Galvanically-active in situ formed particles for controlled rate dissolving tools

Abstract

A castable, moldable, and/or extrudable structure using a metallic primary alloy. One or more additives are added to the metallic primary alloy so that in situ galvanically-active reinforcement particles are formed in the melt or on cooling from the melt. The composite contains an optimal composition and morphology to achieve a specific galvanic corrosion rate in the entire composite. The in situ formed galvanically-active particles can be used to enhance mechanical properties of the composite, such as ductility and/or tensile strength. The final casting can also be enhanced by heat treatment, as well as deformation processing such as extrusion, forging, or rolling, to further improve the strength of the final composite over the as-cast material.

What is claimed: 
     
         1 . A method of controlling the dissolution properties of a magnesium or a magnesium alloy comprising of the steps of:
 heating the magnesium or a magnesium alloy to a point above its solidus temperature;   adding an additive to said magnesium or magnesium alloy while said magnesium or magnesium alloy is above said solidus temperature of magnesium or magnesium alloy to form a mixture, said additive including one or more first additives having an electronegativity of 1.5 or greater, said additive constituting about 0.05-45 wt. % of said mixture;   dispersing said additive in said mixture while said magnesium or magnesium alloy is above said solidus temperature of magnesium or magnesium alloy; and,   cooling said mixture to form a magnesium composite, said magnesium composite including in situ precipitation of galvanically-active intermetallic phases.   
     
     
         2 . The method as defined in  claim 1 , wherein said first additive has an electronegativity of greater than 1.8. 
     
     
         3 . The method as defined in  claim 1 , including the step of controlling a size of said in situ precipitated intermetallic phase by controlled selection of a mixing technique during said dispersion step, controlling a cooling rate of said mixture, or combinations thereof. 
     
     
         4 . The method as defined in  claim 1 , wherein said magnesium or magnesium alloy is heated to a temperature that is less than said melting point temperature of at least one of said additives. 
     
     
         5 . The method as defined in  claim 1 , wherein said magnesium or magnesium alloy is heated to a temperature that is greater than said melting point temperature of said additive. 
     
     
         6 . The method as defined in  claim 1 , wherein said additive includes one or more metals selected from the group consisting of tin, nickel, iron, cobalt, silicon, nickel, chromium, copper, bismuth, lead, tin, antimony, indium, silver, aluminum, gold, platinum, cadmium, selenium, arsenic, boron, germanium, carbon, molybdenum, tungsten, manganese, zinc, rhenium, and gallium. 
     
     
         7 . The method as defined in  claim 1 , wherein said additive includes one or more second additives that have an electronegativity of 1.25 or less. 
     
     
         8 . The method as defined in  claim 7 , wherein said second additive includes one or more metals selected from the group consisting of calcium, strontium, barium, potassium, neodymium, cerium, sodium, lithium, cesium, yttrium, lanthanum, samarium, europium, gadolinium, terbium, dysprosium, holmium, and ytterbium. 
     
     
         9 . The method as defined in  claim 1 , wherein said additive is formed of a single composition, and have an average particle diameter size of about 0.1-500 microns. 
     
     
         10 . The method as defined in  claim 1 , wherein said at least a portion of said additive remains at least partially in still solution in an α-magnesium phase of said magnesium composite. 
     
     
         11 . The method as defined in  claim 1 , wherein said magnesium alloy includes over 50 wt. % magnesium and one or more metals selected from the group consisting of aluminum, boron, bismuth, zinc, zirconium, and manganese. 
     
     
         12 . The method as defined in  claim 1 , wherein said magnesium alloy includes over 50 wt. % magnesium and one or more metals selected from the group consisting of aluminum in an amount of about 0.5-10 wt. %, zinc in amount of about 0.1-6 wt. %, zirconium in an amount of about 0.01-3 wt. %, manganese in an amount of about 0.15-2 wt. %; boron in amount of about 0.0002-0.04 wt. %, and bismuth in amount of about 0.4-0.7 wt. %. 
     
     
         13 . The method as defined in  claim 1 , wherein said magnesium alloy includes over 50 wt. % magnesium and one or more metals selected from the group consisting of aluminum in an amount of about 0.5-10 wt. %, zinc in amount of about 0.1-3 wt. %, zirconium in an amount of about 0.01-1 wt. %, manganese in an amount of about 0.15-2 wt. %; boron in amount of about 0.0002-0.04 wt. %, and bismuth in amount of about 0.4-0.7. wt %. 
     
