Fluid Activated Disintegrating Metal System

Abstract

An engineered composite system designed to be passive or inert under one set of conditions, but becomes active when exposed to a second set of conditions. This system can include a dissolving or disintegrating core, and a surface coating that has higher strength or which only dissolves under certain temperature and pH conditions, or in selected fluids. These reactive materials are useful for oil and gas completions and well stimulation processes, enhanced oil and gas recovery operations, as well as in defensive and mining applications requiring high energy density and good mechanical properties, but which can be stored and used for long periods of time without degradation.

1 - 31 . (canceled) 
     
     
         32 . A method of dissolving, degrading, reacting or combinations thereof a core in the presence of a fluid environment comprising:
 a) providing a core having a surface layer about said core, said core dissolvable, degradable, reactive, or combinations thereof in the present of said fluid environment, said surface layer not or essentially not dissolvable, degradable, or combinations thereof in the presence of said fluid environment until exposed to an activation event;   b) exposing said surface layer to said activation event to cause said surface layer to dissolve, degrade, or combinations thereof to ultimately cause said core to be exposed to said fluid environment, said exposure of said core to said fluid environment causing said core to dissolve, degrade, react, or combinations thereof, said activation event includes one or more events selected from the group consisting of a temperature change of said fluid environment, a pH change of said fluid environment, exposure of said surface layer with an activation compound, a change in composition of fluid environment, exposure of said surface layer to an electrical charge, exposure to of said surface layer to certain electromagnetic waves, a change in salt content of said fluid environment, a change in electrolyte content of said fluid environment, exposure of said surface layer to certain sound waves, exposure of said surface layer to certain vibrations, exposure of said surface layer to certain magnetic waves, and exposure of said surface layer to a certain pressure.   
     
     
         33 . A method for controlling dissolving, degrading, reacting, fracturing or combinations thereof of a component for use in down-hole applications comprising:
 a. providing a down-hole component for use in down-hole applications, said down-hole component at least partially formed of a hierarchically-designed reactive component, said hierarchically-designed reactive component includes:
 i. a core, said core dissolvable, reactive, or combinations thereof in the presence of a fluid environment, at least 70 weight percent of said core includes a core material selected from the group consisting of metal, metal alloy, metal composite, and metal compound; and, 
 ii. a surface layer that partially or fully encapsulates said core, said surface layer having a different composition from said core, said surface layer includes one or more materials selected from the group consisting of zinc, zinc alloy, and polymer; said surface layer forming a protective layer about said core to inhibit or prevent said core from degrading, dissolving, reacting, or combinations thereof when said component is exposed to a fluid environment in said down-hole applications, said surface layer is not degradable, dissolvable, reactable, or combinations thereof in said fluid environment until said surface layer is exposed to an activation event which thereafter causes said surface layer to controllably dissolve in said fluid environment; 
   b. inserting said down-hole component into a well, said surface layer of said hierarchically-designed reactive component does not or substantially does not dissolve, degrade, react, or combinations thereof when exposed to said fluid environment in said well;   c. exposing said surface layer of said hierarchically-designed reactive component to said activation event to cause said surface layer to degrade, dissolve, react, or combinations thereof to thereby expose said core to said fluid environment, said activation event includes one or more events selected from the group consisting of a temperature change of said fluid environment, a pH change of said fluid environment, exposure of said surface layer with an activation compound, a change in composition of fluid environment, exposure of said surface layer to an electrical charge, exposure to of said surface layer to certain electromagnetic waves, a change in salt content of said fluid environment, a change in electrolyte content of said fluid environment, exposure of said surface layer to certain sound waves, exposure of said surface layer to certain vibrations, exposure of said surface layer to certain magnetic waves, and exposure of said surface layer to a certain pressure; and,   d. causing said exposed core to degrade, dissolve, react, fracture, or combinations thereof when exposed to said fluid environment, said degradation, dissolving, reacting, fracturing, or combinations thereof of said core thereby causing said down-hole component to at least partially degrade, dissolve, react, fracture, or combinations thereof.   
     
     
         34 . The method as defined in  claim 33 , wherein said down-hole component is selected from the group consisting of a frac ball, valve, plug, ball, sleeve, casing, hydraulic actuating tool, ball/ball seat assembly, fracture plug, sealing elements, and well drilling tool. 
     
