Patent Grant
8672028
The present invention relates to cementing operations and, more particularly, in certain embodiments, to methods and compositions that comprise interground perlite and hydraulic cement.
In general, well treatments include a wide variety of methods that may be performed in oil, gas, geothermal and/or water wells, such as drilling, completion and workover methods. The drilling, completion and workover methods may include, but are not limited to, drilling, fracturing, acidizing, logging, cementing, gravel packing, perforating and conformance methods. Many of these well treatments are designed to enhance and/or facilitate the recovery of desirable fluids from a subterranean well.
In cementing methods, such as well construction and remedial cementing, settable compositions are commonly utilized. As used herein, the term “settable composition” refers to a composition(s) that hydraulically sets or otherwise develops compressive strength. Settable compositions may be used in primary cementing operations whereby pipe strings, such as casing and liners, are cemented in well bores. In performing primary cementing, a settable composition may be pumped into an annulus between a subterranean formation and the pipe string disposed in the subterranean formation. The settable composition should set in the annulus, thereby forming an annular sheath of hardened cement (e.g., a cement sheath) that should support and position the pipe string in the well bore and bond the exterior surface of the pipe string to the walls of the well bore. Settable compositions also may be used in remedial cementing methods, such as the placement of cement plugs, and in squeeze cementing for sealing voids in a pipe string, cement sheath, gravel pack, formation, and the like.
The hydration of the cement in these cementing methods is a complex process because several phases may take part in the reaction simultaneously. In order to control the reaction processes to render the compositions suitable for well cementing, various additives such as retarders, strength enhancers, and accelerators may be added. However, the operating conditions for wells are becoming more challenging and demanding, and the search for new materials continues to meet these challenges. For instance, cement slurries used in well cementing often encounter problems of gaining sufficient strength in a reasonable amount of time for well operations to continue. The costs associated with wait-on-cement (“WOC”) play an important role in well cementing.
The present invention relates to cementing operations and, more particularly, in certain embodiments, to methods and compositions that comprise interground perlite and hydraulic cement.
An embodiment provides a method of cementing comprising: providing a settable composition comprising perlite, hydraulic cement, and water, wherein the perlite and hydraulic cement are interground prior to combination with the water to form the settable composition; and allowing the settable composition to set.
Another embodiment provides a method of cementing comprising: providing a settable composition comprising unexpanded perlite, hydraulic cement, and water, wherein the unexpanded perlite and hydraulic cement are interground prior to combination with the water to form the settable composition; introducing the settable composition into a well bore; and allowing the settable composition to set.
Yet another embodiment provides a composition comprising interground perlite and hydraulic cement.
The features and advantages of the present invention will be readily 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.
Embodiments of the settable compositions of the present invention may comprise perlite. Perlite suitable for use in embodiments of the present invention includes expanded perlite and unexpanded perlite. In some embodiments, the settable composition may comprise perlite interground with a hydraulic cement. In some embodiments, the settable compositions may comprise unexpanded perlite with cement kiln dust (“CKD”), pumicite, or a combination thereof. There may be several potential advantages to the methods and compositions of the present invention, only some of which may be alluded to herein. One of the many potential advantages of embodiments of the present invention is that the inclusion of the unexpanded perlite in embodiments of the settable composition may increase the compressive strength of the settable composition after setting. Another potential advantage of embodiments of the present invention is that the CKD, unexpanded perlite, pumicite, or a combination thereof may be used to reduce the amount of a higher cost component, such as Portland cement, resulting in a more economical settable composition. Yet another potential advantage of embodiments of the present invention is that reduction of the amount of Portland cement can reduce the carbon footprint of the cementing operation.
Perlite is an ore and generally refers to a naturally occurring volcanic, amorphous siliceous rock comprising mostly silicon dioxide and aluminum oxide. A characteristic of perlite is that it may expand to form a cellular, high-porosity particle or hollow sphere containing multi-cellular cores when exposed to high temperatures due to the sudden vaporization of water within the perlite. The expanded perlite may be used as a density-reducing additive for making lightweight settable compositions. Perlite suitable for use in embodiments of the present invention includes expanded perlite and unexpanded perlite. In some embodiments, the perlite may comprise unexpanded perlite.
It has recently been discovered the addition of unexpanded perlite to settable compositions comprising CKD and/or pumicite may provide unexpected increases in compressive strengths. In accordance with embodiments of the present invention, the unexpanded perlite may be used to increase the compressive strength of settable compositions comprising CKD and/or pumicite. In addition, unexpanded perlite can increase the compressive strength of settable compositions comprising Portland cement. It is believed that the unexpanded perlite may be particularly suited for use at elevated well bore temperatures in accordance with embodiments of the present invention, such as at temperatures greater than about 80° F., alternatively greater than about 120° F., and alternatively greater than about 140° F.
In one embodiment, unexpanded perlite may be used, among other things, to replace higher cost cementitious components, such as Portland cement, resulting in more economical settable compositions. In addition, substitution of the Portland cement for the unexpanded perlite should result in a settable composition with a reduced carbon footprint.
In present embodiments, the perlite can be ground to any size suitable for use in cementing operations. In an embodiment, the perlite is ground to a mean particle size of about 1 micron to about 400 microns, alternatively, about 1 micron to about 100 microns and, alternatively, about 1 micron to about 25 microns. The mean particle size corresponds to d50 values as measured by commercially available particle size analyzers such as those manufactured by Malvern Instruments, Worcestershire, United Kingdom. In another embodiment, the perlite has a particle size distribution of about 1 micron to about 1,000 microns with a mean particle size of about 1 micron to about 100 microns. The particle size distribution corresponds to the maximum and minimum sizes allowed in the distribution. An example of a suitable ground perlite that is unexpanded is available from Hess Pumice Products, Inc., Malad City, Id., under the tradename IM-325 with a mesh size of 325.
The perlite may be included in the settable compositions in an amount sufficient to provide the desired compressive strength, density, cost reduction, and/or reduced carbon footprint. In some embodiments, the perlite 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 cementitious components. Cementitious components include those components or combinations of components of the settable compositions that hydraulically set, or otherwise harden, to develop compressive strength, including, for example, perlite, CKD, fly ash, pumicite, slag, lime, shale, and the like. For example, the perlite may be present in an amount ranging between any of and/or including any of about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, or about 70%. In specific embodiments, the perlite may be present in the settable compositions in an amount in the range of from about 5% to about 50% by weight of cementitious components. In another embodiment, the perlite may be present in an amount in the range of from about 10% to about 40% by weight of cementitious components. In yet another embodiment, the perlite may be present in an amount in the range of from about 20% to about 30% by weight of cementitious components. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of perlite to include for a chosen application.
In one particular embodiment, the perlite can be interground with hydraulic cement. In one embodiment, the hydraulic cement may be a Portland cement, such as those classified as ASTM Type V cement. In another embodiment, the perlite can be interground with hydraulic cement and pumicite. In another embodiment, the perlite can be interground with hydraulic cement and CKD. The term “interground” or “intergrinding” as used herein means using a grinder (e.g., ball mill, rod mill, etc.) to reduce the particle size of the specified components. It is believed that intergrinding the perlite and hydraulic cement may improve the properties of the subsequent settable composition. For example, it is believed that intergrinding the perlite and hydraulic cement may provide accelerated strength development, in the subsequent settable compositions, as compared to intergrinding pumicite and hydraulic cement. By way of further example, it is believed that intergrinding the perlite and hydraulic cement may provide increased strength properties of the subsequent settable compositions, as compared to blending separately ground material.
In some embodiments, the interground perlite and hydraulic cement may comprise perlite in an amount of about 0.1% to about 99% by weight of the interground perlite and hydraulic cement and hydraulic cement in an amount of about 0.1% to about 99% by weight of the interground perlite and hydraulic cement. For example, the perlite may be present in an amount ranging between any of and/or including any of about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or about 95% by weight of the interground perlite and hydraulic cement. By way of further example, the hydraulic cement may be present in an amount ranging between any of and/or including any of about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or about 95% by weight of the interground perlite and hydraulic cement.
In accordance with embodiments, the hydraulic cement and perlite may be combined and ground to any size suitable for use in cementing operations. In another embodiment, the hydraulic cement and/or perlite may be ground prior to combination. In yet another embodiment, the perlite may be ground to a first particle size and then interground with the hydraulic cement to a second particle size. In an embodiment, the interground perlite and hydraulic cement has a mean particle size of about 0.1 microns to about 400 microns, including an amount ranging between any of and/or including any of about 0.5 microns, about 1 micron, about 2 microns, about 5 microns, about 10 microns, about 25 microns, about 50 microns, about 75 microns, about 100 microns, about 150 microns, about 200 microns, about 250 microns, about 300 microns, or about 350 microns. For example, the interground perlite and hydraulic cement may have a mean particle size of about 0.5 microns to about 50 microns. By way of further example, the interground perlite and hydraulic cement may have a mean particle size of about 0.5 microns to about 10 microns. The mean particle size corresponds to d50 values as measured by commercially available particle size analyzers such as those manufactured by Malvern Instruments, Worcestershire, United Kingdom. In some embodiments, the interground perlite and hydraulic cement may have a bimodal particle size distribution. For example, the interground perlite and hydraulic cement may have a bimodal particle size distribution with a first peak from about 1 microns to about 7 microns and a second peak from about 7 microns to about 15 microns, alternatively, a first peak from about 3 microns to about 5 microns and a second peak from about 9 microns to about 11 microns, and alternatively, a first peak of about 4 microns and a second peak of about 10 microns.
In some embodiments, the interground perlite and hydraulic cement may be present in an amount in the range of from about 0.1% to about 100% by weight of cementitious components in the settable composition. For example, the interground perlite and hydraulic cement may be present in an amount ranging between any of and/or including any of about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or about 95% by weight of cementitious components. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of the interground perlite and hydraulic cement to include for a chosen application.
