1431 Union Avenue + Bakersfeld, CA 93305 » Telephone (661) 325-5919 1-800-GETSGEO + FAX (651) 325.5648 « E-Mail 0d com Drilling Fluids, Inc. CLAY MINERALS WHY STUDY CLAYS Clay is a mineral, (cither rock or soil), that becomes “plastic” when wet. This property is the result of the small particle size and the plate like nature of the particles. Most clays become sticky and slippery when wetted but only a few clays actually swell to the same degree as Wyo- ming Bentonite (Gel). Almost all drilling fluids contain some clays. In the mud business clays are an essential ingredi- ent in almost all drilling fluids yet they are also one of the most common contaminants, Exces- sive amounts of clay cause problems with rheology and density. This situation is very prolific in California, Clays are found in most drilling locations in the oil and gas fields in California, Shales resplen- dent with clays make up the majority of the formations drilled. Understanding the nature of clays is an important part of controlling drilling mud characteristics and anticipating problems ‘The addition of clay is the primary method of increasing viscosity in many drilling fluids. The graph in Figure 1, below, illustrates how efficient Viscosity vs Concentration of Wyoming Bentonite Wyoming Bentonite (GEO Gel) is at raising 4g9 viscosity. 15 ] 120 | Shale and clay in their many forms are also the primary source of unde- ible changes to vis- cosity/theology. You can see from the graph (Figure 1) that at concen- a zm trations above 30 ppb ee eee ete oy ae ee) each additional unit of ppb Bentonite clay causes a much lar- ger change than the pre- +P —=- 10 mim Gel Strength vious unit. The addition of polymers, thinners, and dispersants can extend the point at which visco increases drama cally, but there comes a point in any water based mud system where every additional ppb of clay causes a significant increase in Yield Point and Gel Strengths. 100 80 60 40 20 YPIGels In addition, filtration control in drilling fluids is usually based on the use of Bentonite with the addition of other products to enhance fluid loss properties. By itself, Bentonite provides sub- www.geodt.com 1-800-GETS GEOGEO Drilling Fluids, Inc. CLAY MINERALS stantial fluid loss control in a mud system. The American Petroleum Institute (API) requires that ‘API Bentonite mixed at 22.5 ppb and aged for 24 hours have a filtrate loss less than or equal to 15.0 ml. The thin, pliable clay platelets are ideally suited to form a semi-permeable barrier to water. However, Bentonite is easily disturbed by contamination of the water with calcium, chloride, or hydroxyl ions, The addition of polymer filtration control products reduces the ef fects of these contaminants and provides broader particle size distribution in the filter cake which aids in filtration control. PARTICLE SIZE Geologists use the term “clay” to describe an alumina silicate mineral with a particle size of four microns ' (um) or less. In general, clays are classified as mineral particles 2 pm or smaller. Particles larger than 4 jum are considered to be silt, larger than 74 jum are considered sand. The internal dimensions of the actual clay particles in Bentonite are measured in Angstroms’, on the order of 10° meters. All clays contain 5%-50% non-clay materials, usually larger than 2 wm. Shale, a metamorphic claystone, is harder and more laminated than clay. There is a continuous grading from shale to clay. These fine grained materials, sometimes referred to as “argillaceous” can have the size of clays but lack the laminated structure. WHERE DO CLAYS COME FROM Clay is also a classification for rocks. It is characte -d by its ability to become plas- flexible when wet. The technical ion of clays involves the molecular structure. A material that has loosely bonded layers which are only molecules 4 ( thick is generally classified as a clay.| eating Wind aly $0 Tsao: showy Some clays absorb a great deal of water "Study Area*S=z—" Shaie Geposition and can produce higher viscosity, others. re merely become flexible. All clays tend to break down to very small particles when immersed in water, especially under high shear conditions. Approximate Extent ot A Clay Spur Ash ition CANADA ay Spi depositions = 2y, CANADA 77 "Micron, symbol = um In the metric system a unit of length equal to one millionth (10°) of a meter. Also called a micrometer. ym ~ 0.00!mm. 1 inch = 23,400 4m ? Angstrom, symbol = Electromagnetic radiation travels in waves. Scientists use the length of the wave (the distance between peaks) 10 define the energy of the radiation. Astronomers measure this length in "angstroms," a unit of measure