The present invention relates to cementing operations, and more particularly in certain embodiments, to the application of an oil-swellable particle to foamed cement compositions, and methods of using such compositions in surface and subterranean applications.
Cement compositions are commonly utilized above ground (e.g., in the construction industry) and in subterranean operations, particularly subterranean well completion and remedial operations. For example, cement compositions are used in primary cementing operations whereby pipe strings such as casings and liners may be cemented in well bores. In performing primary cementing, hydraulic cement compositions may be pumped into the annular space between the walls of a well bore and the exterior surface of the pipe string disposed therein. The cement composition is permitted to set in the annular space, thereby forming an annular sheath of hardened substantially impermeable cement therein that substantially supports and positions the pipe string in the well bore and bonds the exterior surface of the pipe string to the walls of the well bore. Cement compositions also may be used in remedial cementing operations such as plugging highly permeable zones or fractures in well bores, plugging cracks and holes in pipe strings, and the like.
Cement compositions utilized in subterranean operations may be lightweight to prevent excessive hydrostatic pressure from being exerted on subterranean formations penetrated by the well bore, whereby the formations may be unintentionally fractured. One type of lightweight cement composition is a foamed cement composition, i.e., a cement composition that comprises a gas and a foaming surfactant. In addition to being lightweight, the gas contained in the foamed cement composition may improve the ability of the composition to maintain pressure and prevent the flow of formation fluids into and through the cement composition during its transition time, i.e., the time during which the cement composition changes from a true fluid to a set mass. Foamed cement compositions may be advantageous because they can have low fluid loss properties and may act to prevent the loss of fluid during circulation. Additionally, foamed cement compositions when set should have a lower modulus of elasticity than non-foamed cements, which is often desirable as it enables the resultant set cement, inter alia, to resist hoop stresses exerted on the set cement in the annulus.
Once set, the cement sheath may be subjected to a variety of cyclic, shear, tensile, impact, flexural, and/or compressive stresses that may lead to failure of the cement sheath. Such failure may be the result of fractures, cracks, and/or debonding of the cement sheath from the pipe string and/or the formation. Undesirably, cement-sheath failure may lead to loss of zonal isolation, resulting, for example, in the undesirable migration of fluids between formation zones. This may lead to undesirable consequences such as lost production, costly remedial operations, environmental pollution, hazardous rig operations resulting from unexpected fluid flow from the formation caused by the loss of zonal isolation, and/or hazardous production operations. Furthermore, failure of the cement sheath also may be caused by forces exerted by shifts in subterranean formations surrounding the well bore, cement erosion, and repeated impacts from the drill bit and the drill pipe.
The present invention relates to cementing operations, and more particularly in certain embodiments, to the application of an oil-swellable particle to foamed cement compositions, and methods of using such compositions in surface and subterranean applications.
An embodiment of the present invention provides a method comprising: introducing a foamed cement composition into a subterranean formation, wherein the foamed cement composition comprises: a cementitious component; a foaming and stabilizing surfactant; an oil-swellable particle; gas; and water; and allowing the settable composition to set in the subterranean formation.
Another embodiment of the present invention provides a method comprising: introducing a foamed cement composition into an annulus between a pipe string and a subterranean formation, wherein the foamed cement composition comprises comprising: a cementitious component; a foaming and stabilizing surfactant; an oil-swellable particle; gas; and water; and allowing the settable composition to set in the annulus.
Another embodiment of the present invention provides a foamed cement composition comprising: a cementitious component, a foaming and stabilizing surfactant, a swellable particle, gas, and water.
The features and advantages of the present invention will be apparent to those skilled in the art. While numerous changes may be made by those skilled in the art, such changes are within the spirit of the invention.
The present invention relates to cementing operations, and more particularly in certain embodiments, to the application of an oil-swellable particle to foamed cement compositions, and methods of using such compositions in surface and subterranean applications.
The foamed cement compositions of the present invention generally comprise a cementitious component, water, a gas, a foaming and stabilizing surfactant, and an oil-swellable particle. As used herein, the term “cementitious component” refers to a material or combination of materials that sets and hardens by reaction with water. The foamed cement compositions of the present invention should have a density suitable for a particular application as desired by those of ordinary skill in the art, with the benefit of this disclosure. In some embodiments, the foamed settable compositions of the present invention may have a density in the range of from about 8 ppg to about 13 ppg.
Embodiments of the foamed cement compositions of the present invention comprise a cementitious component that may comprise cement kiln dust (“CKD.”) “CKD,” as that term is used herein, refers to a partially calcined kiln feed which may be removed from the gas stream and collected in a dust collector during the manufacture of cement. CKD generally may comprise a variety of oxides, such as SiO2, Al2O3, Fe2O3, CaO, MgO, SO3, Na2O, and K2O. The CKD may be included in the foamed cement compositions in an amount sufficient to provide the desired compressive strength, density, and/or cost reduction. In some embodiments, the CKD may be present in the settable compositions of the present invention in an amount of at least about 25% by weight of the cementitious component. In some embodiments, the CKD may be present in the settable compositions of the present invention in an amount in the range of from about 1% to about 75% by weight of the cementitious component. In some embodiments, the CKD may be present in the settable compositions of the present invention in an amount in the range of from about 25% to about 50% by weight of the cementitious component.
