POLYMER CHEMISTRY

AND
POLYMER MUDS

Polymers in Drilling Fluids

Polymers are used in many types of drilling
fluids and can control properties such as :

– Viscosity

– Fluid Loss Control

– Flocculation / Deflocculation (Thinning)

– Shale Inhibition

– Lubricity

Polymers Used in Drilling Fluids

Natural Polymers :
– Xanthan Gum
– Guar Gum
– Whelan Gum
– Starch
M difi d N
Modified Natural
t l Polymers
P l :
– Carboxymethyl Cellulose (CMC)
– Polyanionic Cellulose (PAC)
– Hydroxyethyl Cellulose (HEC)
– Lignosulphonates

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 Polymers Used in Drilling Fluids

Synthetic Polymers :
– Polyacrylamides
– Polyacrylates
– Glycol
y

Polymers are molecules made up from

smaller chemically identifiable units
(Monomers).

Polymers
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.

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.

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 Polymer Shape
The shape of the
polymer will
depend on :
Branched

– Branching or cross Linear

linking of the
polymer.

Crossed linked

Polymer Shape (cont)

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

Unchanged polymers do not have

groups which repel each other
and hence can form small coils High substitution.
in solution rather than Like charges repel.
Polymers uncoils.
extended chains

Polymer Shape (cont)

The shape of some polymers will depend on the
pH of the solution. For example, polymers
containing carboxylic acid will become
ionized at alkaline pH and will then dissolve
to form extended chains: -ve -ve
neutral
t l ne tral
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

3
 Polymer Shape (cont)
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
Salt Water
are extended; i.e. in
fresh water

Polymer Shape (cont)

- - - -

Multivalent cations will

react with more than
one charged group
on many anionic
polymers or will act
as a bridging
b id i agentt
between anionic -

polymers. This will -

reduce the size or

effectiveness of the
polymer.

Relationship function / structure

F u n c tio n M a in C h a ra c te ris tic s
V is c o s ity H ig h m o le c u la r w e ig h t.
V is c o s ity & G e lla tio n H ig h m o le c u la r w e ig h t a n d h ig h ly
b ra n c h e d s tru c tu re o r c ro s s
lin k in g a g e n t.
V is c o s ity in s a lt s o lu tio n s H ig h m o le c u la r w e ig h t a n d n o n -
io n ic o r h ig h ly s u b s titu te d io n ic
typ e .
D e flo c c u la tio n , d is p e rs io n , o r L o w m o le c u la r w e ig h t n e g a tive ly
th in n in g a c tio n c h a rg e d a t a lk a lin e p H le ve ls .
F lo c c u la n t H ig h m o le c u la r w e ig h t w ith
c h a rg e d g ro u p s to a d s o rb o n to
c la ys .
S u rfa c ta n t H yd ro p h o b ic g ro u p a n d
h yd ro p h ilic g ro u p o n s a m e
m o le c u le .
F lu id lo s s a d d itiv e F o rm c o llo id a l p a rtic le s .

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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)

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.

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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.

Flocculants
Flocculated clay

Deflocculant Flocculant

High
Adsorption of low M.W.
M.W. polymer polymer
creates overall acting as
negative charges bridge
between
particles

Fluid Loss Control by Polymers

Some polymers (eg. Lignosulphonates, Lignins, low

viscosity CMC / PAC, Polyacrylate) deflocculate drill
solids to form a thinner, less permeable filter cake.

Starch forms colloidal particles which fill voids in filter

cake reducing permeability (other fluid loss additives
cake,
also work by this mechanism)

Polymers viscosify liquid phase, making passage

through filter cake more difficult (often minor /
negligible effect)

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 Shale Inhibition by Polymers-
Polyacrylamides
High molecular weight polymers such as partially hydrolysed
polyacrylamide (PHPA) adsorb on clay minerals in shale.
High molecular weight allows polymer to bridge across several
clay particles, reducing shale breakdown and clay dispersion
(i.e. acts as a flocculant).
Typical PHPA inhibitors have molecular weights of 5 - 12 million
although smaller molecules can also be used.
Can be chemically modified to improve stability to divalent
cations.
eg. Copolymer of PHPA and amps
⏐
Amps = - CH2 - CH
⏐ 2
C-O
⏐
NH
CH3 - C⏐ - CH3
CH2 - SO3 - Na+

