POLYMER CHEMISTRY

AND
POLYMER MUDS
Polymers in Drilling Fluids
z 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
A Range of Polymers Are Used in Drilling Fluids
z Natural Polymers :
„ Xanthan Gum
„ Guar Gum
„ Whelan Gum
„ Starch
z Modified Natural Polymers :
„ Carboxymethyl Cellulose (CMC)
„ Polyanionic Cellulose (PAC)
„ Hydroxyethyl Cellulose (HEC)
„ Lignosulphonates
z Synthetic Polymers :
„ Polyacrylamides
„ Polyacrylates
„ Glycols
Polymers
z Polymers are molecules made up from smaller chemically
identifiable units (Monomers).

z 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.

Polymer Types
X Polymerisation
-X-X-X-X-X-X-X-
Monomer Reaction 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 Polymerisation -X-X-X-X-X-X-X-
Add monomer Y
Monomer Reaction

-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)
z This can be varied :

„ By limiting the number

of terminating groups or
chemically degrading

Number of molecules
longer chains. Narrow
distribution

z It is impossible to get all the

chain lengths exactly the Broad
same. Hence there is a distribution

distribution of molecular
weights. Molecular weight
MW
Reactive Groups
z 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

z The shape of the polymer will

depend on :
„ Branching or cross linking of
the polymer.
Branched ( Starch )

Linear ( PAC )

Crossed linked ( ex- XC )

 Polymer Shape (cont)
z The concentration of the groups -ve -ve
on 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 Low substitution.
groups will repel each other. Chain remains coiled.

-ve -ve -ve

z Unchanged polymers do not have
groups which repel each other
and hence can form small coils in
solution rather than extended
chains
High substitution.
Like charges repel.
Polymers uncoils.
Polymer Shape (cont)
z 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:

neutral neutral -ve -ve

acid

base

z Optimum solubility of anionic polymers is normally seen between

pH 8 and 9.5. Higher pH can degrade some polymers or cause
partial dehydration
Polymer Shape (cont)
z The shape of the polymer - - -
will be affected by the
ionic strength of the
solution. Electrolytes will
reduce the electrostatic
repulsion between the Fresh Water
charges.
- - -
z Viscosity will increase
when polymer chains are
extended; i.e. in fresh
water
Salt Water
Polymer Shape (cont)
z 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.
-

-
Relationship between function and structure

F u n c t io n M a in C h a r a c t e r is t ic s
V is c o s it y H ig h m o le c u la r w e ig h t.
V is c o s it y & G e lla t io n H ig h m o le c u la r w e ig h t a n d h ig h ly
b r a n c h e d s tr u c tu r e o r c r o s s
lin k in g a g e n t.
V is c o s it y in s a lt s o lu t io 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
ty p e .
D e f lo c c u la t io n , d is p e r s io n , o r L o w m o le c u la r w e ig h t n e g a tiv e ly
t h in n in g a c t io n c h a r g e d a t a lk a lin e p H le v e 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 r g e d g r o u p s to a d s o r b o n to
c la y s .
S u rfa c ta n t H yd r o p h o b ic g r o u p a n d
h yd r o p h ilic g r o u p o n s a m e
m o le c u le .
F lu id lo s s a d d it iv e F o r m c o llo id a l p a r tic le s .
Viscosifying Polymers
z 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
z 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.

z Deflocculants are negatively charged low molecular weight

polymers.

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

and exhibit a flocculating action.
 Flocculants
z Flocculants are long chain polymers that are able to bridge
particles together.

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

overall particle size bigger, and thus easier to remove.
Deflocculant Flocculated clay Flocculant

High
M.W.
polymer
Adsorption of low acting as
M.W. polymer bridge
creates overall between
negative charges particles
Fluid Loss Control by Polymers
z Some polymers (eg. Lignosulphonates, Lignins, low viscosity
CMC / PAC, Polyacrylate) deflocculate drill solids to form a
thinner, less permeable filter cake.

z Starch forms colloidal particles which fill voids in filter cake,

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

z Polymers viscosify liquid phase, making passage through

filter cake more difficult (often minor / negligible effect)
Shale Inhibition by Polymers-
Polyacrylamides
• High molecular weight polymers such as partially hydroysed
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 - CH2
C - O
NH


CH3 - C - CH3

CH2 - SO3 - Na+

 Polyacrylamide

H2O = CH -CH2 - CH - CH2 - CH - CH2 - CH- CH2 - CH

I I I I I
POLYMERIZATION
C=0 C =O C =O C=O C =O
REACTION I I I I
I
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

Flocculant 3,000,000

Shale Inhibitor 10,000,000

Bentonite Extender 10,000,000

Shale Inhibition by Polymers
(cont)
z 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
z 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”
z Surfactants : Contain a hydrophilic (water-loving) and a
hydrophobic (water-hating) group .eg.,

HYDROCARBON CHAIN + NH4

C00-
SO4 = ETC
HYDROPHOBIC PORTION
HYRDOPHILIC PORTION

z These molecules adsorb at interfaces & surfaces and are

used as corrosion inhibitors, emulsifiers, oil wetting
agents, lubricants, foamers, defoamers, dispersants, etc,
z Lubricants
„ Surfactants
„ Oils
„ Glygols
Common Mud Polymers