Embodiments of the settable compositions further may comprise hydraulic cement. As previously mentioned, the hydraulic cement may be interground with the perlite in accordance with certain embodiments. Any of a variety of hydraulic cements suitable for use in subterranean cementing operations may be used in accordance with embodiments of the present invention. Suitable examples include hydraulic cements that comprise calcium, aluminum, silicon, oxygen and/or sulfur, which set and harden by reaction with water. Such hydraulic cements, include, but are not limited to, Portland cements, pozzolana cements, gypsum cements, high-alumina-content cements, slag cements, silica/lime cements and combinations thereof. In certain embodiments, the hydraulic cement may comprise a Portland cement. The Portland cements that may be suited for use in embodiments of the present invention are classified as Class A, C, H and G cements according to American Petroleum Institute, Recommended Practice for Testing Well Cements, API Specification 10B-2 (ISO 10426-2), First edition, July 2005. In addition, in some embodiments, cements suitable for use in the present invention may include cements classified as ASTM Type I, II, III, IV, or V.
The hydraulic cement may be included in the settable compositions in an amount sufficient for a particular application. In some embodiments, the hydraulic cement may be present in the settable compositions in an amount in the range of from about 0.1% to about 99% by weight of cementitious components. For example, the hydraulic cement may be present in an amount ranging between any of and/or including any of about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, about 85%, about 90%, or about 95% by weight of cementitious components. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of the hydraulic cement to include for a chosen application.
Embodiments of the settable compositions generally further may comprise CKD. It should be understood that embodiments of the present invention also may encompass intergrinding the CKD with the perlite and the hydraulic cement. Usually, large quantities of CKD are collected in the production of cement that are commonly disposed of as waste. Disposal of the waste CKD can add undesirable costs to the manufacture of the cement, as well as the environmental concerns associated with its disposal. The chemical analysis of CKD from various cement manufactures varies depending on a number of factors, including the particular kiln feed, the efficiencies of the cement production operation, and the associated dust collection systems. CKD generally may comprise a variety of oxides, such as SiO2, Al2O3, Fe2O3, CaO, MgO, SO3, Na2O, and K2O.
The CKD generally may exhibit cementitious properties, in that it may set and harden in the presence of water. In accordance with embodiments of the present invention, the CKD may be used, among other things, to replace higher cost cementitious components, such as Portland cement, resulting in more economical settable compositions. In addition, substitution of the Portland cement for the CKD can result in a settable composition with a reduced carbon footprint.
The CKD may be included in the settable compositions in an amount sufficient to provide the desired compressive strength, density, cost reduction, and/or reduced carbon footprint. 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 95% by weight of cementitious components. For example, the CKD may be present in an amount ranging between any of and/or including any of about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, or about 90%. In specific embodiments, the CKD may be present in the settable compositions in an amount in the range of from about 5% to about 95% by weight of cementitious components. In another embodiment, the CKD may be present in an amount in the range of from about 50% to about 90% by weight of cementitious components. In yet another embodiment, the CKD may be present in an amount in the range of from about 60% to about 80% by weight of cementitious components. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of CKD to include for a chosen application.
Embodiments of the settable compositions further may comprise pumicite. It should be understood that embodiments of the present invention also may encompass intergrinding the pumicite with the perlite and the hydraulic cement. Generally, pumicite is a volcanic rock that exhibits cementitious properties, in that it may set and harden in the presence of hydrated lime and water. Hydrated lime may be used in combination with the pumicite, for example, to provide sufficient calcium ions for the pumicite to set. In accordance with embodiments of the present invention, the pumicite may be used, among other things, to replace higher cost cementitious components, such as Portland cement, resulting in more economical settable compositions. As previously mentioned, replacement of the Portland cement should also result in a settable composition with a reduced carbon footprint.
Where present, the pumicite may be included in an amount sufficient to provide the desired compressive strength, density, cost reduction and/or reduced carbon footprint for a particular application. In some embodiments, the pumicite may be present in the settable compositions of the present invention in an amount in the range of from about 1% to about 95% by weight of cementitious components. For example, the pumicite may be present in an amount ranging between any of and/or including any of about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, about 35%, about 40%, about 45%, about 50%, about 55%, about 60%, about 65%, about 70%, about 75%, about 80%, or about 90% by weight of cementitious components. In specific embodiments, the pumicite may be present in the settable compositions of the present invention in an amount in the range of from about 5% to about 95% by weight of cementitious components. In another embodiment, the pumicite may be present in an amount in the range of from about 5% to about 80% by weight of cementitious components. In yet another embodiment, the pumicite may be present in an amount in the range of from about 10% to about 50% by weight of cementitious components. In yet another embodiment, the pumicite may be present in an amount in the range of from about 25% to about 50% by weight of cementitious components. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of the pumicite to include for a chosen application.
Embodiments of the settable compositions further may comprise lime. In certain embodiments, the lime may be hydrated lime. The lime may be included in embodiments of the settable compositions, for example, to form a hydraulic composition with other components of the settable compositions, such as the pumicite, fly ash, slag, and/or shale. Where present, the lime may be included in the settable compositions in an amount sufficient for a particular application. In some embodiments, the lime may be present in an amount in the range of from about 1% to about 40% by weight of cementitious components. For example, the lime may be present in an amount ranging between any of and/or including any of about 5%, about 10%, about 15%, about 20%, about 25%, about 30%, or about 35%. In specific embodiments, the lime may be present in an amount in the range of from about 5% to about 20% by weight of cementitious components. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of the lime to include for a chosen application.
In accordance with certain embodiments, a mixture of pumicite and hydraulic cement, such as Portland cement may be included in the settable composition. In an embodiment, the cement/pumicite mixture contains hydraulic cement in an amount of about 25% to about 75% by weight of the mixture and pumicite in an amount of about 25% to about 75% by weight of the mixture. In an embodiment, the cement/pumicite mixture contains about 40% hydraulic cement by weight and about 60% pumicite by weight. In an embodiment, the cement/pumicite mixture may comprise hydraulic cement interground with pumicite. In one embodiment, the hydraulic cement may comprise Portland cement classified as ASTM Type V cement. In accordance with embodiments, the Portland cement and pumicite may be combined and ground to any size suitable for use in cementing operations. In another embodiment, the Portland cement and pumicite may be ground prior to combination. In an embodiment, the cement/pumicite mixture of Portland cement and pumicite has a mean particle size of about 0.1 microns to about 400 microns, alternatively, about 0.5 microns to about 50 microns, and alternatively, about 0.5 microns to about 10 microns. The mean particle size corresponds to d50 values as measured by commercially available particle size analyzers such as those manufactured by Malvern Instruments, Worcestershire, United Kingdom. An example of a suitable cement/pumicite mixture is available from Halliburton Energy Services, Inc., under the trade name FineCem™ 925 cement.
It is believed that hydraulic cement interground with pumicite when used in a settable composition in combination with unexpanded perlite may provide synergistic effects. For example, it is believed that the combination of unexpanded perlite and the cement/pumicite mixture may provide significantly higher compressive strength, particularly at elevated well bore temperatures. Accordingly, the combination of unexpanded perlite and the cement/pumicite mixture may be particularly suited for use in settable compositions at elevated well bore temperatures, such as at temperatures greater than about 80° F., alternatively greater than about 120° F., and alternatively greater than about 140° F.
Embodiments of the settable compositions further may comprise fly ash. 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 should set to form a hardened mass. Class F fly ash generally does not contain sufficient lime, so an additional source of calcium ions is typically required for the Class F fly ash to form a hydraulic composition. In some embodiments, lime may be mixed with Class F fly ash in an amount in the range of 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.
Where present, the fly ash generally may be included in the settable 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 settable compositions of the present invention in an amount in the range of about 1% to about 75% by weight of cementitious components. For example, the fly ash may be present in an amount ranging between any of and/or including any of about 5%, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, or about 70% by weight of cementitious components. In specific embodiments, the fly ash may be present in an amount in the range of about 10% to about 60% by weight of cementitious components. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of the fly ash to include for a chosen application.
Embodiments of the settable compositions further may comprise slag cement. In some embodiments, a slag cement that may be suitable for use may comprise slag. Slag generally does not contain sufficient basic material, so slag cement further may comprise a base to produce a hydraulic 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 settable 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 settable compositions of the present invention in an amount in the range of about 1% to about 75% by weight of cementitious components. For example, the slag cement may be present in an amount ranging between any of and/or including any of about 5%, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, or about 70% by weight of cementitious components. In specific embodiments, the slag cement may be present in an amount in the range of about 5% to about 50% by weight of cementitious components. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of the slag cement to include for a chosen application.
Embodiments of the settable compositions 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 about 600° C. 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 about 1% to about 75% by weight of cementitious components. For example, the metakaolin may be present in an amount ranging between any of and/or including any of about 5%, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, or about 70% by weight of cementitious components. In specific embodiments, the metakaolin may be present in an amount in the range of about 10% to about 50% by weight of cementitious components. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of the metakaolin to include for a chosen application.
Embodiments of the settable compositions 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 may be 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. 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 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 the settable compositions of the present invention in an amount in the range of about 1% to about 75% by weight of cementitious components. For example, the shale may be present in an amount ranging between any of and/or including any of about 5%, about 10%, about 20%, about 30%, about 40%, about 50%, about 60%, or about 70% by weight of cementitious components. In specific embodiments, the shale may be present in an amount in the range of about 10% to about 35% by weight of cementitious components. 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.
Embodiments of the settable compositions 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. Examples of suitable zeolites are described in more detail in U.S. Pat. No. 7,445,669. 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 about 1% to about 65% by weight of cementitious components. For example, the zeolite may be present in an amount ranging between any of and/or including any of about 5%, about 10%, about 20%, about 30%, about 40%, about 50%, or about 60% by weight of cementitious components. In specific embodiments, the zeolite may be present in an amount in the range of about 10% to about 40% by weight of cementitious components. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of the zeolite to include for a chosen application.
