School of Science and Engineering

Capstone Final Report

Drilling Fluids:
Rheological
Properties and Shear Banding

Submitted in

Spring 2015

By

FAYCAL JAALI

Supervised by

DR. ASMAE KHALDOUN

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AKNOWLEDMENT

First of all, I would like to express my deep and sincere feelings of gratitude to my

supervisor Dr. Asmae Khaldoun for her tremendous assistance from the very beginning

although she was exceptionally busy this semester by having other tasks to handle without her,

this work could not be done.

Besides, I would like to thank my family and especially my parents for their sensitiveness

and patience and their psychological and material support during this tough period. Their love

and support were my incentive to move forward toward success.

I finally would like to thank all my friends for giving me the opportunity to share this

enjoyable opportunity. Special thanks go to Zakaria Tbany, Fatima Zahra Chakir, Ayoub Firkri

and Labib Mohamed Yassine.

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TABLE OF CONTENTS:
I. INTRODUCTION ................................................................................................................ 6
II. LITERATURE REVIEW: ................................................................................................. 7
II.1 Rheology............................................................................................................................. 7
II.1.1 Deformation .............................................................................................................................7
II.1.2 Viscosity ....................................................................................................................................8
II.1.3 Newtonian Fluids ......................................................................................................................9
II.1.4 Newtonian Fluids ......................................................................................................................9
II.2 Emulsion ............................................................................................................................11
II.3 Invert Emulsion ..................................................................................................................12
III. UNDERSTANDING DRILLING FLUIDS ................................................................... 13
III.1 Overview .................................................................................................................................. 13

III.2 Functions of Drilling Fluids ...............................................................................................13

III.3 Types of Drilling Fluids .....................................................................................................14
III.3.1 Water-Based Mud ............................................................................................................... 14
III.3.2 Oil-Based Mud..................................................................................................................... 15
III.4 STEEPLE Analysis ..............................................................................................................16
III.4.1 Economical .......................................................................................................................... 16
III.4.2 Environmental ...................................................................................................................... 17
IV. EXHIBITION OF SHEAR BANDING.......................................................................... 18
IV.1 Overview ...........................................................................................................................18

IV.2 how can a material become a “shear-banding” material?....................................................18

IV.3 how does the transition towards shear-banding occur in time for a given material? ............21

IV.4 Materials and procedures ..................................................................................................22

IV.5 Experimental results ..........................................................................................................23

IV.6 Explanation .......................................................................................................................24

V. ELASTICITY IN INVERT EMULSIONS ..................................................................... 25

V.1 Experiment Overview ..........................................................................................................25

V.2 Experimental results ............................................................................................................25

V.3 Explanation .........................................................................................................................26

VI. THIXOTROPIC BEHAVIOR ........................................................................................ 29

VI.1 why does thixotropy occur? ...............................................................................................30

VI.2 Materials and procedures ..................................................................................................30

VI.3 Experimental results ..........................................................................................................30

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 VI.4 Explanation .......................................................................................................................31

VII. SHEAR BANDING ........................................................................................................ 33

VIII. CONCLUSION ............................................................................................................. 35
REFERENCES ....................................................................................................................... 34
APPENDIX A ......................................................................................................................... 35
APPENDIX B.......................................................................................................................... 43
APPENDIX C ......................................................................................................................... 44
APPENDIX D ......................................................................................................................... 46

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ABSTRACT
Drilling fluids are generally used to help drilling the wellbore for the extraction of oil

and natural gas. These fluids are indispensable for the removal of cuttings generated by the

drilling process, cool and lubricate the drillstring, and keep the hydrostatic force in balance. In

fact, there are two types of drilling fluids: water based and oil based. In this work, we are

particularly focusing on the latter because of the frequency that the anomaly studied appears.

Oil based drilling fluids (or muds) are, actually, complex fluids called invert emulsion materials

composed of droplets of water dispersed in an oily continuous phase plus clay, emulsifiers and

several other components added for specific rheological properties. In fact, these fluids exhibit

shear banding when shear stresses are applied to it after a period of rest. Shear bands are actually

macroscopic bands of different viscosity that appears in the fluid to overcome a certain shear

stress (and shear rate). In this paper, we will try to understand the occurrence of shear banding

and what causes them in oil-based drilling fluids. However, before attacking the analysis of

shear localization, one should answer two important questions: how can a material become a

“shear-banding” material? And how does the transition towards shear-banding occur in time

for a given material? To answer our question and explain the shear localization in oil-based

muds, we used the results of simple invert emulsions prepared previously by Dr. Asmae

Khaldoune by varying the concentration of clay and emulsifiers. The conducted experiments

investigate the elasticity, viscosity and thixotropic behavior of these fluids. From the results of

the experiments, we explained the nature and the cause of these shear localizations. As a result,

the adhesion caused by the interaction between droplets in invert emulsions, and the aggregation

of these clay particles forming a network, add thixotropy to the material. Nonetheless, also the

aggregation of surfactant in pure emulsions form a wormlike micelles that gives yield stress to

the material. This yield stress makes the material susceptible for shear banding through

heterogeneity in the material.

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INTRODUCTION
In a world where the primary source of energy is fossil fuel, the optimization of the

process of oil drilling from underground became necessary in order to maximize the extraction

cost and reduce the expenses on materials. To achieve the latter, an expertise in this area is

needed to overcome the recurrent problems that could be faced in the different stages of drilling

by conducting extensive studies and researches on the field of chemistry, physics and petroleum

engineering.

One of the problems that is quite common while drilling in the wellbore is the change

in the properties of drilling fluids. These fluids are essential and indispensable in the process,

since it is through them that cuttings are removed from the wellbore, the drillstring and bit are

kept cool and lubricate and the formation pressure are kept balanced. However, it has been

noticed that a certain category of drilling fluids have a tendency to become brittle and break

under stress when they stay at rest for a prolonged time. Therefore, this problem can’t neglected

since its repetitiveness drive the company to huge losses in terms of money and sustainability.

Since I am willing to pursue my education in chemical engineering, and after

experiencing this field in my internship, I decided to conduct my capstone project with Dr.

Khaldoune on drilling fluids and expand my knowledge in this area. In this project, I will try to

analyze the rheological behavior of drilling fluids under stress and understand the cause behind

the occurrence of shear banding.

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 I. LITERATURE REVIEW:

1. Rheology:

Rheology is the science that deals with the flow, deformation, and more generally the

viscosity of materials under the action of stresses. Rheology is able to integrate the study of all

substances that are liquid or solid. But in most cases, the formulator must deal with problems

concerning the pasty solids or thick liquids. The terms used here are intentionally ambiguous.

Indeed, one must be aware that the term liquid encompasses both very fluid liquids such as

water, organic solvents, solutions and dilute dispersions but also much more consistent and

viscous substances in pasty appearance , semi-solid or even solid [2]. These differences are

often due to the wide range of time scale regarding the flow mechanism. The flow of a fluid

such as water occurs instantaneously under the effect of gravity. In some cases, it will take a

few hours to observe a significant flow beginning [2].

The viscosity is not the only quantity to be observed, most of the materials also have

elastic properties more marked that they have a complex molecular organization.

Viscoelasticity examines in concert viscous and elastic properties of materials.

