US5688844A - Resilient well cement compositions and methods - Google Patents

Resilient well cement compositions and methods Download PDF

Info

Publication number
US5688844A
US5688844A US08/673,970 US67397096A US5688844A US 5688844 A US5688844 A US 5688844A US 67397096 A US67397096 A US 67397096A US 5688844 A US5688844 A US 5688844A
Authority
US
United States
Prior art keywords
sub
composition
cement
latex
range
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US08/673,970
Inventor
Jiten Chatterji
Bobby J. King
Patty L. Totten
David D. Onan
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Halliburton Co
Original Assignee
Halliburton Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Halliburton Co filed Critical Halliburton Co
Priority to US08/673,970 priority Critical patent/US5688844A/en
Assigned to HALLIBURTON COMPANY reassignment HALLIBURTON COMPANY ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: ONAN, DAVID D., TOTTEN, PATTY L., CHATTERJI, JITEN, KING, BOBBY J.
Priority to CA002209232A priority patent/CA2209232C/en
Priority to DE69704183T priority patent/DE69704183T2/en
Priority to NO19973048A priority patent/NO321191B1/en
Priority to EP97304734A priority patent/EP0816302B1/en
Application granted granted Critical
Publication of US5688844A publication Critical patent/US5688844A/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
    • C04B28/04—Portland cements
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/428—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells for squeeze cementing, e.g. for repairing
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K8/00—Compositions for drilling of boreholes or wells; Compositions for treating boreholes or wells, e.g. for completion or for remedial operations
    • C09K8/42—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells
    • C09K8/46—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement
    • C09K8/467—Compositions for cementing, e.g. for cementing casings into boreholes; Compositions for plugging, e.g. for killing wells containing inorganic binders, e.g. Portland cement containing additives for specific purposes
    • C09K8/473—Density reducing additives, e.g. for obtaining foamed cement compositions
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/50—Flexible or elastic materials
    • C04B2111/503—Elastic materials

Definitions

  • the present invention relates generally to cementing subterranean wells, and more particularly, to cement compositions and methods whereby the compositions set into highly resilient solid masses.
  • Hydraulic cement compositions are commonly utilized in subterranean well completion and remedial operations.
  • hydraulic cement compositions are used in primary cementing operations whereby pipes such as casings and liners are cemented in well bores.
  • a hydraulic cement composition is pumped into the annular space between the walls of the well bore and the exterior surfaces of pipe disposed therein.
  • the cement composition is permitted to set in the annular space thereby forming an annular sheath of hardened substantially impermeable cement therein.
  • the cement sheath physically supports and positions the pipe in the well bore and bonds the exterior surfaces of the pipe to the walls of the well bore whereby the undesirable migration of fluids between zones or formations penetrated by the well bore is prevented.
  • the cement compositions utilized in primary cementing must often be lightweight to prevent excessive hydrostatic pressures from being exerted on formations penetrated by well bores.
  • the transition time of a well cement composition is the time after its placement in a subterranean zone penetrated by a well bore during which the cement composition changes from a true fluid to a hard set mass.
  • the cement composition becomes partially self-supporting which lowers the hydrostatic pressure exerted by the cement composition on formations containing pressurized fluid penetrated by the well bore. That is, when the cement composition becomes partially self-supporting, volume reductions in the cement composition caused by fluid loss to adjacent formations and hydration of the cement result in rapid decreases in the hydrostatic pressure exerted by the cement composition.
  • the formation fluids When the fluid phase within the cement matrix is not compressible and the pressure exerted by the cement composition falls below the pressure of formation fluids, the formation fluids enter the annulus and flow through the cement composition forming undesirable flow passages which remain after the cement composition sets.
  • a highly compressible fluid component, like gas, in the cement composition improves the composition's ability to maintain pressure and thus prevents the flow of formation fluids into and/or through the cement composition.
  • Such multi-lateral wells include vertical or deviated (including horizontal) principal well bores having one or more ancillary laterally extending well bores connected thereto. Drilling and completion equipment has been developed which allows multiple laterals to be drilled from a principal cased and cemented well bore. Each of the lateral well bores can include a liner cemented therein which is tied into the principal well bore. The lateral well bores can be vertical or deviated and can be drilled into predetermined producing formations or zones at any time in the productive life cycle of the well.
  • the cement composition utilized for cementing casing or liners in the well bores must develop high bond strength after setting and also have sufficient resiliency, i.e., elasticity and ductility, to resist loss of pipe or formation bond, cracking and/or shattering as a result of pipe movement, impacts and/or shocks subsequently generated by drilling and other well operations.
  • the bond loss, cracking and/or shattering of the set cement allows leakage of formation fluids through at least portions of the well bore or bores which can be highly detrimental.
  • Set cement in wells and particularly the set cement forming the cement sheaths in the annuli between pipes and the walls of well bores, often fail due to shear and compressional stresses exerted on the set cement.
  • Such stress conditions are commonly the result of relatively high fluid pressures and/or temperatures inside pipe cemented in well bores during testing, perforating, fluid injection and/or fluid production.
  • the high internal pipe pressure and/or temperature results in expansion of the pipe, both radially and longitudinally, which places stresses on the cement sheath causing it to crack or the bonds between the exterior surfaces of the pipe and/or the well bore walls and the cement sheath to fail in the form of loss of hydraulic seal.
  • Another condition results from exceedingly high pressures which occur inside the cement sheath due to the thermal expansion of fluids trapped within the cement sheath.
  • This condition often occurs as a result of high temperature differentials created during the injection or production of high temperature fluids through the well bore, e.g., wells subjected to steam recovery or the production of hot formation fluids from high temperature formations.
  • the pressure of the trapped fluids exceeds the collapse pressure of the cement and pipe causing leaks and bond failure.
  • Yet another compressional stress condition occurs as a result of outside forces exerted on the cement sheath due to formation shifting and overburden pressures.
  • a well cement composition of this invention is comprised of a hydraulic cement, fumed silica present in an amount in the range of from about 5% to about 30% by weight of hydraulic cement in the composition, an aqueous rubber latex present in an amount in the range of from about 2.5% to about 45% by weight of hydraulic cement in the composition and an effective amount of a latex stabilizer.
  • Another well cement composition of this invention is comprised of a hydraulic cement, fumed silica present in an amount in the range of from about 5% to about 30% by weight of hydraulic cement in the composition, an aqueous rubber latex present in an amount in the range of from about 2.5% to about 45% by weight of hydraulic cement in the composition, an effective amount of a latex stabilizer, a defoaming agent, a gas, a foaming agent and a foam stabilizer.
  • this foamed cement composition is lightweight and contains a compressible gas whereby pressurized formation fluid migration through the setting cement is prevented.
  • Another foamed cement composition of this invention is comprised of a hydraulic cement, an aqueous rubber latex present in an amount in the range of from about 2.5% to about 45% by weight of hydraulic cement in the composition, an effective amount of a latex stabilizer, a defoaming agent, a gas, a foaming agent and a foam stabilizer.
  • the methods of the invention basically comprise the steps of introducing a well cement composition of this invention which sets into a high bond strength, highly resilient solid mass having elasticity and ductility into a subterranean well and allowing the cement composition to set in the well.
  • the present invention provides resilient well cement compositions having improved mechanical properties including elasticity and ductility and methods of utilizing the resilient cement compositions in cementing operations carried out in subterranean wells. While the compositions and methods are useful in a variety of well completion and remedial operations, they are particularly useful in primary cementing, i.e., cementing casings and liners in well bores including the cementing of multi-lateral subterranean wells.
  • a non-foamed well cement composition of this invention is basically comprised of a hydraulic cement, fumed silica present in an amount in the range of from about 5% to about 30% by weight of hydraulic cement in the composition (from about 4.5 pounds to about 30 pounds per 94 pound sack of cement), an aqueous rubber latex present in an amount in the range of from about 2.5% to about 45% by weight of hydraulic cement in the composition (from about 0.25 gallons to about 5 gallons per 94 pound sack of cement) and an effective amount of a latex stabilizer.
  • hydraulic cements can be utilized in accordance with the present invention including those comprised of calcium, aluminum, silicon, oxygen and/or sulfur which set and harden by reaction with water.
  • Such hydraulic cements include Portland cements, pozzolana cements, gypsum cements, high aluminum content cements, silica cements and high alkalinity cements.
  • Portland cements are generally preferred for use in accordance with the present invention.
  • Portland cements of the types defined and described in API Specification For Materials And Testing For Well Cements, API Specification 10, 5th Edition, dated Jul. 1, 1990 of the American Petroleum Institute are particularly suitable.
  • Preferred API Portland cements include classes A, B, C, G and H, with API classes G and H being more preferred and class G being the most preferred.
  • Fumed silica is a colloidal form of silica made by the combustion of silicon tetrachloride in hydrogen-oxygen furnaces. Fumed silica is of a fine particle size, and in combination with the other components of the cement compositions of this invention provides improved mechanical properties to the compositions, particularly the ability to withstand a wide range of stresses associated with subterranean well conditions without bond loss, cracking, shattering or other form of failure.
  • the term "fumed silica” is used herein to mean the fumed silica made as described above and equivalent forms of silica made in other ways.
  • the fumed silica is present in the above described composition of this invention in an amount in the range of from about 5% to about 30% by weight of the hydraulic cement in the composition (from about 4.5 to about 30 lb/sack), more preferably from about 7.5% to about 15% (from about 7 to about 14 lb/sack) and most preferably about 10% (about 9.4 lb/sack).
  • the fumed silica reacts with lime liberated by the hydraulic cement during hydration to form an amorphous metal silicate hydrate.
  • a variety of well known rubber materials can be utilized in accordance with the present invention. Such materials are commercially available in aqueous latex form, i.e., aqueous dispersions or emulsions. For example, natural rubber (cis-1,4-polyisoprene) and most of its modified types can be utilized.
  • aqueous latex form i.e., aqueous dispersions or emulsions.
  • natural rubber cis-1,4-polyisoprene
  • most of its modified types can be utilized.
  • Synthetic polymers of various types can also be used including styrene/butadiene rubber, cis-1,4-polybutadiene rubber and blends thereof with natural rubber or styrene/butadiene rubber, high styrene resin, butyl rubber, ethylene/propylene rubbers, neoprene rubber, nitrile rubber, cis-1,4-polyisoprene rubber, silicone rubber, chlorosulfonated rubber, polyethylene rubber, epichlorohydrin rubber, fluorocarbon rubber, fluorosilicone rubber, polyurethane rubber, polyacrylic rubber and polysulfide rubber.
  • a particularly preferred latex for use in accordance with this invention is a styrene/butadiene copolymer latex emulsion prepared by emulsion polymerization.
  • the aqueous phase of the emulsion is an aqueous colloidal dispersion of the styrene/butadiene copolymer.
  • the latex dispersion usually includes water in an amount in the range of from about 40% to about 70% by weight of the latex, and in addition to the dispersed styrene/butadiene particles, the latex often includes small quantities of an emulsifier, polymerization catalysts, chain modifying agents and the like.
  • the weight ratio of styrene to butadiene in the latex can range from about 10%:90% to about 90%:10%.
  • styrene/butadiene latexes are often commercially produced as terpolymer latexes which include up to about 3% by weight of a third monomer to assist in stabilizing the latex emulsions.
  • the third monomer when present, generally is anionic in character and includes a carboxylate, sulfate or sulfonate group.
  • Other groups that may be present on the third monomer include phosphates, phosphonates or phenolics. Non-ionic groups which exhibit stearic effects and which contain long ethoxylate or hydrocarbon tails can also be present.
  • a particularly suitable styrene/butadiene aqueous latex has a styrene/butadiene weight ratio of about 25%:75%, and the styrene/butadiene copolymer is suspended in a 50% by weight aqueous emulsion.
  • This styrene/butadiene aqueous latex in combination with the other components of the cement compositions of this invention provides excellent resiliency to a set cement composition without the appreciable loss of bond strength in the set cement.
  • a latex of this type is available from Halliburton Energy Services of Duncan, Okla.
  • the aqueous latex used is included in the cement compositions of this invention in an amount in the range of from about 2.5% to about 45% by weight of the hydraulic cement in the composition (from about 0.25 to about 5.0 gal/sack), more preferably from about 4.5% to about 22% (from about 0.5 to about 2.5 gal/sack) and most preferably about 9% (about 1 gal/sack).
  • Latex stabilizers are comprised of one or more surfactants which function to prevent latex coagulation. Those which are particularly suitable for use in accordance with the present invention are surfactants having the formula
  • R is an alkyl group having from about 5 to about 30 carbon atoms
  • Ph is phenyl
  • m is an integer in the range of from about 5 to about 50
  • R 1 is selected from the group consisting of alkyl groups having from 1 to about 30 carbon atoms, cycloalkyl groups having 5 or 6 carbon atoms, C 1 -C 4 alkyl substituted cycloalkyl groups, phenyl, alkyl substituted phenyl of the general formula (R 3 ) a Ph-- wherein Ph is phenyl, R 3 is an alkyl group having from 1 to about 18 carbon atoms and a is an integer of from 1 to 3, and phenyl-alkyl groups wherein the alkyl groups have from 1 to about 18 carbon atoms and the phenyl-alkyl groups have a total of from about 8 to about 28 carbon atoms, R 2 is a substituted ethylene group of the formula --CH 2 CH 2 R 4 wherein R 4 is selected from hydrogen, methyl, ethyl or mixtures thereof, and n is a number from 0 to about 40 provided that when R 1 is phenyl or alkyl substituted phen
  • Another preferred surfactant in the group is a sodium salt having the general formula
  • R 5 is an alkyl group having in the range of from 1 to about 9 carbon atoms
  • R 6 is the group --CH 2 CH 2 --
  • o is an integer from about 10 to about 20
  • X is a compatible cation.
  • Yet another preferred surfactant in the group is a sodium salt having the formula
  • R 7 is an alkyl group having in the range of from about 5 to about 20 carbon atoms
  • R 8 is the group --CH 2 CH 2 --
  • p is an integer in the range of from about 10 to about 40
  • X is a compatible cation.
  • a particularly preferred surfactant of this type is the sodium salt of a sulfonated compound derived by reacting a C 12 to C 15 alcohol with about 15 moles of ethylene oxide having the formula
  • ethoxylated nonylphenol containing in the range of from about 15 to about 40 moles of ethylene oxide and "AVANEL S150TM", i.e., the sodium salt of a sulfonated and ethoxylated compound having the formula H(CH 2 ) 12-15 (CH 2 CH 2 O) 15 SO 3 Na are preferred, with H(CH 2 ) 12-15 (CH 2 CH 2 O) 15 SO 3 Na being the most preferred.
  • the latex stabilizer is usually included in the cement composition in an amount in the range of from about 9% to about 35% by weight of the aqueous rubber latex included therein (from about 0.02 to about 1.75 gal/sack of cement).
  • the latex stabilizer utilized is preferably included in the cement composition in an amount in the range of from about 9% to about 35% by weight of the aqueous rubber latex included in the composition (from about 0.02 to about 1.75 gal/sack of cement), more preferably from about 15% to about 25% (from about 0.04 to about 1.25 gal/sack) and most preferably about 20% (about 0.2 gal/sack).
  • water in the aqueous rubber latex used in forming the cement compositions of this invention can be adequate for producing a pumpable slurry and hydrating the cementitious materials therein, additional water can be added to the composition as required for pumpability.
  • the water can be from any source provided it does not contain in excess of compounds that adversely affect other components in the cement composition.
  • the water can contain various salts such as sodium, potassium and calcium chloride or the like.
  • water is present in a cement slurry composition of this invention in an amount in the range of from about 22% to about 95% by weight of hydraulic cement therein (from about 2.5 to about 10.7 gal/sack).
  • a light weight, foamed, highly resilient well cement composition of this invention is comprised of a hydraulic cement of the type described above, fumed silica as described above present in an amount in the range of from about 5% to about 30% by weight of hydraulic cement in the composition (from about 4.5 to about 30 lb/sack), an aqueous rubber latex of the type described above present in an amount in the range of from about 2.5% to about 45% by weight of hydraulic cement in the composition (from about 0.25 to about 5.0 gal/sack), an effective amount of a latex stabilizer of the type described above, an effective amount of a defoaming agent, a compressible gas present in an amount sufficient to foam the composition and produce a density in the range of from about 8 pounds per gallon to about 16 pounds per gallon, an effective amount of a foaming agent and an effective amount of a foam stabilizer.
  • the defoaming agent prevents foaming during mixing of the cement composition prior to foaming the composition. That is, because the aqueous rubber latex includes surfactants for emulsifying the latex and latex stabilizer which also function as foaming agents, a large bubble, unstable foam is produced when the hydraulic cement and silica are mixed with the latex.
  • the defoaming agent prevents the formation of the large bubble foam so that a small bubble stable foam can be subsequently formed.
  • the defoaming agent can comprise any of the compounds well known for such capabilities such as the polyol silicon compounds.
  • a preferred such defoaming agent is polydimethylsiloxane which is commercially available from Halliburton Energy Services of Duncan, Okla., under the trade designation "D-AIRTM.”
  • the defoaming agent is generally included in the cement composition in an amount in the range of from about 0.1% to about 0.9% by weight of the hydraulic cement therein (from about 0.01 to about 0.1 gal/sack), more preferably from about 0.18% to about 0.7% (from about 0.02 to about 0.08 gal/sack) and most preferably about 0.18% (about 0.02 gal/sack).
  • the compressible gas functions to foam the cement composition, to prevent pressurized formation fluid influx into the cement composition when setting and contributes to the resiliency of the set composition.
  • the gas is preferably nitrogen or air, with nitrogen being the most preferred.
  • the gas is present in an amount sufficient to foam the cement slurry and produce a slurry density in the range of from about 8 to about 16 pounds per gallon, more preferably from about 12 to about 15 pounds per gallon and most preferably about 13 pounds per gallon.
  • the amount of gas which is present in a foamed cement composition of this invention generally ranges from about 8.5% to about 50% by volume of the resulting foamed cement composition.
  • a foaming agent is included in the cement composition.
  • Suitable foaming agents are surfactants having the general formula:
  • a is an integer in the range of from about 5 to about 15;
  • b is an integer in the range of from about 1 to about 10;
  • X is any compatible cation.
  • a particularly preferred foaming agent is a surfactant of the above type having the formula:
  • a is an integer in the range of from about 6 to about 10.
  • This surfactant is commercially available from Halliburton Energy Services of Duncan, Okla., under the trade designation "CFA-STM.”
  • Another particularly preferred foaming agent of the above mentioned type is a surfactant having the formula:
  • a is an integer in the range of from about 5 to about 15;
  • b is an integer in the range of from about 1 to about 10.
  • Another foaming agent which can be utilized in the cement compositions of this invention includes polyethoxylated alcohols having the formula:
  • a is an integer in the range of from about 10 to about 18;
  • b is an integer in the range of from about 6 to about 15.
  • foaming agent which can be used is a sodium salt of alpha-olefinic sulfonic acid (AOS) which is a mixture of compounds of the formulas:
  • n and m are individually integers in the range of from about 6 to about 16;
  • p and q are individually integers in the range of from about 7 to about 17;
  • X and Y are fractions with the sum of X and Y being 1.
  • This foaming agent is available from Halliburton Energy Services under the trade name "AQF-2TM.”
  • Still another foaming surfactant which can be used is an alcohol ether sulfate of the formula:
  • a is an integer in the range of from about 6 to about 10;
  • b is an integer in the range of from about 3 to about 10.
  • foaming agent employed will depend on various factors such as the types of formations in which the foamed cement is to be placed. Generally, the foaming agent utilized is included in a cement composition of this invention in an amount in the range of from about 1.5% to about 10% by weight of water in the composition. When the foaming agent is one of the preferred surfactants described above, it is included in the composition in an amount in the range of from about 4% to about 9.5% by weight of water therein.
  • a foam stabilizer is also included in the foamed cement composition to enhance the stability of the foamed cement slurry.
  • One such foam stabilizing agent is a compound of the formula: ##STR1## wherein: R is hydrogen or a methyl radical; and
  • n is an integer in the range of from about 20 to about 200.
  • a particularly preferred foam stabilizing agent of the above type is a methoxypolyethylene glycol of the formula:
  • n is in the range of from about 100 to about 150.
  • This foam stabilizing agent is commercially available from Halliburton Energy Services under the trade designation "HALLIBURTON FOAM STABILIZERTM.”
  • the preferred foam stabilizing agent is a compound having the formula:
  • R is a C 10 to C 18 saturated aliphatic hydrocarbon group or an oleyl group or a linoleyl group.
  • a particularly preferred stabilizing agent of the above type is an amidopropylbetaine of the formula:
  • R is a cocoyl group.
  • This foam stabilizing agent is commercially available from Halliburton Energy Services under the trade designation "HC-2TM.”
  • the foam stabilizer is included in a cement composition of this invention in an amount in the range of from about 0.75% to about 5% by weight of water utilized.
  • the foam stabilizing agent is one of the particularly preferred agents described above, it is preferably present in the composition in an amount in the range of from about 2% to about 5% by weight of water.
  • Another foamed well cement composition of this invention is comprised of a hydraulic cement of the type described above, an aqueous rubber latex described above present in an amount in the range of from about 2.5% to about 45% by weight of hydraulic cement in the composition (from about 0.25 to about 5 gal/sack), an effective amount of a latex stabilizer described above, an effective amount of a defoaming agent described above, a compressible gas described above present in an amount sufficient to foam the cement composition and produce a cement composition density in the range of from about 8 pounds per gallon to about 16 pounds per gallon, an effective amount of a foaming agent described above and an effective amount of a foam stabilizer described above.
  • This foamed cement composition which is preferred in some applications does not include fumed silica, but it is also light weight, resilient and resists pressurized formation fluid migration.
  • the well cement compositions useful herein can include other additives which are well known to those skilled in the art including fluid loss control additives, set retarding additives, dispersing agents, formation conditioning additives, set accelerators and the like.
  • Dispersing agents can be utilized to facilitate the use of lower quantities of water and to promote higher set cement strength.
  • a particularly suitable dispersing agent for use with the well cement compositions of this invention is comprised of the condensation polymer product of an aliphatic ketone, an aliphatic aldehyde and a compound which introduces acid groups into the polymer, e.g., sodium sulfite.
  • a dispersant is described in U.S. Pat. No. 4,557,763 issued to George et al. on Dec. 10, 1985 which is incorporated herein by reference.
  • fluid loss control additives examples include cellulose derivatives such as carboxymethylhydroxyethylcellulose, hydroxyethylcellulose, modified polysaccharides, polyacrylamides, guar gum derivatives, 2-acrylamido-2-methylpropane sulfonic acid copolymers, polyethyleneamine and the like.
  • Set retarding additives are included in the cement compositions when it is necessary to extend the time in which the cement composition can be pumped so that it will not thicken or set prior to being placed at a desired location in the well being cemented.
  • set retarders which can be used include lignosulfonates such as calcium and sodium lignosulfonate, organic acids such as tartaric acid and gluconic acid, copolymers and others.
  • the proper amount of retarder required for particular conditions can be determined by conducting a "thickening time test" for the particular retarder and cement composition. Such tests are described in the API Specification For Materials and Testing for Well Cements, API Specification 10 mentioned above.
  • a particularly preferred set retarder for use in accordance with the present invention is a copolymer or copolymer salt of 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid.
  • the copolymer comprises from about 40 to about 60 mole percent 2-acrylamido-2-methylpropanesulfonic acid with the balance comprising acrylic acid, and the copolymer or salt preferably has an average molecular weight below about 5,000.
  • This copolymer set retarder is preferably utilized in the composition when the bottom hole circulating temperature exceeds about 200° F.
  • the retarder has been found to both retard the setting of the cement at elevated formation temperatures and to stabilize the aqueous styrene/butadiene latex against agglomeration or inversion at the elevated temperature.
  • the set retarder is generally added to the cement composition in an amount in the range of from about 0.1% to about 6% by weight of hydraulic cement in the composition.
  • the cement compositions of this invention may be prepared in accordance with any of the well known mixing techniques so long as the latex and latex stabilizing surfactant are not directly admixed without prior dilution by other liquids present.
  • a quantity of water is introduced into a cement blender and defoamer, latex and latex stabilizer are then sequentially added with suitable agitation to disperse the constituents.
  • Any other liquid additives may then be admixed with the slurry followed by the hydraulic cement, fumed silica and other dry solids. The mixture is agitated for a sufficient period of time to admix the components and form a pumpable non-foamed slurry.
  • the slurry When the slurry is foamed, it is pumped to the well bore and the foaming agent and foam stabilizer followed by the gas are injected into the slurry on the fly. As the slurry and gas flow through the well bore to the location where the resulting foamed cement composition is to be placed, the cement composition is foamed and stabilized.
  • the methods of this invention for cementing a zone in a well basically comprise the steps of placing a cement composition of this invention which sets into a highly resilient, high bond strength, substantially impermeable mass in the subterranean zone to be cemented, and maintaining the cement composition in the zone for a time sufficient for the cement composition to set therein.
  • Test samples of non-foamed cement compositions of this invention comprised of API Portland Class H hydraulic cement, fumed silica, a dispersant, an aqueous styrene/butadiene latex, a latex stabilizer, and a defoaming agent were prepared. Two of the test samples also included an expansion additive. Descriptions of the test samples are set forth in Table I below.
  • test samples Portions of each of the test samples were placed in shear bond and hydraulic bond test apparatus and allowed to set for time periods of 1 week at a temperature of 140° F. and atmospheric pressure. The test samples were then tested for shear bond strength and hydraulic bond strength.
  • the shear bond strength of set cement in the annulus between a pipe disposed in a well bore and the walls of the well bore is defined as the strength of the bond between the set cement and a pipe mechanically supported by the cement.
  • the test sample shear bond strengths were determined by measuring the force required to initiate movement of pipe sections cemented by the test samples in test apparatus simulating a well bore, i.e., larger diameter pipe sections. The determined forces were divided by the cement-pipe contact surface areas to yield the shear bond strengths in psi.
  • the hydraulic bond strength of the set cement blocks migration of pressurized fluids in a cemented annulus.
  • the test sample hydraulic bond strengths were determined by applying pressure at the pipe-set cement interfaces until leakage occurred.
  • the hydraulic bond strength of a set cement test sample in psi is equal to the hydraulic pressure applied when leakage took place. The results of these tests are also set forth in Table I below.
  • test samples of foamed cement compositions of this invention comprised of hydraulic cement, fumed silica, an aqueous rubber latex, a latex stabilizer, a defoaming agent, air, a foaming agent and a foam stabilizer were prepared.
  • One of the foamed cement, compositions also included hemitite weighting material, 100 mesh sand, a set retarder and a retarder intensifier.
  • an unfoamed cement slurry including the defoaming agent was first prepared utilizing a mixing device. A predetermined amount of the resulting slurry was then placed in a fixed volume blender jar having a stacked blade assembly. The foaming agent and foam stabilizer were then added to the jar and the contents were mixed at high speed. The high speed mixing by the stacked blade assembly caused the slurry to be foamed with air. Descriptions of the test samples are set forth in Table IIA below.
  • the foamed test samples were allowed to set for 1 week at 140° F. and atmospheric pressure after which portions of the test samples were subjected to various tests to determine their properties. More specifically, unconfined uniaxle and confined triaxial strength tests were conducted and Young's Moduli and Poisson's Ratios were determined as well as bulk compressibilities, shear moduli and tensile strengths, all in accordance with the standardized tests and procedures of the American Society for Testing and Materials (ASTM) set forth, for example, in ASTM Section D 1456. The results of the tests and determinations are set forth in Table IIB below.
  • Test samples of additional foamed cement compositions of this invention comprised of API Portland Class G hydraulic cement, an aqueous rubber latex, a latex stabilizer, a fluid loss control agent, a set accelerator, a defoaming agent, air, a foaming agent, and a foam stabilizer were prepared.
  • a base unfoamed cement slurry including the defoaming agent was first prepared followed by foaming of the base slurry with a foaming agent and foam stabilizer as described in Example 2 above.
  • Example 2 The various strength tests and modulus and ratio determinations described in Example 2 were conducted and determined.
  • test samples are set forth in Table IIIA below and the results of the tests and determinations are set forth in Table IIIB below.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Structural Engineering (AREA)
  • Curing Cements, Concrete, And Artificial Stone (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

