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

POLYMERS IN DRILLING FLUIDS 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 its 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.

POLYMERS IN DRILLING FLUIDS 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

POLYMERS IN DRILLING FLUIDS 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.

POLYMERS IN DRILLING FLUIDS Polymer Types

Monomer

Polymerisation Reaction

-X-X-X-X-X-X-XLinear Homopolymer

X-X-X

X-X-X-X-

X-X-X-X-

Branched Homopolymer

X+Y
Monomers

-X-Y-X-Y-X-Y-X-YAlternating Copolymer

-X-Y-Y-X-X-X-Y-XRandom Copolymer

-X-X-X-Y-Y-Y-X-X-XBlock Copolymer

POLYMERS IN DRILLING FLUIDS Polymer Types (cont)

Monomer

Polymerisation
Reaction

-X-X-X-X-X-X-XAdd monomer Y

-X-X-X-X-X-X-X

Branched Graft Copolymer

Monomer

-X-X-X-X-X-X-XAdd reactant (R)

-X-X-X-X-X-X-X

Functionalised/Derivatised Polymer

POLYMERS IN DRILLING FLUIDS The Molecular Weight (or Chain Length)

This can be varied : By limiting the number of terminating groups or chemically degrading longer chains.

Number of molecules

Narrow distribution

It is impossible to get all the chain lengths exactly the same. Hence there is a distribution of molecular weights.

Broad distribution

Molecular weight MW

POLYMERS IN DRILLING FLUIDS 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.

POLYMERS IN DRILLING FLUIDS Polymer Shape

The shape of the polymer will depend on :

Branching or cross linking of the polymer.
Branched

Linear

Crossed linked

POLYMERS IN DRILLING FLUIDS Polymer Shape (cont)

The concentration of the groups 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 groups will repel each other. Unchanged polymers do not have groups which repel each other and hence can form small coils in solution rather than extended chains
-ve -ve

Low substitution. Chain remains coiled.

-ve -ve -ve

High substitution. Like charges repel. Polymers uncoils.

POLYMERS IN DRILLING FLUIDS Polymer Shape (cont)

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:
neutral neutral -ve -ve

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

POLYMERS IN DRILLING FLUIDS Polymer Shape (cont)

The shape of the polymer will be affected by the ionic strength of the solution. Electrolytes will reduce the electrostatic repulsion between the charges.
Viscosity will increase when polymer chains are extended; i.e. in fresh water
-

Fresh Water
-

Salt Water

POLYMERS IN DRILLING FLUIDS Polymer Shape (cont) 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.
-

POLYMERS IN DRILLING FLUIDS 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)

POLYMERS IN DRILLING FLUIDS Viscosifying Polymers

high molecular weight

solution viscosity

low molecular weight

polymer concentration

POLYMERS IN DRILLING FLUIDS 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.

POLYMERS IN DRILLING FLUIDS

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.
Deflocculant Flocculated clay Flocculant

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

High M.W. polymer acting as bridge between particles

POLYMERS IN DRILLING FLUIDS 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

POLYMERS IN DRILLING FLUIDS Classification of Polymers

Microbial Polymers Xanthan Gum (XC Polymer) Synthetic Polymers Sulfonated styrene maleic anhydride copolymer Polyacrylates Polyacrylamides Partially hydrolyzed polyacrylamide (PHPA)

POLYMERS IN DRILLING FLUIDS 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 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

POLYMERS IN DRILLING FLUIDS

Viscosifiers

POLYMERS IN DRILLING FLUIDS 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

POLYMERS IN DRILLING FLUIDS

Guar Gum

POLYMERS IN DRILLING FLUIDS 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.

POLYMERS IN DRILLING FLUIDS 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).

POLYMERS IN DRILLING FLUIDS

Xanthan Gum

POLYMERS IN DRILLING FLUIDS 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 its a slime thats secreted by the bacteria. Following fermentation, the gum is recovered by precipitation in an alcohol, dried and milled.