Rheometers allow to obtain rheograms called curves that describe the flow properties of the

material. To begin, it is necessary to define the shear movement which is the movement type

being implemented in rheology. Here are some key terms that should be well understood in

order to undergo the rheology of a fluid.

1.1 Deformation:

Deformation is defined as the relative displacement of points when a force is applied to

it. Deformation can be either reversible or irreversible. The reversible deformation is the

product recover its original shape after the removal of the force applied on it. It is said that the

product has elastic properties. The irreversible deformation are products that do not show elastic

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properties, they would flow when a force is applied on them. The points will not align with their

previous placement before the application of the stress [2].

1.2. Viscosity:

Viscosity is a measure of the resistance of a fluid to change in shape: the viscosity

determines the speed of movement of the fluid (for example, the speed of movement of a spoon

in a bowl: the higher the liquid viscosity, the more the movement is slow). Let’s take for

example water and cream. Cream is thicker than water; its shows more resistance to flowing.

Hence, cream is more viscous than water [2].

In fact, the addition of a small amount of substance in suspension or solution can greatly

increase the viscosity of the liquid. Molecular viscosity is denoted by μ; it is expressed in Pa.s

or P (poise). Generally, liquids have a viscosity greater than that of the gas. Because the

molecules are closer together in liquids, connections are established between them more

frequently which increase the cohesion of the assembly. Of course, the viscosity varies

inversely with temperature [2].

Figure1: Viscosity of different fluids [27]

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 1.3. Newtonian Fluids:

It is called a Newtonian fluid when the viscosity of said fluid is independent of the

pressure applied thereto. In fact, the deformations are proportional to the stresses [3].

The water under the prevailing conditions is the perfect example. Actually, water is not more

viscous when at rest compared with when turning it slowly or quickly.

Perfectly Newtonian fluids do not exist in real life. It is considered that fluids such as

water or air are common conditions in Newtonian or approaching (water becomes non-

Newtonian in extreme pressure conditions) [3]. The definition of a Newtonian fluid is rather

restrictive: the shear stresses are proportional to the velocity gradient, which implies that:

- In a simple shear flow, the only constraints are created by the flow shear stress.

- The viscosity is independent of shear rate.

- The viscosity is independent of time and the stresses vanish immediately when the flow is

stopped.

Figure2: Graphs showing properties a of Newtonian fluid [28]

1.4.Non-Newtonian Fluids:

Unlike Newtonian fluids, non-Newtonian fluids are liquids (or any deformable matter)

that have their viscosity changing with the change in the applied mechanical stress, or the time

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in which the stress is applied [3]. As we can see in the figures, the non-Newtonian fluids have

a nonlinear graph when opposing shear stress and shear rate in contrast with the Newtonian

fluids. There are actually numerous types of the non-Newtonian fluids. We can name

Viscoplastic, Pseudoplastic, dilatant and thixotropic fluid [3].

Pseudoplastic fluid occurs when there is an increase in the shear rate resulting in a

tendency to become thinner until it reaches a limit of viscosity. The continuous increase in shear

rate will cause a deformation at the level of the fluid structure making any further increase in

viscosity impossible. However, these fluids are non-memory materials, which means that if the

structure is modified due to an application of a force, the fluid will not recover its original

structure. An example of the Pseudoplastic fluid is ketchup [3].

Viscoplastic fluids have a certain threshold of stress in order to flow. Once that threshold

reached or exceeded, the fluid go from high viscosity to low viscosity. A type of these is

Bingham plastic which require a minimum yield stress to flow, once reached, the relationship

between the shear stress and the shear rate will find its linearity [3]. Example of Bingham plastic

is blood.

Dilatant fluid behaves in reverse of Pseudoplastic fluid, which means, it becomes thicker

when an increasing shear rate is applied on it. Similar now to Pseudoplastic fluid, it is not

affected by the duration of the stress. Hence, once the structure is disturbed or destroyed, the

material will recover its original state [3]. Some examples are honey and cement.

Thixotropic fluid is generally dispersion, which means that the material thicken and its

viscosity increase as fluid remains at rest due to a construction of a system of intermolecular

forces [3]. Therefore, to make the fluid flow again, these intermolecular bindings should be

overcome by exceeding the yield stress with a strong enough external energy. The viscosity

will decrease until reaching the minimum possible with respect to a constant shear rate.

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However, in contrast to Pseudoplastic and dilatant fluids, Thixotropic fluid is time dependent:

which means that the fluid will recover its previous structure when it comes to rest [3].

Figure3: Graphs showing properties of non-Newtonian fluids [29]

2. Emulsion:

Oil generally do not dissolve in water. In fact, when poured in a container filed with

water, a two distinct layers of both fluids will form [4]. This is due to the buoyancy effect; the

oil is less dense than water which make it float. Therefore, emulsion is when forcing two

immiscible fluids to merge and form a mixture [4]. Emulsions are generally more viscous than

the two fluids originated from. To achieve this state, an emulsifier is needed to maintain the

mixture and avoid the separation again. An example of emulsifier is Lecithin that is found in

eggs. Lecithin has a water-loving head and Water-hating tail; the water-loving head dissolves

in water and Water-hating tail dissolves in oil, for example, making the mixture unable for

separation [4].

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 Figure4: Structure of Lecithin [4]

3. Invert Emulsion:

The invert emulsion is when we use the emulsion “backward”, which means that the

normally continuous phase becomes the dispersed and vice versa [5]. For example, we will

proceed an invert emulsion if we prepare a water-in-oil emulsion.

This technique is generally used in oil drilling. They use an invert emulsion drilling fluids when

good wellbore stability and high temperature tolerance are required.

Figure5: Image showing Water-in-oil and oil-in-water emulsions [5].

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 II. UNDERSTANDING DRILLING FLUIDS:

1. Overview:

The mud or drilling fluids are generally constituted of water, clay and other few

chemicals. Sometimes oil is used as the continuous phase instead of water to obtain some

specific and desired properties. The purpose of using drilling fluids is to raise the cuttings made

by the bit out of the wellbore for disposal or analysis. But equally important, drilling fluids are

also used to keep the formation pressure in the well under control. The pressure that mud exerts

on the walls of the well depends on the density or weighing of the mud. The heavier it is, the

more pressure it exerts. This is why, to increase the pressure that the mud exerts, weighing

materials like barite could be added [6].

Figure6: Illustration showing mud circulation [6].

2. Functions of Drilling Fluids

 Transport the cuttings out of the well to be remover mechanically before it is

recirculated in the wellbore again, and keep the hole clean.

 Keep the formation pressure balanced and avoid any overwhelm of the hydrostatic

forces that could endanger the drilling operation.

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  Support the walls of the wellbore until it is cemented or the installation and completion

of the equipment

 Prevents or minimizes damage to the producing formation(s).

 The drillstring and bit are kept lubricated and cool

 Transmission of hydraulic horsepower to the bit.

 Allow the gathering of information concerning the wellbore through the analysis of the

cuttings transported outside.

3. Types of drilling fluids:

An intensive research was done on the difference between the types of the drilling fluids.

Here is a summary of what was collected.

There are two main types of drilling fluids, each one used for specific purposes and

under specific conditions.