The present invention provides resilient cement compositions and methods which are particularly useful in the construction and repair of oil and gas wells. The cement compositions have improved mechanical properties including elasticity and ductility and are basically comprised of cementitious material, an aqueous rubber latex and a latex stabilizer.

Description

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to cementing subterranean wells, and more particularly, to cement compositions and methods whereby the compositions set into highly resilient solid masses.
2. Description of the Prior Art
Hydraulic cement compositions are commonly utilized in subterranean well completion and remedial operations. For example, hydraulic cement compositions are used in primary cementing operations whereby pipes such as casings and liners are cemented in well bores. In performing primary cementing, a hydraulic cement composition is pumped into the annular space between the walls of the well bore and the exterior surfaces of pipe disposed therein. The cement composition is permitted to set in the annular space thereby forming an annular sheath of hardened substantially impermeable cement therein. The cement sheath physically supports and positions the pipe in the well bore and bonds the exterior surfaces of the pipe to the walls of the well bore whereby the undesirable migration of fluids between zones or formations penetrated by the well bore is prevented. The cement compositions utilized in primary cementing must often be lightweight to prevent excessive hydrostatic pressures from being exerted on formations penetrated by well bores.
The transition time of a well cement composition is the time after its placement in a subterranean zone penetrated by a well bore during which the cement composition changes from a true fluid to a hard set mass. During the transition time, the cement composition becomes partially self-supporting which lowers the hydrostatic pressure exerted by the cement composition on formations containing pressurized fluid penetrated by the well bore. That is, when the cement composition becomes partially self-supporting, volume reductions in the cement composition caused by fluid loss to adjacent formations and hydration of the cement result in rapid decreases in the hydrostatic pressure exerted by the cement composition. When the fluid phase within the cement matrix is not compressible and the pressure exerted by the cement composition falls below the pressure of formation fluids, the formation fluids enter the annulus and flow through the cement composition forming undesirable flow passages which remain after the cement composition sets. The use of a highly compressible fluid component, like gas, in the cement composition improves the composition's ability to maintain pressure and thus prevents the flow of formation fluids into and/or through the cement composition.
The development of wells including one or more laterals to increase production has recently taken place. Such multi-lateral wells include vertical or deviated (including horizontal) principal well bores having one or more ancillary laterally extending well bores connected thereto. Drilling and completion equipment has been developed which allows multiple laterals to be drilled from a principal cased and cemented well bore. Each of the lateral well bores can include a liner cemented therein which is tied into the principal well bore. The lateral well bores can be vertical or deviated and can be drilled into predetermined producing formations or zones at any time in the productive life cycle of the well.
In both conventional single bore wells and multi-lateral wells having several bores, the cement composition utilized for cementing casing or liners in the well bores must develop high bond strength after setting and also have sufficient resiliency, i.e., elasticity and ductility, to resist loss of pipe or formation bond, cracking and/or shattering as a result of pipe movement, impacts and/or shocks subsequently generated by drilling and other well operations. The bond loss, cracking and/or shattering of the set cement allows leakage of formation fluids through at least portions of the well bore or bores which can be highly detrimental.
Set cement in wells, and particularly the set cement forming the cement sheaths in the annuli between pipes and the walls of well bores, often fail due to shear and compressional stresses exerted on the set cement. Such stress conditions are commonly the result of relatively high fluid pressures and/or temperatures inside pipe cemented in well bores during testing, perforating, fluid injection and/or fluid production. The high internal pipe pressure and/or temperature results in expansion of the pipe, both radially and longitudinally, which places stresses on the cement sheath causing it to crack or the bonds between the exterior surfaces of the pipe and/or the well bore walls and the cement sheath to fail in the form of loss of hydraulic seal.
Another condition results from exceedingly high pressures which occur inside the cement sheath due to the thermal expansion of fluids trapped within the cement sheath. This condition often occurs as a result of high temperature differentials created during the injection or production of high temperature fluids through the well bore, e.g., wells subjected to steam recovery or the production of hot formation fluids from high temperature formations. Typically, the pressure of the trapped fluids exceeds the collapse pressure of the cement and pipe causing leaks and bond failure. Yet another compressional stress condition occurs as a result of outside forces exerted on the cement sheath due to formation shifting and overburden pressures.
In multi-lateral wells wherein pipe has been cemented in well bores using conventional well cement slurries which set into brittle solid masses, the brittle set cement cannot withstand impacts and shocks subsequently generated by drilling and other well operations carried out in the multiple laterals without cracking or shattering.
The above described failures can result in loss of production, environmental pollution, hazardous rig operations and/or hazardous production operations. The most common hazard is the presence of gas pressure at the well head.
Thus, there are needs for well cement compositions and methods whereby after setting the cement compositions are highly resilient and can withstand the above described stresses without failure. That is, there is a need for well cement compositions and methods whereby the set cement has improved mechanical properties including elasticity and ductility and failures due to pipe movement, impacts and shocks are reduced or prevented.
SUMMARY OF THE INVENTION
The present invention provides highly resilient well cement compositions having improved mechanical properties including elasticity and ductility and methods of using the compositions which meet the needs described above and overcome the deficiencies of the prior art. A well cement composition of this invention is comprised of a hydraulic cement, fumed silica present in an amount in the range of from about 5% to about 30% by weight of hydraulic cement in the composition, an aqueous rubber latex present in an amount in the range of from about 2.5% to about 45% by weight of hydraulic cement in the composition and an effective amount of a latex stabilizer.
Another well cement composition of this invention is comprised of a hydraulic cement, fumed silica present in an amount in the range of from about 5% to about 30% by weight of hydraulic cement in the composition, an aqueous rubber latex present in an amount in the range of from about 2.5% to about 45% by weight of hydraulic cement in the composition, an effective amount of a latex stabilizer, a defoaming agent, a gas, a foaming agent and a foam stabilizer. In addition to being highly resilient, this foamed cement composition is lightweight and contains a compressible gas whereby pressurized formation fluid migration through the setting cement is prevented.
Another foamed cement composition of this invention is comprised of a hydraulic cement, an aqueous rubber latex present in an amount in the range of from about 2.5% to about 45% by weight of hydraulic cement in the composition, an effective amount of a latex stabilizer, a defoaming agent, a gas, a foaming agent and a foam stabilizer.
The methods of the invention basically comprise the steps of introducing a well cement composition of this invention which sets into a high bond strength, highly resilient solid mass having elasticity and ductility into a subterranean well and allowing the cement composition to set in the well.
It is, therefore, a general object of the present invention to provide improved resilient well cement compositions and methods.
Other and further objects, features and advantages of the present invention will be readily apparent to those skilled in the art upon a reading of the description of preferred embodiments which follows.
DESCRIPTION OF PREFERRED EMBODIMENTS
The present invention provides resilient well cement compositions having improved mechanical properties including elasticity and ductility and methods of utilizing the resilient cement compositions in cementing operations carried out in subterranean wells. While the compositions and methods are useful in a variety of well completion and remedial operations, they are particularly useful in primary cementing, i.e., cementing casings and liners in well bores including the cementing of multi-lateral subterranean wells.
A non-foamed well cement composition of this invention is basically comprised of a hydraulic cement, fumed silica present in an amount in the range of from about 5% to about 30% by weight of hydraulic cement in the composition (from about 4.5 pounds to about 30 pounds per 94 pound sack of cement), an aqueous rubber latex present in an amount in the range of from about 2.5% to about 45% by weight of hydraulic cement in the composition (from about 0.25 gallons to about 5 gallons per 94 pound sack of cement) and an effective amount of a latex stabilizer.
A variety of hydraulic cements can be utilized in accordance with the present invention including those comprised of calcium, aluminum, silicon, oxygen and/or sulfur which set and harden by reaction with water. Such hydraulic cements include Portland cements, pozzolana cements, gypsum cements, high aluminum content cements, silica cements and high alkalinity cements. Portland cements are generally preferred for use in accordance with the present invention. Portland cements of the types defined and described in API Specification For Materials And Testing For Well Cements, API Specification 10, 5th Edition, dated Jul. 1, 1990 of the American Petroleum Institute are particularly suitable. Preferred API Portland cements include classes A, B, C, G and H, with API classes G and H being more preferred and class G being the most preferred.
Fumed silica is a colloidal form of silica made by the combustion of silicon tetrachloride in hydrogen-oxygen furnaces. Fumed silica is of a fine particle size, and in combination with the other components of the cement compositions of this invention provides improved mechanical properties to the compositions, particularly the ability to withstand a wide range of stresses associated with subterranean well conditions without bond loss, cracking, shattering or other form of failure. The term "fumed silica" is used herein to mean the fumed silica made as described above and equivalent forms of silica made in other ways.
The fumed silica is present in the above described composition of this invention in an amount in the range of from about 5% to about 30% by weight of the hydraulic cement in the composition (from about 4.5 to about 30 lb/sack), more preferably from about 7.5% to about 15% (from about 7 to about 14 lb/sack) and most preferably about 10% (about 9.4 lb/sack). As will be understood by those skilled in the art, the fumed silica reacts with lime liberated by the hydraulic cement during hydration to form an amorphous metal silicate hydrate.
A variety of well known rubber materials can be utilized in accordance with the present invention. Such materials are commercially available in aqueous latex form, i.e., aqueous dispersions or emulsions. For example, natural rubber (cis-1,4-polyisoprene) and most of its modified types can be utilized. Synthetic polymers of various types can also be used including styrene/butadiene rubber, cis-1,4-polybutadiene rubber and blends thereof with natural rubber or styrene/butadiene rubber, high styrene resin, butyl rubber, ethylene/propylene rubbers, neoprene rubber, nitrile rubber, cis-1,4-polyisoprene rubber, silicone rubber, chlorosulfonated rubber, polyethylene rubber, epichlorohydrin rubber, fluorocarbon rubber, fluorosilicone rubber, polyurethane rubber, polyacrylic rubber and polysulfide rubber.
Of the various latexes which can be utilized, those prepared by emulsion polymerization processes are preferred. A particularly preferred latex for use in accordance with this invention is a styrene/butadiene copolymer latex emulsion prepared by emulsion polymerization. The aqueous phase of the emulsion is an aqueous colloidal dispersion of the styrene/butadiene copolymer. The latex dispersion usually includes water in an amount in the range of from about 40% to about 70% by weight of the latex, and in addition to the dispersed styrene/butadiene particles, the latex often includes small quantities of an emulsifier, polymerization catalysts, chain modifying agents and the like. The weight ratio of styrene to butadiene in the latex can range from about 10%:90% to about 90%:10%.
It is understood that styrene/butadiene latexes are often commercially produced as terpolymer latexes which include up to about 3% by weight of a third monomer to assist in stabilizing the latex emulsions. The third monomer, when present, generally is anionic in character and includes a carboxylate, sulfate or sulfonate group. Other groups that may be present on the third monomer include phosphates, phosphonates or phenolics. Non-ionic groups which exhibit stearic effects and which contain long ethoxylate or hydrocarbon tails can also be present.
A particularly suitable styrene/butadiene aqueous latex has a styrene/butadiene weight ratio of about 25%:75%, and the styrene/butadiene copolymer is suspended in a 50% by weight aqueous emulsion. This styrene/butadiene aqueous latex in combination with the other components of the cement compositions of this invention provides excellent resiliency to a set cement composition without the appreciable loss of bond strength in the set cement. A latex of this type is available from Halliburton Energy Services of Duncan, Okla. under the trade designation "LATEX 2000™." The aqueous latex used is included in the cement compositions of this invention in an amount in the range of from about 2.5% to about 45% by weight of the hydraulic cement in the composition (from about 0.25 to about 5.0 gal/sack), more preferably from about 4.5% to about 22% (from about 0.5 to about 2.5 gal/sack) and most preferably about 9% (about 1 gal/sack).
In order to prevent the aqueous latex from prematurely coagulating and increasing the viscosity of the cement composition, an effective amount of a latex stabilizer is included in the cement composition. Latex stabilizers are comprised of one or more surfactants which function to prevent latex coagulation. Those which are particularly suitable for use in accordance with the present invention are surfactants having the formula
R--Ph--O(OCH.sub.2 CH.sub.2).sub.m OH
wherein R is an alkyl group having from about 5 to about 30 carbon atoms, Ph is phenyl and m is an integer in the range of from about 5 to about 50, and surfactants of the general formula
R.sub.1 (OR.sub.2).sub.n SO.sub.3 X
wherein R1 is selected from the group consisting of alkyl groups having from 1 to about 30 carbon atoms, cycloalkyl groups having 5 or 6 carbon atoms, C1 -C4 alkyl substituted cycloalkyl groups, phenyl, alkyl substituted phenyl of the general formula (R3)a Ph-- wherein Ph is phenyl, R3 is an alkyl group having from 1 to about 18 carbon atoms and a is an integer of from 1 to 3, and phenyl-alkyl groups wherein the alkyl groups have from 1 to about 18 carbon atoms and the phenyl-alkyl groups have a total of from about 8 to about 28 carbon atoms, R2 is a substituted ethylene group of the formula --CH2 CH2 R4 wherein R4 is selected from hydrogen, methyl, ethyl or mixtures thereof, and n is a number from 0 to about 40 provided that when R1 is phenyl or alkyl substituted phenyl n is at least one, and X is any compatible cation. A preferred surfactant in this group is ethoxylated nonylphenyl containing in the range of from about 20 to about 30 moles of ethylene oxide.
Another preferred surfactant in the group is a sodium salt having the general formula
R.sub.5 --Ph(OR.sub.6).sub.o SO.sub.3 X
wherein R5 is an alkyl group having in the range of from 1 to about 9 carbon atoms, R6 is the group --CH2 CH2 --, o is an integer from about 10 to about 20 and X is a compatible cation.
Yet another preferred surfactant in the group is a sodium salt having the formula
R.sub.7 (OR.sub.8).sub.p SO.sub.3 X
wherein R7 is an alkyl group having in the range of from about 5 to about 20 carbon atoms, R8 is the group --CH2 CH2 --, p is an integer in the range of from about 10 to about 40 and X is a compatible cation. A particularly preferred surfactant of this type is the sodium salt of a sulfonated compound derived by reacting a C12 to C15 alcohol with about 15 moles of ethylene oxide having the formula
H(CH.sub.2).sub.12-15 (CH.sub.2 CH.sub.2 O).sub.15 SO.sub.3 Na
which is commercially available under the name "AVANEL S150™" from PPG Mazer, Mazer Chemicals, a Division of PPG Industries, Inc., 3938 Porett Drive, Gurnee, Ill. 60031.
Of the various latex stabilizers described above which can be used, ethoxylated nonylphenol containing in the range of from about 15 to about 40 moles of ethylene oxide and "AVANEL S150™", i.e., the sodium salt of a sulfonated and ethoxylated compound having the formula H(CH2)12-15 (CH2 CH2 O)15 SO3 Na are preferred, with H(CH2)12-15 (CH2 CH2 O)15 SO3 Na being the most preferred.
While different amounts of latex stabilizer are included in the cement composition depending on the particular aqueous rubber latex used, the latex stabilizer is usually included in the cement composition in an amount in the range of from about 9% to about 35% by weight of the aqueous rubber latex included therein (from about 0.02 to about 1.75 gal/sack of cement). When the aqueous latex is an aqueous styrene/butadiene latex, the latex stabilizer utilized is preferably included in the cement composition in an amount in the range of from about 9% to about 35% by weight of the aqueous rubber latex included in the composition (from about 0.02 to about 1.75 gal/sack of cement), more preferably from about 15% to about 25% (from about 0.04 to about 1.25 gal/sack) and most preferably about 20% (about 0.2 gal/sack).
While the water in the aqueous rubber latex used in forming the cement compositions of this invention can be adequate for producing a pumpable slurry and hydrating the cementitious materials therein, additional water can be added to the composition as required for pumpability. The water can be from any source provided it does not contain in excess of compounds that adversely affect other components in the cement composition. For example, the water can contain various salts such as sodium, potassium and calcium chloride or the like. Generally, water is present in a cement slurry composition of this invention in an amount in the range of from about 22% to about 95% by weight of hydraulic cement therein (from about 2.5 to about 10.7 gal/sack).
A light weight, foamed, highly resilient well cement composition of this invention is comprised of a hydraulic cement of the type described above, fumed silica as described above present in an amount in the range of from about 5% to about 30% by weight of hydraulic cement in the composition (from about 4.5 to about 30 lb/sack), an aqueous rubber latex of the type described above present in an amount in the range of from about 2.5% to about 45% by weight of hydraulic cement in the composition (from about 0.25 to about 5.0 gal/sack), an effective amount of a latex stabilizer of the type described above, an effective amount of a defoaming agent, a compressible gas present in an amount sufficient to foam the composition and produce a density in the range of from about 8 pounds per gallon to about 16 pounds per gallon, an effective amount of a foaming agent and an effective amount of a foam stabilizer.
The defoaming agent prevents foaming during mixing of the cement composition prior to foaming the composition. That is, because the aqueous rubber latex includes surfactants for emulsifying the latex and latex stabilizer which also function as foaming agents, a large bubble, unstable foam is produced when the hydraulic cement and silica are mixed with the latex.
The defoaming agent prevents the formation of the large bubble foam so that a small bubble stable foam can be subsequently formed. The defoaming agent can comprise any of the compounds well known for such capabilities such as the polyol silicon compounds. A preferred such defoaming agent is polydimethylsiloxane which is commercially available from Halliburton Energy Services of Duncan, Okla., under the trade designation "D-AIR™." The defoaming agent is generally included in the cement composition in an amount in the range of from about 0.1% to about 0.9% by weight of the hydraulic cement therein (from about 0.01 to about 0.1 gal/sack), more preferably from about 0.18% to about 0.7% (from about 0.02 to about 0.08 gal/sack) and most preferably about 0.18% (about 0.02 gal/sack).
The compressible gas functions to foam the cement composition, to prevent pressurized formation fluid influx into the cement composition when setting and contributes to the resiliency of the set composition. The gas is preferably nitrogen or air, with nitrogen being the most preferred. Generally, the gas is present in an amount sufficient to foam the cement slurry and produce a slurry density in the range of from about 8 to about 16 pounds per gallon, more preferably from about 12 to about 15 pounds per gallon and most preferably about 13 pounds per gallon. The amount of gas which is present in a foamed cement composition of this invention generally ranges from about 8.5% to about 50% by volume of the resulting foamed cement composition.
In order to facilitate foaming and to stabilize the foamed slurry, a foaming agent is included in the cement composition. Suitable foaming agents are surfactants having the general formula:
H(CH.sub.2).sub.a (OC.sub.2 H.sub.4).sub.b OSO.sub.3 X
wherein:
a is an integer in the range of from about 5 to about 15;
b is an integer in the range of from about 1 to about 10; and
X is any compatible cation.
A particularly preferred foaming agent is a surfactant of the above type having the formula:
H(CH.sub.2).sub.a (OC.sub.2 H.sub.4).sub.3 OSO.sub.3 Na
wherein:
a is an integer in the range of from about 6 to about 10.
This surfactant is commercially available from Halliburton Energy Services of Duncan, Okla., under the trade designation "CFA-S™."
Another particularly preferred foaming agent of the above mentioned type is a surfactant having the formula:
H(CH.sub.2).sub.a (OC.sub.2 H.sub.4).sub.b OSO.sub.3 NH.sub.4
wherein:
a is an integer in the range of from about 5 to about 15; and
b is an integer in the range of from about 1 to about 10.
This surfactant is available from Halliburton Energy Services under the trade name "HALLIBURTON FOAM ADDITIVE™."
Another foaming agent which can be utilized in the cement compositions of this invention includes polyethoxylated alcohols having the formula:
H(CH.sub.2).sub.a (OC.sub.2 H.sub.4).sub.b OH
wherein:
a is an integer in the range of from about 10 to about 18; and
b is an integer in the range of from about 6 to about 15.
This surfactant is available from Halliburton Energy Services under the trade name "AQF-1™."
Yet another foaming agent which can be used is a sodium salt of alpha-olefinic sulfonic acid (AOS) which is a mixture of compounds of the formulas:
X H(CH.sub.2).sub.n --C=C--(CH.sub.2).sub.m SO .sub.3 Na!
and
Y H(CH.sub.2).sub.p --COH--(CH.sub.2).sub.q SO.sub.3 Na!
wherein:
n and m are individually integers in the range of from about 6 to about 16;
p and q are individually integers in the range of from about 7 to about 17; and
X and Y are fractions with the sum of X and Y being 1.
This foaming agent is available from Halliburton Energy Services under the trade name "AQF-2™."
Still another foaming surfactant which can be used is an alcohol ether sulfate of the formula:
H(CH.sub.2).sub.a (OC.sub.2 H.sub.4).sub.b SO.sub.3 NH.sub.4
wherein:
a is an integer in the range of from about 6 to about 10; and
b is an integer in the range of from about 3 to about 10.
The particular foaming agent employed will depend on various factors such as the types of formations in which the foamed cement is to be placed. Generally, the foaming agent utilized is included in a cement composition of this invention in an amount in the range of from about 1.5% to about 10% by weight of water in the composition. When the foaming agent is one of the preferred surfactants described above, it is included in the composition in an amount in the range of from about 4% to about 9.5% by weight of water therein.
A foam stabilizer is also included in the foamed cement composition to enhance the stability of the foamed cement slurry. One such foam stabilizing agent is a compound of the formula: ##STR1## wherein: R is hydrogen or a methyl radical; and
n is an integer in the range of from about 20 to about 200.
A particularly preferred foam stabilizing agent of the above type is a methoxypolyethylene glycol of the formula:
CH.sub.3 O(CH.sub.2 CH.sub.2 O).sub.n CH.sub.2 OH
wherein:
n is in the range of from about 100 to about 150.
This foam stabilizing agent is commercially available from Halliburton Energy Services under the trade designation "HALLIBURTON FOAM STABILIZER™."
The preferred foam stabilizing agent is a compound having the formula:
R--CONHCH.sub.2 CH.sub.2 CH.sub.2 N.sup.+ (CH.sub.3).sub.2 CH.sub.2 CO.sub.2.sup.-
wherein:
R is a C10 to C18 saturated aliphatic hydrocarbon group or an oleyl group or a linoleyl group.
A particularly preferred stabilizing agent of the above type is an amidopropylbetaine of the formula:
R--CONHCH.sub.2 CH.sub.2 CH.sub.2 N.sup.+ (CH.sub.3) .sub.2 CH.sub.2 CO.sub.2.sup.-
wherein:
R is a cocoyl group.
This foam stabilizing agent is commercially available from Halliburton Energy Services under the trade designation "HC-2™."
The foam stabilizer is included in a cement composition of this invention in an amount in the range of from about 0.75% to about 5% by weight of water utilized. When the foam stabilizing agent is one of the particularly preferred agents described above, it is preferably present in the composition in an amount in the range of from about 2% to about 5% by weight of water.
Another foamed well cement composition of this invention is comprised of a hydraulic cement of the type described above, an aqueous rubber latex described above present in an amount in the range of from about 2.5% to about 45% by weight of hydraulic cement in the composition (from about 0.25 to about 5 gal/sack), an effective amount of a latex stabilizer described above, an effective amount of a defoaming agent described above, a compressible gas described above present in an amount sufficient to foam the cement composition and produce a cement composition density in the range of from about 8 pounds per gallon to about 16 pounds per gallon, an effective amount of a foaming agent described above and an effective amount of a foam stabilizer described above.
This foamed cement composition which is preferred in some applications does not include fumed silica, but it is also light weight, resilient and resists pressurized formation fluid migration.
The well cement compositions useful herein can include other additives which are well known to those skilled in the art including fluid loss control additives, set retarding additives, dispersing agents, formation conditioning additives, set accelerators and the like.
Dispersing agents can be utilized to facilitate the use of lower quantities of water and to promote higher set cement strength. A particularly suitable dispersing agent for use with the well cement compositions of this invention is comprised of the condensation polymer product of an aliphatic ketone, an aliphatic aldehyde and a compound which introduces acid groups into the polymer, e.g., sodium sulfite. Such a dispersant is described in U.S. Pat. No. 4,557,763 issued to George et al. on Dec. 10, 1985 which is incorporated herein by reference.
Examples of fluid loss control additives are cellulose derivatives such as carboxymethylhydroxyethylcellulose, hydroxyethylcellulose, modified polysaccharides, polyacrylamides, guar gum derivatives, 2-acrylamido-2-methylpropane sulfonic acid copolymers, polyethyleneamine and the like.
Set retarding additives are included in the cement compositions when it is necessary to extend the time in which the cement composition can be pumped so that it will not thicken or set prior to being placed at a desired location in the well being cemented. Examples of set retarders which can be used include lignosulfonates such as calcium and sodium lignosulfonate, organic acids such as tartaric acid and gluconic acid, copolymers and others. The proper amount of retarder required for particular conditions can be determined by conducting a "thickening time test" for the particular retarder and cement composition. Such tests are described in the API Specification For Materials and Testing for Well Cements, API Specification 10 mentioned above.
A particularly preferred set retarder for use in accordance with the present invention is a copolymer or copolymer salt of 2-acrylamido-2-methylpropanesulfonic acid and acrylic acid. The copolymer comprises from about 40 to about 60 mole percent 2-acrylamido-2-methylpropanesulfonic acid with the balance comprising acrylic acid, and the copolymer or salt preferably has an average molecular weight below about 5,000. This copolymer set retarder is preferably utilized in the composition when the bottom hole circulating temperature exceeds about 200° F. The retarder has been found to both retard the setting of the cement at elevated formation temperatures and to stabilize the aqueous styrene/butadiene latex against agglomeration or inversion at the elevated temperature. The set retarder is generally added to the cement composition in an amount in the range of from about 0.1% to about 6% by weight of hydraulic cement in the composition.
The cement compositions of this invention may be prepared in accordance with any of the well known mixing techniques so long as the latex and latex stabilizing surfactant are not directly admixed without prior dilution by other liquids present. In one preferred method, a quantity of water is introduced into a cement blender and defoamer, latex and latex stabilizer are then sequentially added with suitable agitation to disperse the constituents. Any other liquid additives may then be admixed with the slurry followed by the hydraulic cement, fumed silica and other dry solids. The mixture is agitated for a sufficient period of time to admix the components and form a pumpable non-foamed slurry. When the slurry is foamed, it is pumped to the well bore and the foaming agent and foam stabilizer followed by the gas are injected into the slurry on the fly. As the slurry and gas flow through the well bore to the location where the resulting foamed cement composition is to be placed, the cement composition is foamed and stabilized.
The methods of this invention for cementing a zone in a well basically comprise the steps of placing a cement composition of this invention which sets into a highly resilient, high bond strength, substantially impermeable mass in the subterranean zone to be cemented, and maintaining the cement composition in the zone for a time sufficient for the cement composition to set therein.
In order to further illustrate the improved cement compositions and methods of this invention, the following examples are given.
Example 1
Test samples of non-foamed cement compositions of this invention comprised of API Portland Class H hydraulic cement, fumed silica, a dispersant, an aqueous styrene/butadiene latex, a latex stabilizer, and a defoaming agent were prepared. Two of the test samples also included an expansion additive. Descriptions of the test samples are set forth in Table I below.
Portions of each of the test samples were placed in shear bond and hydraulic bond test apparatus and allowed to set for time periods of 1 week at a temperature of 140° F. and atmospheric pressure. The test samples were then tested for shear bond strength and hydraulic bond strength.
The shear bond strength of set cement in the annulus between a pipe disposed in a well bore and the walls of the well bore is defined as the strength of the bond between the set cement and a pipe mechanically supported by the cement. The test sample shear bond strengths were determined by measuring the force required to initiate movement of pipe sections cemented by the test samples in test apparatus simulating a well bore, i.e., larger diameter pipe sections. The determined forces were divided by the cement-pipe contact surface areas to yield the shear bond strengths in psi.
The hydraulic bond strength of the set cement blocks migration of pressurized fluids in a cemented annulus. The test sample hydraulic bond strengths were determined by applying pressure at the pipe-set cement interfaces until leakage occurred. The hydraulic bond strength of a set cement test sample in psi is equal to the hydraulic pressure applied when leakage took place. The results of these tests are also set forth in Table I below.
                                  TABLE I                                 
__________________________________________________________________________
Non-Foamed Cement Composition Bond Strength Test Results                  
Cement Composition Components                                             
           Fumed                                                          
                Aqueous                                                   
                     Latex Expansion                                      
                                Defoaming                                 
           Silica,                                                        
                Latex.sup.1,                                              
                     Stabilizer.sup.2,                                    
                           Additive.sup.3,                                
                                Agent.sup.4,                              
                                      Water,                              
                                           Dispersant.sup.5,              
                                                     Shear                
                                                          Hydraulic       
Sam-       % by gal per                                                   
                     gal per                                              
                           % by gal per                                   
                                      % by % by      Bond Bond            
ple                                                                       
   Hydraulic                                                              
           Weight                                                         
                94 lb sack                                                
                     94 lb sack                                           
                           Weight                                         
                                94 lb sack                                
                                      Weight                              
                                           Weight                         
                                                 Density,                 
                                                     Strength,            
                                                          Strength,       
No.                                                                       
   Cement  of Cement                                                      
                of Cement                                                 
                     of Cement                                            
                           of Cement                                      
                                of Cement                                 
                                      of Cement                           
                                           of Cement                      
                                                 lb/gal                   
                                                     psi  psi             
__________________________________________________________________________
1  Portland Class H                                                       
           10   0.5  0.05  --   0.02  52.83                               
                                           0.5   15   86  1074            
2  Portland Class H                                                       
           10   0.5  0.05  5    0.02  55.97                               
                                           0.5   15  355  998             
3  Portland Class H                                                       
           10   1.0  0.1   --   0.02  47.98                               
                                           0.5   15  200  285             
4  Portland Class H                                                       
           10   1.0  0.1   5    0.02  51.12                               
                                           0.5   15  292  290             
__________________________________________________________________________
 .sup.1 Aqueous styrene/butadiene (25%:75% by wt.) latex containing 50% by
 weight water ("LATEX 2000 ™" from Halliburton Energy Services).       
 .sup.2 Sodium salt of sulfonated and ethoxylated compound having the     
 formula H(CH.sub.2).sub.12-15 (CH.sub.2 CH.sub.2 O).sub.15 SO.sub.3 Na   
 ("AVANEL S150 ™" from PPG Mazer).                                     
 .sup.3 Cement expansive additive ("MICROBOND M ™" from Halliburton    
 Energy Services, Duncan, Oklahoma).                                      
 .sup.4 Polydimethylsiloxane.                                             
 .sup.5 Condensation polymer product of ketone, aldehyde and sodium sulfit
 ("CFR3 ™" from Halliburton Energy Services of Duncan, Oklahoma).
From Table I, it can be seen that the non-foamed cement compositions of this invention have excellent shear and hydraulic bond strengths.
Example 2
Test samples of foamed cement compositions of this invention comprised of hydraulic cement, fumed silica, an aqueous rubber latex, a latex stabilizer, a defoaming agent, air, a foaming agent and a foam stabilizer were prepared. One of the foamed cement, compositions also included hemitite weighting material, 100 mesh sand, a set retarder and a retarder intensifier. For each test sample, an unfoamed cement slurry including the defoaming agent was first prepared utilizing a mixing device. A predetermined amount of the resulting slurry was then placed in a fixed volume blender jar having a stacked blade assembly. The foaming agent and foam stabilizer were then added to the jar and the contents were mixed at high speed. The high speed mixing by the stacked blade assembly caused the slurry to be foamed with air. Descriptions of the test samples are set forth in Table IIA below.
The foamed test samples were allowed to set for 1 week at 140° F. and atmospheric pressure after which portions of the test samples were subjected to various tests to determine their properties. More specifically, unconfined uniaxle and confined triaxial strength tests were conducted and Young's Moduli and Poisson's Ratios were determined as well as bulk compressibilities, shear moduli and tensile strengths, all in accordance with the standardized tests and procedures of the American Society for Testing and Materials (ASTM) set forth, for example, in ASTM Section D 1456. The results of the tests and determinations are set forth in Table IIB below.
                                  TABLE IIA                               
__________________________________________________________________________
Foamed Cement Composition                                                 
__________________________________________________________________________
Cement Composition Components                                             
            Fumed Silica,                                                 
                    Aqueous                                               
                           Latex       Fluid                              
            % by Weight of                                                
                    Rubber Stabilizer.sup.2,                              
                                       Loss Control                       
                                             Sand  Set   Set Retarder     
            Cement, or gal                                                
                    Latex, gal per                                        
                           gal per                                        
                                 Hemitite,                                
                                       Agent.sup.3,                       
                                             (100 Mesh),                  
                                                   Retarder.sup.4,        
                                                         Intensifier.sup.5
                                                         8                
Sample                                                                    
    Hydraulic                                                             
            per 94 lb Sack                                                
                    94 lb Sack                                            
                           94 lb Sack                                     
                                 % by Weight                              
                                       % by Weight                        
                                             % by Weight                  
                                                   % by                   
                                                         % by Weight      
No. Cement  of Cement                                                     
                    of Cement                                             
                           of Cement                                      
                                 of Cement                                
                                       of Cement                          
                                             of Cement                    
                                                   of Cement              
                                                         of               
__________________________________________________________________________
                                                         Cement           
1   Portland Class H                                                      
            10%     1      0.2   --    --    --    --    --               
2   Portland Class H                                                      
            10%     2      0.2   --    --    --    --    --               
3   Portland Class H                                                      
            1.63    1      0.3.sup.10                                     
                                 200   0.5   40    3.3   2.4              
            gal/sk.sup.9                                                  
__________________________________________________________________________
                  Cement Composition Components                           
                  Defoaming Agent.sup.6,                                  
                           Foaming Agent.sup.7,                           
                                   Foam Stabilizer.sup.8,                 
                                           Water,                         
              Sample                                                      
                  gal per 94 lb                                           
                           % by Weight                                    
                                   % by Weight                            
                                           gal per 94 lb                  
                                                   Density of             
                                                           Density,       
              No. Sack of Cement                                          
                           of Water                                       
                                   of Water                               
                                           Sack of Cement                 
                                                   Slurry,                
                                                           lb/gal         
__________________________________________________________________________
              1   0.02     7.5     3.75    5.41    15      13.6           
              2   0.02     9.4     4.7     4.32    15      13.6           
              3   0.02     4.5     2.3     5.01    22      17             
__________________________________________________________________________
 .sup.1 Aqueous styrene/butadiene (25%:75% by wt.) latex containing 50% by
 weight water ("LATEX 2000 ™" from Halliburton Energy Services).       
 .sup.2 Sodium salt of a sulfonated and ethoxylated compound having the   
 formula H(CH.sub.2).sub.12-15 (CH.sub.2 CH.sub.2 O).sub.15 SO.sub.3 Na   
 ("AVANEL S150 ™" from PPG Mazer).                                     
 .sup.3 Copolymer of "AMPS ™" and N,Ndimethylacrylamide (U.S. Pat. No. 
 4,555,269).                                                              
 .sup.4 Copolymer of "AMPS ™" and acrylic acid (U.S. Pat. No.          
 4,941,536).                                                              
 .sup.5 Tartaric acid.                                                    
 .sup.6 Polydimethylsiloxane.                                             
 .sup.7 Sodium salt of alphaolefinic sulfonic acid.                       
 .sup.8 Cocoylamidopropylbetaine.                                         
 .sup.9 Aqueous dispersion of 50% fumed silica by weight of water.        
 .sup.10 Ethoxylated nonylphenol with 15-40 moles of ethylene oxide       
 substituted for latex stabilizer described in footnote 2.                

