may cause excessive
pumping pressure and decrease rate of drilling. Therefore, it is an important issue to
design a suitable fluid rheology. Lee et al. (2009), who investigated the application of
NPs for maintaining viscosity of drilling fluids at high temperature and high pressure,
reported that the rheological behavior may depend on the particle type, size,
concentration and inter-particle distance of NPs within the fluid. It was also reported that
adding very small amount of mixed metal oxide did not change fluid rheological
properties. It was shown that with an increase in temperature, the viscosity of drilling
fluid containing 0.05 wt% cobalt NPs unchanged at 100 cP and remained stable.
Therefore, potential application of NPs is to use them to stabilize in water-in-oil
emulsion where NPs (solid/semi solid) dispersed in clays and electrolyte (NaCl salt)
produced during the NP-based fluid formulation also work as a bridging material
between the platelets of organophillic clays to form gel structure. The rheological
properties of the in-house NP-based drilling fluid thus could suitably fulfill the drilling
requirements. The comparison of the gel strength behavior of the drilling fluid, drilling
fluid with LCM, drilling fluid with LCM and NPs together and NPs only are shown in

88
Figure 4.15. The gel strength property of the NP-based drilling fluid compared to the
progressive type gel strength of DF and DF+LCM also demonstrates superior functional
behavior of NP-based drilling fluid. Similar observation was reported by Amanullah et al.
(2011). Very high gel strength values are practically undesirable because they retard
the separation of drilled cuttings at the surface and also raise the pressure required to
re-establish circulation after changing bits. Furthermore, when pulling pipe, high gel
strength may reduce the pressure of the mud column nearby the bit. If the reduction in
pressure exceeds the differential pressure between the mud and the formation fluids,
the fluid will enter the hole and cause a blow-out (ASTM, 2005; Amanullah et al., 2011;
Chilingarian and Vorabutr, 1983).

a) b)

Figure 4.14: Rheological behavior of drilling fluid containing a) LCM together with in-
house prepared 1 wt% Fe(OH)3 NPs, b) 1 wt% Fe(OH)3 NPs no LCMs.

From Figure 4.16 and Figure 4.17 we observe the time dependent rheological
and gel strength behavior of the drilling fluid. The measurement was done immediately
after the preparation and also after 1 month. After 4 weeks the fluid was found
compliant with all specification for re-use. Analyses of the rheological profiles of the
drilling fluids shown in Figure 4.16 indicate no significant changes of the viscous profile

89
of the NP-based fluid. The NP-based fluid immediately after preparation and static aging
after 1 month demonstrate that the short as well as long term stability exist in the NP-
based fluid. The 10 seconds and 10 minutes gel strength shown in Figure 4.17 also
demonstrate the short and long term stability of the NP-based fluid to fulfill its functional
task during drilling operation.

90
 a)

b) Gel Strenth (10 sec)

5
Gel Strenth (10 min)
4.5
4
3.5
3
2.5
lb /100 ft²

2
1.5
1
0.5
0
DF DF+In-situ DF+Ex-
NPs situ NPs

Figure 4.15: Gel strength behavior of drilling fluid a) with LCM and NPs together ex-situ
and in-situ method b) in the absence of LCM,with NPs only ex-situ and in-situ method.

91
Figure 4.16: Shelf life of drilling fluid samples in terms of rheology behavior.

Figure 4.17: Aging effect of drilling fluid samples in terms of gel strength
behavior.

92
4.2.9 Drilling fluid density and pH
Mud density is one of the important drilling fluid properties, because it balances and
controls formation pressure and wellbore stability (Chilingarian and Vorabutr, 1983). A
mud density of 0.93 g/cm3 of the 90:10 (V/V) oil/water invert emulsion was found to be
constant for all samples with and without NPs as shown in Table 4.12. The addition of
NPs did not increase the mud weight given the fact that their concentration was low and
also due to the electrochemical behavior of NPs with clays. As discussed above, this is
advantageous since it is one way of improving fluid filtration properties while maitaining
the same mud density. Similar advantage of NPs was exploited to increase mud density
while maintaining low mud visocistiy.
A pH level of 12.5 was also found in all samples as also shown in Table 4.12,
even with NPs addition. It should be noted with the fact that NaOH was added at the
stoichiometric amount and NaCl was the reaction by-product, no changes in the pH of
the aqueous pools is expected. Generally, changes in the pH of the water pools of invert
emulsions could lead to unstability of the colloidal system by neutralizing charged
surfaces at the water/oil interface or particles.

Table 4.12: Density and pH values of drilling fluid in the presence and absence of LCM
and in-house prepared Fe(OH)3 NPs.
Test samples
DF DF +LCM DF+LCM with 1 DF+LCM with 1
Samples Properties
wt% ex-situ NPs wt% in-situ NPs
Types
Density 0.93±0.02 0.93±0.02 0.93±0.02 0.93±0.02
90:10 (v/v) (g/cm3)
Oil: Water pH 12.5 12.5 12.5 12.5

4.2.10 Drilling fluid lubricity

Even if a drilling fluid successfully meets all of the requirements, there is no guarantee
that the rate of penetration will be acceptable, since poor lubricity and high friction and
drag increase pipe sticking and drilling cycle (Amanullah et al., 2011). It needs to
overcome frictional forces which is very much encountered during all stages of well

93
construction; including drilling, completion and maintenance. Friction originates from the
rotation and/or sliding of a pipe inside the well in contact with either the wellbore (metal-
to-rock) or the casing (metal-to-metal). These forces hinder directional and extended
reach drilling by creating excessive torque and drag (Amanullah et al., 2011; Hoskins,
2010). Excessive torque and drag in highly directional and extended-reach wells can
exceed the mechanical limits of the drilling equipment, which may expedite wear and
tear of down hole tools and equipment and thereby limit production. These problems
can be minimized by using drilling fluid with high capabilities of lubricating the different
components. In fact, the switch from water-based to oil-based or invert emulsion muds,
despite the increase in cost, was originally proposed to help improving lubricity
(Kercheville et al.,1986).Friction dissipates energy and causes wear resulting in damage
to the equipment. The way to ensure that frictional effects are minimized is through
proper lubrication. In carrying out this function, lubricants create a lubricant film on
surfaces of moving parts.
The effect of the in-house prepared NPs on the lubricity of the invert emulsion
drilling fluid considered in this study was measured by evaluating the coefficient of
friction, as detailed in the experimental work. The hypothesis was that under the
conditions of load and temperature resulting from the contacting surfaces, these NPs
may furnish a thin film of lubricant layer on the contacting surfaces leading to reduced
friction between the surfaces. These NPs may act as nano-bearings and contribute
increasing the lubricity. Table 4.13 displays values for the coefficient of friction (CoF)
and the accompanying reduction in torque and drag in the presence of 1 wt% in-house
prepared Fe(OH)3 NPs.

Table 4.13: Co-efficient of friction (CoF) of drilling mud samples.

Coefficient of friction % torque reduction
NPs and DF without NPs DF with ex- DF with in- DF with ex- DF with in-
conc. used (control) situ NPs situ NPs situ NPs situ NPs
Fe(OH)3
(1 wt%) 0.095±0.002 0.081±0.004 0.039±0.002 14.73% 58.94%

94
It appears that in-situ prepared NPs disperse better and communicate better with the
mother drilling fluid as opposed to the ex-situ prepared ones. Therefore, in-situ prepared
NPs may carry a proportion of the load benefiting the improvement of antiwear property
more than NPs prepared ex-situ. Thus using tailormade NPs in drilling fluid can reduce
coefficient of friction and substantially increase lubricity. Improvement in lubricity
reduces energy consumption, which, in turn, increases profitability.
Oil-based drilling fluids have the inherent advantage of significantly lower
coefficients of friction (CoF). The typical CoF for an oil-based drilling fluid is 0.10 or less
(metal to metal) (Chang et al., 2011). In comparison, water has a CoF of 0.34 and the
CoF of water-base drilling fluids typically ranges between 0.2 and 0.5 (Chang et al.,
2011). Comparing between the typical oil based mud and NP-containing mud the friction
mechanism is most likely a transfer of NPs to the counterface. This suggests that NPs
in the contact zone act like ball bearings in the interface between the two surfaces. The
small size allows the particles to penetrate into the surface and van der Waals forces
ensure that the particles adhere to the surfaces. Regular lubricants, or oil as continuous
phase, in drilling fluid can only form a single oil film (Kostic, 2010; Mosleh et al., 2009;
Malshe et al., 2008), whereas NPs in drilling fluid can create an additional ball bearings
action leading to better lubrication effect. Nonetheless, iron oxide/hydroxide
nanoparticles act as a lubricious material (Reed, 2008). Sodium salts, e.g. NaCl salt
formed as a by-product during the Fe(OH)3 NP-based fluid formulation, may act as a
lubricant as per some literature (Scoggins and Ke, 2011; Ke and Foxenberg, 2010).
Table 4.14 shows that these side products, in fact, slightly increase the coefficient of
friction. Therefore, the increase in lubricity observed when iron-based NP-drilling fluids
are used can entirely be attributed to the nanoparticles only.

95
Table 4.14: Coefficient of friction (CoF) and % torque reduction in the presence and
absence of 1 wt% NaCl salt in the invert emulsion drilling fluid.
Coefficient of friction
Salt and conc. DF without salt DF with salt % torque reduction
(control sample)
NaCl (1 wt%) 0.0980±0.002 0.100±0.004 -2%

Nanosized particles are much more readily dispersible than micron-sized ones (Canter,
2009). When dispersed in a drilling fluid, minimum agglomeration and settling occur and
a stable suspension form. The stable dispersion is also supported by the presence of
surfactant molecules. Both in-situ and ex-situ prepared NPs are so small in size that a
stable colloidal dispersion in drilling fluids can be achieved, which probably avoid the
undesired precipitation caused by gravitation. With the formation of a stable well-
proportioned dispersion through proper method, NPs are more prone to be trapped in
the rubbing surfaces due to its excessive surface energy. Besides, dispersed NPs are
deposited on the friction surface, trapped NPs at the interface and finally roughness of
the surface is reduced by its polishing effect (Wu et al., 2007; Mosleh et al., 2009).
Moreover, as the NPs tend to disperse uniformly, a more uniform contact stress
between the contacting surfaces may result (Chang and Friedrich, 2010). Moshkovith et
al. (2007) studied the lubricity properties of IF-WS2 and reported that dispersion impacts
the lubricity performance as the dispersed NPs possess solid lubrication properties due
to its stability. It was also found that the aggregate size of the NPs depend on the
mixing time. The in-house prepared NPs in this work can be engineered to have specific
size ranges so that they can find their way into intricate spaces and maintain lamellar
structure. It is, therefore, speculated that the coefficient of friction reduction is due to the
surface boundary films provided by NPs that slide easily over one another like ball
bearings. Similar findings have been reported in the literature on the effect of dispersing
carbon and metallic-based NPs on tribological performance of lubricating oils (Zhang et
al., 2009; Abdullah, 2008; Malshe et al., 2008; Verma et al., 2008). Specifically, a
reduction in the coefficient of friction by over 25 percent was observed when adding
nickel-based NPs to lubricants (Kostic, 2010).

96
 In addition to reducing torque, higher lubricity also lowers the incidence of stuck
pipe, which can significantly lower drilling efficiency. Estimates by exploration
companies showed that stuck pipe while drilling costs more than $250 million each year
(Q’Max Technical Bulletin #7). Minimizing friction and the ability to transfer the weight to
the bit are very important factors in drilling highly deviated extended reach and
horizontal wells. Moreover, reduction in torque in the presence of NPs imply higher
extended reach wells at a given torque and load on bit.
From the aforementioned discussion it can be concluded that the ability of NPs to
increase lubricity depends on the following features:
1. NPs can adsorb physically on any metal surface due to van der Waals forces.
2. The size of the NPs is so small that they can easily enter a macroscopic sliding
contact.
3. The lubrication effect can be generated by the chemical nature of surfactant as
described by Yang et al. (2012) and NPs altogether or NPs alone. Dispersed
nanoparticles can help in reducing the agglomeration at the interface and
improving the co-efficient of friction. The role of surfactant molecules is to
improve the dispersion quality and stability of the NPs, since the level of
improvement is measured relative to a control sample that contains the same
amount of surfactant.
4. Coefficient of friction significantly reduced by NPs alone and the by-product salt
did not have a significant impact on lubricity.

