Oil and natural gas wells often utilize wellbore components or tools that, due to their function, are only required to have limited service lives that are considerably less than the service life of the well. After a component or tool service function is complete, it must be removed or disposed of in order to recover the original size of the fluid pathway for use, including hydrocarbon production, CO2 sequestration, etc. Disposal of components or tools has conventionally been done by milling or drilling the component or tool out of the wellbore, which are generally time consuming and expensive operations. Recently, self-disintegrating or interventionless downhole tools have been developed. Instead of milling or drilling operations, these tools can be removed by dissolution of engineering materials using various wellbore fluids.
A system for degrading a structure, the system including the structure formed of a degradable-on-demand material, an ignitor arranged to transfer heat to the structure, and a mechanical impactor movable with respect to the structure, wherein the ignitor increases in temperature upon impact of the mechanical impactor into the ignitor, and heat from the ignitor initiates degradation of the structure.
A method of degrading a structure, the method including moving a mechanical impactor with respect to the structure, impacting the impactor into an ignitor to increase a temperature of the ignitor, transferring heat from the ignitor to the structure to initiate degradation of a degradable-on-demand material of the structure, and degrading the degradable-on-demand material of the structure.
The following descriptions should not be considered limiting in any way. With reference to the accompanying drawings, like elements are numbered alike:
With reference now to
With reference to
Once the ignitor 16 releases heat at or above the threshold temperature, and the structure 12 is exposed to the threshold temperature or above to begin the degradation of the structure 12, the structure 12 will begin to degrade, as schematically depicted in
The energetic material 22 can be in the form of continuous fibers, wires, foils, particles, pellets, short fibers, or a combination comprising at least one of the foregoing. In the structure 12, the energetic material 22 is interconnected in such a way that once a reaction of the energetic material 22 is initiated at one or more starting locations or points 28, the reaction can self-propagate through the energetic material 22 in the structure 12. As used herein, interconnected or interconnection is not limited to physical interconnection. The energetic material 22 may include a thermite, a reactive multi-layer foil, an energetic polymer, or a combination comprising at least one of the foregoing. Use of energetic materials 22 disclosed herein is advantageous as these energetic materials 22 are stable at wellbore temperatures but produce an extremely intense exothermic reaction following activation, which facilitates the rapid disintegration of the structure 12.
The energetic material 22 may include a thermite, a thermate, a solid propellant fuel, or a combination comprising at least one of the foregoing. The thermite materials include a metal powder (a reducing agent) and a metal oxide (an oxidizing agent), where choices for a reducing agent include aluminum, magnesium, calcium, titanium, zinc, silicon, boron, and combinations including at least one of the foregoing, for example, while choices for an oxidizing agent include boron oxide, silicon oxide, chromium oxide, manganese oxide, iron oxide, copper oxide, lead oxide and combinations including at least one of the foregoing, for example.
Thermate materials comprise a metal powder and a salt oxidizer including nitrate, chromate and perchlorate. For example thermate materials include a combination of barium chromate and zirconium powder; a combination of potassium perchlorate and metal iron powder; a combination of titanium hydride and potassium perchlorate, a combination of zirconium hydride and potassium perchlorate, a combination of boron, titanium powder, and barium chromate, or a combination of barium chromate, potassium perchlorate, and tungsten powder.
Solid propellant fuels may be generated from the thermate compositions by adding a binder that meanwhile serves as a secondary fuel. The thermate compositions for solid propellants include, but are not limited to, perchlorate and nitrate, such as ammonium perchlorate, ammonium nitrate, and potassium nitrate. The binder material is added to form a thickened liquid and then cast into various shapes. The binder materials include polybutadiene acrylonitrile (PBAN), hydroxyl-terminated polybutadiene (HTPB), or polyurethane. An exemplary solid propellant fuel includes ammonium perchlorate (NH4ClO4) grains (20 to 200 μm) embedded in a rubber matrix that contains 69-70% finely ground ammonium perchlorate (an oxidizer), combined with 16-20% fine aluminum powder (a fuel), held together in a base of 11-14% polybutadiene acrylonitrile or hydroxyl-terminated polybutadiene (polybutadiene rubber matrix). Another example of the solid propellant fuels includes zinc metal and sulfur powder.
