DEGRADABLE AND/OR DEFORMABLE DIVERTERS AND SEALS

Abstract

A variable stiffness engineered degradable ball or seal having a degradable phase and a stiffener material. The variable stiffness engineered degradable ball or seal can optionally be in the form of a degradable diverter ball or sealing element which can be made neutrally buoyant.

Claims

1-39. (canceled)

40. A method of forming a temporary seal in a well formation that includes: a. providing a plurality of degradable components capable of forming a fluid seal; each of said degradable components includes a core structure and an extension structure; said extension structure secured to a portion of an outer surface of said core structure; said extension structure extending outwardly from said outer surface of said core structure; said core structure has a shape selected from the group consisting of a sphere, ellipsoid, cone, cube, a three dimensional shape that is equiaxed, and a three dimensional shape having an aspect ratio of 1-8; said extension structure that includes one or more structures selected from the group consisting of a flap and a tail; said extension structure is deformable and includes a material selected from the group consisting of a degradable polymer, a degradable elastomer, a degradable rubber, and a degradable metal; said core structure includes a material selected from the group consisting of a degradable polymer, a degradable elastomer, a degradable rubber, and a degradable metal; b. combining said plurality of degradable components with a fluid to be inserted into said well formation; c. inserting said fluid including said plurality of degradable components into said well formation to cause said plurality of degradable components to be positioned at or at least partially in an opening located in the well formation; d. at least partially sealing said opening by causing said plurality of degradable components located at or at least partially in said opening to deform to at least partially form a seal in said opening to partially or fully block or divert a flow of said fluid into and/or through said opening, said deformation of said plurality of degradable components at least partially caused by fluid pressure of said fluid at said opening; e. performing operations such as drilling, circulating, pumping, and/or hydraulic fracturing in said well formation for a period of time after said plurality of degradable components have deformed in said opening and have at least partially sealed said opening; and, f. causing at least a portion of said plurality of degradable components to degrade and be partially or fully removed from said opening to thereby allow 80-100% of fluid flow rates into said opening that existed prior to said plurality of degradable components to partially or fully sealing said opening.

41. The method as defined in claim 40, further including the step of causing a plurality of said degradable components to agglomerate with one another at and/or at least partially in said seal opening during said step of at least partially sealing; said plurality of said degradable components caused to at least partially agglomerated together by said fluid pressure of said fluid at said opening.

42. The method as defined in claim 40, wherein said flap has a width that is less than 50% a diameter of said core structure; said flap is a) a disc-shaped flap and is located about a mid-region of said outer surface of said core structure; said disc-shaped flap tapers from said outer surface of said core structure to an outer edge of said disc-shaped flap, b) a band-shaped flap that is positioned about said mid-region of said outer surface of said core structure; said band-shaped flange a band body and a flange portion that extends perpendicularly from an outer surface of said the band body; a thickness of said flange portion is less than a thickness of said band body; said thickness of flange portion is constant along the longitudinal length of said flange portion, c) a wavy-shaped flap that is positioned about said mid-region of said outer surface of said core structure, d) a downward mid-section flap that is positioned about said mid-region of said outer surface of said core structure; said downward mid-section flap angling downwardly from said mid-region of said outer surface of said core structure, or e) a downward top flap that is connected to a top region of said outer surface of said core structure; said downward top flap angling downwardly from said top region of said outer surface of said core structure.

43. The method as defined in claim 41, wherein said flap has a width that is less than 50% a diameter of said core structure; said flap is a) a disc-shaped flap and is located about a mid-region of said outer surface of said core structure; said disc-shaped flap tapers from said outer surface of said core structure to an outer edge of said disc-shaped flap, b) a band-shaped flap that is positioned about said mid-region of said outer surface of said core structure; said band-shaped flange a band body and a flange portion that extends perpendicularly from an outer surface of said the band body; a thickness of said flange portion is less than a thickness of said band body; said thickness of flange portion is constant along the longitudinal length of said flange portion, c) a wavy-shaped flap that is positioned about said mid-region of said outer surface of said core structure, d) a downward mid-section flap that is positioned about said mid-region of said outer surface of said core structure; said downward mid-section flap angling downwardly from said mid-region of said outer surface of said core structure, or e) a downward top flap that is connected to a top region of said outer surface of said core structure; said downward top flap angling downwardly from said top region of said outer surface of said core structure.

44. The method as defined in claim 40, wherein said extension member on one or more of said plurality of degradable components includes said tail; said tail is a) a bar-shaped tail connected to a bottom portion of said outer surface of said core structure; said bar-shaped tail having a straight shape along a longitudinal length of said bar-shaped tail and a constant width along said longitudinal length of said bar-shaped tail; a longitudinal length of said bar-shaped tail is greater than 50% a diameter of said core structure; said width of said bar-shaped tail is less than 50% said diameter of said core structure, b) a cone-shaped tail structure connected to a bottom portion of said outer surface of said core structure; a thickness of said cone-shaped tail is variable along a longitudinal length of said cone-shaped tail; a maximum which of said cone-shaped tail structure is greater than 30% said diameter of said core structure; a longitudinal length of said cone-shaped tail is at least 30% said diameter of said core structure, or c) a wavy-shaped tail connected to a bottom portion of said outer surface of said core structure; said wavy-shaped tail has a constant width along said longitudinal length of said wavy-shaped tail; a longitudinal length of said wavy-shaped tail is greater than 50% a diameter of said core structure; said width of said wavy-shaped tail is less than 50% said diameter of said core structure.