4.2.11 Preparation and performance evaluation of Fe(OH) 3 NPs in invert emulsion

drilling fluids provided by different suppliers
Three invert emulsion muds were obtained from three different suppliers having same
oil:water ratio (90:10 v/v). These drilling fluids mainly differ in terms of the amount of
organophillic clays and nature of emulsifiers. It is important to note that the nature of
drilling fluids emulsifiers was not studied separately in this current study. The in-house
in-situ and ex-situ NPs preparation techniques were employed to form Fe(OH) 3 NPs and
the performance of the NP-based drilling fluids was evaluated. For a drilling fluid;

97
filtration, rheology, density, pH need to be suitable to fulfill the drilling requirements. The
results in Table 4.15 compare the density, pH and the API LTLP fluid loss at 30 min for
samples with and without Fe(OH) 3 NPs. The density and the pH of the samples
remained constant, while fluid loss was decreased significantly. Moreover, the in-situ
prepared NPs displayed better performance and reduced fluid loss to a higher extent.
This fact can be attributed to better dispersion and communication with the rest of the
drilling fluid constituents, as discussed earlier.

Table 4.15: Effect of ex situ and in situ prepared Fe(OH) 3 NPs on the performance of
three different invert emulsion samples of drilling fluids provided by three different
suppliers. Concentration of NPs 1 wt%, composition of invert emulsion: (90:10) oil:water
(v/v).

Samples Density pH API LPLT fluid loss

(g/mL) (mL/30 min)
Supplier A
DF 0.93±0.02 12.5 3.9±0.2
DF+LCM 0.93±0.02 12.5 3.6±0.1
DF+LCM+Ex situ NPs 0.93±0.02 12.5 1.1±0.1
DF+LCM+In situ NPs 0.93±0.02 12.5 0.5±0.2
Supplier B
DF 0.93±0.02 12.5 16.5±0.3
DF+LCM 0.93±0.01 12.5 12.7±0.4
DF+LCM+Ex situ NPs 0.93±0.02 12.5 7.5±0.2
DF+LCM+In situ NPs 0.93±0.02 12.5 6.5±0.1
Supplier C
DF 0.90±0.02 12.5 1.2±0.2
DF+LCM 0.90±0.02 12.5 1.0±0.1
DF+LCM+Ex situ NPs 0.90±0.01 12.5 0.5±0.1
DF+LCM+In situ NPs 0.90±0.01 12.5 0.1±0.1

NPs were found to be suitable for use in drilling fluids due to its functional
characteristic of maintaining low viscosity and expected to minimize the drilling
problems. In-situ control of viscosity of drilling fluids in deep well bores is currently

98
limited (Lee et al., 2009). During operation, and as drill cuts suspend into the drilling
fluid, viscosity increases and alters the rheology in the subterranean wells (Adekomaya
and Olafuyi 2011; Herzhaft et al., 2006). Therefore, a gradual tuning of the rhelogical
properties of the drilling fluids is required to maintain good performance. As noticed
from a previous experiment, NPs, especially in-situ prepared ones, generally reduce the
viscosity of drilling fluids due to their electrochemical behavior with clays. The
decreased in viscosity with the addition of NPs may provide the in-situ
tunability/controllability of the fluid viscosity during drilling in subterranean wells. The
rheological properties of the drilling fluids obtained from different suppliers were
evaluated in the presence and absence of the in-house prepared NPs. Apparent
viscosities at 600 rpm were plotted for comparison in Figure 4.18. The results show
consistent decrease in the apparent viscosity in the presence of in-house prepared NPs.
This also confirms the fact that in-situ prepared NPs better interact with the drilling fluid
displaying more reduction in the apparent viscosity. Similar observation was reported by
Abdo and Haneef (2010) when using Montmorillonite NPs compare with regular
commercial bentonite particles.
Apparent viscosity (cP) at 600 rpm

Figure 4.18: Apparent viscosity at 600 rpm of 3 invert emulsion drilling fluids provided
by different supplies in the presence and absence of 1 wt% Fe(OH)3 NPs. Composition
of invert emulsion: (90:10) oil:water (v/v).‎

99
The data in Figure 4.18 suggest that in the presence of NPs lower the viscosity can
reduce the pumping power requirement without compromising the carrying capacity of
the drilling fluid to transport and drop off cuttings efficiently.

4.2.12 Performance of Fe(OH)3 NPs in water based mud (WBM)

Fluid invasion into porous formations can damage reservoirs and reduce productivity by
blocking hydrocarbon exit flow paths or causing formation damage. Fluid penetration
while drilling using WBM can lead to shale formation swelling and, subsequently, well
bore instability (Sensoy et al, 2009). Currently most fluid loss additives in WBMs have
formulations based on bentonite clays, lignite, asphaltite and organic polymers
(Kosynkin et al., 2011; Moore et al., 1974). In terms of environmental and economical
considerations, WBM would be preferred if the interaction between the fluid and the
shale could be controlled.
Water based muds are suitable only for relatively low temperature and pressure
drilling operation (Agarwal et al., 2009). Xanthan gum is a rheological modifier that
typically used in WBM to increase viscosity and improve dispersion stability. In the
current experiment, few mg of surfactants (Dioctyl sodium sulfosuccinate) were used to
provide adequate stability of NPs. Table 4.16 displays fluid loss results after 30 minutes
for WBM containing 0.60 wt% Fe(OH)3 NPs formed ex-situ and in-situ methods.

Table 4.16: API LTLP WBM fluid loss at 30 min in the presence and absence of 0.60
wt% in-house prepared Fe(OH)3 NPs.
Water based DF+ ex- Water based DF+ in-
Water based DF
situ NPs situ NPs
8.8±0.6 8.0±0.2 (9%*) 6.3±0.2 (28.4%*)
*Fluid loss reduction, %.

Comparison of the fluid loss behavior of invert emulsion and water based fluids ‎shows
that emulsion fluids exhibited a better fluid loss control. The types of clays used in both
muds were different. Organophillic clays (surface modified bentonite clays) which are
normally treated with amines in order to make them oil dispersible and largely used in
invert emulsion mud formulation, whereas regular unmodified bentonite clays are used

100
in water based mud. Due to surface modification, organophillic clays extended the clay
properties in terms of rheology, carrying capacity, fluid loss control, etc. (Paiva et
al.,2008; Juppe et al.,2003).
Comparing the results for WBM alone to the samples containing the NPs it can
be concluded that the NPs probably contributed to the mud cake and resulted in an
overall reduction in fluid loss. It can also be inferred that the in-situ prepared NPs
interacted better with the mud cake, again, probably as a result of better dispersion in
the original mud. Cei et al. (2011) used commercial and non-modified silica NPs with
sizes ranging from 5 nm to 22 nm in a WBM and showed that concentrations ≥10 wt%
NPs reduced fluid loss by 25-30%. Similarly Kosynkin et al. (2011) showed that using
graphene oxide (GO), a combination of large flake GO and powdered GO in a 3:1 ratio
to perform, in WBM with a concentration of 0.2% (w/w) based on carbon content
resulted in 15.3% fluid loss reduction. Amanullah et al. (2011) used 0.14% (w/w) silica
NPs in WBM formulation along with different additives including polymeric additives.
Their study showed that the API fluid loss behavior of nano-based fluid showed similar
fluid loss as the original water based mud and did not improve the fluid loss reduction
performance.
It was observed by Flask and Jamison et al. (1989) that fluid penetration into the
pore space was controlled by the size of the aggregates in the drilling fluid relative to
the pore size of the formation. The size of aggregates in the drilling fluid controlled initial
bridging and formation of the filter cake. There are few guidelines used in oil and gas
industry to choose particle size in order to optimize their role as bridging materials.
Among the guidelines, Suri and Sharma (2004) showed that in order to form bridges,
particle sizes should not be larger than one third of the pore throat size. This implies
that wide range of NPs used in the current work makes it more effective in plugging
nano to micro pore throat. Of course, NPs plugged primarily the ones that fit that size
and then in some cases aggregate together to plug the big pore size. Similar
observation was reported by Sensoy et al. (2009).
Overall, WBM loss reduction contributes to reducing wellbore instability
problems.

101
4.2.13 Toxicity evaluation Fe(OH)3 samples
In recent years, the usage of inorganic NPs has increased exponentially for a variety of
applications (Buzea et al., 2007). In this context, it is necessary to assess the
environmental and biological risks of NPs used in this work. It should be noted,
nevertheless, one of the advantages of the in-house methods developed in this work is
the fact that the resultant NPs is contained within a liquid mixture rather than being
airborne. This minimizes inhalation and reduces health risk significantly. In Alberta, on-
site disposal of the drilling waste is allowed, provided that criteria imposed by the
Alberta Energy and Utilities Board (AEUB) are met (AEUB, G50, 1996). To be rated
essentially non-toxic, an EC50 of at least 75% of the original waste concentration must
be obtained. This threshold limit is compatible with pass/fail results in bioassay. It is
therefore useful to have an estimate of the ferric hydroxide NPs concentration that could
cause bioassay failure, i.e EC50 (15 min)< 75% (Ashworh and Walker,2006). Iron
hydroxide NPs were broadly used and selected for their low toxicity. Commercial Fe 3O4
NPs exhibited toxicity at 45% of initial concentration (García et al., 2010). Iron hydroxide
NPs prepared in this work only showed toxicity when NPs concentration increased to
concentrations > 15 % by volume, as per Table 4.17. Therefore, it is safe to say that at
the concentrations employed in this work, 1 wt%, Fe(OH)3 NPs is nontoxic.

Table 4.17: Microtox bioassay of Fe(OH)3 NPs.

Test Fe(OH)3 Results Interpretation (AEUB,G-50)

Concentration Pass/Fail; (Pass if EC50>75%)
(V/V)
EC50 50% 18.7 Fail
EC50 35% 22.5 Fail
EC50 35% 37.5 Fail
EC50 20% 64.8 Fail
EC50 15% 100 Pass

102
4.3 CaCO3 Nanoparticles (NPs) Characterization

As described in Section 3.2 of the experimental work, two methods were adopted to
form CaCO3 NPs; namely ex-situ and in-situ. Moreover, in-situ CaCO3 was prepared
from salt precursors as well as CO2 injection.

4.3.1 X-ray diffraction analysis

The structure prepared by precipitating CaCO3 NPs ex-situ starting from aqueous
Ca(NO3)2 and Na2CO3 precursors is shown in the X-ray diffraction (XRD) patterns of
Figure 4.19. The X-ray diffraction pattern shows that there is evidence of distinct peaks
which would be expected from a crystalline material.
Calcium carbonate has three crystal structures; calcite, aragonite and vaterite
(Kabalah-Amitai et al., 2013). Typically, calcium carbonate exists as calcite, which is the
most thermodynamically stable structure at ambient temperatures and pressures (Lee
et al., 2001), whereas vaterite is most unstable. Aragonite is less stable than calcite
and commonly found in marine organisms (Tai and Chen, 2008). The data obtained
from the X-ray diffraction patterns in Figure 4.19 demonstrates the crystalline nature of
the sample under analysis. The X-ray diffraction pattern of the synthesized calcium
carbonate exhibits characteristics peaks at 2θ values of 34.28°. These are the strongest
peaks observed in the X-ray diffraction patterns of the analysed samples which
represent calcite (CaCO3). Knowles and Freeman (2004) and later Jamaluddin and
Ahmad,(2010) stated that CaCO3 crystals overlapping each other induced the fibrous
morphology of the crystal, thus creating rough glaze surface. Due to its fiborous nature,
calcite can cement the existing rock grains or fill the fracture and act as a bridging
agent. All the precursors were assumed to react completely to form calcium carbonate.
This observation is agreeable with previous studies (Yao et al., 2010; Rahman and
Oomeri, 2009; Tong et al., 2004).

103
 Figure 4.19: X-ray diffraction pattern of ex-situ prepared CaCO3 NPs starting from the
aqueous precursor salts.

4.3.2 Size distribution of ex-situ prepared CaCO3

The TEM photographs and the corresponding particle size distribution histogram for the
ex-situ prepared CaCO3 are shown in Figures 4.20 and 4.21. The histogram shows a
wide size distribution with most of the population falling in the range between 31-60 nm
and a mean particle size of 60 nm. Figure 4.20b demonstrates a high degree of NPs
crystalline nature of the sample taken from an illuminated area of crystals are known to
form easily under laboratory conditions, especially when calcium carbonate precipitates
quickly (Lee et al. 2001). It can be assumed that Ca2+ ion concentration on the surfaces
of nanoparticles resulting in the growth of CaCO3 crystals as shown in Figure 4.20a.
The TEM image shows that the ex-situ prepared NPs have different shapes, from
subrounded to subangular. The picture clearly shows that there is crystalline particles
overlapping and affinity towards formation of polycrystalline. The images were
consistent with the D spectra which showed the crystal structure of CaCO3 NPs.
During NPs preparation, higher collisions rate of NPs might increase the probability of

104
the formation of larger particles and aggregation of fine particles (Nassar and Husein,
2007a), especially since no capping agents were used to prevent aggregation and
shearing was the only way to control particle size.

a) b)

Figure 4.20 : TEM photographs of ex-situ CaCO3 NPs at two different

magnifications.
Number of Particles, %

Figure 4.21 : Particle size distributions of ex-situ prepared CaCO3 NPs.