Embodiments of the settable compositions 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, organic acids (e.g., hydroxycarboxy acids), copolymers that comprise acrylic acid or maleic acid, and combinations thereof. One example of a suitable sulfoalkylated 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 trademarks HR® 4, HR® 5, HR® 7, HR® 12, HR®15, HR®25, HR®601, SCR™ 100, and SCR™ 500 retarders. 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 the settable compositions of the present invention an amount in the range of about 0.1% to about 5% by weight of cementitious components, including an amount ranging between any of and/or including any of about 0.5%, about 1%, about 2%, about 3%, or about 4% by weight of cementitious components. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of the set retarding additive to include for a chosen application.
Embodiments of the settable compositions further may include water. The water that may be used in embodiments of the settable compositions include, for example, freshwater, saltwater (e.g., water containing one or more salts dissolved therein), brine (e.g., saturated saltwater produced from subterranean formations), seawater, or combinations thereof. Generally, the water may be from any source, provided that the water does not contain an excess of compounds that may undesirably affect other components in the settable composition. In some embodiments, the water may be included in an amount sufficient to form a pumpable slurry. In some embodiments, the water may be included in the settable compositions of the present invention in an amount in the range of about 40% to about 200% by weight of cementitious components. For example, the water may be present in an amount ranging between any of and/or including any of about 50%, about 75%, about 100%, about 125%, about 150%, or about 175% by weight of cementitious components. In specific embodiments, the water may be included in an amount in the range of about 40% to about 150% by weight of cementitious components. One of ordinary skill in the art, with the benefit of this disclosure, will recognize the appropriate amount of water to include for a chosen application.
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, strength-retrogression additives, set accelerators, weighting agents, lightweight additives, gas-generating additives, mechanical property enhancing additives, lost-circulation materials, filtration-control additives, dispersants, fluid loss control additives, defoaming agents, foaming agents, oil-swellable particles, water-swellable particles, thixotropic additives, and combinations thereof. Specific examples of these, and other, additives include crystalline silica, amorphous silica, fumed silica, salts, fibers, hydratable clays, microspheres, rice husk ash, elastomers, elastomeric particles, resins, latex, combinations thereof, and the like. A person having ordinary skill in the art, with the benefit of this disclosure, will readily be able to determine the type and amount of additive useful for a particular application and desired result. Embodiments of the settable compositions may be foamed and/or extended as desired by those of ordinary skill in the art.
The settable 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 settable compositions may have a density in the range of from about 8 pounds per gallon (“lb/gal”) to about 16 lb/gal. In other embodiments, the settable compositions may be foamed to a density in the range of from about 8 lb/gal to about 13 lb/gal.
As will be appreciated by those of ordinary skill in the art, embodiments of the settable compositions may be used in a variety of subterranean applications, including primary and remedial cementing. The settable compositions of the present invention also may be used in surface applications, for example, construction cementing. Embodiments may include providing a settable composition and allowing the settable composition to set. In some embodiments, the settable composition may be allowed to set in a location that is above ground, for example, in construction cementing. In other embodiments, the settable composition may be introduced into a well bore and allowed to set. For example, the settable composition may be placed into a space between a subterranean formation and a conduit located in the well bore. Embodiments of the settable compositions may comprise, for example, water and one or more of perlite, CKD, or pumicite. Embodiments of the settable compositions may comprise, for example, perlite interground with hydraulic cement (e.g., Portland cement).
In primary cementing embodiments, for example, a settable composition may be introduced into a space between a subterranean formation and a conduit (e.g., pipe strings, liners) located in the well bore. The settable composition may be allowed to set to form an annular sheath of hardened cement in the space between the subterranean formation and the conduit. Among other things, the set settable composition may form a barrier, preventing the migration of fluids in the well bore. The set settable composition also may, for example, support the conduit in the well bore.
In remedial cementing embodiments, a settable composition may be used, for example, in squeeze-cementing operations or in the placement of cement plugs. By way of example, the settable composition may be placed in a well bore to plug a void or crack in the formation, in a gravel pack, in the conduit, in the cement sheath, and/or a microannulus between the cement sheath and the conduit.
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 series of samples were prepared and subjected to 24-hour crush strength tests in accordance with API Specification 10 to analyze force resistance properties of settable compositions that comprise unexpanded perlite. The sample compositions were allowed to cure in a water bath at the temperature indicated in the table below for twenty-four hours. Immediately after removal from the water bath, crush strengths were determined using a Tinius Olsen tester. The results of the crush strength tests are set forth in the table below.
Test Nos. 1-6 were performed on samples with a 14.2 ppg and containing water, Portland class H cement, ground unexpanded perlite, lime, and water, as indicated in the table below. The ground unexpanded perlite was IM-325 from Hess Pumice Products with a particle size of about 325 U.S. Standard Mesh.
Test Nos. 7-8 were performed on samples with a density of 14.2 ppg and containing water, Portland class H cement, pumicite, and lime, as indicated in the table below. The pumicite was about 200 U.S. Standard Mesh in size.
Test Nos. 9-14 were performed on samples with a density of 14.2 ppg and containing water, a ground cement/pumicite mixture (FineCem™ 925 cement), unexpanded perlite, lime, and water, as indicated in the table below. The ground cement/pumicite mixture comprised Portland Type V cement (about 40% by weight) interground with pumicite (about 60% by weight). The ground cement/pumicite mixture had a mean particle size in the range of about 1 to about 4 microns. The ground unexpanded perlite was IM-325 from Hess Pumice Products with a particle size of about 325 U.S. Standard Mesh.
In the following table, percent by weight is based on the weight of the Portland cement, cement/pumicite mixture, pumicite, and unexpanded perlite in the sample, and gallons per sack (gal/sk) is based on a 94-pound sack of the Portland cement, cement/pumicite mixture, pumicite, and unexpanded perlite.
Example 1 thus indicates that replacement of at least a portion of the Portland cement with unexpanded perlite may increase the crush strength of the settable compositions. At 140° F., for example, the Test Nos. 2 and 4 with unexpanded perlite had crush strengths of 886 psi and 777 psi as compared to a crush strength of 674 psi for Test No. 1 with 100% Portland cement by weight.
Example 1 further indicates that the ground pumicite/cement mixture in combination with the unexpanded perlite may have synergistic effects on the settable composition, in that this combination may provide increased crush strengths at elevated temperatures. At 140° F., for example, Test Nos. 12 and 14 with the ground pumicite/cement mixture and unexpanded perlite had crush strengths of 2740 psi and 2610 psi. This crush strength is markedly higher than the crush strengths for compositions with 100% Portland cement (674 psi at 140° F.) and compositions with Portland cement and pumicite that were not ground to fine particle sizes (835 psi and 734 psi at 140° F.). This increased compressive strength for combinations of ground pumicite/cement mixture and unexpanded perlite cannot be attributed solely to the addition of expanded perlite as the combination had significantly higher crush strength than seen with addition of unexpanded perlite to Portland cement (777 psi and 886 psi at 140° F.). In addition, this increased compressive strength for combinations of ground pumicite/cement mixture and unexpanded perlite cannot be attributed solely to the addition of expanded perlite as the combination had significantly higher crush strength than seen with the ground pumicite/cement mixture alone (1877 at 140° F.).
An additional series of sample settable compositions were prepared and tested to analyze the force resistance properties of settable compositions that comprise CKD and unexpanded perlite. The sample compositions were allowed to cure in a water bath at the temperature indicated in the table below for either 24 or 72 hours. Immediately after removal from the water bath, crush strengths were determined using a Tinius Olsen tester. The results of the crush strength tests are set forth in the table below.
Test Nos. 15-28 were performed on samples with a density of 14.2 ppg and containing water, CKD, ground unexpanded perlite, and lime, as indicated in the table below. The samples further contained a cement set retarder (CFR-3™ cement set retarder, Halliburton Energy Services, Inc.) in an amount of about 0.4% by weight. The ground unexpanded perlite was IM-325 from Hess Pumice Products with a particle size of about 325 U.S. Standard Mesh.
In the following table, percent by weight is based on the weight of the CKD and unexpanded perlite in the sample, and gallons per sack (gal/sk) is based on a 94-pound sack of the CKD and unexpanded perlite.
Example 2 thus indicates that unexpanded perlite may be used to enhance the crush strength of CKD-containing compositions. In addition, this effect is particularly pronounced at increased temperatures. At 140° F., for example, Test No. 22 with 75% CKD and 25% unexpanded perlite had a 72-hour crush strength of 1004 psi as compared to a 72-hour crush strength of 457 psi for Test No. 18 with 100% CKD.
An additional series of sample settable compositions were prepared and tested to further analyze the force resistance properties of settable compositions that comprise CKD and unexpanded perlite. The sample compositions were allowed to cure in a water bath at the temperature indicated in the table below for 24 hours. Immediately after removal from the water bath, crush strengths were determined using a Tinius Olsen tester. The results of the crush strength tests are set forth in the table below.
Test Nos. 29-37 were performed on samples with a density of 14.2 ppg and containing water, CKD, ground unexpanded perlite, and lime, as indicated in the table below. The samples further contained a cement dispersant in an amount of about 0.4% by weight. The ground unexpanded perlite was IM-325 from Hess Pumice Products with a particle size of about 325 U.S. Standard Mesh.
In the following table, percent by weight is based on the weight of the CKD and unexpanded perlite in the sample, and gallons per sack (gal/sk) is based on a 94-pound sack of the CKD and unexpanded perlite.
Example 3 thus indicates that unexpanded perlite may be used to enhance the crush strength of CKD-containing compositions. For example, as indicated in the table above, the crush strength of the samples steadily increased as the concentration of unexpanded perlite in the sample was increased from 0% by weight to 40% by weight.
An additional series of sample settable compositions were prepared and tested to further analyze the force resistance properties of settable compositions that comprise CKD and unexpanded perlite. The sample compositions were allowed to cure in a water bath at the temperature indicated in the table below for 24 hours. Immediately after removal from the water bath, crush strengths were determined using a Tinius Olsen tester. The results of the crush strength tests are set forth in the table below.
