Polymer y Chemistry y

Polymer Chemistry

Introduction A polymer is a large molecule composed of a relatively small molecules called monomers bonded together. The molecular weight of polymers range from a few thousand to several million molecular weight g units. Polymers can have thousands of repeating units. The lower molecular weight polymers serve as deflocculants; whereas the high molecular weight molecules serve as viscosifiers whereas, and flocculants.

Polymer Chemistry

Clay polymer interactions: Depends on a number of factors: Molecular weight A high molecular weight material, such as a synthetic polyacrylate will have a chain length g larger g the clay yp particles. It is possible for one molecule to adsorb onto more than one particles then acts as flocculants. Low molecular weight can alter the charge on individual clay particules, then are defloccumlated.

Polymer Chemistry

Adsorption onto the clay Generally, negatively charged polymers can adsorb on cationic sites generated on the edges. Most polymer used in drilling fluids tends to of this type.

Polymer Chemistry

Charges on Polymer Molecules Drilling fluid polymers may carry electrostatic charges. The behavior of solvated polymers is dependant on their ionic character. Drilling fluid polymers may be categorized as: Nonionic, Anionic, Cationic Drilling fluid polymers are usually anionic or nonionic since cationic polymers tend to flocculate clays. clays The solubility of these poly- electrolytes will be affected by the chemical makeup of the drilling fluid, pH, salts and presence of divalent cations, etc.

Polymer Chemistry

Polymer Types Each type of polymer has its own characteristics in terms of how it functions in a particular type of drilling fluid. Polyacrylate, Polyacrylamide, and PHPA (Synthetic) These polymers are referred to as PHPA, (partially hydrolyzed polyacrylamide), and are used as clay extenders, flocculants, and encapsulating colloids.

Polymer Chemistry

Cellulose Derivatives The cellulose molecule is modified by reacting with an acid, then an oxidizing group, and then, an anionic radical is attached to the existing i ti h d hydroxyl l group. Carboxymethylcellulose y y (CMC) ( ) Low viscosity types are used to lower fluid loss in fresh water, bentonite-based systems, and in saline conditions up to saturation. The molecule may exhibit deflocculation effects especially in flocculated systems, as it has a low molecular size and increases the net negative charge on the clay particles. More tolerance to salts and cation contamination.

Polymer Chemistry

High

viscosity

types

are

used

to

develop

shear

thinning

characteristics in water-based fluids. Thermal degradation of CMC begins to accelerate rapidly at

t temperatures t above b 140 C. C The anionic CMC molecules are susceptible p to form insoluble complexes with polyvalent cations such as calcium or aluminum. CMC can be used in lime-based systems if the calcium level is reduced to below 500 mg/l. The high viscosity grades of PAC posses inhibitive properties when used in sufficiently high concentrations, due to the adsorption of the polymer on the solids.

Polymer Chemistry

Polyanionic Cellulose (PAC) The PAC materials generally are more expensive than CMC due to higher processing costs, but show a greater tolerance to hardness and d chlorides. hl id PAC begins b i t thermally to th ll degrade d d at t 250F. 250F Hydroxyethylcellulose y y y (HEC) ( ) It is non-ionic so its dimensions do not change in the presence of electrolytes, making it relatively stable in most moderate, basic environments. HEC has a tendency to foam when mixing. HEC imparts high viscosity to water or brines but exhibits no gel strengths. It is susceptible to degradation through shear or heat and has a maximum thermal stability of about 225F.

Polymer Chemistry

Starch Starches used in the drilling industry are primarily derived from corn and other cereals, potatoes and tapioca. Th starches The t h are pre-gelatinized l ti i d in i order d t permit to it them th t readily to dil hydrate. Starches are used mainly for fluid loss control and are viable in a large range of fluid systems, such as seawater, saturated saltwater, KCl muds and lime muds. Starches are thermally stable to about 250F. Starches are not resistant to bacteria and require a biocide to retard fermentation, except in saturated salt and high pH muds.

Polymer Chemistry

Guar Gum Guar Gum is a natural, essentially non-ionic polymer that has an excellent application as a viscofier for spud-in fluids and as a viscosifier in waters ranging from fresh to saturated salt (NaCl). Guar is derived from the seed of the guar plant. plant

Hi h levels High l l of f hardness h d and d alkalinity lk li it will ill slow l or even eliminate li i t the th hydration process and can cause a significant decrease in viscosity. Guar has a maximum thermal stability of about 200F and a biocide is necessary to retard fermentation. Guars have greater application to workover/completion operations.