105
4.3.3 Determination of particle size of in-situ prepared CaCO3
Calcium carbonate NPs are considered ideal bridging materials of the pore throats of
the mud cake. The particle sizes in nano domain might generate slurries and
suspensions in drilling fluid that will show a reduced tendency to sediment or sag and
minimize the differential sticking problems (Ballard and Massam,2009). TEM results
show that the ex-situ prepared CaCO3 NPs are bigger than their Fe(OH)3 counterparts.
SEM images of the mud cake without and with in-situ prepared CaCO3 NPs are shown
in Figure 4.22. It should be noted that WBM was used this time due to limitations
associated with EM imaging of oil-based mud cake, especially gold coating, which
took much longer time. As discussed earlier, SEM imaging of the filter cake was the
only way of evaluating in-situ prepared NPs. One thing to note at this stage of
discussion, there is no smooth surface like the one obtained with in-situ Fe(OH)3 NPs
formulated in invert emulsion mud. This fact is reflective of the overall poor fluid loss
prevention when the two cases are compared. The mud cakes surface roughness was
varied from cake to cake and particle sizes varied as well. Texture changes could also
happen during evaporation of water and gold coating of the surface of water based mud
cakes (Chenevert, 1991). Mud cake without NPs was rough and the surface was
composed of chunks of large mud particles, which explains the poor loss prevention
capability of the mud cake. In the presence of in-situ NPs prepared from aqueous
precursors as per reaction (R2), the surface became smoother, although roughness is
still apparent. Nevertheless, particles were much smaller in size and could tighten up
fluid intrusion through the surface. Similarly mud cake with in-situ NPs prepared by
bubbling CO2 as per reaction (R5) surfaces was even smoother than the in-situ NPs
prepared per reaction (R2). Comparing the results of with and without NPs clearly
demonstrates that CaCO3 NPs are effective in forming bridges. Clay surfaces were
covered with CaCO3 particles in both NP-based mud cake, as was evident from the
white color of the cake surface. The observed morphologies of the samples showed
distinct features in terms of particle sizes and as well as surface composition evaluated
by EDX of Figure 4.23.

106
 a) b)

100 nm

c) d)

100 nm

e) f)

100 nm

Figure 4.22 : SEM images of mud cake a&b) without NPs ;c&d) in-situ CaCO3 NPs
(R2); and e&f) in-situ CaCO3 NPs (R5).

107
From the SEM images it is evident that the pore openings in the mud cake without NPs
were filled with NPs leading to reduced fluid loss, as will be discussed in the following
section. EDX spectra of Figure 4.23 provide elemental composition of the surface of the
mud cakes as shown in Figure 4.22. Magnification of mud cakes showing the grain
sizes and particles size distributions were estimated by using ImageJ software as
shown in Figures 4.24 and 4.25. The SEM images of mud cake without NPs revealed
that the grains mostly irregular from subrounded to subangular (Figure 4.22a). It is also
noted that the pore opening sizes range from 4 nm to 180 nm with average pore
openings were located in 31-60 nm range. These pore openings are resembled as a
pore throat in shale formation. The EDX analysis revealed that Ca content in mud cake
without NPs was below the detection limit or trace amount of Ca content was present
(Figure 4.23a). The in-situ NPs formation was confirmed by the presence of Ca content
and increased amount of Ca element, as per EDX images of Figure 4.23b-c.
Figure 4.25 shows the particle size distribution of in-situ prepared CaCO3 NPs
used as fluid loss additive (bridging agent) in our experiment. The NPs particle size
distribution (1-200 nm range) were confirmed by the SEM images and reported only
those were on the surface of the cake. More than 50% of NPs were 1-30 nm range as
shown in Figure 4.25 and potential to plug the nanometer sized pore openings of the
mud cake as shown in Figure 4.24. A wide particle size distribution was available that
covered some large particles available to bridge across large openings or fracture.
However, it is also to be noted that some NPs might diffuse into the cavity of the pores
permanently and were not counted in the measurements. A magnified photograph of
NPs indicated that particles entangled together to form aggregates and deposited on
the clay pores to form a low permeability mud cake as shown in Figure 4.22c-f.

108
 a)

b)

c)

Figure 4.23 : Elements containing mud cake a) without NPs,b) with insitu NPs (R2) and
c) with insitu NPs (R5) from EDX data.

109
 70

60

50
Frequency,%

40

30

20

10

0
1-30 31-60 61-90 91-120 121-180

Pore openinigs in mud cake (nm)

Figure 4.24 : Available pore openings (nm) in mud cake of DF without NPs.

Figure 4.25: Particle size distribution of in-situ CaCO3 NPs, prepared by reactions (R2)
and (R5), in the mud cake.

110
The range of NPs size is narrow and it can be seen that the method followed is an
appropriate method for NPs production. The selection of CaCO3 NPs as bridging
material with a specific particle size distribution was in accordance with the physical-
chemical characteristics of formations to be drilled. It is important to have a substantial
colloidal fraction of particles in the mud with a broad PSD (particle size distribution). The
criterion of selection of particle size of bridging agent is particles about one-seventh to
one-third the size of the maximum “pore throat” and the fluid must maintain a significant
concentration of those particles throughout the interval (Cargnel and Luzardo,1999).
Thus, if NPs, for example, is larger than the diameter of the pores, it will simply sit on
top of that pore. There are other various guidelines used in industry to choose the
particle size of bridging materials that can form an efficient external filter cake. A median
particle size of the bridging agent equal or slightly greater than one third of the median
pore size of formation and concentration of bridging agents must be at least 5% by
volume in final mud mix (Abrams,1977), 90% of the particles are smaller than or equal
to the pore size of the rock ( Hands et al.1998). In the mud cake pore throat size
diameter falls below 10% at 61-180 nm range and 90% of nanoparticles lies between 1-
60 nm range. According to the relationship stated above, the NPs size is more suitable
for bridging materials at the cake surface and ensure that tailor made NPs are potential
to reduce the permeability of mud cake. As the dimension of NPs lies in the contiguous
area between the clusters and the macroscopic materials, they will not directly dictate
macroscopic properties, but bring their own unique effects such as surface effect, size
effect etc (Nabhani et al.2011).
Mud cake contains interconnecting pore spaces more like those of permeable
rock considered as a theoretical pore throat diameter of shale and is just an
approximation. A mud having wide range of particle size distribution adsorbed by clay
might slow down the filtrate. It presumably would seal the surface pores, stuck on the
surface of the clay and filter paper and establish the formation of low permeability filter
cake, whereas without NPs mud containing only clay start to form highly permeability
filter cake. The correct particle size distribution provides better compaction medium with
constrained flow of liquid from the drilling fluid. Therefore, drilling fluid containing CaCO3

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NPs of sizes ranging up to 200 nm, the requisite maximum were able to effectively
bridge the formation and formed filter cake.
The relative pore size openings of the mud cake of drilling fluid without NPs
explained that the SEM result was found to be in good agreement with NPs considered
as a bridging or plugging agent to reduce the fluid loss.

4.3.4 LTLP Filtration of in-house prepared CaCO3 NPs

Drilling muds can cause large irreversible damage to fractures and dramatically reduce
the productivity of wells. Leoppke et al. (1990) found that if the particle size is not
compatible with the fracture width, a stable bridge cannot be formed and therefore
tailored particle size distribution provides the best plugging capabilities. It is essential to
drill the wells with minimum cost in loss of fluids. Al-Riyamy and Sharma (2004) used 5
wt% CaCO3 of narrow size distribution and found that volume of the filtrate decreased
when CaCO3 was used and reduced the invasion of emulsion droplets into the
formation, although granular CaCO3 LCM were found much less effective (Jiao and
Sharma, 1996). Currently all types of CaCO3 are used largely as fluid loss control
additives in drilling fluid. But the current size range of CaCO3 used does not serve the
purpose of the complete fluid loss control. More interestingly, the nanometer CaCO3
could result in much thinner filter cakes than those obtained using large sized CaCO3.
Isambourg and Matri (1999) showed how much force required to free a stuck pipe with a
change in mud cake thickness. This highlights the importance of nano drilling fluid with
thin mud cake development. The first step when choosing the particle size distribution of
bridging agent specifically CaCO3 in drilling fluid is the petrophysical characterization
and pore geometry determination of the rock. In consolidated sands, the criterion of
selecting particle size as bridging agent is (Cargnel and Luzardo,1999) :

1/7 DPore throat < Dparticle < 1/3 DPore throat

Bentonite clay particles have sizes of ~1-2 μm (at dispersed phase) according to
the supplier. During the migration of particles through the paper filter (2.7 µm pore
diameter) in our case resembling pore throats of the rock, they began to accumulate in

112
the filter surface. To avoid internal blocking, it is necessary to create a mud cake at the
surface of the pore throat in wellbore.
Static filter loss tests are relative, i.e, they can compare on a qualitative level
which mud systems are preferable and widely used by drilling crews for routine field
tests (Nyland et al., 1988). Total fluid loss is the indicator of the filtration controllability of
mud and its additives. It is apparent from the Table 4.18 that more than 60% of the API
fluid loss reduction occurred using ex-situ NPs and 55% when used in-situ CaCO3 NPs
prepared by reaction (R2). NPs primarily form a impermeable filter cake surface on the
filter paper. Permeability decreases with increasing fraction of colloids and is affected
strongly by particle size and shape of NPs. Flocculation causes particles to form a loose
and open network leading to higher filtration rate as indicated by the drilling fluid without
NPs where clays are dominant. After adding CaCO3 NPs in the drilling fluid probably
acted as a cementing and bridging agent that stabilized the bentonite clay aggregates
and could decrease the clay swelling and prevented their disintegration. Due to CaCO 3
concentration in drilling fluid, which probably below the flocculation value caused the
migration of dispersed NPs into the pores of mud cake during filtration.
Comparison between Tables 4.18 and 4.19 shows that total filtrate is the highest
for the water based mud than the invert emulsion based mud. In both cases, the invert
emulsion NP-based mud had a very low filtration rate during the first 7.5 min and the
rate still lower during the 30 min. The water based NPs mud had a much higher initial
filtrate rate but after 30 min it was still closely two times greater than the invert emulsion
NP-based mud. CaCO3 in water based mud might have a flocculating effect seen by the
relative fluid loss performance with respect to invert emulsion mud and also affected by
the difference in mud constituents in the two fluid systems. Using 3 wt% nano CMC and
nanopolymer as a fluid loss additives in water based mud, 14% and 19% respective
fluid loss reduction was noticed in literatures (Saboori et al,2012; Manea et al.2012),
whereas 3 wt% CaCO3 NPs addition in the current experiments yielded 30% fluid loss
reduction.

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Table 4.18: API LTLP fluid loss comparing invert emulsion drilling fluid as base case
with invert emulsion drilling fluid samples containing 4 wt% in-house prepared CaCO3
NPs using reaction (R2). No LCMs added
Samples Time LTLP Fluid Loss (mL)
Types
(min) DF DF + ex-situ NPs DF +in-situ NPs

90:10 (v/v) 7.5 3.9±0.2 0.7±0.6 1.1±0.6

Oil: Water 30 8.7±0.2 2.8±0.6 (68%*) 3.9±0.3 (55%*)
*Fluid loss reduction,%

Table 4.19: API LTLP fluid loss comparing water based drilling fluid as base case with
water based drilling fluid samples containing 3 wt% in-house prepared CaCO3 NPs by
reaction (R2).
Samples Types LTLP Fluid Loss (mL/30 min)
DF DF + ex-situ NPs DF +in-situ NPs

Water based DF 9.5±0.2 6.5±0.2 (32%*) 6.8±0.2 (28%*)

*Fluid loss reduction,%

When Ca(NO3)2 and Na2CO3 precursors are added in the drilling fluid in order to form
CaCO3 NPs, a bi-product of NaNO3 salt was also produced. This formation increased
the ionic atmospheric charge on clay sheets. The attractive force between the ionic
atmosphere might force the individual clay sheets to regrouping, decrease the pore
openings and interlock at random angles, thereby fluid loss reduction would happen.
Since, such regrouping is a matter of statistical probability, some clay sheets may still
have openings difficult to move and, therefore, complete fluid loss reduction was not
possible. On the other hand, sodium nitrate itself acts as nitrogen based fertilizer.
Adding nitrates encourages the proliferation of nitrate-reducing bacteria in the oil-
seawater mixture. When present in the appropriate numbers these bacteria help loosen
oil from the rocks containing the reservoir. For this reason, since long Statoil Norway is
injecting sodium nitrate along with seawater to pump oil from the underground reservoir
(RSC,2003).

114
 A 4 wt% CaCO3 NPs concentration represents the optimum concentration in
which the volume of filtrate reached minimum values and better arrangement of
particles occurred in the filter cake surface turning into an impermeable cake. Besides,
the spurt losses are found lowest. Comparing between Tables 4.18 and 4.20, it can be
easily seen that in-situ CaCO3 NPs reaction (R5) yields lower spurt loss, filtration rates
and total filtration volume. The cake formation was instantaneous and effective. During
the initial stage of filter cake forming, NPs plug or bridge the near surface pores and
reduces formation permeability. Bailey et al. (1999) showed that the particle bridging
reduced the spurt loss. Because of this bridging tendency, quick external filter cake
formation is obvious in case of the in-house prepared CaCO3 NPs using reaction (R5).