The energetic material 22 may also include energetic polymers possessing reactive groups, which are capable of absorbing and dissipating energy. During the activation of energetic polymers, energy absorbed by the energetic polymers causes the reactive groups on the energetic polymers, such as azido and nitro groups, to decompose releasing gas along with the dissipation of absorbed energy and/or the dissipation of the energy generated by the decomposition of the active groups. The heat and gas released promote the degradation of the structure 12.
Energetic polymers include polymers with azide, nitro, nitrate, nitroso, nitramine, oxetane, triazole, and tetrazole containing groups. Polymers or co-polymers containing other energetic nitrogen containing groups can also be used. Optionally, the energetic polymers further include fluoro groups such as fluoroalkyl groups.
Exemplary energetic polymers include nitrocellulose, azidocellulose, polysulfide, polyurethane, a fluoropolymer combined with nano particles of combusting metal fuels, polybutadiene; polyglycidyl nitrate such as polyGLYN, butanetriol trinitrate, glycidyl azide polymer (GAP), for example, linear or branched GAP, GAP diol, or GAP triol, poly[3-nitratomethyl-3-methyl oxetane](polyNIMMO), poly(3,3-bis-(azidomethyl)oxetane (polyBAMO) and poly(3-azidomethyl-3-methyl oxetane) (polyAMMO), polyvinylnitrate, polynitrophenylene, nitramine polyethers, or a combination comprising at least one of the foregoing.
The energetic material 22 of the structure 12 may be provided within a matrix material 20, with the energetic material 22 dispersed or positioned within the matrix material 20, such that the DOD material 18 includes both the energetic material 22 and the matrix material 20. The matrix material 20 is distributed throughout the three dimensional network 30. The energetic material 22 may form an interconnected network 30. The structure 12 can be formed by forming a porous preform from the energetic material 22, and filling or infiltrating the matrix material 20 into the preform under pressure at an elevated temperature. In another embodiment, the energetic material 22 is randomly distributed in the matrix material 20 in the form of particles, pellets, short fibers, or a combination comprising at least one of the foregoing. The structure 12 can be formed by mixing and compressing the energetic material 22 and the matrix material 20. In yet another embodiment, the structure 12 includes an inner portion and an outer portion disposed on the inner portion, where the inner portion includes a core material that is corrodible in a downhole fluid; and the outer portion includes the matrix material 20 and the energetic material 22. Core materials may include corrodible materials that have a higher corrosion rate in downhole fluids than the matrix material 20 of the outer portion when tested under the same conditions. Once the energetic material 22 in the outer portion of the structure 12 is activated, the outer portion disintegrates exposing the inner portion of the structure 12. Since the inner portion of the structure 12 has an aggressive corrosion rate in a downhole fluid, the inner portion of the structure 12 can rapidly disintegrate once exposed to a downhole fluid.
The matrix material 20 may include a polymer, a metal, a composite, or a combination comprising at least one of the foregoing, which provides the general material properties such as strength, ductility, hardness, density for tool functions. As used herein, a metal includes metal alloys. The matrix material 20 can be corrodible or substantially non-corrodible in a downhole fluid, although if corrodible the corrosion rate within downhole fluid may be slow enough in order for the structure 12 to perform its intended function prior to degradation. The downhole fluid comprises water, brine, acid, or a combination comprising at least one of the foregoing. In an embodiment, the downhole fluid includes potassium chloride (KCl), hydrochloric acid (HCl), calcium chloride (CaCl2), calcium bromide (CaBr2) or zinc bromide (ZnBr2), or a combination comprising at least one of the foregoing. The heat generated by the energetic material 22 when activated by the ignitor 16 accelerates the corrosion of the matrix material 20.
In an embodiment, the corrodible matrix material 20 comprises Zn, Mg, Al, Mn, an alloy thereof, or a combination comprising at least one of the foregoing. The corrodible matrix material 20 can further comprise Ni, W, Mo, Cu, Fe, Cr, Co, an alloy thereof, or a combination comprising at least one of the foregoing.