3.1 Water Based Muds:

First, the water based muds, is generally constituted of four elements: water, inert solids,

active colloidal solids and chemicals [6]. Water represents the continuous phase of any water

based mud. The continuous phase are primarily used to provide the initial viscosity, and through

addings, these rheological properties could be modified as desired. The continuous phase is also

used to suspend the reactive colloidal solids, such as bentonite, inert solids, such as barite [6].

Thirdly, the water serves as medium for the transportation of the horsepower from the surface

downhole to the bit. Without forgetting that water also serves as medium for added chemicals

in the drilling fluids [6].

To increase the viscosity of the water-based mud, clay is generally used because it increases

of the density of mud, gel strength and yield point, and it decreases fluid loss. We can divide

the clay used in drilling fluids into three parts:

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  Montmorillonites (bentonite)

 Kaolinites

 Illites

3.2 Oil Based Muds

Second, the oil-based mud, which is any drilling fluid that has as continuous phase any

suitable oil. In fact, there are two types of system in which the continuous phase is oil: invert

emulsion mud’s and true oil muds [6]. The latter consist of the following components:

 Suitable oil

 Asphalt

 Water

 Emulsifiers

 Surfactants

 Calcium hydroxide

 Weighting materials

 Other chemical additives

Among all these components, only the first two are indispensable for the functioning of oil-

based mud. The remaining components are just added in order to enhance some specific

rheological properties and plastering characteristics [6]. Even if water is not required among

the constituents of oil mud systems, it is generally added with other chemical additives to

enhance also some specific rheological properties. Numerous bodying agents are used in oil

muds to find to a specific filtration loss characteristics [6]. We can divide these bodying agents

into two groups:

 Colloidal size materials

 High molecular weight metal soaps

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Asphalt, one the colloidal-size organophilic materials is used in oil muds for its absorption

characteristic to limit the fluid loss. It is basically the same concept as clay in water muds.

Meanwhile, emulsifiers in the form of Heavy metal soaps of fatty acids are added in the oil

muds for the invert emulsion process [6].

The functions of emulsifiers in oil mud’s are as follows:

 Transmit to the oil muds the strength to be able to suspend the cuttings in the gel.

 Proceed to emulsify any droplet of water in the oil mud during the drilling operation.

 Control of the tightening of any emulsion of the water resulting from the contamination

of the water, therefore, control the loss of fluid.

4. STEEPLE Analysis:
4.1 Economic
Drilling fluids are subject to shear banding when a critical shear stresses and shear rates

are not attained. Shear banding can damage the drilling fluid through fracture when remaining

at rest for a long period of time, make it unusable. By understanding this phenomenon, scientists

can prevent huge economic loses to the company. How? First, drilling fluids are highly

expensive, and their importance to the drilling operation make the oil company loses money

because of this phenomenon. Hence understanding the processes of shear banding will reduce

the damages caused by the latter, which will therefore reduce the cost spent on muds in general.

Another point in which the company reduces its expenses through this research is time. When

fracture occurs in drilling fluids, the process of changing is time consuming making the

extraction of oil delayed, and hence huge losses for the company.

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4.2 Environmental:

As discussed in previously, drilling fluids make the hydrostatic forces inside the

wellbore balanced preventing any overwhelm. A damaged drilling fluids can no longer support

these forces endangering the wellbore from collapsing. If this happened, all the drilling

apparatus would be under sol polluting all the area countering it and nearby. Therefore,

understanding the cause of these fracture will prevent these unbalancing forces to occurs and

decrease the chance of any polluting incident.

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 III. EXHIBITION OF SHEAR BANDING

1. Overview

Systems as foams colloidal suspensions, or as in our example emulsions are constituted

of small particles that are subject to soft interaction between them, which means that the

distance between them (particles) change progressively. The change in state of these systems

from solid to liquid after undergoing on them stress have always created a certain curiosity and

interest. Normally, the rheological behavior of systems are described by the mean of the simple

yield stress model which provide a velocity profile containing unsheared regions when the

stress distribution is heterogeneous. Now, several papers and experiments showed that the flow

of these materials exhibits true shear banding, which means two regions with significantly

different shear rates in geometries in which the shear stress is homogeneous. The latter behavior

is not predicted by the simple model of yield stress since it considers the solid-liquid transition

as being smooth. Therefore two questions rises: (1) how can a material become a “shear-

banding” material? and (2) how does the transition towards shear-banding occur in time for a

given material?

2. How can a material become a “shear-banding” material?

There are numerous ways by which a fluid can lose its ability to flow; we can cite

lowering the temperature, increasing volume fraction or releasing some external stress. This

happens to huge variety of materials that extend from polymers and colloids to granular

assemblies, also known as “soft glassy materials”. These systems show different responses

depending on the external shear stress. If the shear stress is below the critical value, the system

will behave elastically and resist motion, however if it is above, the flow will occur. Hence the

importance of acknowledgement of the yield stress. The oscillatory shear experiments is the

obvious response for how to extract the yield stress since from this experiment, we can get the

18
viscoelastic moduli of the system that procure us with useful information about the yielding

behavior. Generally, one can add the dynamic light scattering experiment on the system to

determine besides the yield stress, the local arrangement inside the material. To our paper, the

question should be asked more specifically in order to be relevant to our analysis. Consequently,

the question becomes: how can an invert emulsion becomes a “shear-banding” material??

Bécu et al, in their experiments showed that the adhesive behavior of the droplets created

by their mutual interaction provoke a shear-banding in a simple yielding emulsion [7]. The

originality of their work was the control of the short-range attraction between droplets by

varying the concentration of surfactant in the emulsion. By this mean, they compared the flow

behavior of adhesive emulsion (i.e. attractive glass) with non-adhesive emulsion (i.e.

repulsion). The velocity profiles are well described and explained by showing the shear banding

expressed on adhesive systems in the contrary of non-adhesive emulsions which shows

homogenous flow throughout the yielding transition. Actually, in their experiment, they noticed

that free Sodium Dodecyl Sulfate (SDS) forms micelles that do not absorb and are repulsed

from the nearby droplets, which creates an excess in osmotic pressure pushing the droplets

together[22]. Also, by increasing the SDS concentration therefore the concentration of micelle

leads to the depletion forces and later flocculation. As we can notice from the figure below, the

first sample constitutes of Brownian droplets meanwhile second is aggregated in one large

entity. They concluded from below that low concentration of SDS (1%) leads to non-adhesive

emulsion and relatively high SDS concentration (8%) to an adhesive one [Fig.7] [7].

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 Figure 7: a) Emulsion with 1% wt. SDS. b) 8% wt. SDS [7]

Also, from the experiment done by varying the velocity profiles on adhesive and non-

adhesive emulsions using a Rheometer, Bécu et al found that both emulsion were subject to

shear localization in thin lubrication films at the walls and total wall slip was observed: since

the velocity was under the critical value, the rotation was that of a solid body [7]. As the velocity

increased, both emulsions start to be sheared, yet not in the same way. In the non-adhesive

emulsions, the flow stays homogenous (see c-d below) meanwhile in the adhesive emulsions,

Bécu et al remarked a huge shear band at the inner wall (fig 8 b and c below) [7]. The band’s

width continued to grow as the velocity increased until it filled all the gap caused by shear

stress, after that the flow recovered its homogeneity (fig 9 d).

Figure 8: Velocity profiles in the non-adhesive emulsion for (a) v0 = 0.98, (b) v0 = 1.47, (c) v0 = 1.96,

(d) v0 = 2.94 [7].

