Resilient well cement compositions and methods

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, and effective amounts 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, fumed silica present in an amount in the range of from about 5% to about 30% by weight of hydraulic cement in the composition, water present in an amount in the range of from about 22% to about 95% by weight of hydraulic cement in the composition, and effective amounts of a gas, a foaming agent and a foam stabilizer.
Yet 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, and effective amounts 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 THE 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 and the like 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, Oklahoma under the trade designation "LATEX 2000.TM.." 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(O CH.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 R.sub.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.sub.1 -C.sub.4 alkyl substituted cycloalkyl groups, phenyl, alkyl substituted phenyl of the general formula (R.sub.3).sub.a Ph- wherein Ph is phenyl, R.sub.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.sub.2 is a substituted ethylene group of the formula --CH.sub.2 CH.sub.2 R.sub.4 wherein R.sub.4 is selected from hydrogen, methyl, ethyl or mixtures thereof, and n is a number from 0 to about 40 provided that when R.sub.1 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 R.sub.5 is an alkyl group having in the range of from 1 to about 9 carbon atoms, R.sub.6 is the group --CH.sub.2 CH.sub.2 --, 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 R.sub.7 is an alkyl group having in the range of from about 5 to about 20 carbon atoms, R.sub.8 is the group --CH.sub.2 CH.sub.2 --, 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 C.sub.12 to C.sub.15 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.TM." 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 the "AVANEL.TM." series of surfactants, i.e., the 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.15-40 SO.sub.3 Na are preferred, with H(CH.sub.2).sub.12-15 (CH.sub.2 CH.sub.2 O).sub.15 SO.sub.3 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 which contain an aqueous rubber latex can be adequate for producing a pumpable slurry and hydrating the cementitious materials therein, additional water can be added to the compositions as required for pumpability. Also, water must be added to the compositions that do not include an aqueous rubber latex in an amount at least sufficient to form a pumpable slurry.
The water can be from any source provided it does not contain in excess of compounds that adversely affect other components in the cement compositions. 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.TM.." 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.TM.."
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.TM.."
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.TM.."
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.TM.."
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.TM.."
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 C.sub.10 to C.sub.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--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.TM.."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 lightweight, 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), water present in an amount in the range of from about 22% to about 95% by weight of hydraulic cement in the composition (from about 2.5 gal/sack to about 10.7 gal/sack), 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.
This foamed cement composition does not include an aqueous rubber latex, but it has unexpected and surprisingly improved physical and mechanical properties including high degrees of elasticity and ductility and a high resistance to pressurized formation fluid migration.
Yet 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 useful 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, polyethyleneimine 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.degree. 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.degree. 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 ResultsCement 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 % by gal per gal per % by gal per % by % by Bond BondSample 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 lblgal psi psi__________________________________________________________________________1 Portland Class H 10 0.5 0.05 -- 0.02 52.83 0.5 15 86 10742 Portland Class H 10 0.5 0.05 5 0.02 55.97 0.5 15 355 9983 Portland Class H 10 1.0 0.1 -- 0.02 47.98 0.5 15 200 2854 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 .TM." from PPG Mazer). .sup.3 Cement expansive additive ("MICROBOND M .TM." from Halliburton Energy Services, Duncan, Oklahoma). .sup.4 Polydimethylsiloxane. .sup.5 Condensation polymer product of ketone, aldehyde and sodium sulfit ("CFR3 .TM." 