                                  TABLE IIB                               
__________________________________________________________________________
Bond Strength And Resiliency Test Results                                 
__________________________________________________________________________
                               Confined Triaxial                          
                               Young's                                    
Shear     Hydraulic                                                       
               Unconfined Uniaxial                                        
                               Modulus     Poisson's                      
    Bond  Bond Young's   Compressive                                      
                               (E × 10.sup.6)                       
                                           Ratio                          
Sample                                                                    
    Strength,                                                             
          Strength,                                                       
               Modulus                                                    
                    Poissons                                              
                         Strength,                                        
                               Confining Pressure, psi                    
                                           Confining Pressure, psi        
No. psi   psi  (E × 10.sup.6)                                       
                    Ratio                                                 
                         psi   500 1000                                   
                                       2000                               
                                           500 1000                       
                                                   2000                   
__________________________________________________________________________
1   163(13.8).sup.1                                                       
          630  --   --   1388.sup.2                                       
                               0.048                                      
                                   0.312                                  
                                       0.091                              
                                           0.158                          
                                               0.1494                     
                                                   0.079                  
2   154(13.85).sup.1                                                      
          720  --   --   1460.sup.2                                       
                               0.076                                      
                                   0.304                                  
                                       0.026                              
                                           0.090                          
                                               0.2883                     
                                                   0.065                  
3   --    --   0.35 0.107                                                 
                         2700.sup.2                                       
                               0.26                                       
                                   0.3 0.282                              
                                           0.086                          
                                               0.144                      
                                                   0.109                  
__________________________________________________________________________
                     Confined Triaxial                                    
                     Plastic     Bulk   Shear     Failure                 
                     Failure,    Compressiblity                           
                                        Modulus                           
                                             Tensile                      
                                                  Envelope                
                     psi         at 1000                                  
                                        at 1000                           
                                             Strength                     
                                                  Friction                
                 Sample                                                   
                     Confining Pressure, psi                              
                                 psi, 10.sup.5                            
                                        psi, 10.sup.4                     
                                             (Briquet),                   
                                                  Angle,                  
                 No. 500 1000                                             
                             2000                                         
                                 psi    psi  psi  Degrees                 
__________________________________________________________________________
                 1   2900                                                 
                         4200                                             
                             4000                                         
                                 0.94   13.57                             
                                             194.sup.3                    
                                                  31.5                    
                 2   2255                                                 
                         3200                                             
                             3100                                         
                                 0.418  11.8 250.sup.3                    
                                                  19.5                    
                 3   3850                                                 
                         4925                                             
                             6950                                         
                                 6.2    --   --   22                      
__________________________________________________________________________
 .sup.1 The number in parentheses is the test sample density in lb/gal.   
 .sup.2 The base pressure was 2220 psi.                                   
 .sup.3 The base pressure was 286 psi.
From the results set forth in Table IIB, it can be seen that the foamed cement compositions of this invention have excellent bond strengths and resiliencies.
Example 3
Test samples of additional foamed cement compositions of this invention comprised of API Portland Class G hydraulic cement, an aqueous rubber latex, a latex stabilizer, a fluid loss control agent, a set accelerator, a defoaming agent, air, a foaming agent, and a foam stabilizer were prepared. For each test sample, a base unfoamed cement slurry including the defoaming agent was first prepared followed by foaming of the base slurry with a foaming agent and foam stabilizer as described in Example 2 above.
The various strength tests and modulus and ratio determinations described in Example 2 were conducted and determined.
The descriptions of the test samples are set forth in Table IIIA below and the results of the tests and determinations are set forth in Table IIIB below.
                                  TABLE IIIA                              
__________________________________________________________________________
Foamed Cement Compositions                                                
__________________________________________________________________________
Cement Composition Components                                             
                  Aqueous    Fluid                                        
                  Rubber                                                  
                       Latex Loss             Defoaming                   
            Sand  Latex.sup.1                                             
                       Stabilizer.sup.2,                                  
                             Control          Agent.sup.6,                
                                                    Foaming               
                                                         Foam             
            (100 mesh),                                                   
                  gal per                                                 
                       gal per                                            
                             Agent.sup.3,                                 
                                  Biopolymer.sup.4,                       
                                        Accelerator.sup.5,                
                                              gal per                     
                                                    Agent.sup.7,          
                                                         Stabilizer.sup.8,
                                                         1                
            % by  94 lb                                                   
                       94 lb % by % by  % by  94 lb % by % by             
Sample                                                                    
    Hydraulic                                                             
            Weight of                                                     
                  Sack of                                                 
                       Sack of                                            
                             Weight of                                    
                                  Weight of                               
                                        Weight of                         
                                              Sack of                     
                                                    Weight                
                                                         Weight of        
No. Cement  Cement                                                        
                  Cement                                                  
                       Cement                                             
                             Cement                                       
                                  Cement                                  
                                        Cement                            
                                              Cement                      
                                                    Water                 
                                                         Water            
__________________________________________________________________________
1   Portland Class G                                                      
            100   1    0.3   0.2  0.14  4     0.02  4.3  2.2              
2   Portland Class G                                                      
            100   1    0.3   0.2  0.14  4     0.02  4.3  2.2              
3   Portland Class G                                                      
            100   2    0.3   0.2  0.22  4     0.02  5.1  2.6              
4   Portland Class G                                                      
            100   2    0.3   0.2  0.22  4     0.02  5.1  2.6              
5   Portland Class G                                                      
            --    5    0.3   0.5  --    2     0.02  5.2  2.6              
__________________________________________________________________________
                                       Cement Compositon Components       
                                       Water,                             
                                       gal per 94 lb                      
                                               Density of                 
                                                       Foamed Density     
                                 Sample No.                               
                                       Sack of Cement                     
                                               Slurry, lb/gal             
                                                       lb/gal             
__________________________________________________________________________
                                 1     6.28    16.3    14                 
                                 2     6.28    16.3    12                 
                                 3     5.28    16.3    14                 
                                 4     5.28    16.3    12                 
                                 5     3.33    17.5    15                 
__________________________________________________________________________
 .sup.1 Aqueous styrene/butadiene (25%:75% by wt.) latex containing 50% by
 weight water ("LATEX ™" from Halliburton Energy Services).            
 .sup.2 Sodium salt of a sulfonated and ethoxylated compound having the   
 fomulra H(CH.sub.2).sub.12-15 (CH.sub.2 CH.sub.2 O).sub.15 SO.sub.3 Na   
 ("AVANEL S150 ™" from PPG Mazer).                                     
 .sup.3 Copolymer of "AMPS ™" and N,Ndimethylacrylamide (U.S. Pat. No. 
 4,555,269).                                                              
 .sup.4 Welan gum.                                                        
 .sup.5 Calcium chloride.                                                 
 .sup.6 Polydimethylsiloxane.                                             
 .sup.7 Sodium salt of alphaolefinic sulfonic acid.                       
 .sup.8 Cocoylamidopropylbetaine.                                         

                                  TABLE IIIB                              
__________________________________________________________________________
Bond Strength And Resiliency Test Results                                 
__________________________________________________________________________
                               Confined Triaxial                          
                               Young's                                    
Shear     Hydraulic                                                       
               Unconfined Uniaxial                                        
                               Modulus     Poisson's                      
    Bond  Bond Young's   Compressive                                      
                               (E × 10.sup.6)                       
                                           Ratio                          
Sample                                                                    
    Strength,                                                             
          Strength,                                                       
               Modulus                                                    
                    Poissons                                              
                         Strength,                                        
                               Confining Pressure, psi                    
                                           Confining Pressure, psi        
No. psi   psi  (E × 10.sup.6)                                       
                    Ratio                                                 
                         psi   500 1000                                   
                                       2000                               
                                           500 1000                       
                                                   2000                   
__________________________________________________________________________
1   303   780  --   --   --    --  0.039                                  
                                       --  --  0.1187                     
                                                   --                     
2   244(12.1).sup.1                                                       
          660  --   --   --    --  0.029                                  
                                       --  --  0.0436                     
                                                   --                     
3   322(14.1).sup.1                                                       
          775  --   --   --    --  0.048                                  
                                       --  --  0.1478                     
                                                   --                     
4   287(12.2).sup.1                                                       
          660  --   --   --    --  0.0353                                 
                                       --  --  0.1808                     
                                                   --                     
5    86(15.4).sup.1                                                       
          700  0.0025                                                     
                    0.102                                                 
                         392.sup.2                                        
                               0.013                                      
                                   0.013                                  
                                       0.025                              
                                           0.078                          
                                               0.128                      
                                                   0.171                  
__________________________________________________________________________
                     Confined Triaxial                                    
                     Plastic     Bulk   Shear     Failure                 
                     Failure,    Compressiblity                           
                                        Modulus                           
                                             Tensile                      
                                                  Envelope                
                     psi         at 1000                                  
                                        at 1000                           
                                             Strength                     
                                                  Friction                
                 Sample                                                   
                     Confining Pressure, psi                              
                                 psi, 10.sup.5                            
                                        psi, 10.sup.4                     
                                             (Briquet),                   
                                                  Angle,                  
                 No. 500 1000                                             
                             2000                                         
                                 psi    psi  psi  Degrees                 
__________________________________________________________________________
                 1   --  3220                                             
                             --  5.86   1.745                             
                                             --   --                      
                 2   --  2000                                             
                             --  9.44   1.389                             
                                             --   --                      
                 3   --  3700                                             
                             --  4.4    2.09 --   --                      
                 4   --  2200                                             
                             --  5.47   1.482                             
                                             --   --                      
                 5   1948                                                 
                         3096                                             
                             4857                                         
                                 17.169 0.576                             
                                             232.sup.3                    
                                                  9                       
__________________________________________________________________________
 .sup.1 The number in parentheses is the test sample density in lb/gal.   
 .sup.2 The base pressure was 2220 psi.                                   
 .sup.3 The base pressure was 286 psi.
From the results set forth in Table IIIB, it can be seen that the additional foamed cement compositions of this invention also have excellent bond strengths and resiliencies.
Thus, the present invention is well adapted to carry out the objects and advantages mentioned as well as those which are inherent therein. While numerous changes may be made by those skilled in the art, such changes are encompassed within the spirit of this invention as defined by the appended claims.

