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Oil Base Mud. Part I: Synthesis of Some Local Surfactants Used as Primary
Emulsifiers for Oil Base Mud and Evaluation of Their Rheology Properties

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DOI: 10.1080/01932690802598754

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Oil Base Mud. Part I: Synthesis of Some Local

Surfactants Used as Primary Emulsifiers for Oil Base
Mud and Evaluation of Their Rheology Properties
a a a
A. M. Al-Sabagh , M. R. Noor El-Din & H. M. Mohamed
a
Department of Petroleum Applications , Egyptian Petroleum Research Institute (EPRI) ,
Nasr City, Cairo, Egypt
Published online: 22 Jul 2009.

To cite this article: A. M. Al-Sabagh , M. R. Noor El-Din & H. M. Mohamed (2009) Oil Base Mud. Part I: Synthesis of Some Local
Surfactants Used as Primary Emulsifiers for Oil Base Mud and Evaluation of Their Rheology Properties, Journal of Dispersion
Science and Technology, 30:7, 1079-1090, DOI: 10.1080/01932690802598754

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 Journal of Dispersion Science and Technology, 30:1079–1090, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0193-2691 print=1532-2351 online
DOI: 10.1080/01932690802598754

Oil Base Mud. Part I: Synthesis of Some Local Surfactants

Used as Primary Emulsifiers for Oil Base Mud and
Evaluation of Their Rheology Properties
A. M. Al-Sabagh, M. R. Noor El-Din, and H. M. Mohamed
Department of Petroleum Applications, Egyptian Petroleum Research Institute (EPRI), Nasr City,
Cairo, Egypt

Six oil soluble nonionic surfactants with different HLBs have been prepared. Their HLBs situate
between 3.9 and 6.7. Transesterification was carried out for glycerol and triethanol amine with
oleic acid at different moles to obtain six emusilifiers. They named glycerol momooleate (I),
glycerol diooleate (II), glycerol trioleate (III), triethanol amine mono-, di- and tri-oleate (IV),
(V,) and (VI). The chemical structure was confirmed using; the elemental analysis, FTIR and
1
HNMR. They were evaluated as a primary emulsifiers (PE) for thdrilling fluids (oil base
Downloaded by [Purdue University] at 07:14 18 January 2015

mud) comparing with a currently used primary emulsifier (Fc). The water in oil base mud
(w/o emulsions) was prepared. The concentration of emulsifiers and their HLB exhibited interest-
ing rheology properties including shear-thinning behavior, yield value, viscoelastic effects,
thixtropy, gel strength, and filtration loss. The rheology properties of such emulsions strongly
depended on the average size distribution of the dispersed droplets that could be varied both with
the bulk concentration and HLB value of the emulsifiers. The interfacial and surface properties of
these emulsifiers suggest that the droplet size of the dispersed phase and bulk concentration are
strongly related to the HLB value of emulsifiers. The w/o emulsion (mud formulation) stability is
sensitive to the droplet size of the dispersed phase and HLB value of the used emulsifier. The
results were discussed on the light the chemical structure of the primary emulsifiers and the
emulsion ingredients.
Keywords Drilling fluids, drilling mud, filtration loss, gel strength, interfacial properties, oil
soluble emulsifiers, rheology

INTRODUCTION fluids (water and gas-oil) and suspended fierily divided

In many wells drilled with aqueous drilling fluids suffer
serious decreases in permeability of oil bearing zones as
results of water blocking of the pore spaces and swelling
of anhydrous clays within the pore spaces. This water
contamination difficulty can be avoided by the use of oil,
such as crude petroleum oil as a drilling fluid. This means
usually involve adding materials such as blown finally
divide solids to the oil to increase the density, viscosity
and gel strength, and to give the fluid plastering properties
to decrease loss of the fluid to the permeable formation.[1,2]
The success of any well drilling operation depends on
many factors; one of the important of which is the drilling
fluid. The fluid performs a variety of functions that
influence the drilling rate and the cost, efficiency and safety
of the operation. Drilling fluids generally are composed of
Received 24 January 2008; accepted 6 February 2008.
Address correspondence to A. M. Al-Sabagh, Department of
Petroleum Applications, Egyptian Petroleum Research Institute
(EPRI), 1 Ahmed El- Zomor St., Nasr City, Cairo 11727, Egypt.
E-mail: alsabaghh@gmail.com
solid of various types. The proportions determine the
treatment strategy, the efficiency of the mud- handling
equipment, and affect the amounts of materials needed to
bull up density and viscosity.[4–6] No additives are used in
dry-air-, or gas-drilling operation. Gas based fluids are
not recalculated and materials are added continuously.[7]
The functional properties include water loss, gel strength,
viscosity and thixotropy, and resistance to salts and alka-
line earth ions.[8,9] One of the most widely used ingredients
in water base drilling mud is carboxy methyl cellulose. It is
very effective in preventing water loss and in controlling
the viscosity.[10,11]
Freshwater mud may be operated at pH levels ranging
from 7 to 11. When drilling flocculent may be added to
remove drill solids in large settling with clear, and a small
amount of pit in order to maintain a clean fluid for fast
drilling. Generally, seawater mud is formulated and
maintained in the same way that freshwater mud is used.
However, because of the presence of salts in seawater, more
additives are needed to achieve the desired flow and
filtration properties.[12,13] Fresh- or seawater mud may be