Embodiments of the foamed cement compositions of the present invention may comprise a cementitious component that also comprises a hydraulic cement. In certain embodiments, the cementitious component may comprise hydraulic cement and CKD. A variety of hydraulic cements may be utilized in accordance with the present invention, including, but not limited to, those comprising calcium, aluminum, silicon, oxygen, iron, and/or sulfur, which set and harden by reaction with water. Suitable hydraulic cements include, but are not limited to, Portland cements, pozzolana cements, gypsum cements, high alumina content cements, slag cements, silica cements, and combinations thereof. In certain embodiments, the hydraulic cement may comprise a Portland cement. In some embodiments, the Portland cements that are suited for use in the present invention include those classified as Classes A through H according to American Petroleum Institute, API Specification for Materials and Testing for Well Cements, API Specification 10, Fifth Ed., Jul. 1, 1990. In certain embodiments, API Class A, C, G and H hydraulic cements may be preferred.
Where present, the hydraulic cement generally may be included in the cement compositions in an amount sufficient to provide the desired compressive strength, density, and/or cost. In some embodiments, the hydraulic cement may be present in the cement compositions of the present invention in an amount of about 0.1% to about 100% by weight of cementitious materials. In some embodiments, the hydraulic cement may be present in the cement compositions of the present invention in an amount of about 0.1% to about 95% by weight of cementitious materials. In some embodiments, the hydraulic cement may be present in the cement compositions of the present invention in an amount of about 20% to about 95% by weight by weight of cementitious materials. In some embodiments, the hydraulic cement may be present in the cement compositions of the present invention in an amount in the range of from about 50% to about 90% by weight of cementitious materials.
In some embodiments, a pozzolana cement that may be suitable for use comprises fly ash. As used herein, “fly ash” refers to the residue from the combustion of powdered or ground coal, wherein the fly ash carried by flue gases may be recovered, for example, by electrostatic precipitation. A variety of fly ashes may be suitable, including fly ash classified as Class C and Class F fly ash according to American Petroleum Institute, API Specification for Materials and Testing for Well Cements, API Specification 10, Fifth Ed., Jul. 1, 1990. Class C fly ash comprises both silica and lime so that, when mixed with water, it sets to form a hardened mass. Class F fly ash generally does not contain sufficient lime, so an additional source of calcium ions is required for the Class F fly ash to form a cement composition with water. In some embodiments, lime may be mixed with Class F fly ash in an amount in the range of from about 0.1% to about 25% by weight of the fly ash. In some instances, the lime may be hydrated lime. Suitable examples of fly ash include, but are not limited to, “POZMIX® A” cement additive, commercially available from Halliburton Energy Services, Inc., Duncan, Okla.
Where present, the fly ash generally may be included in the cement compositions in an amount sufficient to provide the desired compressive strength, density, and/or cost. In some embodiments, the fly ash may be present in the cement compositions of the present invention in an amount of about 5% to about 75% by weight of cementitious materials. In some embodiments, the fly ash may be present in the cement compositions of the present invention in an amount of about 5% to about 50% by weight of cementitious materials.
In some embodiments, a slag cement that may be suitable for use may comprise slag. As used herein, “slag” refers to a granulated, blast furnace by-product formed in the production of cast iron and generally comprises oxidized impurities found in iron ore. Slag generally does not contain sufficient basic material, so slag cement further may comprise a base to produce a cement composition that may react with water to set to form a hardened mass. Examples of suitable sources of bases include, but are not limited to, sodium hydroxide, sodium bicarbonate, sodium carbonate, lime, and combinations thereof.
Where present, the slag cement generally may be included in the cement compositions in an amount sufficient to provide the desired compressive strength, density, and/or cost. In some embodiments, the slag cement may be present in the cement compositions of the present invention in an amount of 0% to about 75% by weight of cementitious materials. In some embodiments, the slag cement may be present in the cement compositions of the present invention in an amount of about 5% to about 40% by weight of cementitious materials.
The water used in the foamed cement compositions of the present invention may be freshwater, saltwater (e.g., water containing one or more salts dissolved therein), brine (e.g., saturated saltwater produced from subterranean formations), or seawater, or combinations thereof. Generally, the water may be from any source, provided that it does not contain an excess of compounds that may adversely affect other components in the cement composition. The water may be present in an amount sufficient to form a pumpable slurry. More particularly, the water may be present in an amount in the range of from about 33% and about 200% by weight of the cementitious materials. In some embodiments, the water may be present in an amount in the range of from about 35% and about 70% cementitious materials.
The gas utilized in the foamed cement compositions of the present invention may be any gas suitable for foaming a cement composition, including, but not limited to, air or nitrogen, or combinations thereof. Generally, the gas should be present in the foamed cement compositions of the present invention in an amount sufficient to form a suitable foam. In certain embodiments, the gas may be present in an amount in the range of from about 10% and about 80% by volume of the composition.
Any suitable foaming and stabilizing surfactant may be used in the foamed cement composition of the present invention. Among other things, the foaming and stabilizing surfactants may facilitate the foaming of a cement composition and/or also stabilize the resultant foamed cement composition formed therewith. Suitable foaming and stabilizing surfactants may include, but are not limited to: mixtures of an ammonium salt of an alkyl ether sulfate, a cocoamidopropyl betaine surfactant, a cocoamidopropyl dimethylamine oxide surfactant, sodium chloride, and water; mixtures of an ammonium salt of an alkyl ether sulfate surfactant, a cocoamidopropyl hydroxysultaine surfactant, a cocoamidopropyl dimethylamine oxide surfactant, sodium chloride, and water; hydrolyzed keratin; mixtures of an ethoxylated alcohol ether sulfate surfactant, an alkyl or alkene amidopropyl betaine surfactant, and an alkyl or alkene dimethylamine oxide surfactant; aqueous solutions of an alpha-olefinic sulfonate surfactant and a betaine surfactant; and combinations thereof. An example of a suitable hydrolyzed keratin is described in U.S. Pat. No. 6,547,871, the disclosure of which is incorporated herein by reference. Example of suitable mixtures of an ethoxylated alcohol ether sulfate surfactant, an alkyl or alkene amidopropyl betaine surfactant, and an alkyl or alkene dimethylamine oxide surfactant is described in U.S. Pat. No. 6,063,738, the disclosure of which is incorporated herein by reference. Examples of suitable aqueous solutions of an alpha-olefinic sulfonate surfactant and a betaine surfactant are described in U.S. Pat. No. 5,897,699, the disclosure of which is incorporated herein by reference. In one embodiment, the foaming and stabilizing surfactant comprises a mixture of an ammonium salt of an alkyl ether sulfate, a cocoamidopropyl betaine surfactant, a cocoamidopropyl dimethylamine oxide surfactant, sodium chloride, and water.