Claims (20)

What is claimed is:
1. A well cement composition having improved mechanical properties including elasticity and ductility comprising:
a hydraulic cement;
an aqueous rubber latex present in an amount in the range of from about 2.5% to about 45% by weight of hydraulic cement in said composition;
an effective amount of a latex stabilizer;
a defoaming agent comprised of polydimethylsiloxane present in an amount in the range of from about 0.1% to about 0.9% by weight of cement in said composition;
a gas present in an amount sufficient to foam said cement composition and produce a cement composition density in the range of from about 8 to about 16 pounds per gallon;
an effective amount of a foaming agent; and
an effective amount of a foam stabilizer.
2. The composition of claim 1 wherein said latex stabilizer is selected from the group consisting of surfactants having the formula
R--Ph--O(OCH.sub.2 CH.sub.2).sub.m OH
wherein R is an alkyl group having from about 5 to about 30 carbon atoms, Ph is phenyl and m is an integer in the range of from about 5 to about 50,
and surfactants of the general formula
R.sub.1 (OR.sub.2).sub.n SO.sub.3 X
wherein R1 is selected from the group consisting of alkyl groups having from 1 to about 30 carbon atoms, cycloalkyl groups having 5 or 6 carbon atoms, C1 -C4 alkyl substituted cycloalkyl groups, phenyl, alkyl substituted phenyl of the general formula (R3)a Ph-- wherein Ph is phenyl, R3 is an alkyl group having from 1 to about 18 carbon atoms and a is an integer of from 1 to 3, and phenyl-alkyl groups wherein the alkyl groups have from 1 to about 18 carbon atoms and the phenyl-alkyl groups have a total of from about 8 to about 28 carbon atoms, R2 is a substituted ethylene group of the formula --CH2 CH2 R4 wherein R4 is selected from hydrogen, methyl, ethyl or mixtures thereof, and n is a number from 0 to about 40 provided that when R1 is phenyl or alkyl substituted phenyl n is at least one, and X is any compatible cation.
3. The composition of claim 1 wherein said foaming agent is comprised of the sodium salt of alpha-olefinic sulfonic acid and is present in an amount in the range of from about 4% to about 9.5% by weight of water in said composition.
4. The composition of claim 1 wherein said foam stabilizer is comprised of an amidopropylbetaine of the formula:
R--CONHCH.sub.2 CH.sub.2 CH.sub.2 N.sup.+ (CH.sub.3) .sub.2 CH.sub.2 CO.sub.2.sup.-
wherein R is a cocoyl group, and present in an amount in the range of from about 2% to about 5% by weight of water in said composition.
5. The composition of claim 1 wherein water is present in said composition in an amount in the range of from about 22% to about 95% by weight of cement therein.
6. The composition of claim 1 wherein said hydraulic cement is Portland cement.
7. The composition of claim 1 wherein said aqueous rubber latex is an aqueous styrene/butadiene latex.
8. The composition of claim 7 wherein said aqueous styrene/butadiene latex contains water in an amount of about 50% by weight of said latex, and the weight ratio of styrene to butadiene in said latex is about 25%:75%.
9. The composition of claim 7 wherein said latex stabilizer is present in said cement composition in an amount in the range of from about 9% to about 35% by weight of said aqueous styrene/butadiene latex therein.
10. The composition of claim 9 wherein said latex stabilizer is selected from the group consisting of nonylphenol ethoxylated with in the range of from about 15 to about 40 moles of ethylene oxide and the sodium salt of a sulfonated and ethoxylated compound having the formula H(CH2)12-15 (CH2 CH2 O)15 SO3 Na.
11. A method of cementing in a subterranean well whereby the set cement can withstand impacts, shocks and cemented pipe movements subsequently generated by drilling and other well operations without cracking, shattering or otherwise failing comprising the steps of:
introducing a cement composition which sets into a high strength solid mass having elasticity and ductility into said well, said cement composition comprising:
a hydraulic cement,
an aqueous rubber latex present in an amount in the range of from about 2.5% to about 45% by weight of hydraulic cement in said composition,
an effective amount of a latex stabilizer,
a defoaming agent comprised of polydimethylsiloxane present in an amount in the range of from about 0.1% to about 0.9% by weight of hydraulic cement in said composition,
a gas present in an amount sufficient to foam said cement composition and produce a cement composition density in the range of from about 8 to about 16 pounds per gallon,
an effective amount of a foaming agent, and
an effective amount of a foam stabilizer; and
allowing said cement composition to set in said well.
12. The method of claim 11 wherein said latex stabilizer in said cement composition is selected from the group consisting of surfactants having the formula
R--Ph--O(OCH.sub.2 CH.sub.2).sub.m OH
wherein R is an alkyl group having from about 5 to about 30 carbon atoms, Ph is phenyl and m is an integer in the range of from about 5 to about 50,
and surfactants of the general formula
R.sub.1 (OR.sub.2).sub.n SO.sub.3 X
wherein R1 is selected from the group consisting of alkyl groups having from 1 to about 30 carbon atoms, cycloalkyl groups having 5 or 6 carbon atoms, C1 -C4 alkyl substituted cycloalkyl groups, phenyl, alkyl substituted phenyl of the general formula (R3)a Ph-- wherein Ph is phenyl, R3 is an alkyl group having from 1 to about 18 carbon atoms and a is an integer of from 1 to 3, and phenyl-alkyl groups wherein the alkyl groups have from 1 to about 18 carbon atoms and the phenyl-alkyl groups have a total of from about 8 to about 28 carbon atoms, R2 is a substituted ethylene group of the formula --CH2 CH2 R4 wherein R4 is selected from hydrogen, methyl, ethyl or mixtures thereof, and n is a number from 0 to about 40 provided that when R1 is phenyl or alkyl substituted phenyl n is at least one, and X is any compatible cation.
13. The method of claim 11 wherein said foaming agent in said composition is comprised of the sodium salt of alpha-olefinic sulfonic acid and is present in an amount in the range of from about 4% to about 9.5% by weight of water in said composition.
14. The method of claim 11 wherein said foam stabilizer in said composition is comprised of an amidopropylbetaine of the formula:
R--CONHCH.sub.2 CH.sub.2 CH.sub.2 N.sup.+ (CH.sub.3) .sub.2 CH.sub.2 CO.sub.2.sup.-
wherein R is a cocoyl group and is present in an amount in the range of from about 2% to about 5% by weight of water in said composition.
15. The method of claim 11 wherein water is present in said cement composition in an amount in the range of from about 22% to about 95% by weight of cement therein.
16. The method of claim 11 wherein said hydraulic cement in said composition is Portland cement.
17. The method of claim 11 wherein said aqueous rubber latex in said composition is an aqueous styrene/butadiene latex.
18. The method of claim 17 wherein said aqueous styrene/butadiene latex contains water in an amount of about 50% by weight of said latex, and the weight ratio of styrene to butadiene in said latex is about 25%:75%.
19. The method of claim 17 wherein said latex stabilizer is present in said cement composition in an amount in the range of from about 9% to about 35% by weight of said aqueous styrene/butadiene latex therein.
20. The method of claim 19 wherein said latex stabilizer in said composition is selected from the group consisting of nonylphenol ethoxylated with in the range of from about 20 to about 30 moles of ethylene oxide and a sodium salt of a sulfonated and ethoxylated compound having the formula H(CH2)12-15 (CH2 CH2 O)15 SO3 Na.
US08/673,970 1996-07-01 1996-07-01 Resilient well cement compositions and methods Expired - Fee Related US5688844A (en)

Priority Applications (5)

Application Number Priority Date Filing Date Title
US08/673,970 US5688844A (en) 1996-07-01 1996-07-01 Resilient well cement compositions and methods
CA002209232A CA2209232C (en) 1996-07-01 1997-06-27 Resilient well cement compositions and methods
DE69704183T DE69704183T2 (en) 1996-07-01 1997-06-30 Well cement composition
NO19973048A NO321191B1 (en) 1996-07-01 1997-06-30 Bronze cement compositions and method of cementing in underground wells
EP97304734A EP0816302B1 (en) 1996-07-01 1997-06-30 Well cement compositions

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
US08/673,970 US5688844A (en) 1996-07-01 1996-07-01 Resilient well cement compositions and methods

Publications (1)

Publication Number Publication Date
US5688844A true US5688844A (en) 1997-11-18

Family

ID=24704820

Family Applications (1)

Application Number Title Priority Date Filing Date
US08/673,970 Expired - Fee Related US5688844A (en) 1996-07-01 1996-07-01 Resilient well cement compositions and methods

Country Status (5)

Country Link
US (1) US5688844A (en)
EP (1) EP0816302B1 (en)
CA (1) CA2209232C (en)
DE (1) DE69704183T2 (en)
NO (1) NO321191B1 (en)

