Introduction

1
INTRODUCTION

I.1 Statement of Problem

Lost of circulation is one of the primary problems in the drilling industry. There are
several ways for treatment of the lost of circulation. Using the Lost Circulation Material
(LCM) is the most popular way for treating lost circulation because of simplicity of
usage and economic reasons. It is important to determine the type, composition, particle
size, and the rheology of the fluid successfully [1].

The aim of this work is to evaluate different natural and synthetic polymers as loss
circulation control agents for high permeable zones. During the study different particle
sizes and chemical compositions from water-insoluble natural polymers had been used.
The results were discussed on the light of adsorption and micellization in case of water-
soluble natural polymers. Potassium and sodium poly acrylic, three potassium acrylic
based copolymers and three sodium acrylic based copolymers were synthesized using
different monomers (acrylic, methacrylic or acrylamide) and (sodium acrylic or
potassium acrylic) and their results were discussed on the light of swelling properties
and the reactivity ratios for monomers.

I.2. Drilling Fluids:

Drilling fluids are mixtures of natural and synthetic chemical compounds. The
drilling fluid mud was pumped from the mud tanks down the hollow drill pipe and
through nozzles into the drill bit. The flowing mud swapped the crushed rock cuttings
from under the bit and carried them back up the annular space between the drill pipe and
the bore hole or casing to the surface [1-3].

After reaching the surface, the drilling fluid was passed through a series of
vibrating screens, settling tanks or pits, hydrocyclones and centrifuges to remove the
cuttings brought to the surface [4]. It was then treated with additives to obtain a set of
the desired physical and chemical properties. Once treated, the fluid was pumped back
into the well and the cycle was repeated. [5]

Introduction

2

I.3 Functions of the Drilling Fluids:

The drilling muds are a special class of drilling fluids used to drill most of the
deep oil wells. Muds were referred to the thick consistency of the formulation. Some of
the most important functions (see Figure I-1) of drilling mud were [6-8]:
1. To remove rock bit cuttings from the bottom of the hole and carry them to the
Surface.
2. To overcome the fluid pressure of the formation.
3. To avoid damage of the producing formation.
4. To cool and lubricate the drill string and the bit.
5. To prevent drill pipe corrosion fatigue.
6. To allow the acquisition of information about the formation being drilled (e.g.,
electric logs, cutting analysis).
7. To support the borehole wall.















Figure I-1: The Functions of Mud



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3
I.4. Classification of Drilling Fluids (Muds):

Drilling fluids could be classified according to the nature of the continuous phase:
gas, water, oil or synthetic. Within each classification, there were divisions based on the
composition or the chemistry of the fluid or the dispersed phase [9-11].

I.4.1 Gas-Based Muds.

Gas-based drilling fluids were used mostly for hard-rock drilling [12]. These
fluids ranged from compressed dry air or natural gas to water-based mist and stable
foams. Foams were considered gas based since the gas comprised the bulk of the fluid
volume. Bottom hole pressures imposed by gas-based fluids were low. Therefore,
formation strengths must be relatively high, having little or no influx or formation fluid
[13]. Air, gas, or mist drilling required a high annular velocity to remove the drill
cuttings. On the other hand, large cuttings could be removed at low annular velocities
when using stable foams [14].

Chemical additives for gas-based drilling fluids were generally biodegradable
mixtures of surfactants, certain polymers and occasionally salts such as sodium or
potassium chloride. Aqueous solutions of the additives were injected into the air or gas
flow to generate a mist or foam [15]. No additives were used in dry air or gas drilling
operations. Gas-based fluids were not recirculated and materials were added
continuously [16].

I.4.2. Water-Based Mud

The term water base mud was referred to any drilling fluid having water as the liquid
continuous phase and in which certain materials were held in suspension and other
materials were dissolved [17]. They were the simplest and oldest type of drilling fluids.
Modern water-base drilling fluids used bentonite as a major ingredient although other
typed of related colloidal aluminum silicate hydrates were sometimes used [18-21]. The
formation of drilling mud had become a complicated art. The types and quantities of

Introduction

4
ingredients that were added to the mud depended, on very large extent, on the local
conditions at the well, and in particular, on the salt concentration or the concentration of
soluble alkaline earth salts.

I.4.3. Oil-Based Muds.

Oil-based drilling fluids had diesel or mineral oil as a continuous phase with both
internal water and solid phases [23]. Fluids having no or very low water content were
usually called oil-base muds or all oil muds. Fluids having higher water contents were
called invert oilemulsion muds, or simply inverts. Most oil muds maintained a fixed
oilwater ratio depending on the desired properties. Oil muds were employed for high
angle wells where good lubricity is required for high temperature wells where water-
based systems may be thermally unstable, for drilling water-sensitive shale formations
or where corrosive gases such as hydrogen sulfide and carbon dioxide may be
encountered [24,25].

Environmental restrictions and cost often limited the use of oil-based muds although
higher drilling rates were achievable using oil muds and polycrystalline diamond
compact (PDC). PDC bits can often offset the high fluid and disposal costs [26].

Oil-base muds had diesel or mineral oil as the continuous phase and either are
formulated using no internal aqueous phase or have only a minimal water content.
Organophilic clays or colloidal asphalts were used to control the viscosity and the
filtration rates. The internal water phase was added as a part of the formulation or
incorporated while drilling was stabilized using emulsifiers [27, 28].

I.4.4. The synthetic-based muds

Synthetic drilling fluids were a relatively new class of drilling muds that were
particularly useful for deepwater and deviated hole drilling [29]. These muds were
developed to provide an environmentally superior alternative to oil-based drilling muds
as well as offering an alternative to the high costs associated with the disposal of drill

Introduction

5
cuttings generated when diesel or mineral oil based muds were used [30]. The synthetic
muds had a continuous phase that was consisted of synthetic organic liquid [31-33]. The
synthetic-based liquids, because of their similarity with the oil-based muds, were often
called pseudo-oil muds [34]. The environmental impacts of the discharged drill cuttings
produced were not well understood. While the drill cuttings themselves were considered
toxicologically inert. There was some concern that any adhering drilling fluid
ingredients may be toxic, particularly if the cuttings were produced during the drilling
with oil-based or synthetic-based fluids. The high cost of the synthetic-based fluids
(SBFs) could be offset by the enhanced drilling performance for fast drilling achieved
when using them and the on-site discharge of the SBFs, when this is permitted [35].


I.5. Rheological Properties

The rheological properties of the drilling fluids played a very important role in
determining the success of overall drilling operations [36]. The importance of
rheological properties for evaluating drilling fluid behavior solved many problems like
[37]:
- Hole cleaning and erosions.
- Suspension of cuttings.
- Hydraulic calculations.
- Mud treatment [37].
I.5.1. Plastic Viscosity (
pl.
)
Plastic Viscosity is a parameter of the Bingham plastic rheological model as
shown in Figure I-2.
pl.
is the slope of the shear stress-shear rate plot above the yield
point as indicated in Figure I-3 [38]. The Plastic Viscosity is derived from the 600 rpm
reading minus the 300 rpm reading and the
pl.
is in centipoises (cp). A low
pl.

indicated that the mud was capable of drilling rapidly because of the low viscosity of
the mud existing at the bit. The high
pl.
was caused by a viscous base fluid and by
excess colloidal solids [39]. To lower the
pl.
, a reduction in the solids content can be
achieved by dilution. There are many rheological models shown in Figure I-2.

Introduction

6
Normally Bingham Plastic Model was used to describe the mud properties as Plastic
Viscosity and Yield Point as shown in Figure I-3 [40].