     
         35 . The method as defined in  claim 33 , wherein at least 70 weight percent of said core includes a core material selected from the group consisting of aluminum, calcium, lithium, magnesium, potassium, sodium, lithium aluminum hydride, sodium aluminum hydride, potassium aluminum hydride, magnesium aluminum hydride, lithium borohydride, sodium borohydride, calcium borohydride, magnesium hydride, n-Al, borohydride mixed with alanates, metal hydrides, borohydrides, and divalent cation alanates. 
     
     
         36 . The method as defined in  claim 33 , wherein said fluid environment is a water-containing environment, said core has a dissolution rate in said fluid environment of 0.1-100 mm/hr at 100-300° F. 
     
     
         37 . The method as defined in  claim 33 , wherein said activation event includes a temperature increase of said fluid environment which causes said surface layer to degrade, dissolve, of combinations thereof. 
     
     
         38 . The method as defined in  claim 33 , wherein said activation event includes a change in pH of said fluid environment which causes said surface layer to degrade, dissolve, of combinations thereof. 
     
     
         39 . The method as defined in  claim 33 , wherein said activation event includes exposure of said surface layer to a chemical trigger. 
     
     
         40 . The method as defined in  claim 39 , wherein said surface layer includes a silicon-containing compound. 
     
     
         41 . The method as defined in  claim 40 , wherein said chemical trigger is a fluorine ion source. 
     
     
         42 . The method as defined in  claim 33 , wherein said core has a compression strength above 5000 psig, a density of no more than 1.7 g/cc and a tensile strength of less than 30,000 psig. 
     
     
         43 . The method as defined in  claim 33 , wherein said surface layer includes a fiber-reinforced metal. 
     
     
         44 . The method as defined in  claim 33 , wherein said core includes a propellant, said propellant includes one or more water-reactive material selected from the group consisting of lithium, sodium, potassium, lithium aluminum hydride, sodium aluminum hydride, potassium aluminum hydride, magnesium aluminum hydride, lithium borohydride, sodium borohydride, calcium borohydride, magnesium hydride, n-Al, borohydride mixed with alanates, metal hydrides, borohydrides, divalent cation alanates, and/or other water-reactive materials, said propellant formulated to react with said fluid environment to cause rapid heat generation which in turn causes said core to ignite. 
     
     
         45 . The method as defined in  claim 33 , wherein said core includes a metal fuel and oxidizer composite which includes one or more mixtures of a reactive metal, an oxidizer, or thermite pair, said reactive metal including one or more metals selected from the group consisting of magnesium, zirconium, tantalum, titanium, hafnium, calcium, tungsten, molybdenum, chrome, manganese, silicon, germanium and aluminum, said oxidizer or thermite pair including one or more compounds selected from the group consisting of fluorinated or chlorinated polymer, oxidizer, and intermetallic thermite. 
     
     
         46 . The method as defined in  claim 33 , wherein said core includes a reactive polymeric material that includes one or more materials selected from the group consisting of aluminum-potassium perchlorate-polyvinylidene difluoride and tetrafluoroethylene (THV) polymer. 
     
     
         47 . The method as defined in  claim 33 , wherein said surface layer includes one or more materials selected from the group consisting of zinc, zinc alloy, ethylene-α-olefin copolymer, linear styrene-isoprene-styrene copolymer, ethylene-butadiene copolymer, styrene-butadiene-styrene copolymer, copolymer having styrene endblocks and ethylene-butadiene or ethylene-butene midblocks, copolymer of ethylene and alpha olefin, ethylene-octene copolymer, ethylene-hexene copolymer, ethylene-butene copolymer, ethylene-pentene copolymer, ethylene-butene copolymer, polyvinyl alcohol, polyvinyl butyral, silicone-based coating, and polyurethane-based coating. 
     
     
         48 . The method as defined in  claim 45 , wherein said surface layer includes polyvinyl alcohol, polyvinyl alcohol modified with a silicone component, polyvinyl acetate phthalate, silicone, polymer-based polyurethane, polymer-based polyvinyl butyral. 
     