Polymer Chemistry

Xanthan Gum Xanthan Gum (XC polymer), is an anionic, water-soluble

polysaccharide biopolymer and classified as a natural polymer. It has been used as a viscofier and suspending agent in fresh or saltwater solutions. The polymer also functions as a fluid loss control agent in that its molecular size contributes to a filter cake plugging effect. Xanthan Gum has desirable properties for workover and completion applications, begins to degrade thermally at temperatures of about 225 F. 225F. Xanthan Gum is the only polymer that provides thixotropy.

Polymer Chemistry

Polymer Uses Viscosity Bentonite Extension Deflocculation D fl l ti Filtration Control Shale Stabilization Surfactant Viscosity These are high molecular weight polymers, usually branched, and water soluble. Vi Viscosity it is i due d t interactions to i t ti b t between: (1) polymer l molecules l l and d water, (2) polymers themselves, and (3) polymers and solids.

Polymer Chemistry

Bentonite Extension The bentonite extenders work by cross-linking bentonite particles to increase the physical interaction between particles. These polymers are termed extenders. They improve the suspension and carrying y g abilities of a g gel system y without the further addition of solid particles.

Polymer Chemistry

Flocculation Flocculants are high molecular weight, long chain, anionic molecules which bridge between individual solids causing them to form an aggregate. t Polymers y flocculate solid p particles by y linking g them into large g agglomerates. If the mass of linked particles becomes great enough, gravity causes them to drop out of suspension.

Polymer Chemistry

Deflocculation These products are always anionic and of low molecular weight. Anionic polymers act as deflocculant by absorbing onto the positive edge sites of clay plates and neutralizing positives charges and creating g an overall negative g charge. g

They are adsorbed; causing the plates to behave as through they were completely anionic. These polymers are sensitive to divalent cations and are less effective when hardness exceeds about 400 mg/l.

Polymer Chemistry

Filtration Control Starches, CMCs, PACs, and hydrolyzed polyacrylates are effective filtration control agents. Filtration control may be provided by: A deflocculated filter cake, will pack down to form a thinner, more impermeable filter cake such as low viscosity CMC or lignosulfonate. Anionic polymers control filtration by viscosifying the water phase to restrict fluid flow through the filter cake. cake Polymers, which contribute to this effect, are in the high molecular weight category such Guar and Xanthan Gum, HEC, and high highviscosity Cellulose polymers.

Polymer Chemistry

Colloidal particles that can compress and deform to plug the pore in the filter cake. For this process to occur, the polymer must not be completely soluble such h the th starch, t h some asphalt h lt derivatives d i ti and d lignin li i derivatives. d i ti

Polymer Chemistry

Anionic polymers promote the dissociation or deflocculation of suspended solids. The anionic charge density and molecular weight of the polymer di t t its dictates it effectiveness ff ti as a deflocculant. d fl l t Lignosulfonates, g , low molecular weight g Cellulose derivatives, , and Polyacrylates are the most effective.

Polymer Chemistry

Shale Stabilization The term shale stabilization usually refers to a mechanism which retards the water adsorption and the subsequent swelling clays. Shale stabilization is provided through polymer attachment to the positively p y charged g sites on the edge g of clay yp particles in shales. This attachment minimizes water invasion into the clay particle and reduces hydration and dispersion. These polymers have been used with success in conjunction with salt and potassium-based muds for added inhibition.

Polymer Chemistry

Theories suggests that: Hydrogen bonding occurs between the polymer and the water-wet surface of the clay. Possible to stablish covalent bonds between the polymer molecule and the q quartz matrix typical yp of most clay y formations.

Polymer Chemistry

Surfactants They are sometimes called surface-active agents. Th They usually ll lowering l i th tension the t i at t the th point i t of f contact t t between b t two immiscible fluids or between the fluid and solids. The polar group is soluble in water, and is termed hydrophilic, water loving. loving The other end is non-polar and seeks non-polar substances, hydrophobic or water hating group.

Polymer Chemistry

Summary of Relationship Between Function of a Polymer in a Drilling Fluid and its General Structure

Polymer Chemistry

Types and funnctions of polymers in drilling fluids

Polymer Chemistry

Types and functions of polymers in drilling fluids