Polymers in Drilling Fluids

•
POLYMERS IN
DRILLING
FLUIDS
POLYMERS IN DRILLING FLUIDS
Polymers are used in many types of Drilling

Fluids to control properties such as:-
•Viscosity
•Fluid Loss Control
•Flocculation / Deflocculation (Thinning)
•Shale Inhibition
•Lubricity
The Basics
• Polymers are large molecules (macromolecules) built

up from numerous smaller molecules known as
monomers.
• The large molecule may be linear, slightly branched, or
highly interconnected whereby the structure develops
into a large three-dimensional network.
• The size of the molecule may be defined by it’s mass or
by the number of repeat units (monomer) in the
molecule - the degree of polymerisation (DP).
• The relative molar mass (molecular weight) is thus the
product of the relative molar mass and the DP.
The Basics
The properties of polymers depend on :
•The type of monomer or monomers used.

•The number of monomers used to form the polymer (i.e.
the molecular weight).
•The number of cross-linking or branching groups in the
chain.
•The type and extent of any subsequent chemical
modification
Simple Example
• Ethene, CH2=CH2, is polymerised to poly(ethene) -

IUPAC name.
• More generally known as Polythene.
• Formula [-CH2-CH2-]n.
• Produced by 4 processes. The Phillips process
employs 5% CrO3 on finely divided silica/alumina as the
catalyst. Reaction conditions are 15 - 35 atm, 130 -
160 °C.
• Product density is 0.945 g cm-3.
• Good chemical resistance but low molar mass product
is prone to environmental stress cracking on exposure
to sunlight.
Polymer Types
X Polymerisation
Reaction
-X-X-X-X-X-X-X-
Monomer Linear Homopolymer
X-X-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
Polymer Types (cont)

-X-X-X-X-X-X-X-
X Polymerisation
Reaction Add monomer Y

Monomer
-X-X-X-X-X-X-X-
  
Y Y Y
  
Y Y Y
Branched Graft Copolymer
X -X-X-X-X-X-X-X-
Monomer Add reactant (R)
-X-X-X-X-X-X-X-
  
R R R
Functionalised/Derivatised Polymer
The Molecular Weight (or Chain Length)
• This can be varied :
– By limiting the number

of terminating groups
or chemically
Number of molecules
Narrow
degrading longer distribution
chains.
Broad
• It is impossible to get all the distribution
chain lengths exactly the

same. Hence there is a Molecular weight
MW
distribution of molecular
weights.
Reactive Groups
• The reactivity or effectiveness of a polymer

depends on :
– The type(s) of reactive groups.
– The number of reactive groups.
– The distribution of the groups on the polymer

backbone.
Polymer Shape
• The shape of the

polymer will depend
on :
– Branching or cross Branched
linking of the
polymer. Linear
Crossed linked
Polymer Shape (cont)

• 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
charged groups. This is because the
charged groups will repel each Low substitution.
other. Chain remains coiled.
• Unchanged polymers do not have -ve -ve -ve
groups which repel each other and

hence can form small coils in
solution rather than extended chains
High substitution.
Like charges repel.
Polymers uncoils.
• 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
dehydration
• The shape of the polymer - - -

will be affected by the ionic
strength of the solution.
Electrolytes will reduce the
electrostatic repulsion
between the charges. Fresh Water
• Viscosity will increase - - -

when polymer chains are
extended; i.e. in fresh
water
Salt Water
• 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.
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)
Viscosifying Polymers
high molecular weight
solution
viscosity low molecular weight
polymer concentration
Deflocculants
• Deflocculants achieve their results by adsorption of the

negatively charged polymers onto the clay platelets, thus
neutralizing any positive charges, and creating an overall
negative charge.
• Deflocculants are negatively charged low molecular

weight polymers.
• If the polymer is too long, it will bridge between particles

and exhibit a flocculating action.
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
Adsorption of low
M.W. polymer
High M.W. polymer
creates overall acting as
negative charges bridge between
particles
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
Classification of Polymers
 Microbial Polymers
– Xanthan Gum (XC Polymer)
 Synthetic Polymers
– Sulfonated styrene maleic anhydride
copolymer
– Polyacrylates
– Polyacrylamides
– Partially hydrolyzed polyacrylamide
(PHPA)
Colloidal Nature
• The size of many high relative molar mass polymers is

such that it puts them into the area of colloids, i.e. up to
1000 nanometres.
• As a consequence their behaviour is similar to colloids.