Polyacrylamide

-CH2 - CH - CH2 - CH - CH2 - CH- CH2 - CH

H2O = CH I I I I
I C =O C =O C=O C =O
C = 0 POLYMERIZATION I I I I
I REACTION
NH2 NH2 NH2 NH2
NH2
POLYACRYLAMIDE
ACRYLAMIDE
MONOMER

Relationship Between Molecular Weight and

Function of Polyacrylamide Polymers.

Function Molecular Weight

Deflocculant 7000

Fluid Loss Additive 600 000

600,000

Flocculant 3,000,000

Shale Inhibitor 10,000,000

Bentonite Extender 10,000,000

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 Shale Inhibition by Polymers
Glycols
– Low molecular weight (typically < 2000)
– Based on ethylene oxide : HO - (CH2 - CH2O)nH
– or Ethylene oxide / propylene oxide copolymers :
HO -(CH2 - CH2O)n (CH2CH2CH3O)mH
– Used in polymer muds at 3 - 6 %, usually with KCl
Cationics
– Often based on polyquaternary amines :
+ +
N CH3 N CH3
CH3 CH3
CH3 CH3

– Effective inhibitors but incompatible with most mud

polymers.
– High maintenance costs
– Toxic to some marine species

Other “Polymers”
Surfactants : Contain a hydrophilic (water-loving) and a hydrophobic
(water-hating) group .eg.,
O
+
HYDROCARBON CHAIN NH4
C00-
SO4 = ETC
HYDROPHOBIC PORTION HYRDOPHILIC PORTION

These molecules adsorb at interfaces & surfaces and are used as

corrosion inhibitors, emulsifiers, oil wetting agents, lubricants,
foamers, defoamers, dispersants, etc,
Lubricants
– Surfactants
– Oils
– Glycols

Common Mud Polymers

STRUCTURE AND PROPERTIES

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 Polysaccharides
H
Polysaccharides are the I CH2 OH
HO - - -C I
largest group of C C
I H
polymers used in H I
C C
drilling fluids. HO- I I
I OH
C-H
I
These include cellulose H
I
OH
derivatives starches,
derivatives, starches
bacterial 6 CH2OH
I
polysaccharides and 5C O
I
gums. H H H
I I
4C C1
OH H
The basic unit is glucose.
I I
HO I I
HO
C C
I I
H OH

Carboxymethyl Cellulose
(CMC)
A carboxy methyl group, (- CH2 COONa) is attached
to a carbon atom via ether linkage

CH2 OH H OH

o HO - - - I
o I
I
H H
HO O
I I I
I I
O I
I I I
CH2 O CH2 COO- Na+
H OH
1 4

CMC (cont)
There are potentially three reactive hydroxyl groups per ring. The
extent of the reaction is called the degree of substitution (D.S.).
This is normally 0.4 - 1.2 for CMC's used in drilling fluids. The
greater the D.S. the greater the tolerance for salt and hardness.
This product has been used extensively in drilling fluids due to it's
moderate cost and stability. It is rarely broken down by bacteria.
The NaCl byproduct is removed by washing to form a pure grade
CMC.
CMC
Technical grades are cheaper and are approximately 75 - 80% pure
CMC, the remainder is salt.
The degree of polymerisation (D.P.) ranges from 500 to 5 000 units.
The D.P. determines the thickening action of the CMC. eg. Low
D.P. = low viscosity.
In the manufacturing process the NaCl can be replaced with KCl. KCl
is much more desirable in the product than NaCl due to it's
inhibiting properties.

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 PAC
PAC's are essentially the same as CMC's except they have a
higher D.S.

The advantages of this are:

– The tolerance for hardness is much higher.

– Greater solubility in high chloride muds.

Once again these can be supplied in premium or technical

grade.