45. The method as defined in claim 43, wherein said extension member on one or more of said plurality of degradable components includes said tail; said tail is a) a bar-shaped tail connected to a bottom portion of said outer surface of said core structure; said bar-shaped tail having a straight shape along a longitudinal length of said bar-shaped tail and a constant width along said longitudinal length of said bar-shaped tail; a longitudinal length of said bar-shaped tail is greater than 50% a diameter of said core structure; said width of said bar-shaped tail is less than 50% said diameter of said core structure, b) a cone-shaped tail structure connected to a bottom portion of said outer surface of said core structure; a thickness of said cone-shaped tail is variable along a longitudinal length of said cone-shaped tail; a maximum which of said cone-shaped tail structure is greater than 30% said diameter of said core structure; a longitudinal length of said cone-shaped tail is at least 30% said diameter of said core structure, or c) a wavy-shaped tail connected to a bottom portion of said outer surface of said core structure; said wavy-shaped tail has a constant width along said longitudinal length of said wavy-shaped tail; a longitudinal length of said wavy-shaped tail is greater than 50% a diameter of said core structure; said width of said wavy-shaped tail is less than 50% said diameter of said core structure.

46. The method as defined in claim 40, wherein said core structure is formed of the same material as said extension structure.

47. The method as defined in claim 40, wherein said core structure is formed of a different material from said extension structure.

48. The method as defined in claim 40, wherein said plurality of degradable component each have has a size and shape that inhibits or prevents said degradable component from fully passing through said opening to be sealed.

49. The method as defined in claim 40, wherein said step of causing at least a portion of said plurality of degradable components is at least partially accomplished by a) changing a temperature of said fluid in contact with said first degradable component, b) changing a pressure of said fluid in contact with said first degradable component, c) changing a composition of said fluid in contact with said first degradable component, d) changing a pH of said fluid in contact with said first degradable component, e) changing a salinity of said fluid in contact with said first degradable component, and/or f) selecting a composition of said first degradable component that dissolves or degrades at a certain rate when exposed to said fluid.

50. The method as defined in claim 40, wherein said plurality of degradable components include first and second degradable components; an average size of said second degradable component is 10-90% smaller than an average size of said first degradable component.

51. The method as defined in claim 40, wherein said degradable component is a) a degradable metal and 10-80 vol. % of a stiffness component, or b) degradable elastomer or polymer and 10-80 vol. % of a stiffness component.

52. The method as defined in claim 51, wherein said degradable component is formed of said degradable elastomer or polymer and said stiffness component; said degradable elastomer or polymer forming a continuous phase in said degradable component; said degradable elastomer or polymer having a 50-100 shore A hardness and a strain to failure in tension or compression of at least 20%; said stiffness component forming a discontinuous second phase in said degradable component; said stiffness component includes one or more of a flake, fiber, foil, microballoon, ribbon, or sphere; said stiffness component having a different composition from said degradable elastomer or polymer; said stiffness component i) has a stiffness or hardness of at least five times a stiffness or hardness of said degradable elastomer or polymer and/or ii) allows for deformation of said degradable component when said degradable component is exposed to a force that is 10-75% of a strength of said degradable component prior to being deformed; a stiffness or yield strength of said degradable component changes when said degradable component deforms; a maximum stiffness and/or yield strength of said degradable component after deformation of said degradable component is at least 1.3 times a stiffness of said degradable component prior to deformation of said degradable component.

53. The method as defined in claim 51, wherein said stiffness component is aligned perpendicular to a primary direction of strain of said degradable component.

54. The method as defined in claim 51, wherein said stiffness component is aligned parallel to a principle direction of strain of said degradable component.

55. The method as defined in claim 51, wherein a composition of said stiffness component includes is selected from the group consisting of calcium carbonate, titanium dioxide, silica, talc, mica, sand, gravel, crushed rock, bauxite, granite, limestone, sandstone, glass, aerogels, xerogels, clay, alumina, kaolin, ceramic, gypsum dihydrate, insoluble salts, magnesium carbonate, calcium hydroxide, calcium aluminate, and magnesium carbonate.

56. The method as defined in claim 52, wherein said degradable elastomer or polymer includes one or more of natural rubber, vulcanized rubber, silicone, polyurethane, synthetic rubber, polybutadienece, nitrile rubber (NBR), polyisobutylene, acrylater-butadinene rubber and styrene butadine rubber.

57. The method as defined in claim 51, wherein said degradable metal is a degradable magnesium alloy.

58. The method as defined in claim 40, wherein said core structure of said degradable component is in the form of a sphere having a diameter of 0.3-1.5 in.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0165] Reference may now be made to the drawings, which illustrate various embodiments that the disclosure may take in physical form and in certain parts and arrangements of parts wherein:

[0166] FIG. 1 illustrates the stress versus displacement for three different variable stiffness elastomer composites;

[0167] FIG. 2 illustrates a variable stiffness elastomeric composite consisting of hard spheres added at 30-70 vol. % to a dissolvable elastomer matrix;

[0168] FIG. 3 illustrates a textured, directionally-compliant variable stiffness engineered degradable thermoplastic elastomer material that can be used to form a ball or seal;

[0169] FIG. 4 illustrates a method of using flake or fiber that accomplishes a similar result as the approach illustrated in FIG. 3 in a pultruded or more easily moldable structure;

[0170] FIG. 5 illustrates a variable stiffness sealing ball or element encountering an opening in a well formation and deforming to form a seal in the opening;

[0171] FIG. 6 illustrates the orientation and the type of rigid (hard) filler in used in the elastomer structured seal/packer control deformation and to inhibit or prevent extrusion and creep;

[0172] FIG. 7 illustrates the compressive strength as a function of strain for syntactic aluminum alloys that can be dissolved using an acid or gelbreaker or, alternatively, a hot caustic solution;

[0173] FIG. 8 is a graph illustrating the pressure ratings of various elastomeric composite balls over time;

[0174] FIG. 9 illustrates a partially degraded elastomeric composite ball; and

[0175] FIGS. 10-14 illustrate various non-limiting configurations of deformable structures that can be used on the variable stiffness engineered degradable thermoplastic elastomer ball or seal or degradable metallic composite ball or seal.

DETAILED DESCRIPTION OF NON-LIMITING EMBODIMENTS

[0176] A more complete understanding of the articles/devices, processes and components disclosed herein can be obtained by reference to the accompanying drawings. These figures are merely schematic representations based on convenience and the ease of demonstrating the present disclosure, and are, therefore, not intended to indicate relative size and dimensions of the devices or components thereof and/or to define or limit the scope of the exemplary embodiments.