Polymers in Drilling Fluids
• Classification is by origin and function.

• Origin
– Natural (biopolymer)
– Synthetic or modified natural polymers
• Function
– Bentonite Extenders
– Viscosifiers
– Filtration Control Agents
– Flocculants
– Deflocculants and Thinners
– Shale Stabilizers
– General Borehole Lubricants
– Lost Circulation Curatives
Viscosifiers
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
Guar Gum
Guar Gum
• Natural polymer derived from beans of leguminous plants (Cyamopsis
Tertagonalobus & Psoraloides).
• The endosperm which contains the polymer is separated from the husk
by various processing techniques and ground to set particles sizes.
• It is then tested and classified
– 3000 cps, 4000 cps, food grade, industrial grade, etc
• Carbohydrate alternating copolymer containing galactose and mannose
as the structural building blocks.
• Note that the polymer is completely non-ionic.
It is an agricultural crop grown during monsoon –
July to September normally. It can be grown in
areas which have small rainfalls of about 400 to
900 mm. in two to three spells, with an interval of
about a month or so, because it requires not much
water unlike other crops.
The plant is thin but strong and reaches the height

of 1 to 2 meters at full growth. The main stem and
its branches bear pods which may contain upto 10
seeds. Seeds have a diameter of around 8 mm.
Plant is sensitive to frost, viral, fungal and bacterial
diseases.
Pods when ripe are harvested and dried under the

sun. Seeds are removed from within when beans
have fully dried up.

Guar Gum
• Guar forms a pseudoplastic, non-newtonian solution

with zero yield value.
• They will degrade with long exposure to shear.
• Will viscosify a wide variety of brines (because it is
non-ionic) at relatively low concentrations.
• It will not hydrate in the presence of alkali but is is
resistant to alkalinity or pH increases once hydrated in
non-alkaline solutions such as seawater or fresh water.
• Main use is in preparing viscous pills for flushing large
diameter holes.
• Mixed at 7.5 to 10 kg/m3 (2 to 3 ppb).
• Can be cross linked by reagents such as sodium
borate (borax).
Xanthan Gum
Xanthan Gum
• Polysaccharide biopolymer produced in a pure culture

fermentation by the micro-organism Xanthamonas
Campestris (originally isolated from the Rutabaga
plant).
• Pathogen which attacks brassicas and causes rotting.
• Basically it’s a slime that’s secreted by the bacteria.
• Following fermentation, the gum is recovered by
precipitation in an alcohol, dried and milled.
Structure of Xanthan
• Primary Structure
– A repeating unit formed
from chains of five sugar
units, 2 mannose, 2 glucose
and 1 glucuronic acid.
• Secondary Structure
– stiff extended or crumpled
ribbons
– loose double helical coils
– flexible random helices
• Molecular weight about 15
million.
• High viscosity at low
concentration
• Strongly pseudoplastic
• Side chains provides
shielding against enzyme
High Resolution Image of Xanthan
High resolution image of several molecules of the polysaccharide

xanthan illustrating its helical secondary structure. Scanned under 1,2
propane diol. Scan size: 0.2 x 0.2 microns
Properties and Use
• Xanthan is highly shear thinning.

• It’s ability to form networks and gels (a unique
properties of certain biopolymers) is the main reason
why xanthan is used so widely in drilling fluids.
• Exhibits good suspension properties. A feature which is
not shared with polymers, particularly synthetics.
• Used in a wide range of fluids, from potassium systems
to bentonite / CMC fluids.
• High cost but used in low concentration 1.5 - 3 kg/m3.
At high concentrations (10 kg/m3) the product will
compete with MMH fluids in milling.
• Stable to 135°C
Viscosity vs. Shear
XCD Polymer in seawater at 24°C
Courtesy Kelco Inc.