Generally, the foaming and stabilizing surfactants should be present in the foamed cement compositions of the present invention in an amount sufficient to provide a suitable foam. In some embodiments, the foaming and stabilizing surfactant may be present in an amount in the range of from about 0.8% and about 5% by volume of the water (“bvow”) present in the foamed cement composition.
Embodiments of the foamed cement compositions may comprise an oil-swellable particle. As used herein, a particle is characterized as oil-swellable when it swells upon contact with oil. Oil-swellable particles suitable for use in embodiments of the present invention may generally swell by up to about 50% of their original size at the surface. Under downhole conditions, this swelling may be more, or less, depending on the conditions presented. For example, the swelling may be at least 10% at downhole conditions. In some embodiments, the swelling may be up to about 50% under downhole conditions. However, as those of ordinary skill in the art, with the benefit of this disclosure, will appreciate, the actual swelling when the oil-swellable particles are included in a foamed cement composition may depend on, for example, the concentration of the swellable particles included in the settable composition. In accordance with embodiments of the present invention, the swellable particles may be included in the settable composition, for example, to counteract the formation of cracks in the cement sheath and/or micro-annulus between the cement sheath and the pipe string or the formation. In general, the oil-swellable particles should be capable of swelling when contacted by oil to inhibit fluid flow through the crack and/or micro-annulus. Accordingly, the oil-swellable particles may prevent and/or reduce the loss of zonal isolation in spite of the formation of cracks and/or micro-annulus, potentially resulting in an improved annular seal for the foamed cement compositions.
An example of an oil-swellable particle that may be utilized in embodiments of the present invention comprises an oil-swellable elastomer. Oil-swellable elastomers suitable for use in embodiments of the present invention may generally swell by up to about 100% of their original size at the surface when contacted by oil. Under downhole conditions, this swelling may be more, or less, depending on the conditions presented. For example, the swelling may be at least 10% at downhole conditions. In some embodiments, the swelling may be up to about 50% under downhole conditions. However, as those of ordinary skill in the art, with the benefit of this disclosure, will appreciate, the actual swelling when the swellable elastomer is included in a foamed cement composition may depend on, for example, the concentration of the oil-swellable elastomer included in the foamed cement composition, downhole pressure, and downhole temperature, among other factors. Some specific examples of suitable swellable elastomers include, but are not limited to, natural rubber, acrylate butadiene rubber, polyacrylate rubber, isoprene rubber, choloroprene rubber, butyl rubber (IIR), brominated butyl rubber (BIIR), chlorinated butyl rubber (CIIR), chlorinated polyethylene (CM/CPE), neoprene rubber (CR), styrene butadiene copolymer rubber (SBR), styrene butadiene block copolymer rubber, sulphonated polyethylene (CSM), ethylene acrylate rubber (EAM/AEM), epichlorohydrin ethylene oxide copolymer (CO, ECO), ethylene-propylene rubber (EPM and EDPM), ethylene-propylene-diene terpolymer rubber (EPT), ethylene vinyl acetate copolymer, fluorosilicone rubbers (FVMQ), silicone rubbers (VMQ), poly 2,2,1-bicyclo heptene (polynorborneane), alkylstyrene, and crosslinked vinyl acrylate copolymers. Combinations of suitable oil-swellable elastomers may also be utilized. One example of a suitable oil-swellable elastomer comprises a block copolymer of a styrene butadiene rubber. Other swellable elastomers that behave in a similar fashion with respect to oil also may be suitable. Those of ordinary skill in the art, with the benefit of this disclosure, will be able to select an appropriate oil-swellable elastomer for use in the compositions of the present invention based on a variety of factors, including the application in which the composition will be used and the desired oil-swellable characteristics.
Where used, the oil-swellable particle generally may be included in the cement compositions in an amount sufficient to provide the desired mechanical properties. In some embodiments, the oil-swellable particle may be present in the foamed cement compositions in an amount up to about 27% bwoc (e.g., about 1%, about 5%, about 10%, about 15%, about 20%, about 25%, etc.), alternatively in a range of about 1% to about 25% bwoc, and alternatively in a range of about 4% to about 20% bwoc.
In addition, the oil-swellable particle that is utilized may have a wide variety of shapes and sizes of individual particles suitable for use in accordance with embodiments of the present invention. By way of example, the oil-swellable particle may have a well-defined physical shape as well as an irregular geometry, including the physical shape of platelets, shavings, fibers, flakes, ribbons, rods, strips, spheroids, beads, toroids, pellets, tablets, or any other physical shape. In some embodiments, the oil-swellable particle may have a particle size in the range of about 5 microns to about 1,500 microns. In some embodiments, the oil-swellable particle may have a particle size in the range of about 20 microns to about 500 microns. However, particle sizes outside these defined ranges also may be suitable for particular applications. Particle sizes may be measured using a laser light scattering particle size analyzer from the Malvern Company.