Hydroxyethyl Cellulose (HEC)

This polymer is similar to CMC only instead of substitution by carboxy
methyl groups there is substitution by hydroxyethyl groups. (CH2
CH2 OH)
The D.S. is normally 0.6 - 2.1. Very long polymer chains give high
viscosities.
HEC is non-ionic, it is water soluble because the hydroxyethyl groups
increase hydrogen bonding, which increases solubility. The polymer
exhibits shear thinning characteristics but does not exhibit any yield
stress or gellation properties.
properties CH CH OH 2 2

CH2 O
HEC is subject to bacterial CH OH
degradation
2

o CH2 CH2
CH2 CH2
o
CH2 H O

o HO - - - I O
o I
I
H
HO O
I
O I
I
OH OH
CH2 O
CH2 CH2

Starch
Starch is
present in
plants as a
form of food
storage

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 Starch
For the starch to exhibit fluid loss control the amylopectin outer
shell has to be ruptured in a process known as pre-
gelatinization, which releases the water-swellable amylose.
This is then further modified to decrease the viscosity and
crosslinked to increase temperature stability.
The properties may vary with the source of the crude starch eg.,
potato, corn or tapioca.
The colloidal water-swellable particles will seal pores in the filter
cake
A slight increase in viscosity may be noted with starch
additions
Starch is biodegradable; a biocide needs to be added when it is
used
Starch is effective in saline solutions

Xanthan Gum
Produced by single cell bacteria (Xanthomonas
campestris)

The gum is extracted, dried and milled. The final mud

polymer is usually referred to as XC Polymer

Molecular weight of XC is greater than 1 million

It forms viscous solutions that are highly shear-

thinning. This is due to rod-like structures that
physically interact at low shear rates. Additions of
XC increase yield point and gel strength

The polymer is not affected by salt or hardness

Xanthan Gum
Double coiled helix gives polymer rigid
rod structure

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 Guar Gum
Guar gum is a non-ionic (or slightly
anionic) natural polymer
It consists of long chains of alternating
galactose and mannose units.
Guar gum hydrates quickly in fresh to
saturated salt water. It is not affected
by multivalent cations at neutral pH’s
however is very susceptible to
b t i l attack.
bacterial tt k
High pH’s can destroy the viscosity. Guar
gum is normally used in top hole
drilling, either for viscous pills or as a
circulating system.
Guar gum can be crosslinked with borax
and, depending on the concentrations
of both materials, the resultant
viscosity increase will be anything from
slight to a rigid mass that has been
used to seal off lost circulation zones.

PHPA- Partially Hydrolysed Polyacrylamide

These polymers usually have a very high molecular
weight, in the region of 5-12 million.
They are generally hydrolyzed 15-35% to the
acrylate. They contain carboxyl and amide
groups
pH
H is
i best
b t kept
k t below
b l 9.5
95
– Not biodegradable
It is sometimes called “Copolymer of sodium
acrylate and acrylamide”

Trends in Polymers
Temperature stability

Guar gum Increasing

Starch Temperature
HEC,CMC,PAC Stability
XC polymer, crosslinked starch
Polyacrylates
The polymers usually break down at higher temperatures due to
oxidation (reaction with O2 )or hydrolysis, (reaction with H+ or OH-
OH-)

Anionic Strength
Increasing
XC polymer
Anionic
CMC
Strength
PAC
Increasing inhibition)
PHPA

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 Polymer Muds
Advantages
– Shear thinning, low viscosities at the bit
– Good hole cleaning
– Not subject to flocculation
– Decreased storage space and transport costs
– Can be used in saline muds
– Maximum horsepower at bit
– Can stabilize hydratable shales
– May be used for high densities
– Lower solids content
– Aids in solids control
– Decreased ECD reduces risk of formation fracture
– Relatively simple mud system

Polymer Muds
Disadvantages
– Bacterial degradation
– Temperature limitations
– Cost, especially if solids control
q p
equipment is poor
p
– Sensitive to divalent cations
– Corrosive, oxygen easily entrained
– Polymers can be depleted by adsorption
on drilled solids