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 Figure 9: Velocity profiles in the adhesive emulsion for (a) v0 = 0.49, (b) v0 = 0.98 (◦), 1.17 (•), (c) v0

=1.47 (◦), 1.96 (•),(d) v0 = 4.78 (◦), 9.78 (•) [7].

3. How does the transition towards shear-banding occur in time for a given

material?

Now, let’s focus on question (2) and try to elucidate the origin and the effect of time on

shear banding behavior for a given material as the transition from purely solid ( starting from

rest) or purely liquid (starting from intense preshear) toward shear banding is a quite complex

phenomenon. This phenomenon can be related to thixotropic systems (variation of viscosity

over time), and particularly the shear-banding behavior occurring in clay-oil systems. For

example, several cases of shear banding or even fractures were reported on latter systems like

drilling fluids after undergoing a stress when these systems spent some time at rest. Hence, the

specific evolution of shear rate at stoppage agrees with the model predicting the progressive

aggregation of droplets with time.

To investigate the transition toward thixotropy of emulsions, Ragouilliaux, et al. have

compared the behavior of pure emulsions and the loaded emulsions with colloidal particles [8].

In a vision to understand the behavior of these two systems, they analyzed the characteristics

21
of their flow over time using the Magnetic Resonance velocimetry (MR). From their analysis,

they found that the pure emulsion showed a negligible thixotropic behavior meanwhile the

loaded emulsion was significantly thixotropic. At the liquid state, the two fluids share the same

behavior, however the aggregation of the colloidal particles that constitutes the loaded

emulsions and the links they form in the fluid increases its viscosity making it thixotropic.

Therefore, the apparent yield stress of the loaded emulsion will also increase.

In our experiment, we investigated also the thixotropic behavior of the loaded emulsions

versus the pure emulsion. However, we tried, by varying the concentration of surfactants and

clay and analyzing their characteristics to understand how the concentration could affect the

behavior of the emulsions.

4. Materials and procedures

We started by preparing the pure emulsion by adding progressively water to the oil-

surfactant solution under high shear. We used as surfactant Sorbitan monoleates and Vitrea 13

for oil (smells like fuel). For the loaded emulsion, we added progressively the water in an oil-

surfactant/clay solution under high shear; the water droplet concentration was 80%. The oil

surfactant/clay solution was prepared by mixing the surfactant with the colloidal particles “oil

soluble clay particles” called Bentone 38. Let’s keep in mind that oil-clay suspension is a simple

solution which means it does not show any yield stress, meanwhile the oil surfactant/clay

solution is a more viscous pasty material even at low fraction of water. We can conclude that

the clay particles are most likely responsible for this behavior through their aggregation by

creating links and even networks inside the material.

In fact, we planned to prepare the emulsions by variation of the clay content and

surfactant content in the oil solution. The first experimental design given was the variation of

the amount of clay from 0 to 5 %clay, and the surfactant from 1 to 10%. However, the

22
combination 1% surfactant with clay wasn’t enough to prepare stable invert emulsion then we

changed the proportion of surfactant to 2%. The 2% surfactant wasn’t also enough when we

added 5% clay then prepared an emulsion with 3% surfactant and 5%clay. We put the emulsions

that we prepared in the Rheometer and let it stabilize during the night.

5. Experimental results

After a comparison of ours samples at their solid regime with (frequency1 Hz, strain

amplitude 1%), we conducted an Oscillatory measurements by measuring the variation of the

elastic modulus G' of the emulsion over time (see figure x). At first, we notice that G’ of the

pure emulsions (10%, 2% of surfactant) increased very briefly, which indicated that their aging

is negligible over time. Meanwhile, in the loaded emulsions, G’ has increased significantly over

time which can be explained by aggregation of the clay particles with time forming links and

networks, and strengthening the material.

Graph 1: Modulus of elasticity versus time for all samples

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 6. Explanation

That being said, not all pure emulsions exhibit the same behavior. We can notice that

the solution with 5.5% concentration of surfactant shows a higher viscosity compared to the

other pure emulsions. This can be explained by the network that the surfactant can make

throughout the medium by aggregating in wormlike micelles once the critical micelle

concentration (CMC) has been crossed. This wormlike micelle can grow and tangle around

each other with the increase of concentration forming a complex network. Nonetheless, as we

can see in the graph, a very high concentration of the surfactant reduces its viscosity as the

repulsive force between the heads prevent those surfactants from aggregating.

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 IV. ELASTICITY IN INVERT EMULSIONS

1. Experiment Overview

Historically, the normal stress difference was firstly used to prove elasticity in shear

flow. Nowadays, other tools are being used for same purpose like getting G’ using sinusoidal

oscillations which shows to be a more convenient measurement. Nonetheless, normal stresses

are still widely used in different applications. In fact, when sealing with large strains, using

normal stresses is both appropriate and sensible to the microstructures generated by that large

strain.

In the following experiments, we measure the variation of the Normal stress difference as a

function of strain by keeping shear rate constant at 0.01 s-1.

2. Experimental results:

As we can see from the graph 2, there are two types of lines. Lines that are, with different

slopes, showing increasingly higher negative value of normal stress difference (N1), and lines

that are quasi constant at N1 equals 0. Interestingly, the first type is composed of loaded

emulsions containing different concentrations of clay, and the second type represent the pure

emulsion with only surfactants. As a result, the elasticity is higher in the loaded emulsions

compared with the pure emulsion.

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 Graph 2: First normal stress difference versus shear strain

3. Explanation:

In fact, the negative value of normal stress difference was first extensively explained by

Marrucci and Guido who observed at an intermediate shear rate, N1 becomes negative. In their

analysis on lyotropic LCPs, they stated that, due the deformation of the ellipsoid shape of

domain, the rotation of molecules drive them to become perpendicular to the flow axis at

significantly large shear rates. Moreover, taking into consideration the rotational movement of

molecules around their axis, these latter rotate from tumbling to wagging state. Therefore, N1

becomes negative at reasonable shear rates.

Now we will proceed by isolating the three pure emulsions (2%, 5.5% and 10%) and

analyze their behavior before and after adding clay. Indeed, we will examine the change in first

normal stress difference with change in strain and compare it with another experiment. In this

experiment, we will prepare three pure emulsions with the same concentration of surfactant as

our previous graph (2%, 5.5% and 10%) and add a constant amount of clay (concentration

2.5%) in the three solutions. Then we will again measure the first normal stress difference

26
versus shear strain, and we will compare it with the graph where pure emulsions results were

plotted.

Graph 3: First normal stress difference versus shear strain (pure emulsions only)

Graph 4: First normal stress difference versus shear strain (keeping clay constant and varying surfactant
concentration)

From graph 3, we can see that the three concentrations exhibit a slight increase in the

first normal stress difference with some exhibition of few peaks or shoulders. These peaks

represent the structures being broken and aligning during shear. As discussed earlier, surfactants

27
when reaching their critical concentration tend to aggregate and form network throughout the

material. So, during the shear, these structure are broken, however for larger concentration

(10%) we notice two distinct peaks which indicates that a relaxation time where a new structure

was being constructed. In the overall, we deduct a poor elasticity with a few to none resistance

to the flow.