In certain embodiments, the settable compositions of the present invention further may comprise metakaolin. Generally, metakaolin is a white pozzolan that may be prepared by heating kaolin clay, for example, to temperatures in the range of from about 600° to about 800° C. In some embodiments, the metakaolin may be present in the settable compositions of the present invention in an amount in the range of from about 1% to about 50% by weight. In some embodiments, the metakaolin may be present in an amount in the range of from about 10% to about 50% by weight.
In certain embodiments, the settable compositions of the present invention further may comprise shale. Among other things, shale included in the settable compositions may react with excess lime to form a suitable cementing material, for example, calcium silicate hydrate. A variety of shales are suitable, including those comprising silicon, aluminum, calcium, and/or magnesium. An example of a suitable shale comprises vitrified shale. Suitable examples of vitrified shale include, but are not limited to, “PRESSUR-SEAL® FINE LCM” material and “PRESSUR-SEAL® COARSE LCM” material, which are commercially available from TXI Energy Services, Inc., Houston, Tex. Generally, the shale may have any particle size distribution as desired for a particular application. In certain embodiments, the shale may have a particle size distribution in the range of from about 37 micrometers to about 4,750 micrometers.
Where present, the shale may be included in the settable compositions of the present invention in an amount sufficient to provide the desired compressive strength, density, and/or cost. In some embodiments, the shale may be present in an amount in the range of from about 1% to about 75% by weight. In some embodiments, the shale may be present in an amount in the range of from about 5% to about 35% by weight. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of the shale to include for a chosen application.
In certain embodiments, the settable compositions of the present invention further may comprise zeolite. Zeolites generally are porous alumino-silicate minerals that may be either a natural or synthetic material. Synthetic zeolites are based on the same type of structural cell as natural zeolites, and may comprise aluminosilicate hydrates. As used herein, the term “zeolite” refers to all natural and synthetic forms of zeolite.
In certain embodiments, suitable zeolites for use in present invention may include “analcime” (which is hydrated sodium aluminum silicate), “bikitaite” (which is lithium aluminum silicate), “brewsterite” (which is hydrated strontium barium calcium aluminum silicate), “chabazite” (which is hydrated calcium aluminum silicate), “clinoptilolite” (which is hydrated sodium aluminum silicate), “faujasite” (which is hydrated sodium potassium calcium magnesium aluminum silicate), “ferrierite”, “harmotome” (which is hydrated barium aluminum silicate), “heulandite” (which is hydrated sodium calcium aluminum silicate), “laumontite” (which is hydrated calcium aluminum silicate), “mesolite” (which is hydrated sodium calcium aluminum silicate), “natrolite” (which is hydrated sodium aluminum silicate), “paulingite” (which is hydrated potassium sodium calcium barium aluminum silicate), “phillipsite” (which is hydrated potassium sodium calcium aluminum silicate), “scolecite” (which is hydrated calcium aluminum silicate), “stellerite” (which is hydrated calcium aluminum silicate), “stilbite” (which is hydrated sodium calcium aluminum silicate), and “thomsonite” (which is hydrated sodium calcium aluminum silicate), and combinations thereof. In certain embodiments, suitable zeolites for use in the present invention include chabazite and clinoptilolite. An example of a suitable source of zeolite is available from the C2C Zeolite Corporation of Calgary, Canada.
In some embodiments, the zeolite may be present in the settable compositions of the present invention in an amount in the range of from about 1% to about 40% by weight. In certain embodiments, the zeolite may be present in an amount in the range of from about 5% to about 25% by weight.
In certain embodiments, the settable compositions of the present invention further may comprise a set retarding additive. As used herein, the term “set retarding additive” refers to an additive that retards the setting of the settable compositions of the present invention. Examples of suitable set retarding additives include, but are not limited to, ammonium, alkali metals, alkaline earth metals, metal salts of sulfoalkylated lignins, hydroxycarboxy acids, copolymers that comprise acrylic acid or maleic anhydride, and combinations thereof. One example of a suitable sulfoalkylate lignin comprises a sulfomethylated lignin. Suitable set retarding additives are disclosed in more detail in U.S. Pat. No. Re. 31,190, the entire disclosure of which is incorporated herein by reference. Suitable set retarding additives are commercially available from Halliburton Energy Services, Inc. under the tradenames “HR® 4,” “HR® 5,” HR® 7,” “HR® 12,” “HR® 15,” HR® 25,” “SCR™ 100,” and “SCR™ 500.” Generally, where used, the set retarding additive may be included in the settable compositions of the present invention in an amount sufficient to provide the desired set retardation. In some embodiments, the set retarding additive may be present in an amount in the range of from about 0.1% to about 5% by weight.
Optionally, other additional additives may be added to the settable compositions of the present invention as deemed appropriate by one skilled in the art, with the benefit of this disclosure. Examples of such additives include, but are not limited to, accelerators, weight reducing additives, heavyweight additives, lost circulation materials, filtration control additives, dispersants, and combinations thereof. Suitable examples of these additives include crystalline silica compounds, amorphous silica, salts, fibers, hydratable clays, microspheres, pozzolan lime, latex cement, thixotropic additives, combinations thereof and the like.