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.degree. F. and atmospheric pressure after which portions of the test samples were subjected to various tests to determine their properties. More specifically, shear and hydraulic bond strength tests were conducted in accordance with the procedures of Example 1, and unconfined uniaxial and confined triaxial strength tests were conducted and Young's Moduli (also known as moduli of elasticity) and Poisson's as 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 Compositions__________________________________________________________________________ Cement Composition Components Fumed Silica, % by Fluid Weight Aqueous Loss Sand of Rubber Latex Control (100 Cement, Latex.sup.1, Stabilizer.sup.2, Hemitite, Agent.sup.3, Mesh), or gal gal per gal per % by % by % bySample per 94 lb 94 lb 94 Lb Weight Weight WeightDensity, Hydraulic Sack of Sack of Sack of of of ofNo. Cement Cement Cement Cement Cement Cement Cement__________________________________________________________________________1 Portland Class H 10% 1 0.2 -- -- --2 Portland Class H 10% 2 0.2 -- -- --3 Portland Class H 1.63 1 03.sup.10 200 0.5 40 gal/sk.sup.9__________________________________________________________________________Cement Composition Components Set Set Retarder Defoaming Foaming Foam Retarder.sup.4, Intensifier.sup.5, Agent.sup.6, Agent.sup.7, Stabilizer.sup.8, Water, % by % by gal per % by % by gal per DensitySample Weight Weight 94 lb Weight Weight 94 lb of BaseDensity, of of Sack of of of Sack of Slurry, FoamedNo. Cement Cement Cement Water Water Cement lb/gal lb/gal__________________________________________________________________________1 -- -- 0.02 7.5 3.75 5.41 15 13.62 -- -- 0.02 9.4 4.7 4.32 15 13.63 3.3 2.4 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 .TM." from Unical Corp.). .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 .TM." from PPG Mazer). .sup.3 Copolymer of "AMPS.RTM." and N,Ndimethytacrylamide (U.S. Pat. No. 4,555,269). .sup.4 Copolymer of "AMPS.RTM." 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 Nonylphenol ethoxylated 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'Envelope Shear Hydraulic Unconfined Uniaxial ModulusFriction Bond Bond Young's Compressive (EX 10.sup.6)Sample Strength, Strength, Modulus Poissons Strength, Confining Pressure, psiNo. psi psi (EX 10.sup.6) Ratio psi 500 1000 2000__________________________________________________________________________1 163 (13.8).sup.1 630 -- -- 1388.sup.2 0.048 0.312 0.0912 154 (13.85).sup.1 720 -- -- 1460.sup.2 0.076 0.304 0.0263 -- -- 0.35 0.107 2700.sup.2 0.26 0.3 0.282__________________________________________________________________________Confined Triaxial Plastic Bulk ShearEnvelope Poisson's Failure, Compressibility Modulus TensileFriction Ratio psi at 1000 at 1000 Strength FailureSample Confining Pressure, psi Confining Pressure, psi psi, 10.sup.5 psi, 10.sup.4 (Briquet), AngleNo. 500 1000 2000 500 1000 2000 psi psi psi Degrees__________________________________________________________________________1 0.158 0.1494 0.079 2900 4200 4000 0.94 13.57 194.sup.3 31.52 0.090 0.2883 0.065 2255 3200 3100 0.418 11.8 250.sup.3 19.53 0.086 0.144 0.109 3850 4925 6950 6.2 -- -- 22__________________________________________________________________________ .sup.1 The number in parentheses is the test sampte 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 tested have excellent bond strengths and resiliencies.
Example 3
Test samples of additional foamed cement compositions of this invention comprised of hydraulic cement, fumed silica, water, air, a foaming agent and a foam stabilizer were prepared. For each test sample, an unfoamed cement slurry 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 IIIA below.
The foamed test samples were allowed to set for 6 days at 140.degree. F. in atmospheric pressure after which portions of the test samples were subjected to the various tests and determinations described in Example 2 above to determine their properties. The results of these tests and determinations are set forth in Table IIIB below.
TABLE IIIA__________________________________________________________________________Non-Foamed and Foamed CompositionsComponents Cement Composition Foaming Foam Water, Density Density Fumed Silica, Dispersant.sup.1, Agent.sup.2, Stabilizer.sup.3, gal. per of Base Of FoamedSample Hydraulic % By Weight % By Weight % By Weight % By Weight 94 lb. Sack Slurry, Slurry,No. Cement Of Cement of Cement Of Water of Water of Cement lb/gal lb/gal.__________________________________________________________________________1 Portland Class G 10 0.25 -- -- 6.55 15 --2 Portland Class G 10 0.25 1.5 0.8 6.55 15 133 Portland Class G 20 0.75 -- -- 7.08 15 --4 Portland Class G 20 0.75 1.5 0.8 7.08 15 13__________________________________________________________________________ .sup.1 Condensation polymer product of ketone, aldehyde and sodium sulfit ("CFR3 .TM. from Halliburton Energy Services of Duncan, Oklahoma). .sup.2 Sodium salt of alphaolefinic sulfonic acid. .sup.3 Cocoylamidopropylbetaine.