Table 4.20: API LTLP fluid loss comparing invert emulsion drilling fluid as base cases
with invert emulsion drilling fluid samples containing 4 wt% in-house prepared CaCO3
NPs using reaction (R5).

Samples Time LTLP Fluid Loss (mL)

Types
(min) DF DF +4 wt% in-situ NPs

90:10 (v/v) 7.5 2.6±0.2 0.5±0.3

Oil: Water 30 6.4±0.3 2.2±0.4 (66%*)
*Fluid loss reduction,%

NPs of CaCO3 modify the structure of clay due to Ca2+ cation exchange leading to
agglomeration of clay particles, which also increases internal friction among the
agglomerates and thereby reduced permeability of mud cake. As far as these NPs are
considered as fluid loss reducing agent, it gains better properties of keeping the
cumulative volume of filtrate at low values. It is due to the fact that when these NPs are
brought into the clay particles, the interaction area was considerably increased due to
higher surface area of NPs. Increased area to volume ratio in NPs cause the increase of
ionic group molecular weights for adsorption on the clay particle surface and attached
them to each other leading to form more colloidal particles. In addition, the presence of
CaCO3 NPs may induce a Brownian diffusion with clay particles. Spurt losses observed

115
with CaCO3 are acceptable from a drilling point of view. Looking at the above tables, it
is obvious that the effect of NPs presence intensified the flow resistance of the system.

4.3.5 HTHP Filtration of in-house prepared CaCO3 NPs

High temperature filtration rates could not be predicted from low temperature filtration.
Filtration rates increased at high temperature that could be attributed to the reduced
viscosity of oil alone. The samples exhibited a very low fluid loss at low temperatures
and same relative performance at high temperatures. Nanos having an excellent
thermal conductivity are expected to be the materials of choice in HTHP wells (Agarwal
et al., 2009). When the pressure is applied (500 psi differential in the HPHT tests) the
filtration became slow due to the bridging/agglomeration tendency of NPs at high
temperature. The HTHP fluid loss property of CaCO3 NP-based drilling fluid prepared
through reaction (R2) is shown in Table 4.21. It showed that NPs concentration equal to
4 wt% reduced more than 70% of the fluid loss. Similar trends were observed at
previous Fe(OH)3 NPs. The differences are thought to be a result of the surface
morphologies of the two different NPs. In order to determine the HTHP fluid loss with
CaCO3 NPs prepared in reaction (R5), results are reflected in Table 4.20. It is shown
that NP-based mud provided the lowest spurt loss and total filtrate loss. Addition of
optimum concentration of NPs improved filtration properties, however the extent of the
improvement depend on the mud type, nature of NPs material, NPs synthesis method,
size distribution of NPs and concentration of surfactants. As it can be seen, the total
filtrate passes through is minimum in the case of in-situ CaCO3 NPs prepared through
reaction (R2). But more interestingly, fluid loss towards zero is apparent in reaction
(R5).

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Table 4.21: HTHP fluid loss comparing invert emulsion drilling fluid as base cases with
invert emulsion drilling fluid samples containing 4 wt% in-house prepared CaCO3 NPs
using reaction (R2).
Samples Time HTHP Fluid Loss (mL)
Types (min)
DF DF+ ex-situ NPs DF+in-situ NPs

90:10 (v/v) 7.5 10±0.2 2.4±0.1 1.8±0.2

Oil: Water 30 19.2±0.2 5.6±0.1 (71%*) 5.4±0.2 (72%*)

*Fluid loss reduction,%

Table 4.22: HTHP fluid loss comparing invert emulsion drilling fluid as base cases with
invert emulsion drilling fluid samples containing 4 wt% in-house prepared CaCO3 NPs
using reaction (R5).
Samples Time HTHP Fluid Loss (mL)
Types
(min) DF DF +4 wt% in-situ NPs

90:10 (v/v) 7.5 10±0.2 0

Oil: Water 30 19.2±0.2 0 (100%*)

*Fluid loss reduction,%

High pressure and high temperature filtration tests clearly demonstrated that
CaCO3 NPs have the ability to reduce filtrate loss to the formation. No emulsion droplets
were observed in the filtrate means emulsion droplets containing NPs were needed to
form a stable external filter cake. The acid soluble CaCO 3 NPs could be concentrated at
oil/water interface as like Fe(OH) 3 NPs and restricted the flow of fluid to the porous
media.

4.3.6 Drilling fluid density and pH

As different formations are encountered with depth increases, the densities of drilling
fluids shall be proportionately adjusted to balance the drilling system while drilling. So
weighting materials should be continuously added to drilling fluids. CaCO3 NPs used as
weighting materials in adjusting drilling fluid density could reduce the extra additive cost.

117
As shown in Table 4.23, a significant change in the drilling fluid density was seen. Due
to its distinctive nature as weighting material, addition of CaCO3 NPs can increase the
fluid density. But no change in pH was observed. It can be observed that the pH is 12.5
remains constant even after addition of CaCO3 NPs. This effect is probably explained
by the absence of chemical interactions between CaCO3 NPs with other materials used
in drilling fluids. Apart from that the NPs concentration was too low to increase and/or
decrease of density and pH of CaCO3 NP-based invert emulsion fluid. NPs may be
embedded in the clay matrix.

Table 4.23 : Density and pH measurements of drilling fluid samples in the presence
and absence of 4 wt% in-house prepared CaCO3 NPs.
Test samples
DF DF+ 4 wt% ex- DF+ 4 wt% in-
Samples Properties
situ NPs situ NPs
Types
Density 0.89±0.06 0.93±0.02 0.93±0.02
90:10 (v/v) (g/cm3)
Oil: Water pH 12.5 12.5 12.5

4.3.7 Rheology behavior of NP-based fluid

When rheological properties are considered, CaCO3 NPs provide satisfactory mud
system. Mud rheological properties (viscosity vs. shear rate) were measured at room
temperature and pressure. Analyses of the rheological properties of the drilling fluids
shown in Figure 4.27 indicated a viscous profile of the nano-based fluid at low shear
rate, but at high shear rate there was no significant changes. Using CaCO3
microparticles, the viscosity of drilling fluids were increased substantially as shown by
Manea et al. (2012). Properties measured at 10-sec and 10-min gel strength were also
shown in Figure 4.28.

118
 DF DF+4wt% Ex-situ NPs(R2)
DF+4wt% In-situ NPs (R2) DF+4wt% In-situ NPs(R5)
1000
Apparent Viscosity

100
(cP)

10

1
1 10 100 1000 10000
Shear Rate (Sec-1)

Figure 4.27: Rheological behavior of invert emulsion drilling in presence and absence
of 4 wt% in-house prepared CaCO3 NPs. No LCMs added.

Figure 4.28: Gel strength behavior of invert emulsion drilling fluid in presence and
absence of 4 wt% in-house prepared CaCO3 NPs. No LCMs added.

119
 All the muds had almost similar viscosities in the high shear range although NP-
based muds were slightly thicker in the low shear range than conventional invert
emulsion based muds (DF). The shear thinning properties of drilling fluid would be
advantageous in providing better hole cleaning. Similar trends were observed by
Simpson, (1979) and Sensory, (2010). With the addition of CaCO3 NPs (both ex-situ
and in-situ), the gel strength was also increased. Similar observations were also
reported by Manea et al.(2012). CaCO3 NPs as a bridging agent might have proper
mechanical and chemical consistency to be used in NP-based drilling fluid design.
Chemically, it is acid soluble so that CaCO3 laden mud cake can be removed easily
from the porous matrix to recover the permeability of the rock.
On the basis of the results, we believe NPs size and ability to keep particles
dispersed throughout the mud system allowing fluid loss reduction. CaCO3 NPs based
mud system proved versatile enough to provide better fluid loss control while retaining a
consistent viscous profile.

4.3.8 Drilling fluid lubricity

Lubricity is a very important parameter that was considered due to long extended reach
characteristics of wells. Coefficient of friction less than 0.1 or less is generally
advantageous as it helps the cuttings to travel as discrete particles over shaker screens
(ASME, 2005). The choice of CaCO3 NPs as a lubricity additive is due to its availability.
With the help of surface activity of CaCO3, NPs can effectively lower the friction
between drilling tools and borehole walls and reduce the difficulty in drilling of highly
deviated wells and horizontal wells. 4 wt% of CaCO3 NPs induced appreciable reduction
in the coefficient of friction. A comparative performance with regular base drilling fluid is
shown in Table 4.24. The friction of coefficient was reduced to 2.1% and 38% by using
ex-situ and in-situ prepared CaCO3 NPs, respectively. Using commercial silica as NPs
in drilling fluids improved lubricity by 3-5% as reported by Riley et al. (2012). High
drilling cost can be caused by slow drilling rates due to improper lubricity quality.
Therefore the results indicated the feasibility of CaCO3 NPs that could permit the
improved drilling rate.

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Table 4.24 : Coefficient of friction of invert emulsion drilling fluid in presence and
absence of 4 wt% in-house prepared CaCO3 NPs. No LCMs added.
Co-efficient of friction % torque reduction
DF without DF+ex-situ DF+in-situ DF+ex-situ DF+in-situ
NPs (control) NPs NPs NPs NPs
0.095 0.093 0.059 2.1% 37.89%

4.4 Invert emulsion drilling fluid API fluid loss characterization using other NPs

From a practical point of view, the presence of NPs in drilling fluid is worth to be studied,
evaluated and therefore found promising. The advantages of using these NPs are that,
there is formation of more continuous and integrated mud cake. Having low permeability
and low porosity mud cake, there is less volume of filtrate entering into the formation
and mud cake thickness is less compared to DF and DF with LCM cases. Regular mud
systems contain large quantities of fine solids that penetrate the productive formation
causing irreversible plugging and influence negatively in the productivity of the wells.
Barite (BaSO4) of drilling fluids is such a component and when it invades the productive
area, it creates internal block within the formation which is difficult to remove (Cargnel
and Luzardo,1999). In normal, barite in drilling fluid is used as weighting material.
Conventional powdered barite exhibit an average particle diameter in the range of 10-30
microns. To adequately suspend these materials requires the addition of gellant such as
bentonite. However more gellants addition could increase fluid viscosity and undesirable
fluid properties (Ballard and Massam, 2009). The nano barite could alleviate those
problems in drilling fluid and may control colloidal interaction of particles.
Different NPs are prepared in the novel method described in the experimental
section to validate the prepared method. The techniques provide novel insight in fluid
loss reduction problems while drilling wells and help in counting the problems in a more
efficient and environment friendly manner. BaSO 4 and FeS NPs were tested to check
their specific performance in fluid loss control as shown in Table 4.25. Addition of 3 wt%
NPs in drilling fluid reduced fluid loss from 68 to 85 % for BaSO 4 and 90% for FeS NPs.
The adsorption process in clay involves a negative global charge in its surface, is

121
generally balanced by inorganic cations (Ba 2+, Fe2+) in the internal and external
surfaces of clay material. Some nanoparticles may also aggregate and deposit into the
cake, therefore the Brownian motion of the particles and the van der Waals and
repulsive forces for the nanoparticles are equally important.

Table 4.25 : API LTLP fluid loss of invert emulsion DF in presence and absence of 3
wt% in-house BaSO4 and FeS NPs. No LCMs added.

DF DF+ ex‐situ BaSO4 DF+ in-situ BaSO4

3.5±0.3 (68%*) 1.6±0.3 (85.3%*)

mL/ 30 min
10.95±0.3 DF+ ex-situ FeS DF+ in-situ FeS

1.15±0.3 (89.5%*) 0.93±0.1 (91.5%*)

*Fluid loss reduction,%

4.5 Summary of the API fluid loss study of different NPs in Invert emulsion

The most frequently encountered problems while drilling oil and gas wells are lost
circulation causing substantial financial loss. This problem occurs during the
uncontrolled flow of drilling fluids into vicinity of porous and permeable zones. The
proposed method incorporates using different nanoparticles in drilling fluid to decrease
fluid penetration and mud cake thickness. In the current study, the multifunction of NPs
in drilling fluid system is considered as the new hotspot in the field.
Results show that existence of nanoparticles caused the amount of fluid loss
reduction and mud cake thickness to decrease. By forming a thin, low permeability filter
cake NP-based fluid simulates sealing pores and other openings in the formations
penetrated by the drill bit. Different NPs were used as bridging agent to control the fluid
loss. Figure 4.29 and Figure 4.30 showed the effectiveness of different ex-situ and in-
situ NPs respectively in terms of fluid loss over a period of 30-min.

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 Figure 4.29: LTLP fluid loss behavior of different ex-situ NPs in invert emulsion.