1079
 1080 A. M. AL-SABAGH ET AL.
treated with gypsum on lime to alleviate or clay bearing
problems that may arise from drilling water-sensitive shale
or clay bearing formation.[14–18] Fluid with less than (5 to
10 vol% water) is called oil base mud. Most oil mud
maintain a fixed oil-water ratio depending on the desired
properties. Oil mud are employed for high temperature
wells, where water-based system may be unstable and a
problem may be raised from sensitive shale formations,
or where corrosive gases such as hydrogen sulfide and
carbon dioxide may be encountered. Usually, the cutting
removal efficiency increase with increasing the viscosity
and the density. Viscosity depends on the concentration,
quality, and state of dispersion of suspended colloidal
solids.[19–22] Most concentrated emulsions show shear rate
dependent non-Newtonian type shear thinning behavior
at low and intermediate shear rate domain, where the shear
viscosity (g) decays exponentially as a function of shear
rate. On the contrary, at high shear rate domain, these
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emulsions show Newtonian type shear rate independent
shear viscosity. Materials with such mixed flow profiles,
viscosity shear rate in steady state shear mode are usually
known as pseudoplastic materials,[23] and these generally
show a combination of shear thinning behavior and yield
stress, it means that flow on these materials can only be
induced with the application of a certain minimum amount
of force=stress which is referred to as yield stress. High
value of yield stress is indicative of higher degree of
material structuring and good emulsion stability[24] Rheol-
ogy of most viscoelastic materials, including surfactants
solution,[25] and surfactant stabilized emulsions tend to
show Maxwell model type fluid flow behavior.[26] The first
goal of this work is focusing on the preparation of some
primary emulsifiers based on glycerol and triethanol amine
with oleic acid. The second goal is to make six formula-
tions of oil base mud using the prepared emulsifiers to
increase the plstic and dynamic viscosity, yield value,
thixtropy, gel strength, and filtration loss properties.
EXPERIMENTAL
Preparation of Emulsifiers Based on Glycerol and
Triethanol Amine
Into three-necked flask, 1.0 mol of glycerol and trietha-
nol amine were added to (1.0, 2.0, 3.0 mol) of oleic acid
individually. The reaction was carried out in the presence
of 0.1% p-toluenesulfonic acid as a catalyst and xylene as
a solvent. The reaction was heated with continuous stirring
and the reflux of solvent was carried out until the theoreti-
cal amount of water was collected. The product was
purified by washing it with 5% worm solution sodium car-
bonate then was dissolved in petroleum ether (40–60
C),
and the organic layer was separated. The solvent was
distilled off. This method was carried out to obtain six
emulsifiers named; glycerol monooleate (I), glycerol
dioleate (II), and glycerol trioleate (III), triethanol amine
monooleate (IV), triethanol amine dioleate (V) and trietha-
nol amine trioleate (VI).
Emulsion Preparation
To 100 ml of gas-oil, 1, 2, and 3% of the prepared
primary emulsifier (I to VI) was added individually at room
temperature with continuous stirring and then 10% of
distal water was added gradually with continuous stirring
until a milky emulsions were formed. The solids added to
form the mud formulation were (3.5% guiletane, 1.4%
durtane and 1.4% soda lime, wt=wt) were added and they
mixed gradually. Finally, 1.2% of E.Z mud as a second
emulsifier was added with stirring. The ingredients were
mixed well for 10 minutes to form six different formula-
tions (F1 to F6).
Surface and Interfacial Tension Measurements
The surface tension of surfactants solutions was mea-
sured at 25
C against the hydrocarbon system (gas-oil)
using a Krüss made surface tensiometer K12. An oil bath
was used in this case to maintain the temperature. The Du
Noüy ring method was employed, where the ring is dipped
into the solution whose surface tension is to be measured
and pulled out afterward. The maximum force needed to
pull the ring through the interface is expressed as the surface
tension in mN=m. On the other hand, the interfacial tension
at the w=o interface was measured at 25
C using Krüss
made Drop Volume Tensiometer DVT 10.
Droplet Size Measurements
The droplet sizes distribution can be measured with help
of optical microscopy. An account of the use the optical
microscopy to measure the emulsion droplet size is
extensive.[27] In this study, a German made leica DMRXP
light polarizing microscopy was used. This system consists
of a high voltage beam source, a polarizing unit and a
detector unit. The detector unit is interfaced with a camera.
Note that the images were focused both under the dark and
bright field mode as well as between the cross polarizer
using long working distance objectives with magnification
ranging from 20 to 50 to 100. This microscope unit
is controlled by computer which is equipped with image
analysis software. This software not only helps capture
images from the stage of the microscope, but with its help
one can process these images as electronic documents
including measuring droplet size.
High Pressure–High Temperature Filter Press
Measurements
High pressure-high temperature filter press is especially
designed for testing mud at elevated temperature and
pressure. It consists of a heating unit with a thermostat,
 OIL BASE MUD. PART I
250 ml filter cell, and the pressure unit. The fluid loss value
obtained with this apparatus more truly represents the
actual fluid loss in the well pore. For tests which are to