Filtration Control Polymers

Filtration Controllers
• Cellulosics
– Low viscosity carboxy methyl cellulose
– Poly anionic cellulose
– CMHEC
• Starch and it’s derivatives
• Sodium Polyacrylates
• 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.
CMC
CMC
• CMC is an anionic polymer in varying forms of purity.

• Formed form reacting cellulose hydroyls (obtained from
many sources e.g. caustic soda on wood or cotton
linters) with sodium monochloroacetic acid.
• Product is washed to get rid of reaction by products -
salt and sodium glycolate.
• 99% pure sodium CMC can be produced.
Degree of Substitution
• Defined as the average number of the three hydroxyl

groups in the anhydroglucose unit which have been
reacted
1
2
3
DS = 1
• The structure opposite

depicts a sodium CMC
where the degree of
substitution is 1.
• Most CMC’s have a DS
of 0.7 to 0.8.
• CMC’s with at degree of

sunstitution of 1 are
called poly anionic
cellulose. PAC.
CMC Grades
• Grades vary from 60% active matter to 99%.
• Technical grades have improved to approximately 80%.
– Economic trade-off between cost of shipping the
waste products in the CMC’s against the purification
process and disposal costs.
• A wide range of viscosity grades can be produced.
– High molecular weight (600,000) variants are used
as viscosifiers in a wide range of fluids.
– Low viscosity grades that are used for filtration
control exhibit molecular weights in the order of
250,000 whereas ultra low viscosity grades can be
as low as 100,000.
Application
• Calcium tolerance. Recommended maximum

concentration for calcium is circa 400 mg l-1.
• This highly anionic molecule is subject to electric
double layer effects.
• Pure grade PAC’s can viscosify to the same degree as
xanthans, but they do not exhibit the same suspension
characteristics.
• The ultra low viscosity PAC’s can act as thinners.
• Temperature stabe to 125°C.
Starch
Starch
• Starch differs from cellulose only in the bonding and orientation of

the structure.
• In Amylose the linkage is beta-glucosidic and in cellulose alpha
glucoside is the linkage conformation.
Condensation Polymer
• Starch is a natural molecule formed in a variety of plants.

• It can be considered a condensation polymer of glucose
Types
• The main sources of starch are potatoes, corn and other grain.
• Most starches contain a mixture of two polysaccharides, amylose and
amylopectin.
• Amnylose is linear consisting of a chain of glucose units.
• Molecular weights of 40,000 to 650,000 have been reported for amylose, with
potatoe and Tapioca starches providing the amylose at the higher end of the
range.
• Amylopectin is a highly branched molecule, one of the largest ones in nature
at 10 to 1000 million molecular weight.
• Processing conditions can cause a reduction in molecular weight.
Amylopectin Branching
• Depending on the source, the starch is separated from the kernel and other
detritus by a range of methods.
Electron Micrographs - Starch Granules
Potato Corn
Tapioca Wheat
Product
• The produced polymer is non-ionic, of relatively low

molecular weight.
• Used in hard and saline solutions.
• Thermal limit is circa 110°C.
• Cross-linking can extend the thermal limit to 140°C.
• Starches, being natural are prone to enzyme and
bacterial attack, mostly in fresh or brackish water.
• In saturated salt solutions a preservative is generally
not required.
• Biocide is added to HT starches.
Modified Starches
• Carboxy methylation is one of the ways in which starch

is modified.
• Can equal technical grade CMC’s (60%) in it’s filtration
control properties.
• CMS has a very low viscosity and is fermentation
resistant due to increased degree of substitution.
• Hydroxyethylation is also performed but such products
are not widely used.
• Starches are very widely used in a range of water
based drilling fluids for filtration control at ‘normal’
temperatures.
Other Polymers
Shale Control Additives
• Polyacrylamide Copolymers (PHPA - ENCAPSUL-8)

