GB2462389A - Drill bit seal including nanotubes - Google Patents

Abstract

A bit for drilling subterranean formations that includes a bit body 10; a bearing surface; a cutting structure mounted on the bit body. Also present is a bearing surface, and an annular seal 33 for retaining a grease between the bearing surfaces The annular seal 33 includes a flexible and resilient seal body formed from an elastomer composition, wherein the elastomer composition comprises an elastomer material, a curing agent, and 10% or less by volume functionalized nanotubes. Various compositions for the elastomer are claimed.

Description

USE OF NANO SIZED PARTICULATES AND FIBERS IN ELASTOMER

SEALS FOR IMPROVED PERFORMANCE METRICS FOR ROLLER

CONE BITS

CROSS-REFERENCE TO RELATED APPLICATIONS

[0001] This application, pursuant to 35 U.S.C. � 119(e), claims priority to U.S. Patent Application No. 60/954,272, filed on August 6, 2007, which is herein incorporated by reference in its entirety.

BACKGROUND OF INVENTION

Field of the Invention

[0002] Embodiments disclosed herein relate generally to the use of composite materials in seals for cutting tools. More particularly, embodiments disclosed herein relate to the incorporation of nanosized particulates and fibers into elastomer seals for improved wear resistance, thereby enhancing the performance and service life of the roller cone bit.

Background Art

100031 Drill bits are commonly used in, for example, the oil and gas exploration industry for drilling wells in earth formations. One type of drill bit commonly used in the industry is the roller cone drill bit. Roller cone drill bits generally comprise a bit body connected to a drill string or bottom hole assembly (BHA). Roller cone drill bits typically include a plurality of roller cones rotatably attached to the bit body. The roller cones are generally mounted on steel journals integral with the bit body at its lower end. The roller cones further comprise a plurality of cutting elements disposed on each of the plurality of roller cones. The cutting elements may comprise, for example, inserts (formed from, for example, polycrystalline diamond, boron nitride, and the like) and/or milled steel teeth that are coated with appropriate hardfacing materials.

0004J When drilling an earth formation, the roller cone drill bit is rotated in a welibore, and each roller cone contacts the bottom of the wellbore being drilled and subsequently rotates with respect to the drill bit body. Drilling generally continues until, for example, a bit change is required because of a change in formation type is encountered in the welibore or because the drill bit is worn and/or damaged. High temperatures, high pressures, tough, abrasive formations, and other factors all contribute to drill bit wear and failure.

10005] When a drill bit wears out or fails as the weilbore is being drilled, it is necessary to remove the BHA from the well so that the drill bit may be replaced. The amount of time required to make a bit replacement trip produces downtime in drilling operations.

The amount of downtime may be significant, for example, when tripping in and out of relatively deep wells. Downtime may be add to the cost of completing a well and is a particular problem in offshore operations where costs are significantly higher. It is therefore desirable to maximize the service life of a drill bit in order to avoid rig downtime.

[00061 One reason for the failure of a roller cone drill bit is the wear that occurs on the journal bearings that support the roller cones. The journal bearings may be friction-type or roller-type bearings, and are subjected to high loads, high pressures, high temperatures, and exposure to abrasive particles originating from the formation being drilled. The journal bearings are typically lubricated with grease adapted to withstand tough drilling environments. Thus, such lubricants are an important element in the life of a drill bit.

[0007] Lubricants are retained by a journal bearing seal, which is typically an 0-ring type seal, typically located in a seal groove formed on an interior surface of a roller cone. The seal generally includes a static seal surface adapted to form a static seal with the interior surface of the roller cone and a dynamic seal surface adapted to form a dynamic seal with the journal upon which the roller cone is rotatably mounted. The seal must endure a range of temperature and pressure conditions during the operation of the drill bit to prevent lubricants from escaping andlor contaminants from entering the journal bearing.

Elastomer seals known in the art are conventionally formed from a single type of rubber or elastomer material, and are generally formed having identically configured dynamic and static seal surfaces with a generally regular cross section.

[0008] The rubber or elastomer material selected to form the seal for the journal bearings has particular hardness, modulus of elasticity, wear resistance, temperature stability, and coefficient of friction, among other properties. Additionally, the particular geometric configuration of the seal surfaces produces a selected amount of seal deflection that defines the degree of contact pressure or "squeeze" applied by the dynamic and static seal surfaces against respective journal bearing and roller cone surfaces.

[0009] The wear, temperature, and contact pressures encountered at the dynamic seal surface are different than those encountered at the static seal surface. Therefore, the type of seal material and seal geometry that is ultimately selected to form both seal surfaces represents a compromise between satisfying the operating conditions that occur at the different dynamic and static seal surfaces.

[0010] Conventional seals formed from a single-type of material, having symmetric axial cross-sectional geometries, may have reduced wear resistance and temperature stability at the dynamic seal surface where wear and temperature conditions are generally more severe than at the static seal surface. Therefore, the service life of drill bits that contain such seals may be limited by the service life of the journal bearing seal. It is desirable to produce a seal that is capable of withstanding the harsh downhole conditions, such as high pressures and temperatures. Accordingly, there exists a need for a tough, long-lasting seal, and drill bits containing such seals.

SUMMARY OF INVENTION

[0011] In one aspect, embodiments disclosed herein relate to a bit for drilling subterranean formations that includes a bit body including a bearing surface; a cutting structure mounted on the bit body, and including a bearing surface, and an annular seal for retaining a grease between the bearing surfaces, the annular seal comprising a flexible and resilient seal body formed from an elastomer composition, wherein the elastomer composition comprises an elastomer material, a curing agent, and 10% or less by volume of a nanomaterial additive selected from one of nanotubes and clustered nanodiamonds.