be run above 200 F, the back pressure receiver must be used
in place of the graduated cylinder to prevent evaporation of
the filtrate.
Procedure
Into a clean aging cell, 200 ml of the mud formulation
was transferred. Be sure that the sealing edge of the cell
is clean and put the inner cap in its place. Then use an
Allen Wrench to tighten the small center screw in the
middle of the screw cap. The cell was placed in a portable
aging oven and adjusted to the desired aging temperature.
A hot air oven may also be used provided a constant
temperature (200
F). A graduated dry cylinder was placed
under the filtrate tube. A 500 psi pressure was applied to
the cell, and the time of the test was started. At the end
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of 30 minutes, first close of the pressure source valve was
carried out and then the safety bleeder value was opened
to release the pressure from entire the system. The volume
of filtrate was collected and expressed on the filtration
loss in ml.
Rheology Properties Measurements
The rheological properties of emulsions were measured
using a rotational viscometer with coaxial cylinders
(Rheotest 2, Germany). Samples were placed in the
temperature-controlled measurement vessel and equilibra-
ted to required temperature for 5 min period to making the
measurements. The rheological behavior of the emulsions
FIG. 1. FTIR spectra of glycerol dioleate (II).
1081
was measured 24 hours after preparation. The measure-
ments were only accepted when the emulsion had not
shown any coalescence before and after shearing. The shear
rate (D.S1) was changed from 3 to 1024 (s1).
Determination of Gel Strength and Thixotropy of Mud
The gel strength of mud using the rheometer was deter-
mined. The mud sample was stirred at high speed
(4000 rpm) for 15 seconds. The mud emulsion left to rest
about 10 minutes and then the gel strength knob was
turned on the hub of the speed change level clockwise
slowly and steadily. The maximum deflection of the dial
before the gel breaks is considered the gel strength in
1 b=100 ft2. The difference between the low readings after
10 seconds and 10 minutes is considered to be the measure
of thixotropy of the undertaken mud formulations (F1 to
F6 þ Fc).
RESULTS AND DISCUSSION
FTIR and 1HNMR Spectroscopes for Chemical Structure
Justification
The FTIR of glycerol dioleate is shown in Figure 1, The
characteristic broad bands are 3498 cm1 assigned to OH
group stretching vibration, two bands at 2921 and
2862 cm1 for asymmetric and symmetric aliphatic CH
stretching vibration of fatty acid moiety, respectively.
A band at 1732 cm1 characteristic for C¼O stretching
of the ester group confirming the ester formation, a band
at 1490 cm1 pair for C¼C stretching absorption. The
1
HNMR spectra in Figure 2 for triethanol amine dioleate
 1082 A. M. AL-SABAGH ET AL.
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1
FIG. 2. HNMR spectra of triethanolamine dioleate of (V).
shows splitting at chemical shift d ¼ 5.34–5.27 ppm (s, 1H,
1OH), d ¼ 4.97–4.38 (s, 1H, of CH¼CH of oleic alkyl
group, d ¼ 2.71–2.35 (s, 2H, CH2 of oleic alkyl group),
d ¼ 1.45–1.40 (s, 2H, CH2 adjacent to oxygen or nitrogen
atom in the tri ethanolamine structure, and d ¼ 0.99–0.64
(s, 3H, of CH3 of the alkyl group). The elemental analysis
(C, H, and N) for all the prepared emulsifiuers was carried
out and the data are presented also in Table 1. The all
used analysis tools together introduced the evident of the
chemical structure as excepted.
Interfacial Properties
The HLB values of the emulsifiers employed in this
work is given in Table 2. The HLB value is the balance
between the hydrophilic and lipophilic strength of the
emulsifier. It can be calculated using Griffin approach
as:[28]
MH
HLB ¼ 20 
MS
Where MH is the molecular weigh of the hydrophilic head
group and Ms is the total molecular weight of the emulsi-
fier, this relation suggests that the HLB value is closely
related to the size and molecular weight of the head group.
The hydrophobic effect of an emulsifier is better described
by its surface and interfacial properties. The surface and
interfacial properties of these emulsifiers are given in
Table 2, which suggests that the critical micelle concentra-
tion (CMC) value of these emulsifiers is related to their
HLB values. With decreasing HLB value, the CMC of gly-
cerol and triethanol amine series of emulsifiers shifts to a
higher bulk concentration. Since the alkyl tail hydrophilic
head of the emulsifier tested here is different, it is evident
that the head group polarity and the hydrophopicity of
the alkyl chain play a strong role in the micellization and
adsorption processes. The lower the CMC of an emulsifier
enhances its performs as emulsifying agent. From the data
obtained in Table 2, it was found that the CMC increased
by the degree of estrification with oleic acid in the two
groups of emulsifiers; glycerol (I and II) or triethanolamine
derivatives (IV and VI). In this case the surface tension was
measured in gas-oil. From the obtained results, it was
found that the decrease in HLB increases the CMC because
in the emulsifiers I–III, the hydrophobes were mono-, di-,
and trioleate groups. The increase of hydrophobe branch
leads to increase the solubility of the emulsifier in the oil
phase, therefore the CMC increased. This behavior has
been seemed also for the second series (IV–VI). By inspec-
tion the data of Table 2, it was found that, the decrease of
HLB and increases the Amin as a result of the increase
hydrophopic tail. These results reflected on the data of
Cmax, which decreased by decreasing of HLB. The Cmax
and Amin were calculated as:
 