     
         49 . A method for controlling dissolving, degrading, reacting, fracturing or combinations thereof of a component for use in down-hole applications comprising:
 a. providing a down-hole component for use in down-hole applications, said down-hole component is selected from the group consisting of a frac ball, valve, plug, ball, sleeve, casing, hydraulic actuating tool, ball/ball seat assembly, fracture plug, sealing elements, and well drilling tool, said down-hole component at least partially formed of a hierarchically-designed reactive component, said hierarchically-designed reactive component includes:
 i. a core, said core dissolvable, reactive, or combinations thereof in the presence of a fluid environment, at least 70 weight percent of said core includes a core material selected from the group consisting of aluminum, calcium, lithium, magnesium, potassium, sodium, lithium aluminum hydride, sodium aluminum hydride, potassium aluminum hydride, magnesium aluminum hydride, lithium borohydride, sodium borohydride, calcium borohydride, magnesium hydride, n-Al, borohydride mixed with alanates, metal hydrides, borohydrides, and divalent cation alanates; and, 
 ii. a surface layer that partially or fully encapsulates said core, said surface layer having a different composition from said core, said surface layer includes polymer; said surface layer forming a protective layer about said core to inhibit or prevent said core from degrading, dissolving, reacting, or combinations thereof when said component is exposed to a fluid environment in said down-hole applications, said surface layer is not degradable, dissolvable, reactable, or combinations thereof in said fluid environment until said surface layer is exposed to an activation event which thereafter causes said surface layer to controllably dissolve in said fluid environment; 
   b. inserting said down-hole component into a well, said surface layer of said hierarchically-designed reactive component does not or substantially does not dissolve, degrade, react, or combinations thereof when exposed to said fluid environment in said well;   c. exposing said surface layer of said hierarchically-designed reactive component to said activation event to cause said surface layer to degrade, dissolve, react, or combinations thereof to thereby expose said core to said fluid environment, said activation event includes one or more events selected from the group consisting of a temperature change of said fluid environment, a pH change of said fluid environment, exposure of said surface layer with an activation compound, a change in composition of fluid environment, exposure of said surface layer to an electrical charge, exposure to of said surface layer to certain electromagnetic waves, a change in salt content of said fluid environment, a change in electrolyte content of said fluid environment, exposure of said surface layer to certain sound waves, exposure of said surface layer to certain vibrations, exposure of said surface layer to certain magnetic waves, and exposure of said surface layer to a certain pressure; and,   d. causing said exposed core to degrade, dissolve, react, fracture, or combinations thereof when exposed to said fluid environment, said degradation, dissolving, reacting, fracturing, or combinations thereof of said core thereby causing said down-hole component to at least partially degrade, dissolve, react, fracture, or combinations thereof.   
     
     
         50 . The method as defined in  claim 47 , wherein said surface layer includes one or more materials selected from the group consisting of ethylene-α-olefin copolymer, linear styrene-isoprene-styrene copolymer, ethylene-butadiene copolymer, styrene-butadiene-styrene copolymer, copolymer having styrene endblocks and ethylene-butadiene or ethylene-butene midblocks, copolymer of ethylene and alpha olefin, ethylene-octene copolymer, ethylene-hexene copolymer, ethylene-butene copolymer, ethylene-pentene copolymer, ethylene-butene copolymer, polyvinyl alcohol, polyvinyl butyral, silicone-based coating, and polyurethane-based coating. 
     
     
         51 . The method as defined in  claim 48 , wherein said surface layer includes polyvinyl alcohol, polyvinyl alcohol modified with a silicone component, polyvinyl acetate phthalate, silicone, polymer-based polyurethane, polymer-based polyvinyl butyral. 
     
     
         52 . The method as defined in  claim 47 , wherein said fluid environment is a water-containing environment, said core has a dissolution rate in said fluid environment of 0.1-100 mm/hr at 100-300° F. 
     
     
         53 . The method as defined in  claim 47 , wherein said activation event includes a temperature increase of said fluid environment which causes said surface layer to degrade, dissolve, of combinations thereof. 
     
     
         54 . The method as defined in  claim 47 , wherein said activation event includes a change in pH of said fluid environment which causes said surface layer to degrade, dissolve, of combinations thereof. 
     
     
         55 . The method as defined in  claim 47 , wherein said activation event includes exposure of said surface layer to a chemical trigger. 
     
     
         56 . The method as defined in  claim 53 , wherein said surface layer includes a silicon-containing compound. 
     
     
         57 . The method as defined in  claim 54 , wherein said chemical trigger is a fluorine ion source. 
     
     
         58 . The method as defined in  claim 47 , wherein said core has a compression strength above 5000 psig, a density of no more than 1.7 g/cc and a tensile strength of less than 30,000 psig.