The foamed cement compositions of the present invention may be prepared in accordance with any suitable technique. For example, the cementitious component and water may be combined and mixed for a sufficient period of time to form a pumpable cement composition. Liquid additives, if any, may be mixed with the water prior to combination with the cementitious component. Dry solid additives, if any, may be dry blended with the cement prior to combination with the water. In certain embodiments, the cement composition then may be pumped to the well bore, and the foaming and stabilizing surfactant followed by the gas may be injected into the cement composition, e.g., at a foaming mixing “T,” as the cement composition is being pumped, in an amount sufficient to form a foamed cement composition. After foaming, the foamed cement composition, may be placed in a desired location within the well bore and allowed to set. Those of ordinary skill in the art, with the benefit of this disclosure, will recognize other suitable techniques for preparing the foamed cement compositions of the present invention.
An example of a method of cementing of the present invention comprises: placing a foamed cement composition in a location to be cemented, wherein the foamed cement composition comprises a cementitious component comprising a hydraulic cement and CKD, water, a foaming and stabilizing surfactant, and an oil-swellable particle; and allowing the foamed cement composition to set. The location to be cemented may be any suitable location, including a location above ground or a portion of a subterranean formation, such as between the walls of a well bore and the exterior surface of a pipe string disposed therein.
Another example of a method of cementing of the present invention comprises: providing a cement composition that comprises a cementitious component comprising a hydraulic cement and CKD, water, a foaming and stabilizing surfactant, and an oil-swellable particle; combining the cement composition with a gas to form a foamed cement composition; placing the foamed cement composition in a portion of a subterranean formation; and allowing the foamed cement composition to set therein.
To facilitate a better understanding of the present invention, the following examples of certain aspects of some embodiments are given. In no way should the following examples be read to limit, or define, the scope of the invention.
A 14 lb/gal Portland class H cement slurry was prepared. The slurry contained 5% amorphous silica (by weight of cement) and 20% oil-swellable elastomer (by weight of cement). The oil-swellable rubber was a block polymer of styrene-butadiene. The slurry was foamed down to 11 lb/gal using 2% foamer 760 by volume of water. Foam weight reached the desired level by mixing in a pressurized foam blending jar for five seconds. For comparison purposes, a slurry was also prepared without the oil-swellable elastomer. The foamed slurries were cured at 140° F. for 24 hours. Physical and mechanical properties are reported in Table 1. Compressive strength testing was performed in accordance with API Recommended Practices 10B, Twenty-Second Edition, December 1997. The Young's Modulus of Elasticity and the Poisson's Ratio were determined in accordance with ASTM D3148-02.
Therefore, the present invention is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. While numerous changes may be made by those skilled in the art, such changes are encompassed within the spirit of this invention as defined by the appended claims. The terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee.
The present application is a continuation-in-part of U.S. patent application Ser. No. 12/283,398, filed on Sep. 11, 2008, entitled “Settable Compositions Comprising Cement Kiln Dust and Swellable Particles,” which is a continuation-in-part of U.S. patent application Ser. No. 11/223,669, filed on Sep. 9, 2005, now U.S. Pat. No. 7,445,669, entitled “Settable Compositions Comprising Cement Kiln Dust and Additives(s).” The present application is also a continuation-in-part of U.S. patent application Ser. No. 12/152,327, filed on May 14, 2008, entitled “Extended Cement Compositions Comprising Oil-Swellable Particles and Associated Methods.” The disclosures of these related applications are incorporated herein by reference in their entirety.