In graph 4, where we kept the clay constant and varying the concentration of surfactant,

we can notice a huge difference in the change of the values of N1. Indeed, the elasticity

increases highly with the presence of clay particles. This is due to the change in orientation of

surfactants which obstruct the flow. This anomalous orientation of surfactants can be explained

by the effect of the clay on them. In fact, the interaction between surfactants and clay particles

offsets the force attempting to align the surfactants in the direction of the flow where substantial

resistances to deformation were observed at low shear rates. Of course, at higher shear rates

these interactions will be overcome and the orientation will follow the flow because the

arrangement of the matrix will be disrupted.

28
 V. THIXOTROPY BEHAVIOR

First, one should make a distinction between the two types of yield stress behavior: the

simple yield stress fluids and the thixotropic. The non- thixotropic fluids, when the applied

stress is removed, they revert back to their original form. That is the upward curve of shear

stress versus shear strain will be identical to the downward curve. This behavior is shown in the

experiment done by Peder Moller et al. on a 0.1% carbopol under increasing and decreasing

shear stresses [7]. This can be explained by the fact that viscosity does not change. On the other

hand, if the material is thixotropic, it will gain in “liquefaction” at high shear stresses, meaning

that the decreasing curve will be slightly below the upward curve. An example from 10%

bentonite solution under an increasing and then decreasing is stated below.

Figure 10: a) 0.1% carbopol and (b) 10% bentonite material behavior [7]

29
 1. Why does thixotropy occur?

Thixotropic materials is a subclass yield stress materials, which means they need a non-

zero critical stress to be able to flow as liquid. Several examples of materials show this behavior

(yield stress): we can cite colloidal suspensions and emulsions such as oil-surfactant solutions,

liquid foods, and mud. However, the particularity of thixotropy is the variation of the value of

this yield stress depending on the amount of time the material stayed at rest. K.L. Maki and Y.

Renardy explained that once the applied stress is removed, the material tries to recover reaching

an apparent equilibrium. After enough time has passed, the microstructures start to reconstitute

their original state. Therefore, the waiting time is crucial for the value of the yield because, if a

stress is applied before the thixotropic material have fully recovered, the yield stress will be

lower. In the same manner, if a constant stress that induces the flow is removed, the

microstructure will continue to be built after the fluid will come to rest.

2. Materials and procedures

To test the yield stress behavior of our samples and test the change in this behavior when

varying the concentration of surfactants and clay, we conducted a thixotropy experiment in

which we applied on all our emulsions an increase in shear rate from 0.01s-1 to 1000s-1 then

decrease from 1000s-1 to 0.01s-1, then we measured the variation of shear stress versus shear

rate. We came out with flow curve (shear stress versus shear rate) for all our sample.

3. Experimental results:

We deduct from the results that all our samples show a more or less thixotropic behavior.

This can be shown by the difference between the upper and lower curve as it is more or less

shifted to the left, depending on the sample. That being said not all the behaviors are the same

even between pure emulsions and loaded emulsions. For example, we can notice a degree of

30
hysteresis (i.e. the difference between the upward and downward curve) of 10% surfactant that

is lower than that of 2% surfactant. Same remark for the loaded emulsions since we can see a

lower degree of hysteresis of 2.5% clay 10% surfactant and 5% clay 3% surfactant (See

appendix A).

4. Explanation

The first differentiation of the thixotropic behavior between our samples is the molecular

weight. Products with high molecular weight take longer to recover, and heir degree of

hysteresis will hence be larger than systems with low molecular weight particles. However, this

could not be the reason since we are using the same type of surfactant and clay in all our

samples.

The second component that could affect thixotropic behavior is the attractive forces

between the components of the material. Let’s take for example the bentone in our loaded

emulsions, the Van der Walls interactions between its polar particles make them aggregate and

form a percolated structure which in turn is the origin of the thixotropy. But also, in the pure

emulsions, we cannot neglect the interaction between the surfactant particles forming a

wormlike micelles in the material, which also give it a thixotropic behavior. However, the

concentration of these two components can affect the forces inside the material increasing or

decreasing its thixotropy. As we can see from the 10% surfactant graph, the hysteresis region

is lower than the two other concentrations of pure emulsions. However, the 2% and 5%

surfactant samples shows a very distinguishable thixotropic behavior, nonetheless we can

remark a higher viscosity for 5.5% due to a stronger network created through the wormlike

micelles.

31
 Now, for the loaded emulsions, we can notice some differences between our samples

also at the level hysteresis region. As stated by Pham et al., the hard-sphere colloids, in our

example bentone clay, when mixed with polymers, surfactant in our example (called living

polymers by M.E. Cates) can form attractive glasses, which means the polymers mediate a more

strong attractive force between the colloids influencing its rheology [9]. We can see a clear

evidence of this analysis by comparing the loaded emulsions and their concentration of clay

and surfactant. Of course, we can’t neglect that a higher concentration can affect the attraction

forces making the network unstable and weaker, hence reducing thixotropy.

Another remark can be done concerning systems that ages spontaneously at rest. They

are called Brownian in a sense that temperature is important. The best example is the very

thixotropic system of bentonite. Peder Moller et al. pointed out that the difference between

Brownian and non-Brownian particle systems is often considered between 1-5 μm [7]. Smaller

particles remains in suspension by Brownian motion, whereas large systems kept immobile.

For Brownian systems, we can see an increase in the modulus of elasticity due to ageing as a

function of time, which is exactly what we found in our previous experiment, some samples

more than others. On the other hand, for systems constituted of large particle, no ageing is

observed.

32
 VI. SHEAR BANDING

We can extract an interesting connection from the distinction that we made between the

simple and thixotropic yield stress systems, and the occurrence of shear banding or not. Shear

banding has always been viewed as being the result of heterogeneity of flow in the system. If

one part of the fluid is under yield stress and another part is above, following the logic, we can

easily say that the flow will not happen, yet it will. Nonetheless, it is not the whole story since

Bonn et al. and Moller et al. put other observations concerning the shear banding of thixotropic

yield stress materials after conducting a cone-plate geometry [23]. The observations are as

follows:

 If during an imposed shear rate measurement the shear rate imposed is lower that

the critical value, shear banding will occur.

 The material inside the shear band is sheared exactly at the critical shear rate.

 The quantity of sheared material can be calculated by deducting the macroscopically

imposed shear rate over the critical shear rate.

From the observations above, we can say that shear banding cannot only occur due to stress

heterogeneity, but also due to having a critical shear rate that is closely linked to the thixotropic

behavior of the material. According to Peder Moller et al., this analysis follows exactly their λ-

model arguing that if using this model (n>1 corresponding to thixotropic systems) for

calculating the steady-state flow curve, it will show a decrease of shear rate which correspond

to flow instability [23]. Which means that not only the thixotropic material has a critical shear

rate, but also below that value, the flow will be unstable. The instability of the flow is indeed

shear banding flow as observed by Bonn et al. and Moller et al [23].

33
 In brief, if we applied stresses on thixotropic yield stress material, either the stresses are

small which will lead to ageing, or large which will lead to liquefaction. This will affect the

viscosity in such a way that at higher stresses, the viscosity is null and at lower stresses the

viscosity is infinite. This implied that the values of shear rate between zero and total liquefaction

are not accessible by the applied stress. This arise a question: what will happen if a shear rate

is imposed in between no flow and total liquefaction flow? Of course shear banding. This

implies that the stress versus strain curve exhibit a stress plateau that is only accessible under

imposed shear rate. This plateau is observed in all our samples.

