Patent Grant
10202820
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, in order to improve well operations and reduce costs by reducing the need for milling or drilling operations, various interventionless, selectively removable wellbore components or tools have been developed. These selectively removable components or tools include or are formed from various dissolvable, degradable, corrodible, or otherwise removable materials and can be removed from a wellbore without mechanical intervention, such as by changing the conditions in the wellbore, including the temperature, pressure or chemical constituent makeup of a wellbore fluid. While these materials are very useful, it is also very desirable that these materials be lightweight and have high strength, including a strength comparable to that of conventional engineering materials used to form wellbore components or tools, such as various grades of steel, stainless steel and other Ni-base, Co-base and Fe-base alloys. As an example, Fe-base selectively removable materials have been developed. These Fe-base removable materials are high strength and have an ultimate compressive strength of about 100 ksi at room temperature and a density of about 5.3 g/cm3. While very useful, these materials are not ideal for use in certain applications, such as in horizontal portions of the wellbore, because they are more dense than the wellbore fluids and have a tendency to settle out of the fluid requiring higher fluid pressures to affect their movement or run-in into horizontal portions of the wellbore
While it is very desirable to use selectively removable components and tools in all portions of a well, selectively removable components and tools are particularly desirable for use in horizontal portions of the well, since a single vertical well may include a plurality of horizontal portions at a given depth, and this plurality of horizontal portions may be established at a plurality of depths. The extensive and expanding use of horizontal drilling makes the development of improved high strength, lightweight, selectively removable materials very desirable.
Thus, the further improvement of high strength, lightweight, selectively removable materials and articles, including downhole tools and components, is very desirable.
A lightweight, selectively degradable composite material includes a compacted powder mixture of a first powder and a second powder. The first powder comprises first metal particles comprising Mg, Al, Mn, or Zn, or an alloy of any of the above, or a combination of any of the above, having a first particle oxidation potential. The second powder comprises low-density ceramic, glass, cermet, intermetallic, metal, polymer, or inorganic compound second particles. At least one of the first particles and the second particles includes a metal coating layer of a coating material disposed on an outer surface having a coating oxidation potential that is different than the first particle oxidation potential. The compacted powder mixture has a microstructure comprising: a matrix comprising the first metal particles; the second particles dispersed within the matrix; and a network comprising interconnected adjoining metal coating layers that extends throughout the matrix, the lightweight, selectively degradable composite material having a density of about 3.5 g/cm3 or less.
Referring now to the drawings wherein like elements are numbered alike in the several Figures:
Referring to the figures, and particularly
The lightweight, selectively degradable composite material 100 includes a powder compact 110 of powder mixture 10 of a first powder 20 and a second powder 30. The first powder 20 comprises first metal particles 22 comprising Mg, Al, Mn, or Zn, or an alloy of any of the above, or a combination of any of the above, having a first particle oxidation potential. The second powder 30 comprises low-density, lightweight, high strength ceramic, glass, cermet, intermetallic, metal, polymer, or inorganic compound second particles 32. At least one of the first metal particles 22 and the second particles 32 includes a metal coating layer 40 of a coating material 42 disposed on an outer surface having a coating oxidation potential that is different than the first particle oxidation potential. The compacted powder mixture 10 has a microstructure 50 comprising: a matrix 52 comprising the deformed and compacted first metal particles 22; the second particles 32 dispersed within the matrix 52 as dispersed particles 54; and a network 56 comprising interconnected adjoining metal coating layers 40 that are joined or bonded by the compaction and associated deformation and extends throughout the matrix 52. The lightweight, selectively degradable composite material 100 has a density of about 3.5 g/cm3 or less, as described herein. This microstructure 50 is very advantageous because the network 56 of the coating material 34 that extends throughout and is metallurgically bonded within and to the matrix 52 of the first metal particles 22 provides an oxidation potential difference between these materials that extends throughout the composite material. The oxidation potential difference between the coating material 42 and the matrix 52 of the compacted and metallurgically bonded first metal particles 22 provides for rapid degradation and removal of the composite material 100, such as, for example, rapid dissolution or corrosion of the more anodic material in a predetermined wellbore fluid 6. The rapid degradation and removal of the composite material 100 may also be enhanced by other predetermined wellbore conditions, including selection of a predetermined wellbore temperature and/or a predetermined wellbore pressure that triggers or enhances or accelerates the degradation. This invention discloses a new lightweight, selectively degradable composite material 100 and method of making and use. This lightweight, selectively degradable composite material encompasses high strength (e.g. a UCS of at least about 80 ksi, and in some embodiments at least about 100 ksi) and a controlled degradation, or dissolution, and/or disintegration rate while maintaining a low density (e.g about 1.5 to about 3.5 g/cm3). Low density is achieved by introducing high strength, light weight, nano- or micro-size, solid or hollow particles in the system. The ultrahigh strength characteristic provides the high pressure rating of the downhole tools 230 or components 240 and the lightweight characteristic guarantees the buoyancy of the tools in a wellbore fluid 6, both of which are imperative for downhole applications, particularly horizontal downhole applications, such as flow control devices including frac balls 300, darts 340, disks 330 or plugs 320 and associated sealing seats 340, for example.