Fe(OH)3 CaCO3 (R2) CaCO3 (R5) FeS BaSO4

100
Fluid loss reduction, %

80

60

40

20

0
Fe(OH)3 CaCO3 (R2) CaCO3 (R5) FeS BaSO4

Figure 4.30: LTLP fluid loss behavior of different in-situ NPs in invert emulsion.

The nanoparticle concentration in drilling fluid was varied from less than 1 wt% to 4 wt%
(1 wt% Fe(OH)3 NPs, 4 wt% CaCO3 NPs, 3 wt% BaSO 4 NPs and 3 wt% FeS NPs).
From the experimental trials, it can be concluded that zero spurt loss was achieved with
thin mud cake in all NP-based fluid. However, in-situ NPs responded with lower fluid

123
loss than ex-situ NPs. Due to different physio-chemical nature, sizes and interaction
potential with clays caused the NPs to behave differently. Therefore, optimum
concentrations of NPs were required to meet the desired fluid loss control property.
If the NPs formed were not well dispersed, stabilization of fluid systems were
hindered and then particles tempted to agglomerate and precipitate. Figure 4.31 shows
the different ex-situ prepared NPs and their stability performance. Adequate usage of
emulsifiers prevented the phase separation through steric or electrostatic means of
adsorbed dispersed NPs on clay matrix and/or emulsifiers surface. Increased viscosity
of the continuous phase system can also prevent separation of dispersed phase (Riley
et al., 2012). As nanoparticles addition in drilling fluid did not increase the fluid viscosity
significantly, it is therefore, best prefer in our current works to support steric or
electrostatic way of NPs stabilization.
Mud having low filtration characteristics deposited as thick filter cakes (Nyland et
al.,1988). Conversely, good filtration characterized by all the NP-based fluids yielded
thin mud cakes as shown in Figure 4.32. The thickness of the mud cake and its integrity
can reveal that NPs deposited on the cake with optimum concentration establish an
effective seal. For combating formation damage, NP-based invert emulsion as well as
water based mud would offer better protection. The filtrate invasion from the invert
emulsion would be less at the downhole pressure and offer better protecting against
differential pressure sticking.

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 FeS NPs BaSO4 NPs CaCO3 NPs Fe(OH)3 NPs

Figure 4.31: Different NPs and NPs-containing drilling fluid stability evaluation.

BaSO4 NPs filter cake FeS NPs filter cake

Fe(OH)3 NPs filter cake

CaCO3NPs filter cake Base filter cake filter

cake
Figure 4.32: NPs-containing drilling fluid filter cakes (thickness <1 mm).

125
 Chapter Five: Modelling

In this chapter, Darcy filtration equation was used to model drilling fluid loss for LTLP
filtration experiments only. Based on the results, permeability of the mud cake at
different times was estimated. In this section, time-dependent behavior of filter cake
build up model was also evaluated. An attempt to address how the nanoparticles
transport during filtration was made. Bingham plastic rheology was used to predict the
relationship between the shear rate and shear stress for the drilling fluids under study
and allowed to calculate several other important attributes of the fluid.

5.1 LTLP API filtration model using Darcy’s law

Drilling fluid filtration rate and its behavior with respect to time were estimated from the
experimental results using Darcy’s law (Maduka, 2010; Kumar, 2010; Hoff et al., 2005;
Donaldson and Chernoglazov, 1987; Ferguson and Klotz, 1954; Williams and Cannon,
1938). The LTLP API filtration test was static, dead end filtration, as the mud was not
circulated during filtration and the filter cake was allowed to grow without disruption by
shear forces. Under this condition, certain volume of a stable suspension is filtered out
against a permeable substrate, e.g. filter paper, with time. At time t, certain volume of
filtrate is removed by filtration at constant temperature and pressure (25°C, 100 Psi).
During the filtration process, filter cake accumulates and the volume of the mud sample
in the filter press is decreased. Assuming constant density (temperature must be
constant in order for Darcy’s law to be valid. If temperature changes with time, density is
also a function of time), the material balance equation expressed as a volume balance
for mud filtration process can be written as follows.

Drilling fluid volume in the filter press = Wet Filter cake volume + Filtrate Volume

126
The filter cake is assumed uniform throughout and the rate of growth of the filter cake is
proportional to the rate of filtrate. According to the volume balance, if a unit volume of a
stable suspension of solids is filtered against a permeable substrate and x volume of
filtrate is collected, then 1-x volume of cake (solids plus liquid) will be deposited on the
substrate. The following equation can be written (Maduka, 2010; Hoff et al., 2005).

QC x
 r (E 5.1)
Q f 1- x

where Qc and Qf are the volumes of the filter cake and filtrate at a given time,
respectively, r is the ratio between the volume of the filter cake at a given time to the
volume of the fluid filtrated in the filter press. From our experimental works and
filteration curves provided by Barkman and Davidson(1972), we can assume the
QC
following criterion for the ratio of .
Qf

QC
if <1 ; initial fluid pass through the filter cake and happens only at the
Qf
early stage of filtration

QC
if =1 ; fluid loss during filtration approximated by the linear relationship
Qf
between volume of filtrate vs. time. It can be termed as equilibrium filtration

QC
if >1 ; saturation occurs, curve departs from linear relationship
Qf
between volume of filtrate vs. time and slows fluid loss due to the compact cake
layer formation. Filtrate decrease with increase of cake volume

127
The cross sectional area of the filter cake A is constant under static filtration. The
volume of the filter cake, Qc, is given by the product of cross sectional area of the filter
press, A, and the thickness of the mud cake at a given time, hmc.

Qc  A.hmc (E 5.2)

Therefore,

Qc Qf .r
hmc   (E 5.3)
A A

From Darcy’s law, the flow rate of filtrate through the mud cake (an unconsolidated
porous medium) is given by,

dQ f kA P
 (E 5.4)
dt  hmc

Substituting (E5.3) into (E5.4) gives,

dQ f kA 2 P
 (E 5.5)
dt  r Qf

Integrating (E5.5) assuming constant permeability, viscosity and pressure difference

gives,

2kA 2 P t
Qf 
2
(E 5.6)
r

It should be noted that the ∆P was maintained constant throughout the filtration process.
Darcy’s law is obtained empirically and defines the permeability k as a proportionality
coefficient in the relationship between flow rate and pressure gradient (Costa, 2005).
Cake permeability is much lower than the permeability of filter medium.Finally, Darcy’s

128
law under the above assumptions leads to the following expression of filtrate volume
versus time.
2k P t
 Qf  .A (E 5.7)
r

The rates of mud filtration and mud cake formation are both function of time and
proportional to each other during filtration. Therefore, under equilibrium filtration
assumption, r can be taken as 1 (Hoff et al., 2005) and consequently,
2k P
Q f  k / t ; where k /  .A (E5.8)


It is well known that when an external mud cake begins to form and grow, the filtrate
volume is proportional to (Kumar, 2010; Hoff et al., 2005). From (E5.8) and (E5.3),
the thickness of the mud cake, hmc, at any time, t, during the filtration process, can be
simplified to,
2 k Pt
hmc  (E5.9)

At the initial exposure of a permeable formation to a drilling fluid, three stages of
mud cake build up evolve: 1) spurt loss, which corresponds to the initial loss of fluid to
the formation, 2) buildup of filter cake, during which fluid filtration is proportional to the
square root of time as reported by many researchers (Kumar, 2010; Hoff et al., 2005;
ASME,2005) and 3) filter cake growth, which might be limited by the erosive action of
mud stream within the dynamic context of real time drilling (Outmans, 1963). It should
be noted that the last stage does not exist under static filtration. The surface of the
“dynamic” filter cakes erode to an extent that depends on the shear stress exerted by
the hydrodynamic force of the mud stream relative to the shear strength of cake’s upper
layers (Caenn et al., 2011). Spurt loss can be obtained by extrapolating filtrate volume

versus t to zero time and is given approximately by the y-axis intercept of the plot as
shown in Figures 5.1 and 5.2. In all cases the NP-based fluids were compared with the
corresponding control DF samples. Although DF samples were composed using the

129
same constituents and obtained from the same suppliers, nevertheless, this does not
guarantee no variation from one batch to another. Therefore, NP-based fluid
performance was compared with respect to its own DF control samples. From the
current experiments, addition of NPs significantly reduced the bridging time and,
therefore, the spurt loss. In Figure 5.2, symbols (R2) and (R5) stand for the reactions
used in the experimental methods described in Chapter 3. The plot of filtrate volume, Q f,

versus ‎ t suggests a different filtration mechanism in the presence of NPs. The very
low Y-intercept for the case were NPs are used suggest that time needed to completely
bridge the porous mud cake to reduce the fluid loss is much faster in case of NP-
mediated DF, and more specifically in the case of Fe(OH) 3 NPs relative to CaCO3 NPs.
This suggests that Fe(OH)3 NPs are more effective than CaCO3 NPs at bridging across
the face of fracture of porous formation. A coefficient of determination, R2, approaching

1 for a straight line fit, not going through the origin, between Q f and t with positive
intercept in the case of no NPs, i.e. control samples and drilling fluid with LCM, indicates
that spurt loss is important, whereas for the NP-based fluids it was negligible. Spurt loss
is largely caused by the tendency of the particles to pass through the filter paper until its
pores become partially plugged, which eventually leads to linear relation between filtrate
volume and square root of time. Typically, a linear relationship w.r.t. square-root of time
represents wall building fluids (Clark,1990; Chin, 1995). Conversely, a region of non-
linear relationship appeared in the case of NP-based fluid at the beginning of filtration
due to the absence of spurt loss. An extrapolation of the linear portion of these curves
can lead to a negative spurt loss value. So it is evident from the trend that early portion
of curve did not follow the Darcy’s law. Therefore, (E5.9) does not provide a good
estimate of cake growth in the case of NP-based mud. The role of Brownian diffusion
during the initiation of filter cake will be explained in the next section.

130
 DF
4.5 DF+LCM
Volume of filtrate , 𝑄𝑓 (cm³)

4 DF+Ex-situ NPs R² = 0.99

3.5 DF+In-situ NPs R² = 0.98
3
2.5
2
1.5 R² = 0.99
1 R² = 0.97
No spurt loss
0.5
0
-0.5 0 200 400 600 800 1000
Time ( ), sec½

Figure 5.1: Filtrate volume variation with square root of time in the presence and
absence of in-situ and ex-situ prepared Fe(OH)3 NPs.

10 DF
Volume of filtrate , 𝑄𝑓 (cm³)

9 DF+Ex-situ NPs (R2) R² = 0.98

8 DF+In-situ NPs (R2)
7
6
5
4 R² = 0.98
3 R² = 0.99
2 R² = 1.00
1
0
0 200 400 600 800 1000
Time ( ), sec½

Figure 5.2: Filtrate volume variation with square root of time in the presence and
absence of in-situ and ex-situ prepared CaCO3 NPs. (R2) and (R5) refer to the
reaction used to prepare the CaCO3 NPs per Section 3.2.

The permeability of filter cake is the fundamental parameter that controls static filtration
(Caenn et al., 2011; Byck, 1940). During filtration of mud with and without conventional
LCMs, the trend seem to follow Darcy’s equation throughout, and mud cake
permeability (fitted parameter) was reduced exponentially with time as shown in Figures

131
5.3 and 5.4. The figures show a different behaviour for the mud cake permeability with
time for the NP-based fluid. The term k / were determined during each filtration times
from the data points of the Figure 5.1 and 5.2. Then using (E5.8), mud cakes
permeabilities were estimated at each time interval. The results were presented for the
sake of simple comparison between the drilling fluid with and without NPs using Darcy
equation. Spurt loss was nil during the initiation of the filter cake of NP-based mud, and
when filtration was stopped at a certain time, the mud cake growth reached a constant
value. It appears that the highly compacted filter cake contributed to significantly less
permeability and static filtration rate as evident from the smaller thickness of the filter
cake.

0.012
DF
DF+LCM
Permeability of mud cake

0.01 DF+Ex-situ NPs

DF+In-situ NPs
0.008
(nD)

0.006

0.004

0.002

0
0 500 1000 1500 2000

Time (sec)

Figure 5.3: Mud cake permeability variation with time in the presence and absence of
in-situ and ex-situ prepared Fe(OH)3 NPs. Permeability obtained from fitting E5.8.

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 0.35 DF
Permeability of mud cake 0.3 DF+Ex-situ NPs (R2)
DF+In-situ NPs (R2)
0.25
DF+In-situ NPs(R5)
0.2
(nD)

0.15
0.1
0.05
0
0 500 1000 1500 2000
Time (sec)

Figure 5.4: Mud cake permeability variation with time in the presence and absence of
in-situ and ex-situ prepared CaCO3 NPs. Permeability obtained from fitting E5.8. (R2)
and (R5) refer to the raction used to prepare the CaCO 3 NPs per Section 3.2.