Cited By (128)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5779787A (en) * 1997-08-15 1998-07-14 Halliburton Energy Services, Inc. Well cement compositions containing rubber particles and methods of cementing subterranean zones
EP0922834A2 (en) * 1997-11-26 1999-06-16 Halliburton Energy Services, Inc. Method and composition for sealing a subterranean zone
US5913364A (en) * 1997-03-14 1999-06-22 Halliburton Energy Services, Inc. Methods of sealing subterranean zones
US5996693A (en) * 1998-09-15 1999-12-07 Halliburton Energy Services, Inc. Methods and compositions for cementing pipe in well bores
EP0980957A1 (en) * 1998-08-18 2000-02-23 Halliburton Energy Services, Inc. (a Delaware corp.) Composition for sealing pipe in well bore
FR2784095A1 (en) * 1998-10-06 2000-04-07 Schlumberger Cie Dowell CEMENTING COMPOSITIONS AND APPLICATION THEREOF FOR CEMENTING OIL WELLS OR THE LIKE
US6060434A (en) * 1997-03-14 2000-05-09 Halliburton Energy Services, Inc. Oil based compositions for sealing subterranean zones and methods
EP1031544A2 (en) * 1999-02-22 2000-08-30 Halliburton Energy Services, Inc. Well Cementing compositions
US6145591A (en) * 1997-12-12 2000-11-14 Bj Services Company Method and compositions for use in cementing
US6176314B1 (en) 1999-07-15 2001-01-23 Phillips Petroleum Company Low density well cement compositions and method of use
US6227294B1 (en) 2000-05-12 2001-05-08 Halliburton Energy Services, Inc. Methods of cementing subterranean zones
US6231664B1 (en) 1998-06-30 2001-05-15 Halliburton Energy Services, Inc. Well sealing compositions and methods
US6230804B1 (en) 1997-12-19 2001-05-15 Bj Services Company Stress resistant cement compositions and methods for using same
US6244344B1 (en) 1999-02-09 2001-06-12 Halliburton Energy Services, Inc. Methods and compositions for cementing pipe strings in well bores
US6258757B1 (en) 1997-03-14 2001-07-10 Halliburton Energy Services, Inc. Water based compositions for sealing subterranean zones and methods
US6271181B1 (en) 1999-02-04 2001-08-07 Halliburton Energy Services, Inc. Sealing subterranean zones
US6273191B1 (en) * 1999-07-15 2001-08-14 Halliburton Energy Services, Inc. Cementing casing strings in deep water offshore wells
EP1112987A3 (en) * 1999-12-16 2001-10-31 Omnova Solutions Inc. Gypsum wallboard
US6321841B1 (en) 2001-02-21 2001-11-27 Halliburton Energy Services, Inc. Methods of sealing pipe strings in disposal wells
US6328106B1 (en) 1999-02-04 2001-12-11 Halliburton Energy Services, Inc. Sealing subterranean zones
US6336505B1 (en) * 1999-07-15 2002-01-08 Halliburton Energy Services, Inc. Cementing casing strings in deep water offshore wells
US6372037B1 (en) 2000-05-12 2002-04-16 Lignotech Usa, Inc. Set retarders for foamed cements
US6419016B1 (en) 2000-09-29 2002-07-16 Halliburton Energy Services, Inc. Methods of cementing in subterranean zones
US6454004B2 (en) 1999-07-15 2002-09-24 Halliburton Energy Services, Inc. Cementing casing strings in deep water offshore wells
US6508305B1 (en) 1999-09-16 2003-01-21 Bj Services Company Compositions and methods for cementing using elastic particles
US6516884B1 (en) 2002-07-23 2003-02-11 Halliburton Energy Services, Inc. Stable well cementing methods and compositions
US6569923B1 (en) 1999-03-19 2003-05-27 John T. Slagter Polymer-cement composites and methods of making same
US6579923B2 (en) 2001-02-05 2003-06-17 3M Innovative Properties Company Use of a silicone surfactant in polishing compositions
US20030116319A1 (en) * 2001-12-04 2003-06-26 Brothers Lance E Methods and compositions for sealing an expandable tubular in a wellbore
US6626243B1 (en) 1999-08-24 2003-09-30 Bj Services Company Methods and compositions for use in cementing in cold environments
US20030224946A1 (en) * 2002-06-04 2003-12-04 Halliburton Energy Services, Inc. Sealing composition
US6668928B2 (en) 2001-12-04 2003-12-30 Halliburton Energy Services, Inc. Resilient cement
WO2004001183A1 (en) * 2002-06-21 2003-12-31 Halliburton Energy Services, Inc. Methods of sealing expandable pipe in well bores and sealing compositions
US20040055748A1 (en) * 2002-09-19 2004-03-25 Reddy B. Raghava Elastomeric admixtures for improving cement elasticity
US6729405B2 (en) 2001-02-15 2004-05-04 Bj Services Company High temperature flexible cementing compositions and methods for using same
US20040112598A1 (en) * 2002-12-17 2004-06-17 Nguyen Philip D. Permeable cement composition and method for preparing the same
US6762156B2 (en) 2002-01-31 2004-07-13 Halliburton Energy Services, Inc. Reactive cement compositions for sealing hydrocarbon containing subterranean zones and methods
FR2850647A1 (en) 2003-01-30 2004-08-06 Rhodia Chimie Sa COMPOSITION COMPRISING A HYDRAULIC BINDER AND A LATEX HAVING A SULFONATE, SULFONIC OR SULFOBETAN FUNCTIONAL GROUP
US20040163812A1 (en) * 2003-02-25 2004-08-26 Brothers Lance E. Cement compositions with improved mechanical properties and methods of cementing in subterranean formations
US6832651B2 (en) 2002-08-29 2004-12-21 Halliburton Energy Services, Inc. Cement composition exhibiting improved resilience/toughness and method for using same
US20050009710A1 (en) * 2002-01-31 2005-01-13 Halliburton Energy Services Reactive sealing compositions for sealing hydrocarbon containing subterranean formations and methods
US20050054760A1 (en) * 1999-01-26 2005-03-10 Ira John Westerman Gypsum wallboard
US20050092211A1 (en) * 2003-10-31 2005-05-05 Lewis Samuel J. Dispersant compositions for cement compositions and related methods
US20050124501A1 (en) * 2003-05-13 2005-06-09 Reddy B. R. Sealant compositions and methods of using the same to isolate a subterranean zone from a disposal well
US20050167106A1 (en) * 2004-01-29 2005-08-04 Reddy B. R. Emulsion admixtures for improving cement elasticity
US20050230112A1 (en) * 2004-04-19 2005-10-20 Reddy B R Sealant compositions comprising colloidally stabilized latex and methods of using the same
US20060032407A1 (en) * 2003-07-31 2006-02-16 Halliburton Energy Services, Inc. Compositions for preventing coagulation of water-in-oil emulsion polymers in aqueous saline well treating fluids
US7022755B1 (en) 2005-02-04 2006-04-04 Halliburton Energy Services, Inc. Resilient cement compositions and methods of cementing
US20060122071A1 (en) * 2004-12-08 2006-06-08 Hallbiurton Energy Services, Inc. Oilwell sealant compositions comprising alkali swellable latex
US20060166837A1 (en) * 2005-01-24 2006-07-27 Lijun Lin Methods of treating subterranean formations with heteropolysaccharides based fluids
US20060167133A1 (en) * 2005-01-24 2006-07-27 Jan Gromsveld Sealant composition comprising a crosslinkable material and a reduced amount of cement for a permeable zone downhole
US20060166836A1 (en) * 2005-01-24 2006-07-27 Alejandro Pena Energized fluids and methods of use thereof
US20060162930A1 (en) * 2005-01-24 2006-07-27 Jan Gronsveld Methods of plugging a permeable zone downhole using a sealant composition comprising a crosslinkable material and a reduced amount of cement
US20060174805A1 (en) * 2005-02-04 2006-08-10 Halliburton Energy Services, Inc. Resilient cement compositions and methods of cementing
US20060175060A1 (en) * 2005-02-09 2006-08-10 Halliburton Energy Services, Inc. Servicing a wellbore with wellbore fluids comprising perlite
US7156172B2 (en) 2004-03-02 2007-01-02 Halliburton Energy Services, Inc. Method for accelerating oil well construction and production processes and heating device therefor
US20070017676A1 (en) * 2005-07-21 2007-01-25 Halliburton Energy Services, Inc. Methods for wellbore strengthening and controlling fluid circulation loss
US7172022B2 (en) 2004-03-17 2007-02-06 Halliburton Energy Services, Inc. Cement compositions containing degradable materials and methods of cementing in subterranean formations
US20070042913A1 (en) * 2005-08-17 2007-02-22 Hutchins Richard D Wellbore treatment compositions containing foam extenders and methods of use thereof
US20070062691A1 (en) * 2005-09-16 2007-03-22 Reddy B R Methods of formulating a cement composition
US20070125534A1 (en) * 2005-12-01 2007-06-07 Halliburton Energy Services, Inc. Methods of using wellbore sealant compositions containing cationic latexes
US20070125276A1 (en) * 2005-12-01 2007-06-07 Halliburton Energy Services, Inc. Wellbore sealant compositions containing cationic latexes
US20070151484A1 (en) * 2005-12-29 2007-07-05 Reddy B R Cement compositions comprising particulate carboxylated elastomers and associated methods
US20070151730A1 (en) * 2005-12-29 2007-07-05 Reddy B R Cement compositions comprising particulate carboxylated elastomers and associated methods
US20070187099A1 (en) * 2006-02-10 2007-08-16 Ling Wang Methods and Compositions for Sealing Fractures, Voids, and Pores of Subterranean Rock Formations
US20070203028A1 (en) * 2006-02-28 2007-08-30 Halliburton Energy Services, Inc. Salt water stable latex cement slurries
US20080026957A1 (en) * 2005-01-24 2008-01-31 Gurmen M N Treatment and Production of Subterranean Formations with Heteropolysaccharides
US20080078550A1 (en) * 2006-09-28 2008-04-03 Halliburton Energy Services, Inc. Prevention of latex inversion in saltwater cement compositions for use in subterranean formations and associated methods
WO2008037976A1 (en) * 2006-09-28 2008-04-03 Halliburton Energy Services, Inc. Prevention of latex inversion in saltwater cement compositions for use in subterranean formations and associated compositions
US20080280786A1 (en) * 2007-05-07 2008-11-13 Halliburton Energy Services, Inc. Defoamer/antifoamer compositions and methods of using same
US20080305971A1 (en) * 2005-01-24 2008-12-11 Leiming Li Polysaccharide Treatment Fluid and Method of Treating A Subterranean Formation
US20090023613A1 (en) * 2005-01-24 2009-01-22 Leiming Li Polysaccharide Treatment Fluid and Method of Treating a Subterranean Formation
US20090038800A1 (en) * 2007-08-08 2009-02-12 Ravi Krishna M Sealant Compositions and Methods of Use
US20090038801A1 (en) * 2007-08-08 2009-02-12 Ravi Krishna M Sealant Compositions and Methods of Use
US20090105097A1 (en) * 2007-10-22 2009-04-23 Carlos Abad Degradable Friction Reducer
US7530396B1 (en) 2008-01-24 2009-05-12 Halliburton Energy Services, Inc. Self repairing cement compositions and methods of using same
US7607484B2 (en) 2005-09-09 2009-10-27 Halliburton Energy Services, Inc. Foamed cement compositions comprising oil-swellable particles and methods of use
US7607482B2 (en) 2005-09-09 2009-10-27 Halliburton Energy Services, Inc. Settable compositions comprising cement kiln dust and swellable particles
US7617870B1 (en) * 2008-05-14 2009-11-17 Halliburton Energy Services, Inc. Extended cement compositions comprising oil-swellable particles and associated methods
US20090308616A1 (en) * 2001-11-14 2009-12-17 Halliburton Energy Services, Inc. Method and Apparatus for a Monodiameter Wellbore, Monodiameter Casing, Monobore, and/or Monowell
US20100035772A1 (en) * 2004-12-08 2010-02-11 Halliburton Energy Services, Inc. Sealant compositions comprising solid latex
US20100036017A1 (en) * 2005-01-24 2010-02-11 Eoff Larry S Sealant Compositions Comprising Diutan and Associated Methods
US7678745B2 (en) 2007-09-24 2010-03-16 Schlumberger Technology Corporation Viscosity reduction
US20100075029A1 (en) * 2008-08-18 2010-03-25 Wilson Jr Jack H Pavement life extension product and method
US20100116497A1 (en) * 2004-12-08 2010-05-13 Halliburton Energy Services, Inc. Method of servicing a wellbore with a sealant composition comprising solid latex
US7743828B2 (en) 2005-09-09 2010-06-29 Halliburton Energy Services, Inc. Methods of cementing in subterranean formations using cement kiln cement kiln dust in compositions having reduced Portland cement content
US20100193191A1 (en) * 2009-02-03 2010-08-05 Roddy Craig W Methods and Compositions Comprising a Dual Oil/Water-Swellable Particle
US7776796B2 (en) 2006-03-20 2010-08-17 Schlumberger Technology Corporation Methods of treating wellbores with recyclable fluids
US20100212892A1 (en) * 2009-02-26 2010-08-26 Halliburton Energy Services, Inc. Methods of formulating a cement composition
US7792250B1 (en) 2009-04-30 2010-09-07 Halliburton Energy Services Inc. Method of selecting a wellbore cement having desirable characteristics
US7789150B2 (en) 2005-09-09 2010-09-07 Halliburton Energy Services Inc. Latex compositions comprising pozzolan and/or cement kiln dust and methods of use
US20110083503A1 (en) * 2009-10-09 2011-04-14 Halliburton Energy Services, Inc. Methods and Apparatus for Designing a Cement Composition
US8122959B2 (en) 2005-06-30 2012-02-28 Schlumberger Technology Corporation Methods and materials for zonal isolation
WO2012085508A1 (en) 2010-12-21 2012-06-28 Halliburton Energy Services Methods for cementing in a subterranean formation using a cement composition containing calcium silicate hydrate seeds
US8261827B2 (en) 2005-09-09 2012-09-11 Halliburton Energy Services Inc. Methods and compositions comprising kiln dust and metakaolin
US8281859B2 (en) 2005-09-09 2012-10-09 Halliburton Energy Services Inc. Methods and compositions comprising cement kiln dust having an altered particle size
US8297357B2 (en) 2005-09-09 2012-10-30 Halliburton Energy Services Inc. Acid-soluble cement compositions comprising cement kiln dust and/or a natural pozzolan and methods of use
US8327939B2 (en) 2005-09-09 2012-12-11 Halliburton Energy Services, Inc. Settable compositions comprising cement kiln dust and rice husk ash and methods of use
US8333240B2 (en) 2005-09-09 2012-12-18 Halliburton Energy Services, Inc. Reduced carbon footprint settable compositions for use in subterranean formations
US8403045B2 (en) 2005-09-09 2013-03-26 Halliburton Energy Services, Inc. Settable compositions comprising unexpanded perlite and methods of cementing in subterranean formations
US8476203B2 (en) 2007-05-10 2013-07-02 Halliburton Energy Services, Inc. Cement compositions comprising sub-micron alumina and associated methods
US8505629B2 (en) 2005-09-09 2013-08-13 Halliburton Energy Services, Inc. Foamed spacer fluids containing cement kiln dust and methods of use
US8505630B2 (en) 2005-09-09 2013-08-13 Halliburton Energy Services, Inc. Consolidating spacer fluids and methods of use
US8522873B2 (en) 2005-09-09 2013-09-03 Halliburton Energy Services, Inc. Spacer fluids containing cement kiln dust and methods of use
US8555967B2 (en) 2005-09-09 2013-10-15 Halliburton Energy Services, Inc. Methods and systems for evaluating a boundary between a consolidating spacer fluid and a cement composition
US8586512B2 (en) 2007-05-10 2013-11-19 Halliburton Energy Services, Inc. Cement compositions and methods utilizing nano-clay
US20130319673A1 (en) * 2012-05-31 2013-12-05 Halliburton Energy Services, Inc. Cement Compositions Comprising Saponins and Associated Methods
US8609595B2 (en) 2005-09-09 2013-12-17 Halliburton Energy Services, Inc. Methods for determining reactive index for cement kiln dust, associated compositions, and methods of use
US8672028B2 (en) 2010-12-21 2014-03-18 Halliburton Energy Services, Inc. Settable compositions comprising interground perlite and hydraulic cement
US8685903B2 (en) 2007-05-10 2014-04-01 Halliburton Energy Services, Inc. Lost circulation compositions and associated methods
US8703659B2 (en) 2005-01-24 2014-04-22 Halliburton Energy Services, Inc. Sealant composition comprising a gel system and a reduced amount of cement for a permeable zone downhole
US8887806B2 (en) 2011-05-26 2014-11-18 Halliburton Energy Services, Inc. Method for quantifying cement blend components
US8950486B2 (en) 2005-09-09 2015-02-10 Halliburton Energy Services, Inc. Acid-soluble cement compositions comprising cement kiln dust and methods of use
US9006155B2 (en) 2005-09-09 2015-04-14 Halliburton Energy Services, Inc. Placing a fluid comprising kiln dust in a wellbore through a bottom hole assembly
US20150114649A1 (en) * 2013-10-30 2015-04-30 Halliburton Energy Sevices, Inc. Sealant compositions for use in subterranean formation operations
US9023150B2 (en) 2005-09-09 2015-05-05 Halliburton Energy Services, Inc. Acid-soluble cement compositions comprising cement kiln dust and/or a natural pozzolan and methods of use
US9051505B2 (en) 2005-09-09 2015-06-09 Halliburton Energy Services, Inc. Placing a fluid comprising kiln dust in a wellbore through a bottom hole assembly
US9150773B2 (en) 2005-09-09 2015-10-06 Halliburton Energy Services, Inc. Compositions comprising kiln dust and wollastonite and methods of use in subterranean formations
US9199879B2 (en) 2007-05-10 2015-12-01 Halliburton Energy Serives, Inc. Well treatment compositions and methods utilizing nano-particles
US9206344B2 (en) 2007-05-10 2015-12-08 Halliburton Energy Services, Inc. Sealant compositions and methods utilizing nano-particles
WO2016039988A1 (en) * 2014-09-11 2016-03-17 Schlumberger Canada Limited Cement slurry compositions and methods
US9512352B2 (en) 2007-05-10 2016-12-06 Halliburton Energy Services, Inc. Well treatment fluids and methods utilizing nano-particles
US9676989B2 (en) 2005-09-09 2017-06-13 Halliburton Energy Services, Inc. Sealant compositions comprising cement kiln dust and tire-rubber particles and method of use
WO2017137354A1 (en) * 2016-02-08 2017-08-17 Shell Internationale Research Maatschappij B.V. Method for providing zonal isolation in an underground wellbore
US9809736B2 (en) 2012-08-31 2017-11-07 Halliburton Energy Services, Inc. Wellbore servicing compositions and methods of making and using same
US9809737B2 (en) 2005-09-09 2017-11-07 Halliburton Energy Services, Inc. Compositions containing kiln dust and/or biowaste ash and methods of use
CN113046049A (en) * 2021-03-29 2021-06-29 西南石油大学 Multi-water-layer four-dispersion foam scrubbing agent for natural gas horizontal well
CN113880502A (en) * 2020-07-01 2022-01-04 中国石油化工股份有限公司 Well wall repairing enhancer for deep well broken stratum and preparation method and application thereof

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105505352B (en) * 2015-12-29 2021-03-26 中国石油化工股份有限公司 Plugging agent for high-sulfur-content gas well
DE102016106196B4 (en) * 2016-04-05 2017-10-19 ML 7 Entwicklungs GmbH Use of stabilizers for stabilizing a foam, foaming agent, process for producing an air-entrained building material and air-pore-containing building materials and construction products obtainable by the processes

Citations (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB904973A (en) * 1960-08-30 1962-09-05 Us Rubber Co Synthetic rubber latex and hydraulic cement compositions
USRE28722E (en) * 1957-09-20 1976-02-24 The Dow Chemical Company Butadiene-styrene copolymer-cement composition and method of preparation
US4039345A (en) * 1974-06-03 1977-08-02 The Dow Chemical Company Shrinkage-compensating portland cement concrete and mortar compositions
US4057528A (en) * 1976-04-19 1977-11-08 The Dow Chemical Company Process for repairing concrete structures using pneumatically sprayable cement mortar compositions containing portland cement, mineral aggregate, a styrene-butadiene copolymer latex and water
US4202809A (en) * 1977-07-15 1980-05-13 The Dow Chemical Company Styrene-butadiene-acrylonitrile interpolymer latex based cement additives
US4398957A (en) * 1981-02-13 1983-08-16 Polysar International S.A. Mortar latex mix
US4537918A (en) * 1982-04-06 1985-08-27 Etudes Et Fabrication Dowell Schlumberger Cement compositions for cementing wells, allowing pressure gas-channeling in the cemented annulus to be controlled
US4721160A (en) * 1984-11-15 1988-01-26 Dowell Schlumberger Incorporated Composition for a lightweight cement slurry for cementing oil and gas wells
US4767460A (en) * 1985-01-29 1988-08-30 Dowell Schlumberger Incorporated Cement compositions for cementing of wells enabling gas channelling in the cemented annulus to be inhibited by right-angle setting
US4927462A (en) * 1988-12-23 1990-05-22 Associated Universities, Inc. Oxidation of carbon fiber surfaces for use as reinforcement in high-temperature cementitious material systems
US5004506A (en) * 1987-05-07 1991-04-02 Merck & Co., Inc. Welan gum in cement compositions
US5159980A (en) * 1991-06-27 1992-11-03 Halliburton Company Well completion and remedial methods utilizing rubber latex compositions
US5185389A (en) * 1986-08-26 1993-02-09 Gemeng, Ltd. Latex modified mortar and concrete
US5188176A (en) * 1991-11-08 1993-02-23 Atlantic Richfield Company Cement slurries for diviated wells
US5258428A (en) * 1992-09-04 1993-11-02 Sridhar Gopalkrishnan Additive composition for oil well cementing formulations
US5262452A (en) * 1992-09-04 1993-11-16 Basf Corp. Oil well cementing formulations
US5300542A (en) * 1992-09-04 1994-04-05 Basf Corp. Additive composition for oil well cementing formulations having nonionic and anionic surfactant stablizers to improve the fluid loss properties thereof
US5389706A (en) * 1992-10-09 1995-02-14 Halliburton Company Well cement compositions having improved properties and methods
US5401786A (en) * 1992-09-04 1995-03-28 Basf Corporation Additive composition for oil well cementing formulations
US5476343A (en) * 1992-11-30 1995-12-19 Sumner; Glen R. Offshore pipeline insulated with a cementitious coating
US5588488A (en) * 1995-08-22 1996-12-31 Halliburton Company Cementing multi-lateral wells

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6317273A (en) * 1986-07-03 1988-01-25 株式会社　ベルセンタ− Heat insulating composition
US5133409A (en) * 1990-12-12 1992-07-28 Halliburton Company Foamed well cementing compositions and methods
CA2109960C (en) * 1991-05-31 2000-07-18 Li-Chien Hsu Thromboresistant coating for defoaming applications
US5258072A (en) * 1992-06-01 1993-11-02 Basf Corporation Additive composition for oil well cementing formulations

Patent Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
USRE28722E (en) * 1957-09-20 1976-02-24 The Dow Chemical Company Butadiene-styrene copolymer-cement composition and method of preparation
GB904973A (en) * 1960-08-30 1962-09-05 Us Rubber Co Synthetic rubber latex and hydraulic cement compositions
US4039345A (en) * 1974-06-03 1977-08-02 The Dow Chemical Company Shrinkage-compensating portland cement concrete and mortar compositions
US4057528A (en) * 1976-04-19 1977-11-08 The Dow Chemical Company Process for repairing concrete structures using pneumatically sprayable cement mortar compositions containing portland cement, mineral aggregate, a styrene-butadiene copolymer latex and water
US4202809A (en) * 1977-07-15 1980-05-13 The Dow Chemical Company Styrene-butadiene-acrylonitrile interpolymer latex based cement additives
US4398957A (en) * 1981-02-13 1983-08-16 Polysar International S.A. Mortar latex mix
US4537918A (en) * 1982-04-06 1985-08-27 Etudes Et Fabrication Dowell Schlumberger Cement compositions for cementing wells, allowing pressure gas-channeling in the cemented annulus to be controlled
US4721160A (en) * 1984-11-15 1988-01-26 Dowell Schlumberger Incorporated Composition for a lightweight cement slurry for cementing oil and gas wells
US4767460A (en) * 1985-01-29 1988-08-30 Dowell Schlumberger Incorporated Cement compositions for cementing of wells enabling gas channelling in the cemented annulus to be inhibited by right-angle setting
US5185389A (en) * 1986-08-26 1993-02-09 Gemeng, Ltd. Latex modified mortar and concrete
US5004506A (en) * 1987-05-07 1991-04-02 Merck & Co., Inc. Welan gum in cement compositions
US4927462A (en) * 1988-12-23 1990-05-22 Associated Universities, Inc. Oxidation of carbon fiber surfaces for use as reinforcement in high-temperature cementitious material systems
US5159980A (en) * 1991-06-27 1992-11-03 Halliburton Company Well completion and remedial methods utilizing rubber latex compositions
US5293938A (en) * 1991-06-27 1994-03-15 Halliburton Company Well completion and remedial methods utilizing cement-ladened rubber
US5188176A (en) * 1991-11-08 1993-02-23 Atlantic Richfield Company Cement slurries for diviated wells
US5258428A (en) * 1992-09-04 1993-11-02 Sridhar Gopalkrishnan Additive composition for oil well cementing formulations
US5262452A (en) * 1992-09-04 1993-11-16 Basf Corp. Oil well cementing formulations
US5300542A (en) * 1992-09-04 1994-04-05 Basf Corp. Additive composition for oil well cementing formulations having nonionic and anionic surfactant stablizers to improve the fluid loss properties thereof
US5401786A (en) * 1992-09-04 1995-03-28 Basf Corporation Additive composition for oil well cementing formulations
US5389706A (en) * 1992-10-09 1995-02-14 Halliburton Company Well cement compositions having improved properties and methods
US5476343A (en) * 1992-11-30 1995-12-19 Sumner; Glen R. Offshore pipeline insulated with a cementitious coating
US5588488A (en) * 1995-08-22 1996-12-31 Halliburton Company Cementing multi-lateral wells