100121 In another aspect, embodiments disclosed herein relate to a rock bit for drilling subterranean formations that includes a bit body including at least one journal pin, each having a bearing surface; a roller cone mounted on the at least one journal pin and including a bearing surface; an annular seal for retaining a grease between the bearing surfaces, the annular seal comprising a flexible and resilient seal body formed from an elastomer composition, wherein the elastomer composition comprises: 100 parts by weight of highly saturated nitrile elastomer; furnace black in the range of up to 70 parts by weight; peroxide curing agent in the range of from 7 to 10 parts by weight; zinc oxide in the range of from 4 to 7 parts by weight; stearic acid in the range of from 0.5 to 2 parts by weight; nanomaterial additives selected from one of nanotubes and clustered nanodiamonds in the range of up to 10 percent by volume, and sufficient plasticizer to provide a Shore Hardness of no more than A 80.

[0013] Other aspects and advantages of the invention will be apparent from the following

description and the appended claims.

BRIEF DESCRIPTION OF DRAWINGS

[0014] FIG. I is a semi-schematic perspective of a drill bit according to one embodiment of the present invention.

100151 FIG. 2 is a partial cross-section of the drill bit according FIG. 1.

DETAILED DESCRIPTION

[0016] In one aspect, embodiments disclosed herein relate to elastomer seals used in components of downhole cutting tools, including drill bits, core bits, etc. In particular, embodiments disclosed herein relate to seals reinforced with nanomaterials.

100171 In addition, embodiments of the present disclosure provide rock bits comprising seals which are reinforced by nanornaterials, Such a reinforced seal may have enhanced bulk properties such as tensile modulus, elastic modulus, hardness, and such like, as compared with the native seal, while maintaining wear and erosion resistance.

Embodiments of the present disclosure are based, in part, on the determination that the life of a seal is directly related to the service life of the rock bit.

I0018 It is therefore desirable to provide a consistently reliable seal for maintaining the lubricant within a rock bit, where the seal has a long useful life, is resistant to oil well chemical compositions, has high heat resistance, and is highly resistant to abrasion.

100191 Referring to FIG. I, a drill bit in accordance with an embodiment of the invention is shown. In this embodiment, as shown in FIG. 1, a drill bit 5 comprises a body 10 having three roller cones 11 mounted on its lower end. A threaded pin 12 is at the upper end of the body 10 for assembly of the drill bit 5 onto a drill string (not shown separately) for drilling oil wells or the like. A plurality of cutting elenients 13 are pressed into holes in the surfaces of the roller cones 11 for bearing on the rock formation being drilled.

Nozzles 15 in the bit body 10 introduce drilling mud into the space around the roller cones 11 for cooling and carrying away formation chips drilled by the drill bit 5. While reference is made to an insert-type bit, the scope of the present invention should not be limited by any particular cutting structure. Embodiments of the present invention generally apply to any rock bit (whether roller cone, disc, etc.) that requires an elastomer seal to retain grease.

(00201 FIG. 2 shows a part of a longitudinal cross section of the drill bit 5 of FIG. 1, extending radially from the rotational axis 14 of the rock bit through one of the three legs on which the roller cones 11 are mounted. Each leg includes a journal 16 extending downwardly and radially inwardly on the rock bit body 10. The journal 16 includes a cylindrical bearing surface having a hard metal insert 17 on a lower portion of the journal 16.

[0021] Each roller cone 11 is in the form of a hollow, frustoconical steel body having cutting elements 13 pressed into holes on the external surface. For long life, the cutting elements 13 may be tungsten carbide inserts tipped with a polycrystalline diamond layer.

Such tungsten carbide inserts provide the drilling action by engaging a subterranean rock formation as the rock bit is rotated. Some types of bits have hard-faced steel teeth milled on the outside of the cone instead of carbide inserts.

100221 The cavity in the cone 11 contains a cylindrical bearing surface including a copper nickel tin insert 21 deposited in a groove in the steel of the cone 11 or as a floating insert in a groove in the cone 11. The alloy insert 21 in the cone 11 engages the hard metal insert 17 on the leg and provides the main bearing surface for the cone 11 on the bit body 10. A nose button 22 is between the end of the cavity in the cone 11 and the nose 19 and carries the principal thrust loads of the cone 11 on the journal 16. A bushing 23 surrounds the nose and provides additional bearing surface between the cone 11 and journal 16. Other types of bits, particularly for higher rotational speed applications, may have roller bearings instead of the exemplary journal bearings illustrated herein.

100231 A plurality of bearing balls 24 are fitted into complementary ball races in the cone 11 and on the journal 16. These balls 24 are inserted through a ball passage 26, which extends through the journal 16 between the bearing races and the exterior of the drill bit 5. A cone 11 is first fitted on the journal 16, and then the bearing balls 24 are inserted through the ball passage. The balls 24 carry any thrust loads tending to remove the cone 11 from the journal 16 and thereby retain the cone 11 on the journal 16. The balls 24 are retained in the races by a ball retainer 27 inserted through the ball passage 26 after the balls are in place. A plug 28 is then welded into the end of the ball passage to keep the ball retainer in place.

100241 The bearing surfaces between the journal 16 and cone 11 are lubricated by a lubricant or grease composition. Preferably, the interior of the drill bit is evacuated, and lubricant or grease is introduced through a fill passage (not shown separately). The lubricant or grease thus fills the regions adjacent the bearing surfaces plus various passages and a grease reservoir. The grease reservoir comprises a cavity 29 in the bit body 10, which is connected to the ball passage 26 by a lubricant passage 31. Lubricant or grease also fills the portion of the ball passage 26 adjacent the ball retainer, the open groove 18 on the upper side of the journal 16, and a diagonally extending passage 32 therebetween. Lubricant or grease is retained in the bearing structure by a resilient and flexible seal 33 between the cone 11 and journal 16.