Figure I-2: The Rheological Models.
I.5.2 Yield Point (
B
)
The physical meaning of the yield Point was the resistance of the fluids to initial
flow or the stress required to start fluid movement [41]. The Bingham plastic fluid plots
as a straight line on a shear-rate (x-axis) versus the shear stress (y-axis) plot, in which
B
is the zero-shear-rate intercept (
pl.
is the slope of the line) [42].
The
B
was calculated from 300-rpm and 600-rpm viscometer dial readings by
subtracting the
pl.
of the 300-rpm viscometer dial reading from the 600-rpm reading
and it is reported as l bf/100 ft
2
.The
B
was used to evaluate the ability of mud to lift

Introduction

7
cuttings out of the annulus. The higher
B
implied that the drilling fluids had the ability
to carry the cuttings better than the fluids of similar density but with lower
B
[43-46].












Figure I-3: Bingham Plastic Model describes
pl.
and
B


I. 5. 3. Relationship between the Shear stress and the Shear rate

The measurements of the shear stress, the shear rate and their relationship were
very important because it enabled mathematical description of the flow of drilling fluids
[47-49]. The amount of force applied to a fluid determined the shear rate which in oil
field terms is determined by the flow rate of a fluid through a particular geometrical
configuration. The resistance of the fluid to the applied rate of the shear or force is
called the shear stress, which in oil field is the pump pressure. The shear rate is
dependent, to same extent, upon the viscous properties of the fluid. The conversion from
rpm to the shear rate (in sec
-1
) was given by the following formula [50]:

Introduction

8
(sec
-1
) = rpm X 1.7034

Where, The shear stress,I from this concentric cylinder viscometer was taken
from dial reading R, which in degrees of a circle. The formula as for converting R to
is as follows [50]
= (1b/100ft
2
) = R X 1.067
= (dyne/cm
2
) = R X 5.1

I. 5. 4. Gel strength of the drilling fluids:

The gel strength of the drilling fluids was a measure of the minimum shearing
stress necessary to produce slip-wise movement of the fluids [51]. The strength of the
gel structure formed was a function of the amount and the type of solid, time,
temperature and the chemical constitution of the mud. Two readings were generally
taken: (1) immediately after agitation of the mud in the cup, (2) after the mud in the cup
had been quiescent for a period of ten minutes [52].


I.5.5. Thixotropy

Most drilling muds are thixotropic (i.e. they gel under static condition). This
characteristic keeps the cuttings suspended when the mud is not moving during, for
example, maintenance.
Two readings were generally taken, one immediately after the agitation of the mud
in the cup, and the second after the mud in the cup had been quiescent for a period of
ten minutes. The difference in the two readings may be appreciable for the suspensions
of such drilling fluids [53]. This difference was considered to be the measure of
thixotropy of the mud system (the low thixotropy, the better the mud).




Introduction

9

I.5.6. Effective viscosity

The mud being pumped at a constant volume would experience different flow
rates at these different shear rates, so that the mud had different viscosities, which were
best termed the effective viscosities [54]. The effective viscosity was defined as the
viscosity exhibited by the fluid at the existing shear rate.


I.6. Lost Circulation Problem:

One of the problems which were encountered in the drilling of oil wells was the
"lost circulation" [55]. This occurred when the openings in the formation allowed the
passage of the whole fluid into the formation resulting in losses ranging from 1 bbl/hr to
complete loss of the returns [56]. Economics was the foremost problem associated with
lost returns. When the circulation was lost, the drilling fluids costs were raised
appreciably, along with the expenses associated with rig and equipment delays. Beside
economics, lost circulation adversely affects the overall drilling operation by:
a. The loss of hydrostatic head that may result in well-control situation.
b. The reduction in the pressure gradient that may led to wellbore instability which
could result in hole collapse and/or stuck pipe.
c. The side tracks or complete loss of the well.
d. The failure to achieve adequate annular cement coverage.
e. The good quality formation evaluation may not be possible [57-59].

Lost circulation is caused by one of the two following mechanisms:
1. Natural losses; where invasion or whole fluid is lost to the formations that are
highly permeable, unconsolidated, fractured, cavernous or vugular.
2. Induced losses; where the drilling fluid is lost due to excessively induced
pressure that hydraulically fractures the formation [60].



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10

I.7. Classification of drilling fluids according to losses:

I.7.1. Seepage Losses Muds (SLM):

It is the drilling fluids which lost 1-5 bbl/hr during the circulation. This took the
form of very slow losses, sometimes in the form of highly permeable formations. If the
seepage losses were suspected, the bit must be pulled off-bottom and the drilling fluid
volumes checked with and without circulation. All mixing equipment and non-essential
solids removal equipment should be turned off and the base line values should be
recorded [61]. Once it was established that the fluids was being lost, a decision must be
made on whether to tolerate or to cure this situation. Depending on the economics of the
drilling fluid and/or the rig time, it might be more prudent to continue drilling with
seepage looses. If the pressure constraints were tight, a good cement job was required. If
the formation damage and the stuck pipe are the primary concerns, attempts should be
made to cure the losses before proceeding with drilling [62].

I.7.2. Partial Losses Muds (PLM):

When the drilling fluid loss was 5-100 bbl/hr it was called the partial loss. Partial
losses were more than the seepage losses when the cost of the fluid became the
overriding criteria in the decision to drill ahead or combat the losses [63].
Once again, all the above factors would be determined if the drilling with losses was to
be tolerated. Drilling with partial losses can be considered if the fluid was cheap and the
pressures were within operating limits.

I.7.3. Severe Losses Muds (SVLM):

Severe losses occurs when the drilling fluids loss were more than 100 bbl/hr. In
almost all circumstances when the losses of this type were encountered, regaining full
circulation was required.


Introduction

11

Start with pumping a lighter-weight fluid down the annulus (drilling fluid, water or
other light-weight fluid) and then the volumes required to fill the hole were monitored.
If the well became stable, the hydrostatic head required to fill the well was calculated. If
the losses persisted, the conventional lost circulation control agents were spotted. Due to
the reduction of the hydrostatic head, the well must be monitored closely at all times for
an influx of fluids. In some areas it might be possible to continue drilling if the fluid
cost was low and the pressures were manageable [64].



I.8. Types of Loss Circulation Zones:

In the eighties J. F. Gockel and M. Brinemann [65] demonstrated a common
misconception concerning the probability of the occurrence of lost circulation was
based on the idea that if the mud weight did not exceed the fracture of the pressure of a
given zone, no loss was likely to occur. For subnormal pressure zones it was not the
right way of thinking. Subnormal pressure zones might occur naturally or could be the
result of the production of depletion of a zone. In either case the fracture gradient could
be normal, but the pore pressure is not able to withstand the equal circulating pressure
of mud [66]. Commonly four types of formation were responsible for the lost circulation
and were illustrated in Figure I-4:

a) High permeability unconsolidated sands and gravel.
b) Cavernous or vugular zones in carbonates limestone or dolomite.
c) Natural fractures, faults and transition zones in carbonates.
d) Induced fractures from extensive pressure.






Introduction

12















Figure I-4: The Drilling Fluids Loss Zones


a) Unconsolidated sands and gravels have high permeability. Because of that, the whole
mud could be invaded through the formation. The high permeability resulted from lost
circulation could be presented in shallow sands. In these type of formations lost
circulation caused a cavity. Producing formations in the same field, especially in sands,
subnormal pressure might be observed because of the extraction of fluids. In such a case
unless mud weight was controlled mud might invade the formation. Moreover, low
pressure depleted formations could cause differential stuck [67].

b) Another potential lost zone was the cavernous or vugular zones with low pressure in
carbonate or volcanic formations. Vugs were created due to the continuous water flow
through the dissolved parts of the rock matrix in limestone. Caverns and Vugs could be
also developed during the cooling of magma. The amount of the lost circulation
depended on the degree to which the Vugs were interconnected [68].

High Permeability
Formation

Introduction

13
c) Mud loss also occurred due to fissures or fractures where no coarsely permeable or
cavernous formation existed. These fissures or fractures might occur naturally or may
be initiated or extended by hydraulically imposed pressures [69]. The last potential lost
zone was induced fractures occurring from extensive pressure. The reason of this type
of fracturing was the exceeding of the critical pressure of the formation. These losses
often occurred from the intermediate casing being set in the wrong place or by excessive
down-hole circulating and surge pressures [70-72].