TABLE IIIB__________________________________________________________________________Bond Strength And Resiliency Test Results__________________________________________________________________________ Confined Triaxial Young'sShear Hydraulic Unconfined Uniaxial Modulus, Bond Bond Young's Compressive Ex 10.sup.6Sample Strength, Strength, Modulus, Poissons Strength, Confining PressureNo. psi psi Ex 10.sup.6 Ratio psi 500 1000 2000__________________________________________________________________________1 68.8 264 1.37 0.1038 4433 0.6 0.656 0.3092 1050 470 1.189 0.0915 2770 0.592 0.616 0.1983 226 545 1.282 0.1431 3506 -- 0.837 0.7964 1400 315 0.76 0.1372 3949 0.497 0.44 0.532__________________________________________________________________________Confined Triaxial Plastic Failure Poissons Failure, Bulk Shear Tensile Envelope Ratio psi Compressibility Modulus Strength FrictionSample Confining Pressure Confining Pressure @ 1000 psi, @ 1000 psi (Briquet), Angle,No. 500 1000 2000 500 1000 2000 10.sup.5 psi 10 psi psi Degrees__________________________________________________________________________1 0.0948 0.1119 0.1291 5984 7008 8856 2.817 2.95 305 262 0.1669 0.1426 0.1347 4979 5765 8035 2.8721 2.6956 190 223 -- 0.2915 0.1568 -- 9394 12465 6.6906 3.2404 490 404 0.165 0.1294 0.189 6569 6881 9932 1.9787 1.9479 207 31__________________________________________________________________________
From the results set forth in Table IIIB, it can be seen that the foamed cement compositions comprised of hydraulic cement, fumed silica, water, air, foaming agent and foam stabilizer have unexpected and surprisingly improved ductility and resiliency properties as primarily shown by the Young's modulus test data.
EXAMPLE 4
Comparative tests were conducted between foamed cement compositions of this invention comprised of hydraulic cement, fumed silica, water, air, a foaming agent and a foam stabilizer and various lightweight unfoamed and foamed compositions of the prior art containing hydraulic cement, fumed silica and other components. The foamed compositions of this invention were prepared in the manner described in Example 3 above and are identified in Table IVA below as samples 1, 2, 3 and 4.
The prior art compositions tested are as follows:
A. The two 9.0 pound per gallon unfoamed cement compositions described in Examples I and II of U.S. Pat. No. 5,188,176 issued to Carpenter on Feb. 23, 1993 comprised of water, hydraulic cement, fumed silica and fly ash microspheres. These compositions are described in Table IVA below and identified as samples 1a and 2a.
B. The 9.0 pound per gallon unfoamed cement composition described in Example II of U.S Pat. No. 5,188,176 issued to Carpenter on Feb. 23, 1993 comprised of water, hydraulic cement, fumed silica, dispersant, fly ash microspheres, styrene-butadiene latex, surfactant and defoamer. This composition is described in Table IVA below and identified as sample 3a.
C. The 9.0 pound per gallon foamed cement composition described in Example 2 of U.S. Pat. No. 4,927,462 issued to Sugama on May 22, 1990 comprised of water, hydraulic cement, fumed silica (substituted for silica flour--see col. 2, lines 43-55), treated chopped polypropylene fibers (substituted for carbon fibers--see col. 2, lines 63-66), air, a foaming agent and a foam stabilizer. This composition is described in Table IVA below and identified as sample 4a.
The unfoamed compositions were prepared using a conventional mixing device. The foamed composition was prepared in the manner described in Example 3 above.
The various test samples were allowed to set for 6 days at 140.degree. F. and atmospheric pressure after which portions of the test samples were subjected to a number of the tests and determinations described in Example 2 above to determine their properties, i.e., unconfined compressive strength tests, tensile strength tests and yield strength tests at 1,000 psi confining pressure were conducted and Young's Moduli and Poisson's ratios were determined. The results of the tests and determinations are set forth in Table IVB below.