100251 A pressure compensation subassembly is included in the grease reservoir 29. This subassembly comprises a metal cup 34 with an opening 36 at its inner end. A flexible rubber bellows 37 extends into the cup 34 from its outer end. The bellows 37 is held in place by a cap 38 with a vent passage 39. The pressure compensation subassembly is held in the grease reservoir by a snap ring 41.

[0026] When the drill bit is filled with lubricant or grease, the bearings, the groove 18 on the journal 16, passages in the journal 16, the lubrication passage 31, and the grease reservoir on the outside of the bellows 37 are filled with lubricant or grease. If the volume of lubricant or grease expands due to heating, for example, the bellows 37 is compressed to provide additional volume in the sealed grease system, thereby preventing accumulation of excessive pressures. High pressure in the grease system may be damage the seal 33 and permit abrasive drilling mud or the like to enter the bearings. Conversely, if the grease volume should contract, the bellows 37 may be expand to prevent low pressures in the sealed grease systems, which could cause flow of abrasive and/or corrosive substances past the seal 33.

100271 To maintain the desired properties of the seal at the harsh pressure and temperature conditions prevalent in a rock bit, to inhibit undesired pumping of lubricant through the seal, and to promote a long and useful life, it is desirable that the seal be chemically and physically resistant to chemical compositions found downhole, have a high heat and abrasion resistance, have a low rubbing friction, and not be readily deformed under the pressure and temperature conditions found in a well. Therefore, for certain applications it is desirable that the seal have a modulus of elasticity at 100% elongation from 800 to 1275 psi, a minimum tensile strength of 2300 psi, elongation from to 300 percent, die C tear strength of at least 25Olbs/inch, durometer hardness Shore A in the range from 75 to 85, and a compression set after 70 hours at 100°C of less than about 1 8% and preferably about 16%.

100281 A variety of seals have been employed in such rock bits. These seals usually are made of synthetic rubbers, Other components in the seal are usually curing agents, other additives such as plasticizers, fillers, coagents, accelerators, retardants, aritioxidants and lubricants. Seals of the type found in embodiments of the present disclosure further comprise nanomaterial additives.

100291 Polymers and Elastomer Materials 100301 Seals typically used in rock bits are usually made of acrylonitrile polymers or acrylonitrile/butadiene copolymers. However, these synthetic rubbers typically exhibit poor heat resistance and become brittle at elevated temperatures after extended periods of time. Additionally, these rubbers often exhibit undesirably low tensile strength and high coefficients of friction. Such properties are undesirable in a seal to be used in a rock bit, because the high operating temperatures of the bit may be result in failure of the seal.

100311 Preferred seals may be be formed from elastomer compositions such as fluoroelastomers, carboxylated nitriles, highly saturated nitrile (HSN) elastomers, nitrile-butadiene rubbers, highly saturated nitrile-butadiene rubbers (HNBR), fluorocarbons, ethylene-propylenes, si licones, chioroprenes, neopreries, fluorosi licones, polyurethanes, perfluoroelastomers, polyacrylates, copolymers of tetrafluoroethylene and propylene, ethylene-acrylic rubbers, chlorosulfonyl polyethylene rubbers, epichiorohydrin polymers, styrene butadiene polymers, and mixtures or copolymers thereof.

100321 HSM elastomer seals are disclosed in U.S. Patent No. 5,323,863, which is assigned to the same assignee as the present disclosure and is hereby incorporated by reference. An exemplary elastomer composition may comprise per 100 parts by weight of elastonier (e.g. HSN, HNI3R, etc.), furnace black in the range of from 40 to 70 parts by weight, peroxide curing agent in the range of from 7 to 10 parts by weight, graphite in the range from 10 to 20 parts by weight, zinc oxide or magnesium oxide in the range of from 4 to 7 parts by weight, stearic acid in the range from 0.5 to 2 parts by weight, and plasticizer up to about 10 parts by weight.

[0033J In elastomer materials, the tensile modulus of the elastomer, its tear strength, and its hardness are positively correlated. As such, when the hardness of the elastomer is increased, one normally finds that the tear strength and tensile modulus similarly increase. Hardness is therefore a convenient method to compare elastomer compositions.

100341 The hardness of an elastomer material is defined as the material's ability to withstand indentation. Durometer is typically used as a measure of hardness for polymers, elastomers, and rubbers, and is described in U.S. Patent No. 1,770,045 issued to A.F. Shore. Commonly called the Shore hardness, durometer is measured using the ASTM D2240-00 testing standard. There are a total of 12 scales, depending on the intended use: types A, B, C, D, DO, E, M, 0, 00, 000, 000-S, and R. The A scale is usually reserved for softer plastics, while the D scale is for harder ones. Each scale results in a value between 0 and 100, with higher values indicating a harder material. For a rock bit seal, it is desirable that the durorneter hardness is in the range of from about 75 to 85 on the Shore A scale. A hardness of 85 or higher may result in premature failure of the seal.

[0035] Curing Agents [0036] Curing refers the thickening or hardening of a polymer material, which is also called vulcanization when the polymer is rubber. Curing agents are agents or substances added to a polymer composition to promote or control the curing reaction, either catalytically or as a reactant, such as cross-linkers, heat, electron beam, UV radiation, or chemical catalysts.