Number | Name | Date | Kind |
---|---|---|---|
2094316 | Cross et al. | Sep 1937 | A |
2329940 | Ponzer | Sep 1943 | A |
2842205 | Allen et al. | Jul 1958 | A |
2848051 | Willaims | Aug 1958 | A |
2871133 | Palonen et al. | Jan 1959 | A |
2880096 | Hurley | Mar 1959 | A |
2890169 | Prokop | Jun 1959 | A |
2945769 | Gama et al. | Jul 1960 | A |
3168139 | Kennedy et al. | Feb 1965 | A |
3381748 | Peters et al. | May 1968 | A |
3454095 | Messenger et al. | Jul 1969 | A |
3467193 | Messenger | Sep 1969 | A |
3499491 | Wyant et al. | Mar 1970 | A |
3557876 | Tragesser | Jan 1971 | A |
3748159 | George | Jul 1973 | A |
3876005 | Fincher et al. | Apr 1975 | A |
3887009 | Miller et al. | Jun 1975 | A |
3887385 | Quist et al. | Jun 1975 | A |
4018617 | Nicholson | Apr 1977 | A |
4031184 | McCord | Jun 1977 | A |
4036301 | Powers et al. | Jul 1977 | A |
4176720 | Wilson | Dec 1979 | A |
4268316 | Wills et al. | May 1981 | A |
4341562 | Ahlbeck | Jul 1982 | A |
RE31190 | Detroit et al. | Mar 1983 | E |
4407677 | Wills et al. | Oct 1983 | A |
4432800 | Kneller et al. | Feb 1984 | A |
4435216 | Diehl et al. | Mar 1984 | A |
4460292 | Durham et al. | Jul 1984 | A |
4494990 | Harris | Jan 1985 | A |
4515635 | Rao et al. | May 1985 | A |
4519452 | Tsao et al. | May 1985 | A |
4555269 | Rao et al. | Nov 1985 | A |
4614599 | Walker | Sep 1986 | A |
4624711 | Styron | Nov 1986 | A |
4633950 | Delhommer et al. | Jan 1987 | A |
4676317 | Fry et al. | Jun 1987 | A |
4676832 | Childs et al. | Jun 1987 | A |
4700777 | Luers | Oct 1987 | A |
4741782 | Styron | May 1988 | A |
4784223 | Worrall et al. | Nov 1988 | A |
4883125 | Wilson et al. | Nov 1989 | A |
4941536 | Brothers et al. | Jul 1990 | A |
4953620 | Bloys et al. | Sep 1990 | A |
4992102 | Barbour | Feb 1991 | A |
5030366 | Wilson et al. | Jul 1991 | A |
5049288 | Brothers et al. | Sep 1991 | A |
5058679 | Hale et al. | Oct 1991 | A |
RE33747 | Hartley et al. | Nov 1991 | E |
5086850 | Harris et al. | Feb 1992 | A |
5121795 | Ewert et al. | Jun 1992 | A |
5123487 | Harris et al. | Jun 1992 | A |
5125455 | Harris et al. | Jun 1992 | A |
5127473 | Harris et al. | Jul 1992 | A |
5183505 | Spinney | Feb 1993 | A |
5213160 | Nahm et al. | May 1993 | A |
5238064 | Dahl et al. | Aug 1993 | A |
5266111 | Barbour | Nov 1993 | A |
5295543 | Terry et al. | Mar 1994 | A |
5305831 | Nahm | Apr 1994 | A |
5314022 | Cowan et al. | May 1994 | A |
5327968 | Onan et al. | Jul 1994 | A |
5337824 | Cowan | Aug 1994 | A |
5352288 | Mallow | Oct 1994 | A |
5358044 | Hale et al. | Oct 1994 | A |
5358049 | Hale et al. | Oct 1994 | A |
5361841 | Hale et al. | Nov 1994 | A |
5361842 | Hale et al. | Nov 1994 | A |
5368103 | Heathman et al. | Nov 1994 | A |
5370185 | Cowan et al. | Dec 1994 | A |
5372641 | Carpenter | Dec 1994 | A |
5382290 | Nahm et al. | Jan 1995 | A |
5383521 | Onan et al. | Jan 1995 | A |
5383967 | Chase | Jan 1995 | A |
5398758 | Onan et al. | Mar 1995 | A |
5423379 | Hale et al. | Jun 1995 | A |
5439056 | Cowan | Aug 1995 | A |
5456751 | Zandi et al. | Oct 1995 | A |
5458195 | Totten et al. | Oct 1995 | A |
5464060 | Hale et al. | Nov 1995 | A |
5472051 | Brothers | Dec 1995 | A |
5476144 | Nahm et al. | Dec 1995 | A |
5494513 | Fu et al. | Feb 1996 | A |
5499677 | Cowan | Mar 1996 | A |
5515921 | Cowan et al. | May 1996 | A |
5518996 | Maroy et al. | May 1996 | A |
5520730 | Barbour | May 1996 | A |
5529624 | Riegler | Jun 1996 | A |
5536311 | Rodrigues | Jul 1996 | A |
5542782 | Carter et al. | Aug 1996 | A |
5569324 | Totten et al. | Oct 1996 | A |
5575841 | Dry | Nov 1996 | A |
5580379 | Cowan | Dec 1996 | A |
5585333 | Dahl et al. | Dec 1996 | A |
5588489 | Chatterji et al. | Dec 1996 | A |
5660624 | Dry | Aug 1997 | A |
5663230 | Haman | Sep 1997 | A |
5673753 | Hale et al. | Oct 1997 | A |
5688844 | Chatterji et al. | Nov 1997 | A |
5711383 | Terry et al. | Jan 1998 | A |
5716910 | Totten et al. | Feb 1998 | A |
5728654 | Dobson et al. | Mar 1998 | A |
5779787 | Brothers et al. | Jul 1998 | A |
5851960 | Totten et al. | Dec 1998 | A |
5866516 | Costin | Feb 1999 | A |
5874387 | Carpenter et al. | Feb 1999 | A |
5897699 | Chatterji et al. | Apr 1999 | A |
5900053 | Brothers et al. | May 1999 | A |
5913364 | Sweatman | Jun 1999 | A |