The microstructure of the selectively degradable composite material is different from selectively degradable nanomatrix materials, such as those taught in US Patent Publication US2011/0132143A1, US2011/0135953A1, US2011/0135530A1, US2011/0136707A1, US2013/0047785A1, US2013/0052472A1, and US2013/0047784A1, which are incorporated herein by reference in their entirety, because it either does not have a substantially continuous cellular nanomatrix with dispersed meal particles, or because it includes dispersed lightweight (i.e. low density) particles. Rather, in the embodiments of the present invention, the interaction and joining or interconnection of the metal coating layers 40 of adjoining particles form a network 56, which may be partially continuous, locally continuous or discontinuous, or a combination thereof, as described herein.
The powder mixtures 10 of first powder 20 and second powder 30 described herein may be formed in any suitable manner, including all manner of mechanical mixing, including various powder mills and blenders. In one embodiment, the powder mixture 10 is substantially homogeneous mixture, and more particularly a homogeneous mixture, where the first powder 20 particles and second powder 30 particles are substantially uniformly dispersed or uniformly dispersed, respectively, within one another. As used herein, substantially homogeneous means that there is uniformity within substantial portions of the mixture, but that there may be localized instances of non-uniformity within the mixture. In other embodiments, the powder mixture 10 may be heterogeneous mixtures of first powder 20 and second powder 30, including gradient mixtures of these particles analogous to the particle mixtures used to form functionally gradient articles as described in US Patent Publication US20120276356A1, which is incorporated herein by reference in its entirety.
In one embodiment, as illustrated in
In another embodiment, as illustrated in
In yet another embodiment, as illustrated in
The first metal particles 22 include Mg, Al, Mn, or Zn, or an alloy of any of the above, or a combination of any of the above. The first metal particles 22 may have any suitable size or shape. In one embodiment, the first metal particles 22 have an average size of about 5 to about 300 μm, and more particularly an average size of about 75 to about 150 μm. In one embodiment, the first metal particles 22 comprise a magnesium-base alloy. The magnesium-base alloy may include any suitable magnesium-base alloy, including an Mg—Si, Mg—Al, Mg—Zn, Mg—Mn, Mg—Al—Zn, Mg—Al—Mn, Mg—Zn—Zr, or Mg—X alloy, where X comprises a rare earth element, or an alloy of thereof, or any other combination of the aforementioned alloys. As used herein, rare earth elements include Sc, Y, La, Ce, Pr, Nd, or Er, or a combination of rare earth elements.