Cited By (241)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6258757B1 (en) 1997-03-14 2001-07-10 Halliburton Energy Services, Inc. Water based compositions for sealing subterranean zones and methods
US6060434A (en) * 1997-03-14 2000-05-09 Halliburton Energy Services, Inc. Oil based compositions for sealing subterranean zones and methods
US5913364A (en) * 1997-03-14 1999-06-22 Halliburton Energy Services, Inc. Methods of sealing subterranean zones
US6167967B1 (en) 1997-03-14 2001-01-02 Halliburton Energy Services, Inc. Methods of sealing subterranean zones
US5779787A (en) * 1997-08-15 1998-07-14 Halliburton Energy Services, Inc. Well cement compositions containing rubber particles and methods of cementing subterranean zones
EP0922834A3 (en) * 1997-11-26 1999-08-18 Halliburton Energy Services, Inc. Method and composition for sealing a subterranean zone
EP0922834A2 (en) * 1997-11-26 1999-06-16 Halliburton Energy Services, Inc. Method and composition for sealing a subterranean zone
US6059036A (en) * 1997-11-26 2000-05-09 Halliburton Energy Services, Inc. Methods and compositions for sealing subterranean zones
US6145591A (en) * 1997-12-12 2000-11-14 Bj Services Company Method and compositions for use in cementing
US6230804B1 (en) 1997-12-19 2001-05-15 Bj Services Company Stress resistant cement compositions and methods for using same
US6231664B1 (en) 1998-06-30 2001-05-15 Halliburton Energy Services, Inc. Well sealing compositions and methods
US6098711A (en) * 1998-08-18 2000-08-08 Halliburton Energy Services, Inc. Compositions and methods for sealing pipe in well bores
EP0980957A1 (en) * 1998-08-18 2000-02-23 Halliburton Energy Services, Inc. (a Delaware corp.) Composition for sealing pipe in well bore
US6270565B1 (en) 1998-09-15 2001-08-07 Halliburton Energy Services, Inc. Methods and compositions for cementing pipe in well bores
US5996693A (en) * 1998-09-15 1999-12-07 Halliburton Energy Services, Inc. Methods and compositions for cementing pipe in well bores
WO2000020350A1 (en) * 1998-10-06 2000-04-13 Sofitech N.V. Cementing compositions and the use of such compositions for cementing oil wells or the like
FR2784095A1 (en) * 1998-10-06 2000-04-07 Schlumberger Cie Dowell CEMENTING COMPOSITIONS AND APPLICATION THEREOF FOR CEMENTING OIL WELLS OR THE LIKE
US20050054760A1 (en) * 1999-01-26 2005-03-10 Ira John Westerman Gypsum wallboard
US6401817B1 (en) 1999-02-04 2002-06-11 Halliburton Energy Services, Inc. Sealing subterranean zones
US6448206B1 (en) 1999-02-04 2002-09-10 Halliburton Energy Services, Inc. Sealing subterranean zones
US6271181B1 (en) 1999-02-04 2001-08-07 Halliburton Energy Services, Inc. Sealing subterranean zones
US6328106B1 (en) 1999-02-04 2001-12-11 Halliburton Energy Services, Inc. Sealing subterranean zones
US6555507B2 (en) 1999-02-04 2003-04-29 Halliburton Energy Services, Inc. Sealing subterranean zones
US6244344B1 (en) 1999-02-09 2001-06-12 Halliburton Energy Services, Inc. Methods and compositions for cementing pipe strings in well bores
US6350309B2 (en) 1999-02-09 2002-02-26 Halliburton Energy Services, Inc. Methods and compositions for cementing pipe strings in well bores
US6593402B2 (en) 1999-02-22 2003-07-15 Halliburton Energy Services, Inc. Resilient well cement compositions and methods
US6234251B1 (en) 1999-02-22 2001-05-22 Halliburton Energy Services, Inc. Resilient well cement compositions and methods
EP1031544A3 (en) * 1999-02-22 2000-10-18 Halliburton Energy Services, Inc. Well Cementing compositions
US6330917B2 (en) 1999-02-22 2001-12-18 Halliburton Energy Services, Inc. Resilient well cement compositions and methods
EP1031544A2 (en) * 1999-02-22 2000-08-30 Halliburton Energy Services, Inc. Well Cementing compositions
US6569923B1 (en) 1999-03-19 2003-05-27 John T. Slagter Polymer-cement composites and methods of making same
US6793730B2 (en) 1999-07-15 2004-09-21 Halliburton Energy Services, Inc. Methods of cementing
US20030217847A1 (en) * 1999-07-15 2003-11-27 Reddy B. Raghava Methods of cementing
US6176314B1 (en) 1999-07-15 2001-01-23 Phillips Petroleum Company Low density well cement compositions and method of use
US6454004B2 (en) 1999-07-15 2002-09-24 Halliburton Energy Services, Inc. Cementing casing strings in deep water offshore wells
US6273191B1 (en) * 1999-07-15 2001-08-14 Halliburton Energy Services, Inc. Cementing casing strings in deep water offshore wells
US6336505B1 (en) * 1999-07-15 2002-01-08 Halliburton Energy Services, Inc. Cementing casing strings in deep water offshore wells
US6630021B2 (en) 1999-07-15 2003-10-07 Halliburton Energy Services, Inc. Cementing casing strings in deep water offshore wells
US6626243B1 (en) 1999-08-24 2003-09-30 Bj Services Company Methods and compositions for use in cementing in cold environments
US6508305B1 (en) 1999-09-16 2003-01-21 Bj Services Company Compositions and methods for cementing using elastic particles
EP1112987A3 (en) * 1999-12-16 2001-10-31 Omnova Solutions Inc. Gypsum wallboard
US6227294B1 (en) 2000-05-12 2001-05-08 Halliburton Energy Services, Inc. Methods of cementing subterranean zones
US6372037B1 (en) 2000-05-12 2002-04-16 Lignotech Usa, Inc. Set retarders for foamed cements
US6558461B2 (en) 2000-05-12 2003-05-06 Lignotech Usa, Inc. Set retarders for foamed cements
US6419016B1 (en) 2000-09-29 2002-07-16 Halliburton Energy Services, Inc. Methods of cementing in subterranean zones
US6579923B2 (en) 2001-02-05 2003-06-17 3M Innovative Properties Company Use of a silicone surfactant in polishing compositions
US20040194960A1 (en) * 2001-02-15 2004-10-07 Bj Services Company High temperature flexible cementing compositions and methods for using the same
US6729405B2 (en) 2001-02-15 2004-05-04 Bj Services Company High temperature flexible cementing compositions and methods for using same
US6321841B1 (en) 2001-02-21 2001-11-27 Halliburton Energy Services, Inc. Methods of sealing pipe strings in disposal wells
US20090308616A1 (en) * 2001-11-14 2009-12-17 Halliburton Energy Services, Inc. Method and Apparatus for a Monodiameter Wellbore, Monodiameter Casing, Monobore, and/or Monowell
US8011446B2 (en) 2001-11-14 2011-09-06 Halliburton Energy Services, Inc. Method and apparatus for a monodiameter wellbore, monodiameter casing, monobore, and/or monowell
US20030116319A1 (en) * 2001-12-04 2003-06-26 Brothers Lance E Methods and compositions for sealing an expandable tubular in a wellbore
US6668928B2 (en) 2001-12-04 2003-12-30 Halliburton Energy Services, Inc. Resilient cement
US7040404B2 (en) 2001-12-04 2006-05-09 Halliburton Energy Services, Inc. Methods and compositions for sealing an expandable tubular in a wellbore
US20050009710A1 (en) * 2002-01-31 2005-01-13 Halliburton Energy Services Reactive sealing compositions for sealing hydrocarbon containing subterranean formations and methods
US6762156B2 (en) 2002-01-31 2004-07-13 Halliburton Energy Services, Inc. Reactive cement compositions for sealing hydrocarbon containing subterranean zones and methods
EP1369401A3 (en) * 2002-06-04 2010-07-07 Halliburton Energy Services, Inc. Sealing composition
US20030224946A1 (en) * 2002-06-04 2003-12-04 Halliburton Energy Services, Inc. Sealing composition
US6875729B2 (en) * 2002-06-04 2005-04-05 Halliburton Energy Services, Inc. Sealing composition
US6722433B2 (en) 2002-06-21 2004-04-20 Halliburton Energy Services, Inc. Methods of sealing expandable pipe in well bores and sealing compositions
US20040167248A1 (en) * 2002-06-21 2004-08-26 Brothers Lance E. Methods of sealing expandable pipe in well bores and sealing compositions
US7213647B2 (en) 2002-06-21 2007-05-08 Halliburton Energy Services, Inc. Methods of sealing expandable pipe in well bores and sealing compositions
WO2004001183A1 (en) * 2002-06-21 2003-12-31 Halliburton Energy Services, Inc. Methods of sealing expandable pipe in well bores and sealing compositions
US6641660B1 (en) 2002-07-23 2003-11-04 Halliburton Energy Services, Inc. Stable well cementing methods and compositions
US6516884B1 (en) 2002-07-23 2003-02-11 Halliburton Energy Services, Inc. Stable well cementing methods and compositions
US6832651B2 (en) 2002-08-29 2004-12-21 Halliburton Energy Services, Inc. Cement composition exhibiting improved resilience/toughness and method for using same
US20040198872A1 (en) * 2002-09-19 2004-10-07 Reddy B. Raghava Elastomeric admixtures for improving cement elasticity
US20040055748A1 (en) * 2002-09-19 2004-03-25 Reddy B. Raghava Elastomeric admixtures for improving cement elasticity
US7138446B2 (en) 2002-09-19 2006-11-21 Halliburton Energy Services, Inc. Elastomeric admixtures for improving cement elasticity
US7007755B2 (en) 2002-09-19 2006-03-07 Halliburton Energy Services, Inc. Elastomeric admixtures for improving cement elasticity
US7040405B2 (en) 2002-12-17 2006-05-09 Halliburton Energy Services, Inc. Permeable cement composition and method for preparing the same
US7052543B2 (en) 2002-12-17 2006-05-30 Halliburton Energy Services, Inc. Permeable cement composition and method for preparing the same
US6938692B2 (en) 2002-12-17 2005-09-06 Halliburton Energy Services, Inc. Permeable cement composition and method for preparing the same
US20050145141A1 (en) * 2002-12-17 2005-07-07 Halliburton Energy Services, Inc. Permeable cement composition and method for preparing the same
US20050145386A1 (en) * 2002-12-17 2005-07-07 Halliburton Energy Services, Inc. Permeable cement compostion and method for preparing the same
US20040112598A1 (en) * 2002-12-17 2004-06-17 Nguyen Philip D. Permeable cement composition and method for preparing the same
FR2850647A1 (en) 2003-01-30 2004-08-06 Rhodia Chimie Sa COMPOSITION COMPRISING A HYDRAULIC BINDER AND A LATEX HAVING A SULFONATE, SULFONIC OR SULFOBETAN FUNCTIONAL GROUP
US6962201B2 (en) 2003-02-25 2005-11-08 Halliburton Energy Services, Inc. Cement compositions with improved mechanical properties and methods of cementing in subterranean formations
US7351279B2 (en) 2003-02-25 2008-04-01 Halliburton Energy Services, Inc. Cement compositions with improved mechanical properties and methods of cementing in subterranean formations
US20040163812A1 (en) * 2003-02-25 2004-08-26 Brothers Lance E. Cement compositions with improved mechanical properties and methods of cementing in subterranean formations
US20050120920A1 (en) * 2003-02-25 2005-06-09 Halliburton Energy Services, Inc. Cement compositions with improved mechanical properties and methods of cementing in subterranean formations
US7662755B2 (en) 2003-05-13 2010-02-16 Halliburton Energy Services, Inc. Sealant compositions and methods of using the same to isolate a subterranean zone from a disposal well
US20050124501A1 (en) * 2003-05-13 2005-06-09 Reddy B. R. Sealant compositions and methods of using the same to isolate a subterranean zone from a disposal well
US7378377B2 (en) 2003-07-31 2008-05-27 Halliburton Energy Services, Inc. Compositions for preventing coagulation of water-in-oil emulsion polymers in aqueous saline well treating fluids
US7032669B2 (en) 2003-07-31 2006-04-25 Halliburton Energy Services, Inc. Compositions and methods for preventing coagulation of water-in-oil emulsion polymers in aqueous saline well treating fluids
US20060032407A1 (en) * 2003-07-31 2006-02-16 Halliburton Energy Services, Inc. Compositions for preventing coagulation of water-in-oil emulsion polymers in aqueous saline well treating fluids
US20050092211A1 (en) * 2003-10-31 2005-05-05 Lewis Samuel J. Dispersant compositions for cement compositions and related methods
US7240732B2 (en) * 2003-10-31 2007-07-10 Halliburton Energy Services, Inc. Dispersant compositions for cement compositions and related methods
US7294194B2 (en) 2004-01-29 2007-11-13 Halliburton Energy Services, Inc. Emulsion admixtures for improving cement elasticity
US20050167106A1 (en) * 2004-01-29 2005-08-04 Reddy B. R. Emulsion admixtures for improving cement elasticity
US7143828B2 (en) 2004-01-29 2006-12-05 Halliburton Energy Services, Inc. Emulsion admixtures for improving cement elasticity
US20060272552A1 (en) * 2004-01-29 2006-12-07 Reddy B R Emulsion admixtures for improving cement elasticity
US7156172B2 (en) 2004-03-02 2007-01-02 Halliburton Energy Services, Inc. Method for accelerating oil well construction and production processes and heating device therefor
US7172022B2 (en) 2004-03-17 2007-02-06 Halliburton Energy Services, Inc. Cement compositions containing degradable materials and methods of cementing in subterranean formations
US20070287639A1 (en) * 2004-04-19 2007-12-13 Halliburton Energy Services, Inc. Sealant compositions comprising colloidally stabilized latex and methods of using the same
US7607483B2 (en) 2004-04-19 2009-10-27 Halliburton Energy Services, Inc. Sealant compositions comprising colloidally stabilized latex and methods of using the same
US20050230112A1 (en) * 2004-04-19 2005-10-20 Reddy B R Sealant compositions comprising colloidally stabilized latex and methods of using the same
US8062999B2 (en) 2004-04-19 2011-11-22 Halliburton Energy Services Inc. Sealant compositions comprising colloidally stabilized latex and methods of using the same
US20100035772A1 (en) * 2004-12-08 2010-02-11 Halliburton Energy Services, Inc. Sealant compositions comprising solid latex
US20060122071A1 (en) * 2004-12-08 2006-06-08 Hallbiurton Energy Services, Inc. Oilwell sealant compositions comprising alkali swellable latex
US7488705B2 (en) 2004-12-08 2009-02-10 Halliburton Energy Services, Inc. Oilwell sealant compositions comprising alkali swellable latex
US20090137431A1 (en) * 2004-12-08 2009-05-28 Halliburton Energy Services, Inc. Oilwell sealant compositions comprising alkali swellable latex
US8100180B2 (en) 2004-12-08 2012-01-24 Halliburton Energy Services Inc. Method of servicing a wellbore with a sealant composition comprising solid latex
US8383558B2 (en) 2004-12-08 2013-02-26 Halliburton Energy Services, Inc. Oilwell sealant compositions comprising alkali swellable latex
US20100116497A1 (en) * 2004-12-08 2010-05-13 Halliburton Energy Services, Inc. Method of servicing a wellbore with a sealant composition comprising solid latex
US20060166837A1 (en) * 2005-01-24 2006-07-27 Lijun Lin Methods of treating subterranean formations with heteropolysaccharides based fluids
US20060166836A1 (en) * 2005-01-24 2006-07-27 Alejandro Pena Energized fluids and methods of use thereof
US20060162930A1 (en) * 2005-01-24 2006-07-27 Jan Gronsveld Methods of plugging a permeable zone downhole using a sealant composition comprising a crosslinkable material and a reduced amount of cement
US20060167133A1 (en) * 2005-01-24 2006-07-27 Jan Gromsveld Sealant composition comprising a crosslinkable material and a reduced amount of cement for a permeable zone downhole
US20080004187A1 (en) * 2005-01-24 2008-01-03 Alejandro Pena Energized Fluids and Methods of Use Thereof
US20080026957A1 (en) * 2005-01-24 2008-01-31 Gurmen M N Treatment and Production of Subterranean Formations with Heteropolysaccharides
US20100036017A1 (en) * 2005-01-24 2010-02-11 Eoff Larry S Sealant Compositions Comprising Diutan and Associated Methods
US8703659B2 (en) 2005-01-24 2014-04-22 Halliburton Energy Services, Inc. Sealant composition comprising a gel system and a reduced amount of cement for a permeable zone downhole
US20060178276A1 (en) * 2005-01-24 2006-08-10 Alejandro Pena Energized fluids and methods of use thereof
US7267174B2 (en) 2005-01-24 2007-09-11 Halliburton Energy Services, Inc. Methods of plugging a permeable zone downhole using a sealant composition comprising a crosslinkable material and a reduced amount of cement
US8343896B2 (en) * 2005-01-24 2013-01-01 Halliburton Energy Services, Inc. Sealant compositions comprising diutan and associated methods
US7569522B2 (en) * 2005-01-24 2009-08-04 Schlumberger Technology Corporation Energized fluids and methods of use thereof
US7781380B2 (en) * 2005-01-24 2010-08-24 Schlumberger Technology Corporation Methods of treating subterranean formations with heteropolysaccharides based fluids
US7531483B2 (en) * 2005-01-24 2009-05-12 Schlumberger Technology Corporation Energized fluids and methods of use thereof
US8367589B2 (en) 2005-01-24 2013-02-05 Schlumberger Technology Corporation Polysaccharide treatment fluid and method of treating a subterranean formation
US7833949B2 (en) 2005-01-24 2010-11-16 Schlumberger Technology Corporation Polysaccharide treatment fluid and method of treating a subterranean formation
US7494957B2 (en) * 2005-01-24 2009-02-24 Schlumberger Technology Corporation Energized fluids and methods of use thereof
US20080305971A1 (en) * 2005-01-24 2008-12-11 Leiming Li Polysaccharide Treatment Fluid and Method of Treating A Subterranean Formation
US20090023613A1 (en) * 2005-01-24 2009-01-22 Leiming Li Polysaccharide Treatment Fluid and Method of Treating a Subterranean Formation
US7404855B2 (en) 2005-02-04 2008-07-29 Halliburton Energy Services, Inc. Resilient cement compositions and methods of cementing