[0177] Although specific terms are used in the following description for the sake of clarity, these terms are intended to refer only to the particular structure of the embodiments selected for illustration in the drawings and are not intended to define or limit the scope of the disclosure. In the drawings and the following description below, it is to be understood that like numeric designations refer to components of like function.

[0178] The singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise.

[0179] As used in the specification and in the claims, the term “comprising” may include the embodiments “consisting of” and “consisting essentially of.” The terms “comprise(s),” “include(s),” “having,” “has,” “can,” “contain(s),” and variants thereof, as used herein, are intended to be open-ended transitional phrases, terms, or words that require the presence of the named ingredients/steps and permit the presence of other ingredients/steps. However, such description should be construed as also describing compositions or processes as “consisting of” and “consisting essentially of” the enumerated ingredients/steps, which allows the presence of only the named ingredients/steps, along with any unavoidable impurities that might result therefrom, and excludes other ingredients/steps.

[0180] Numerical values in the specification and claims of this application should be understood to include numerical values which are the same when reduced to the same number of significant figures and numerical values which differ from the stated value by less than the experimental error of conventional measurement technique of the type described in the present application to determine the value.

[0181] All ranges disclosed herein are inclusive of the recited endpoint and independently combinable (for example, the range of “from 2 grams to 10 grams” is inclusive of the endpoints, 2 grams and 10 grams, all the intermediate values and all intermediate ranges).

[0182] The terms “about” and “approximately” can be used to include any numerical value that can vary without changing the basic function of that value. When used with a range, “about” and “approximately” also disclose the range defined by the absolute values of the two endpoints, e.g. “about 2 to about 4” also discloses the range “from 2 to 4.” Generally, the terms “about” and “approximately” may refer to plus or minus 10% of the indicated number.

[0183] Percentages of elements should be assumed to be percent by weight of the stated element, unless expressly stated otherwise.

[0184] The disclosure is directed to a sealing arrangement using an engineered degradable thermoplastic elastomer or degradable metallic device (e.g., degradable metallic ball, etc.) to form seals in various openings in a well formation. The sealing of the engineered degradable thermoplastic elastomer or degradable metallic device is achieved by causing the engineered degradable thermoplastic elastomer or degradable metallic device to deform at the opening in the well formation. The deformation of the engineered degradable thermoplastic elastomer or degradable metallic device causes the stiffness and/or strength of the engineered degradable thermoplastic elastomer or degradable metallic device to increase. The density of the engineered degradable thermoplastic elastomer or degradable metallic device can be controlled (e.g., neutrally buoyant) to facilitate placement of the engineered degradable thermoplastic elastomer or degradable metallic device at or partially in the opening in the well formation. The engineered degradable thermoplastic elastomer or degradable metallic device is formulated to dissolve/degrade (e.g., dissolve/degrade in a completion fluid, including brine, guar gel, freshwater, produced water, etc., as a function of temperature or time, or accelerated or initiated under the action of a gelbreaker or other activator or controlled fluid) so the deformed engineered degradable thermoplastic elastomer or degradable metallic device can be removed from the opening in the well formation, thereby resulting in the unsealing of the opening in the well formation. The engineered degradable thermoplastic elastomer or degradable metallic device is formulated to dissolve/degrade to be safely removed from the opening without damaging the well formation.

[0185] Referring now to FIG. 1, there is illustrated the stress versus displacement for three different variable stiffness engineered degradable thermoplastic elastomers. As illustrated in FIG. 1, as load is applied to the variable stiffness engineered degradable thermoplastic elastomer ball or seal, significant deformation of the soft phase occurs in the variable stiffness engineered degradable thermoplastic elastomer ball or seal. After a certain point, the load in the variable stiffness engineered degradable thermoplastic elastomer ball or seal is transferred to the hard phase of the variable stiffness engineered degradable thermoplastic elastomer ball or seal, and the load increases at 5-100× (and all values and ranges therebetween) the slope of the soft phase. Deformations of the variable stiffness engineered degradable thermoplastic elastomer ball or seal of about 5-50% are common before shifting from the low to high stiffness (slope). The increase in stiffness and hardness of the variable stiffness engineered degradable thermoplastic elastomer results in less deformation of the variable stiffness engineered degradable thermoplastic elastomer. As such, after the variable stiffness engineered degradable thermoplastic elastomer has undergone some deformation to partially or fully conform to the shape about an opening in a well formation to form a seal in/about the opening, further deformation of the variable stiffness engineered degradable thermoplastic elastomer is reduced or terminated so the deformed variable stiffness engineered degradable thermoplastic elastomer is retained in its sealing position at/about the opening. As can be appreciated, if the stiffness of the variable stiffness engineered degradable thermoplastic elastomer does not increase, the variable stiffness engineered degradable thermoplastic elastomer would continue to deform and thereby be formed through the opening in the well formation and compromise the seal in the opening. The unique feature of the variable stiffness engineered degradable thermoplastic elastomer is its ability to deform to partially or fully conform to a shape of an opening in the well formation, thereby creating a seal in/about the opening, and thereafter resisting further deformation to maintain the deformed shape, thereby maintaining the seal in/about the opening. Generally, the variable stiffness engineered degradable thermoplastic elastomer is designed to deform about 10-75% (and all values and ranges therebetween). For example, a 3 in. diameter diverter ball formed of the variable stiffness engineered degradable thermoplastic elastomer could be caused to deform such that, if the diverter ball was flattened by a fluid pressure, the diameter of the diverter ball would decrease to about 2.7 in. (10% deformation) to 0.75 in. (75% deformation). As will be discussed in more detail with respect to FIG. 5, deformation of the variable stiffness engineered degradable thermoplastic elastomer does not need to be uniform throughout the variable stiffness engineered degradable thermoplastic elastomer when partially or fully sealing an opening. As illustrated in FIG. 5, only a portion of the spherical diverter ball has deformed, and wherein such deformation is at the location of the opening in the well formation. In the deformed region of the spherical diverter ball, the stiffening components have moved in close proximity to one another and/or are contacting one another, thereby resulting in increased stiffness and/or hardness in such deformed region, thus resisting further deformation in such region.