100371 In some embodiments, the catalyst may include organometallic catalysts such as organic complexes of Sn, Ti, Pt, Pb, Sb, Zn, or Rh, inorganic oxides such as manganese (IV) oxide, calcium peroxide, or lead dioxide, and combinations thereof, metal oxide salts such as sodium perborates and other borate compounds, or organic peroxides such as cumene hydroperoxide. In a particular embodiment, the organometallic catalyst may be dibutyltin dilaurate, a titanate / zinc acetate material, tin octoate, a carboxylic salt of Pb, Zn, Zr, or Sb, and combinations thereof.

(0038] The catalyst may be present in an amount effective to catalyze the curing of the liquid elastomer composition. In various embodiments, the catalyst may be used in an amount ranging from about 0.01 to about 10 weight percent, based on the total weight of the elastomer(s), from about 0.05 to about 5 weight percent in other embodiments, and from about 0.10 to about 2 weight percent in yet other embodiments.

100391 In general, the crosslinker may be any nucleophilic or electrophilic group that may react with the reactive groups available in the elastonier composition. In a further embodiment, the crosslinking agent may comprise a polyfunctional molecule with more than one reactive group. Such reactive groups may include for example, amines, alcohols, phenols, thiols, carbanions, orgaiiofunctional silanes, and carboxylates.

100401 Other Additives 100411 Additives are widely used in elastomer compositions to tailor the physical properties of the resultant elastomer composition. In some embodiments, additives may include accelerators and retardants, plasticizers, thermal and light stabilizers, flame-retardants, fillers, adhesion promoters, or rheological additives.

100421 Accelerators and retardants may optionally be used to control the cure time of the liquid elastomer. For example, an accelerator may be used to shorten the cure time while a retardant may be used to prolong the cure time. In some embodiments, the accelerator may include an amine, a sulfonamide, or a disulfide, and the retardant may include a stearate, an organic carbamate and salts thereot a lactone, or a stearic acid.

100431 Addition of plasticizers may reduce the modulus of the polymer at the use temperature by lowering its Tg. This may allow control of the viscosity and mechanical properties of the elastomer seal. In some embodiments, the plasticizer may include phthalates, epoxides, aliphatic diesters, phosphates, sulfonamides, glycols, polyethers, trimellitates or chlorinated paraffin. In some embodiments, the plasticizer may be a diisooctyl phthalate, epoxidized soybean oil, di-2-ethylhexyl adipate, tricresyl phosphate, or trioctyl trimellitate.

100441 Fillers are usually inert materials which may reinforce the elastomer seal or serve as an extender. Fillers therefore affect elastomer processing, storage, and curing. Fillers may also affect the properties of the elastomer such as electrical and heat insulting properties, modulus, tensile or tear strength, abrasion resistance and fatigue strength. In some embodiments, the fillers may include carbonates, metal oxides, clays, silicas, mica, metal sulfates, metal chromates, or carbon black. In some embodiments, the filler may include titanium dioxide, calcium carbonate, non-acidic clays, or fumed silica.

[00451 Addition of adhesion promoters may improve adhesion to various substrates. In some embodiments, adhesion promoters may include epoxy resins, modified phenolic resins, modified hydrocarbon resins, polysiloxanes, silanes, or primers.

100461 Addition of rheological additives may control the flow behavior of the compound.

In some embodiments, rheological additives may include fine particle size fillers, organic agents, or combinations of both. In some embodiments, rheological additives may include precipitated calcium carbonates, non-acidic clays, fumed silicas, or modified castor oils.

100471 Nanomaterial Additives 100481 Nanomaterials possess dimensions on the order of a billionth of a meter. In a particular embodiment, the nanomaterial additive may have dimensions ranging from about 0.1 to 100 nanometers. In another embodiment, the nanomaterial may have dimensions ranging from 0.5 to 50 nanometers. In yet another embodiment, the nanomaterial may have dimensions ranging from about 1.0 to 10 nanometers.

100491 Nanomaterials typically have a very high aspect ratio, that is, the ratio of length to diameter. in a particular embodiment, the nanomaterials used in the present disclosure may have an aspect ratio ranging from about 1.0 to 1,000,000. In one embodiment, the nanomaterial may have an aspect ratio ranging from 1.0 to 300. In yet another embodiment, the nanomaterial may have an aspect ratio ranging from 3.0 to 100.

100501 In particular embodiments, the at least one nanomaterial additive may be selected from at least one of nanoclays, carbon nanotubes, functionalized nanotubes, inorganic nanotubes, clustered nanodiamonds, fullerenes, other inorganic nanomaterial additives, and mixtures thereof. Nanornaterial additives may be added to elastorner composition disclosed herein in an amount greater than about 0.1, 0.2, 0.3, 0.5, 1, and 2 volume percent in some embodiments, and less than 10, 5, 4, 2, and I volume percent in other embodiments.

j0051 I Nanoctays 100521 The nanoclay raw material may be rnontmorillonite (magnesium aluminum silicate) or bentonite (aluminum phyllosilicate), a 2-to-! layered smectite clay mineral with a platy or tubular structure. Individual plate thickness of nanoclays may be just one nanometer, but the surface dimensions may generally range from about 300 to more than 600 nanometers, resulting in an unusually high aspect ratio. Naturally occurring montmorillonite is hydrophilic. Since polymers are generally organophilic, unmodified nanoclays disperse in polymers with great difficulty. Through clay surface modification, montmorillonite may be made organophilic and, therefore, compatible with conventional organic polymers.

100531 A number of chemistries may be conventionally applied to modify the surfaces of nanoclays. For example, in the traditional "onuim ion" modification, a clay-chemical complex is formed using an intercalant (surface treatment) containing an ammonium or phosphoniuni functional group. These groups modify the nanoclay surface by lonically bonding to it, thereby converting the surface from a hydrophilic to an organophilic species.