I.9. The Cause Of Fracture May Be Due To The Mechanical Forces:

I.9.1. Improper hydraulics
Excessive flow rates and fluid rheological properties resulted in high Equivalent
Circulating Density (ECD) pressures [73].

I.9.2. Drilling practices
a) The pump surging caused by increasing the pumping rate too rapidly after
connections and trips. Such a case was extremely important when dealing with inverted
emulsions. Failure to bring the pumps up to speed slowly could resulted in much higher
circulating pressures on the formation because of the tendencies of the inverts to have
higher viscosities when cooled. These conditions occurred after trips and were
exacerbated when drilling in deep water.
b) Raising and lowering the pipe too quickly on connections.
c) Excessive Rate of Penetration (ROP) [73].

I.9.3. Hole Conditions
a. Sloughing or caving shales would increase the solids loading in the annulus,
resulting in a high ECD. This condition might also result in a pack off.
b. Washouts led to cuttings accumulations in the enlarged the hole section.
c. Cuttings beds or barite sag in deviated wells might result in localized density
increase.
d. Kicks and well-controlled procedures.


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14
Especially, while drilling in depleted zones, the lost circulation is the most
probable and fatal problems because of stability problems could occur [74].
Moreover if it was a productive zone, the fluid loss might cause productivity loss. The
loss of circulation in the productive zones was highly damaging [75]. When invasion of
the pay zones occurred, the fluid-fluid and the fluid- rock interactions were caused.
These interactions were due to the invasion of mud filtrate, mud solids and in some
cases, whole mud to the porous media [76].

I.10. Mud Properties that Will Affect the Pressure Loss in the Annulus

The mud properties that will affect the pressure loss in the annulus were:
a. Excessive viscosities, gel strengths and a build-up of the drilled solids [77].
b. Thick filter cakes that reduced the hydraulic diameter of the wellbore [78].
c. Excessive drilling fluid weight or increasing the density too rapidly [79].
d. Unbalanced drilling fluid columns [80].
e. Barite sag and Excessive Low-Gravity Solids (LGS) and high Methylene Blue
Test (MBT) values [81].

I.11. Loss Circulation Treatment:

J.C. Rojas et al. (1997) [82] stated that 7 options for controlling the fluid loss which
were related to planning and execution stages of the well;

I.11.1. Wellbore and drill string geometry:

The hole size and the annular clearances had a big impact on the frictional pressure
loss. The sensitivity of the equivalent circulating density on the hole size, casing design
and drill-string geometry should be determined at the planning stage of an extended
reach well. It was also possible to use bi-centered bits to reduce the equivalent
circulating density [82].



Introduction

15
I.11.2. Casing design:
Where possible it was advisable to select casing seats to minimize the exposure
time of the potential loss zones. Consideration should also be given to running drilling
liners rather than full casing strings back to surface. This could help reduce the
equivalent circulating densities, although the benefits must be balanced against the
potential downside of a poorer hole cleaning in the wider annular gap created above the
drilling liner [82].

I.11.3. Mud rheology and flow rate:

The mud rheology and the flow rate influenced the equivalent circulating density.
The mud properties and the flow rate needed to be optimized in order to provide
adequate hole cleaning as well as fulfilling the hydraulic requirements of downhole
equipment, while at the same time minimizing the equivalent circulating density [82].

I.11.4. Mud weight selection:

The appropriate selection of mud weight was critical for the extended-reach wells where
wellbore stability issues existed. In practice it was often not possible to reduce
equivalent circulating density by lowering the mud weight because of the increased risk
of the wellbore collapse [82].

I.11.5. Sealing capacity of drilling mud:
The physical properties of the mud could influence the tendency to lose circulation.
In particular the inclusion of sized bridging material could be used to control losses to
high permeability formations and small fractures [82].

I.11.6. Hole cleaning efficiency:
The effective cuttings transport was critical for the extended reach wells. Failure
to transport cuttings effectively to the surface would result in a cuttings accumulation in
the annulus. In addition, cuttings beds which were formed on the low side of the hole

Introduction

16
will further restricted the annular gap. This led to a higher frictional pressure drops in
the annulus and hence higher circulating densities [82].

I.11.7. Lost circulation treatment:
As well as treating of the mud to reduce its potentials for lost circulation. These
function either by forming physical bridges or by using increases in the fluid viscosity
to limit fluid penetration into the formation [82].

These seven options were related to stabilize and optimize the equivalent
circulating density and precaution for the lost circulation. In spite of these options the
loss circulation might occur. Then the lost circulation treatment should be applied.
There were several methods to combat the loss of circulation [82].

I.12. Lost-Circulation Control Materials (LCM):

LCM should be effective in sealing unconsolidated formations and fractures or
Vugs in hard formations. For different differential pressure conditions LCM should
form a useful seal [83 and 84]. Among other things, the additive must not so modify the
properties of the drilling fluid such as viscosity, pH and temperature stability, as to
render it unmanageable, particularly when used in large quantities and/or under severe
conditions. Also, the additive must have such physical characterics as to facilitate the
formation of a seal in the mud cake which lined the wellbore, such as, for example, the
plating affect of wood chips or the matting effect of fibers [85-87].
There are several types of LCMs used in the drilling industry. They have different
sizes, shapes, and characteristics. The use of LCM type was chosen by the influence of
economics and technical limitations. For the purposes of classification, LCMs could be
divided in to fibers, flakes, granules and mixtures. The fibrous LCMs were used
mainly in the drilling mud to lessen mud loss through large face and within fractures or
vugular formations, where as flaky type LCMs could plug and bridge many types of
porous formation to stop the mud loss or establish an effective seal over many
permeable formations [88]. The granular type of LCMs formed bridges at the
formation face and within the formation matrix, thus providing an effective seal, which

Introduction

17
depended primarily on the proper particle size distribution to build a bridge that had a
decreasing permeability, as it is being laid down. Finally blended LCMs are
combination of granular, flake and fibrous materials that would penetrate fractures,
Vugs or extremely permeable zones and seal them off more effectively. These materials
could be natural or synthetic and it could be provided in fine, medium and coarse size.
Fine materials under most circumstances would pass through the shaker screens and
stay in the system. Medium materials tended to be screened out, but most likely will
not plug the jets tools. Coarse materials could plug off everything except the open-
ended drill pipe [89].

Abrams in 1977 established the fundamental aspects of the particle sealing
technology and the effect of the mud physical properties and their effect on the mud
loss. The results of the study could be briefly stated as;
Particle size: For effective sealing the mud should contain a wide range of
particles
Particle shape: It is not critical for sealing capability
Particle concentration: The high concentration provided a better sealing.
Particle density: Low density LCM could be used if the mud weight resections
existed [90].

In selecting an appropriate particle size range for the particles, any desired lower limit
may be combined with any desired upper limit in order to define a suitable particle size
range [91].
In general, micro particles were more effective for controlling fluid losses to a
tight formation where a filter cake was formed. Small macro particles are also effective.
As compared to larger particles, smaller particles and micro particles tended to integrate
into the filter cake and could affect the properties of the filter cake being formed such as
increased hydrophobicity, stability and adhesion to the wellbore wall. If the particles are
sufficiently small, they could also seal off or enter small pores in the formation while
the filter cake was being formed in order to control the fluid loss and to prevent further
passage of damaging fine solids into the formation [92-93].