[0186] FIG. 2 illustrates a variable stiffness elastomeric composite consisting of hard spheres added at 30-70 vol. % (and all values and ranges therebetween) to a dissolvable elastomer matrix. The hard spheres (e.g., microballoons, solid spheres, etc.) are illustrated as being generally uniformly dispersed in the dissolvable elastomer matrix prior to deformation of the variable stiffness elastomeric composite (State 1). In State 1, the variable stiffness elastomeric composite has a lower stiffness than in State 2. As a strain or load (indicated by the arrows) is applied to one or more regions of the variable stiffness elastomeric composite, the variable stiffness elastomeric composite is caused to be deformed when a sufficient strain or load is applied (State 2). The dissolvable elastomer matrix controls the stiffness of the variable stiffness elastomeric composite until the spheres begin to contact each other (e.g., dissolvable elastomer matrix is extruded from between the microballoons, bringing them into close or direct contact), at which point the stiffness of the variable stiffness elastomeric composite dramatically increases. In State 2, the hardness and stiffness of the variable stiffness elastomeric composite is greater than the hardness and stiffness of the variable stiffness elastomeric composite in State 1.

[0187] FIG. 3 illustrates a textured, directionally-compliant variable stiffness elastomeric composite used to form a ball or seal. The crimped stiffness component (e.g., metal component, graphite component, plastic component, etc.) deforms with the dissolvable elastomer matrix until the stiffness component is straightened out or flattened, at which point the stiffness component becomes non-compliant (e.g., no long can be compressed) and the hardness and stiffness of the variable stiffness elastomeric composite dramatically increases. As illustrated in FIG. 3, the configuration of the stiffness component has a shape (e.g., repeating V-shape, sinusoidal shape, other non-straight shape, etc.) such that when a load or strain is applied to a top of the variable stiffness elastomeric composite, the stiffness component can no longer be compressed in the Y direction and can no long increase in length in the X direction, thus becomes rigid or stiff in the X direction, thereby inhibiting or preventing deformation of the variable stiffness elastomeric composite in the X direction. As can be appreciated, some further deformation of the variable stiffness elastomeric composite in the Y direction may occur due to the spacing of the stiffness components from one another in the Y direction. As such, in State 1 prior to deformation, the variable stiffness elastomeric composite can be deformed in the X and Y direction. After deformation in State 2, the variable stiffness elastomeric composite is stiff for further deformation in the X direction but is still able to further deform in the Y direction. As can be appreciated, the orientation of the stiffness component in the variable stiffness elastomeric composite can be selected such that stiffness occurs in a direction other than or in addition to the X direction when a load is applied to the variable stiffness elastomeric composite on the top and/or other outer surfaces of the variable stiffness elastomeric composite.

[0188] As can be appreciated, by combining the stiffness components illustrated in FIGS. 2 and 3 in the variable stiffness elastomeric composite, control over stiffness/compliance in both X and Y directions can be obtained. By controlling the straightness of the stiffness components, which can be continuous or discontinuous, the amount of strain in the X direction before the variable stiffness elastomeric composite becomes rigid can be controlled with a high degree of precision. Such variable stiffness elastomeric composites can be highly useful in seals and can be fabricated by laminating, compounding, or rolling (e.g., foil or ribbon winding) processes.

[0189] FIG. 4 illustrates a variable stiffness elastomeric composite including a plurality of flakes or fibers for the stiffness component that accomplishes a similar result described above with regard to the variable stiffness elastomeric composite illustrated in FIG. 3. The variable stiffness elastomeric composite illustrated in FIG. 4 is generally a more easily moldable structure than the variable stiffness elastomeric composite illustrated in FIG. 3 due to the configuration of the stiffness components. As illustrated in FIG. 4, as the flakes and/or fibers align in the variable stiffness elastomeric composite during deformation of the variable stiffness elastomeric composite in the X and/or Y direction, the flakes and/or fibers inhibit or prevent further deformation in a direction to the applied force on the variable stiffness elastomeric composite. As can be appreciated, the stiffness components illustrated in FIGS. 2 and/or 3 can be combined with the stiffness components illustrated in FIG. 4.

[0190] The techniques for creating increased stiffness and/or hardness of the variable stiffness elastomeric composite when the variable stiffness elastomeric composite is deformed are particularly effective in controlling extrusion or creep of a seal formed of the variable stiffness elastomeric composite under load.

[0191] A non-limiting application for use of the variable stiffness elastomeric composite to sealing an opening in a well formation is illustrated in FIG. 5. Generally, the shape of the opening in a well formation is not uniformly circular. In fact, the openings in a well formation are typically non-uniform in shape, thereby making it difficult to seal the non-uniform opening using traditionally shaped spherical diverter balls. As illustrated in FIG. 5, the spherically-shaped variable stiffness elastomeric composite or variable stiffness degradable deformable metallic material is caused to deform and readily conform to the irregular surface and/or shape of the opening to create a seal at/in the opening. As illustrated in FIG. 5, the portion of the variable stiffness elastomeric composite or variable stiffness degradable deformable metallic material that is deformed increases in stiffness and/or hardness and thereby resists further deformation once a portion of the variable stiffness elastomeric composite or variable stiffness degradable deformable metallic material deforms at/in the opening and forms a seal at/in the opening. As illustrated in FIG. 5, only the region of the variable stiffness elastomeric composite or variable stiffness degradable deformable metallic material located about the opening is illustrated as being deformed; however, it can be appreciated that other regions of the variable stiffness elastomeric composite or variable stiffness degradable deformable metallic material can be deformed. Due to the increased hardness and/or stiffness of the deformed variable stiffness elastomeric composite or variable stiffness degradable deformable metallic material, the variable stiffness elastomeric composite or variable stiffness degradable deformable metallic material resists being pushed through the opening as illustrated in FIG. 5.

