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chemistry
section 9
polymer chemistry
Section 9
contents
introduction ..........................................................................................................................1
polymer types .......................................................................................................................1
polyacrylate, polyacrylamide, and phpa ............................................................2
carboxymethylcellulose (cmc) and polyanionic cellulose (pac) ................2
hydroxyethylcellulose (hec) ...................................................................................4
starch .............................................................................................................................4
guar gum .......................................................................................................................5
xanthan gum ...............................................................................................................5
other naturally derived polymers ........................................................................5
polymer uses .........................................................................................................................5
viscosity .........................................................................................................................6
bentonite extension ..................................................................................................6
flocculants .....................................................................................................................6
deflocculants ...............................................................................................................6
surfactants ....................................................................................................................6
filtration control .........................................................................................................7
shale stabilisation ......................................................................................................7
polymer limitations ............................................................................................................7
01 polymer chemistry
Section 9
introduction
A polymer is a molecule consisting of a series of repeating units. The
number of units can vary from several to tens of thousands with
corresponding variance in chain length and molecular weight. The
polymer can be linear or branched and can be synthetic or naturally
derived.
The repeating unit need not always be the same. Copolymers consist of
two or more different groups joined together and may be ‘random’ or
‘block’ depending on how the groups are distributed on the chain.
polymer types
Each type of polymer has its own characteristics in terms of how it
functions in a particular type of drilling fluid. Therefore, selection of the
polymer chemistry 02
Section 9
correct type of polymer is critical to good performance. Below are listed
five general types of commonly used polymers.
Acrylonitrille
Polyacrylonitrile (Polymer)
(Monomer)
CH CH CH CH CH CH CH
CONH
Co _ Co _ 2 Co _ Co _ CONH Co _
2 2 2 2 2 2
+ + Na + + +
Na Na Na Na
PHPA Polymer
Cellulose Structure
H OH CH2OH H OH CH2OH
HO H H O H H O
O
4 OH H1 4 H OH H H H.OH
H OH H H OH H
O O
H O H H O
CH2OH H OH CH2OH n H OH
Carboxymethylcellulose Structure
CH2COO-Na+ CH2COO-Na+
H OH CH2O H OH CH2O
HO H H O H H O
O
4 OH H1 4 H OH H H H.OH
H OH H H OH H
O O
H O H H O
CH2COO-Na+ CH2COO-Na+
CH2O H OH CH2O n H OH
Section 9
hydroxyethylcellulose (hec)
Hydroxyethyl cellulose. This is used mainly as a viscosifier for completion
fluids. Its non ionic nature means that it is not affected by salt. Key factors
are purity and high acid solubility.
CH2OCH2CH2OCH2CH2OH H OCH2CH2OH
O
H O H
H H H OH H
Cellulose + C C OH H H O
H H
O
H H O
H OH
n
CH2OCH2CH2OH
Ethylene oxide
Hydroxyethylcellulose
Although HEC is non ionic, it is still water soluble due to the hydroxy
ethyl groups. HEC imparts high viscosity to water or brines but exhibits
no gel strengths. It is prone to degradation through shear or heat and
has a maximum thermal stability of about 225° F.
starch
Widely used as fluid loss reducing agents, particularly in salty muds. Can
be potato or grain derived. Quality and temperature stability can be
improved by various processes.
Starches are used mainly for fluid loss control and are effective in a large
range of fluid systems, such as seawater, saturated saltwater, KCl muds
and lime muds. Starches are thermally stable to about 250° F. Starches,
unless chemically modified are not resistant to bacteria and require a
biocide to prevent fermentation, except in saturated salt and high pH
muds.
05 polymer chemistry
Section 9
guar gum
Viscosifier used to make spud muds. Derivatives (eg.hydroxy propyl guar)
may be used in certain completion /workover fluids.
Guar gum is manufactured from the seed of the guar plant. Guar is a
naturally occurring non ionic polymer used as a viscosifier in waters
ranging from fresh to saturated salt (NaCl). High levels of hardness and
alkalinity will slow or even eliminate the hydration process and can cause
a significant decrease in viscosity.
xanthan gum
Excellent viscosifier giving shear stable rheology with progressive gels.
It is derived from bacteria.
polymer uses
Some of the major uses of polymers in drilling fluids are:
ƒ Viscosity
ƒ Bentonite Extension
ƒ Deflocculation
ƒ Filtration Control
ƒ Shale Stabilisation
polymer chemistry 06
Section 9
viscosity
Viscosity is due to the interactions between the polymer molecules and
water, between the polymers themselves and between polymers and
solids.
The longer the molecules the greater the viscosity. The interaction
between the polymers, water and solids can be disrupted by applying
energy or shear. The result is that the higher the shear, the lower the
viscosity.
bentonite extension
The bentonite extenders work by cross-linking bentonite particles to
increase the physical interaction between particles. There is a narrow
band of concentrations which allow this cross-linking to occur, but above
which a viscosity decrease may occur.
flocculants
These polymers are characterised by a anionic high molecular weight
which will enable the polymer to bridge from particle to particle. The ionic
groups of the polymer will allow it to absorb strongly on the ionic sites of
solids and form an aggregate. The aggregates will settle or be removed by
shakers or centrifuges.
deflocculants
The deflocculants or thinners are usually negatively charged polymers.
These products absorb onto the edges of clay particles resulting in an
overall negative charge.
surfactants
These are discussed in the “OBM Fundamentals” section. They are polymers
with a polar, water loving end and a non polar oil soluble end.
07 polymer chemistry
Section 9
filtration control
Three mechanisms can be envisaged for polymers to act as fluid loss
additives.
a. Deflocculants. These pack down the filter cake forming a flatter, less
permeable medium.
b. Viscosity of the filtrate. The thicker the liquid phase being forced
through the filter cake, the lower rate of filtration.
c. Colloidal particles. Compressible colloidal particles will deform to plug
pores in the filter cake.
shale stabilisation
Shale stabilisation is provided through polymer attachment to the
positively charged sites on the edge of clay particles in shales. This
attachment minimises water invasion into the clay particle and reduces
hydration and dispersion. These polymers have been used with success
in conjunction with salt and potassium-based muds for added inhibition.
polymer limitations
Polymers have many advantages, particularly for formulating drilling
fluids from sea water or salt saturated brine or for making highly
inhibitive muds such as the KCl/PHPA systems. They do have limitations
however.
polymer chemistry 08
Section 9
Rheological Characteristics
Linear polymers such as CMC, PAC, HEC , produce almost ideal power law
fluids with poor viscosities at low shear rates and flat, low gel strengths.
Thus suspension properties are poor. Xanthan gum is the exception and
has good suspension characteristics. Note, however, that gels increase as
the low gravity solids build up.
Tolerance to Contaminants
Most polymers tolerate salt or KCl very well, but the anionic ones e.g.
CMC or PAC can be precipitated by calcium if the pH is high. Cement is
the worst contaminant. Calcium values over 1000 mg/l (as in, for
example, gyp muds) can be tolerated if the pH is below 10. Polymer yields
are higher in fresh water than in saturated salt.
Temperature
The polysaccharides have relatively poor temperature stability max. BHT
250 - 300˚ F depending on grade). This can be increased by using stabilisers.
The synthetic polymers can tolerate much higher temperatures (350˚ F
– 500˚ F).
Bacteria
Starch, guar gum and Xanthan gum are quite easily attacked. The use
of a biocide is recommended. CMC and PAC are more resistant to attack.
Cost
Polymer muds are generally more expensive in terms of cost/bbl than
bentonite muds. However, the advantages obtained by their use (better
hole stability, ROP etc.) will normally outweigh the extra cost.