1 dr
Cmax ¼  T
Rt d ln c
1016
Amin ¼
CN
Whereas, R is the gas constant in Joul, d is the surface
tension at 25
C, C is the surfactant concentration and N
is the Avogadro’s number.
The surface tension decreased from 40 mNm1 (gas-oil)
to 31 and 29 mNm1 against the glycerol monooleats (I)
 Downloaded by [Purdue University] at 07:14 18 January 2015

TABLE 1
General characterization of the investigated emulsifiers
Elemental analysis

C% H% N%
Oil mud
Primary emulsifier (Ex) Chemical strcuture formulation M. Wt. Found Calc. Found Calc. Found Calc.

Glycerolmonooleate (I) HO-CH2-CHOH-CH2CO2-CH17H33 F1 356 69.9 70.74 11.2 11.3 – –

Glyceroldioleate (II) CH17H33CO2CHOHCH2CO2CH17H33 F2 606 74.5 75.19 11.3 11.6 – –
Glyceroltrioleate (III) C17H33CO2CH(CH2CO2C17H33)2 F3 885 74.8 75.69 11.1 11.03 – –
Triethanolamine monooleate (IV) [HO-(CH2)2]2N(CH2)2CO2 C17H33 F4 328 69 69.4 11.52 11.65 3.9 4.2
Triethanolamine dioleate (V) HO-(CH2)2N[(CH2)2 CO2C17H33]2 F5 678 73.8 74.34 11.81 11.74 1.9 2.06
Triethanolamine trioleate (VI) N[(CH2)2CO2C17H33]3 F6 942 75.7 76.45 11.92 11.87 1.2 1.48
Envermol, commercial sample (PEc) n.a Fc n.a. n.a. n.a. n.a. n.a. n.a. n.a.
n.a. ¼ not available.

1083
TABLE 2
Surface and thermodynamic properties of primary emulsifier
CMC  103, rcmc, Pcmc Amin Cmax X  1010 DGad, ceq. int
Emulsifier code HLB (mol dm3) (mNm1) (mNm1) (nm2) (cm2) (Kj mol1) (mNm1)

I 6.7 0.016 31 7 61.5 2.7 27.6 0.11

II 4.4 0.038 29 9 66.4 2.5 25.6 0.01
III 3.9 0.049 34 4 79.1 2.1 24.8 0.55
IV 6.3 0.011 29 9 47.4 3.5 28.6 0.14
V 5.9 0.020 26 12 48.8 3.4 27.2 0.02
VI 4.9 0.045 31 7 53.6 3.1 25.0 0.78
 1084 A. M. AL-SABAGH ET AL.

and glycerol dioleate (II), respectively, then it increased

again with the glycerol trioleate (III) [34 mNm1]. This
behavior also was noticed with triethanol amine mono,
di, and trioleate (r ¼ 29, 26, and 31 mNm1, respectively).
This may be explained as; in emulsifiers (I) and (IV) one
tail hydrophope and the two hydrophils terminate by
two hydroxyl group. In this case the structure is look like
surfactant structure (head and tail). In the case of (II) and
(V), the surfactant molecule has tow hydrophope tails and
one terminal hydrophil –OH group. In this case the emulsi-
fier molecule is look like to gemmini surfactant molecule
(excellent surfactant model), so that these surfactants
pronounced a maximum reduction in the surface tension.
But in the case of (III) and (VI) the molecule is completely
surrounded by three hydrophope and the hydrophil is not
terminal but may be concentrate on the carbonyl group in FIG. 3. Viscosity shear rate curves for mud formulations obtained
(III) or carbonyl and nitrogen atom in (VI). This structure with 2% PE 10:90 water oil ratio at 25
C.
may be deactivates the molecule to adsorb regularly on
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the surface to reduce the surface tension.