The permeability was calculated from the equation (E5.8) and compared with the base
drilling fluid after 30 min filtration as shown in Table 5.1. It is shown that more than 90%
mud cake premeability reduction was achieved in the presence of NPs, whereas
conventional LCM reduced the permeability by 77%. The extent of permeability
reduction varied with NP type and method of preparation. Data in Table 5.1 suggest
potential use of NPs to plugg shale formation. As indicated in the results section, NPs
are capable of providing effective sealing since they displayed wide range of size
distribution, which could effectively bridge between clay particles initially forming the
cake.
Table 5.1: Permeability reduction of mud cake in the presence and absence of NPs.
(R2) and (R5) refer to the reaction used to prepare the CaCO 3 NPs per Section 3.2.

Cake Permeability after 30 % Reduction in

NPs Test Fluid
min filtration (nD) Permeability
DF(Control samples) 2.59X10-3 0
DF+LCM 5.84 X10-4 77.6
Fe(OH)3 DF+Ex-situ NPs 2.59 X10-4 90
DF+In-situ NPs 1.62 X10-5 99.4
DF( Control samples) 1.04 X10-2 0
DF+Ex-situ NPs (R2) 5.84 X10-4 94.4
CaCO3 DF+In-situ NPs (R2) 2.59 X10-4 97.5
DF+In-situ NPs (R5) 2.59 X10-4 97.5

133
On the other hand, inappropriate size of plugging materials results in the formation of a
thick and permeable filter cake leading to continuous filtration, which seems to be the
case for drilling fluids alone and DF with conventional LCMs. Therefore, pore throat
diameter of formation must be known to help ensuring effective bridging. A general rule
of thumb for estimating the unknown pore throat diameter (microns) is to take the
square root of the permeability in milli Darcies as per (E5.10). For effective bridging 20-
30% by weight of the bridging material should be one-third of the pore size in microns
as per (E5.11) (kumar, 2010).

Pore throat diameter (microns) = Permeabili ty (mD) (E5.10)

Pore diameter
D(50) = (E 5.11)
3

Following Darcy equation, (E5.4), calculation gave permeability available of the

filter cake of drilling fluid control sample after 30 min filtration was approximately from
0.0001 to 0.000051 mD= 102 to 51 nD. This permeability is low and actually is of the
same order magnitude of as in shale (Chenevert and Sharma, 1991). According to the
above equations, estimated pore throat size of the control sample mud cake after
filtration is 17-34 nm. It does suggest that pore throat sizes are on the nm scale within
the cake. NP-based drilling fluids contain 70% of NPs with sizes ranging from 1 to 30
nm as shown in Figure 4.4, which could easily ensure effective bridging and plugging of
the pores. Therefore, when NPs were introduced, further reduction in cake permeability
occurred, which was not achieved by using conventional LCMs.
Materials accumulation, which is commonly referred to as fouling may arise from
particles deposits on the filter surface, adsorbed on the cake surface, or within the cake
pores. The concentrations of fouling materials at the cake surface typically increases
with time. Consequently, resistance to permeate flow increases with time. NPs
accumulate in the cake surface due to convective deposition and reach a threshold
where the formation of cake layer can be predicted. This cake provides significant

134
resistance to fluid loss. Cake growth performance can be evaluated in terms of
permeate flux as follows:
V
Permeate (filtrate) flux = (E5.12)
t.S

where V is the volume of permeate in mL, t is the permeate collection time in sec and S
is the filter effective surface area = 62.06 cm2, from LTLP apparatus.

Figure 5.5 shows that permeate flux decreased with time probably due to cake layers
formation. The results show that the flux declined rapidly during the first 300 and 450
sec for DF and DF+LCM, respectively, followed by gradual decrease during the period
of 500 and 1500 sec. This type of decline is indicative of fouling, or resistance, gradually
building up on the surface of the filter paper. Although not on the same scale, permeate
flux for DF+NPs experienced sudden increase with time and approached a steady flow
as shown in Figures 5.5. The trend in permeate flow for NP-containing fluids can only
be explained by changes in cake structure. This influence of particle size on the
permeate flux was also described by Sethi (1997). Smaller particles (less than 0.01 µm)
formed thin filter cakes, which resulted in higher permeate flux, whereas monotonic
decline in flux occurred when larger particles (greater than 1 µm) were used.

135
 NPs+DF

Figure 5.5: Comparison of permeate (filtrate) flux with time in the presence and
absence of in-situ and ex-situ prepared Fe(OH)3 NPs.

NPs+DF

Figure 5.6: Comparison of permeate (filtrate) flux with time in the presence and
absence of in-situ and ex-situ prepared CaCO3 NPs. (R2) and (R5) refer to the reaction
used to prepare the CaCO3 NPs per Section 3.2.

136
It is believed that the cake build up was first initiated by clay particles, which were large
particles, even before the actual filtration started. These particles may deposit under
gravity effect by virtue of their large size. During the NP-based fluid filtration, NPs move
towards the large particles only by virtue of bulk flow. Similar observation was reported
by Chellam and Wisber (1997) for smaller particles transport in cross flow membrane
filters. Moreover, with large accessible surface area NPs can be adsorbed onto the cake
surface readily following travelling for short distances only. This leads to plugging
formation near the surface of the filter cake at early stages of its maturity and Brownian
motion becomes important in controlling particle deposition, since the pore openings are
generally not large.
Tran (2011) modeled the mud cake thickness for deadend filtration as an
exponential function of time until it attains its maximum thickness. Based on our
observation, the mud cake without NPs reached its maximum permeability reduction
after 30 min, whereas more reduction of the mud cake permeability was attained when
NPs were used. Therefore, a phenomenological model for cake growth of NP-based
fluid is proposed based on the experimental results obtained in this work. Similar
modelling approach was generally used for population and biomass growth (Edwards
and Edwards, 2011; Spier et al., 2009). The initial stage of growth is approximately
exponential, and then as saturation begins, the growth slows and at maturity, growth
stops. With this in mind, the following equation can be written to describe cake
thickness in the presence of NPs.
dhmc  h 
 ghmc 1  mc  (E5.13)
dt  X 

Equation (E5.13) can be integrated using separation of variables approach as follows.

dhmc
  hmc  
 gdt (E 5.14)
hmc 1  
 X 

137
Rearranging the LHS of (E5.14) gives,

1 X 1 1 (E5.15)
  
 h  h X  h  h X  h 
h 1   mc mc mc mc mc

 X
mc

The steps below follow,

dhmc dhmc
h mc

X  hmc  
 g dt (E 5.16)

ln hmc  ln X - hmc   gt  C (E5.17)

ln
X - hmc   gt  C (E5.18)
hmc

X - hmc  e gt  C (E5.19)

hmc

X - hmc   Ae gt
hmc
, where A  e  c
(E5.20)


hmc 1  Ae gt  X  (E5.21)

X
hmc (t) 

1  Ae gt  (E5.22)

where, A relative cake growth rate=

X - h 0  , h0= initial cake growth at time t=0
h0
measured experimentally before the actual filtration starts, i.e. hmc(0) = h0 and relative
cake growth rate coefficient, g, is obtained from the exponential differential equation
dhmc
=ghmc, g is positive and X is the maximum cake thickness in mm after 30 min.
dt

138
Finally, a model for cake thickness estimation in the presence of NPs can be written as
follows.

X
hmc (t)  (E5.23)
 X - h0  gt 
1  e 
 h0 

Assuming that all mud cakes attain their maximum thickness of X (mm) after 30 min of
mud filtration, the proposed cake thickness model (E5.23) can be used as the best
approximation to the mud cake deposition throughout the static filtration period for NP
based fluid. Bezemer and Havenaar (1966) proposed that for certain mud additives, the
mud cake permeabilities can be reduced significantly during the mud filtration process.
Equation (E5.10) shows that mud cake build up can be modeled as an exponential
growth. Mud cake porosity decreases as the NPs deposition increases and,
consequently, the filtrate flow through the cake decreases. With the above assumption,
the increase in cake layer thickness over time can be fitted from the initial cake
thickness until a steady state region is reached. From the API LTLP filter press
experiments after 30 min, the filter cake thickness was measured to be 0.35 mm for the
Fe(OH)3 NP-based fluid and 0.52 mm for the CaCO 3 NP-based fluid as shown in
Figures 5.7. The model, (E5.23), was used to estimate the time for filter cake buildup
with the following parameters h0 =0.01 mm (initial cake growth at time t=0 measured
experimentally before the actual filtration starts which is natural cake build up) and X
=0.35 mm for Fe(OH)3 NP-based fluid and h0 =0.01 mm (initial cake growth at time t=0
measured experimentally before the actual filtration starts which is natural cake build
up) and X =0.52 mm for CaCO3 NP-based fluid. From the model curves mud cake
thickness attained its maximum thickness, h mc= 0.35 mm at 40 min for Fe(OH) 3 and
0.52 mm 40 min for CaCO3 NP-based fluid, showing a fair agreement with the
experiments. The time-dependent behavior of the filter cake build up of NP-based fluids
to a maximum value was captured. Similar time dependent mud cake growth behavior
was also investigated in the literature (Tran, 2011; Wu et al., 2005 ; Mackley and
Sherman,1992).

139
 0.52 mm
0.52 mm

0.35 mm
0.35 mm

Figure 5.7: Variation of Mud cake thickness with time for NP-based fluid.

5.2 NP based fluid transport using Stoke-Einstein equation

Nanoparticle transport during filtration is predominantly influenced by convection and

Brownian diffusion with negligible contributions from gravitational settlings and shear
induced diffusion (Hwang et al., 1998; Mcdonogh et al., 1984; Song and Elimelech,
1995). Previous studies found that between microparticle and nanoparticle transport
models, particulate deposition greatly depends on the particle size (Ding and Wen,
2005; Kleinstreuer et al., 2008). This current model suggested that the nanoparticles get
dispersed due to diffusion and convection, whereas microparticle transport is governed
by convection and sedimentation. For micron sized particles Brownian diffusion
mechanism is not important (Ives, 1970).

140
The general diffusion equation for nanoparticle transport can be written as

CNP
 .J  0 (E5.24)
t

At a given location within the flow, the total flux, J of particle migration can also be
described at any time as (Zamani, 2009; Ding and Wen, 2005),

J  JDiffusion  Jadvection (E5.25)

The diffusion flux of NPs, JDiffusion (moles/cm2-s), can be expressed as a function of the

concentration gradient using the first law of Fick, which in one dimension can be written
as

CNP
JDiffusion  -DNP (E5.26)
x

For unsteady diffusion, Fick’s second law is,

CNP   CNP 
 DNP   (E5.27)
t x  x 

Equation (E5.26) can be simplified as:

JDiffusion  DNP .CNP (E5.28)

where, DNP is the diffusion co-efficient of nanoparticles due to Brownian effect. In the

second term of (E5.25), Jadvection, is the overall convection or flow and considered as an

associated flux called advection flux and can be expressed as:

Jadvection= U. CNP (E5.29)

where, U is the particle velocity induced by fluid flow (cm/s).

141
Then, the convection diffusion, equation (E 5.24), simplifies to

CNP
 .(DNP .CNP  U. CNP ) 0 (E 5.30)
t

Equation E5.30 can be further simplified to (Ghesmat et al., 2011; Zamani, 2009; Bird et
al., 2002):

CNP
 .(U. CNP )  DNP .2CNP (E 5.31)
t

Diffusion happens randomly due to molecular motion. In the absence of surface

interaction forces, nanoparticles diffusivity due to Brownian motion replaces ordinary
diffusion coefficient (Tien, 1989). Small particles can be diffused to the cake surface
where they can stick. Therefore, the diffusion coefficient of nanoparticles in liquid can be
calculated by using the Stokes-Einstein relationship:

kBT
DNP  (E 5.32)
3   dNP

where k B = 1.38X10-23 J/K is the Boltzmann constant, T is the absolute temperature, μ is

the dynamic viscosity, and dNP is the nanoparticle diameter. If mass deposition rate
(micro or nanoparticles) from the drilling fluid over API filter paper having 2.7 μm grain
size is considered, Peclet number, Pe, for mass transfer is defined as

dgU
Pe  (E 5.33)
DNP

where, is the characteristic velocity determined from the filtrate flow rate till 30 min
and is the filter grain diameter. Peclet number reflects the ratio of particle migration
due to convection to that due to Brownian diffusion. If Pe >>1, transport by convection
and/or sedimentation, in the case of microparticles, is the main driver, whereas if Pe
<<1, diffusion dominates transport (Russel et al., 1999). Pe was calculated using

142
(E5.33) employing Brownian diffusion coefficient, (E5.32) and base oil viscosity of 3.44
cP at 25°C and different particle sizes at LTLP API filtration condition. The effect of
Peclet number is associated mainly with particle size as shown in Figures 5.8 and 5.9.
The calculated data tables were listed in Appendix C. From Figure 5.8 it can be shown
that Peclet number increases rapidly with increasing particle sizes. Both DF control
samples exhibited similar trend close to each other. Particles in the micro domain, e.g.
2-200 μm which is typical for conventional LCMs, display relatively high Peclet number,
Pe>>1. This, in turn, suggests that for LCM and clay particles the effect of Brownian
motion is not important. Conversely, many earlier studies have found that the migration
of NPs can be described by Brownian motion (Phillips et al., 1992; Lam et al., 2004;
Ding and Wen, 2005). In the present study, in the low-Pe regime, dispersion, molecular
diffusion, plays a very important role in NPs transport as shown in Figure 5.9. Although
both Fe(OH)3 and CaCO3 NPs show a similar trend, the slight differences are assumed
to be their size ranges. Migration of nanoparticles to the filters cake may also
encourage formation of clusters/aggregates due to diffusion on the surface.
Microscopically, it is the balance between different forces (hydrodynamic, van der
Waals, electrostatic, steric due to the presence of surfactant rich NPs) that affects the
force-distance dependency between the particles. Note that shear thinning behavior of
fluid was not considered in this study. This is because particle concentration of NPs
used in drilling fluid formulation, 1-4 wt%, was low and no significant effect on fluid
viscosity was reported as detailed in the results and discussion section.