Test Nos. 38-43 were performed on samples with a density of 14.2 ppg and containing water, CKD, perlite, and lime, as indicated in the table below. The samples further contained a cement dispersant in an amount of about 0.4% by weight. Test Nos. 38 and 39 contained a ground unexpanded perlite (IM-325) from Hess Pumice Products with a particle size of about 325 U.S. Standard Mesh. Test Nos. 40 and 41 contained unground perlite ore having a mean particle size (d50) of about 190 microns. Test Nos. 42 and 43 contained expanded perlite.
In the following table, percent by weight is based on the weight of the CKD and perlite in the sample, and gallons per sack (gal/sk) is based on a 94-pound sack of the CKD and perlite.
Example 4 thus indicates that unexpanded perlite provides superior strength enhancement to CKD-containing compositions when compared to unground perlite ore and expanded perlite. Indeed, the sample with the expanded perlite could not even be tested due to mixability problems.
An additional series of sample settable compositions were prepared and tested to further analyze settable compositions that comprise CKD and unexpanded perlite. The sample compositions were allowed to cure in a water bath at the temperature indicated in the table below for 24 hours. Immediately after removal from the water bath, crush strengths were determined using a Tinius Olsen tester. The results of the crush strength tests are set forth in the table below. The thickening time for each sample was also determined at 140° F. in accordance with API Specification 10.
Test Nos. 44-56 were performed on samples with a density of 12.5 ppg and containing CKD, perlite, and lime, as indicated in the table below. The samples further contained a cement dispersant in an amount of about 0.4% by weight and a cement set retarder (HR® 5 cement retarder, Halliburton Energy Services, Inc.). Test Nos. 45, 48, 51, and 54 contained a ground unexpanded perlite (IM-325) from Hess Pumice Products with a particle size of about 314 U.S. Standard Mesh. Test Nos. 46, 49, 52, and 55 contained unground perlite ore having a mean particle size (d50) of about 190. Test Nos. 47, 50, 53, and 56 contained expanded perlite.
In the following table, percent by weight is based on the weight of the CKD and perlite in the sample, and gallons per sack (gal/sk) is based on a 94-pound sack of the CKD and perlite.
Example 5 thus indicates that unexpanded perlite provides enhanced strength to CKD-containing compositions when compared to unground perlite ore and expanded perlite. In a similar manner to the preceding example, the samples with expanded perlite could not even be tested due to mixability problems.
An additional series of sample settable compositions were prepared and tested to further analyze settable compositions that comprise CKD and unexpanded perlite. The sample compositions were allowed to cure in a water bath at the temperature indicated in the table below for 24 hours. Immediately after removal from the water bath, crush strengths were determined using a Tinius Olsen tester. The results of the crush strength tests are set forth in the table below.
Test No. 57 was performed on a sample with a density of 12.5 ppg and containing water, Portland Type V cement, CKD, unground perlite ore, and pumicite, as indicated in the table below. The unground perlite ore had a mean particle size (d50) of about 190. The pumicite had a mean particle size (d50) of about 4 microns.
Test No. 58 was performed on a sample with a density of 12.5 ppg and containing water, ground cement/pumicite mixture pumicite, CKD, and ground unexpanded perlite. The ground cement/pumicite mixture comprised Portland Type V cement (about 40% by weight) interground with pumicite (about 60% by weight). The ground cement/pumicite mixture had a mean particle size of about 1-4 microns. The ground unexpanded perlite was IM-325 from Hess Pumice Products with a particle size of about 325 U.S. Standard Mesh.
In the following table, percent by weight is based on the weight of the CKD, cement, perlite, pumicite, and/or pumicite/cement mixture in the sample, and gallons per sack (gal/sk) is based on a 94-pound sack of the CKD, cement, perlite, pumicite, and/or pumicite/cement mixture in the sample.
Example 6 thus indicates that unexpanded perlite in combination with ground pumicite provides enhanced strength to CKD-containing compositions in comparison to compositions with standard cement, pumicite, and unground perlite ore.
An additional series of sample settable compositions were prepared and tested to analyze settable compositions that comprised interground perlite and hydraulic cement.
The sample settable compositions were formed by mixing the components in the amounts set forth in the table below. The interground pumicite and cement comprised pumicite (about 60% by weight) and Portland Type V cement (about 40% by weight) and had a mean particle size of about 1-4 microns. The interground pumicite and cement are available from Halliburton Energy Services, Inc., under the trade name FineCem™ 925 cement. The interground perlite and cement comprised ground unexpanded perlite (about 60% by weight) and Portland Type V cement (about 40% by weight) and had a bimodal particle size distribution with peak particle sizes of about 4 microns and about 10 microns. The interground perlite and cement was obtained from Hess Pumice Products, Malad City, Id. The lime was hydrated lime, obtained from Univar USA.
The sample compositions were subjected to 24-hour crush strength tests in accordance with API Specification 10. The sample compositions were allowed to cure in a water bath at the temperature indicated in the table below for 24 hours. Immediately after removal from the water bath, crush strengths were determined using a Tinius Olsen tester.
The results of the crush strength tests are set forth in the table below.
602
1The term “% bwc” refers to by weight of cement, which in this example is either by weight of the interground pumicite and cement or by weight of the interground perlite and cement.
21.2 grams of CFR-3 ™ friction reducer were added to the sample settable composition for Test No. 60.
Example 7 thus indicates that interground perlite and hydraulic cement generally provides enhances compressive strength development as compared to interground pumicite and hydraulic cement. It should be noted that the CFR-3™ included in Test No. 60 retarded the setting resulting in the lower 24-hour crush strength as compared to Test No. 59 with the interground pumicite and cement.
An additional series of sample settable compositions were prepared and tested to further analyze settable compositions that comprised interground perlite and hydraulic cement.
The sample settable compositions were formed by mixing the components in the amounts set forth in the table below. The interground pumicite and cement comprised pumicite (about 60% by weight) and Portland Type V cement (about 40% by weight) and had a mean particle size of about 1-4 microns. The interground pumicite and cement are available from Halliburton Energy Services, Inc., under the trade name FineCem™ 925 cement. The interground perlite and cement comprised ground unexpanded perlite (about 60% by weight) and Portland Type V cement (about 40% by weight) and had a bimodal particle size distribution with peak particle sizes of about 4 microns and about 10 microns. The interground perlite and cement was obtained from Hess Pumice Products, Malad City, Id.
The sample compositions were subjected to 24-hour crush strength tests in accordance with API Specification 10. The sample compositions were allowed to cure in a water bath at the temperature indicated in the table below for 24 hours. Immediately after removal from the water bath, crush strengths were determined using a Tinius Olsen tester. The thickening time for each sample was also determined at 140° F. in accordance with API Specification 10.
The results of the crush strength and thickening time tests are set forth in the table below.
1The abbreviation “% bwc” refers to by weight of cement, which in this example is either by weight of the interground pumicite and cement or by weight of the interground perlite and cement.
2The abbreviation “Bc” refers to Bearden units of consistency.
Example 8 thus indicates that settable compositions comprising interground perlite and hydraulic cement may have acceptable thickening times for use in subterranean applications. Example 8 further indicates that interground perlite and hydraulic cement generally provides enhanced compressive strength development and can be similarly controlled with retarders as compared to interground pumicite and hydraulic cement.
An additional series of sample settable compositions were prepared and tested to further analyze settable compositions that comprised interground perlite and hydraulic cement.
The sample settable compositions were formed by mixing the components in the amounts set forth in the table below. The interground pumicite and cement comprised pumicite (about 60% by weight) and Portland Type V cement (about 40% by weight) and had a mean particle size of about 1-4 microns. The interground pumicite and cement are available from Halliburton Energy Services, Inc., under the trade name FineCem™ 925 cement. The interground perlite and cement comprised ground unexpanded perlite (about 60% by weight) and Portland Type V cement (about 40% by weight) and had a bimodal particle size distribution with peak particle sizes of about 4 microns and about 10 microns. The interground perlite and cement was obtained from Hess Pumice Products, Malad City, Id.
Free water data was then gathered for each sample composition in accordance with API Specification 10. The free water data is set forth in the table below.
1The abbreviation “% bwc” refers to by weight of cement, which in this example is either by weight of the interground pumicite and cement or by weight of the interground perlite and cement.
2The abbreviation “cc” refers to cubic centimeters.
Example 9 thus indicates that settable compositions comprising interground perlite and hydraulic cement may have provide lower levels of free water as compared to interground pumicite and hydraulic cement.
It should be understood that the compositions and methods are described in terms of “comprising,” “containing,” or “including” various components or steps, the compositions and methods can also “consist essentially of” or “consist of” the various components and steps.
For the sake of brevity, only certain ranges are explicitly disclosed herein. However, ranges from any lower limit may be combined with any upper limit to recite a range not explicitly recited, as well as, ranges from any lower limit may be combined with any other lower limit to recite a range not explicitly recited, in the same way, ranges from any upper limit may be combined with any other upper limit to recite a range not explicitly recited. Additionally, whenever a numerical range with a lower limit and an upper limit is disclosed, any number and any included range falling within the range is specifically disclosed. In particular, every range of values (of the form, “from about a to about b,” or, equivalently, “from approximately a to b,” or, equivalently, “from approximately a-b”) disclosed herein is to be understood to set forth every number and range encompassed within the broader range of values even if not explicitly recite. Thus, every point or individual value may serve as its own lower or upper limit combined with any other point or individual value or any other lower or upper limit, to recite a range not explicitly recited.
Therefore, the present invention is well adapted to attain the ends and advantages mentioned as well as those that are inherent therein. The particular embodiments disclosed above are illustrative only, as the present invention may be modified and practiced in different but equivalent manners apparent to those skilled in the art having the benefit of the teachings herein. Although individual embodiments are discussed, the invention covers all combinations of all those embodiments. Furthermore, no limitations are intended to the details of construction or design herein shown, other than as described in the claims below. Also, the terms in the claims have their plain, ordinary meaning unless otherwise explicitly and clearly defined by the patentee. It is therefore evident that the particular illustrative embodiments disclosed above may be altered or modified and all such variations are considered within the scope and spirit of the present invention.