This observation was noticed also for the equilibrium
interfacial tension (ceq.int), the Amin increased by increasing
of hydrophope branch which increases the molecular
weight of the emulsifier molecule.
As can be seen, the Gibbs free energy of adsorption
DGad, also varies strongly with the variation of HLB value
of the used emulsifiers. The DGad, increased with decreas-
ing of HLB. The increasing of the negative value of DGad
with increasing of HLB value in its turn indicates that a
higher degree of interface stabilization is achieved with
increasing HLB value in the water-in-oil emulsion case.
This can be accounted for the fact that owing to enhance
the degree of hydrophobic interactions with decreasing
HLB value, the adsorption at the given w=o interface
decreases with decreasing HLB value. The more negative
the DGad the greater the degree of interfacial adsorption.
The DGad was calculated by:
DGad ¼ DGmic  0:6032  Amin pCMC
The same behavior had been also seen for the triethanol
amine oleate derivatives as cleared in Table 2. This is a
further indication that given the hydrophope tail branch
is strongly related to adsorb the surfactants molecule on
the w=o interface and to reduce the interfacial tension.
Rheoloigy Characterization of Oil Base Emulsions
The viscosity concepts were firstly announced by Isaac
Newton. It is synonymous with internal friction and a
measure of the resistance to the flow. The force per unit
area, s (donated as a required shear stress). The gradient
producing the motion is proportional to the viscosity
gradient (denoted as shear rate coefficient dd=dt).
The constant of proportionality, g, is called the viscosity
coefficient, that is,
dd
s¼g
dt

Where; DGmic ¼ RT lin CMC

pCMC ¼ p of solvent (40 mNm1) – p surfactant
(measured).
The greater the degree of interfacial adsorption, the
greater the emulsifying effect. The interfacial adsorption
Cmax, also referred to as surface excess concentration.
The value of Cmax imply that all emulsifiers examined here
tend to adsorb strongly at the given interface, and that the
degree of adsorption enhanced with increasing the HLB
value of the emulsifiers. The equilibrium interfacial tension,
(ceq.int) also varied strongly with HLB value of the surfac-
tant. As shown in Table 2, a higher degree of reduction
of (ceq.int) is achieved with decreasing HLB value from
6.7 to 4.4 then the value increased against HLB 3.9 for the
different glycerol derivatives (I), (II), and (III) respectively. FIG. 4. Flow curves of mud formulations prepared with PEs.
 OIL BASE MUD. PART I 1085

TABLE 3
Viscosity Shear rate and shear stress of mud emulsions with 2% PE and 10:90 water oil ratios at different temperature
25
C 35
C 45
C 55
C 65
C

Temp.
C gd sB gd sB gd sB gd sB gd sB Dg=
C DsB=
C

Fc 75 42.4 74 40.4 73 35.7 72 33.6 70 30.6 0.13 0.29

F1 70 39.5 69 39.3 69 38.4 68 30.2 67 31.3 0.10 0.21
F2 78 40.3 77 40.2 76 33.9 74 28.8 74 30.8 0.10 0.24
F3 90 52.2 85 50.2 87 48.2 86 44.2 84 35.2 0.17 0.43
F4 65 39.5 64 36.3 63 35.2 62 35.9 63 30.6 0.10 0.22
F5 70 40.1 69 40.1 68 38.1 66 35.2 65 31.6 0.13 0.21
F6 85 55.0 82 52.1 80 45.6 79 40 78 35.1 0.18 0.37

A fluid is said to be Newtonian, if the viscosity indepen- base mud. Otherwise, the Dsb=
C for the F1, F2, F4, and
dent on the shear rate. The viscosity decreases with inc- F5 were 0.21, 0.24, 0.22, and 0.21, respectively. They were
reasing the shear rate, which is called shear thinning or also closely with the Dsb obtained by the Fc (0.29). But the
Downloaded by [Purdue University] at 07:14 18 January 2015