TABLE IVA__________________________________________________________________________Foamed Inventive Cement Compositions And Prior Art Cement__________________________________________________________________________Compositions Foaming FoamDensity, Fumed Silica, Dispersant.sup.1, Agent.sup.2 Stabilizer.sup.3,Sample Hydraulic % By Weight % By Weight % By Weight % By WeightNo. Cement Of Cement Of Cement Of Water Of Water__________________________________________________________________________1 (Inventive) Portland Class C 10% -- 2.08 1.121a (Prior Art) Portland Class C 10% -- --2 (Inventive) Portland Class C 10% -- 2.08 1.122a (Prior Art) Portland Class C 10% -- -- --3 (Inventive) Portland Class G 10% -- 2.08 1.123a (Prior Art) Portland Class G 10% 1 -- --4 (Inventive) Portland Class H 10% -- 2.08 1.124a (Prior Art) Portland Class H 17% -- 2.08 1.12__________________________________________________________________________ Fly Ash Treated.sup.5Density, Water, Defoamer.sup.4, Microspheres, Fibers,Sample % By Weight gal per 94 lb % By Weight % By Weight lb perNo. of Cement Sack of Cement of Cement of Mix gal__________________________________________________________________________1 (Inventive) 55.8 -- -- -- 91a (Prior Art) 116.5 -- 100 -- 92 (Inventive) 55.8 -- -- -- 92a (Prior Art) 140.0 -- 100 -- 93 (Inventive) 44.3 0.05 -- -- 93a (Prior Art) 109.8 -- 100 -- 94 (Inventive) 38.1 -- -- -- 94a (Prior Art) 32.sup.6 -- -- 0.3 9__________________________________________________________________________ .sup.1 Condensation polymer product of ketone, aldehyde and sodium sulfit ("CFR3 .TM." from Halliburton Energy Services of Duncan, Oklahoma). .sup.2 Sodium salt of alphaolefinic sulfonic acid. .sup.3 Cocoylamidopropylbetaine .sup.4 Polydimethylsiloxane .sup.5 Chopped fibers were boiled with 10% NaOH at 80.degree. C. for 1 hour; then cooled and washed until free from NaOH. .sup.6 % by weight of composition
TABLE IVB__________________________________________________________________________Comparative Test Results Yield Strength Unconfined at 1000 psi Compressive Tensile Confining Young'sSample Strength, Strength, Pressure, Modulus, Poisson'sNo. psi psi psi psi .times. 10.sup.-6 Ratio__________________________________________________________________________1 (Inventive) 280 136 1325 0.013 .+-. 0.0035 0.102835 .+-. 0.0180111a (Prior Art) 1092 133 1800 0.139 .+-. 0.0029 0.019314 .+-. 0.0053592 (Inventive) 280 136 1325 0.013 .+-. 0.0029 0.019314 .+-. 0.0180112a (Prior Art) 1260 175 2300 0.130 .+-. 0.0026 0.081631 .+-. 0.0090283 (Inventive) 282 109 1300 0.019 .+-. 0.0032 0.225041 .+-. 0.0242083a (Prior Art) 347 140 1500 0.077 .+-. 0.00085 0.106248 .+-. 0.0256184 (Inventive) 219 97 1275 0.026 .+-. 0.0021 0.084400 .+-. 0.0062134a (Prior Art) 350 125 2400 0.028 .+-. 0.0001 0.141158 .+-. 0.000791__________________________________________________________________________
From the results set forth in Table IVB and particularly the Young's moduli, it can be seen that the foamed compositions of this invention comprised of hydraulic cement, fumed silica, water, air, a foaming agent and a foam stabilizer have unexpected and surprisingly improved ductility and resiliency properties as compared to the prior art compositions tested.
EXAMPLE 5
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 VA below and the results of the tests and determinations are set forth in Table VB below.