100541 Other means for modification involve leaving the sodium ion on the surface and coordinating it via ion-dipole interaction. Regardless of the modification technology used, the resulting clay-chemical complex, which exhibits a definite gallery spacing between the plates, may be easily dispersed in a polymer matrix to form a nanocomposite material.

10055] In some embodiments, nanoclays are dispersed into the elastonier composition of the seal body, generally at less than 5wt% levels. When a nanoclay is substantially dispersed within the polymer it is said to be exfoliated. Exfoliation is facilitated by surface modification chemistries described above, which through ionic interactions, separate the nanoclay plates to the point where individual plates may be be further separated from another by mechanical shear or heat of polymerization. Nanocomposites may be created using both thermoplastic and thermoset polymers, and the specific surface modification chemistries designed and employed are necessarily a function of the host polymer's unique chemical and physical characteristics. In some cases, the final nanocomposite will be prepared in the reactor during the polymerization stage. For other polymer systems, processes may be used to incorporate nanoclays into a hot-melt compounding operation.

100561 In general, nanocomposites exhibit gains in barrier, flame resistance, structural, and thermal properties yet without significant loss in hardness or clarity. Because of the nanometer-sized dimensions of the individual plates in one direction, exfoliated nanoclays are transparent in most polymer systems. However, with surface dimensions extending to 1 micron, the tightly bound structure in a polymer matrix is impermeable to gases and liquids, and offers superior barrier properties over the native polymer. Such nanocomposites may also exhibit enhanced heat resistive properties.

10057] Nanoclays are commercially available as Nanorner� nanoclays from Nanocor�, Cloisite� additives from Southern Clay Products, Nanoliri from FCC Inc., Halloysite from Nanoclay Technologies.

100581 Fullerenes and Nanotubes 100591 Fullerenes are a family of carbon allotropes named after Richard Buckminster Fuller and are sometimes called buckyballs. They are closed cages molecules composed entirely of sp2-hybridized carbons and may be iii the form of a hollow sphere, ellipsoid, or tube. Cylindrical fullerenes are called carbon nanotubes or buckytubes. Fullerenes are similar in structure to graphite, which is composed of a sheet of linked hexagonal rings, but they contain pentagonal (or sometimes heptagonal) rings that prevent the sheet from being planar. Fullerenes may be produced by carbon arc methods of condensation of vaporized carbon.

100601 As used herein, the term "nanotube" refers to various materials having having a cylindrical or tubular configuration with at least one dimension, such as length or diameter, between I and 100 nanometers. Types of nanotubes that may find use as a reinforcing nanotubes material in the present disclosure may include carbon nanotubes (CNTs), including single-walled (SWNT), double-walled (DWNT), multi-walled (MWNT), inorganic nanotubes, mul tibranched nanotubes, functionalized nanotubes, and CNT-C0 hybrids. Additionally, in some embodiments, at least a portion of the surface of the reinforcing nanotubes may be modified.

100611 Carbon nanotubes are polymers of pure carbon, which may be functionalized or otherwise modified. Both SWNTs and MWNTs are known in the art and the subject of a considerable body of published literature, Examples of literature on the subject are Dresselhaus, M. S., et al., Science of Fullerenes and Carbon Nanotubes, Academic Press, San Diego (1996), and Ajayan, P. M., et al., "Nanometre-Size Tubes of Carbon," Rep.

Prog. Phys. 60 (1997): 1025-1062. The structure of a single-wall carbon nanotube may be described as a single graphene sheet rolled into a seamless cylinder whose ends are either open or closed. When closed, the ends are capped by either half fullerenes or more complex structures including pentagons.

100621 Nanotubes frequently exist as "ropes," or bundles of 10 to 100 nanotubes held together along their length by van der Waals forces, with individual nanotubes branching off and joining nanotubes of other "ropes." Multi-walled carbon nanotubes are multiple concentric cylinders of graphene sheets. The cylinders are of successively larger diameter to fit one inside another, forming a layered composite tube bonded together by van der Waals forces, with a typical distance of approximately 0.34 nm between layers, as reported by Peigney, A., et al., "Carbon nanotubes in novel ceramic matrix nanocomposites," Ceram. Inter. 26 (2000) 677-683.

100631 Carbon nanotubes are commonly prepared by arc discharge between carbon electrodes in an inert gas atmosphere. The product is generally a mixture of single-wall and multi-wall nanotubes, although the formation of single-wall nanotubes can be favored by the use of transition metal catalysts such as iron or cobalt. The electric arc method, as well as other methods for the synthesis of carbon nanotubes is described in, for example, "Nanometre-Size Tubes of Carbon," P.M. Ajayan and T.W. Ebbesen, Rep.

Prog. Phys., 60, 1025-1062 (1997).

100641 Inorganic nanotubes may include those prepared from a range of materials including boron nitride, silicon nitride, silicon carbide, dichalcogenides, for example, WS2, oxides such as Hf02 and MoO3, metallic nanotubes, such as Co and Au, and materials having a composition BXCYNZ, where x, y, and z may be independently selected from 0 to 4, including for example, BC2N2 and BC4N, and combinations thereof.

100651 In a particular embodiment, the average diameter of the nanotube materials may range from about I to 100 nanometers. In various other embodiments, the reinforcing phase may include SWNTs having an average diameter of about Ito 2 nanometers and/or MWNTs having an average diameter of about 2 to 30 nanometers. Nanotube materials typically have a very high aspect ratio. In a particular embodiment, the nanotubes used in the present disclosure may have an aspect ratio ranging from about 25 to 1,000,000, and preferably from about 100 to about 1,000.