Polymer Muds
Polymer muds may be made with just
polymers and weighting material, or
may also have some prehydrated
bentonite is added for the following
reasons:
– Achieving some viscosity and gel
strengths, this may be cheaper than
deriving all the viscosity from polymers
– Some bentonite in the system will
improve the fluid loss characteristics

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 Spud muds
Polymer spud muds can be mixed with 2 - 3 ppb guar
gum

This is run at neutral pH

The concentration is adjusted to achieve Funnel

Viscosities of 100 second plus

Polymer muds

– The choice of polymer depends on the level of

inhibition required, the chloride level and the
temperature requirements

Xanthan Gum Polymer Muds

In the following formulations the XC polymer can be replaced with 12-15 ppb
prehydrated gel
– Muds with chloride levels below 20 000 mg/l
• 1 -2 ppb XC polymer
• 1 -2 ppb CMC Hi Vis
• Weighting material as required
• Caustic
• Soda Ash
– Muds with chloride levels up to 50 000 mg/l chlorides
• 1 - 2 ppb
b XC polymer
l
• 1 ppb CMC
• 1 ppb PAC
• Weighting material as required
• Caustic
• Soda Ash
– Muds with chloride levels above 50 000 mg/l
• 1 - 2 ppb XC polymer
• 1 - 2 ppb PAC
• Weighting material as required

Starch in Polymer Muds

Starch has not been found to be very cost effective

– eg If the cost of PAC is 3 times that of a
starch, pilot test with 1 ppb PAC and 3 ppb
starch
At high chloride levels or to achieve very low fluid loss
rates, starch may become more cost effective.
Starch does not provide any inhibition

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 Engineering Polymer Muds
To increase viscosity
– Add XC, prehydrated gel or Hi Vis PAC’s, CMC’s and PHPA.
(Viscosity from PAC’s , CMC’s and PHPA may be short lived
due to removal with solids).
– Starch additions will also increase the viscosity slightly

To reduce viscosity:
– Reduce solids content by dumping mud and adding new
mud.
– Reduce solids with solids control equipment.
– If viscosity is due to flocculation (indicated by high YP’s, low
PV’s and high F/L) add a deflocculant e.g. CMC Lo vis or PAC
Lo vis.
– A dispersant can be added, but this should be avoided as it
may promote formation hydration. It maybe acceptable prior
to running the casing.

Improving Fluid Loss

Add PAC lo vis or CMC if viscosity is normal

Add PAC hi vis or CMC hi vis if viscosity is low.

Add starch if more cost effective than the above.

PHPA has a secondary fluid loss property. It also

should be added if increased inhibition is also
required.

Increasing inhibition
• The need for this can be indicated by sticky cuttings
and an increase in the low gravity solids.
• Increase anionic polymer concentration and /or use
polymers with higher anionic strength.
• Add other inhibitive polymers (e.g. glycols)
• Increase chloride concentration
• More potassium ions
• More calcium ions (in lime/gyp muds)
• Use K+ CMC
• Change pH

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 Solids
• Polymer requirements will increase considerably with
the volume of drilled solids. The smaller the size of
the solids, the greater the surface area, the greater
the polymer requirement.
• The low gravity solids content should be maintained
around 5% byy volume, with 6% as a maximum figure.
g
• At elevated temperatures polymers will degrade.
Check the fluid loss of bottoms up samples after trips.
This will be a good indication of whether polymer
degradation is taking place.

Bacterial degradation
• Evidence of bacterial degradation is:
– Odour, may start off being sweet but will eventually turn
bad
– An increase in the Mf may be seen.
• Treatments
– A biocide kill dose needs to be added to all systems
containing biodegradable products before they are
added.
– A daily maintenance biocide addition needs to be added
– If there is any evidence of biological activity, increase
the biocide additions. Increasing the pH and chloride
levels will also reduce bacterial attack.
– At every opportunity ensure all the sludge in the flow
lines and pits is cleaned out as this provides an ideal
environment for bacteria to grow.

Questions?

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