Introduction

18
Actually, macro particles are more effective than smaller ones for controlling
seepage losses since larger particles could bridge pores and fracture the formations,
block together or layer onto the wellbore wall or any filter cake that is being formed to
provide a barrier thereon to control or reduce the lost circulation [94]. The particles
could also enter large pores and fractures in the formation, particularly at areas where
no filter cake formation or bridging could occur and can block together inside the
formation to form a plug or seal to control the fluids losses [95]. If the particles were
slowed down as they are being pressurized or deformed into the pores or fractures in the
formations. This might aid in promoting agglomeration of the particles at the surface of
the loss zone and enabled a mat or a plug to form against the well bore wall. Where very
large particles were selected, a skilled operator should be considered the potential for
rejection by solids control equipment [96].
By using a blend of particles of different particle sizes, the added and combined
benefits of seepage loss reduction and fluid loss reduction could be achieved. The
particles of different particle size might be combined in any suitable ratio [97].
It should be noted that particle size did not necessarily referred to rounded
particles. The particles can be of any suitable or desired shape, such as spheres, pellets,
flakes, slivers, sheets, chunks, chips, or may be irregularly shaped. The term micron was
thus used to describe the general size of the particle and might refer to diameter, width,
length, cross-section or the like, depending on the shape of the particle or may be used
to describe the dominant dimension of the particles. In some cases, the shape of the
particles might reflect the shape of the solid(s) in the additive [98].
The injection of dispersed solids created new problems even while solving others.
In fact, a higher concentration of solids also increased the likelihood of an induced
fracture of the formation [99,100]. A recent refinement in the sealing techniques known
as "sweeping", called for the deliberate injection of a "slug" or a "pill, that was a
volume of mud with a solid content. In the ideal case the slug did not mix with the rest
of the mud, but instead travelled within the well bore until it encountered a loss
zone. At that point, sealing occurred, while the now slightly depleted slug completed its
circuit by returning to the rig, where the operator diverted the mud flow briefly in order
to take the heavy pill out of the system [101,102].


Introduction

19
I.13 Micronized Cellulose Fibers

In early 1980s micronized cellulose fibers had become widely used as LCM
worldwide for seepage or whole mud losses. They could be classified as flaky type of
materials. Losses of great volume of fluids had been considered as acceptable in the
history because of the thinking of it was not harmful for producing zones [103].
Whereas nowadays it is better to achieve a rapid and near surface sealing, even if it was
100% damaging, at least to minimize any invasion of the fluids or the solids [104].

Micronized cellulose fibers were flexible, highly compressible and swellable so
that they had a rapid sealing characteristic than brittle and incompressible particles like
calcium carbonates. The compressibility allowed micronized cellulose fiber extruded
into the pore throats or fractures. They could form near the surface seals and prevented
damaging of the fluids and the solid invasion into the producing zones during the drill-
in, completion and work over operation near the surface sealing of bulk micronized
cellulose [105].

Fibers had a wide range of particle sizes. Moreover fibers tended to drag the
slowest flow in dynamic conditions which allowed the migration to the lost zones and
therefore, acquired a better sealing [106].

Micronized cellulose fibers had a limitation of usage in producing formation.
Because of their lack of high sealing capacity micronized cellulose fiber might damage
the productive zones [107].

A variety of naturally-occurring products had been used as lost circulation materials
in the past. G.C. Peter (1984) used ground and sized cocoa bean shells [108]. James
and Wesley (1986) disclosed in their patent that the ground durum, derived from the
outer portion of the endosperm of the durum kernel, could be used to control the lost
circulation [109]. Jerome and Bonnie (1989) used a mass of small particles of the
shells of crustaceous animals selected from a class consisting of crab and crayfish to
reduce the amount of drilling fluids losses [110]. Jake et al. (1991) used cotton burrs as

Introduction

20
a drilling mud additive to prevent fluid loss [111]. B.D. Boyce (1992) used rice fraction
[112]. B.D. Boyce (1994) used corn cobs outers or mixtures with comminuted rice
products as lost circulation control agents [113]. W.R. James (1994) used a by-product
of corn and bees wings in the drilling fluid while drilling boreholes to reduce loss of
drilling fluids during the circulation [114].

New approaches to cure severe losses were settable plugs. This term was used
for slurries which gelled or solidified in seal zones. The main advantages of the settable
fluids were, firstly, no risk of bit nozzles plugging, and secondly, the ability of invading
a wide range of fracture widths contrary to conventional Lost Circulation Materials.
When these fluids were being lost to the formation they should gel quickly as it travels
away from the wellbore, as the fluid velocity decreased. Some examples of such
plugging products were junks or cross-linked polymers [115-116].

I.14. Crosslinked Polymer Gels

A simple cross linked polymer gels definition was the linking of two independent
polymer chains by a grouping (cross linked agent) that spanned or linked two polymer
chains. This pill was activated by cross-linking when set and it produced a substance
described as rubbery, spongy and ductile [117]. The final set time was defined as the
time required for the fluid to exhibit hard, viscoelastic properties. This was the time
taken for the polymer complex to reach maximum shear strength. The setting time was
fully controllable by using either a retarder or an accelerator that was based upon the
thief formation. For losses in a large natural fractures or vugular zones, the crosslinking
polymer has been designed as a blend of high molecular weight cross-linked polymers,
cross-linked agents and fibrous medium-to-coarse lost circulation materials. When
activated with time, it produced a soft-to-medium strength, rubbery ductile, spongy set
gel [118].

For a natural fractures or vugular thief zones at the bit, the polymer placement was
a straight forward spotting technique across the thief zone, requiring rapid setting after
the slurry leaves the bit. Thus, the polymer designed for natural fractures or Vugs

Introduction

21
incorporated the cross-linker in the pre-blend of products and for maximum agitation
was mixed at the same time as the cross linked polymers [119].

For induced fractures or matrix losses (i.e., micro-fractures network or permeable
formations) the cross linked polymer system had been re-engineered for maximum
penetration and higher strength. In this case, the blend consisted of medium molecular
weight cross linked polymers and fine sized fibrous materials. When added with
biopolymer and activated with a combination of cross linked agent, time and
temperature, it produced a medium to hard strength, rubbery and ductile plug.

The smaller particle-size distribution of the bridging material enhanced the ability
of the cross linked polymer slurry to penetrate a porous or induced a fractured zone.
Pressure is another factor that could affect the polymer setting time. Higher pressure
reduced the setting time of the polymer system and it gelled sooner [120]. The most
efficient gel plug corresponded to the formulation with the highest viscoelastic
properties (relating to the consistency of the gel) and the shear strength. If the flow of a
Bingham fluid between two plates was considered in order to simulate the invasion of a
fracture by the sealing fluid, it can be seen that the shear stress is maximum at the walls
[121].

Therefore, to ensure an efficient plugging, the shear stress at the wall must not exceed
the yield stress. The higher the yield stress, the higher the value of the pressure drop that
can be sustained by the gel. Other factors that might cause unsuccessful polymer
application to seal the fractures opening could be mentioned such as pH, salinity and
polymer ratios/concentrations. These properties should be compatible with the target
formations [122].

A major disadvantage of this system lied in the placement of the gel. Because the
reaction of this mixture was initiated at surface, therefore gelation time should be at
fluid loss zone. As mentioned before, gelation time depends upon three variables:
bottomhole Conditions (BHC), cross linker concentration and mixing time [123].


Introduction

22
Transmitting and placement of these materials are very important. Therefore a good
program and methods to place the materials before dealing the loss zone is necessary.
As planning and establishing a strategy prior to drilling a potential lost circulation zone
is critical for preventing and controlling mud loss, it is imperative that the right process
in decision making takes place [123].

Three methods can be mentioned about the placement of the polymers;
1. Injecting (squeezing)
2. Pump and pull and,
3. Bullhead the pill

According to loss zone and well condition a method can be used. But the last two
methods are risky and are not recommended as standard procedures. Nowadays these
materials are used in most extreme lost circulation problems, due to easy applications
and effectiveness [124].