equal to 1 Inundred-millionth of a centimeter. It's convenient shorthand to avoid writing lots of zeroes when talking about the wavelengths of light. In everyday terms, a sheet of paper is approximately 1,000,000 angstroms thick. Visible light Covers the range from 4,000 to 8,000 angstroms. One micron is equal to 10,000 X. PAGE 2 www.geodt.com 1-800-GETS GEOGEO Drilling Fluids, Inc. CLAY MINERALS. Drilling muds generally use Wyoming Bentonite if itis available because it meets the spe cations set by the American Petroleum Institute (API). These “Wyoming” Bentonite deposits spread across several states and are formed from massive voleanic ash falls. During the Creta- ‘ceous period, 135 to 65 million years ago, there were nearly continuous eruptions of ash from a string of volcanoes in the area that is now Idaho. East of these volcanoes covering what is now Montana, Wyoming and North and South Dakota there was a large inland sea. The prevailing winds blew the ash into the sea where it was under the unique conditions needed to developed into nearly pure Sodium Montmorillonite Other types of clay are formed by the weathering of granite into decomposed granite which is easily broken into smaller and smaller particles. Granite contains primarily Quartz, Mica and Feldspar. The quartz particles remain unchanged and only get smaller, producing most of the sand we find. However, Feldspar and Mica degrade into very small particles that are subject to molecular changes when exposed to various chemicals found in the water that washes through them. With extended exposure to this water and chemicals they will eventually form clays such as kaolin. Classification of the clay minerals * I. Amorphous Allophane group IL Crystalline ‘A. Two-layer type (sheet structures composed of units of one layer of silica tetra- hedrons and one layer of alumina octahedrons) 1. Equidimensional Kaolinite group Kaolinite, nacrite, etc. 2. Elongate Halloysite group B. Three-layer types (sheet structures composed of two layers of sil group Montmorillonite, sauconite, etc. Vermiculite Elongate Montmorillonite group Nontronite, saponite, hectorite 2. Nonexpanding lattice Illite group C Regular mixed-layer types (ordered stacking of alternate layers of different types) Chlorite group D. Chain-structure types (hornblende-like chains of silica tetrahedrons linked together by octahedral groups of oxygens and hydroxyls containing Al and Mg atoms) Attapulgite Sepiolite Palygorskite * From “Clay Mineralogy, Second Edition,” p. 32. PAGES wow. geodt.com 1-800-GETS GEOGEO Drilling Fluids, Inc. CLAY MINERALS Clays can also be formed from the weathering products of sedimentary rocks, igneous rocks or even through hydrothermal re THE FAMILY OF CLAY MINERALS Amorphous clays are in a group called Allo- phanes. The makeup of these clays is silica Fal termixed with crystalline material. The Allo- P| phane clays have little or no discernable Cation Exchange Capacity (CEC) measures the exchangeable cations. Anions also can be exchanged but they are not as well und stood. The size of various cations deter- Bee mines how readily they are exchanged and ie % cite 5 PM how tightly it is held once replaced, Figure ow wi A 11. The larger the non-hydrated size of the FIGURE 3 |cation the more easily it drives out the exist- ing cation. In addition, the smaller the hy- drated size of the ion is the more strongly it holds onto its position in the clay matrix. The tetra- hedral sheets form a series of holes which perfectly match the Potassium ion size such that once it has replaced Sodium or Calcium it is very hard to displace it. This helps explain the impor- tance of K’ in the long term inhibition of clays. es Kaolinite, Figure 3, has a two layered erys- talline structure bonded by hydrogen. The clay is non-swelling due to its tight bonds © 6 and resistance to substitution within the lat- tice structure, The CEC ranges from 3-15] OCTAHEDRAL GROUP _ TETRAHEDRAL GROUP milliequivalents (meq)/100 gram. See ure 10 for CEC of other clays. FIGURE 4 The Smeetites are layered crystalline clays with an expanding lattice which makes them highly susceptible to swelling. The group includes Aliettite, Beidellite, Hectorite, Montmorillonite, Nontronite, Saponite, Sauconite, Stevensite, Swinefordite, Volkonskoite, Yakhontovite, and Zinesilite. All these clays are very fine grained, no large crystals are known to exist. They have a small layer charge allowing exchange of interlayer cations. The weak bonding between layers allows water to form a spacing between the molecules of 10A to 18A. Bentonite is a generic name given to a rock type, not a mineral classification like