143
 Peclet number,Pe

dp, microns

Figure 5.8: Effect of particle sizes of DF (dp =2-200 μm in DF) on Peclet number.
Peclet number,Pe

dp, microns

Figure 5.9: Effect of Fe(OH)3 and CaCO3 NPs size in DF ranges from 0.001-0.3 μm (1-
300 nm) on Peclet number.

144
5.3 Rheology model of NP based fluid

A rheological model describes the relationship between the shear stress and shear rate.
Most drilling fluids are non-Newtonian. Analysis on correlation between shear stress
and shear rate for drilling fluids showed that they generally follow the Bingham plastic
model (Jihua and Sui, 2011; Lee et al., 2009; Agarwal et al., 2009; Peng, 1990).

(E5.34)

In order to better understand the effect of adding nanoparticles on the rheological

properties, data were best fitted to the model in (E5.34). In all cases, the coefficient of
determination, R2, was 0.99 suggesting an excellent fit.
All the muds had almost similar viscosities in the high shear range although
NP-based mud was slightly thinner than the base invert emulsion mud as shown in
Figures 5.10 and 5.11. Compared with the drilling fluid and the drilling fluid with LCMs,
increasing the shear rate did not increase the shear stress to the same extent in the
presence of ex-situ and in-situ prepared Fe(OH)3 NPs. This observation can be
attributed to the fact that smaller particles were dispersed more effectively than the
larger particles and, in the case of Fe(OH) 3, NPs provided bridging between clay
particles due to the larger degree of interaction than the CaCO 3 NPs. In the low shear
range, however, the CaCO3 NP-based mud had similar effective viscosities. The shear
thinning property of NP-based fluid would be advantageous in providing better hole
cleaning. Similar fluid flow behavior trends were reported by Simpson et al. (1979),
Baird and Walz (2006) and Srivatsa (2012).
Plastic viscosity (PV) measures the internal resistance to fluid flow attributable to
the amount, type and size of NPs present in the fluid system (Cai et al.,2012). If PV is
excessive, the equivalent circulating density will be excessive. This results in an
increased risk of lost returns (Shelton, 2005). PV is generally desired to be as low as
possible. Conversely the yield point is the resistance to initial flow and it represents the
stress required to start the fluid movement. This resistance is believed to be due to the
electrical charges located on or near the surface of the particles (Lyons, 1996). If this

145
property is too high, the consequence will be the same as for high plastic viscosity
(Shelton 2005). By fitting the experimental results to the model, the yield strength and
plastic viscosity were obtained for different drilling fluids as shown in Table 5.2. Both
plastic viscosity and yield strength decreased upon adding nanoparticles except for
CaCO3.
35 DF y = 0.0253x + 3.3138 R² = 0.9932
DF+LCM y = 0.0263x + 2.9952 R² = 0.9932
30
DF+Ex-situ NPs y = 0.0179x + 1.3536 R² = 0.9985
Shear Stress (Pa)

25 DF+In-situ NPs y = 0.0179x + 1.3536 R² = 0.9985

20

15

10

0
0 200 400 600 800 1000 1200
Shear rate (Sec-1)

Figure 5.10: Bingham Plastic model in the presence and absence of Fe(OH) 3 NPs

20 y = 0.0167x + 1.2007 R² = 0.9945

DF
18 DF+Ex-situ NPs (R2) y = 0.0143x + 1.6547 R² = 0.9905
16 DF+In-situ NPs (R2) y = 0.0154x + 1.682 R² = 0.9887
Shear Stress (Pa)

14 DF+In-situ NPs (R5) y = 0.0167x + 1.2007 R² = 0.9945

12
10
8
6
4
2
0
0 200 400 600 800 1000 1200
Shear rate (Sec-1)

Figure 5.11: Bingham Plastic model in the presence and absence of CaCO3 NPs. (R5)
and (R2) refer to the reaction used to prepare the particles as detailed in section 3.2.

146
Due to the differences in the nature of NPs, their concentration, each sample behaves
differently. Moreover, surfactant act as a dispersion agent of NPs generally decreases
the viscosity. Model and experimental results were very close for Fe(OH)3 NPs and
CaCO3 NPs, nevertheless. Figures 5.10 and 5.11 show a perfect straight line. Drilling
fluid and drilling fluid with LCM displayed high plastic viscosity (PV) and yield point (YP),
which could result in increased equivalent circulating density (ECD) (Nicora, 2001) and
also could show detrimental effect on the rate of penetration (ROP). An increase in the
population of solid particles in fluid slows down the rate of penetration (ROP). A
desirable invert emulsion fluid would be the one which not only has a low PV but shows
good low shear viscosity and yield point (Okrajni and Azar,1986; Becker et al.1991;
Maghrabi et al.2011). NP-based fluid with low PV and low shear yield point serves
improved sag resistance (Bern, 1996) and cuttings carrying capacity. It was observed
that, in case of Fe(OH)3 NP-based fluid, PV and YP decreased by 26% and 60%,
respectively, in comparison with the base formulations. But in case of CaCO3 NPs,
these changes were insignificant. Javeri et al. (2011) and Paiaman and Al-Anazi (2008)
investigated the plastic viscosity and yield point of drilling fluid after addition of NPs.
With the addition of 2~3 vol% carbon black and silica NPs to the mud, these
researchers reported decreased plastic viscosity and yield point.

147
Table 5.2: Experimental and Bingham Plastic viscosity and Yield point.

NP Used Samples Types PV and YP values, Pa

Exp. PV Bingham,PV Exp.YP Bingham,YP

DF 0.023 0.025 3.4 3.3

Fe(OH)3 DF+LCM 0.023 0.026 5.3 3.0

DF+exsitu NPs 0.017 0.018 1.3 1.4
DF+insitu NPs 0.017 0.018 1.4 1.4
DF 0.015 0.017 2.4 1.2

CaCO3 DF+exsitu NPs 0.013 0.014 2.4 1.7

(R2)
DF+insitu NPs 0.013 0.015 3.4 1.7
(R2)
DF+insitu NPs 0.015 0.017 2.4 1.2
(R5)

In conclusion , the study shows that:

a) A plot of fluid loss versus square root of time gave a linear relationship for drilling
fluid without NPs arising from spurt loss. Conversely a non-linear relationship
was applicable to NP-based fluid, due to absence of spurt loss.
b) It was found that more than 90% of mud cake premeability reduction occurred
using NP-based fluid, whereas conventional LCM reduced the permeability by
77%.
c) It was also shown that nanoparticles transported in filtration was predominantly
influenced by the Brownian diffusion.
d) Bingham plastic model satisfied for both Fe(OH)3 and CaCO3 NP-based drilling
fluid.

148
 Chapter Six: Conclusions‎, Contributions to Knowledge‎and Recommendations

In this work novel methods for in-house preparation of stable nanoparticles in drilling
fluids were introduced. The product nanoparticles were very stable in the invert
emulsion as well as the water-based muds. Different nanoparticles were prepared and
at the low concentrations involved, these particles did not alter the properties of the
drilling fluid; including pH, viscosity, density (except for weighting materials based NPs)
etc. Despite the low concentrations, the particles significantly reduced the fluid loss and
improved the drilling fluid lubricity property.

6.1 Conclusions

The specific conclusions of this research program are summarized as follows.

1. Various in-house NPs were prepared by ex-situ and in-situ method

2. In-house NPs addition to drilling fluids dramatically improved fluid performance
3. Low concentration of NPs were used ( 1-5 wt%) for fluid formulation
4. Addition of ex-situ NPs and in-situ NPs reduced the LTLP fluid loss by 70-80%,
exhibited thin mud cake and similar performance was obtained at HTHP filtration
5. Density and pH of the drilling fluids were unaltered after addition of in-house
NPs; the only exception to the weighting materials type of NP-based drilling fluid
6. Introducing NPs to drilling fluid did not change the rheology of the drilling fluid at
low as well as high shear range
7. Addition of ex-situ NPs and in-situ NPs enhanced the lubricity property of the
drilling fluid

Drilling fluids have a wide range of chemical and physical properties which are
specifically optimized for drilling conditions and the special problems that must be
handled while drilling a well. In this work, water and invert emulsion based muds have
been formulated to incorporate in-house prepared nanoparticles starting from aqueous
precursors at a very reasonable cost. Relative to commercial NPs, in-house prepared
ones produced much better fluid loss control, probably due to limited dispersion

149
associated with the commercial counterparts. The in-house techniques developed in
this study for the preparation of NPs and NP-based drilling fluids followed two different
routes; namely ex-situ and in-situ. The ex-situ technique for nanoparticle preparation
consisted of providing aqueous-based precursor solutions for forming the nanoparticles,
mixing the precursor solutions under 200 rpm at 25oC, and adding the mixed precursor
solution to the drilling fluid. To form the nanoparticle-containing fluid, the fluids were
mixed/sheared at 2500 rpm to achieve a uniform mixture using Hamilton beach mixer.
The purpose of stirring is to form a stable and homogenous emulsion by breaking large
liquid drops into smaller drops. In case of in-situ nanoparticles aqueous precursor salts
are added to two separate samples of the drilling fluid under 200 rpm of mixing at 25oC.
NPs were formed via precipitation reactions, which took place in the drilling fluid upon
mixing the two drilling fluid samples and shearing at 2500 rpm to achieve a uniform
mixture using Hamilton beach mixer. Formation of nanoparticles in this way minimizes
particles aggregation allowing easier handling than ex-situ prepared NPs. The method
developed in this work is versatile and different types of precipitates of NPs were
prepared using both techniques; including Fe(OH)3, CaCO3, FeS and BaSO4. Complete
investigation was, nevertheless, focused on the performance of Fe(OH) 3 and CaCO3
NPs. Moreover, a method was developed for the in-situ synthesis of calcium carbonate
NPs using carbon dioxide, CO2, gas allowing inside the wellbore to generate this NPs.
Comparing the two different methods of in-situ CaCO3 NPs preparation, the second
method showed the lowest spurt loss and total filtrate volume. The mechanism leading
to CaCO3 NPs formation in this method involved the nucleation of CaCO3, particle
growth and may induce a Brownian diffusion with clay particles. Spurt losses observed
with all the in-house NPs are acceptable from a drilling point of view.
With all the different particles prepared in this study, the incorporation of the NPs
in invert emulsion fluid system reduced the fluid loss substantially at relatively low
concentration of the NPs. NPs as lost circulation materials are typically designed to
accomplish three goals: 1) to bridge across the face of fractures, 2) to prevent the
growth of any fractures that may be induced during drilling and 3) to change the mud
density while keeping the viscosity almost constant when NPs are used as weighting

150
materials. It was found that muds were quite stable and offered a wide range of
nanoparticle sizes that controlled the fluid loss efficiently and effectively, with and
without conventional loss circulation materials (LCMs), e.g. Gilsonite. Commercial invert
emulsion drilling fluid without NPs and LCM and with 1.6 wt% LCM only were
considered as baseline drilling fluids for comparative evaluation of API filtration
experiments. The NPs concentration was varied between 1 wt% and 5 wt% for both in-
situ and ex-situ prepared particles. At the low concentration ‎of NPs, it is most likely that
the particles interacted with the rest of the mud constituent ‎rather than merely
aggregating. ‎These muds also offer good lubrication and are, therefore, appropriate for
applications in drilling extended reach wells.
Test results showed that in-situ and ex-situ prepared NPs were not uniform in
size and shape. Testing also demonstrated that NPs covered a wide range of particle
sizes from nanometer to micrometer scale, but 70-80% of the prepared particles fell into
1-60 nm range. Properly prepared, these NPs have the potential to build structural
barriers in the fluid loss paths according to their size. Although different shapes of NPs
were visible in the TEM images but this property was not investigated in the current
study. In-house prepared NPs per current work behaved as a new generation fluid loss
additives. For example, it was found that Fe(OH)3 NPs at 1 wt% showed excellent
performance. They prevented fluid loss of invert emulsion mud up to 70-80%, and
contributed to a thin mud cake, < 1 mm, for LTLP and < 2 mm for HTHP conditions. At
this low concentration, the in-house prepared NPs out performed conventional LCMs,
e.g. Gilsonite to a great extent. 4 wt% CaCO3 NPs represent the optimum concentration
in which the volume of filtrate reached minimum values and better arrangement of
particles occurred in the filter cake surface turning into an impermeable cake. Besides,
the spurt losses are found lowest using NPs. Approximately, 60 % of the API fluid loss
reduction was happened using both ex-situ and in-situ prepared CaCO3 NPs. The
samples exhibited a very low fluid loss at low temperatures and same relative
performance at high temperatures. Similarly, addition of 3 wt% BaSO4 and FeS NPs in
drilling fluid reduced the API LTLP fluid loss more than 80%. The low concentration of
NPs addition to mud was mainly dependent on the physio-chemical nature of NPs and