T. W. Hoskins (2010) provided drilling fluid additives for reducing or controlling
lost circulation in a drilling operation. The additives comprised particles. The particles
comprise one or more solids in association a wax or waxy substance. the natural wax is
beeswax, lanolin wax, lanocerin wax, shellac wax, soy wax, carnauba wax, candellila
wax, jojoba wax, flax wax, sugarcane wax, ouricouri wax, petroleum wax, earth wax,
fossil wax, paraffin wax, petrolatum wax, microcrystalline wax, semi-microcrystalline
wax, intermediate wax, ozocerite wax, ceresin wax or Montana wax and the synthetic
wax is polypropylene, polyethylene, high density polyethylene, polytetrafluoroethylene,
Fischer-Tropsch, fatty acid amine, fatty amide, polyolefin, alpha olefin, polyamide wax,
chlorinated wax, or other chemically modified wax [125].

W. J. Paul and et al (2008) uses polypropylene granules to reduce loss of drilling
fluids during circulation [126]. B.R. Reddy and et al (2003) a composition basically
comprises a mixture of latex, melamine-formaldehyde resin, and a catalyst, for
introduction into a subterranean zone penetrated by a well bore and restoring lost
circulation. The ratio of latex to melamine-formaldehyde resin varies from 30:70 to

Introduction

23
70:30 percent by weight [127]. R. E. Sweatman et. Al (2001); R. E. Sweatman (2001)
use mixtures of clay and aqueous hydratable polymer to treat loss of drilling fluids
during its circulation [128-129]. R. E. Sweatman et. Al (2000); R. E. Sweatman (1999)
used for reducing loss circulation of drilling fluid with using mixtures of clay and
aqueous rubber latex [130-131].

A lot of remedial products have been developed to cure severe lost returns. The
required properties of lost circulation pills are numerous:

1. It should provide an effective seal under both low and high differential pressure
conditions.
2. It should not have harm effect on mud chemistry.
3. It should not plug bottomhole assembly or any circulation devices.
4. Final plug shear strength should be high enough to support fluid column, but
low enough to ensure removal by washing or jetting.
5. It should have workable/controllable set time and should be functional in oil-,
synthetic- or water-based systems.
6. It must allow permeability recovering of production layers [132].

I.15. Hydrogels

Hydrophilic polymers when they were cross linked chemically or physically
forming three dimensional networks swell but do not dissolve in aqueous media. They
were termed as hydrogels and were capable of absorbing water from 10-20% up to
thousands times of their dry weight. Due to their unique characteristics, they have found
applications in personal hygiene products, agriculture and other specialized areas like
controlled drug delivery systems [133, 134].

I.15.1 Classification of Hydrogels

Hydrogels were mainly classified as natural or synthetic according to their
origin. Poly sodium acrylate was an example of synthetic hydrogel while carboxymethyl

Introduction

24
cellulose was considered to be a natural one. Hydrogels could also be classified as
physical or chemical gels based on their crosslinking. Chemical gels are usually
covalently-crosslinked networks produced by crosslinking of water-soluble polymers or
by the conversion of hydrophobic polymers to hydrophilic polymers to form a network.
These gels are permanent or thermoset, meaning the bonds did not break at elevated
temperatures and hence did not reform at lower temperatures [135].

Physical gels were held together by molecular entanglements or secondary
forces including ionic interactions, hydrogen bonds [136-138], crystallization [139] and
hydrophobic interactions [140]. These gels were thermo-reversible and demonstrated a
transition from solid to liquid at a characteristic temperature. There were many other
means of classifying hydrogels:

1- Source: natural, synthetic.
2- Preparation Method: Simultaneous polymerization-Crosslinking of polymers.
3- Electric Charge: Nonionic Anionic Cationic - zwitter ionic.
4- Physical Structure: Amorphous Semicrystalline Hydrogen bonded.
5- Functions: Biodegradable Stimuli responsive Responsive.
6- Physical Appearance: Matrix Film Microsphere [140].

I.16. Preparation Methods of Hydrogels

Hydrogels were polymeric networks. This implied that crosslinked polymeric
hydrogels had to be present in order to avoid dissolution of the hydrophilic polymer
chain in aqueous solution. Chemically crosslinked gels had ionic or covalent bonds
connecting the polymer chains [141]. These adverse effects could be removed with the
use of physically crosslinked gels. In physically crosslinked gels, dissolution was
prevented by physical interactions between different polymer chains. Both of these
methods were used recently for the preparation of synthetic hydrogels and were
discussed in detail [142].



Introduction

25
I.16.1 Physically Crosslinked Gels
Chemically crosslinked gels implied the use of chemicals as crosslinking agents,
which were often toxic. This required that the crosslinking agents had to be removed
from the gels which can affect the gel integrity. For these reasons, physically
crosslinked gels were coming into prominence. Several methods had been investigated
exploring the preparation of physically crosslinked gels. Some of the most widely used
methods and their areas of application were investigated [143].

A. Crosslinking by Ionic Interactions

An example of crosslinking via ionic interactions was the crosslinking of Alginate.
Alginate consisted of glucuronic acid residues and mannuronic residues and could be
crosslinked by calcium ions [144]. These gels were used as matrix for the encapsulation
of cells and for the release of proteins. Also chitosan based hydrogels [145], as well as
dextran based hydrogels were crosslinked with potassium ions were also other gels that
were synthesized with ionic interactions. In addition to anionic polymers being
crosslinked with metallic ions, hydrogels could also be obtained by the complexation of
polyanions and polycations [146].

B. Crosslinking by Crystallization

An aqueous solution of poly vinylalchol (PVA) that underwent a freeze-thaw
process yielded a strong highly elastic gel. Gel formation was attributed to the formation
of PVA crystallites which acted as physical crosslinking sites in the network. The gel
properties could be modified by varying the polymer concentration, the temperature, the
freezing and thawing cycle times [147].

C. Crosslinking by Hydrogen Bonding

Poly(acrylic acid) and poly(methacrylic acid) formed complexes with poly(ethylene
glycol) through hydrogen bonding between the oxygen of the poly(ethylene glycol) and
the carboxylic acid group of the poly((meth)acrylic acid) [148]. Also hydrogen bonding

Introduction

26
had been observed in poly(methacrylic acid-g-ethylene glycol). The hydrogen bonds
were only formed when the carboxylic acid groups were protonated. This also implied
that the swelling of the gels was pH dependent [149].

I.16.2 Chemically Crosslinked Gels

Chemical crosslinking could be achieved by the copolymerization of (crosslinking
reactions), radical polymerization, chemical reaction of the complementary groups,
photo polymerization or by cross linking using enzymes. Copolymerization reactions
were used to produce polymer gels. Many hydrogels were produced in this fashion, for
example poly (hydroxyalkyl methacrylates). Initiators used in these reactions were
radicals and anionic initiators. Various initiators were used, such as
Azobisisobutyronitrile (AIBN), benzoyl peroxide... etc. Solvents could be added during
the reaction in order to decrease the viscosity of the solution [150].

A. Crosslinking by High Energy Radiation

High energy radiation, such as gamma radiation [151] and electron beam radiation
could be used to polymerize unsaturated compounds. Water soluble polymeric
derivative with vinyl groups could be converted into hydrogels using the high energy
radiation techniques. For example, poly ethylene glycol (PEG) derivative to poly
ethylene glycol diactylate (PEGDA) could form hydrogels once irradiated with UV
radiations. Polymers without additional vinyl groups could also be crosslinked via
radiation. On exposure to gamma radiation or electron beam radiation, aqueous
solutions of polymers formed radicals on the polymer chains (e.g. by the homolytic
fission of C-H bonds). Also the radiolysis of water molecules generated the formation of
hydroxyl groups, which could attack the polymer chains, which resulted in the
formation of micro radicals. Recombination of these micro radicals on different chains
resulted in the formation of covalent bonds and finally in the production of crosslinked
structure. The swelling and the permeability characteristics of the gel depended on the
extent of polymerization and the radiation dose (in general crosslinking density
increased with the increase of the radiation dose) [152].