The second particles 32 may include any suitable low density particle. In one embodiment the second particles 32 include low-density ceramic, glass, cermet, intermetallic, metal, polymer, or inorganic compound second particles 32. The second particles 32 may have any suitable size or shape. In one embodiment, the second particles 32 have a density of about 0.1 to about 4.5 g/cm3. The metal particles may include any suitable metal particles, including hollow or porous metal particles. In one embodiment, the metal particles may include pure titanium particles. In another embodiment the metal particles may include titanium alloy particles, including titanium-base alloy particles. Titanium alloy particles may include particles of any suitable commercially available titanium alloy or grade (e.g. Grades 1-38), including, for example, Ti-6A1-4V, which has a nominal composition comprising, by weight: about 6 percent aluminum, about 4 percent vanadium, and the balance titanium and incidental impurities. In another embodiment, the metal particles include hollow metal particles, particularly hollow iron alloy particles, and more particularly hollow iron-base alloy particles, and even more particularly hollow steel particles. In one embodiment, the metal particles may have an average particle size of about 10 to about 200 μm. The use of metal particles as second particles 32 is highly advantageous because while providing low density, lightweight powder compacts 100 as described herein, the powder compact materials 110 made using metal particles as second particles 32 are also capable of being rapidly formed to a near-net shape, such as by dynamic forging, which is highly desirable. In addition, powder compact materials 110 made using metal particles as second particles 32 are metallic materials and are also readily formable and/or machinable using any of a number of commercial metal working and finishing processes to a final or net shape. They may, for example, be finished to precise tolerances and surface finishes, which is useful in the manufacture of articles from these materials that require mating seating and/or sealing surfaces, such as balls, plugs, darts and the like that have mating seating and/or sealing surfaces. In addition to being lightweight and high strength, as described herein, the powder compact materials 110 made using metal particles as second particles 32 are also capable of providing relatively higher ductility and fracture toughness. In another embodiment, the second particles 32 include ceramic, glass, polymer, or inorganic compound particles, including hollow or porous particles of these materials. In another embodiment, the second particles 32 include ceramic particles comprising metal carbide, nitride, or oxide particles, or a combination thereof. One embodiment of ceramic particles includes silicon carbide particles, and more particularly silicon carbide particles that have an average particle diameter of about 5 to about 200 μm. In one embodiment, the second particles 32 may have a substantially spherical particle shape. In another embodiment, the second particles 32 may comprise substantially non-spherical particles, including irregularly shaped particles, having rounded edges.
The metal coating layer 40 of a metal coating material 42 disposed on the outer surfaces 26 of the first metal particles 22 or the outer surfaces 36 of the second particles 32, or both, as described above, may be any suitable metal coating material 42 that is configured to provide a potential difference with the matrix 50 of first metal particles 22 as described herein. In one embodiment, the metal coating layer 40 includes a single metal layer. In this embodiment, the metal coating material 42 may include Al, Ni, Fe, Cu, In, Ga, Mn, Zn, Mg, Mo, Ca, Co, Ta, W, Si, or Re, or an alloy thereof, or any combination thereof. In other embodiments, the metal coating layer 40 may include a plurality of metal coating layers. In this embodiment, an inner layer is disposed on the metal coated powder particle (e.g. first metal particle 22, second particle 32 or both particles), and an outer layer is disposed over the inner layer. In one embodiment, the inner layer 46 may include Fe, Co, Cu, or Ni, or an alloy thereof, or a combination of any of the aforementioned inner layer materials, and the outer layer comprises Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re, or Ni, or an alloy thereof, or an oxide, nitride or carbide thereof, or a combination of any of the aforementioned outer layer materials. In another embodiment, the inner layer may include Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re, or Ni, or an alloy thereof, or an oxide, nitride or carbide thereof, or a combination of any of the aforementioned inner layer materials, and the outer layer may include Fe, Co, Cu, or Ni, or an alloy thereof, or a combination of any of the aforementioned outer layer materials. In one embodiment, where the first metal particles 22 include a magnesium-base alloy, the metal coating material includes Ni, Fe, Cu, or Co, or an alloy thereof, or any combination thereof. The metal coating layers 40 may have any suitable thickness, including a thickness of about 0.1 to about 10 μm, and more particularly a thickness of about 1 to about 5 μm.