Illite or Kao- linite. It is usually a distinetive bed formed by the deposition and alteration of voleanic ash. Typically, Bentonite is composed of Montmorillonite but may also contain other minerals in- cluding other types of clay. PAGE 4 www. geodt.com 1-800-GETS GEOGEO Drilling Fluids, Inc. CLAY MINERALS Montmorillonite has oxygen bonding which makes for weak attraction and substantial cleavage between layers. It is a 2:1 clay, meaning that it has two tetrahedral sheets sandwiching a central octahedral sheet (see Figure 4). The average diameter of a single platelet is approximately 1 ium. The particle thickness is extremely small, about one nanometer (1/1000 4m). Chemically Montmorillonite is hydrated Sodium Calcium Aluminum Magnesium Silicate Hy- droxide (Na,Ca),(Al,Mg)x(SisQo(OH)2"nl,0. Its many uses include performing as a soil addi- tive to hold water in drought prone soils, in the construction of earthen dams and levees, to pre~ vent the leakage of fluids from ponds, as a component of foundry sand, and as a desiccant to remove moisture from air and gases. It is the major constituent in non-explosive agents for splitting rock in natural stone quarries in order to limit the amount of waste and for the demoli- tion of conerete structures where the use of explosive charges is unacceptable. It also has been used in cosmetics and has reputed therapeutic effects having been used for medicinal purposes by the ancient Egyptia Water and other polar molecules can enter between the layers causing expansion, It is extremely active due to the exchangeable cations between layers. Volume changes of 1400 to 2000 per- cent are reported from laboratory tests in which samples of dry Sodium Montmorillonite were immersed in water, and changes of 45 to 145 percent are reported for Calcium Montmorillonite. The CEC for Montmorillonite ranges from 80-150 meq/100 grams. Nonexpanding lattice clays have a similar structure to the expanding lattice but due to the varia- tions in the atoms included in the matrix the behavior is greatly altered. The Illite group include micas. The crystalline structure is identical to Montmorillonite except some silicon is always replaced by Aluminum. Kaolinite can be converted to Illite by the addition of Potassium, PL Z Vy LZ PAGE 5 www.geodt.com 1-800-GETS GEOGEO Drilling Fluids, Inc. CLAY MINERALS The activity of Illite is due to the missing silicon in the matrix which results in a negative charge between layers. Potassium ions are attracted to the negative charge. The size fit is almost perfect for K” ions and once they are in place it is very hard to remove them. Ifillitic clay ma- terial is subjected to acidie water the Potassium ion may be replaced by Magnesium. This would cause some limited swelling in the otherwise non-swelling clay. The illitic minerals ‘would then be referred to as Degraded Illites. The CEC ranges from 10 meq/100 grams to about 40 meq/100 grams, still a fairly low level of activity. Illites can be a source of increased vis ity but to a much lesser extent than Montmorillonite. It can cause formation damage by swelling and thus the potassiu ;portant in completion fluids for zones with Illite in the sand matrix. Mixed layer clays show stacking of alternate layers of different types of clays. The vertical stacking can be regular (ordered), segregated regular, or random. Chlorite is essentially non- swelling in nature. There is no precise construction of the lattice but it always has the same gen- eral framework. The basic structure of chlorites consists of negatively charged mica-like (2:1) layers regularly alternating with positively charged brucite-like (octahedral) sheets. The CEC can range from 10-40 meq/100 gram. Chain structure clays include Attapulgite, Figure 5, Sepiolite, Figure 6, and Palygoskite. They are all non-swelling and require substantial shear to generate viscosity. The chains are com- posed of only tetrahedrons, forming a material similar to the silica sheets of Smectite but only 11.5 A thick. The range of CEC is only 3-15 meq/100 gram. ‘THE STRUCTURE OF MONTMORILLONITE The structure of clay minerals ranges from very organized to totally disorganized. Because the particles are so smal and their arrangement being slightly irregular it is very difficult to arrive at a clear picture of their structure. Two different molecular structures are presented at the end of this paper (Figures 9 and Figure 10). The basic components shown in Figure 4 are octahedral groups (blue) and tetrahedral groups (red). These are arranged in sheets that are repeated in (wo directions many times over. The fundamental structure has two tetrahedral sheets