Introduction

27

B. Free radical polymerization
Free radical polymerization had been an important research area in the preparation
of synthetic polymers over the last hundred years [153]. It was one of the most
important techniques used for producing polymers from vinyl monomers. It was used
extensively in the drilling industry for more than 70% of the vinyl polymers, which
themselves comprise 50% of all the commercially made polymers that were synthesized
via free radical polymerization [154 and 155]. The polymerization could be performed
in homogeneous (e.g. solution/bulk polymerization) and heterogeneous media (e.g.
emulsion polymerization). One of the major advantages of free radical polymerization
over other polymerization techniques was its relative tolerance to media impurities such
as oxygen, water, additives and metal ions. The technique could be conducted at
moderate temperatures and pressures. Another advantage of this technique was its
compatibility with a broad range of vinyl monomers [156].

Polystyrene, poly (methylmethacrylate), polybutadiene and branched polyethylene
were examples of polymers made via free radical polymerization technique [157].
However, free radical polymerization was inherently limited in its ability to synthesize
multiblock copolymers such as stars and graft copolymers. It was unable to control the
molar mass, and produced polymers with high polydispersity indexes (PDI > 1.5). It
was difficult to control the polymerization stereochemistry in free radical
polymerization as the technique produced only atactic or partially syndiotactic polymers
[158,159].

For a molecule to generate radicals, an amount of energy (bond dissociation
energy) must be added to the system. The lower the amount of the energy needed to
form a free radical, the more stable the free radical will be. [160]

CH
3
< R-

CH
2
< R
2
-

CH < R
3
-

C
Least Stable More Stable


Introduction

28
The reactivity of vinyl monomers in free radical polymerization reactions depended on
the ability of the substituents, R and X in Figure I-5, to stabilize the propagating
radical. For example, in styrene where the substituent X is H and R is a benzene ring,
the radical formed upon addition to the propagating chain would be stable and had low
reactivity compared to the vinyl chloride radical where R is Cl and X is H. As a result,
the styrene monomer was more susceptible to radical addition. Thus, different
monomers had different radical reactivities and different propagation rate coefficients
depending on the substituent X. The reactivity of the derived radicals was the opposite
of their respective monomers. The more stable the monomer was, the more reactive the
radical would be [161].
X

CH
2
C

R
Figure I-5: Propagating polymeric radical with substituents X and R, where R is H,
CH
3
,etc and X is Cl, OH, etc

- Free radical polymerization kinetics
Free radical polymerization is generally described in three reaction steps: initiation,
propagation and termination.

The initiation step
For a radical polymerization to occur, radicals were needed to be generated. This
process was known as the initiation step. There are numerous classes of initiator
compounds that had the ability to generate radical species upon decomposition.
The initiation step was considered to involve two reactions. The first step was the
homolytic dissociation of an initiator molecule into one or more primary radicals. The
second step of the initiation involved the addition of the initiator derived (primary)
radical to a single vinyl monomer molecule to form a chain initiating radical [162 and
163].

K
d


Introduction

29
I I 2I

I

+ M R
1

The rate of dissociation of the initiator was described by the following equation:
_ d[I] = K
d
[I]
d[t]

Integration of above equation led to the following equation which described the
decrease of the initiator concentration as a function of time:
[I] = [I]
0
e

K
d
t


Where [I]
0
represented the initial initiator concentration, [I] represented the initiator
concentration at time t, and k
d
corresponded to the rate coefficient of initiator
decomposition at a specific temperature.

In case two radicals were produced from the decomposition of one initiator molecule
(not always the case), the rate of initiation R
i
was given by the following equation
R
i
= 2 K
d
f [I]

The initiator efficiency f was the fraction of radicals that were successfully initiated the
chain reactions, which took into account the solvent cage effects and always had a value
between zero and unity. As the monomer viscosity of the reaction medium increased,
the diffusion of the radicals away from each other became difficult. Hence the primary
radicals remained in close proximity and recombination could occur. Typical values for
f were between 0.5 and 0.8, and these values decreased as the reaction viscosity
increased until it reached the limiting value of zero. [164] Different initiators have
different properties. Each had its own unique requirement to decompose and to form a
radical. The most common ways to generate radicals are via thermal initiation, chemical
initiation (Redox) and photo initiation. [165]

Thermal initiation could be divided into two main classes: azo- and peroxy-type
initiators (Figure I-6).
h
K
i


Introduction

30


Figure I-6: General structures of the azo and peroxy-type initiators.

These initiators decomposed on addition of thermal energy to the system and were
characterized by an initiator half-life (t
1/2
) i. e. the time period during which half of the
initiator molecules were decomposed. In photo-initiated free radical polymerization, the
reaction temperature had almost no effect on the rate of decomposition of most photo-
initiators. The rate of decomposition generally depended on the intensity of the UV
light. [166] Photo-initiators decomposed upon irradiation with visible or UV light
source. The most commonly used photo- initiators contained a benzoyl group (Figure I-
7).
Figure I-7: Formation of a benzoyl radical.

In a Redox initiation process radicals were generated by the reaction between a reducing
agent and an oxidizing agent. These radicals could initiate radical polymerization
processes as shown in Figure I-8.
Fe
2+
+ HO OH HO

+ HO
-
+ Fe
3+


Figure I-8 A typical Redox initiation step.


Introduction

31
Other initiating techniques, which were less commonly used, included the high intensity
ultrasonic initiation, the high energy radiation (g-radiation), the plasma initiation, the
self-initiation and the electro initiation [164]. The molecular structure, nature and
solubility of the initiators, must be considered when choosing an initiator. The selection
of a specific initiator for a particular polymerization system depended on the reaction
conditions [166].

The propagation step

After the reactions were initiated, the radicals formed in the initiation step were
capable of adding successive monomer units to yield growing polymer chains as shown
in Figure I-9.


Figure I-9: Propagation of a radical by subsequent monomer addition.

Figure I-9 illustrated the multiple monomer additions that took place during the
propagation of the polymer chain. The rate at which the addition of monomer to
propagating radicals took place was affected by the nature of the monomer unit and the
reactivity of the propagating radical [166,167]. The substituent X and Y played
important roles in determining both the reactivity of the monomer and the reactivity of
the radical species in a polymerization reaction. The rate of monomer consumption is
expressed as:
-d[M] = K
P
[M][M]
dt

Where [M

], [M] and k
p
are the propagating radical concentration, monomer
concentration at time t and the propagation rate coefficient. These values could be

Introduction

32
determined by means of methods such as calorimetry and pulsed laser photolysis. It was
proposed by Olaj et al. [168] that the propagation rate coefficient depended on the
reaction temperature and the chain length, especially for the first few addition steps,
where kp was higher compared to the long chain propagation rate constant. [164]. In
free radical polymerization the entire propagation reaction usually took place within a
fraction of a second. Thousands of monomer units were added to the growing chain
within this time period. The entire propagation process will continue until some
termination process occurred. However, the polymerization was carried on because the
radicals were continuously generated by the decomposition of the initiator.
Polymerization continued until it was limited by other factors such as the viscosity of
the reaction medium or the depletion of monomers and initiators.

The termination step

The termination steps were referred to any steps in which radicals were consumed and
no new radicals were produced. Theoretically, in free radical polymerization the chain
growth should continue until chain termination occurred. The most common termination
steps were bimolecular reaction of propagating radicals that led to the deactivation of
the propagating radical chain ends. The two dominating bimolecular reactions were
known as coupling (combination) and disproportionation as illustrated in Figure I-10.
However, these were not the only possible methods by which termination could take
place. Reactions between the propagating radicals and the inhibitors (e.g. oxygen,
phenol, quinone etc.) would also terminate the chain.


Introduction

33

Where, Y is H, CH
3
,etc and X is Cl, OH, etc

Figure I-10: Termination pathways for free radical polymerization.

The coupling reaction occurs between two growing polymer chains that react with each
other to form a single terminated (dead) polymer chain of the length equal to the sum of
the lengths of the original growing chains. In disproportionation reactions two radicals
meet but, instead of coupling, a proton is exchanged to give two terminated (dead)
polymer chains. One is saturated and the other has a terminal double bond, each with a
length equal to one of the original growing chains.