     
         14 . The method as defined in  claim 1 , including the step of forming said magnesium composite into a final shape or near net shape by a) sand casting, permanent mold casting, investment casting, shell molding, or other pressureless casting technique at a temperature above 730° C., 2) using either pressure addition or elevated pouring temperatures above 710° C., or 3) subjecting the magnesium composite to pressures of 2000-20,000 psi through the use of squeeze casting, thixomolding, or high pressure die casting techniques. 
     
     
         15 . The method as defined in  claim 1 , wherein said magnesium composite has a hardness above 14 Rockwell Harness B. 
     
     
         16 . The method as defined in  claim 1 , wherein said magnesium composite has a dissolution rate of at least 5 mg/cm 2 -hr. in 3% KCl at 90° C. 
     
     
         17 . The method as defined in  claim 1 , wherein said additive includes about 0.05-35 wt. % nickel, copper, cobalt, antimony, tin, bismuth or gallium. 
     
     
         18 . The method as defined in  claim 1 , further including the step of rapidly solidifying said magnesium composite by atomizing the molten mixture and then subjecting the atomized molten mixture to ribbon casting, gas and water atomization, pouring into a liquid, high speed machining, saw cutting, or grinding into chips, followed by powder or chip consolidation below its liquidus temperature. 
     
     
         19 . A magnesium composite that includes in situ precipitation of galvanically-active intermetallic phases comprising a magnesium or a magnesium alloy and an additive constituting about 0.05-35 wt. % of said magnesium composite, said magnesium having a content in said magnesium composite that is greater than 50 wt. %, said additive forming metal composite particles or precipitant in said magnesium composite, said metal composite particles or precipitant forming said in situ precipitation of said galvanically-active intermetallic phases, said additive having an electronegativity of 1.5 or greater. 
     
     
         20 . The magnesium composite as defined in claim  20 , wherein said additive has an electronegativity of greater than 1.8. 
     
     
         21 . The magnesium composite as defined in  claim 20 , wherein said additive includes one or more metals selected from the group consisting of tin, nickel, iron, cobalt, silicon, nickel, chromium, copper, bismuth, lead, tin, antimony, indium, silver, aluminum, gold, platinum, cadmium, selenium, arsenic, boron, germanium, carbon, molybdenum, tungsten, manganese, zinc, rhenium, and gallium. 
     
     
         22 . The magnesium composite as defined in  claim 20 , wherein said additive includes one or more metals selected from the group consisting of copper, nickel, cobalt, bismuth, tin, antimony, indium, and gallium. 
     
     
         23 . The magnesium composite as defined in  claim 20 , further including one or more secondary additives that have an electronegativity of 1.25 or less. 
     
     
         24 . The magnesium composite as defined in claim  24 , wherein said secondary additive includes one or more metals selected from the group consisting of calcium, strontium, barium, potassium, neodymium, cerium, sodium, lithium, cesium, yttrium, lanthanum, samarium, europium, gadolinium, terbium, dysprosium, holmium, and ytterbium. 
     
     
         25 . The magnesium composite as defined in  claim 20 , wherein said magnesium alloy includes over 50 wt. % magnesium and one or more metals selected from the group consisting of aluminum, boron, bismuth, zinc, zirconium, and manganese. 
     
     
         26 . The magnesium composite as defined in  claim 20 , wherein said magnesium alloy includes over 50 wt. % magnesium and one or more metals selected from the group consisting of aluminum in an amount of about 0.5-10 wt. %, zinc in amount of about 0.1-3 wt. %, zirconium in an amount of about 0.01-1 wt. %, manganese in an amount of about 0.15-2 wt. %, boron in amount of about 0.0002-0.04 wt. %, and bismuth in amount of about 0.4-0.7 wt. %. 
     
     
         27 . The magnesium composite as defined in  claim 20 , wherein said additive includes about 0.05-35 wt. % nickel, copper, cobalt, antimony, tin, bismuth or gallium. 
     
     
         28 . The magnesium composite as defined in  claim 20 , wherein said magnesium composite has a hardness above 14 Rockwell Harness B. 
     