[0192] As partially illustrated in FIG. 5, as the diverter ball or seal that is at least partially formed of a variable stiffness elastomeric composite or variable stiffness degradable deformable metallic material encounters the opening in the well formation (which can be non-circular or ragged), the variable stiffness elastomeric composite or variable stiffness degradable deformable metallic material deforms until a seal is made about/in the opening. Under continued applied pressure, the rigid or hard phase formed by the stiffening component begins to dominate in the variable stiffness elastomeric composite or variable stiffness degradable deformable metallic material after a controlled or certain amount of deformation of the variable stiffness elastomeric composite or variable stiffness degradable deformable metallic material. The deformed variable stiffness elastomeric composite or variable stiffness degradable deformable metallic material densifies, thereby becoming stiffer and/or stronger, and thus forms a high strength, rigid plug that seals the opening in the well formation, but which deformed variable stiffness elastomeric composite or variable stiffness degradable deformable metallic material resists further deformation to inhibit or prevent the deformed variable stiffness elastomeric composite or variable stiffness degradable deformable metallic material from being extruded or pushed through the hole in the well formation.

[0193] The deformable variable stiffness elastomeric composite or variable stiffness degradable deformable metallic material can also be fabricated in situ in the well formation. This can be accomplished by combining in the well formation the deformable and more stiffness components that are used to form the variable stiffness elastomeric composite or variable stiffness degradable deformable metallic material. The deformable and more stiffness components can be separately flowed into the well formation; however, this is not required. For example, a deformable variable stiffness elastomeric composite can be formed in situ in the well formation by flowing into the well formation a pill that is combination of metallic flakes or foil elastomeric material (e.g., powdered coating, etc.), whereby the pills are pressed together at or near an opening in the well formation to form a network of connected pills, thereby forming a deformable variable stiffness elastomeric composite that can be built up to form a seal in an opening in the well formation. The use of different cross-section stiffener components (e.g., X-shaped, hollow rods, syntactic metallic rods, etc.) combined with PVA or other plastic or elastic dissolvable material can be used to form a deformable variable stiffness elastomeric composite from this function in situ in the well formation for sealing an opening in the well formation.

[0194] The variable stiffness elastomeric composite or variable stiffness degradable deformable metallic material can be used as a sealing element, O-ring, ring seal, packing element, or other type seal. FIG. 6 illustrates four (4) non-limiting useful variable stiffness elastomeric composites or variable stiffness degradable deformable metallic materials in a symmetric (only one-half shown) cross-section, and illustrate the stiffening component (e.g., rigid spheres, aligned flakes, fibers, or ribbons [oriented parallel to the compression orientation], random flakes or fibers, and/or chevron or structured stiff phase designs) in various configurations. These four non-limiting designs are particularly effective at preventing compression set, extrusion, and creep, particularly at elevated temperatures and pressures.

[0195] Another non-limiting design includes the use of metal encapsulation of all or part of the degradable elastomer (e.g., elastomer-filled degradable metal tube or shape/extrusion), wound or laminated structure, or stacked ring or cone structure to prevent extrusion and enable higher pressure ratings to be met.

[0196] FIG. 7 illustrates the compressive strength as a function of strain for syntactic aluminum alloys that can be dissolved using an acid or a gelbreaker or, alternatively, a hot caustic solution. Initial crush strengths of 5,000-10,000 psi (and all values and ranges therebetween) are typical for 40 vol. % microballoon-reinforced alloys. Initial crush strength can be controlled by alloy and heat treatment selection, as well as microballoon size, strength (e.g., wall thickness), and content. Generally, microballoon content of the variable stiffness degradable deformable metallic material is 10-60 vol. % (and all values and ranges therebetween), and typically 30-50 vol. %. The microballoons generally have crush strengths of 1000-8,000 psig (and all values and ranges therebetween), and typically microballoons have crush strengths of 1500-6000 psig crush strength can be used. Degradable aluminum alloys, zinc alloys, and magnesium alloys, as well as degradable polymers (elastomers, PVA, PLA and PGA and their mixtures, PEG, cellulistic polymers, nylon (particularly with CaO, Na.sub.2O, BaSO.sub.4, NH.sub.3SO.sub.4 or other high or low PH creating addition on contact with water) are particularly useful in creating a degradable variable stiffness elastomeric composite or variable stiffness degradable deformable metallic material.

[0197] As illustrated in FIG. 7, after local deformation of the variable stiffness degradable deformable metallic material formed of a degradable aluminum alloy having microballoons dispersed in the degradable aluminum alloy, the strength (and stiffness) increases dramatically, thereby inhibiting or preventing further deformation without the addition of much higher forces. This increase in strength and/or stiffness is the result of the crushing of the microballoons, the resulting reduction of porosity, and density increase of the variable stiffness degradable deformable metallic material. In this manner, the variable stiffness degradable deformable metallic material can “seat-in” to complex cavities and then resist further deformation, becoming a solid plug or seal with reduced leakage. Proper design of a sealing surface can be envisioned by one skilled in the art. The density of a variable stiffness degradable deformable metallic material in the form of a divertor (e.g., [glass, ceramic, and/or carbon microballoon]-magnesium diverter or [glass, ceramic, and/or carbon microballoon]-magnesium frac ball) can be 0.95-1.4 g/cc. As can be appreciated, a divertor or frac ball formed of variable stiffness elastomeric composite can also have similar densities. In addition or alternatively, the diverter or frac ball can include a central cavity constituting no more than 70 vol. % of the diverter or frac ball, and typically about 20-50 vol % of the diverter or frac ball, and more typically 30-50 vol % of the diverter or frac ball to control the density to 1.02-1.15 g/cc to match the density of the completion fluid or brine. The size of the central cavity and/or volume percent of the microballoons in the diverter or frac ball can be selected such that the density of the diverter or frac ball is the same or similar to the sand or proppant-water mixture density used in the completion process, such that flow of the diverter or frac balls matches the flow of the completion fluid.

[0198] To facilitate understanding of several non-limiting aspects of the disclosure, the following non-limiting examples are provided.