The rate of termination was usually determined by the rate of diffusion of the
polymer chain. [169] As the molar mass of the chains increased there was a decrease in
the diffusion rate of the radical chain ends. The diffusivity of these ends was dependent
on the viscosity of the medium, the chain size and shape. Thus, it can be deduced that
the termination was a chain length dependent process. [170-173]. The rate of
termination was given by:
-d[M] = 2K
t
[M]
2

dt

Where [M

] and k
t
are the propagating radical concentration and termination rate
coefficient, respectively.


Introduction

34
In this relationship, the termination rate coefficient k
t
is a linear combination of the
rate coefficient for coupling (k
tc
) and the rate coefficient for disproportionation (k
td
)
[174].

K
t
= K
tc
+ K
td



Chain transfer reactions

Chain transfer reactions referred to the processes whereby the active site is
transferred to an independent molecule such as a monomer, initiator, polymer, solvent
or chain transfer agent. The chain transfer reactions were not formally chain terminating
reactions because the overall radical concentrations were not reduced. [175] However, it
had the tendency to limit the molar mass of the polymer chains. Chain transfer reactions
were also chain length and viscosity dependent processes [176]. The general chain
transfer constant C was given by:

Where k
tr
is the chain transfer rate coefficient and k
p
is the propagation rate coefficient.
The chain transfer constant was the ratio of the chain transfer and the propagation rate
coefficients.

If the radicals were transferred to a monomer then the original growing chain
became a dead chain and a new radical begins to grow:


Where, P is the propagated radical, M is the monomer

In a similar reaction, the solvent (S) could serve to transfer to the radicals:


Introduction

35

A chain transfer agent T could be added to the reaction to enhance the radical transfer
and thereby reduced the molar mass:

The solvent radical S or the transfer agent radical T could initiate a new polymer chain
by adding monomer units. If the chain end radical abstracted an atom from the
backbone of another chain, the result was a new radical that could reinitiated to form a
branch.

Where, 1 + j + i= m

If an inhibitor such as hydroquinone (In) was present in the reaction, then the free
radical would be converted to the unreactive form Q.

In principle, transfer chain reactions could occur to any species in the polymerization
system, and for this reason it was very important to choose solvents with transfer
properties that were suitable for the target system. The chain transfer constants
depended on different factors such as temperature, solvent or monomer. The average
degree of polymerization DP
n
was given by the Mayo equation [177]:




Introduction

36
Where, l is the fraction of termination by disproportionation, k
t
is the termination rate
coefficient, [P] is the overall radical concentration, [M] is the monomer concentration,
C
m
is the chain transfer coefficient for chain transfer to the monomer and [S] is the
concentration of the chain transfer agent in the form of solvent.


C. Copolymerization

There were several ways of changing the properties of polymeric materials. For
example, additives could be used to incorporate desirable properties into an existing
polymer material for new applications. Another approach was to combine the properties
of different polymer structures. The simplest way to achieve this was to blend two
polymers to give a material with mechanical and theological properties that were better
than those of the individual polymers. However, because few polymers were miscible,
they tended to phase separate in most blends which, consequently, often had poor
physical properties due to inadequate interfacial strength between the phases. An
alternative way was to copolymerize different monomers into a single polymeric
material (Figure I-11) [178].

Copolymerization was the best way to produce a polymer with properties that were
intermediate between the properties of the respective homopolymers. It was an
important process from the commercial point of view because it could produce new
polymers with completely different properties. An unlimited number of polymeric
structures with a wide range of properties and applications could be synthesized via
copolymerization of a few different types of co monomers [179].

One way to categorize copolymers was based on their architecture. Figure I-12 shows
how copolymers were classified as statistical, alternating, block, and graft. In statistical
or random copolymers, the placement of the co monomers in the chain was random. In
alternating copolymers, co monomer molecules alternated in the chain. If long
sequences of one co monomer refollowed by long sequences of the other co monomer,
the resultant copolymer is called block copolymer. Block copolymers can be diblock,

Introduction

37
triblock or multiblock depending on the number of comonomer types used during the
polymerization. Graft copolymers were branched polymers where the backbone was
made of one copolymer type and the branches are made of another copolymer type
[180].

H
2
C C
H
A
H
2
C C
H
R
[ (
C C
H
2
H
A
)
X
C
(
H
2
C
H
B
) ]
z
B
X
+Y
Y

Figure I-11: General Copolymerization reaction scheme


Figure I-12: types of copolymer topologies


Binary Copolymerization Reactions:
In order to be able to predict the composition of a copolymer before the
polymerization was extremely useful. This could be accomplished by the copolyrner
composition equation. The four possible propagation steps in the copolymerization are
the following [181-183]:




Introduction

38
k
11
+ M
1
k
11
[M
1
] [M
1
]
k
12
+ M
2
k
12
[M
1
] [M
2
]
k
21
+ M
1
k
21
[M
2
] [M
1
]
k
22
+ M
2
k
22
[M
2
] [M
2
]
Growing
chain
Monomer
Added
Rate
(i)
(ii)
(iii)
(iv)
M
1
M
1
M
1
M
1
M
1
M
2
M
2
M
2
M
2
M
1
M
2
M
2



Where M
1
and M
2
are monomer one and two, respectively, M
1
denoted the polymer
chain with a terminal monomer one, and M
2
is the polymer chain with a terminal
monomer two, (i.e., there is no penultimate unit effect) and K
11
is the rate constant for
the reaction in which monomer M
1
adds to radicals chain ending M
1
and K
12
is the rate
constant for the reaction in which monomer M
2
adds to radicals chain ending M
1
etc.
The analysis was further simplified by a steady-state assumption: the rate of
disappearance of a chain end equals the rate of its appearance. Therefore; the rate of
reaction (ii) must equal the rate of reaction (iii):

k
1 2
[ M
1
] [M
2
]
=
k
2 1
[M
2
] [M
1
]


The rates of disappearance of the monomers one and two are given by:

-d [M
1
]
dt
= k
11
[M
1
] [M
1
]
+
k
21
[M
2
] [M
1
]
-d [M
2
]
dt
=
k
22
[M
2
] [M
2
]
+
k
12
[M
1
] [M
2
]


Introduction

39
After combining and rearranging these equations the following equations were obtained
[179-183]:

] [ ] )[ / ( ] [
] [ ] )[ / ( ] [
] [
] [
1 2 21 22 2
2 1 12 11 1
2
1
M M k k M
M M k k M
M d
M d
+
+
=

We can now define the important quantities termed the monomer reactivity ratios (r
1
,
and r
2
) as follows:

21
22
2
12
11
1
k
k
r and
k
k
r = = =


Thus, the copolymer composition equation was obtained as:

] [ ] [ ] [
] [ ] [ ] [
] [
] [
1 2 2 2
2 1 1 1
2
1
M M r M
M M r M
M d
M d
+
+
=

Monomer Reactivity Ratios:

The reactivity ratios were among the most important parameters for the
composition equation of the copolymers, which could offer information such as the
relative reactivity of the monomer pairs and help estimate the copolymer composition
[184]. To calculate the polymerization rate, the polymer productivity or the copolymer
composition the monomer reactivity ratios must be known. The method which was used
most often recently for estimating the monomer reactivity ratios was to perform a low
conversion copolymerization at various initial monomers feed compositions.
Subsequently, the copolymer composition was determined for each reaction [185]. The
reactivity ratio values might be evaluated by various procedures: linear procedures,
nonlinear procedures and other copolymer composition equations [186-190].