Magnesium alloy is specifically mentioned. Magnesium alloys suitable for use include alloys of magnesium with aluminum (Al), cadmium (Cd), calcium (Ca), cobalt (Co), copper (Cu), iron (Fe), manganese (Mn), nickel (Ni), silicon (Si), silver (Ag), strontium (Sr), thorium (Th), tungsten (W), zinc (Zn), zirconium (Zr), or a combination comprising at least one of these elements. Particularly useful alloys include magnesium alloy particles including those prepared from magnesium alloyed with Ni, W, Co, Cu, Fe, or other metals. Alloying or trace elements can be included in varying amounts to adjust the corrosion rate of the magnesium. For example, four of these elements (cadmium, calcium, silver, and zinc) have to mild-to-moderate accelerating effects on corrosion rates, whereas four others (copper, cobalt, iron, and nickel) have a still greater effect on corrosion. Exemplary commercial magnesium alloys which include different combinations of the above alloying elements to achieve different degrees of corrosion resistance include but are not limited to, for example, those alloyed with aluminum, strontium, and manganese such as AJ62, AJ50x, AJ51x, and AJ52x alloys, and those alloyed with aluminum, zinc, and manganese such as AZ91A-E alloys.
In an embodiment, the matrix formed from the matrix material 20 has a substantially-continuous, cellular nanomatrix comprising a nanomatrix material 20; a plurality of dispersed particles comprising a particle core material that comprises Mg, Al, Zn or Mn, or a combination thereof, dispersed in the cellular nanomatrix; and a solid-state bond layer extending throughout the cellular nanomatrix between the dispersed particles. The matrix comprises deformed powder particles formed by compacting powder particles comprising a particle core and at least one coating layer, the coating layers joined by solid-state bonding to form the substantially-continuous, cellular nanomatrix and leave the particle cores as the dispersed particles. The dispersed particles have an average particle size of about 5 μm to about 300 μm. The nanomatrix material 20 comprises Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or an oxide, carbide or nitride thereof, or a combination of any of the aforementioned materials.
The matrix can be formed from coated particles such as powders of Zn, Mg, Al, Mn, an alloy thereof, or a combination comprising at least one of the foregoing. The powder generally has a particle size of from about 50 to about 150 micrometers, and more specifically about 5 to about 300 micrometers, or about 60 to about 140 micrometers. The powder can be coated using a method such as chemical vapor deposition, anodization or the like, or admixed by physical method such cryo-milling, ball milling, or the like, with a metal or metal oxide such as Al, Ni, W, Co, Cu, Fe, oxides of one of these metals, or the like. The coating layer can have a thickness of about 25 nm to about 2,500 nm. Al/Ni and Al/W are specific examples for the coating layers. More than one coating layer may be present. Additional coating layers can include Al, Zn, Mg, Mo, W. Cu, Fe, Si, Ca, Co, Ta, Re, or No. Such coated magnesium powders are referred to herein as controlled electrolytic materials (CEM). The CEM materials are then molded or compressed forming the matrix by, for example, cold compression using an isostatic press at about 40 to about 80 ksi (about 275 to about 550 MPa), followed by forging or sintering and machining, to provide a desired shape and dimensions of the structure 12.
The matrix material 20 can be degradable polymers and their composites including poly(lactic acid) (PLA), poly(glycolic acid) (PGA), polycaprolactone (PCL), polylactide-co-glycolide, polyurethane such as polyurethane having ester or ether linkages, polyvinyl acetate, polyesters, and the like.
Optionally, the matrix material 20 further comprises additives such as carbides, nitrides, oxides, precipitates, dispersoids, glasses, carbons, or the like in order to control the mechanical strength and density of the structure 12.
The amount of the energetic material 22 is not particularly limited and is generally in an amount sufficient to generate enough energy to facilitate the rapid disintegration of the structure 12 once the energetic material 22 is activated by the ignitor 16. In one embodiment, the energetic material 22 is present in an amount of about 0.5 wt. % to about 45 wt. % or about 0.5 wt. % to about 20 wt. % based on the total weight of the structure 12.
