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Drilling Fluid Technology

Polymer Chemistry
Global Research and Technology Centre
Kuala Lumpur

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Polymers

Polymers are used in Drilling Fluids to get desired end


properties such as -

Viscosity
Bentonite Extension
Fluid Loss Control
Flocculation / Deflocculation (Thinning)
Shale Inhibition
Lubricity
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The Basics
• Polymers are large molecules (macromolecules) built up
from numerous smaller molecules known as monomers.
• Polymers may be linear, branched, or cross linked.
• The size of the polymer is defined by it’s mass or by the
number of repeat units (DP) in the molecule multiplied
by the repeat unit molecular weight.
• The polymer properties depend on the type and number
of monomer/s used, the number of branches and
functional groups in the chain.
• The type and extent of any subsequent chemical
modification
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Polymer Types
X Polymerisation

Reaction
-X-X-X-X-X-X-X-
Monomer Linear Homopolymer

X-X
-X - X - X
X-X-X-X-
Branched Homopolymer

X+Y -X-Y-X-Y-X-Y-X-Y-
Alternating Copolymer
Monomers
-X-Y-Y-X-X-X-Y-X-
Random Copolymer

-X-X-X-Y-Y-Y-X-X-X-
Block Copolymer

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Polymer Types
-X-X-X-X-X-X-X-
X Polymerisation

Reaction Add monomer Y


Monomer

-X-X-X-X-X-X-X-
l l

Y Y
l l

Y Y
Branched Graft Copolymer

X -X-X-X-X-X-X-X-
Monomer Add reactant (R)

-X-X-X-X-X-X-X-
l l l
R R R
Functionalised /Derivatised Polymer
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Molecular Weight (Chain Length)

Expressed in Average Units

Number of molecules
It is rarely possible to get all Narrow
distribution
the chain lengths exactly
the same. Hence there is
a distribution of molecular Broad
distribution
weights.
Molecular weight
MW

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Reactive Groups

The reactivity or effectiveness of a polymer depends on :

• The type(s) of reactive/functional groups.

• The number of reactive/functional groups.

• The distribution of the groups on the polymer


backbone.

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Polymer Shape

The shape of the polymer will


depend on :
Branching or cross linking of
the polymer. Branched

Linear
Crossed linked
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Polymer Shape
• The concentration of the groups on -ve -ve

the polymer.
• Polymers with a higher number of
charge groups will uncoil more
than polymers with only a few Low substitution.
charged groups. Chain remains coiled.
• This is because the charged groups -ve -ve -ve

will repel each other.


• Uncharged polymers do not have
groups which repel each other and
High substitution.
hence can form small coils in Like charges repel.
solution rather than extended Polymers uncoils.
chains
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Polymer Shape

The shape of some polymers will depend on the pH of the


solution. For example, polymers containing carboxylic
acid will become ionised at alkaline pH and will then
dissolve to form extended chains:
-ve -ve
neutral neutral
acid

base

• Optimum solubility of anionic polymers is normally seen


between pH 8 and 9.5.
• Higher pH can degrade some polymers or cause partial
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Polymer Shape
The shape of the polymer will - - -
be affected by the ionic
strength of the solution.

Electrolytes will reduce the Fresh Water


electrostatic repulsion
between the charges. - - -

Viscosity will increase when


polymer chains are
extended; i.e. in fresh water
Salt Water

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Polymer Shape
Multivalent cations will - - - -

react with more than


one charged group on
many anionic polymers
or will act as a bridging
agent between anionic
polymers.
-

This will reduce the size or


effectiveness of the
polymer.

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Classification of Polymers

Natural Polymers
• Starch
• Guar Gum
• Locust Bean Gum

Modified or derivatized natural polymers


• Dextrinized starch
• Hydroxypropyl guar
• Carboxymethyl cellulose (CMC)
• Polyanionic cellulose
• Chrome complexed LSO3
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Classification of Polymers

Microbial Polymers
• Xanthan Gum (XC Polymer)

Synthetic Polymers
• Sulfonated styrene maleic anhydride copolymer
• Polyacrylates
• Polyacrylamides
• Partially hydrolyzed polyacrylamide (PHPA)

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Bentonite Extenders

Bentonite extenders work by cross-linking


bentonite particles to increase physical interaction
between particles.