STRUCTURE AND PROPERTIES

Polysaccharides
H
I CH2 OH
HO - - -C I
z Polysaccharides are the C C
H
largest group of polymers I
I
H
used in drilling fluids. C C
HO- I I
I OH
z These include cellulose I
C-H
I
derivatives, starches, H OH
bacterial polysaccharides
6 CH2OH
and gums. I
5C O
z The basic unit is glucose. H H
I
H
I I
4C C1
I OH H I
HO I I HO
C C
I I
H OH
Carboxymethyl Cellulose (CMC)
z A carboxy methyl group, (- CH2 COONa) is attached to a
carbon atom via ether linkage

CH2 OH H OH

o HO - - -
o I
I
I
H H
HO O
I I I
I I
O I
I I I
CH2 O CH2COO- Na+
H OH
1 4
 CMC (cont)
z 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.
z This product has been used extensively in drilling fluids due to it's
moderate cost and stability. It is rarely broken down by bacteria.
z The NaCl byproduct is removed by washing to form a pure grade CMC.
z Technical grades are cheaper and are approximately 75 - 80% pure
CMC, the remainder is salt.
z 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.
z 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.
PAC
z PAC's are essentially the same as CMC's except they have
a higher D.S.

z The advantages of this are:

„ The tolerance for hardness is much higher.

„ Greater solubility in high chloride muds.

z Once again these can be supplied in premium or technical

grade.
 Hydroxyethyl Cellulose (HEC)
z This polymer is similar to CMC only instead of substitution by carboxy methyl
groups there is substitution by hydroxyethyl groups. (CH2 CH2 OH)
z The D.S. is normally 0.6 - 2.1. Very long polymer chains give high viscosities.
z 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.
z HEC is subject to bacterial degradation
CH2 CH2 OH

CH2 CH2 OH O
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
z Starch is present in
plants as a form of
food storage
Starch
z 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.
z The properties may vary with the source of the crude starch eg.,
potato, corn or tapioca.
z The colloidal water-swellable particles will seal pores in the filler cake
z A slight increase in viscosity may be noted with starch additions
z Starch is biodegradable; a biocide needs to be added when it is used
z Starch is effective in saline solutions
 Xanthan Gum

z Produced by single cell bacteria (Xanthomonas campestris)

z The gum is extracted, dried and milled. The final mud polymer is usually
referred to as XC Polymer

z Molecular weight of XC is greater than 1 million

z 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

z The polymer is not affected by salt or hardness and is not subject to

bacterial degradation
 Xanthan Gum

• Double coiled helix gives polymer rigid rod structure

Guar Gum
z Guar gum is a non-ionic (or slightly anionic)
natural polymer
z It consists of long chains of alternating
galactose and mannose units.
z 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 bacterial attack.
z 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.
z 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

z These polymers usually have a very high molecular weight,

in the region of 5-12 million.
z They are generally hydrolyzed 15-35% to the acrylate.
They contain carboxyl and amide groups
z pH is best kept below 9.5
„ Not biodegradable

z It is sometimes called “Copolymer of sodium acrylate and

acrylamide”
Trends in Polymers
z 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-)

z Anionic Strength
XC polymer Increasing
CMC Anionic
PAC Strength
PHPA Increasing inhibition)
Polymer Muds
z 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 horesepower 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
z Disadvantages
„ Bacterial degradation
„ Temperature limitations
„ Cost, especially if solids control equipment is poor
„ Sensitive to divalent cations
„ Corrosive, oxygen easily entrained
„ Polymers can be depleted by adsorption on drilled solids
Polymer Muds
z 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
Spud muds
z Polymer spud muds can be mixed with 2 - 3 ppb guar gum

z This is run at neutral pH

z The concentration is adjusted to achieve Funnel

Viscosities of 100 second plus

z Polymer muds
„ The choice of polymer depends on the level of inhibition
required, the chloride level and the temperature requirements
Xanthan Gum Polymer Muds
z 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 XC polymer
– 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

z 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

z At high chloride levels or to achieve very low fluid loss rates,

starch may become more cost effective.
z Starch does not provide any inhibition
Engineering Polymer Muds
z 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

z 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

z Add PAC lo vis or CMC if viscosity is normal

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

z Add starch if more cost effective than the above.

z PHPA has a secondary fluid loss property. It also should be

added if increased inhibition is also required.
Increasing inhibition
z The need for this can be indicated by sticky cuttings and
an increase in the low gravity solids.
z Increase anionic polymer concentration and /or use
polymers with higher anionic strength.
z Add other inhibitive polymers (e.g. glycols)
z Increase chloride concentration
z More potassium ions
z More calcium ions (in lime/gyp muds)
z Use K+ CMC
z Change pH
Solids
z 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.
z The low gravity solids content should be maintained
around 5% by volume, with 6% as a maximum figure.
z 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
z Evidence of bacterial degradation is:
„ Odour, may start off being sweet but will eventually turn bad
„ An increase in the Mf may be seen.
z 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.