sandwiching an octahedral sheet (see Fig- ure 7). Between the octahedral sheet and one of the tetrahedral sheets there is very strong bond- ing. This remains in tact. Between the Octahedral sheet and the other tetrahedral sheet the bond- ing is very weak, using a layer of cations (Calcium, Sodium or Potassium) as a link to hold the faces together. Potassium holds the particles close together as seen in the chart, Calcium does a fair job of holding the particles together while Sodium does a poor job. Water is adsorbed (drawn into the gap between the layers) in_varying amounts, depending on the cation. This de- termines what we observe as swelling. With Sodium, the water absorbed can be so great that there is no longer any attraction between the layers. ‘The bonding of the particles within a clay body is the result of the following forces: The attraction of the mass of one particle for another (the force of gravity). Overlapping molecular forces. Cation attraction pulling two platelets together. Water molecules, 1-3 molecules thick, attracting the 2 platelets to one another. vvvv PAGE6 www. geodf com 1-800-GETS GEOGEO Drilling Fluids, Inc. CLAY MINERALS FFetrahedral Sheet THREE IDEALIZED PLATELETS Cation Sites lOctahedral Sheet Cation Sites Tetrahedral Sheet [Cation Sites [Feeansiee fa Cation Sites [Octahedral Sheet Cation Sites Tetrahedral Sheet Cation Sites Frerahedral Sheet cation Sites octahedral Sheet cation Sites retrahedral Sheet Clays with the same chemical constituents may have very different properties and clays with identical properties may have very different chemical constituents. It all depends on how the atoms are arranged. That’s why a scanning electron microscope is needed to determine the types of clays in a sample. PLATELET CHARGE ‘The positive charge sites correspond to the OH sites on the next two pages. Cations, Na+, C: or K+ are found in this interlayer region and can be exchanged for each other. The proclivity to exchange varies with the size of the hydrated ion (Figure 9), the concentration of ions in the electrolyte (the water), and the type of clay. The negative sites correspond to Oxygen atoms at the edges of the platelet. As you can see on the next two pages those Oxygen atoms that are in the middle of the structure have bonds to 6 other atoms while the ones on the edge have only 3 bonds. This deficiency, leads to a net negative charge at the edges. PAGE T www. geod. com 1-800-GETS GEOGEO Drilling Fluids, Inc. CLAY MINERALS. Platelet continues in this direction Platelet continues in this direction |Tetrahedral Platelet continues in this direction Aluminum, Iron, Magnesium, Oeveens, vdroxyls , @ STRUCTURE OF SME‘ E (Montmorillonite / Bentonite) THEORY 1 PAGES www.geodt.com 1-800-GETS GEOGEO Drilling Fluids, Inc. CLAY MINERALS, Platelet continues in this direction PLATELET Platelet continues in this direction ——— in this direction STRUCTURE OF SMECTITE. FIGURE 9 (Montmorillonite / Bentonite) THEORY II PAGE 9 www. geodf. com 1-800-GETS GEOGEO Drilling Fluids, Inc. CLAY MINERALS, Range of Activity based on CEC Kaolinite 3-15 [Palygorskite 3-15 [Chlorite 10-40) ‘Smectite 80-150) odes Montoro Aitapulgie 315 | Halloyste 0 510 [ite T049 clues ‘Sepiolite 3-15 Halloysite 4H:0 40-50 Vermiculite 100-150) Common cations and their radii in angstroms, A, lonic ra Ton Not Hydrated ‘Aluminum: 0.68 Lithium O73 ‘Magnesium 0.84 ‘Sodium 0.98 ‘Ammonium 1.43 Calcium 1.12 Potassium 4.33 Mass Action Chart If cations are present in equal 1. Hydrogen Hw ‘5. Magnesium Mg" mounts they will preferentially react in this order. = os 2. Barium Ba 6. Sodium Nav Different clays will react somewhat | 3. Serium SF 7, Potassium K differently The cation that is most abundant has|4.Caleium | ~ Ca’ ® Lithium! ‘a chance to react first. PAGE 10 www.geodf.com 1-800-GETS GEOGEO Drilling Fluids, Inc. List of Figures Viscosity vs Concentration Graph Bentonite Formation Map... Kaolinite Electron Micrograph Octahedral & Tetrahedral Groups. Attapulgite Electron Micrograph Platelets Graphic... a Structure of Smectite, Theory Structure of Smectite, Theory II CEC Activity of Clays Radius of Common Cations Mass Action Chart... REFERENCES www.geodt.com CLAY MINERALS About.com, About, Inc., A part of The New York Times Company, hitp://composite.about.com/ library/glossary/v/bldef-v5956.htm, 2006. Gershteins, Sergey & Anna, hitp://www.convert-me.com/en/convert/length, Copyright 1996-2005. Grim, Ralph E., “Clay Mineralogy, Second Edition”, McGraw-Hill Book Company, New York, ‘Theng, B. K. T., “Formation and Properties of Clay Polymer Complexes”, Elsevier Scientific Pub- lishing Company, New York, 1979. 1-800-GETS GEO