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Viscosifying Polymers

Polymers can generate viscosity in solution by :

• Interactions between polymer chains - increasing the


length of the chains increases viscosity
• Adsorption of water, effectively increasing the size of
the polymer
• Interacting with solids in a mud to form an
interconnecting network. (eg. Reactive clay drilled
solids and high molecular weight polyacrylamides)
• By undergoing cross-linking reactions between polymer
chains (eg. Borate X-linked guar fracturing fluids)
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Viscosifying Polymers

high molecular weight

solution
low molecular weight
viscosity

polymer concentration

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Viscosifiers
Guar Gum
Xanthan Gum
Welan Gum
Scleroglucan
Hydroxy Ethyl Cellulose
Carboxy Methyl Cellulose
Carboxy Methyl Ethyl Cellulose
Poly Anionic Cellulose
Styrene butadiene latexes in oil based fluids
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Filtration Control

Polymers aid in filtration control by:

• Deflocculating solids, so will form flatter less


permeable filter cake.
• Viscosifying the liquid phase. The thicker the fluid,
the lower the rate of filtration.
• Forming colloidal particles. These particles will
deform to plug pores in filter cake.

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Filtration Controllers
Cellulosics
Low viscosity carboxy methyl cellulose
Poly anionic cellulose
CMHEC
Starch and it’s derivatives
Sodium Polyacrylates

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Filtration Controllers
High temperature copolymers and terpolymers
copolymers contain 2 monomers, terpolymers contain 3.
Many are AMPS based (2-acrylamido-2-methyl-propane
sulphonic acid).
Lignins
Pre cross-linked methyl styrene acrylate copolymer. Oil based
fluid systems.

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Flocculants

• They are negatively charged high molecular weight


polymers.
• Enable polymer to bridge from particle to particle.
• Adsorb strongly on ionic sites of solids and form
aggregate, which will be removed by shakers or
centrifuges.

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Flocculants
• Flocculants are long chain polymers that are able to bridge
particles together.
• They assist in removing particles from the fluid by making the
overall particle size bigger, and thus easier to remove.
Flocculated clay Flocculant
Deflocculant

High M.W.
polymer acting as
bridge between
particles

Adsorption of low
M.W. polymer
creates overall
negative charges

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Deflocculants

• They are negatively charged low molecular weight


polymers.
• Adsorb onto clay edges, thus neutralizing any positive
charges, and creating an overall negative charge.
• If the polymer is too long, it will bridge between
particles and exhibit a flocculating action.
• Sensitive to divalent cations and less effective when
hardness exceeds 400 mg/l.

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Thinner & Deflocculants

Lignosulphonates
Tannins
Sodium Acrylates
AMPS and it’s derivatives (high temperatures)
poly 2- acrylamido 2-methyl propane sulphonic acid
Sulphonated styrene maleic anhydride
Low Molecular weight (c. 3000)

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Shale Stabilization

• Polymers attach themselves to positively charged sites


on clay edges in shales.
• This minimizes water invasion into clay and reduces
hydration and dispersion.
• For added inhibition, use in conjunction with salt and
potassium based muds.

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Polymer Encapsulation (PHPA)

Hydrated
Shale

Long chain polymer

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Shale Encapsulating Polymer

POLYMERS

SHALE

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HYDRO CAP – Adheres to Shale Cuttings

Fresh Water Sea Water

Maintain Ca++ below 300 mg/l

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Shale Control Additives

Cationic Polyamines
PAC’s
Polyhydroxy Compounds
Glycols

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Lost Circulation Materials

Nut hulls and various blended fibrous


materials are natural polymers in origin.
Current trend is to use cross-linked polymers
which set to a very firm consistency.

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Summary
Polymer types Description Examples Functions
Carboxymethyl Polysaccharide
cellulose ether linear polymer
CMC anionic-COO-
groups
High viscosity Viscosifer, fluid
High molecular wt CMC loss additive
Low molecular wt Fluid loss additive
Low viscosity CMC
Hydroxyethyl Polysaccharide
cellulose ether linear polymer HEC Viscosifier –
HEC non-ionic ether particularly for
group brines
High molecular wt
Starch Polysaccharide Corn, potatoes, Fluid loss control
highly branched tapioca, etc. in salt solutions
forms colloidal Variously
solution normally chemically 32
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non-ionic modified
Summary
Polymer types Description Examples Functions
Bacterial gums Polysaccharide Viscosifier
polysaccharide branched complex Xanthan gums particularly in salt
structure some water and where
anionic groups suspension
High molecular wt properties are
required
Natural gums Polysaccharide Guar, gum arabic Viscosifier
from trees and branched – high
shrubs molecular wt
some anionic
groups complex
structure
Lignosulphonate Water soluble Lignosulphonate Thinner,
sulphonate deflocculant, fluid
derivative of lignin loss control
– range of metal
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Summary
Polymer types Description Examples Functions
Mined lignins Metal salts of Lignite Thinner, fluid
petrified humic loss control
acid
Tannin Extracts from Quebracho Thinner
bark and wood

Polyphosphates Molecularly Sodium acid Thinner


dehydrated pyrophosphate
phosphates
Vinyl polymer Co-polymer of Flocculant
acrylic acid and Shale stabiliser
acrylamide in
various ratios

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