     
         29 . The magnesium composite as defined in  claim 20 , wherein said magnesium composite has a dissolution rate of at least 5 mg/cm 2 -hr. in 3% KCl at 90° C. 
     
     
         30 . The magnesium composite as defined in  claim 20 , wherein a dissolution rate of said magnesium composite is about 5-300 mg/cm 2 -hr in 3 wt. % KCl water mixture at 90° C. 
     
     
         31 . A dissolvable component for use in downhole operations that is fully or partially formed of a magnesium composite, said dissolvable component including a component selected from the group consisting of sleeve, frac ball, hydraulic actuating tooling, mandrel, slip, grip, ball, dart, carrier, tube, valve, valve component, plug, or other downhole well component, said magnesium composite includes in situ precipitation of galvanically-active intermetallic phases comprising a magnesium or a magnesium alloy and an additive constituting about 0.05-35 wt. % of said magnesium composite, said magnesium having a content in said magnesium composite that is greater than 50 wt. %, said additive forming metal composite particles or precipitant in said magnesium composite, said metal composite particles or precipitant forming said in situ precipitation of said galvanically-active intermetallic phases, said additive having an electronegativity of 1.5 or greater. 
     
     
         32 . The dissolvable component as defined in claim  32 , wherein said additive has an electronegativity of greater than 1.8. 
     
     
         33 . The dissolvable component as defined in  claim 32 , wherein said additive includes one or more metals selected from the group consisting of tin, nickel, iron, cobalt, silicon, nickel, chromium, copper, bismuth, lead, tin, antimony, indium, silver, aluminum, gold, platinum, cadmium, selenium, arsenic, boron, germanium, carbon, molybdenum, tungsten, manganese, zinc, rhenium, and gallium. 
     
     
         34 . The dissolvable component as defined in  claim 32 , wherein said additive includes one or more metals selected from the group consisting of copper, nickel, cobalt, bismuth, tin, antimony, indium, and gallium. 
     
     
         35 . The dissolvable component as defined in  claim 32 , further including one or more secondary additives that have an electronegativity of 1.25 or less. 
     
     
         36 . The dissolvable component as defined in claim  36 , wherein said secondary additive includes one or more metals selected from the group consisting of calcium, strontium, barium, potassium, neodymium, cerium, sodium, lithium, cesium, yttrium, lanthanum, samarium, europium, gadolinium, terbium, dysprosium, holmium, and ytterbium. 
     
     
         37 . The dissolvable component as defined in  claim 32 , wherein said magnesium alloy includes over 50 wt. % magnesium and one or more metals selected from the group consisting of aluminum, boron, bismuth, zinc, zirconium, and manganese. 
     
     
         38 . The dissolvable component as defined in  claim 32 , wherein said magnesium composite has a hardness above 14 Rockwell Harness B. 
     
     
         39 . The dissolvable component as defined in  claim 32 , wherein said magnesium composite has a dissolution rate of at least 5 mg/cm 2 -hr. in 3% KCl at 90° C. 
     
     
         40 . The dissolvable component as defined in  claim 32 , wherein said magnesium composite has a dissolution rate of at least 10 mg/cm 2 -hr in a 3% KCl solution at 90° C. 
     
     
         41 . The dissolvable component as defined in  claim 32 , wherein said magnesium composite has a dissolution rate of at least 20 mg/cm 2 -hr in a 3% KCl solution at 65° C. 
     
     
         42 . The dissolvable component as defined in  claim 32 , wherein said magnesium composite has a dissolution rate of at least 1 mg/cm 2 -hr in a 3% KCl solution at 65° C. 
     
     
         43 . The dissolvable component as defined in  claim 32 , wherein said magnesium composite has a dissolution rate of at least 100 mg/cm 2 -hr in a 3% KCl solution at 90° C. 
     
     
         44 . The dissolvable component as defined in  claim 32 , wherein said magnesium composite has a dissolution rate of at least 45 mg/cm 2 /hr. in 3 wt. % KCl water mixture at 90° C. and up to 325 mg/cm 2 /hr. in 3 wt. % KCl water mixture at 90° C. 
     
     
         45 . The dissolvable component as defined in  claim 32 , wherein said magnesium composite has a dissolution rate of up to 1 mg/cm 2 /hr. in 3 wt. % KCl water mixture at 21° C. 
     