pseudo- plasticity, while the increasing of the viscosity with other samples F3 and F6 recorded Dsb=
C 0.43 and 0.37.
shear rate is called shear thickening or dilatancy. In this This mean that the former formulations are most tolerance
work, the shear stress and the dynamic viscosity against to the decrease of yield value of the mud emulsions than the
the shear rate were measured at different temperatures others. The formulations F1, F2, F4, and F5 were selected
(25
C to 65
C), different primary emulsifier concentrations as the best formulations to investigate the effect of the pri-
(1, 2, and 3%), and different water content (5, 10, 20%). mary emulsifiers concentration on the mud property.
The emulsifiers were compared using measurements of The chemical structure of the corresponding primary
the flow properties of the model emulsions (Fc). Figures 3 emulsifier was mono- and dioleate of glycerol and mono-
and 4 show the rheolograms (viscosity and shear stress and dioleate of triethanol amine, respectively. In spite of
against shear rate plots) of the emulsion systems at differ- the trioleate esters gave a late results comparing with the
ent values of the dispersed phase concentration and HLB former mono- or dioleate esters. This means that the che-
of the emulsifier used. The shape of the hysteresis loop is mical structure plays a central role to stabilize and enhance
characteristic for the viscoelastic fluids e.g. concentrated the rheological properties of the oil base mud formulations.
emulsions.[11,12] From the data illustrated in Figures 3
and 4, it was found that the rheological behavior of the
Thixotropy of the Oil Base Mud
oil base mud (w=o) emulsion is the data observed almost
Generally, the most drilling fluids contain clays that
Newtonian nearly above 150 D.sec-1 and the non-Newto-
exhibit thixotropic properties. Thixotropic of fluid from
nian behavior appears before this limit. The increasing
tendency toward Newtonian behavior was obtained by gels upon in quiescence static condition and region their
fluidity under dynamic conditions.
increasing the applied temperature for the oil mud. The
The shear- or gel-strength of drilling fluids in a
dynamic viscosities, gd, and Bingham yield values, sB,
measurement of the minimum shearing stress necessary to
for the six complete oil base mud emulsions (F1 to F6)
produce slip-wise movement of the fluid.
and the control sample (Fc) at different temperatures
(25
C to 65
C), 2% and 10=90 w=o are listed in Table 3
and illustrated in Figure 3. F1, F2, F4, and F5 exhibited
dynamic viscosity closed to that obtained by the control TABLE 4
sample (75 mPa.s). But the F3 and F6 exhibited (90 and Thixotropy for mud complete emulsion formulations at 2%
85 mPas), respectively at 25
C. By increasing the tempera- PE and (10=90) w=o ratio
ture from 25
C to 65
C, the viscosity temperature coeffi-
cient (Dg=
C) decreasing for the F1, F2, F4, and F5 was Temp.
C Fc F1 F2 F3 F4 F5 F6
0.08, 0.10, 0.1, and 0.13 was nearly close to Fc. Meanwhile,
25 1 0 0 1 0 0 1
the other samples F3 and F6 recorded Dg=
C higher than
35 1 0 0 1 0 0 1
the former samples (0.17 and 0.18). This means that the
45 0 0 0 1 0 0 1
formulations which used the primary emulsifiers I, II, IV,
55 0 0 0 1 0 0 1
and V are most tolerance to the increase of the temperature
65 0 0 0 1 0 0 1
program than the others. This is a good property of the oil
 1086 A. M. AL-SABAGH ET AL.

TABLE 5
Gel strength for mud formulation at 2% PE and (10=90) w=o ratio
Fc F1 F2 F3 F4 F5 F6

Temp,
C 10 sec 10 min 10 sec 10 min 10 sec 10 min 10 sec 10 min 10 sec 10 min 10 sec 10 min 10 sec 10 min

25 8 8 9 9 8 8 12 12 9 9 9 9 14 14
35 8 8 9 9 8 8 11 11 9 9 9 9 14 13
45 7 7 8 8 7 6 10 9 6 6 8 8 13 12
55 7 7 8 8 7 6 10 8 6 6 8 8 12 11
65 7 6 8 7 6 6 9 7 6 6 7 7 11 10

The data listed in Table 4 clear the thrixotropy of the
prepared six oil base mud formulations. From the repre-
sented data in Table 4, it was found that F1, F2, F4, and
F5 have not thixotropy, while the formulations F3 and
F6 exhibited thixothropy along the term of temperature
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Table 6 shows the stability the mud formulations
expressed by Gel strength=1=T after 10 seconds and 10
minuets. By inspection the presented data in Table 6, it
can be concluded that the maximum stability of the oil base
mud may be exhibited emulsifiers I, II, IV and V corre-