151
stability of the mud system. Therefore, NP-based drilling fluids discussed in this study
are viable and robust systems and compatible to other systems that already exist in the
market. It could potentially have an impact on the total drilling cost, especially in
complex and troublesome drilling operations.
The experimental results also indicated an unchanged viscosity at the low
concentration of NPs, although a slight decrease in gel strength was experienced. It
was also found that Fe(OH)3 and CaCO3 nanoparticles exhibited good load-bearing
capacity, anti-wear and friction-reducing properties. The in-house NPs can be more
effectively dispersed in the drilling fluid if they are formed in-situ and more than 40%
friction of co-efficient is attainable.
Darcy’s law was used to interpret the LTLP fluid loss experimental only. Due to
the similar degree of fluid loss reduction close to LTLP one, HTHP results can also be
interpreted by Darcy’s law which is not included in the current study. A plot of fluid loss
versus square root of time gave a linear relationship for drilling fluid without NPs arising
from spurt loss. Conversely a non-linear relationship was applicable to NP-based fluid,
due to absence of spurt loss. It is also noted that NP-based drilling fluid did not follow
Darcy equation at the initiation of filtration and, therefore the initial region was found flat.
It was found that more than 90% of mud cake premeability reduction occurred using
NP-based fluid, whereas conventional LCM reduced the permeability by 77%. The
model results indicated that nanoparticles reduced the premeability instantly and fluid
invasion decreased siginificantly. It was also shown that nanoparticles transported in
filtration was predominantly influenced by the Brownian diffusion. Compare with the
drilling fluid alone and drilling fluid with LCM, increasing shear rate did not increase the
same extent of shear stress of NP-base fluid (both ex-situ and in-situ prepared), which
can be attributed to the fact that smaller particles were dispersed more effectively than
the larger bulk particles and provided bridging between clay particles due to their larger
surface area. In all cases, the coefficient of determination, R2, for Bingham rheological
model, was 0.99~0.98.
Applying the in-house techniques to prepare NPs in water based muds ‎resulted a
very progressive behavior. Both Fe(OH) 3 and CaCO3 NPs reduced the fluid loss by

152
approximately 30%. NP-based water mud had a much higher initial filtrate rate but after
30 min it was closely two times greater than the invert emulsion NP-based mud.
From the aforementioned discussions, it can be concluded that the use of
nanoparticles in the drilling fluid at the right concentration and adoption of a specific
preparation method leads to a fluid with desirable properties in terms of mud density, pH
and rheological behavior. The addition of nanoparticles does not alter the optimum
values for these properties from the base fluid. Formation damage due to filtrate and
solids invasion is a major contributor to cost, lost time and lost production. One of the
critical factors in avoiding formation damage during drilling is obtaining surface bridging
on the formation face with minimum in-depth solids penetration. Nanoparticles work in
emulsion based fluids, even at high temperatures, providing a thin filter cake that gives
maximum formation protection at minimum concentration and cost. Thin filter cake is
important for reducing differential sticking problem and excessive drag in extremely
permeable formation. Tailor made nanoparticles with specific characteristics is expected
to play a promising role in solving circulation loss and other technical challenges faced
with commercial drilling fluid during oil and gas drilling operations.
Results obtained from this study, give rise to the following characteristics for the
nanobased drilling fluid.
 Thin and firm filter cake.
 Minimal fluid invasion, since sealing takes place at the surface, which leads to
minimal formation damage.
 Extreme high temperature stability.
 Only low NP concentration is required.
 Time and cost savings.

These properties entail the following practical applications.

• Less Fluid loss = Money saving.
• Lower torque and drag = Increase extended reach well.
• Reducing differential pressure sticking problem = Less non-productive time.

153
 • Less solid concentration in mud = Reduce formation damage and increase
productivity index.

6.2 Original contributions to knowledge

1. Development of new in-house methods for preparing wide variety of NPs in drilling
fluids. As per these methods, the birth place of NPs can be outside the drilling fluid, ex-
situ, or inside the drilling fluid, in-situ. In-situ prepared NPs communicated better with
the resultant NP-based drilling fluid, and generally led to high fluid loss prevention,
under LTLP and HTHP conditions.
2. The in-house methods developed in this study were applicable for both invert
emulsion and water based drilling fluids.
3. Use of nanoparticles as a fluid loss additives, lubricity additives and weighting
materials for the drilling fluid, wherein the drilling fluid comprises a base fluid and
nanoparticles present in an amount of about 5 wt % or less.
4. The nanoparticles have a particle size between about 1 and 120 nm, wherein a
majority of the nanoparticles have a particle size between 1 to 30 nm.
5. NPs addition reduced the total solid content usage in the drilling fluid.
6. NPs were found more effective in 80:20 (V/V) Oil/water invert emulsion drilling fluid
interms of fluid loss control.
7. Addition of NPs unchanged the density (except for weighting materials based NPs),
viscosity and pH of the final fluid.
8. The nanoparticles were selected from the group consisting of metal hydroxide (iron
hydroxide) metal oxide (iron oxide), metal carbonate (calcium carbonate), metal sulfide
(iron sulfide) and metal sulfate (barium sulfate). Nanoparticles were formed in situ in the
drilling fluid or formed ex situ and added to the fluid.

6.3 Recommendations for future research

The following recommendations are proposed for the future studies:

• Based on the static filtration tests, it is necessary to conduct the dynamic filtration
test to simulate the bottom hole conditions. Dynamic filtration test determines if

154
 the fluid is properly conditioned to drill through highly permeable formations. For
this purpose, FANN 90 dynamic filtration apparatus can be used. It utilizes
ceramic cores available in a range of different permeabilities. A new filtration
model can be applied to measure the dynamic filtration rate. This model could
consider the effect of shear-induced migration where NPs move regions of higher
shear rate to regions of lower shear rate and deformation of NPs/LCM under
stress that exist in a filter cake. Cake deposition index (CDI) can also be
measured from the dynamic filtration data.
• One of the future filtration studies could be to investigate the formation damage
of known core samples by different nanoparticles. Most of the NPs used in
literature entered into pores and plugged them in the producing
direction, reducing the flow and permeability of the rock for production and finally
leading to formation damage. The NPs used in the current experiments provided
a better bridging effect on the filter cake and did not pass through the filter paper
into the filtrate. Therefore, it is believed that it would be more realistic to test the
filtercake core permeability to investigate the flow and production and return
permeability issues caused from plugged filter cakes. The Permeability Plugging
Apparatus (PPA) can be utilized to measure fluid loss using ceramic discs
available in a variety of permeabilities (5 micron to 190 micron) to simulate
reservoir pore throat diameters.
• Future efforts on field tests could enhance the potential development of low cost
drilling fluid with NPs.
• More studies should be performed on the usage of all existing drilling fluid
additives in nanoscale. A recommendation for future work is the incorporation of
pre-mix bentonite rich NPs, polymeric materials with NPs, nano emulsifiers and
cattle manure with NPs in the drilling fluid. XRD results in the current study
suggests that Fe(OH)3 NPs acted as intercalating agents and had entered into
the crystallite layers of bentonite clay. It is believed that such a structure of
nanometal-clay composite could improve drilling fluid properties and may offer
better functionality than regular bentonite without the requirement of other

155
expensive additives. Nanometer polymer could penetrate to pores, deposit on the
surface and form low permeable mud cake. The mud cake produced by the
insoluble deformable polymer with colloidal materials could reduce the pressure
differential between the hydrostatic pressure of the mud and the pore pressure
around the surface of wellbore and thus prevent differential sticking, promote
borehole stabilization and avoid formation damage (Benaissa, 2006). Similarly
Manea (2011) designed nanopolymer gel using Xanthan gum and fluid loss
additives, and Saboori et al. (2012) used nanoCMC polymer to decrease the
water loss and mud cake thickness in mud drilling. Using the aqueous polymer
base, crosslinked with NPs used in our study can also form nanocomposite
polymeric gel to cure the fluid loss. Lécolier et al. (2005) showed that
nanocomposite polymeric gel could be pumped into naturally fractured
formations or voids, and plug off a wide range of cracks. Nano-emulsion
prepared through a one-step method (Mei et al., 2011) showed a good lubrication
and long term stability. Similarly nano asphalt emulsion can be tested to increase
the lubrication and fluid loss control. Cow dung (manure) is a material highly
cherished by rural dwellers used as a binding agent for plastering houses
(Issaka, 2012). In many developing countries manure with clays are mixed and
used in boring pipe into an underground aquifer to lift water for irrigation. Manure
serves as a binding agent and gives plaster more body. It also contains small
natural fibers that provide additional tensile strength as well as reduce cracking
and water erosion (Guelberth and Chiras, 2003). Manure therefore, could prevent
fluid loss as well enhance lubrication.

156
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Appendix A: Classification of lost-circulation zones

Mud losses vary in type, severity, and location in the hole. Mud losses occur to the
following types of formations (Messenger,1981):

1. Unconsolidated or highly permeable formations (porous sands and gravels)

The permeability of the porous formation that takes the whole mud or cement must
exceed 10 darcies. Gravels and shallow sands often reveal such permeabilities. The
deeper sands seldom exceeds about 3.5 darcies and therefore they are not often
consider as loss zones unless they are not fractured.

2. Natural fractures

Loss is evidenced by gradual lowering of the mud in the pits. If drilling is continued and
more fractures are exposed, complete loss of returns may be experienced. Natural
fractures reservoirs are the reservoir that contains fractures created by the stress that
exceed the rupture strength of the rock (Nelson,2001). These fractures may exist in the
deeper formation with little or no width. That’s why the mud losses to them are small
until the fractures are widened.

3. Induced fractures

There may be some cases when the horizontal fracture can be induced. One of the
most common is in shale. Loss is usually sudden and accompanied by complete loss of
returns.

4. Cavernous formations

Caverns form mainly in limestones. Loss of returns may be sudden and complete. It will
make the sealing more difficult.

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Appendix B: Lost circulation materials size selection methods

There have been several methods given in Table B.1 for the selection of the lost
circulation materials based on their size to keep the mud loss at minimum.

Table B.1: Lost circulation materials selection methods.

The particle size distribution is equal to the

Halliburton Method
(Whitfill,2008)
Vickers et al.,(2006)
IPT (Ideal Packing Theory)
(Dick et al.,2000)
Cargnel and Luzardo,(1999)
Abrams’ Median Particle-Size Rule
(Abram,1977)
estimated fracture width to offset uncertainty in
the estimation. Enough particles smaller and
larger than the fracture are present to plug
smaller and larger fracture width.
For minimal fluid loss in the reservoir, the
following criteria should be met
D(90) = largest pore throat
D(75) < 2/3 of largest pore throat
D(50) +/- 1/3 of the mean pore throat
D(25) 1/7 of the mean pore throat
D(10) > smallest pore throat
The IPT addresses either pore sizing from thin
section analysis or permeability information,
combined with PSD of bridging material, to
determine ideal packing sequence.
The criterion of selection of particle size of
bridging agents is: 1/7 DPore throat < Dparticle
< 1/3 DPore throat. This yields a small invasion of
solids into the porous media.
The median particle size of the bridging
material has to be equal or slightly greater
than 1/3 the median pore size/fracture size of
the formation.

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Appendix C: Diffusion coefficient and Peclet number

The diffusion coefficient and peclet number shown in Figures 5.8 and 5.9 are given in
the following tables C.1-C.4.

Table C.1: Effect of particle sizes of DF (dp =2-200 μm in DF) on Peclet number which
is a control sample of Fe(OH)3 NP-based fluid.

Table C.2: Effect of Fe(OH)3 NPs size in DF ranges from 0.001-0.3 μm (1-300 nm) on
Peclet number.

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Table C.3: Effect of particle sizes of DF (dp =2-200 μm in DF) on Peclet number which
is a control sample of CaCO3 NP-based fluid.

Table C.4: Effect of CaCO3 NPs size in DF ranges from 0.001-0.3 μm (1-300 nm) on
Peclet number.

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