100661 The surface of the carbon nanotubes of fullerene may, in one embodiment, be modified prior to incorporation into the composites of the present disclosure. In some embodiments, the nanostructured carbon material is modified by a chemical means to yield derivatized nanostructured carbon material. As used herein, derivatization" refers to the attachment of other chemical entities to the nanostructured carbon material, which may be by chemical or physical means including, but not limited to, covalent bonding, van der Waals forces, electrostatic forces, physical entanglement, and combinations thereof In other embodiments, the nanostructured carbon material is modified by a physical means selected from the group consisting of plasma treatment, heat treatment, ion bombardment, attrition by impact, milling and combinations thereof. In yet other embodiments, the nanostructured carbon material is modified by a chemical means selected from the group consisting of chemical etching by acids either in liquid or gaseous form, chemical etching by bases either in liquid or gaseous form, electrochemical treatments, and combinations thereof.

100671 One of ordinary skill in the art would appreciate that derivatization or functionalization may be desired so as to increase ease in solubilization and/or disperson of the nanotubes into at least one of the component phases prior to formation of a composite material. Functionalization or derivatization may occur by the incorporation of various chemical moieties on either end caps andlor sidewalls (either exterior or interior) of the nanostructured carbon material, or with a coating placed thereon.

100681 For example, functionalization may occur through covalent and/or non-covalent functionalization, endcap and/or sidewall functionalization, exohedral and/or endohedral functionalization and supramolecular complexation. A variety of functionalized nanostructured carbon materials have been developed so as to enable dispersion of the nanostructures into composite materials, including fluoronanotubes, carboxy-nanotubes, and various covalently bonded nanotubes, including amino-CNTs, vinyl-CNTs, epoxy-CNTs. Oxidation of nanostructured carbon materials may result in carboxyl, hydroxyl, or carbonyl groups, which may be further modified via amidation or etherification, for example. Additionally, functionalization frequently occurs through an initial fluorination, and then subsequent nucleophilic attack, or via a free radical reaction to form a covalent carbon-carbon bond. Further, U.S. Patent Nos. 7,122,165, 7,105,596, 7,048,999, 6,875,412, 6,835,366, 6790,425, 2005/0255030, which are all herein incorporated by reference in their entirety, disclose various sidewall and endcap functionalizations that may, for example, be used to assist in integration of nanostructured carbon materials in an elastomer seal of the present disclosure.

Nanostructured carbon materials may be added to elastomer seals disclosed herein in an amount greater than about 0.1, 0.2, 0.5, 1, and 2 volume percent in some embodiments, and less than 10, 5, 4, 2, and I volume percent in other embodiments.

[0069J Other analogous nanostructures of similar geometry as described above are further contemplated for use in elastomer seals of the present disclosure, For example, the boron analogs of fullerenes recently described by researchers at Rice University, Houston, Texas fall within the spectrum of nanomaterial additives contemplated as a nanomaterial additive to the elastomer seal.

100701 Nanodiamonds 100711 In particular embodiments, the at least one nanomaterial additive may include diamond particles or diamond-like particles. One suitable method for generating iianodiamonds may include, for example, a detonation process as described in Diamond and Related Materials (1993, 160-2), which is incorporated by reference in its entirety, although nanodiamonds produced by other methods may be used. Those having ordinary skill in the art will appreciate how to form nanodiamond particles. Briefly, in order to produce nanodiamond by detonation, detonation of mixed high explosives in the presence of ultradispersed carbon condensate forms ultradispersive diamond-graphite powder (diamond blend or DB), which is a black powder containing 40-60 weight percent of pure diamond. Chemical purification of DB generates pure nanodiamond (ultradispersive detonational diamond or UDD), a grey powder containing up to 99.5 weight percent of pure diamond. The ultrafine diamond particles generated by the detonation process may coniprise a nanodiamond core, a graphite inner coating around the core, and an amorphous carbon outer coating about the graphite. Both the graphite coating and amorphous carbon coating may be optionally removed by chemical etching. In some embodiments, the nanodiamond particles may be clustered in loose agglomerates ranging in size from nanoscale to larger than nanoscale. Diamond or diamond-like particles may be added to elastomer seals disclosed herein in an amount greater than about 0.1, 0.2, 0.5 volume percent in some embodiments, and less than 10, 5, 2, and I volume percent in other embodiments.

100721 In particular embodiments, the nanomaterial additive may include at least one of an inorganic nanomaterial, such as a metal oxide nanoparticle. One suitable method for generating metal oxide nanoparticles is by using plasma synthesis, although metal oxide nanoparticles produced by other methods may be used. Those having ordinary skill in the art will appreciate how to form metal oxide nanoparticles. Metal oxide nanoparticles may comprise oxides of zinc, iron, titanium, magnesium, silicon, aluminium, cerium, zirconium, mixed metal compounds or mixtures thereof. Further, other nanoparticles such as nanopowders, inorganic nanoparticles such as calcium carbonate, nanofibers, and a mixture of nanomaterials can be used in elastomer seals of the present disclosure.

100731 Integration of the nanomaterial additive into the elastomer seal niay include any means as known to those skilled in the art. As used herein, integration refers to any means for adding the nanomaterial additive to a component of the elastomer seal such that the nanomaterial additive is a component of the formed elastomer seal, i.e., by exfoliation, hot-melting, plastic extrusion, or other forms of incorporation of the nanomaterial additive as known to those skilled in the art. In some embodiments, the nanomaterial additives may be integrated in such a manner so as to achieve a generally uniform dispersion of the nanomaterial additives through the formed composite body.