34
 VII. CONCLUSION:

The purpose of this study was to prove and explain the shear banding in invert emulsion

drilling fluid. We started by answering two important questions concerning shear banding and

thixotropy and we tried to bounce from these answers to explain the rheological properties of

invert emulsions. From experiments done on 10 samples varying the concentration of clay and

surfactant, we tried to investigate their viscosity and elasticity through elastic modulus

experiment and normal stress difference.

Next, we made distinction between sample and thixotropic yield stress materials. We

conducted thixotropic experiments on all our sample and we compared their hysteresis region.

From the experiments, we figured out the importance of the aggregation of the particles inside

the material and how that affects its rheological properties. The construction of networks, its

break up and its assembling again are the major component for the thixotropic behavior. Also,

the concentration of the surfactants and/or clay and their interactions through Van der Walls

affecting the network making it weaker or stronger.

We also discussed shear banding in invert emulsion and how the heterogeneity of the

fluids creates shear bands. The difference in yield stress inside the same fluid are a major

component of shear banding, but it is not the only cause. The critical shear rate is also a major

cause for shear banding.

35
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wm/31320.pdf

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http://www.bbc.co.uk/schools/gcsebitesize/science/aqa/plantoilsanduses/vegoilsrev3.shtml

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14. Khaldoun, A. (2002). Comportement Rheologique Des Systemes Viscoelastiques. In Etude des
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foams, and emulsions. Phys. Rev. E 66, 051305.

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J. Non-Newtonian Fluid Mech. 102, 157–178.

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Non-Newtonian Fluid Mech. 143 (2007) 22–37.

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newtonian-fluids/

37
Appendix A:
Results of Thixotropy Experiment
2 1
4·10 10
Pa
2
3.6·10
2
3.4·10
2
3.2·10
2
3·10
2
2.8·10
2
2.6·10
2
2.4·10
2
2.2·10
2
2·10
 2
5% Clay & 5.5% surfactant
1.8·10
2

1.6·10
2
1.4·10
2
1.2·10
2
10
1
8·10
1
6·10
1
4·10
1
2·10
0
0 10
-4 -3 -2 -1 0 1 2 3 4
10 10 10 10 10 10 10 10 1/s 10
.
Shear Rate 
2 1
3·10 10

Pa

2
2.6·10
2
2.4·10
2
2.2·10
2
2·10
2
1.8·10
2
1.6·10
 2 2.5% Clay & 10% surfactant
1.4·10
2

1.2·10
2
10
1
8·10
1
6·10
1
4·10
1
2·10
0
0 10
-4 -3 -2 -1 0 1 2 3
10 10 10 10 10 10 10 1/s 10
.
Shear Rate 

38
 2 1
4·10 10
Pa
2
3.6·10
2
3.4·10
2
3.2·10
2
3·10
2
2.8·10
2
2.6·10
2
2.4·10
2
2.2·10
2
2·10
 2
5% Clay & 10% surfactant
1.8·10
2

1.6·10
2
1.4·10
2
1.2·10
2
10
1
8·10
1
6·10
1
4·10
1
2·10
0
0 10
-5 -4 -3 -2 -1 0 1 2 3 4
10 10 10 10 10 10 10 10 10 1/s 10
.
Shear Rate 
2 1
2·10 10
Pa
2
1.8·10
2
1.7·10
2
1.6·10
2
1.5·10
2
1.4·10
2
1.3·10
2
1.2·10
2
1.1·10
2
10
 1
10% surfactant
9·10
1

8·10
1
7·10
1
6·10
1
5·10
1
4·10
1
3·10
1
2·10
1
10
0
0 10
-5 -4 -3 -2 -1 0 1 2 3 4
10 10 10 10 10 10 10 10 10 1/s 10
.
Shear Rate 

39
 2 1
2·10 10
Pa
2
1.8·10
2
1.7·10
2
1.6·10
2
1.5·10
2
1.4·10
2
1.3·10
2
1.2·10
2
1.1·10
2
10
 1
5.5% surfactant
9·10
1

8·10
1
7·10
1
6·10
1
5·10
1
4·10
1
3·10
1
2·10
1
10
0
0 10
-3 -2 -1 0 1 2 3 4
10 10 10 10 10 10 10 1/s 10
.
Shear Rate 

2 1
3·10 10

Pa

2
2.6·10
2
2.4·10
2
2.2·10
2
2·10
2
1.8·10
2
1.6·10
 2 2.5% Clay & 5.5% surfactant
1.4·10
2

1.2·10
2
10
1
8·10
1
6·10
1
4·10
1
2·10
0
0 10
-4 -3 -2 -1 0 1 2 3
10 10 10 10 10 10 10 1/s 10
.
Shear Rate 

40
 2 1
2·10 10
Pa
2
1.8·10
2
1.7·10
2
1.6·10
2
1.5·10
2
1.4·10
2
1.3·10
2
1.2·10
2
1.1·10
2
10
 1
5.5% surfactant
9·10
1

8·10
1
7·10
1
6·10
1
5·10
1
4·10
1
3·10
1
2·10
1
10
0
0 10
-3 -2 -1 0 1 2 3 4
10 10 10 10 10 10 10 1/s 10
.
Shear Rate 
2 1
3·10 10

Pa

2
2.6·10
2
2.4·10
2
2.2·10
2
2·10
2
1.8·10
2
1.6·10
 2 2.5% Clay & 2% surfactant
1.4·10
2

1.2·10
2
10
1
8·10
1
6·10
1
4·10
1
2·10
0
0 10
-4 -3 -2 -1 0 1 2 3 4
10 10 10 10 10 10 10 10 1/s 10
.
Shear Rate 

41
 2 1
3·10 10

Pa

2
2.6·10
2
2.4·10
2
2.2·10
2
2·10
2
1.8·10
2
1.6·10
 2 5% Clay & 3% surfactant
1.4·10
2

1.2·10
2
10
1
8·10
1
6·10
1
4·10
1
2·10
0
0 10
-4 -3 -2 -1 0 1 2 3 4
10 10 10 10 10 10 10 10 1/s 10
.
Shear Rate 

42
 emulsion
water content oil solution
70% 30%
APPENDIX B:

oil solution
Clay % surfactant % sample nr Experimental process
5 1 1 didn''t work 1-We prepare the pure emulsion by progressively adding the water to
2,5 10 2 the oil solution under high shear
5 5,5 3 2-We put the emulsion in the rheometer and let it stabilize during the
Details of the experiment

5 10 4 night
0 1 5 didn''t work
0 10 6 Oscillatory measurements
5 10 7 frequency1 Hz, strain amplitude 1%
0 10 8 we measure the varition of G' of the emulsion with the time
0 5,5 9