This application is a continuation-in-part of co-pending U.S. patent application Ser. No. 12/975,196, entitled “Settable Compositions Comprising Unexpanded Perlite and Methods of Cementing in Subterranean Formations,” filed on Dec. 21, 2010, the entire disclosure of which is incorporated herein by reference.
| Number | Name | Date | Kind |
|---|---|---|---|
| 2021956 | Gladney et al. | Nov 1935 | A |
| 2045899 | Davis | Jun 1936 | A |
| 2094316 | Cross et al. | Sep 1937 | A |
| 2133622 | Larmour et al. | Oct 1938 | A |
| 2193775 | Stratford | Mar 1940 | A |
| 2193807 | Dieterich | Mar 1940 | A |
| 2329940 | Ponzer | Sep 1943 | A |
| 2772739 | Arie | Dec 1956 | 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 |
| 2945769 | Gama et al. | Jul 1960 | A |
| 3066031 | Schifferle | Nov 1962 | A |
| 3168139 | Kennedy et al. | Feb 1965 | A |
| 3320077 | Prior | May 1967 | A |
| 3411580 | Roberts et al. | Nov 1968 | A |
| 3421703 | Galer | Jan 1969 | A |
| 3454095 | Messenger et al. | Jul 1969 | A |
| 3467193 | Messenger | Sep 1969 | A |
| 3473939 | Mayberry et al. | Oct 1969 | A |
| 3499491 | Wyant et al. | Mar 1970 | A |
| 3557876 | Tragesser | Jan 1971 | A |
| 3574816 | Abbdellatif et al. | Apr 1971 | A |
| 3628973 | Greening et al. | Dec 1971 | A |
| 3748159 | George | Jul 1973 | A |
| 3749173 | Hill et al. | Jul 1973 | A |
| 3863718 | Bruist | Feb 1975 | A |
| 3876005 | Fincher et al. | Apr 1975 | A |
| 3887009 | Miller et al. | Jun 1975 | A |
| 3887385 | Quist et al. | Jun 1975 | A |
| 3921717 | Danjushevsky | Nov 1975 | A |
| 3959007 | Pitt | May 1976 | A |
| 4018617 | Nicholson | Apr 1977 | A |
| 4018619 | Webster et al. | Apr 1977 | A |
| 4031184 | McCord | Jun 1977 | A |
| 4036301 | Powers et al. | Jul 1977 | A |
| 4083407 | Griffin et al. | Apr 1978 | A |
| 4101332 | Nicholson | Jul 1978 | A |
| 4105459 | Mehta | Aug 1978 | A |
| 4141843 | Watson | Feb 1979 | A |
| 4176720 | Wilson | Dec 1979 | A |
| 4268316 | Wills et al. | May 1981 | A |
| 4274881 | Langton | Jun 1981 | A |
| 4304300 | Watson | Dec 1981 | A |
| 4333764 | Richardson | Jun 1982 | A |
| 4341562 | Ahlbeck | Jul 1982 | A |
| RE31190 | Detroit et al. | Mar 1983 | E |
| 4400474 | Copperthwaite et al. | Aug 1983 | A |
| 4407677 | Wills et al. | Oct 1983 | A |
| 4432800 | Kneller et al. | Feb 1984 | A |
| 4435216 | Diehl et al. | Mar 1984 | A |
| 4436850 | Burdick et al. | Mar 1984 | A |
| 4460292 | Durham et al. | Jul 1984 | A |
| 4470463 | Holland | Sep 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 |
| 4741782 | Styron | May 1988 | A |
| 4784223 | Worrall et al. | Nov 1988 | A |
| 4829107 | Kindt | May 1989 | A |
| 4883125 | Wilson et al. | Nov 1989 | A |
| 4941536 | Brothers et al. | Jul 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 |
| 5113943 | Wilson et al. | May 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 |
| 5215585 | Luthra et al. | Jun 1993 | A |
| 5238064 | Dahl et al. | Aug 1993 | A |
| 5252128 | Gopalkrishnan | Oct 1993 | A |
| 5266111 | Barbour | Nov 1993 | A |
| 5290355 | Jakel et al. | Mar 1994 | A |
| 5295543 | Terry et al. | Mar 1994 | A |
| 5305831 | Nahm | Apr 1994 | A |
| 5314022 | Cowan et al. | May 1994 | A |
| 5316083 | Nahm et al. | May 1994 | A |
| 5327968 | Onan et al. | Jul 1994 | A |
| 5337824 | Cowan | Aug 1994 | A |
| 5339902 | Harris | Aug 1994 | A |
| 5346548 | Mehta | Sep 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 |
| 5417759 | Huddleston | May 1995 | A |
| 5423379 | Hale et al. | Jun 1995 | A |
| 5430235 | Hooykaas et al. | Jul 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 |
| 5529123 | Carpenter et al. | Jun 1996 | A |
| 5529624 | Riegler | Jun 1996 | A |
| 5536311 | Rodrigues | Jul 1996 | A |
| 5542782 | Carter et al. | Aug 1996 | A |
| 5554352 | Jaques et al. | Sep 1996 | A |
| 5569324 | Totten et al. | Oct 1996 | A |
| 5580379 | Cowan | Dec 1996 | A |
| 5585333 | Dahl et al. | Dec 1996 | A |
| 5588489 | Chatterji et al. | Dec 1996 | A |
| 5641584 | Andersen et al. | Jun 1997 | A |
| 5673753 | Hale et al. | Oct 1997 | A |
| 5681384 | Liskowitz | 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 |
| 5795924 | Chatterji et al. | Aug 1998 | A |
| 5820670 | Chatterji et al. | Oct 1998 | A |
| 5851960 | Totten et al. | Dec 1998 | A |
| 5866516 | Costin | Feb 1999 | A |
| 5866517 | Carpenter et al. | 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 |
| 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 |
| 6098711 | Chatterji et al. | Aug 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 |
| 6264738 | Lorke et al. | Jul 2001 | B1 |
| 6277189 | Chugh | Aug 2001 | B1 |
| 6312515 | Barlet-Gouedard et al. | Nov 2001 | B1 |
| 6315042 | Griffith et al. | Nov 2001 | B1 |
| 6328106 | Griffith et al. | Dec 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 |
| 6416574 | Steelhammer | Jul 2002 | B1 |
| 6451104 | Mehta | Sep 2002 | B2 |
| 6457524 | Roddy | Oct 2002 | B1 |
| 6478869 | Reddy et al. | Nov 2002 | B2 |
| 6488763 | Brothers et al. | Dec 2002 | B2 |
| 6488764 | Westerman | Dec 2002 | B2 |
| 6494951 | Reddy et al. | Dec 2002 | B1 |
| 6500252 | Chatterji et al. | Dec 2002 | B1 |
| 6502634 | Evans et al. | Jan 2003 | B1 |
| 6508305 | Brannon et al. | Jan 2003 | B1 |
| 6516884 | Chatterji et al. | Feb 2003 | B1 |
| 6524384 | Griffith et al. | Feb 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 |
| 6641658 | Dubey | Nov 2003 | B1 |
| 6645289 | Sobolev | Nov 2003 | B2 |
| 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 |
| 6668927 | Chatterji et al. | Dec 2003 | B1 |
| 6668929 | Griffith et al. | Dec 2003 | B2 |
| 6689208 | Brothers | Feb 2004 | B1 |
| 6702044 | Reddy et al. | Mar 2004 | B2 |
| 6706108 | Polston | Mar 2004 | B2 |
| 6708760 | Chatterji et al. | Mar 2004 | B1 |
| 6715568 | Bailey | Apr 2004 | B1 |
| 6716282 | Griffith et al. | Apr 2004 | B2 |
| 6729405 | DiLullo et al. | May 2004 | B2 |
| 6755905 | Oates | Jun 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 |
| 6823940 | Reddy et al. | Nov 2004 | B2 |
| 6832652 | Dillenbeck et al. | Dec 2004 | B1 |
| 6835243 | Brothers et al. | Dec 2004 | B2 |
| 6837316 | Reddy et al. | Jan 2005 | B2 |
| 6840318 | Lee | Jan 2005 | B2 |
| 6846357 | Reddy et al. | Jan 2005 | B2 |
| 6848519 | Reddy et al. | Feb 2005 | B2 |
| 6869474 | Perez-Pena et al. | Mar 2005 | B2 |
| 6874578 | Garnier | Apr 2005 | B1 |
| 6883609 | Drochon | Apr 2005 | B2 |
| 6887833 | Brothers et al. | May 2005 | B2 |
| 6889767 | Reddy et al. | May 2005 | B2 |
| 6904971 | Brothers et al. | Jun 2005 | B2 |
| 6908508 | Brothers | Jun 2005 | B2 |
| 6911078 | Barlet-Gouedard et al. | Jun 2005 | B2 |
| 7022755 | Chatterji et al. | Apr 2006 | B1 |
| 7048053 | Santra et al. | May 2006 | B2 |
| 7077203 | Roddy et al. | Jul 2006 | B1 |
| 7096944 | Vargo et al. | Aug 2006 | B2 |
| 7101829 | Guichard | Sep 2006 | B2 |
| 7174962 | Roddy et al. | Feb 2007 | B1 |
| 7182137 | Fyten et al. | Feb 2007 | B2 |
| 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 |
| 7284609 | Roddy et al. | Oct 2007 | B2 |
| 7285164 | Luke et al. | Oct 2007 | B2 |
| 7303015 | Fyten et al. | Dec 2007 | B2 |
| 7335252 | Roddy et al. | Feb 2008 | B2 |
| 7337842 | Roddy et al. | Mar 2008 | B2 |
| 7338923 | Roddy et al. | Mar 2008 | B2 |
| 7341104 | Roddy et al. | Mar 2008 | B2 |
| 7341105 | Bingamon | Mar 2008 | B2 |
| 7350573 | Reddy | 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 |
| 7404855 | Chatterji et al. | Jul 2008 | B2 |
| 7409990 | Burts et al. | Aug 2008 | B1 |
| 7445669 | Roddy et al. | Nov 2008 | B2 |