100741 For example, nanomaterial additives may be integrated with the elastomer composition prior to curing. These nanomaterial additives may be added, compounded, or blended with the elastomer seal precursors, prior to the curing process. For instance, the base elastomer may be compounded or mixed with additives or agents such as furnace black, peroxide curing agent, graphite, zinc oxide, stearic acid, plasticizer, and nanomaterial additives. Alternatively, the nanomaterial may be integrated into the elastomer seal post-cure by methods such as spraying, hot melting, plastic extrusion, and other methods known in the art.

[0075] Advantageously, embodiments of the present disclosure contain elastomer seal containing nanomaterial additives, which may confer superior properties such as enhanced elastic and tensile moduli, hardness, and tear strength. These enhanced properties would allow the seal to withstand the harsh conditions of elevated temperatures, pressures, and constant friction for longer periods of time. This may prolong the downhole life of the nanocornposite elastomer seal and ultimately the rock bit. This seal life extension would serve to significantly reduce drilling downtime, and be invaluable in the oil and gas industry.

[0076] While the present disclosure has been described with respect to a limited number of embodiments, those skilled in the art, having benefit of this disclosure, will appreciate that other embodiments may be devised which do not depart from the scope of the present disclosure as disclosed herein. Accordingly, the scope of the present disclosure should be limited only by the attached claims.

100771 One aspect of this disclosure provides a bit for drilling subterranean formations comprising: a bit body including a bearing surface; a cutting structure mounted on the bit body, and including a bearing surface; and an annular seal for retaining a grease between the bearing surfaces, the annular seal comprising a flexible and resilient seal body formed from an elastomer composition, wherein the elastomer composition comprises an elastomer material, a curing agent, and 10% or less by volume of a nanomaterial additive selected from one of nanotubes and clustered nanodiamonds.

[0078] The elastomer material may comprise at least one of a highly saturated nitrile elastomer, a nitrile-butadiene rubber, a highly saturated nitrile-butadiene rubber, a fluorocarbon, an ethylene-propylene, a silicone, a chloroprene, a neoprene, a fluorosilicone, a polyurethane, a perfluoroelastomer, a polyacrylate, a copolymer of tetrafluoroethylene and propylene, an ethylene-acrylic rubber, a chiorosulfonyl polyethylene rubber, an epichlorohydrin polymers, a styrene butadiene polymer, and mixtures or copolymers thereof.

100791 The curing agent may comprise at least one of an organometallic catalyst, an inorganic oxide, an inorganic peroxide, a metal oxide salt, an organic peroxide, an organic hydroperoxide, and mixtures thereof.

100801 The nanomaterial additive may comprise a functionalized nanotube.

10081] The elastomer composition may comprise 0.01 to 1.5% by volume of nanomaterial additives.

100821 The elastomer composition may comprise from about 2 to 4% by volume of nanomaterial additives.

[0083] The bit may further comprise an additive which is at least one of a coagent, a plasticizer, a lubricant, an antioxidant, a filler, an accelerator, and a retardant.

100841 The plasticizer niay comprise at least one of a phthalate, a chlorinated paraffin, an adipate, a trimellitate, a maleate, a sebacate, a benzoate, an epoxidated vegetable oil, sulfonamides, an organophosphate, a glycol and a polyether.

[0085] The lubricant may comprise at least one of a graphite, an oleamide, an erucaniide, a soy oil, waxes, or a mixture of blend thereof.

[0086] The antioxidant may comprise at least one of zinc 2-mercaptotolumirnidazole, 4,4'-Bis(alpha,alpha-dimethylbenzyl) diphenylamine.

[00871 The filler may comprise at least one of a calcium carbonate, a carbon black, a titaniuni dioxide, a non-acidic clay, a fumed silica, a metal oxide, a metal chromate, a metal sulfate, and a mixture thereof.

[00881 The accelerator may comprise at least one of an amine, a sulfonamide, and a disulfide.

10089] The retardant may comprise at least one of a stearate, an organic carbamate and salts thereof a lactone, and a stearic acid.

10090] Another aspect of this disclosure provides a rock bit for drilling subterranean formations comprising: a bit body including at least one journal pin, each having a bearing surface; a roller cone mounted on the at least one journal pin and including a bearing surface; an annular seal for retaining a grease between the bearing surfaces, the annular seal comprising a flexible and resilient seal body formed from an elastomer composition, wherein the elastomer composition comprises: 100 parts by weight of highly saturated nitrile elastomer; furnace black in the range of up to 70 parts by weight; peroxide curing agent in the range of from 7 to 10 parts by weight; zinc oxide in the range of from 4 to 7 parts by weight; stearic acid in the range of from 0.5 to 2 parts by weight; nanomaterial additives selected from one of nanotubes and clustered nanodiamonds in the range of up to 10 percent by volume, and sufficient plasticizer to provide a Shore Hardness of no more than A 80.

10091] The nanoadditive materials may comprise functionalized nanotubes.

10092] The elastomer composition may comprise 0.01 to 1.5% by volume of nanomaterial additives.

100931 The plasticizer may comprise at least one of a phthalate, a chlorinated paraffin, an adipate, a trimellitate, a maleate, a sebacate, a benzoate, an epoxidated vegetable oil, sulfonamides, an organophosphate, a glycol and a polyether.

100941 The rock bit may further comprise an additive which is at least one of a coagent, an antioxidant, and an accelerator.

100951 The coagent may be at least one of polybutadiene. The rock bit of claim 18, wherein the antioxidant comprises at least one of zinc 2-mercaptotolumimidazole, 4,4'-B is(alpha,alpha-dimethylbenzyl) diphenylamine.

10096] The accelerator comprise at least one of an amine, a sulfonamide, and a disulfide.