43
2,5 1 10 didn''t work
2,5 5,5 11
0 1 12 didn''t work Thyxotropy experiments
2,5 5,5 13 increase shear rate from 0.01s-1 to 1000s-1 then decrease from 1000s-1 to 0.01s-1
5 1 14 didn''t work we measure the variation of shear stress versus shear rate
2,5 5,5 15
5 2 16 didn''t work
0 2 17 extra experiments
2,5 2 18 extra experiments Normal force
0 2 19 extra experiments at constant shear rate of 0.01 s-1
5 3 20 extra experiments we measure the variation of the Normal stress difference as a function of strain
APPENDIX C:
Results for Modulus of elasticity versus time

time G'2 G'3 G'4 G'6 G'7 G'8 G'9 G'11 G'13 G'15 G'17 G'18 G'19 G'20
[s] [Pa] [Pa] [Pa] [Pa] [Pa] [Pa] [Pa] [Pa] [Pa] [Pa] [Pa] [Pa] [Pa] [Pa]

20 626 1 220 1 020 165 985 152 105 359 387 460 71,1 575 67,5 156
30 626 1 230 1 030 166 990 152 106 360 390 463 71 575 67,8 174
40 626 1 240 1 030 167 994 153 107 363 390 467 71,8 579 67,7 173
50 627 1 250 1 030 167 1 000 153 108 367 391 468 70,8 583 67,1 182
60 630 1 250 1 030 167 1 000 154 109 370 392 470 69,5 590 67,2 185
70 629 1 250 1 040 168 1 000 155 110 372 393 471 68 591 67,4 186
80 630 1 260 1 040 168 1 010 156 110 375 394 473 69,5 597 67,3 186
90 630 1 260 1 040 168 1 010 157 111 377 395 475 70,3 599 67,8 182
100 631 1 270 1 040 169 1 010 157 112 379 396 477 70,9 599 67,5 193
110 632 1 270 1 040 169 1 010 158 112 381 397 478 69,3 602 67,4 198
120 633 1 270 1 040 169 1 010 158 112 382 397 478 68,9 603 67,2 196
130 633 1 280 1 040 169 1 010 158 113 383 398 479 68 607 67,7 193
140 633 1 270 1 040 169 1 020 159 113 385 399 480 67,9 610 67,4 195
150 634 1 280 1 050 170 1 020 159 113 385 399 481 66,6 610 67,5 196
160 634 1 280 1 050 170 1 020 159 114 387 400 482 61 613 67,3 194
170 634 1 280 1 050 170 1 020 160 114 388 401 482 65,5 615 68,1 186
180 635 1 280 1 050 170 1 020 160 115 389 402 483 65,7 617 67,1 188
190 635 1 290 1 050 171 1 020 161 115 390 402 484 65,6 619 67,7 190
200 635 1 290 1 050 170 1 020 161 115 389 402 484 66 622 67,8 195
210 635 1 290 1 040 171 1 030 161 115 391 403 485 66,4 621 67,6 195
220 637 1 290 1 050 171 1 020 162 115 392 404 485 67,4 623 68,6 196
230 636 1 290 1 060 171 1 030 162 115 393 404 486 67,8 624 68,2 197
240 636 1 290 1 060 171 1 030 162 116 394 405 487 67,9 630 67,8 197
250 636 1 290 1 060 171 1 030 162 116 394 405 487 67 631 69,1 197
260 637 1 290 1 060 171 1 030 162 116 394 406 488 66,1 633 68,4 197
270 638 1 300 1 060 172 1 030 163 116 395 406 488 66,2 638 68,9 198
280 637 1 300 1 060 172 1 030 163 117 396 407 488 65,3 631 68,1 198
290 639 1 300 1 060 172 1 030 163 117 396 407 489 65,4 633 68,7 199
300 638 1 300 1 060 172 1 030 164 117 397 408 489 65,6 637 68,4 217
310 638 1 300 1 060 172 1 030 164 117 397 408 490 65,4 639 68,5 208
320 639 1 300 1 060 172 1 030 164 117 398 409 490 65,7 634 68,3 196
330 640 1 300 1 060 172 1 030 164 117 398 409 490 65,1 649 68,6 211
340 640 1 300 1 060 172 1 030 164 117 399 410 491 65,8 650 68,4 197
350 640 1 300 1 060 172 1 030 165 118 399 410 492 66,1 650 68,5 199
360 640 1 300 1 070 173 1 030 165 118 400 410 492 66,9 653 68,3 201
370 641 1 300 1 070 173 1 040 165 118 401 410 492 67,2 656 68,5 203
380 640 1 300 1 070 173 1 040 165 118 401 410 493 67,4 658 68,3 204
390 641 1 310 1 070 173 1 040 165 118 401 411 493 69,2 659 68,4 199
400 641 1 310 1 070 173 1 040 165 118 402 411 493 65,3 659 68 202
410 642 1 310 1 070 173 1 040 165 119 402 411 494 68,7 661 67,6 191
420 642 1 310 1 070 173 1 040 165 119 403 412 495 69,3 660 68,5 212
430 642 1 310 1 070 173 1 040 166 119 403 412 494 69,6 660 68 205
440 642 1 310 1 070 173 1 040 166 119 403 412 495 70,5 661 68,7 198
450 642 1 310 1 070 173 1 040 166 119 403 414 495 70,6 666 68,6 206
460 642 1 310 1 070 173 1 040 166 119 404 415 494 68 666 68,9 207
470 643 1 310 1 070 174 1 040 166 119 404 414 496 73,9 667 69,5 202
480 643 1 310 1 070 174 1 040 167 119 405 414 495 69,9 669 69 210
490 643 1 310 1 070 174 1 040 167 119 405 415 497 71,2 669 69 200
500 643 1 310 1 070 174 1 040 167 119 406 415 496 71,2 672 68,9 190
510 643 1 310 1 070 174 1 040 167 119 406 416 497 70,9 673 69,1 202
520 644 1 310 1 070 174 1 040 167 119 406 415 497 119 674 68,7 213
530 644 1 310 1 070 174 1 040 167 119 405 415 497 70 676 67,9 212
540 644 1 310 1 070 174 1 050 167 119 406 416 498 69,4 674 69,1 208
550 644 1 310 1 070 174 1 050 167 119 407 416 497 69,8 677 68,8 208