US7022755B1 (en) 2005-02-04 2006-04-04 Halliburton Energy Services, Inc. Resilient cement compositions and methods of cementing
US20060174805A1 (en) * 2005-02-04 2006-08-10 Halliburton Energy Services, Inc. Resilient cement compositions and methods of cementing
US7350573B2 (en) 2005-02-09 2008-04-01 Halliburton Energy Services, Inc. Servicing a wellbore with wellbore fluids comprising perlite
US20060175060A1 (en) * 2005-02-09 2006-08-10 Halliburton Energy Services, Inc. Servicing a wellbore with wellbore fluids comprising perlite
US20080115937A1 (en) * 2005-02-09 2008-05-22 Reddy B R Servicing a Wellbore with Wellbore Fluids Comprising Perlite
US7748453B2 (en) 2005-02-09 2010-07-06 Halliburton Energy Services, Inc. Servicing a wellbore with wellbore fluids comprising perlite
US8122959B2 (en) 2005-06-30 2012-02-28 Schlumberger Technology Corporation Methods and materials for zonal isolation
US20070017676A1 (en) * 2005-07-21 2007-01-25 Halliburton Energy Services, Inc. Methods for wellbore strengthening and controlling fluid circulation loss
US7341106B2 (en) 2005-07-21 2008-03-11 Halliburton Energy Services, Inc. Methods for wellbore strengthening and controlling fluid circulation loss
US20070042913A1 (en) * 2005-08-17 2007-02-22 Hutchins Richard D Wellbore treatment compositions containing foam extenders and methods of use thereof
US8333240B2 (en) 2005-09-09 2012-12-18 Halliburton Energy Services, Inc. Reduced carbon footprint settable compositions for use in subterranean formations
US8555967B2 (en) 2005-09-09 2013-10-15 Halliburton Energy Services, Inc. Methods and systems for evaluating a boundary between a consolidating spacer fluid and a cement composition
US8403045B2 (en) 2005-09-09 2013-03-26 Halliburton Energy Services, Inc. Settable compositions comprising unexpanded perlite and methods of cementing in subterranean formations
US9903184B2 (en) 2005-09-09 2018-02-27 Halliburton Energy Services, Inc. Consolidating spacer fluids and methods of use
US9809737B2 (en) 2005-09-09 2017-11-07 Halliburton Energy Services, Inc. Compositions containing kiln dust and/or biowaste ash and methods of use
US9676989B2 (en) 2005-09-09 2017-06-13 Halliburton Energy Services, Inc. Sealant compositions comprising cement kiln dust and tire-rubber particles and method of use
US9644132B2 (en) 2005-09-09 2017-05-09 Halliburton Energy Services, Inc. Methods for determining reactive index for cement kiln dust, associated compositions and methods of use
US9157020B2 (en) 2005-09-09 2015-10-13 Halliburton Energy Services, Inc. Compositions comprising kiln dust and wollastonite and methods of use in subterranean formations
US7607484B2 (en) 2005-09-09 2009-10-27 Halliburton Energy Services, Inc. Foamed cement compositions comprising oil-swellable particles and methods of use
US9150773B2 (en) 2005-09-09 2015-10-06 Halliburton Energy Services, Inc. Compositions comprising kiln dust and wollastonite and methods of use in subterranean formations
US9051505B2 (en) 2005-09-09 2015-06-09 Halliburton Energy Services, Inc. Placing a fluid comprising kiln dust in a wellbore through a bottom hole assembly
US9023150B2 (en) 2005-09-09 2015-05-05 Halliburton Energy Services, Inc. Acid-soluble cement compositions comprising cement kiln dust and/or a natural pozzolan and methods of use
US9006154B2 (en) 2005-09-09 2015-04-14 Halliburton Energy Services, Inc. Methods for determining reactive index for cement kiln dust, associated compositions and methods of use
US9006155B2 (en) 2005-09-09 2015-04-14 Halliburton Energy Services, Inc. Placing a fluid comprising kiln dust in a wellbore through a bottom hole assembly
US8950486B2 (en) 2005-09-09 2015-02-10 Halliburton Energy Services, Inc. Acid-soluble cement compositions comprising cement kiln dust and methods of use
US8921284B2 (en) 2005-09-09 2014-12-30 Halliburton Energy Services, Inc. Spacer fluids containing cement kiln dust and methods of use
US8895485B2 (en) 2005-09-09 2014-11-25 Halliburton Energy Services, Inc. Methods and compositions comprising cement kiln dust having an altered particle size
US8895486B2 (en) 2005-09-09 2014-11-25 Halliburton Energy Services, Inc. Methods and compositions comprising cement kiln dust having an altered particle size
US7743828B2 (en) 2005-09-09 2010-06-29 Halliburton Energy Services, Inc. Methods of cementing in subterranean formations using cement kiln cement kiln dust in compositions having reduced Portland cement content
US8691737B2 (en) 2005-09-09 2014-04-08 Halliburton Energy Services, Inc. Consolidating spacer fluids and methods of use
US8609595B2 (en) 2005-09-09 2013-12-17 Halliburton Energy Services, Inc. Methods for determining reactive index for cement kiln dust, associated compositions, and methods of use
US8307899B2 (en) 2005-09-09 2012-11-13 Halliburton Energy Services, Inc. Methods of plugging and abandoning a well using compositions comprising cement kiln dust and pumicite
US8551923B1 (en) 2005-09-09 2013-10-08 Halliburton Energy Services, Inc. Foamed spacer fluids containing cement kiln dust and methods of use
US8544543B2 (en) 2005-09-09 2013-10-01 Halliburton Energy Services, Inc. Consolidating spacer fluids and methods of use
US8522873B2 (en) 2005-09-09 2013-09-03 Halliburton Energy Services, Inc. Spacer fluids containing cement kiln dust and methods of use
US8505630B2 (en) 2005-09-09 2013-08-13 Halliburton Energy Services, Inc. Consolidating spacer fluids and methods of use
US7789150B2 (en) 2005-09-09 2010-09-07 Halliburton Energy Services Inc. Latex compositions comprising pozzolan and/or cement kiln dust and methods of use
US8505629B2 (en) 2005-09-09 2013-08-13 Halliburton Energy Services, Inc. Foamed spacer fluids containing cement kiln dust and methods of use
US7607482B2 (en) 2005-09-09 2009-10-27 Halliburton Energy Services, Inc. Settable compositions comprising cement kiln dust and swellable particles
US8297357B2 (en) 2005-09-09 2012-10-30 Halliburton Energy Services Inc. Acid-soluble cement compositions comprising cement kiln dust and/or a natural pozzolan and methods of use
US8399387B2 (en) 2005-09-09 2013-03-19 Halliburton Energy Services, Inc. Settable compositions comprising cement kiln dust and rice husk ash and methods of use
US8486869B2 (en) 2005-09-09 2013-07-16 Halliburton Energy Services, Inc. Methods of plugging and abandoning a well using compositions comprising cement kiln dust and pumicite
US7927419B2 (en) 2005-09-09 2011-04-19 Halliburton Energy Services Inc. Settable compositions comprising cement kiln dust and swellable particles
US8486868B2 (en) 2005-09-09 2013-07-16 Halliburton Energy Services, Inc. Settable compositions comprising unexpanded perlite and methods of cementing in subterranean formations
US8440596B2 (en) 2005-09-09 2013-05-14 Halliburton, Energy Services, Inc. Settable compositions comprising unexpanded perlite and methods of cementing in subterranean formations
US8030253B2 (en) 2005-09-09 2011-10-04 Halliburton Energy Services, Inc. Foamed cement compositions comprising oil-swellable particles
US8318642B2 (en) 2005-09-09 2012-11-27 Halliburton Energy Services, Inc. Methods and compositions comprising kiln dust and metakaolin
US8434553B2 (en) 2005-09-09 2013-05-07 Halliburton Energy Services, Inc. Settable compositions comprising unexpanded perlite and methods of cementing in subterranean formations
US8281859B2 (en) 2005-09-09 2012-10-09 Halliburton Energy Services Inc. Methods and compositions comprising cement kiln dust having an altered particle size
US8327939B2 (en) 2005-09-09 2012-12-11 Halliburton Energy Services, Inc. Settable compositions comprising cement kiln dust and rice husk ash and methods of use
US8261827B2 (en) 2005-09-09 2012-09-11 Halliburton Energy Services Inc. Methods and compositions comprising kiln dust and metakaolin
US8324137B2 (en) 2005-09-09 2012-12-04 Roddy Craig W Latex compositions comprising pozzolan and/or cement kiln dust and methods of use
US20070062691A1 (en) * 2005-09-16 2007-03-22 Reddy B R Methods of formulating a cement composition
US7913757B2 (en) 2005-09-16 2011-03-29 Halliburton Energy Services. Inc. Methods of formulating a cement composition
US20070125276A1 (en) * 2005-12-01 2007-06-07 Halliburton Energy Services, Inc. Wellbore sealant compositions containing cationic latexes
US7694738B2 (en) 2005-12-01 2010-04-13 Halliburton Energy Services, Inc. Methods of using wellbore sealant compositions containing cationic latexes
US7687440B2 (en) 2005-12-01 2010-03-30 Halliburton Energy Services, Inc. Wellbore sealant compositions containing cationic latexes
US20070125534A1 (en) * 2005-12-01 2007-06-07 Halliburton Energy Services, Inc. Methods of using wellbore sealant compositions containing cationic latexes
US7650940B2 (en) 2005-12-29 2010-01-26 Halliburton Energy Services Inc. Cement compositions comprising particulate carboxylated elastomers and associated methods
US20070151730A1 (en) * 2005-12-29 2007-07-05 Reddy B R Cement compositions comprising particulate carboxylated elastomers and associated methods
US7645817B2 (en) 2005-12-29 2010-01-12 Halliburton Energy Services, Inc. Cement compositions comprising particulate carboxylated elastomers and associated methods
US20070151484A1 (en) * 2005-12-29 2007-07-05 Reddy B R Cement compositions comprising particulate carboxylated elastomers and associated methods
US7741247B2 (en) * 2006-02-10 2010-06-22 Ling Wang Methods and compositions for sealing fractures, voids, and pores of subterranean rock formations
US20070187099A1 (en) * 2006-02-10 2007-08-16 Ling Wang Methods and Compositions for Sealing Fractures, Voids, and Pores of Subterranean Rock Formations
US20070203028A1 (en) * 2006-02-28 2007-08-30 Halliburton Energy Services, Inc. Salt water stable latex cement slurries
US7576042B2 (en) 2006-02-28 2009-08-18 Halliburton Energy Services, Inc. Salt water stable latex cement slurries
US7776796B2 (en) 2006-03-20 2010-08-17 Schlumberger Technology Corporation Methods of treating wellbores with recyclable fluids
US7363977B2 (en) * 2006-09-28 2008-04-29 Halliburton Energy Services, Inc. Prevention of latex inversion in saltwater cement compositions for use in subterranean formations and associated methods
US20080078550A1 (en) * 2006-09-28 2008-04-03 Halliburton Energy Services, Inc. Prevention of latex inversion in saltwater cement compositions for use in subterranean formations and associated methods
US20080078307A1 (en) * 2006-09-28 2008-04-03 Halliburton Energy Services, Inc. Prevention of latex inversion in saltwater cement compositions for use in subterranean formations and associated compositions
WO2008037976A1 (en) * 2006-09-28 2008-04-03 Halliburton Energy Services, Inc. Prevention of latex inversion in saltwater cement compositions for use in subterranean formations and associated compositions
US7569108B2 (en) 2006-09-28 2009-08-04 Halliburton Energy Services, Inc. Prevention of latex inversion in saltwater cement compositions for use in subterranean formations and associated compositions
US20080280786A1 (en) * 2007-05-07 2008-11-13 Halliburton Energy Services, Inc. Defoamer/antifoamer compositions and methods of using same
US8586512B2 (en) 2007-05-10 2013-11-19 Halliburton Energy Services, Inc. Cement compositions and methods utilizing nano-clay
US9512352B2 (en) 2007-05-10 2016-12-06 Halliburton Energy Services, Inc. Well treatment fluids and methods utilizing nano-particles
US8940670B2 (en) 2007-05-10 2015-01-27 Halliburton Energy Services, Inc. Cement compositions comprising sub-micron alumina and associated methods
US8476203B2 (en) 2007-05-10 2013-07-02 Halliburton Energy Services, Inc. Cement compositions comprising sub-micron alumina and associated methods
US9512351B2 (en) 2007-05-10 2016-12-06 Halliburton Energy Services, Inc. Well treatment fluids and methods utilizing nano-particles
US8603952B2 (en) 2007-05-10 2013-12-10 Halliburton Energy Services, Inc. Cement compositions and methods utilizing nano-clay
US9206344B2 (en) 2007-05-10 2015-12-08 Halliburton Energy Services, Inc. Sealant compositions and methods utilizing nano-particles
US9765252B2 (en) 2007-05-10 2017-09-19 Halliburton Energy Services, Inc. Sealant compositions and methods utilizing nano-particles
US8741818B2 (en) 2007-05-10 2014-06-03 Halliburton Energy Services, Inc. Lost circulation compositions and associated methods
US8685903B2 (en) 2007-05-10 2014-04-01 Halliburton Energy Services, Inc. Lost circulation compositions and associated methods
US9199879B2 (en) 2007-05-10 2015-12-01 Halliburton Energy Serives, Inc. Well treatment compositions and methods utilizing nano-particles
US20090038801A1 (en) * 2007-08-08 2009-02-12 Ravi Krishna M Sealant Compositions and Methods of Use
US20090038800A1 (en) * 2007-08-08 2009-02-12 Ravi Krishna M Sealant Compositions and Methods of Use
US8276666B2 (en) 2007-08-08 2012-10-02 Halliburton Energy Services Inc. Sealant compositions and methods of use
US7678745B2 (en) 2007-09-24 2010-03-16 Schlumberger Technology Corporation Viscosity reduction
US20090105097A1 (en) * 2007-10-22 2009-04-23 Carlos Abad Degradable Friction Reducer
US7530396B1 (en) 2008-01-24 2009-05-12 Halliburton Energy Services, Inc. Self repairing cement compositions and methods of using same
US7617870B1 (en) * 2008-05-14 2009-11-17 Halliburton Energy Services, Inc. Extended cement compositions comprising oil-swellable particles and associated methods
US20090283269A1 (en) * 2008-05-14 2009-11-19 Roddy Craig W Extended cement compositions comprising oil-swellable particles and associated methods
US20100075029A1 (en) * 2008-08-18 2010-03-25 Wilson Jr Jack H Pavement life extension product and method
WO2010061163A1 (en) * 2008-11-03 2010-06-03 Halliburton Energy Services, Inc. Foamed cement compositions comprising oil-swellable particles and methods of use
AU2009321422B2 (en) * 2008-11-03 2014-01-30 Halliburton Energy Services, Inc. Foamed cement compositions comprising oil-swellable particles and methods of use
US20100193191A1 (en) * 2009-02-03 2010-08-05 Roddy Craig W Methods and Compositions Comprising a Dual Oil/Water-Swellable Particle
US7934554B2 (en) 2009-02-03 2011-05-03 Halliburton Energy Services, Inc. Methods and compositions comprising a dual oil/water-swellable particle
US20100212892A1 (en) * 2009-02-26 2010-08-26 Halliburton Energy Services, Inc. Methods of formulating a cement composition
US7792250B1 (en) 2009-04-30 2010-09-07 Halliburton Energy Services Inc. Method of selecting a wellbore cement having desirable characteristics
WO2010125327A1 (en) 2009-04-30 2010-11-04 Halliburton Energy Services, Inc. Method of selecting a wellbore cement having desirable characteristics
US20110083503A1 (en) * 2009-10-09 2011-04-14 Halliburton Energy Services, Inc. Methods and Apparatus for Designing a Cement Composition
WO2011042705A1 (en) 2009-10-09 2011-04-14 Halliburton Energy Services Inc Methods and apparatus for designing a cement composition
US8322198B2 (en) 2009-10-09 2012-12-04 Halliburton Energy Services, Inc. Methods and apparatus for designing a cement composition
US9376609B2 (en) 2010-12-21 2016-06-28 Halliburton Energy Services, Inc. Settable compositions comprising interground perlite and hydraulic cement
US8672028B2 (en) 2010-12-21 2014-03-18 Halliburton Energy Services, Inc. Settable compositions comprising interground perlite and hydraulic cement
WO2012085508A1 (en) 2010-12-21 2012-06-28 Halliburton Energy Services Methods for cementing in a subterranean formation using a cement composition containing calcium silicate hydrate seeds
US8887806B2 (en) 2011-05-26 2014-11-18 Halliburton Energy Services, Inc. Method for quantifying cement blend components
US20130319673A1 (en) * 2012-05-31 2013-12-05 Halliburton Energy Services, Inc. Cement Compositions Comprising Saponins and Associated Methods
US9809736B2 (en) 2012-08-31 2017-11-07 Halliburton Energy Services, Inc. Wellbore servicing compositions and methods of making and using same
US9796902B2 (en) * 2013-10-30 2017-10-24 Halliburton Energy Services, Inc. Sealant compositions for use in subterranean formation operations
US20150114649A1 (en) * 2013-10-30 2015-04-30 Halliburton Energy Sevices, Inc. Sealant compositions for use in subterranean formation operations
WO2016039988A1 (en) * 2014-09-11 2016-03-17 Schlumberger Canada Limited Cement slurry compositions and methods
WO2017137354A1 (en) * 2016-02-08 2017-08-17 Shell Internationale Research Maatschappij B.V. Method for providing zonal isolation in an underground wellbore
CN113880502A (en) * 2020-07-01 2022-01-04 中国石油化工股份有限公司 Well wall repairing enhancer for deep well broken stratum and preparation method and application thereof
CN113046049A (en) * 2021-03-29 2021-06-29 西南石油大学 Multi-water-layer four-dispersion foam scrubbing agent for natural gas horizontal well
CN113046049B (en) * 2021-03-29 2022-05-06 西南石油大学 Multi-water-layer four-dispersion foam scrubbing agent for natural gas horizontal well