After impact of the mechanical impactor 14 on the ignitor 16, the mechanical impactor 14 can remain intact, and can be either removed in an uphole direction 32 for removal from the downhole tubular 24, or, after the structure 12 has degraded, the mechanical impactor 14 can be moved further in a downhole direction 34 to impact a second ignitor 16 associated with a second structure 12 for the subsequent removal of the second structure 12.
In another embodiment, as shown in
With reference to
The structure 12 is schematically illustrated in
While the structure 12 and the ignitor 16 are schematically depicted as blocking the flowbore 36 of the downhole tubular 24 in
The ignitor 16 depicted in
As further depicted in
The structure 12 disclosed herein can be controllably removed such that significant disintegration only occurs after the structure 12 has completed its function(s). A method of controllably removing the structure 12 includes disposing the structure 12 in a downhole environment; performing a downhole operation that involves the structure 12; impacting an ignitor 16 to raise the temperature of the ignitor 16, transferring heat from the ignitor 16 to the structure 12, and degrading the structure 12.
The methods allow for a full control of the degradation and disintegration profile of the structure 12. The structure 12 can retain its physical properties until degradation is desired. The structure 12 and any associated assemblies can perform various downhole operations while the degradation of the structure 12 is minimized The downhole operation is not particularly limited and can be any operation that is performed during drilling, stimulation, completion, production, or remediation. Because the start of the degradation process can be controlled, the structure 12 can be designed to have an aggressive corrosion rate in order to accelerate the degradation process after ignition once the structure 12 is no longer needed. Once the structure 12 is no longer needed, the degradation of the article is initiated by impacting the ignitor 16 and transferring heat to the structure 12. Degradation of the structure 12 is accelerated by activating the energetic material 22 within the structure 12.
Before activation, the structure 12 may include both the network 30 of the energetic material 22 and the matrix material 20. After activation, heat is generated, and the structure 12 breaks into small pieces. In an embodiment, the small pieces can further corrode in a downhole fluid forming powder particles. The powder particles can flow back to the surface, thus conveniently removed from the borehole.
Set forth below are various embodiments of the disclosure.
Embodiment 1: A system for degrading a structure, the system including the structure formed of a degradable-on-demand material, an ignitor arranged to transfer heat to the structure, and a mechanical impactor movable with respect to the structure, wherein the ignitor increases in temperature upon impact of the mechanical impactor into the ignitor, and heat from the ignitor initiates degradation of the structure.
Embodiment 2: The system as in any prior embodiment, or combination of embodiments, wherein the mechanical impactor is a hammer
Embodiment 3: The system as in any prior embodiment, or combination of embodiments, wherein the hammer is driven in a direction towards the ignitor by hydrostatic pressure.
Embodiment 4: The system as in any prior embodiment, or combination of embodiments, wherein the ignitor and the structure provide a flowbore.
Embodiment 5: The system as in any prior embodiment, or combination of embodiments, wherein the mechanical impactor is formed of the degradable-on-demand material and degrades upon impact with the ignitor.
Embodiment 6: The system as in any prior embodiment, or combination of embodiments, wherein the degradable-on-demand material includes a network of energetic material in a matrix material, and the ignitor transfers heat to at least one starting point of the network of energetic material to facilitate degradation of both the structure and the mechanical impactor.
Embodiment 7: The system as in any prior embodiment, or combination of embodiments, wherein the degradable-on-demand material includes an energetic material configured to generate energy upon activation to facilitate the degradation of the structure.
Embodiment 8: The system as in any prior embodiment, or combination of embodiments, wherein the degradable-on-demand material further includes a matrix material distributed within a network of the energetic material, the network releasing heat to the matrix material after impact of the mechanical impactor into the ignitor.
Embodiment 9: The system as in any prior embodiment, or combination of embodiments, wherein the energetic material is activated when the ignitor transfers heat at or above a threshold temperature at one or more starting points of the network of the energetic material.
Embodiment 10: The system as in any prior embodiment, or combination of embodiments, wherein the ignitor includes an explosive and/or flammable material.
Embodiment 11: The system as in any prior embodiment, or combination of embodiments, wherein the ignitor includes two or more chemicals separated from each other prior to impact by the mechanical impactor, and mixed together after impact by the mechanical impactor, and mixture of the two or more chemicals generates heat.