5988279 | Udarbe et al. | Nov 1999 | A |
5989334 | Dry | Nov 1999 | A |
6022408 | Stokes et al. | Feb 2000 | A |
6060434 | Sweatman et al. | May 2000 | A |
6060535 | Villar et al. | May 2000 | A |
6063738 | Chatterji et al. | May 2000 | A |
6138759 | Chatterji et al. | Oct 2000 | A |
6143069 | Brothers et al. | Nov 2000 | A |
6145591 | Boncan et al. | Nov 2000 | A |
6153562 | Villar et al. | Nov 2000 | A |
6167967 | Sweatman | Jan 2001 | B1 |
6170575 | Reddy et al. | Jan 2001 | B1 |
6230804 | Mueller et al. | May 2001 | B1 |
6244343 | Brothers et al. | Jun 2001 | B1 |
6245142 | Reddy et al. | Jun 2001 | B1 |
6258757 | Sweatman et al. | Jul 2001 | B1 |
6261360 | Dry | Jul 2001 | B1 |
6277189 | Chugh | Aug 2001 | B1 |
6312515 | Barlet-Gouedard et al. | Nov 2001 | B1 |
6315042 | Griffith et al. | Nov 2001 | B1 |
6332921 | Brothers et al. | Dec 2001 | B1 |
6367550 | Chatterji et al. | Apr 2002 | B1 |
6379456 | Heathman et al. | Apr 2002 | B1 |
6402833 | O'Hearn et al. | Jun 2002 | B1 |
6409819 | Ko | Jun 2002 | B1 |
6457524 | Roddy | Oct 2002 | B1 |
6478869 | Reddy et al. | Nov 2002 | B2 |
6488763 | Brothers et al. | Dec 2002 | B2 |
6494951 | Reddy et al. | Dec 2002 | B1 |
6500252 | Chatterji et al. | Dec 2002 | B1 |
6502636 | Chatterji et al. | Jan 2003 | B2 |
6508305 | Brannon et al. | Jan 2003 | B1 |
6524384 | Griffith et al. | Feb 2003 | B2 |
6527849 | Dry | Mar 2003 | B2 |
6547871 | Chatterji et al. | Apr 2003 | B2 |
6547891 | Linden et al. | Apr 2003 | B2 |
6561273 | Brothers et al. | May 2003 | B2 |
6562122 | Dao et al. | May 2003 | B2 |
6565647 | Day et al. | May 2003 | B1 |
6572697 | Gleeson et al. | Jun 2003 | B2 |
6610139 | Reddy et al. | Aug 2003 | B2 |
6626243 | Go Boncan | Sep 2003 | B1 |
6631766 | Brothers et al. | Oct 2003 | B2 |
6645288 | Dargaud et al. | Nov 2003 | B1 |
6645290 | Barbour | Nov 2003 | B1 |
6656265 | Garnier et al. | Dec 2003 | B1 |
6660080 | Reddy et al. | Dec 2003 | B2 |
6666268 | Griffith et al. | Dec 2003 | B2 |
6668929 | Griffith et al. | Dec 2003 | B2 |
6689208 | Brothers | Feb 2004 | B1 |
6702044 | Reddy et al. | Mar 2004 | B2 |
6706108 | Polston | Mar 2004 | B2 |
6716282 | Griffith et al. | Apr 2004 | B2 |
6729405 | DiLullo et al. | May 2004 | B2 |
6767398 | Trato | Jul 2004 | B2 |
6776237 | Dao et al. | Aug 2004 | B2 |
6796378 | Reddy et al. | Sep 2004 | B2 |
6797054 | Chatterji et al. | Sep 2004 | B2 |
6811603 | Brothers et al. | Nov 2004 | B2 |
6823940 | Reddy et al. | Nov 2004 | B2 |
6832651 | Ravi et al. | Dec 2004 | B2 |
6835243 | Brothers et al. | Dec 2004 | B2 |
6837316 | Reddy et al. | Jan 2005 | B2 |
6846357 | Reddy et al. | Jan 2005 | B2 |
6848519 | Reddy et al. | Feb 2005 | B2 |
6887833 | Brothers et al. | May 2005 | B2 |
6889767 | Reddy et al. | May 2005 | B2 |
6902001 | Dargaud et al. | Jun 2005 | B2 |
6904971 | Brothers et al. | Jun 2005 | B2 |
6907929 | LeRoy-Delage et al. | Jun 2005 | B2 |
6908508 | Brothers | Jun 2005 | B2 |
6911078 | Barlet-Gouedard et al. | Jun 2005 | B2 |
6926081 | Sweatman et al. | Aug 2005 | B2 |
6962201 | Brothers | Nov 2005 | B2 |
7007755 | Reddy et al. | Mar 2006 | B2 |
7022179 | Dry | Apr 2006 | B1 |
7026272 | Reddy et al. | Apr 2006 | B2 |
7048053 | Santra et al. | May 2006 | B2 |
7059415 | Bosma et al. | Jun 2006 | B2 |
7077203 | Roddy et al. | Jul 2006 | B1 |
7138446 | Reddy et al. | Nov 2006 | B2 |
7143828 | Reddy et al. | Dec 2006 | B2 |
7143832 | Freyer | Dec 2006 | B2 |
7156173 | Mueller | Jan 2007 | B2 |
7172022 | Reddy et al. | Feb 2007 | B2 |
7174962 | Roddy et al. | Feb 2007 | B1 |
7199086 | Roddy et al. | Apr 2007 | B1 |
7204307 | Roddy et al. | Apr 2007 | B2 |
7204310 | Roddy et al. | Apr 2007 | B1 |
7213646 | Roddy et al. | May 2007 | B2 |
7264053 | Vargo, Jr. et al. | Sep 2007 | B2 |
7284609 | Roddy et al. | Oct 2007 | B2 |
7284611 | Reddy et al. | Oct 2007 | B2 |
7294194 | Reddy et al. | Nov 2007 | B2 |
7296597 | Freyer et al. | Nov 2007 | B1 |
7303014 | Reddy et al. | Dec 2007 | B2 |
7335252 | Roddy et al. | Feb 2008 | B2 |
7337841 | Ravi | Mar 2008 | B2 |
7337842 | Roddy et al. | Mar 2008 | B2 |
7351279 | Brothers | Apr 2008 | B2 |
7353870 | Roddy et al. | Apr 2008 | B2 |
7381263 | Roddy et al. | Jun 2008 | B2 |
7387675 | Roddy et al. | Jun 2008 | B2 |
7395860 | Roddy et al. | Jul 2008 | B2 |