| 7478675 | Roddy et al. | Jan 2009 | B2 |
| 7607482 | Roddy et al. | Oct 2009 | B2 |
| 7607484 | Roddy et al. | Oct 2009 | B2 |
| 7612021 | Chatterji | Nov 2009 | B2 |
| 7627870 | Michaeli et al. | Dec 2009 | B1 |
| 7631692 | Roddy et al. | Dec 2009 | B2 |
| 7655088 | Bethani | Feb 2010 | B2 |
| 7674332 | Roddy et al. | Mar 2010 | B2 |
| 7741841 | Edwards et al. | Jun 2010 | B2 |
| 7743828 | Roddy et al. | Jun 2010 | B2 |
| 7748453 | Reddy | Jul 2010 | B2 |
| 7784542 | Roddy et al. | Aug 2010 | B2 |
| 7789150 | Roddy et al. | Sep 2010 | B2 |
| 7815880 | Constantz et al. | Oct 2010 | B2 |
| 7867954 | Warrender et al. | Jan 2011 | B2 |
| 7922809 | Constantz et al. | Apr 2011 | B1 |
| 7927419 | Roddy | Apr 2011 | B2 |
| 8006446 | Constantz et al. | Aug 2011 | B2 |
| 8029618 | Al-Shafei | Oct 2011 | B2 |
| 8039253 | Asou | Oct 2011 | B2 |
| 8261827 | Roddy | Sep 2012 | B2 |
| 8281859 | Roddy | Oct 2012 | B2 |
| 8297357 | Brenneis | Oct 2012 | B2 |
| 8307899 | Brenneis | Nov 2012 | B2 |
| 8318642 | Roddy | Nov 2012 | B2 |
| 8327939 | Roddy | Dec 2012 | B2 |
| 8333240 | Roddy | Dec 2012 | B2 |
| 8399387 | Roddy | Mar 2013 | B2 |
| 8403045 | Brenneis et al. | Mar 2013 | B2 |
| 8434553 | Brenneis et al. | May 2013 | B2 |
| 8440596 | Brenneis et al. | May 2013 | B2 |
| 8486868 | Brenneis et al. | Jul 2013 | B2 |
| 8486869 | Brenneis et al. | Jul 2013 | B2 |
| 8522873 | Benkley et al. | Sep 2013 | B2 |
| 8544543 | Chatterji et al. | Oct 2013 | B2 |
| 8551923 | Benkley et al. | Oct 2013 | B1 |
| 8554543 | Cherepanov et al. | Oct 2013 | B2 |
| 8555967 | Chatterji et al. | Oct 2013 | 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 |
| 20030188669 | Sobolev et al. | Oct 2003 | A1 |
| 20040007162 | Morioka et al. | Jan 2004 | A1 |
| 20040040474 | Perez-Pena et al. | Mar 2004 | A1 |
| 20040040475 | De La Roij | 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 |
| 20040129181 | Lalande et al. | Jul 2004 | A1 |
| 20040182577 | Chatterji 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 |
| 20040262000 | Morgan 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 |
| 20050061505 | Caveny et al. | Mar 2005 | A1 |
| 20050072599 | Luke et al. | Apr 2005 | A1 |
| 20050077045 | Chatterj et al. | Apr 2005 | A1 |
| 20050084334 | Shi et al. | Apr 2005 | A1 |
| 20050098317 | Reddy et al. | May 2005 | A1 |
| 20050133221 | Chatterji et al. | Jun 2005 | A1 |
| 20050205255 | Gagliano et al. | Sep 2005 | A1 |
| 20060025312 | Santra et al. | Feb 2006 | A1 |
| 20060054319 | Fyten | Mar 2006 | A1 |
| 20060065399 | Luke et al. | Mar 2006 | A1 |
| 20060081372 | Dealy et al. | Apr 2006 | A1 |
| 20060086499 | Badalamenti et al. | Apr 2006 | A1 |
| 20060166834 | Roddy | Jul 2006 | A1 |
| 20060175060 | Reddy | Aug 2006 | A1 |
| 20060260512 | Nordmeyer | Nov 2006 | A1 |
| 20070056475 | Roddy et al. | Mar 2007 | A1 |
| 20070056479 | Gray | Mar 2007 | A1 |
| 20070089643 | Roddy et al. | Apr 2007 | A1 |
| 20070102157 | Roddy et al. | May 2007 | A1 |
| 20070137528 | LeRoy-Delage et al. | Jun 2007 | A1 |
| 20070186820 | O'Hearn | Aug 2007 | A1 |
| 20070289744 | Bingamon | Dec 2007 | A1 |
| 20080092780 | Bingamon et al. | Apr 2008 | A1 |
| 20080156491 | Roddy et al. | Jul 2008 | A1 |
| 20080229979 | Lewis | Sep 2008 | A1 |
| 20080236814 | Roddy | Oct 2008 | A1 |
| 20080300149 | Reddy et al. | Dec 2008 | A1 |
| 20090044726 | Brouillette et al. | Feb 2009 | A1 |
| 20090105099 | Warrender et al. | Apr 2009 | A1 |
| 20090120644 | Roddy et al. | May 2009 | A1 |
| 20090124522 | Roddy et al. | May 2009 | A1 |
| 20090145601 | Bailey | Jun 2009 | A1 |
| 20090266543 | Reddy et al. | Oct 2009 | A1 |
| 20090312445 | Roddy et al. | Dec 2009 | A1 |
| 20090320720 | Roddy et al. | Dec 2009 | A1 |
| 20100025039 | Roddy et al. | Feb 2010 | A1 |
| 20100041792 | Roddy et al. | Feb 2010 | A1 |
| 20100044043 | Roddy et al. | Feb 2010 | A1 |
| 20100044057 | Dealy et al. | Feb 2010 | A1 |
| 20100051266 | Roddy et al. | Mar 2010 | A1 |
| 20100051275 | Lewis et al. | Mar 2010 | A1 |
| 20100077922 | Constantz et al. | Apr 2010 | A1 |
| 20100081584 | Perez | Apr 2010 | A1 |
| 20100196104 | Constantz et al. | Aug 2010 | A1 |
| 20100258035 | Constantz et al. | Oct 2010 | A1 |
| 20100258312 | Brenneis et al. | Oct 2010 | A1 |
| 20100273912 | Roddy et al. | Oct 2010 | A1 |
| 20100282466 | Brenneis et al. | Nov 2010 | A1 |
| 20100292365 | Roddy et al. | Nov 2010 | A1 |
| 20100294496 | Woytowich et al. | Nov 2010 | A1 |
| 20100313793 | Constantz et al. | Dec 2010 | A1 |
| 20110000400 | Roddy | Jan 2011 | A1 |
| 20110017452 | Benkley et al. | Jan 2011 | A1 |
| 20110100626 | Brenneis et al. | May 2011 | A1 |
| 20110297378 | Reddy et al. | Dec 2011 | A1 |
| 20120145393 | Roddy | Jun 2012 | A1 |
| 20120152539 | Karcher et al. | Jun 2012 | A1 |
| 20120227631 | Roddy | Sep 2012 | A1 |
| 20120234541 | Roddy | Sep 2012 | A1 |
| 20120267107 | Benkley et al. | Oct 2012 | A1 |
| 20120285682 | Santra et al. | Nov 2012 | A1 |
| 20120291674 | Brenneis et al. | Nov 2012 | A1 |
| 20120318506 | Benkley et al. | Dec 2012 | A1 |
| 20120325119 | Brenneis et al. | Dec 2012 | A1 |
| 20120325476 | Brenneis et al. | Dec 2012 | A1 |
| 20120325477 | Brenneis et al. | Dec 2012 | A1 |
| 20120328377 | Brenneis et al. | Dec 2012 | A1 |
| 20130008352 | Roddy et al. | Jan 2013 | A1 |
| 20130048286 | Morgan et al. | Feb 2013 | A1 |
| 20130061779 | Brenneis et al. | Mar 2013 | A1 |
| 20130112405 | Chatterji et al. | May 2013 | A1 |
| 20130118752 | Hannegan et al. | May 2013 | A1 |
| 20130126159 | Bryan et al. | May 2013 | A1 |
| 20130153214 | Roddy et al. | Jun 2013 | A1 |
| 20130157903 | Benkley et al. | Jun 2013 | A1 |
| 20130213642 | Chatterji et al. | Aug 2013 | A1 |
| 20130213643 | Chatterji et al. | Aug 2013 | A1 |
| 20130233538 | Chatterjie et al. | Sep 2013 | A1 |
| 20130244911 | Benkley et al. | Sep 2013 | A1 |
| Number | Date | Country |
|---|---|---|
| 2064682 | Apr 1992 | CA |
| 2336077 | Jan 2000 | CA |
| 2153372 | Jan 2006 | CA |
| 1054620 | Nov 1997 | CN |
| 0814067 | Dec 1997 | EP |
| 1092693 | Apr 2001 | EP |
| 1236701 | Sep 2002 | EP |
| 1394137 | Jul 2003 | EP |
| 1348831 | Oct 2003 | EP |
| 1900703 | Mar 2008 | EP |
| 2075303 | Jul 2009 | EP |
| 1469954 | Apr 1997 | GB |
| 2455446 | Jun 2009 | GB |
| 52117316 | Oct 1977 | JP |
| 10110487 | Apr 1998 | JP |
| 2026959 | Jan 1995 | RU |
| 2003136028 | May 2005 | RU |
| 1373781 | Feb 1988 | SU |
| WO 8301443 | Sep 1982 | WO |
| 9321122 | Oct 1993 | WO |
| 9721637 | Jun 1997 | WO |
| WO 9854108 | Dec 1998 | WO |
| WO 0063134 | Jan 2000 | WO |
| WO 03031364 | Apr 2003 | WO |
| WO 2004101951 | Nov 2004 | WO |
| WO 2004101952 | Nov 2004 | WO |
| WO 2005047212 | May 2005 | WO |
| WO 2005061846 | Jul 2005 | WO |
| WO 2006032841 | Mar 2006 | WO |
| WO 2007028952 | Mar 2007 | WO |
| 2007041841 | Apr 2007 | WO |
| WO 2007048999 | May 2007 | WO |
| WO 2007128945 | Nov 2007 | WO |
| 2006074946 | Jun 2009 | WO |
| 2009071962 | Nov 2009 | WO |
| WO 2009138747 | Nov 2009 | WO |
| 2012001343 | Jan 2012 | WO |
| Entry |
|---|
| USPTO Office Action for U.S. Appl. No. 13/431,701 dated Nov. 9, 2012. |
| USPTO Office Action for U.S. Appl. No. 13/620,163 dated Nov. 9, 2012. |
| International Search Report and Written Opinion for International Application No. PCT/US2012/046117 dated Oct. 26, 2012. |
| USPTO Office Action for U.S. Appl. No. 13/669,149 dated Dec. 19, 2012. |
| USPTO Office Action for U.S. Appl. No. 13/606,098 dated Dec. 13, 2012. |
| HES Brochure “Micro Matrix® Cement” dated Nov. 2006. |