[0199] For loss control applications, a larger flexible sheet or foil can be used. Typical loss control materials include rags, etc., which are often tied into a knot and added. A good shape for the variable stiffness elastomeric composite or variable stiffness degradable deformable metallic material to form seals while being pumpable is a V or conical shape, with or without tails, that follow fluid flow but seat and are retained in a fracture.

EXAMPLE 1

[0200] An elastomeric dissolvable composite ball formed of about 50 vol. % soda lime glass microballoons having a particle size of 30 μm and a density of 0.23 g/cc was bonded together with 20 vol. % powdered nitrile-butadiene rubber (NBR) particles and 30 vol. % polyvinyl alcohol. The elastomeric dissolvable composite ball had a size of ⅞ in. diameter and an overall density of 0.95 g/cc. The elastomeric dissolvable composite ball was tested to hold 1500 psi for two hours and, as illustrated in Table 1, loses 50% weight over a period of 72 hours in tap water at 51.7° C., and which left particles in the range of 30-100 μm.

EXAMPLE 2

[0201] An elastomeric dissolvable composite ball formed of about 60 vol. % soda lime glass microballoons having a particle size of 30 micron and a density of 0.23 g/cc was bonded together with 20 vol. % powdered NBR particles and 20 vol. % polyvinyl alcohol. The elastomeric dissolvable composite ball had a size of ⅞ in. diameter and an overall density of 0.80 g/cc. The elastomeric composite ball was tested to hold 1500 psi for four hours and, as illustrated in Table 1, loses 50% weight over a period of 96 hours in tap water at 51.7° C., and which left particles in the range of 30-100 μm.

TABLE-US-00001 TABLE 1 Initial 3 hrs. 6 hrs. 24 hrs. 48 hrs. 72 hrs. Example Wt. (g) (g) (g) (g) (g) (g) 1 5.583 5.790 5.340 4.956 4.709 2.970 2 5.712 5.986 6.150 5.541 4.616 2.907

EXAMPLE 3

[0202] An elastomeric dissolvable composite ball formed of about 60 vol. % soda lime glass microballoons having a particle size of 20 μm and a density of 0.46 g/cc was bonded together with 20 vol. % powdered NBR particles and 20 vol. % polyvinyl alcohol. The elastomeric dissolvable composite ball had a size of ⅞ in. diameter and an overall density of 1.05 g/cc. This elastomeric composite ball was tested to hold 1500 psi for 0.5 hours, as illustrated in FIG. 8, and loses 50% weight over a period of 24 hours in tap water at 51.7° C., and which left particles in the range of 50-70 μm. The partially degraded ball is illustrated in FIG. 9.

EXAMPLE 4

[0203] A degradable magnesium alloy is used as a binder with 40 vol. % hollow ceramic microballoons (fillite 150 cenospheres), having an initial crush strength of 3500 psig and a density of 1.35 g/cc via squeeze casting into a microballoon-magnesium powder preform at 500 psig. The microballoon-magnesium powder was then extruded to form rods. Thereafter, the extruded rods were machined into balls.

[0204] Suitable degradable cast magnesium composites that can be used include degradable cast magnesium composites disclosed in U.S. Pat. Nos. 9,757,796; 9,903,010; 10,329,653 and U.S. Pub. No. 2019/0054523, which are incorporated herein by reference. The dissolvable cast magnesium composite generally includes greater than 50 wt. % magnesium and about 0.5-49.5 wt. % of additive (e.g., aluminum, zinc, tin, beryllium, boron carbide, copper, nickel, bismuth, cobalt, titanium, manganese, potassium, sodium, antimony, indium, strontium, barium, silicon, lithium, silver, gold, cesium, gallium, calcium, iron, lead, mercury, arsenic, rare earth metals [e.g., yttrium, lanthanum, samarium, europium, gadolinium, terbium, dysprosium, holmium, ytterbium, etc.], and zirconium). Generally, the dissolvable cast magnesium composite has a magnesium content of at least 85 wt. %. In one non-limiting embodiment, a magnesium composite that is over 50 wt. % magnesium and about 0.05-49.5 wt. % nickel (and all values or ranges therebetween) is added to the magnesium or magnesium alloy to form intermetallic magnesium-nickel as a galvanically-active in situ precipitate (e.g., 0.05-23.5 wt. % nickel, 0.01-5 wt. % nickel, 3-7 wt. % nickel, 7-10 wt. % nickel, or 10-24.5 wt. % nickel). In another non-limiting embodiment, a magnesium composite that is over 50 wt. % magnesium and about 0.05-49.5 wt. % copper (and all values or ranges therebetween) is added to the magnesium or magnesium alloy to form intermetallic magnesium-copper as a galvanically-active in situ precipitate (e.g., 0.01-5 wt. % copper, 0.5-15 wt. % copper, 15-35 wt. % copper, 0.01-20 wt. % copper). In another non-limiting embodiment, there is provided a magnesium composite that is over 50 wt. % magnesium and about 0.05-49.5 wt. % of an additive (and all values or ranges therebetween) (e.g., calcium, copper, nickel, cobalt, bismuth, silver, gold, lead, tin, antimony, indium, arsenic, mercury, gallium, and rare earth metals). The degradable cast magnesium composite generally has a dissolution rate of at least 5 mg/cm.sup.2-hr. in 3 wt. % KCl at 90° C. (e.g., 40-325 mg/cm.sup.2/hr. in 3 wt. % KCl water mixture at 90° C., 50-325 mg/cm.sup.2/hr. in 3 wt. % KCl water mixture at 90° C.; 75-325 mg/cm.sup.2/hr. in 3 wt. % KCl water mixture at 90° C.; 84-325 mg/cm.sup.2/hr. in 3 wt. % KCl water mixture at 90° C.; 100-325 mg/cm.sup.2/hr. in 3 wt. % KCl water mixture at 90° C.; 110-325 mg/cm.sup.2/hr. in 3 wt. % KCl water mixture at 90° C.). The degradable cast magnesium composites generally have a dissolution rate of up to 1 mg/cm.sup.2/hr. in 3 wt. % KCl water mixture at 20° C. The degradable cast magnesium composites generally include no more than 10 wt. % aluminum.