The difference in the oxidation potential between the first metal particles 22 and the metal coating layers 40 may be any suitable oxidation potential difference, including a predetermined difference, and may be selected to provide a predetermined or selected dissolution or corrosion rate of the lightweight, high strength selectively degradable composite material 100. This may include the differences in the chemical compositions and oxidation potential difference may be configured to provide a selectable and controllable dissolution rate, including a selectable transition from a very low dissolution rate to a very rapid dissolution rate, in response to a controlled change in a property or condition of the wellbore proximate the powder compact material 110, including a property change in a wellbore fluid 6 that is in contact with the powder compact material 110, as described herein. In one embodiment, the first particle oxidation potential is about 0.7 volts or more, and the coating oxidation potential is about 0.5 volts or less. In other embodiments, a difference between the first particle oxidation potential and the coating oxidation potential is about 0.7 to about 2.7 volts.
The powder compact materials 110 disclosed herein may be configured, including a difference between the first particle oxidation potential and the coating oxidation potential as described herein, to be selectively and controllably disposable, degradable, dissolvable, corrodible, or otherwise removable from a wellbore using a predetermined wellbore fluid 6, including those described herein. These materials may, for example, be configured to be selectably dissolvable at a rate that ranges from about 0 to about 7000 mg/cm2/hr depending on the powder compact material 110 and wellbore fluid 6 selected. For example, the powder compact material 100 may be selected to have a temperature dependent corrosion rate in a given wellbore fluid 6, such as a relatively low rate of corrosion in a 3% KCl solution at room temperature that ranges from about 0 to about 10 mg/cm2/hr as compared to relatively high rates of corrosion at 200° F. in the same solution that range from about 1 to about 250 mg/cm2/hr depending on powder compact material 110 selected. An example of a changed condition comprising a change in chemical composition includes a change in a chloride ion concentration or pH value, or both, of the wellbore fluid 6. For example, various powder compact materials 110 described herein may have corrosion rates in 15% HCl that range from about 4,500 mg/cm2/hr to about 7,500 mg/cm2/hr. Thus, selectable and controllable dissolvability in response to a changed condition in the wellbore, namely the change in the wellbore fluid 6 chemical composition from KCl to HCl, may be achieved.
The lightweight, high strength, selectively degradable composite material 100 is a powder compact material 110 that may be formed into any article 200 by any suitable metalworking or forming method. Powder compact 100 may have any desired shape or size, including that of a cylindrical billet, bar, sheet or other form that may be machined, formed or otherwise used to form useful articles of manufacture, including various wellbore tools and components. Pressing may be used to form a precursor powder compact 120 and sintering and pressing processes may be used to form powder compact 100 and deform the first metal powder particles 22, second particles and coating layer 40, to provide the full density and desired macroscopic shape and size of powder compact 100 as well as its microstructure 50. The morphology (e.g. equiaxed or substantially elongated) of the deformed the first metal powder particles 22, second particles 32 and coating layer 40 results from sintering and deformation of these elements powder particles 12 as they are compacted and interdiffuse and deform to fill the interparticle spaces. The sintering temperatures and pressures may be selected to ensure that the density of powder compact 110 achieves substantially full theoretical density.
In an exemplary embodiment, the microstructure 50 is formed at a sintering temperature (TS), where TS is less than the melting temperature of the metal coating layer (TC) and the melting temperature of the first metal particle 22 (TP1) and second particle 32 (TP2). A solid-state metallurgical bond is formed in the solid state by solid-state interdiffusion between the metal coating layers 40 of adjacent metal coated particles, whether first metal particles 22, second particles, or both, that are compressed into touching contact during the compaction and sintering processes used to form powder compact 100, as described herein. As such, sintered metal coating layers 40 of network 56 include a solid-state bond layer that has a thickness defined by the extent of the interdiffusion of the coating materials 42 of the metal coating layers 40, which will in turn be defined by the nature of the coating layers 40, including whether they are single or multilayer coating layers, whether they have been selected to promote or limit such interdiffusion, and other factors, as described herein, as well as the sintering and compaction conditions, including the sintering time, temperature and pressure used to form powder compact 100.