Copolymerization was one of the most important means to improve the
performance of the polymers. Copolymers were extensively used in industrial processes

Introduction

40
because their physical properties, such as elasticity, permeability, glass transition
temperature (Tg) and solvent diffusion kinetics could be varied within wide limits
[191]. Knowledge of the copolymers composition was an important factor in the
evaluation of its utility. Controlling the polymer property parameters, such as
copolymer composition, copolymer sequence distribution and average molecular
weight, was of particular importance in the copolymerization processes. This is because
copolymer density and viscosity, which were two of the most important property
measures used by the polymer manufacturers, depended on these parameters [189,192].
Acrylates and acrylate salts were readily polymerized by free radical
polymerization (FRP) to form linear, branched, or network polymers. Elemental
analysis methods such as C, H and nitrogen analysis offered simple and rapid evaluation
of the copolymer composition when were compared to the other techniques [193].

If r (reactivity ratio for monomer) < 1 the growing chain preferred to add the
comonomer rather than its own kind, and if r > 1 the growing chain preferred to add its
own kind rather than the other comonomer. There were number of different
combinations of the reactivity ratio values that were of special interest:

(a) r
1
> 1 and r
2
> 1 : In this case, two homopolymers would be formed.
(b) r
1
r
2
= 1 : A copolymer that was described by the above reactivity ratios was
termed an ideal copolymer, in which the monomers were randomly distributed through-
out the chain. The amount of any monomer incorporated into the polymer chain was
simply dependent on the concentration of that monomer on the feed and the relative
reactivities of the two monomers.
(c) r
1
= r
2
0 : An alternating copolymer resulted from a system having the above
reactivity ratios. The copolymer had alternating units of the two monomers because
each monomer reacted exclusively with the other monomer. There were many
monomers, such as maleic anhydride, which do not homo-polymerized, except under
special conditions, but readily form copolymers.




Introduction

41

Monomer reactivity ratios: solvent effects

For many years, it was believed that the monomer reactivity ratios were insensitive to
the solvent employed in the copolymerization. However, increasing the experimental
data emerged in which it became apparent that this insensitiveness appeared not to be
true. A pronounced effect of the reaction medium was found for the systems consisting
of, at least, one polar monomer. In fact, a solvent effect had been described for systems
involving monomers such as acrylic acid or methacrylic acid which can associate in
solution [194]. The monomer reactivity ratios of these monomers, when copolymerized
with other monomers, appeared to change dramatically with the nature of the solvent.
The reactivity ratios of acrylic acid (AA) or methacrylic acid (MA) were higher in
nonpolar solvents (e.g. C
6
H
6
or CCl
4
) than in polar solvents (e.g. DMF) [194-197]. The
subject had been reviewed by Plochocka. Besides, the effects of the reaction medium on
the copolymerization of the monomers capable of ionization or H-bond formation, an
effect of solvents upon copolymerization of apparently neutral monomers had also been
found [198].

Ito and Otsu in 1969 were probably the first who described the effect of
benzene, benzonitrile, benzyl alcohol, and phenol on the free-radical copolymerization
of styrene (St) with methylmethacrylate (MMA). In general, small effects of solvents on
the copolymerization reactivity ratios had been observed; their extents have been
strongly dependent on the monomer nature and the solvents involved. First attempts to
explain this behavior were based on the polarity of solvents. Thus, Ito and Otsu
indicated that the observed variations of the reactivity ratios in StMMA
copolymerization were due to the polarized structure of MMA in the transition state
which became more important when the solvent polarity increased. Other studies had
shown linear dependencies between copolymerization parameters and the dielectric
[199].




Introduction

42

Methods of Determination of the Monomer Reactivity Ratios

i. Direct Curve Fitting


The reactivity ratios might be obtained from the direct curve fitting of the polymer-
monomer composition curves which were not a favored method. However, the comp-
osition curve was insensitive to small changes in the reactivity ratios [200].

ii. Mayo and Lewis Method



The most common method used was that of Mayo and Lewis Rearranging the
copolymer composition equation into the form of the equation for a straight line (y = mx
+ b) as follows [201]:

1
] [ ] [
] [ ] [
] [
] [
] [
] [
1 2
2 1
1
1
2
2
1
2
+
|
|
.
|

\
|
=
m M
m M
r
m
m
M
M
r


Every set of M
1
, M
2
and m
1
, m
2
values produced a straight line. By setting r
1
equal to
the arbitrary values and the corresponding values of r
2
could be found and a straight line
could be drawn for a specific set of M
1
, M
2
and m
1
, m
2
values. The probable values of r
1

and r
2
lied in the area cut out by the intersecting lines.

iii. Fineman-Ross method



Fineman and Ross were the first who arrange the differential copolymer
composition equation in the following form [202]:

a-a/b = r
1
(a
2
/b) r
2


Where, a = M
1
/M
2
(molar ratio of the two monomers in the comonomer mixture)
And b = m
1
/m
2
(molar ratio of the two monomers in the copolymer)


Introduction

43
By plotting a - a/b as the ordinate against a
2
/b, the slope of the straight line is r
1
and the
intercept is - r
2
When the polymer composition measurements were precise, this method
was very convenient and frequently was used due to its simplicity and accuracy.

iv. Joshi-Kapur method



This method eliminated the subjective error in the location of the best point in the
intersection method of Mayo-Lewis plot [203].

v. Tidwell-Mortimer method

In detailed critical treatises, Tidwell and Mortimer pointed out the defects of the
different methods, and suggested a standard computerized procedure; the nonlinear least
square method. This method presumed that there was no possible experimental error in
the independent variable, the monomer composition of the feed, and that the absolute
error in the copolymer composition was independent of its value or constant [204].

vi. Yezrielev-Brokhina-Roskin method



Yezrielev, Brokhina and Roskin transformed the linear equation of copolymer
composition into the symmetrical form as [205]:

a/(b
2
.r
1
) b
2
/(a.r
2
) + (1/ b
2
b
2
) = zero

Where, a = M
1
/M
2
(molar ratio of the two monomers in the comonomer mixture)
And b = m
1
/m
2
(molar ratio of the two monomers in the copolymer)

In this method the theoretical line was situated evenly between the experimental points
of the positive and the negative errors which led to the determination of the reactivity
ratios in more accurate way.



Introduction

44
vii. Kelen-Tudos method

Kelen and Tudos published a method for calculating the monomer reactivity ratios
based on a new graphical valuable liner equation as follows [206]:

= (r
1
+r
2
/ ) ( r
2
/ )
Where, , , and are the mathematical functions
= a (b-1)/ ( b +a
2
),
=a
2
/ ( b +a
2
)

max min
max min
.
.
b X b
a X a
=


The variable cannot take any positive value. Thus, plotting the values as a function
of gives r
2
/ and r
1
, respectively (both as intercepts).

Factors affecting monomer reactivity ratios

With respect to the radical copolymerization, it may be stated that the reactivity ratios
were comparatively influenced by the most common variables such as the conversion
percent and the method of polymerization. In the range of temperatures from room
temperature to about 100C there was little variation in reactivity ratios in binary
copolymerization. However, there was a tendency for the r
1
r
2
product to approach 1 as
the temperature increased. Copolymerization had been affected at temperature as -78C
and temperature as high as 130C, with a large change in reactivity ratios. Also, the
reactivity ratio was found to vary with, pressure for example, in the copolymerization of
methylmethacrylate and acrylonitrile, the product of r
1
r
2
increased from 0.16 (at
atmospheric pressure) to 0.91 (at 1000 atmosphere) indicating that increasing the
pressure increased the tendency for this system towards blocks [207].





Introduction

45
I.17 Swelling and Absorption Capacity

The polymer chains in a hydrogel interacted with the solvent molecules (usually
water) and tended to expand to the fully solvated state, while the crosslinked structure
applied a retracting force to pull the chains inside. Equilibrium was achieved when these
expanding and retracting forces counter balance each other. The swelling properties
were determined by many factors, including the type and composition of monomers,
crosslinking density and other environmental factors such as temperature, pH and ionic
strength [208]. The solubility properties of water-soluble polymers are due to the
presence of functional groups (mainly OH, COOH and/or NH
2
). Covalent linkages
between the polymer chains could be established by the reaction of such functional
groups, if they had complementary reactivity [209-210].