[0205] Suitable degradable powdered metallurgy magnesium composites formed from compression and/or sintering include the degradable magnesium composites disclosed in U.S. Pub. No. 2007/0181224 and U.S. Pat. No. 8,663,401, which are incorporated herein by reference. For example, the degradable powdered metallurgy magnesium composites can include one or more reactive metals selected from calcium, magnesium, and aluminum, and one or more secondary metals such as lithium, gallium, indium, zinc, bismuth, calcium, magnesium, tin, copper, silver, cadmium, and lead.

[0206] A plurality of 3.4 in. diverter balls was inserted into a flowing completion fluid containing sand and allowed to reach the completion zone. The near neutral buoyancy of the diverter balls followed the main flow of the completion fluid and then seated into the opening in the well formation. The diverter balls locally crush at the edges to partially conform to the eroded hole geometry in the well formation and divert 80-95 vol. % of the flow of the completion fluid to other openings in the well formation. By periodically inserting additional diverter balls in the completion fluid, a dramatic increase in fracture uniformity and sand placement was achieved in the well formation. After stimulation of the well formation was completed, a gelbreaker, buffered pH addition (e.g., monosodium sulfate, etc.), etc., was added to the completion fluid, which resulted in the complete solubilization of the magnesium of the diverter balls to produce a clear solution that did not degrade the formation geology. In one non-limiting embodiment, a delay release gelbreaker (e.g., encapsulated acid, encapsulated xylanase/hemicellulase complex, encapsulated ammonium persulfate, encapsulated potassium persulfate, encapsulated sodium persulfate, encapsulated sodium bromate, etc.) can be used to remove the seals after an engineered time by controlling fluid conditions.

[0207] After performing their function, the magnesium-based diverters are removed by further exposure to a completion fluid or breaker, which can include fresh, brackish water, or saline solutions, or with breaker fluids, such as those with a reduced or buffered pH that is generally less than about 7, and typically below 5.5-6 pH, and more typically less than about 4 pH. The magnesium alloy and degradation characteristics can be, and usually are, matched to the fluid and wellbore temperature conditions.

EXAMPLE 5

[0208] A degradable magnesium alloy is formed into a ¾ in. hollow ball fabricated to have near neutral buoyancy in drilling mud. The ball is coated with a degradable plastic or elastomeric coating having a thickness of about 0.1 in. The resultant ball is added to mud and circulated into a formation, where it becomes lodged in a fracture. Additional degradable diverter material can be added in the form of magnesium metal turnings and degradable elastomer or polymeric powders. Additional balls and sealant materials can be added and combined to seal multiple fractures or open areas to reduce pumping losses by at least 75%. After completion of drilling activities, an active agent including a pH-lowering gelbreaker (e.g., 5 vol. % HCl or green acid solution, etc.) is added in an encapsulated or unencapsulated form to the completion fluid and circulated through the wellbore formation. The interaction of the active fluid solubilizes the degradable component to create a clean/clear fluid with reduced impact on geologic formation properties.

[0209] Referring now to FIGS. 10-14, there is illustrated various non-limiting structures that can be formed on a variable stiffness engineered degradable thermoplastic elastomer ball or seal or degradable metallic composite ball or seal.

[0210] FIG. 10 illustrates six (6) different non-limiting flaps and provides three views for each flap, namely a cross-sectional view, a top view, and a side view. FIGS. 10A and 10D illustrate a disc-shaped flap located about the mid-region of the ball. The thickness of the flap tapers from the outer side of the ball to the edge of the flap. The width of the flap is illustrated as less than 50% the diameter of the ball. FIG. 10B illustrates a flap that includes a band section about the mid-region of the ball and a flange portion extending perpendicularly from the band section. The thickness of the flange portion is illustrated as less than the band section and the thickness of flange portion is illustrated as constant along the longitudinal length of the flange portion. The width of the flap is illustrated as less than 50% the diameter of the ball. FIG. 10C illustrates a flap located at the mid-region of the ball and which has a wavy cross-sectional shape. The width of the flap is illustrated as less than 50% the diameter of the ball. FIG. 10E illustrates a flap located at the mid region of the ball and which angles downwardly from the ball. The thickness of the flap tapers from the outer side of the ball to the edge of the flap. The width of the flap is illustrated as greater than 50% the diameter of the ball. FIG. 10F illustrates a flap similar to the flap illustrated in FIG. 10E except that the flap is connected to the top region of the ball.

[0211] FIG. 11 illustrates variable stiffness engineered degradable thermoplastic elastomer ball or seal or degradable metallic composite ball or seal having four (4) different non-limiting tail designs, namely a cross-sectional view, a top view, and a side view. FIG. 11A illustrates a ball wherein a tail structure is connected to the bottom of the ball. The thickness of the tail structure is illustrated as constant along the longitudinal length of the tail structure and is less than 50% the diameter of the ball. The longitudinal length of the tail structure is illustrated as greater than 50% the diameter of the ball. The tail structure has a linear profile along the longitudinal length of the tail structure. FIGS. 11B and 11D illustrate a cone-shaped tail structure connected to the bottom of the ball. FIG. 11B illustrates a circular cross-sectional ball and FIG. 11D illustrates an oval cross-sectional ball. The thickness of the tail structure is illustrated as variable along the longitudinal length of the tail structure and is greater than 50% the diameter of the ball as illustrated in FIG. 11B and about 30-70% the diameter of the ball as illustrated in FIG. 11D. The longitudinal length of the tail structure illustrated in FIG. 11B is greater than 50% the diameter of the ball and the longitudinal length of the tail structure illustrated in FIG. 11D is about 30-70% the diameter of the ball as illustrated in FIG. 11D. FIG. 11C illustrates a ball wherein the tail structure is connected to the bottom of the ball. The thickness of the tail structure is illustrated as constant along the longitudinal length of the tail structure and is less than 50% the diameter of the ball. The longitudinal length of the tail structure is illustrated as greater than 50% the diameter of the ball. The tail structure has a wavy profile along the longitudinal length of the tail structure.