– Polyacrylamide and polyacrylate copolymers - PHPA
– 30-40% hydrolysed.
– i.e. The percentage of acrylate in the molecule
CH2-CH CH2-CH
C=O C=O
NH2 O- K+ or Na+
x y
Hydrolysed Polyacrylamide
Ion Exchange - Limit Hydration
Na+ Na+
Na+ Na +
Na+ Na+
KCl
Na+ K+ K+ Na+
+ K+
Na K+ Na+
K+ K+
Na+
Polymer Encapsulation (PHPA)
Hydrated
Shale
Long chain polymer

Hydration and Uncoiling of ENCAPSUL-8 Polymer
H2O H2O
TIME TIME
Polymer Encapsulating Shale
POLYMERS
SHALE
ENCAPSUL-8 Polymer - Encapsulating Shale
Na+
+ +
+
+
Na+
K
+ +
+
+
Na+
+ +
+ +
Na+ +
+ +
ENCAPSUL-8 Polymer
ENCAPSUL-8 Adhered to Shale Cutting
Fresh Water Sea Water
Maintain Ca++ below 300 mg/l

Shale Control Additives
• Cationic Polyamines
• PAC’s
• Polyhydroxy Compounds
– Glycols
Thinners and 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)
Lost Circulation Curatives
• 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.

Polymers in Drilling Fluids

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Polymers in Drilling Fluids

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•

Polymers are used in many types of Drilling

• Polymers are large molecules (macromolecules) built

The properties of polymers depend on :

•The type of monomer or monomers used.

• Ethene, CH2=CH2, is polymerised to poly(ethene) -

Polymer Types (cont)

Reaction Add monomer Y

The Molecular Weight (or Chain Length)

• This can be varied :

– By limiting the number

chain lengths exactly the

• The reactivity or effectiveness of a polymer

– The type(s) of reactive groups.

– The number of reactive groups.

– The distribution of the groups on the polymer

• The shape of the

Polymer Shape (cont)

• Unchanged polymers do not have -ve -ve -ve

groups which repel each other and

Polymer Shape (cont)

• The shape of some polymers will depend on the pH of the solution.

 Optimum solubility of anionic polymers is normally seen between

Polymer Shape (cont)

• The shape of the polymer - - -

• Viscosity will increase - - -

Polymer Shape (cont)

• Multivalent cations will - - - -

react with more than one

• Polymers can generate viscosity in solution by :

– Adsorption of water, effectively increasing the size of the

– Interacting with solids in a mud to form an interconnecting

– By undergoing cross-linking reactions between polymer chains

high molecular weight

• Deflocculants achieve their results by adsorption of the

• Deflocculants are negatively charged low molecular

• If the polymer is too long, it will bridge between particles

• They assist in removing particles from the fluid by making the

 Modified or derivatized natural polymers

• The size of many high relative molar mass polymers is

• As a consequence their behaviour is similar to colloids.

Polymers in Drilling Fluids

• Classification is by origin and function.

The plant is thin but strong and reaches the height

Pods when ripe are harvested and dried under the

have fully dried up.

• Guar forms a pseudoplastic, non-newtonian solution

• Polysaccharide biopolymer produced in a pure culture

High Resolution Image of Xanthan

High resolution image of several molecules of the polysaccharide

Properties and Use

• Xanthan is highly shear thinning.

Viscosity vs. Shear

XCD Polymer in seawater at 24°C

Courtesy Kelco Inc.

Filtration Control Polymers

• CMC is an anionic polymer in varying forms of purity.

• Defined as the average number of the three hydroxyl

• The structure opposite

• CMC’s with at degree of

• Calcium tolerance. Recommended maximum

• Starch differs from cellulose only in the bonding and orientation of

• Starch is a natural molecule formed in a variety of plants.

Electron Micrographs - Starch Granules

• The produced polymer is non-ionic, of relatively low

• Carboxy methylation is one of the ways in which starch

Shale Control Additives