Claims (30)

1. Claims: 1. A bit for drilling subterranean formations comprising: a bit body including a bearing surface; a cutting structure mounted on the bit body, and including a bearing surface; and an annular seal for retaining a grease between the bearing surfaces, the annular seal comprising a flexible and resilient seal body formed from an elastomer composition, wherein the elastomer composition comprises an elastomer material, a curing agent, and 10% or less by volume of functionalized nanotubes.
2. 2. The bit of claim 1, wherein the functionalized nanotubes comprise multi-walled carbon nanotubes.
3. 3. The bit of claim I, wherein the functionalized nanotubes comprise sidewall functionalization.
4. 4. The bit of claim 1, wherein the functionalized nanotubes comprise endcap functionalization.
5. 5. The bit of claim 1, wherein the functionalized nanotubes comprise 11 uoronanotubes.
6. 6. The bit of claim 1, wherein the functionalized nanotubes comprise carboxy-nanotubes.
7. 7. The bit of claim 1, wherein the functionalized nanotubes comprise amino-carbon nanotubes.
8. 8. The bit of claim 1, wherein the functionalized nanotubes comprise vinyl-carbon nanotubes.
9. 9. The bit of claim 1, wherein the functionalized nanotubes comprise epoxy-carbon nanotubes.
10. 10. The bit of claim 1, wherein the functionalized nanotubes comprise amidified carbon nanotubes.
11. 1 1. The bit of claim 1, wherein the functionalized nanotubes comprise etherified carbon nanotubes.
12. 12. The bit of claim 1, wherein the functionalized nanotubes comprise nanotubes having a coating formed thereon.
13. 13. The bit of claim 1, wherein the elastomer material comprises at least one of a highly saturated nitrile elastomer, a nitrile-butadiene rubber, a highly saturated nitrile-butadiene rubber, a fluorocarbon, an ethylene-propylene, a silicone, a chloroprene, a neoprene, a fluorosilicone, a polyurethane, a perfluoroelastomer, a polyacrylate, a copolynier of tetrafluoroethylene and propylene, an ethylene-acrylic rubber, a chiorosulfonyl polyethylene rubber, an epichlorohydrin polymers, a styrene butadiene polymer, and mixtures or copolymers thereof.
14. 14. The bit of claim 1, wherein the curing agent, comprises at least one of an organometallic catalyst, an inorganic oxide, an inorganic peroxide, a metal oxide salt, an organic peroxide, an organic hydroperoxide, and mixtures thereof
15. 15. The bit of claim 1, wherein the elastomer composition comprises 0.01 to 1.5% by volume of the functionalized nanotubes.
16. 16. The bit of claim 1, wherein the elastomer composition comprises from about 2 to 4% by volume of the functionalized nanotubes.
17. 17. The bit of claim 1, further comprising an additive which is at least one of a coagent, a plasticizer, a lubricant, an antioxidant, a filler, an accelerator, and a retardant.
18. 18. The bit of claim 17, wherein the plasticizer comprises at least one of a phthalate, a chlorinated paraffin, an adipate, a trimellitate, a rnaleate, a sebacate, a benzoate, an epoxidated vegetable oil, sulfonamides, an organophosphate, a glycol and a polyether.
19. 19. The bit of claim 17, wherein the lubricant comprises at least one of a graphite, an oleamide, an erucamide, a soy oil, waxes, or a mixture of blend thereof.
20. 20. The bit of claim 17, wherein the antioxidant comprises at least one of zinc 2-mercaptotolumimidazole, 4,4' -Bis(alpha,alpha-dimethylbenzyl) diphenylamine.
21. 21. The bit of claim 17, where the filler comprises at least one of a calcium carbonate, a carbon black, a titanium dioxide, a non-acidic clay, a fumed silica, a metal oxide, a metal chromate, a metal sulfate, and a mixture thereof.
22. 22. The bit of claim 17, wherein the accelerator comprises at least one of an amine, a sulfonamide, and a disulfide.
23. 23. The bit of claim 17, wherein the retardant comprises least one of a stearate, an organic carbamate and salts thereof, a lactone, and a stearic acid.
24. 24. A rock bit for drilling subterranean formations comprising: a bit body including at least one journal pin, each having a bearing surface; a roller cone mounted on the at least one journal pin and including a bearing surface; an annular seal for retaining a grease between the bearing surfaces, the annular seal comprising a flexible and resilient seal body formed from an elastomer composition, wherein the elastomer composition comprises: parts by weight of highly saturated nitrile elastomer; furnace black in the range of up to 70 parts by weight; peroxide curing agent in the range of from 7 to 10 parts by weight; zinc oxide in the range of from 4 to 7 parts by weight; stearic acid in the range of from 0.5 to 2 parts by weight; functionalized nanotubes in the range of up to 10 percent by volume, and sufficient plasticizer to provide a Shore Hardness of no more than A 80.
25. 25. The rock bit of claim 24, wherein the elastomer composition comprises 0.01 to 1.5% by volume of functionalized nanotubes.
26. 26. The rock bit of claim 24, wherein the plasticizer comprises at least one of a phthalate, a chlorinated paraffin, an adipate, a trirnellitate, a maleate, a sebacate, a benzoate, an epoxidated vegetable oil, sulfonamides, an organophosphate, a glycol and a polyether.
27. 27. The rock bit of claim 24, further comprising an additive which is at least one of a coagent, an antioxidant, and an accelerator.
28. 28. The rock bit of claim 27, wherein the coagent is at least one of polybutadiene.
29. 29. The rock bit of claim 27, wherein the antioxidant comprises at least one of zinc 2-mercaptotolumimidazole, 4,4'-Bis(alpha,alpha-dimethylbenzyl) diphenylamine.
30. 30. The rock bit of claim 27, wherein the accelerator comprises at least one of an amine, a sulfonamide, and a disulfide.