| HES Brochure “VersaCem™ Cement” dated Jan. 2007. |
| HES Brochure “FineCem™ Cement” dated Jul. 2010. |
| Office Action from U.S. Appl. No. 13/560,406 dated Oct. 17, 2012. |
| International Search Report for PCT/GB2011/001749 dated Apr. 5, 2012. |
| International Search Report and Written Opinion for PCT/GB2010/000712 dated Jul. 26, 2010. |
| Office Action for U.S. Appl. No. 13/620,013 dated Feb. 26, 2013. |
| PCT International Search Report and Written Opinion for International Application No. PCT/GB2011/000933 dated Sep. 22, 2011. |
| PCT International Search Report and Written Opinion for International Application No. PCT/GB2011/001411 dated Jan. 27, 2012. |
| USPTO Office Action for U.S. Appl. No. 12/264,010 dated Oct. 31, 2011. |
| U.S. Appl. No. 13/872,063 (Chatterji et al.) filed Apr. 23, 2013. |
| U.S. Appl. No. 13/889,398 (Benkley et al.) filed May 8, 2013. |
| U.S. Appl. No. 13/872,063 (Chatterji et al.) filed Apr. 26, 2013. |
| Notice of Allowance, U.S. Appl. No. 13/669,149 (Brenneis et al.) mailed May 13, 2013. |
| U.S. Appl. No. 13/767,710 (Benkley et al.) filed Feb. 14, 2013. |
| U.S. Appl. No. 13/851,391 (Chatterji et al.) filed Mar. 27, 2013. |
| U.S. Appl. No. 13/851,475 (Chatterji et al.) filed Mar. 27, 2013. |
| U.S. Appl. No. 13/851,925 (Chatterji et al.) filed Mar. 27, 2013. |
| U.S. Appl. No. 13/725,833 (Chatterji et al.) filed Dec. 21, 2012. |
| Office Action for U.S. Appl. No. 13/725,833 (Chatterji et al.) dated Apr. 10, 2013. |
| Bartlet-Gouedard, “A Non-Conventional Way of Developing Cement Slurry for Geothermal Wells”, 2001. |
| Poon, “A Study of the Hydration of Natural Zeolite Blended Cement Pastes”, 1999. |
| “Beneficial use of Solid Waste in Maine”, Apr. 14, 2005. |
| Smith, “Cementing” Society of Petroleum Engineers, p. 38, 1990. |
| Smith, “Cementing” Society of Professional Engineers, pp. 14, 38, 1987. |
| Chan, Comparative Study of the Initial Surface Absorption and Chloride Diffusion of High Performance Zeolite Silica Fume and PFA concretes, 1999. |
| Rogers, “Designing a Remedial Acid Treatment for Gulf of Mexico Deepwater Turbidite Sands Containing Zeolite Cement”, 1996. |
| Janotka, “Effect of Bentonite and Zeolite on Durability of Cement Suspension Under Sulfate Attack”, 1998. |
| Ding, “Extreme Vertices Design of Concrete With Combined Mineral Admixtures” 1999. |
| “Kiln Dusts”, Apr. 14, 2005. |
| Sersale, Portland-Zeolite-Cement for Minimizing Alkali-Aggregate Expansion, 1987. |
| “Standards for the Management of Cement Kiln Dust Waste”, Apr. 14, 2005. |
| Naiqian, “Study on the Suppression Effect of Natural Zeolite on Expansion of Concrete Due to Alkali-Aggegate Reaction”, 1998. |
| Janotka, “The Properties of Mortar Using Blends With Portland Cement Clinker, Zeolite Tuff and Gympsum”, 1995. |
| Herndon, “Setting Downhole Plugs: A State-of-the-Art, Petroleum Engineer International”, Apr. 1978. |
| Sugama, “Carbonation of Hydrothermally Treated Phosphate-Bonded Calcium Aluminate Cements”, pp. 1-9 (undated but admitted as prior art). |
| Sugama, “Hot Alkali Carbonization of Sodium Metaphosphate Modified Fly Ash/Calcium Aluminate Blend Hydrothermal Cements”, pp. 1661-1672, Sep. 11, 1996. |
| “Use of Cement Kiln Dust for the Stabilization of Soils”, R. L. Parsons, et al., Apr. 14, 2005. |
| Feng, “Zeolite Ceramiste Cellular Concrete”, 2000. |
| Marfil, “Zeolite Crystallization in Portland Cement Concrete Due to Alkali-Aggregate Reaction”, 1993. |
| Atkins, “Zeolite P in Cements”, “Its Potential for Immobolizing Toxic and Radioactive Waste Species”, 1995. |
| HES Brochure “AQF-2 Foaming Agent”, 1999. |
| HES Brochure “Halad-23 Fluid Loss Additive”, 2000. |
| HES Brochure “Halad-344 Fluid Loss Additive”, 1998. |
| HES Brochure “Halad-413 Fluid Loss Additive”, 1999. |
| HES Brochure “Howco Suds Surfactant”, 1999. |
| HES Brochure “HR-12 Cement Retarder”, 1999. |
| HES Brochure “HR-15 Cement Retarder”, 1999. |
| HES Brochure “HR-25 Cement Retarder”, 1999. |
| HES Brochure “HR-4 Cement Retarder”, 1999. |
| HES Brochure “HR-5 Cement Additive”, 1998. |
| HES Brochure “HR-7 Cement Retarder”, 1999. |
| HES Brochure “Pozmix A Cement Additive”, 1999. |
| HES Brochure “Pozmix Cement and Pozmix 140” (undated but admitted as prior art). |
| HES Brochure “SCR-100 Cement Retarder A Valuable Time Server”, 1994. |
| HES Brochure “SCR-100 Cement Retarder”, 1999. |
| HES Brochure “SCR-500L High Temp Retarder”, 2000. |
| HES Brochure “ThermaLock™ Cement for Corrosive CO2 Environments”, 1999. |
| “3M Scotchlite, Glass Bubbles Floated Product Series Product Information” 1999. |
| “API Specification for Materials and Testing for Well Cements”, API Spec. 10, 5th ed., pp. 7, 19-21, Jul. 1, 1980. |
| “Appendix A”, API RP 13B-2, 2d ed.; pp. 6-8, Dec. 1, 1991. |
| LaFarge brochure “TerraCem™”, Aug. 2006. |
| LaFarge MSDS “Cement Kiln Dust”, Mar. 3, 2005. |
| LaFarge MSDS “LaFarge Blended Cement (cement)”, Mar. 3, 2005. |
| TXI Material Safety Data Sheet for Pressur-Seal, Oct. 2003. |
| “Manufacture of supplementary cementitious materials from cement kiln dust”, Mishulovich et al,, World Cement Research and Development, p. 116-120, Mar. 1996. |
| “Alkali-activated binders by use of industrial by-products”, Buchwald et al., Cement and concrete Research 35, p. 968-973, 2005. |
| Answer 13 of 24 Chemical Abstracts on STN “Manufacture of ceramic particles from floatstone and fly ash”, CN 1182062 (abstract only) (undated but admitted as prior art). |
| Answer 3 of 24 Chemical Abstracts on STN “Effect of cement kiln dust substitution on chemical and physical properties and compressive strength of Portland and slag cements”, Adb El-aleem et al. (abstract only), 2005. |
| Office Action from U.S. Appl. No. 11/223,671, Dec. 15, 2005. |
| Office Action from U.S. Appl. No. 11/271,431, Mar. 6, 2006. |
| Office Action from U.S. Appl. No. 11/223,671, Mar. 31, 2006. |
| Office Action from U.S. Appl. No. 11/271,431, May 17, 2006. |
| Office Action from U.S. Appl. No. 11/271,431 (Advisory Action), Jul. 11, 2006. |
| Office Action from U.S. Appl. No. 11/416,563, Jul. 21, 2006. |
| Office Action from U.S. Appl. No. 11/403,032, Jul. 24, 2006. |
| Office Action from U.S. Appl. No. 11/271,431, Aug. 15, 2006. |
| Office Action from U.S. Appl. No. 11/440,627, Aug 21, 2006. |
| Office Action from U.S. Appl. No. 11/402,741, Oct. 19, 2006. |
| Office Action from U.S. Appl. No. 11/484,951, Oct. 26, 2006. |
| Office Action from U.S. Appl. No. 11/484,951, Dec. 21, 2006. |
| Office Action from U.S. Appl. No. 11/223,703, Jan. 17, 2007. |
| Office Action from U.S. Appl. No. 11/402,741, Feb. 2, 2007. |
| Office Action from U.S. Appl. No. 11/223,485, Feb. 28, 2007. |
| Office Action from U.S. Appl. No. 11/223,669, Feb. 28, 2007. |
| Office Action from U.S. Appl. No. 11/271,690, Mar. 13, 2007. |
| Office Action from U.S. Appl. No. 11/402,741, Mar. 22, 2007. |
| Office Action from U.S. Appl. No. 11/223,703, Apr. 25, 2007. |
| Office Action from U.S. Appl. No. 11/402,741, May 29, 2007. |
| Office Action from U.S. Appl. No. 11/223,669, Jun. 18, 2007. |
| Office Action from U.S. Appl. No. 11/257,261, Aug. 10, 2007. |
| Office Action from U.S. Appl. No. 11/402,741, Sep. 6, 2007. |
| Office Action from U.S. Appl. No. 11/223,669, Oct. 9, 2007. |
| Office Action from U.S. Appl. No. 11/223,750, Oct. 16, 2007. |
| Office Action from U.S. Appl. No. 11/402,741, Oct. 24, 2007. |
| Office Action from U.S. Appl. No. 11/223,669, Jan. 29, 2008. |
| Office Action from U.S. Appl. No. 11/223,669, Apr. 8, 2008. |