(25
C to 65
C). On the other hand, the control sample
(Fc), F3 and F6 exhibited a thixotropy at two temperatures
25
C and 35
C, but they recorded no thixotrpy at higher
temperature (45
C to 65
C). This behavior means that
there are four emulsifiers in the oil base mud (F1, F2, F4,
and F5 are time- independent viscosity. It was also
found that Fc, F3 and F6 have thixotropy and are time-
dependant viscosity at low temperatures (25
C and 45
C),
then their behavior changed at high temperature (55
C to
65
C), this means that they are time- independent viscosity
at high temperature. By analysis the data in Table 4, it was
found that the mono and diester of glycerol (F1 and F2)
and of triethanol amine (F4 and F5), are time-independent
materials especially in the oil base mud formulation (no
thixatropy obtained). This means that, these primary emul-
sifiers can be used successfully in the oil base mud at high
range of applied temperatures. Meanwhile, the emulsifiers
(III) glycerol trioleate ester, and (VI) triethanol amine
monooleate esters are time dependent at low temperature
(25
C and 35
C) but at temperatures (45
C to 65
C) exhib-
ited a non-thixotropy behavior. At the same time, F3 and
F6 were nearly closed with the control sample Fc. Regard-
ing to the chemical structure and the thixotropy behavior,
the emulsifiers can be ranked in the order of the best beha-
vior as, I, II, IV, and V > III, VI corresponding to the oil
base mud, F1, F2, F4, and F5 > F3 and F6, respectively.
sponding to the formulations F1, F2, F4, and F5. Other-
wise, the F3 and F6 exhibited the lowest stability. On the
other hand, this finding may be justified by the emulsion
droplet size (mm) as shown in Table 6. The droplet size of
the internal phase of emulsion plays an important role in
the stability of this emulsion. The low droplet sizes were
obtained from F1, F2, F4, F5, and Fc (4.2, 3.1, 4.6, 3.2,
and 3.5 mm), respectively. These formulations exhibited
the highest stability. The formulations F3 and F6 gave
droplet size 6.3 and 8.3 mm, respectively. These formula-
tions pronounced the lowest emulsion stability. The con-
centration effect of the primary emulsifier on the stability
and droplet size of mud emulsion is shown in Table 7.
From the obtained data, it was found that the stability
(expressed by G=t1) increases by increasing of PE concen-
trations. The stability increased with decreasing the droplet
size of emulsion. The 2% PE exhibited maximum stability
and minimum droplet size. So that, 2% PE is the most
effective concentration on the stability and the emulsions
droplet size of mud emulsion.
TABLE 6
Stability of mud formulations expressed by GS=(1=T) and
the average droplet size during 90 days at 2% PE
GS=1=T

Gel Strength of the Oil Base Mud Formulations 10 sec 10 min Droplet size (mm)
The data in Table 5 reveal the gel-strength for the
complete emulsion formulation (oil base mud) at different F1 2.7 3.1 4.2
temperatures. From the data listed in Table 5, it can be F2 2.5 3.2 3.1
concluded that the six investigated formulations are having F3 6 7 6.3
gel strength greater than the control sample (Fc). In F4 3.5 4 4.6
general, the increasing of the temperature leads to decrease F5 3.2 4.5 3.2
the gel-strength for all the investigated formulations (oil F6 8 8.5 8.3
base mud). Fc 2.7 3.5 3.5
 OIL BASE MUD. PART I 1087

TABLE 7
Relation of G=(1=T) for F5 at different concentrations and
the average droplet size during 90 days
PE Conc. 10 sec 10 min Droplet size (mm)

1% 6.4 10.2 6.3

2% 3.2 4.5 3.2
3% 4.3 7 3.4

Filtration Losses of the Base Mud

The effect of filtration on oil base mud was shown in
Table 8 for the six investigated formulations and the con-
trol sample (Fc). The data show that the F1, F2, F4, and
F5 exhibited 5 ml filtrate at high pressure and temperature
(500 psi and 200
F) and 2% primary emulsifier, respec- FIG. 5. Viscosity shear rate curves for F5, Fc at 2% PE and different
tively. Meanwhile, the filtration loss of the control sample water: oil ratios.
was 9 ml. But, the formulations F3 and F6 exhibited filtra-
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tion loss 10 and 11 ml at 2% emulsifier concentration and

10% water in oil emulsion. This means that the formula-
tions (F1, F2, F4, and F5) are greater than the formula-
tions (F3 and F6). This is the obvious evident that the
derived emulsifiers from the locally materials can be used
as good primary emulsifiers in the formulation of oil base
mud. This means also that there are a direct proportion
relationship between the stability of the oil base mud
formulations and their filtration loss.
The effect of PE concentration on the filtration loss is
clearly from the same Table 8. From the obtained data, it
was found that the filtration loss increased at 1 and 3%
PE. But the optimum loss was exhibited at 2% PE. This
means that at 2% PE, the maximum stability of the emul-
sion was exhibited so that, at which may be the droplet size
of the emulsion particles are nearly the same size.
The ordered adsorption of the PE molecules around the
droplet makes it more regular size and further the stability
increases. Therefore, the distance between the pores
decreases leading to decrease the filtration loss. The low
or high concentration of the PE may enhance the coales-
cence properties of the emulsion particles and the destabi-
lization may be obtained quickly, therefore the filtration
losses increased.
On increasing the dispersed phase concentration of
emulsion, the viscosity was found to increase in all the

TABLE 8
Filtration loss, [ml] for the mud formulations at different
PE concentrations and 10:90 water oil ratio
PE conc. FC F1 F2 F3 F4 F5 F6

1% 9 5.5 5.5 10 7 5 11
2% 6 5 5 8 5 5 9
FIG. 6. Pesidoplatic behavior of (a) Fc, F2, F5, and (b) F3 and F6 at
3% 6 5.5 5.5 9 5.5 5.5 10 2% PE concentration and 10:90 water oil ratio.
 1088 A. M. AL-SABAGH ET AL.