Also Published As

Publication number Publication date
EP0816302B1 (en) 2001-03-07
NO321191B1 (en) 2006-04-03
NO973048L (en) 1998-01-02
DE69704183T2 (en) 2002-03-28
NO973048D0 (en) 1997-06-30
CA2209232C (en) 2004-02-03
EP0816302A3 (en) 1998-01-21
CA2209232A1 (en) 1998-01-01
EP0816302A2 (en) 1998-01-07
DE69704183D1 (en) 2001-04-12

Similar Documents

Publication Publication Date Title
US5688844A (en) Resilient well cement compositions and methods
US5795924A (en) Resilient well cement compositions and methods
US5696059A (en) Methods of preventing well cement stress failure
US6593402B2 (en) Resilient well cement compositions and methods
US5588488A (en) Cementing multi-lateral wells
US5588489A (en) Lightweight well cement compositions and methods
US6814798B2 (en) Storable water-microsphere suspensions for use in well cements and methods
US6244344B1 (en) Methods and compositions for cementing pipe strings in well bores
US5897699A (en) Foamed well cement compositions, additives and methods
US5398759A (en) Set retarded ultra fine cement compositions and methods
US5135577A (en) Composition and method for inhibiting thermal thinning of cement
EP0816300B1 (en) Well cement compositions
GB2247234A (en) Fluid loss reduced cement compositions
CA2076332A1 (en) Method of reducing fluid loss in cement compositions

Legal Events

Date Code Title Description
AS Assignment

Owner name: HALLIBURTON COMPANY, OKLAHOMA

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNORS:CHATTERJI, JITEN;KING, BOBBY J.;TOTTEN, PATTY L.;AND OTHERS;REEL/FRAME:008107/0486;SIGNING DATES FROM 19960822 TO 19960823

FPAY Fee payment

Year of fee payment: 4

FPAY Fee payment

Year of fee payment: 8

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20091118

OSZAR »