| Foreign Search Report from PCT/GB2005/001415, Sep. 9, 2005. |
| Foreign Search Report from PCT/GB2006/000406, Jul. 5, 2006. |
| Foreign Search Report from PCT/GB2006/003163, Oct. 27, 2006. |
| Foreign Search Report from PCT/GB2006/003160, Nov. 2, 2006. |
| Foreign Search Report from PCT/GB2006/003735, Dec. 1, 2006. |
| Foreign Search Report from PCT/GB2006/003694, Dec. 19, 2006. |
| Foreign Search Report from PCT/GB2006/000401, May 8, 2007. |
| Office Action from U.S. Appl. No. 12/263,800, May 1, 2009. |
| Nelson, “Well Cementing”, 1990. |
| “Fly Ash Resource Center-Pozzolan,” available at http://www.rmajko.com/pozzolan.htm, Apr. 20, 2009. |
| Foreign Search Report from PCT/GB2009/000295, Feb. 3, 2009. |
| EPO Application No. 06794648.3 Examination Report, Apr. 17, 2009. |
| EPO Application No. 06779194.7 Examination Report, May 29, 2009. |
| Office Action from U.S. Appl. No. 12/283,398, Jul. 15, 2009. |
| Office Action from U.S. Appl. No. 12/263,800, Jul. 28, 2009. |
| Office Action from U.S. Appl. No. 12/420,630, Aug. 3, 2009. |
| Office Action from U.S. Appl. No. 12/349,676, Nov. 4, 2009. |
| English language translation of Foreign Office Action for Application No. RU2008113765, Jul. 6, 2009. |
| Foreign Office Action for Canadian Patent Application No. 2621835, Oct. 2, 2009. |
| Foreign Office Action for Canadian Patent Application No. 2621832, Oct. 5, 2009. |
| PCT International Search Report and Written Opinion for International Application No. PCT/GB2009/002598, Feb. 11, 2010. |
| PCT International Search Report and Written Opinion for International Application No. PCT/GB2009/002597, Feb. 1, 2010. |
| English language translation of USSR Patent No. RU 2026959, Jan. 20, 1995. |
| Office Action from U.S. Appl. No. 12/606,381, Mar. 23, 2010. |
| Office Action from U.S. Appl. No. 12/609,993, Apr. 9, 2010. |
| Office Action from U.S. Appl. No. 12/609,993, Jun. 15, 2010. |
| Office Action from U.S. Appl. No. 12/558,097, Jun. 30, 2010. |
| Notice of Allowance from USPTO U.S. Appl. No. 12/609,993, Jul. 26, 2010. |
| Foreign Office Action for EP Application No. 06 779 194.7, Jul. 2, 2010. |
| HES Brochure “Enhancer 923™ Cement Agent”, 2010. |
| HES Brochure “Enhancer 923™ Agent—Successes from the Field”, 2010. |
| PCT International Preliminary Report on Patentability (Chapter 1) for International Application No. PCT/GB2009/002018, Mar. 24, 2011. |
| PCT International Search Report and Written Opinion for International Application No. PCT/GB2010/001986, Jan. 19, 2011. |
| PCT International Search Report and Written Opinion for International Application No. PCT/GB2010/002011, Feb. 4, 2011. |
| English language translation of Foreign Office Action for Chinese Application No. 200680042014.3, Dec. 1, 2010. |
| Office Action from U.S. Appl. No. 12/844,612, Jan. 28, 2011. |
| Foreign Office Action for Canadian Application No. 2658155, Nov. 16, 2010. |
| Foreign Office Action for Canadian Application No. 2650630, Oct. 14, 2010. |
| Foreign Office Action for EP Application No. 09 713 469.6, Sep. 28, 2010. |
| PCT International Search Report and Written Opinion for International Application No. PCT/GB2009/000295, Jul. 30, 2009. |
| PCT International Preliminary Report on Patentability for International Application No. PCT/GB2009/000295, Aug. 24, 2010. |
| Office Action for U.S. Appl. No. 12/844,612, Oct. 1, 2010. |
| Foreign Office Action for EP Application No. 06 779 191.3, Mar. 31, 2010. |
| Foreign Office Action for CN Application No. 200680042004.X, May 12, 2010. |
| Foreign Office Action for RU Application No. 2008113766, Jul. 14, 2009. |
| Foreign Office Action for RU Application No. 2008113766, Apr. 8, 2010. |
| Foreign Office Action for EP Application No. 06 794 646.7, Sep. 24, 2010. |
| Office Action for U.S. Appl. No. 12/558,097, Sep. 3, 2010. |
| Foreign Office Action for EP Application No. 06 779 199.6, Mar. 1, 2010. |
| Notice of Allowance from U.S. Appl. No. 13/399,913 dated Aug. 23, 2012. |
| Notice of Allowance from U.S. Appl. No. 13/535,258 dated Sep. 7, 2012. |
| Notice of Allowance from U.S. Appl. No. 12/825,004 dated Sep. 20, 2012. |
| Office Action from U.S. Appl. No. 13/477,777 dated Oct. 15, 2012. |
| Notice of Allowance from U.S. Appl. No. 12/844,612 dated Oct. 18, 2012. |
| Final Office Action from U.S. Appl. No. 12/975,196 dated Oct. 23, 2012. |
| Office Action from U.S. Appl. No. 13/555,624 dated Oct. 19, 2012. |
| U.S. Appl. No. 13/622,821, filed Sep. 19, 2012. |
| U.S. Appl. No. 13/620,163, filed Sep. 14, 2012. |
| U.S. Appl. No. 13/620,013, filed Sep. 14, 2012. |
| U.S. Appl. No. 13/662,111, filed Oct. 26, 2012. |
| U.S. Appl. No. 13/669,149, filed Nov. 5, 2012. |
| USPTO Office Action for U.S. Appl. No. 12/844,612 dated Dec. 23, 2011. |
| USPTO Notice of Allowance for U.S. Appl. No. 12/544,915 dated Aug. 1, 2011. |
| Adaska and Taubert, “Beneficial Uses of Cement Kiln Dust”, 2008 IEEE/PCA 50th Cement Industry Technical Conference, Miami, FL, May 19-22, 2008, pp. 1-19. |
| Office Action from U.S. Appl. No. 12/825,004 dated Jun. 14, 2012. |
| Notice of Allowance from U.S. Appl. No. 13/447,560 dated Jun. 21, 2012. |
| Office Action from U.S. Appl. No. 13/479,476 dated Jul. 2, 2012. |
| Office Action from U.S. Appl. No. 12/975,196 dated Jul. 3, 2012. |
| Final Office Action from U.S. Appl. No. 12/844,612 dated Jul. 30, 2012. |
| Final Office Action from U.S. Appl. No. 12/264,010 dated Apr. 10, 2012. |
| Office Action from U.S. Appl. No. 12/844,612 dated Apr. 11, 2012. |
| Office Action from U.S. Appl. No. 13/399,913 dated May 15, 2012. |
| Office Action from U.S. Appl. No. 13/447,560 dated May 31, 2012. |
| Office Action from U.S. Appl. No. 12/821,412 dated Jun. 5, 2012. |
| Foreign Office Action for Canadian Application No. 2736148 dated May 29, 2012. |
| Final Office Action from USPTO for U.S. Appl. No. 13/477,777 dated May 29, 2013. |
| Office Action from USPTO for U.S. Appl. No. 13/620,013 dated May 28, 2013. |
| Notice of Allowance from USPTO for U.S. Appl. No. 13/560,406 dated May 29, 2013. |
| Notice of Allowance from USPTO for U.S. Appl. No. 12/895,436 dated May 28, 2013. |
| Notice of Allowance from USPTO for U.S. Appl. No. 13/535,145 dated May 24, 2013. |
| Office Action from USPTO for U.S. Appl. No. 13/851,925 dated Jun. 6, 2013. |
| Office Action from USPTO for U.S. Appl. No. 13/851,391 dated Jul. 3, 2013. |
| Office Action from USPTO for U.S. Appl. No. 13/889,398 dated Jun. 20, 2013. |
| Office Action from USPTO for U.S. Appl. No. 13/872,063 dated Jul. 12, 2013. |
| Office Action from USPTO for U.S. Appl. No. 13/767,710 dated Jul. 19, 2013. |
| Notice of Allowance from USPTO for U.S. Appl. No. 13/851,391 dated Jul. 31, 2013. |
| Notice of Allowance from USPTO for U.S. Appl. No. 13/889,398 dated Aug. 20, 2013. |
| Notice of Allowance for U.S. Appl. No. 13/662,111 dated Oct. 21, 2013. |
| Office Action for U.S. Appl. No. 13/620,013 dated Oct. 2, 2013. |
| Office Action for U.S. Appl. No. 13/851,925 dated Sep. 20, 2013. |
| Office Action for U.S. Appl. No. 13/767,710 dated Sep. 20, 2013. |
| International Search Report and Written Opinion for PCT/US2013/048092. |
| Office Action for U.S. Appl. No. 13/477,777 dated Sep. 20, 2013. |
| International Search Report and Written Opinion for PCT/US2013/056719 dated Oct. 25, 2013. |
| Number | Date | Country | |
|---|---|---|---|
| 20120152539 A1 | Jun 2012 | US |
| Number | Date | Country | |
|---|---|---|---|
| Parent | 12975196 | Dec 2010 | US |
| Child | 13180238 | US |