TABLE VA__________________________________________________________________________Foamed Cement Compositions__________________________________________________________________________Cement Composition Components Aqueous Fluid Rubber Latex Loss Sand Latex.sup.1 Stabilizer.sup.2, Control (100 mesh), gal per gal per Agent.sup.3, Biopolymer.sup.4, % by 94 lb 94 lb % by % bySample Hydraulic Weight of Sack of Sack of Weight of Weight ofNo. Cement Cement Cement Cement Cement Cement__________________________________________________________________________1 Portland Class G 100 1 0.3 0.2 0.142 Portland Class G 100 i 0.3 0.2 0.143 Portland Class G 100 2 0.3 0.2 0.224 Portland Class G 100 2 0.3 0.2 0.225 Portland Class G -- 5 0.3 0.5 --__________________________________________________________________________Cement Composition Components Defoaming Agent.sup.6, Foaming Foam Water, Accelerator.sup.5, gal per Agent.sup.7, Stabilizer.sup.8, gal per Density % by 94 lb % by % by 94 lb of Base FoamedSample Weight of Sack of Weight of Weight of Sack of Slurry, DensityNo. Cement Cement Water Water Cement lb/gal lb/gal__________________________________________________________________________1 4 0.02 4.3 2.2 6.28 16.3 142 4 0.02 4.3 2.2 6.28 16.3 123 4 0.02 5.1 2.6 5.28 16.3 144 4 0.02 5.1 2.6 5.28 16.3 125 2 0.02 5.2 2.6 3.33 17.5 15__________________________________________________________________________ .sup.1 Aqueous styrene/butadiene (25%:75% by wt.) latex containing 50% by weight Water ("LATEX 2000 .TM." 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 .TM." from PPG Mazer). .sup.3 Copolymer of "AMPS.RTM." 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 VB__________________________________________________________________________Bond Strength And Resiliency Test Results__________________________________________________________________________ Confined Triaxial Young's Shear Hydraulic Unconfined Uniaxial Modulus Bond Bond Young's Compressive (EX 10.sup.6)Sample Strength, Strength, Modulus Poissons Strength, Confining Pressure, psiNo. psi psi (EX 10.sup.6) Ratio psi 500 1000 2000__________________________________________________________________________1 303 780 -- -- -- -- 0.039 --2 244 (12.1).sup.1 660 -- -- -- -- 0.029 --3 322 (14.l).sup.1 775 -- -- -- -- 0.048 --4 287 (12.2).sup.1 660 -- -- -- -- 0.0353 --5 86 (15.4).sup.1 700 0.0025 0.102 392.sup.2 0.013 0.013 0.025__________________________________________________________________________Confined Triaxial Plastic Bulk Shear Failure Poisson's Failure, Compressibility Modulus Tensile Envelope Ratio psi at 1000 at 1000 Strength FrictionSample Confining Pressure, psi Confining Pressure, psi psi, 10.sup.5 psi, 10.sup.4 (Briquet), Angle,No. 500 1000 2000 500 1000 2000 psi psi psi Degrees__________________________________________________________________________1 -- 0.1187 -- -- 3220 -- 5.86 1.745 -- --2 -- 0.0436 -- -- 2000 -- 9.44 1.389 -- --3 -- 0.1478 -- -- 3700 -- 4.4 2.09 -- --4 -- 0.1808 -- -- 2200 -- 5.47 1.482 -- --5 0.078 0.128 0.171 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 VB, 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.

Number	Name	Date
RE28722	Sanders	Feb 1976
3354169	Shafer et al.	Nov 1967
4039345	Emig et al.	Aug 1977
4057528	Hunt	Nov 1977
4202809	Eash et al.	May 1980
4385935	Skjeldal	May 1983
4398957	Ceska et al.	Aug 1983
4510180	Cornely et al.	Apr 1985
4537918	Parcevaux et al.	Aug 1985
4721160	Parcevaux et al.	Jan 1988
4767460	Parcevaux et al.	Aug 1988
4927462	Sugama	May 1990
5004506	Allen et al.	Apr 1991
5133409	Bour et al.	Jul 1992
5159980	Onan et al.	Nov 1992
5185389	Victor	Feb 1993
5188176	Carpenter	Feb 1993
5207832	Baffreau et al.	May 1993
5258428	Gopalkrishnan	Nov 1993
5262452	Gopalkrishnan	Nov 1993
5293938	Onan et al.	Mar 1994
5300542	Gopalkrishnan	Apr 1994
5389706	Heathman et al.	Feb 1995
5401786	Gopalkrishnan	Mar 1995
5476343	Sumner	Dec 1995
5484019	Griffith	Jan 1996
5588488	Vijn et al.	Dec 1996

Number	Date	Country
0 314 242 A1	May 1989	EPX
0 431 600 A1	Jun 1991	EPX
0 449 360 A1	Oct 1991	EPX
0 572 857 A2	Dec 1993	EPX
0 592 217 A2	Apr 1994	EPX
904973	Sep 1962	GBX
WO 9223187	Dec 1992	WOX

Resilient well cement compositions and methods

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US Referenced Citations (27)

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Entry
Paper entitled "Light, strong foamed cement: A new well tool for problem wells" by Terry Smith; World Oil; May 1984.
Chemical Abstract entitled "Fire-resistant lightweight building maerials" by Kiichi Suzuki; May 1988.