     
         46 . The dissolvable component as defined in  claim 32 , wherein said metal composite particles or precipitant in said magnesium composite has a solubility in said magnesium of less than 5%. 
     
     
         47 . The dissolvable component as defined in  claim 32 , wherein said magnesium alloy includes over 50 wt. % magnesium and one or more metals selected from the group consisting of aluminum, boron, bismuth, zinc, zirconium, and manganese. 
     
     
         48 . The dissolvable component as defined in  claim 32 , wherein said magnesium alloy includes over 50 wt. % magnesium and one or more metals selected from the group consisting of aluminum in an amount of about 0.5-10 wt. %, zinc in an amount of about 0.1-6 wt. %, zirconium in an amount of about 0.01-3 wt. %, manganese in an amount of about 0.15-2 wt. %, boron in an amount of about 0.0002-0.04 wt. %, and bismuth in amount of about 0.4-0.7 wt. %. 
     
     
         49 . The dissolvable component as defined in  claim 32 , wherein said magnesium alloy includes over 50 wt. % magnesium and one or more metals selected from the group consisting of aluminum in an amount of about 0.5-10 wt. %, zinc in an amount of about 0.1-3 wt. %, zirconium in an amount of about 0.01-1 wt. %, manganese in an amount of about 0.15-2 wt. %, boron in an amount of about 0.0002-0.04 wt. %, and bismuth in an amount of about 0.4-0.7 wt. %. 
     
     
         50 . The dissolvable component as defined in  claim 32 , wherein said magnesium alloy includes at least 85 wt. % magnesium and one or more metals selected from the group consisting of 0.5-10 wt. % aluminum, 0.05-6 wt. % zinc, 0.01-3 wt. % zirconium, and 0.15-2 wt. % manganese. 
     
     
         51 . The dissolvable component as defined in  claim 32 , wherein said magnesium alloy includes 60-95 wt. % magnesium and 0.01-1 wt. % zirconium. 
     
     
         52 . The dissolvable component as defined in  claim 32 , wherein said magnesium alloy includes 60-95 wt. % magnesium, 0.5-10 wt. % aluminum, 0.05-6 wt. % zinc, and 0.15-2 wt. % manganese. 
     
     
         53 . The dissolvable component as defined in  claim 32 , wherein said magnesium alloy includes 60-95 wt. % magnesium, 0.05-6 wt. % zinc, and 0.01-1 wt. % zirconium. 
     
     
         54 . The dissolvable component as defined in  claim 32 , wherein said magnesium alloy includes over 50 wt. % magnesium and one or more metals selected from the group consisting of 0.5-10 wt. % aluminum, 0.1-2 wt. % zinc, 0.01-1 wt. % zirconium, and 0.15-2 wt. % manganese. 
     
     
         55 . The dissolvable component as defined in  claim 32 , wherein said magnesium alloy includes over 50 wt. % magnesium and one or more metals selected from the group consisting of 0.1-3 wt. % zinc, 0.01-1 wt. % zirconium, 0.05-1 wt. % manganese, 0.0002-0.04 wt. % boron, and 0.4-0.7 wt. % bismuth. 
     
     
         56 . A dissolvable magnesium alloy in which additions of high electronegative intermetallic formers are selected from one or more elements with an electronegativity of greater than 1.75 and 0.2-5 wt. % of one or more elements with an electronegativity of 1.25 or less, a magnesium content in said magnesium alloy is greater than 50 wt. %, said one or more elements with an electronegativity of greater than 1.75 form a precipitate, particle, and/or intermetallic phase in said magnesium alloy, said one or more elements with an electronegativity of greater than 1.75 include one or more elements selected from the group of tin, nickel, iron, cobalt, silicon, nickel, chromium, copper, bismuth, lead, tin, antimony, indium, silver, aluminum, gold, platinum, cadmium, selenium, arsenic, boron, germanium, carbon, molybdenum, tungsten, manganese, zinc, rhenium, and gallium, said one or more elements with an electronegativity of 1.25 or less selected from the group of calcium, strontium, barium, potassium, neodymium, cerium, sodium, lithium, cesium, yttrium, lanthanum, samarium, europium, gadolinium, terbium, dysprosium, holmium, and ytterbium.