Embodiment 12: The system as in any prior embodiment, or combination of embodiments, wherein the energetic material comprises continuous fibers, wires, or foils, or a combination comprising at least one of the foregoing, which form a three dimensional network; and the matrix material is distributed throughout the three dimensional network.
Embodiment 13: The system as in any prior embodiment, or combination of embodiments, wherein the ignitor is in direct contact with the structure.
Embodiment 14: The system as in any prior embodiment, or combination of embodiments, wherein the ignitor is interposed between the mechanical impactor and the structure.
Embodiment 15: A method of degrading a structure, the method including moving a mechanical impactor with respect to the structure, impacting the impactor into an ignitor to increase a temperature of the ignitor, transferring heat from the ignitor to the structure to initiate degradation of a degradable-on-demand material of the structure, and degrading the degradable-on-demand material of the structure.
Embodiment 16: The method as in any prior embodiment, or combination of embodiments, wherein moving the mechanical impactor includes moving a hammer into the ignitor.
Embodiment 17: The method as in any prior embodiment, or combination of embodiments, further comprising utilizing heat from the ignitor to degrade a degradable-on-demand material of the mechanical impactor.
Embodiment 18: The method as in any prior embodiment, or combination of embodiments, wherein the ignitor includes two or more chemicals separated from each other prior to impact by the mechanical impactor, and mixed together after impact by the mechanical impactor.
Embodiment 19: The method as in any prior embodiment, or combination of embodiments, wherein the ignitor includes an explosive and/or flammable material.
Embodiment 20: The method as in any prior embodiment, or combination of embodiments, wherein the degradable-on-demand material includes an energetic material configured to generate energy upon activation to facilitate the degradation of the structure, the energetic material including a network, and the degradable-on-demand material further including a matrix material, the network releasing heat to the matrix material after impact of the mechanical impactor into the ignitor.
All ranges disclosed herein are inclusive of the endpoints, and the endpoints are independently combinable with each other. As used herein, “combination” is inclusive of blends, mixtures, alloys, reaction products, and the like. All references are incorporated herein by reference in their entirety.
The use of the terms “a” and “an” and “the” and similar referents in the context of describing the invention (especially in the context of the following claims) are to be construed to cover both the singular and the plural, unless otherwise indicated herein or clearly contradicted by context. “Or” means “and/or.” The modifier “about” used in connection with a quantity is inclusive of the stated value and has the meaning dictated by the context (e.g., it includes the degree of error associated with measurement of the particular quantity). Further, it should further be noted that the terms “first,” “second,” and the like herein do not denote any order, quantity, or importance, but rather are used to distinguish one element from another.
The teachings of the present disclosure apply to downhole assemblies and downhole tools that may be used in a variety of well operations. These operations may involve using one or more treatment agents to treat a formation, the fluids resident in a formation, a wellbore, and/or equipment in the wellbore, such as production tubing. The treatment agents may be in the form of liquids, gases, solids, semi-solids, and mixtures thereof. Illustrative treatment agents include, but are not limited to, fracturing fluids, acids, steam, water, brine, anti-corrosion agents, cement, permeability modifiers, drilling muds, emulsifiers, demulsifiers, tracers, flow improvers etc. Illustrative well operations include, but are not limited to, hydraulic fracturing, stimulation, tracer injection, cleaning, acidizing, steam injection, water flooding, cementing, etc.
While the invention has been described with reference to an exemplary embodiment or embodiments, it will be understood by those skilled in the art that various changes may be made and equivalents may be substituted for elements thereof without departing from the scope of the invention. In addition, many modifications may be made to adapt a particular situation or material to the teachings of the invention without departing from the essential scope thereof. Therefore, it is intended that the invention not be limited to the particular embodiment disclosed as the best mode contemplated for carrying out this invention, but that the invention will include all embodiments falling within the scope of the claims. Also, in the drawings and the description, there have been disclosed exemplary embodiments of the invention and, although specific terms may have been employed, they are unless otherwise stated used in a generic and descriptive sense only and not for purposes of limitation, the scope of the invention therefore not being so limited.
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