TABLE 9
Filtration loss, [ml] for the mud formulations at different
water content
Filtration loss, [ml]
Water
content, % FC F1 F2 F3 F4 F5 F6

5 8 6 6.5 9 7.5 6.5 10

10 6 5 5 8 5 5 9
20 7 5.5 5.5 9.5 6.5 7 10.5

emulsion systems studied as shown in Figure 5. When log

viscosity is plotted against log shear rate, the resulting
curve has a shape similar to that for pseudoplastic flow
and shear thinning as shown in Figure 6b for the mud
emulsions F6 and F3. But the plots in Figure 6a show
pesudoplastic flow without shear thinning. For the control
sample (Fc) and the tested mud emulsions (F2 and F5).
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The effect of water content on the filtration loss for F1,

F2, F4, and F5 was remarked also in Table 9. From the FIG. 8. The relationship between viscosity of mud emulsions and
data presented in this table, the increasing of water content HLB of PE; at 25
C, (a) HLB-g at shear rate 64 s1 and (b) HLB-sB.
(5% to 20% water) leads to increase the filtration loss. This
may be due to decrease the internal distance between the
droplets, which leads to increase of the water coalescence
which followed by deformation of the emulsion. Some
investigators (ref) found that as the water content in
the emulsion increases, the distance between the water
droplets decreases. This leads to adjust themselves to regu-
lar shape of pores, followed by decrease in the filtration
loss. In this study at 10% water, the best results was
obtained, but when the concentration of water in the oil
mud increased to 20% the distance between the droplets

FIG. 7. Effect of temperature on viscosity for F5 evaluated for

different shear rates (D.s1) 2% PE and 10:90 water oil ratio. FIG. 9. Effect of PE concentratin on (a) gd and (b) sB for F5.
 OIL BASE MUD. PART I
decrease and adjusting themselves to the irregular shape of
the pores, which leads to increase the filtration loss.
Effect of Temperature on the Property of Oil Base Mud
The relation between viscosity and shear rates at differ-
ent temperatures is shown in Figure 7. From the shown
plots, it can be concluded that the increase of shear rate
and temperature decrease the viscosity. The obtained rela-
tion is following Arrhenius-type relationship. The relation-
ship between viscosity and shear rate versus HLB
properties of the synthesized emulsifiers is shown in Figures
8a and 8b at shear rate was 64 s1. A decrease of emulsion
viscosity with increase of HLB is shown in Figure 8a. But
the same decrease was seen against the shear stress in
Figure 8b for HLBs (3.9, 4.4, and 4.9) and the curve
became steady with HLBs (5.9, 6.3, and 6.7). Figure 9a
shows the effect of temperature on the viscosity of the
emulsion and Figure 9b shows the effect of temperature
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on the shear stress for F5 at different concentrations of
PE with water content. An increase in temperature
FIG. 10. Gel strength 1=T relationship; (a) after 10 seconds and
(b) after 10 minutes.
1089
evidently decreases the viscosity significantly. The viscosity
and shear stress versus the temperature data followed on
Arrhenius- type relationship. The increase of PE concen-
tration increases the viscosity and shear stress.
The effect of temperature after 10 seconds and 10 min-
utes for the prepared emulsions on gel strength is shown
in Figures 10a and 10b. The effect of temperature on the
concentration is shown in Figures 11a and b. the plots
in Figures 10 and 11 are following also Arrhenius-type rela-
tionship. By inspection of Figures 10a and 10b, it was
found that the F1, F2, F4, and F5 have a better results
than of Fc.
Emulsion Stability
The mud emulsion stability was expressed by gel
strength against HLB, ceq.int, Amin and DGad by inspection
the plots in Figures 12a through 12d. It was found that, the
maximum stability of mud emulsions was obtained at
HLB ¼ 5.9 and 6.7 (F5 and F1). The same results were
exhibited on plots of mud stability against Amin, DGad,
and ceq.int. This finding may be used to evaluate and classify
the stability of mud emulsions formulations. Also, it can be
concluded that the stability of mud emulsion is strongly
related to the surface active properties of the used primary
emulsifier (PE).
FIG. 11. Effect of PE concentration on gel strength for F5 (a) after
10 seionds and (b) after 10 mmutes.
 1090 A. M. AL-SABAGH ET AL.
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FIG. 12. Mud stability [gel strength=(1=T)] against (a) HLB; (b) Amin; (c) DGad and (d) ceq.
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