44
 560 644 1 320 1 070 174 1 050 167 120 407 416 498 69,8 677 69,2 209
570 645 1 310 1 070 174 1 050 167 120 407 416 499 69,2 679 68,8 209
580 645 1 320 1 070 174 1 050 168 120 408 417 499 69,4 680 68,8 208
590 645 1 320 1 070 174 1 040 167 120 408 417 498 68,9 680 69,4 218
600 645 1 320 1 070 175 1 050 168 120 408 417 498 69,5 683 69,2 204
610 645 1 320 1 070 174 1 050 168 120 408 418 500 68,5 686 69,5 213
620 645 1 320 1 070 175 1 050 168 120 409 418 500 67,6 681 69,7 209
630 646 1 320 1 080 175 1 050 168 120 409 418 499 68,3 684 69,7 214
640 646 1 320 1 080 175 1 050 168 120 410 418 501 68,1 688 69,9 212
650 646 1 320 1 070 175 1 050 168 120 410 419 501 67,7 685 69,8 210
660 646 1 320 1 080 175 1 050 168 120 411 419 501 69,7 686 69,7 214
670 647 1 320 1 070 175 1 050 168 120 410 419 501 67,2 691 70 209
680 646 1 320 1 070 175 1 050 168 120 410 419 501 66,9 688 69,9 214
690 647 1 320 1 070 175 1 050 168 120 410 419 502 66,8 689 69,8 212
700 647 1 320 1 080 175 1 050 169 120 411 420 502 67 690 70,1 212
710 646 1 320 1 080 175 1 050 169 121 411 420 502 66,9 689 70 213
720 647 1 320 1 080 175 1 050 169 121 412 420 503 67 694 70 214
730 648 1 320 1 080 175 1 050 169 121 413 420 503 66,8 697 70,1 214
740 647 1 320 1 080 175 1 050 169 121 412 420 501 67,1 693 69,8 215
750 648 1 320 1 080 175 1 050 169 120 412 421 502 67,1 695 69,8 213
760 648 1 320 1 080 176 1 050 169 121 413 421 502 67,4 689 69,8 213
770 648 1 320 1 080 175 1 050 169 121 413 421 503 66,8 696 70 213
780 648 1 330 1 080 175 1 050 169 121 413 421 503 66,6 693 70 217
790 649 1 330 1 080 176 1 050 169 121 413 421 503 66,6 696 70,5 212
800 647 1 330 1 080 175 1 050 170 121 413 421 503 66,4 700 70,2 211
810 649 1 330 1 080 176 1 050 170 121 414 422 503 66,7 692 70,4 223
820 649 1 330 1 080 175 1 050 170 121 412 422 504 66,7 700 70,1 223
830 649 1 330 1 080 176 1 050 170 121 413 422 504 66,8 702 70,1 209
840 650 1 330 1 080 176 1 060 170 121 413 422 504 65,8 703 70,6 225
850 649 1 330 1 080 176 1 050 170 121 413 422 504 69,1 701 70,6 222
860 649 1 330 1 080 175 1 050 170 121 414 422 504 65,9 699 70,3 214
870 651 1 330 1 080 176 1 050 170 121 414 422 504 66,5 701 70 219
880 649 1 330 1 080 176 1 050 170 121 415 423 505 66,8 705 70,6 215
890 650 1 330 1 070 176 1 060 170 121 415 423 504 66,5 697 70,3 218
900 650 1 330 1 090 176 1 060 170 122 415 423 505 67 705 70 220
910 650 1 330 1 090 176 1 060 170 122 415 423 505 66,6 708 70,2 215
920 649 1 330 1 090 176 1 060 170 122 415 423 505 66,9 709 70,2 219
930 651 1 330 1 090 176 1 060 170 122 415 423 505 65,9 707 70,2 219
940 650 1 330 1 090 176 1 060 170 122 415 423 506 65,9 707 70,6 218
950 650 1 330 1 090 176 1 060 170 122 417 423 506 66,4 707 70,1 218
960 651 1 330 1 090 176 1 060 171 121 416 423 506 66,5 709 70,6 217
970 651 1 330 1 090 176 1 060 170 122 416 424 506 16,5 709 70 218
980 653 1 330 1 090 176 1 060 170 122 416 424 506 68,7 708 70,6 220
990 652 1 330 1 090 176 1 060 170 122 415 423 506 66,2 710 70,4
1000 651 1 330 1 090 176 1 060 171 122 416 424 507 66,5 710 69,2

45
APPENDIX D:
Results for Normal Stress Difference: Samples 2 and 9
Sample 2:
Meas. Pts.Shear Rate Shear Stress Viscosity Normal Force Strain 1st Normal Stress Diff.
[1/s] [Pa] [Pa·s] [N] [%] [Pa]
1 0,000536 2,01 3 750 -0,0565 0,384 -57,7
2 0,000605 4,67 7 710 -0,0919 0,954 -93,9
3 0,000709 7,3 10 300 -0,136 1,62 -139
4 0,00088 9,9 11 200 -0,178 2,39 -182
5 0,00131 12,4 9 480 -0,235 3,44 -240
6 0,00257 14,7 5 730 -0,315 5,29 -322
7 0,00548 16,4 3 000 -0,421 9,16 -430
8 0,00809 17,3 2 130 -0,522 16,2 -533
9 0,0101 17,5 1 730 -0,575 25,4 -588
10 0,00967 17,6 1 820 -0,587 35,1 -600
11 0,00922 17,6 1 910 -0,621 44,9 -634
12 0,0098 17,8 1 820 -0,665 54,3 -680
13 0,00927 18 1 940 -0,667 63,6 -681
14 0,00903 18,2 2 010 -0,67 73,1 -684
15 0,00969 18,4 1 900 -0,674 82,3 -689
16 0,00915 18,6 2 030 -0,722 91,5 -737
17 0,00916 18,7 2 040 -0,749 101 -765
18 0,00965 19 1 960 -0,76 110 -777
19 0,00906 19,2 2 110 -0,789 119 -806
20 0,00934 19,3 2 070 -0,806 129 -823
21 0,00971 19,5 2 010 -0,831 138 -849
22 0,00908 19,7 2 170 -0,87 148 -889
23 0,00948 19,8 2 090 -0,883 157 -902
24 0,00968 20 2 070 -0,898 166 -917
25 0,00907 20,2 2 220 -0,873 176 -892
26 0,00957 20,3 2 120 -0,91 185 -929
27 0,0098 20,5 2 090 -0,938 195 -958
28 0,00914 20,6 2 250 -0,93 204 -950
29 0,00964 20,7 2 150 -0,948 214 -968
30 0,00978 20,9 2 140 -0,944 223 -964

46
Sample 9:

Meas. Pts.Shear Rate Shear Stress Viscosity Normal Force Strain 1st Normal Stress Diff.
[1/s] [Pa] [Pa·s] [N] [%] [Pa]
1 0,00232 1,66 715 -0,035 1,63 -35,8
2 0,00426 3,67 860 -0,0166 4,5 -16,9
3 0,01 4,28 428 -0,00311 12,3 -3,18
4 0,00983 4,27 435 0,00136 22,3 1,39
5 0,0101 4,23 421 0,00204 32,5 2,09
6 0,0102 4,24 414 -0,00715 42,4 -7,3
7 0,00999 4,24 424 -0,00899 52,4 -9,18
8 0,00983 4,2 428 0,00755 62,6 7,71
9 0,0102 4,21 412 0,0143 72,6 14,6
10 0,0101 4,22 419 0,00862 82,5 8,81
11 0,00973 4,21 432 0,0139 92,6 14,2
12 0,0101 4,19 413 0,0179 103 18,3
13 0,0102 4,2 412 0,0146 113 14,9
14 0,00978 4,2 430 0,0122 123 12,4
15 0,00998 4,18 418 0,0155 133 15,9
16 0,0102 4,19 411 0,0231 143 23,6
17 0,00993 4,21 424 0,0171 153 17,5
18 0,00982 4,18 425 0,0183 163 18,7
19 0,0102 4,18 410 0,0192 173 19,6
20 0,0101 4,2 416 0,0289 183 29,6
21 0,00973 4,18 430 0,0267 193 27,3
22 0,0101 4,17 412 0,0279 203 28,5
23 0,0102 4,19 412 0,023 213 23,5
24 0,00982 4,19 427 0,028 223 28,6
25 0,00997 4,16 417 0,0224 233 22,9
26 0,0102 4,18 410 0,0359 243 36,7
27 0,00993 4,2 423 0,0406 253 41,5
28 0,0098 4,17 426 0,0363 263 37,1
29 0,0102 4,17 410 0,0447 273 45,7
30 0,0101 4,19 415 0,0604 283 61,7

47