[0212] FIG. 13 illustrates a variable stiffness engineered degradable thermoplastic elastomer ball or seal or degradable metallic composite ball or seal having two (2) different non-limiting flap designs, namely a cross-sectional view, a top view, and a side view. FIG. 12A illustrates a flap design similar to FIGS. 10E and 10F except that the flap is connected at or near the bottom region of the ball. FIG. 13B illustrates a flap that has a “dog eared” shape. The flap is connected at or near the top region of the ball and extends downwardly below the bottom the ball. The thickness of the flap varies along the longitudinal length of the ball. The longitudinal length of the ball is greater than 75% the diameter of the ball.

[0213] FIG. 14 illustrates a variable stiffness engineered degradable thermoplastic elastomer ball or seal or degradable metallic composite ball or seal having five (5) different non-limiting flap designs formed on a ball with a cavity, namely a cross-sectional view, a top view, and a side view. Each of the balls is illustrated as being hollow. FIG. 14A illustrates a flap configuration similar to FIG. 10A. FIG. 14B illustrates a flap configuration similar to FIG. 10E. FIG. 14C illustrates a flap configuration similar to FIG. 10E. FIG. 14D illustrates a flap configuration similar to FIG. 13A. FIG. 14E illustrates a flap configuration similar to FIG. 13B.

[0214] FIG. 12 illustrates a variable stiffness engineered degradable thermoplastic elastomer ball or seal or degradable metallic composite ball or seal having four (4) different non-limiting flap and tail designs, namely a cross-sectional view, a top view, and a side view. FIG. 12A has a flap configuration similar to FIG. 10A and a tail structure similar to FIG. 11D. FIG. 12B has a flap configuration similar to FIG. 10F and a tail structure similar to FIG. 11D. FIG. 12C has a flap configuration similar to FIG. 10F and a tail structure similar to FIG. 11C. FIG. 12D has a flap configuration similar to FIG. 10D and a tail structure similar to FIG. 11D.

[0215] As can be appreciated, the variable stiffness engineered degradable thermoplastic elastomer ball or seal or degradable metallic composite ball or seal can have any combination of the flap and tail configurations of FIGS. 10-14.

EXAMPLE 6

[0216] A flap formed of a rubber component was made (as illustrated in the second configuration of FIG. 12) out of a degradable rubber. The engineered degradable device has a density of about 1.1 g/cc. The engineered degradable device achieved neutral buoyancy in a saltwater solution. While under flow in a clear flow loop, the engineered degradable device was seen to align with the flow of water. A group of engineered degradable devices were added to a test setup with irregular holes approximately ½ in. in diameter. The engineered degradable device in the flow plugged the holes by settling into the holes. The flaps of the engineered degradable device started filling the irregularities of the holes after a pressure increase of between 1 and 2 ksi. When the irregularities were plugged with the engineered degradable device, the pressure raised to about 6 ksi and was held. The same engineered degradable device in a different test in di water at 60° C. degraded over five days into a flowable gel.

EXAMPLE 7

[0217] A NBR rubber component was made as per the fourth configuration of FIG. 13. While under flow in a clear flow loop, the component was seen to align with the flow of water. A group of components were added to a test setup with irregular holes approximately ½ in. in diameter. The components in the flow plugged the holes by settling into the holes. The flaps of the components started filling the irregularities of the holes after a pressure increase of between 1 and 2 ksi. When the irregularities were plugged with the component, the pressure raised up to about 8 ksi and was held.

EXAMPLE 8

[0218] A NBR rubber component was made as per the first configuration of FIG. 10. While under flow in a clear flow loop, the component was seen to tumble randomly in the flow of water. A group of components were added to a test setup with irregular holes approximately ½ in. in diameter. The components in the flow plugged the holes by settling into the holes. The flaps of the components started filling the irregularities of the holes after a pressure increase of between 500 and 800 psi. When the irregularities were plugged with the component, the pressure raised up to about 3000 psi and was held. A comparison of a ⅞ in. ball of the same material was tested and the same setup only pressurized to 800 psi with significant leaks from the irregular holes.

EXAMPLE 9

[0219] A degradable rubber component flap was overmolded onto a dissolvable hollow metal core made as per the third configuration of FIG. 14. The degradable rubber has a density of about 1.2 g/cc. The component achieved neutral buoyancy in a saltwater solution. While the component flows in a clear flow loop, the component was seen to align with the flow of water. A group of components were added to a test setup with irregular holes approximately ½ in. in diameter. The components in the flow plugged the holes by settling into the holes. The flaps of the components started filling the irregularities of the holes after a pressure increase of between 1 and 2 ksi. When the irregularities were plugged with the component, the pressure raised up to about 9 ksi and was held. The same component in a different test in 0.1% KCl water at 60° C. degraded over five days into powder and a flowable gel.

[0220] It will thus be seen that the objects set forth above, among those made apparent from the preceding description, are efficiently attained, and since certain changes may be made in the constructions set forth without departing from the spirit and scope of the disclosure, it is intended that all matter contained in the above description and shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense. The disclosure has been described with reference to preferred and alternate embodiments. Modifications and alterations will become apparent to those skilled in the art upon reading and understanding the detailed discussion of the disclosure provided herein. This disclosure is intended to include all such modifications and alterations insofar as they come within the scope of the present disclosure. It is also to be understood that the following claims are intended to cover all of the generic and specific features of the disclosure herein described and all statements of the scope of the disclosure, which, as a matter of language, might be said to fall there between. The disclosure has been described with reference to the preferred embodiments. These and other modifications of the preferred embodiments as well as other embodiments of the disclosure will be obvious from the disclosure herein, whereby the foregoing descriptive matter is to be interpreted merely as illustrative of the disclosure and not as a limitation. It is intended to include all such modifications and alterations insofar as they come within the scope of the appended claims.