POLYMERS IN DRILLING FLUIDS 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

POLYMERS IN DRILLING FLUIDS 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

POLYMERS IN DRILLING FLUIDS Properties and Use Xanthan is highly shear thinning. Its 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 135C

POLYMERS IN DRILLING FLUIDS Viscosity vs. Shear

XCD Polymer in seawater at 24C

Courtesy Kelco Inc.

POLYMERS IN DRILLING FLUIDS Filtration Control Polymers

POLYMERS IN DRILLING FLUIDS Filtration Controllers Cellulosics

Low viscosity carboxy methyl cellulose Poly anionic cellulose CMHEC

Starch and its 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.

POLYMERS IN DRILLING FLUIDS CMC

POLYMERS IN DRILLING FLUIDS 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.

POLYMERS IN DRILLING FLUIDS Degree of Substitution Defined as the average number of the three hydroxyl groups in the anhydroglucose unit which have been reacted 1

POLYMERS IN DRILLING FLUIDS DS = 1

The structure opposite depicts a sodium CMC where the degree of substitution is 1. Most CMCs have a DS of 0.7 to 0.8. CMCs with at degree of sunstitution of 1 are called poly anionic cellulose. PAC.

POLYMERS IN DRILLING FLUIDS 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 CMCs 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.

POLYMERS IN DRILLING FLUIDS 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 PACs can viscosify to the same degree as xanthans, but they do not exhibit the same suspension characteristics. The ultra low viscosity PACs can act as thinners. Temperature stabe to 125C.

POLYMERS IN DRILLING FLUIDS

Starch

POLYMERS IN DRILLING FLUIDS 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.

POLYMERS IN DRILLING FLUIDS Condensation Polymer

Starch is a natural molecule formed in a variety of plants. It can be considered a condensation polymer of glucose

POLYMERS IN DRILLING FLUIDS 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.

POLYMERS IN DRILLING FLUIDS Electron Micrographs - Starch Granules

Potato Corn

Tapioca

Wheat

POLYMERS IN DRILLING FLUIDS Product

The produced polymer is non-ionic, of relatively low molecular weight. Used in hard and saline solutions. Thermal limit is circa 110C. Cross-linking can extend the thermal limit to 140C. 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.

POLYMERS IN DRILLING FLUIDS Modified Starches

Carboxy methylation is one of the ways in which starch is modified. Can equal technical grade CMCs (60%) in its 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.

POLYMERS IN DRILLING FLUIDS

Other Polymers

POLYMERS IN DRILLING FLUIDS 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 C=O CH2-CH C=O
x

NH2

O- K+ or Na+

Hydrolysed Polyacrylamide

POLYMERS IN DRILLING FLUIDS Ion Exchange - Limit Hydration

Na+ Na+ Na+

Na+ Na + + Na

KCl

+ Na + Na

K+ K+ K+ K+

K+

+ Na + Na + Na

K+

POLYMERS IN DRILLING FLUIDS Polymer Encapsulation (PHPA)

Hydrated Shale

Long chain polymer

POLYMERS IN DRILLING FLUIDS Hydration and Uncoiling of ENCAPSUL-8 Polymer

H2O TIME

H2O TIME

POLYMERS IN DRILLING FLUIDS Polymer Encapsulating Shale

POLYMERS

SHALE

POLYMERS IN DRILLING FLUIDS ENCAPSUL-8 Polymer - Encapsulating Shale

Na+

+
+ + K

+
Na+

+
+ +

+
Na+

+
+ +

+
Na+

ENCAPSUL-8 Polymer

POLYMERS IN DRILLING FLUIDS ENCAPSUL-8 Adhered to Shale Cutting

Fresh Water

Sea Water

Maintain Ca++ below 300 mg/l

POLYMERS IN DRILLING FLUIDS Shale Control Additives

Cationic Polyamines PACs Polyhydroxy Compounds Glycols

POLYMERS IN DRILLING FLUIDS Thinners and Deflocculants

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

POLYMERS IN DRILLING FLUIDS 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.