7404440 | Reddy et al. | Jul 2008 | B2 |
7409991 | Reddy et al. | Aug 2008 | B2 |
7422060 | Hammami et al. | Sep 2008 | B2 |
7451817 | Reddy et al. | Nov 2008 | B2 |
7461696 | Nguyen et al. | Dec 2008 | B2 |
7478675 | Roddy et al. | Jan 2009 | B2 |
7482309 | Ravi et al. | Jan 2009 | B2 |
20020033121 | Marko | Mar 2002 | A1 |
20020073897 | Trato | Jun 2002 | A1 |
20020117090 | Ku | Aug 2002 | A1 |
20030116065 | Griffith et al. | Jun 2003 | A1 |
20030116887 | Scott | Jun 2003 | A1 |
20030167970 | Polston | Sep 2003 | A1 |
20040007162 | Morioka et al. | Jan 2004 | A1 |
20040040475 | De La Roij et al. | Mar 2004 | A1 |
20040055748 | Reddy et al. | Mar 2004 | A1 |
20040079260 | Datta et al. | Apr 2004 | A1 |
20040107877 | Getzlaf et al. | Jun 2004 | A1 |
20040108113 | Luke et al. | Jun 2004 | A1 |
20040112600 | Luke et al. | Jun 2004 | A1 |
20040144537 | Reddy et al. | Jul 2004 | A1 |
20040171499 | Ravi et al. | Sep 2004 | A1 |
20040187740 | Timmons | Sep 2004 | A1 |
20040188091 | Luke et al. | Sep 2004 | A1 |
20040191439 | Bour et al. | Sep 2004 | A1 |
20040211562 | Brothers et al. | Oct 2004 | A1 |
20040211564 | Brothers et al. | Oct 2004 | A1 |
20040244650 | Brothers | Dec 2004 | A1 |
20040244977 | Luke et al. | Dec 2004 | A1 |
20040256102 | Trato | Dec 2004 | A1 |
20040261990 | Bosma et al. | Dec 2004 | A1 |
20050000734 | Getzlaf et al. | Jan 2005 | A1 |
20050034867 | Griffith et al. | Feb 2005 | A1 |
20050056191 | Brothers et al. | Mar 2005 | A1 |
20050061206 | Reddy et al. | Mar 2005 | A1 |
20050072599 | Luke et al. | Apr 2005 | A1 |
20050084334 | Shi et al. | Apr 2005 | A1 |
20050098317 | Reddy et al. | May 2005 | A1 |
20050113260 | Wood | May 2005 | A1 |
20050113262 | Ravi et al. | May 2005 | A1 |
20050133221 | Chatterji et al. | Jun 2005 | A1 |
20050199401 | Patel et al. | Sep 2005 | A1 |
20060025312 | Santra et al. | Feb 2006 | A1 |
20060086503 | Reddy et al. | Apr 2006 | A1 |
20060089851 | Silby et al. | Apr 2006 | A1 |
20060122071 | Reddy et al. | Jun 2006 | A1 |
20060162926 | Roddy | Jul 2006 | A1 |
20060166834 | Roddy | Jul 2006 | A1 |
20060260512 | Nordmeyer | Nov 2006 | A1 |
20060278131 | Hunt | Dec 2006 | A1 |
20070012436 | Freyer | Jan 2007 | A1 |
20070017676 | Reddy et al. | Jan 2007 | A1 |
20070056475 | Roddy et al. | Mar 2007 | A1 |
20070056479 | Gray | Mar 2007 | A1 |
20070056733 | Roddy et al. | Mar 2007 | A1 |
20070062691 | Reddy et al. | Mar 2007 | A1 |
20070102157 | Roddy et al. | May 2007 | A1 |
20070137528 | Le Roy-Delage et al. | Jun 2007 | A1 |
20070151484 | Reddy et al. | Jul 2007 | A1 |
20070151724 | Ohmer et al. | Jul 2007 | A1 |
20070151730 | Reddy et al. | Jul 2007 | A1 |
20070186820 | O'Hearn | Aug 2007 | A1 |
20070204765 | Le Roy-Delage et al. | Sep 2007 | A1 |
20070227734 | Freyer | Oct 2007 | A1 |
20070246225 | Hailey, Jr. et al. | Oct 2007 | A1 |
20070255457 | Whitcomb et al. | Nov 2007 | A1 |
20080017376 | Badalamenti et al. | Jan 2008 | A1 |
20080099203 | Mueller et al. | May 2008 | A1 |
20080108524 | Willberg et al. | May 2008 | A1 |
20080135250 | Bosma et al. | Jun 2008 | A1 |
20080156491 | Roddy et al. | Jul 2008 | A1 |
20080261027 | Li et al. | Oct 2008 | A1 |
20080261834 | Simon | Oct 2008 | A1 |
20080261934 | Simon et al. | Oct 2008 | A1 |
20090124522 | Roddy | May 2009 | A1 |
Number | Date | Country |
---|---|---|
2153372 | Jan 2006 | CA |
0814067 | Dec 1997 | EP |
1236701 | Sep 2002 | EP |
1394137 | Jul 2003 | EP |
1348831 | Oct 2003 | EP |
1469954 | Apr 1997 | GB |
2429725 | Mar 2007 | GB |
52117316 | Oct 1977 | JP |
10110487 | Apr 1998 | JP |
1373781 | Feb 1988 | SU |
WO 8301443 | Apr 1983 | WO |
WO 9854108 | Dec 1998 | WO |
WO 0063134 | Jan 2000 | WO |
WO 0308756 | Jan 2003 | WO |
WO 03031364 | Apr 2003 | WO |
WO 2004057715 | Jul 2004 | WO |
WO 2004101951 | Nov 2004 | WO |
WO 2004101952 | Nov 2004 | WO |
WO 2005047212 | May 2005 | WO |
WO 2005061846 | Jul 2005 | WO |
WO2006032841 | Mar 2006 | WO |
WO 2006053896 | May 2006 | WO |
Number | Date | Country | |
---|---|---|---|
20090071650 A1 | Mar 2009 | US |
Number | Date | Country | |
---|---|---|---|
Parent | 12283398 | Sep 2008 | US |
Child | 12263800 | US | |
Parent | 11223669 | Sep 2005 | US |
Child | 12283398 | US | |
Parent | 12263800 | US | |
Child | 12283398 | US | |
Parent | 12152327 | May 2008 | US |
Child | 12263800 | US |