As the network 56 of metal coating layers 40 is formed, including the metallurgical bond and bond layer, the chemical composition or phase distribution, or both, of metal coating layers 40 may change. Network 56 also has a melting temperature (TM). As used herein, TM includes the lowest temperature at which incipient melting or liquation or other forms of partial melting will occur within network 56, regardless of whether the metal coating material 42 comprises a pure metal, an alloy with multiple phases each having different melting temperatures or a composite, including a composite comprising a plurality of layers of various coating materials having different melting temperatures, or a combination thereof, or otherwise. As the matrix 52 and dispersed particles 54 are formed in conjunction with network 56, diffusion of constituents of metallic coating layers 40 into the first metal particles 22 and/or second particles 32 is also possible, which may result in changes in the chemical composition or phase distribution, or both, of first metal particles 22 and/or second particles 32. As a result, matrix 52, network 56, dispersed particles 54 may have a melting temperature (TDP) that is different than TP. As used herein, TDP includes the lowest temperature at which incipient melting or liquation or other forms of partial melting will occur within matrix 52, regardless of whether metal first particle material that forms the matrix 52 comprises a pure metal, an alloy with multiple phases each having different melting temperatures or a composite, or otherwise. In one embodiment, powder compact 110 is formed at a sintering temperature (TS), where TS is less than TC, TP, TM and TDP, and the sintering is performed entirely in the solid-state resulting in a solid-state bond layer. In another exemplary embodiment, powder compact material 110 is formed at a sintering temperature (TS), where TS is greater than or equal to one or more of TC, TP, TM or TDP and the sintering includes limited or partial melting within the powder compact material 110 as described herein, and further may include liquid-state or liquid-phase sintering resulting in a bond layer that is at least partially melted and resolidified. In this embodiment, the combination of a predetermined TS and a predetermined sintering time (tS) will be selected to preserve the desired microstructure 50 as described herein. For example, localized liquation or melting may be permitted to occur, for example, within all or a portion of network 56 so long as the network, matrix 52 and dispersed particle 54 structure and morphology is preserved, such as by selecting first metal particles 22, TS and tS that do not provide for complete melting of the first metal particles 22. Similarly, localized liquation may be permitted to occur, for example, within all or a portion of matrix 52 so long as the microstructure 50 morphology is preserved, such as by selecting metal coating layers 40, TS and tS that do not provide for complete melting of the coating layer or layers 40. Melting of metal coating layers 40 may, for example, occur during sintering along the metal coating layer 40/first metal particle 22 interface, or along the interface between adjacent layers of multi-layer metal coating layers 40. It will be appreciated that combinations of TS and tS that exceed the predetermined values may result in other microstructures 50, such as an equilibrium melt/resolidification microstructure 50 if, for example, both the network 56 (i.e., combination of metal coating layers 40) and matrix 52 (i.e., the first metal particles 22) are melted, thereby allowing rapid interdiffusion of these materials.
The powder compact 110 is formed by a method that includes selecting the first metal particles 22 and the second particles 32. The method also includes coating at least one of the first metal particles 22 and the second particles 32 with a metal coating layer 40. The method also includes mixing the first metal particles 22 and the second particles 32 to form the powder mixture 10. Mixing may be performed to provide a homogeneous mixture 10 or a non-homogeneous or heterogeneous mixture as described herein. Mixing to provide a homogeneous powder mixture may be performed in any suitable mixing apparatus, including Attritor mixers, drum mixers, ball mills, blenders, including conical blenders, and the like, and by any suitable mixing method. In one embodiment, mixing was performed in an Attritor mixer having a central vertical shaft and one or more blending arms disposed thereon, such as a plurality of lateral extending axially and vertically spaced arms or a laterally and axially disposed helical arm. The Attritor mixer was water cooled and the mixing chamber purged with an inert gas during mixing. The powders are disposed therein together with a milling medium, such as ceramic or stainless steel beads having a diameter of about 6 to about 10 mm, while the shaft or mixing chamber is rotated for a predetermined mixing interval to mix or blend the powders and form the desired powder mixture 10. The mixing interval may be any suitable period, and in one embodiment may be about 10 to about 90 minutes, and more particularly about 30 to about 60 minutes. The method also includes forming the powder compact 110 with microstructure 50 from the powder mixture 10. The microstructure 50 formed of the network 56 of sintered metal coating layers 40, matrix 52 and dispersed particles 54 is formed by the compaction and sintering of the plurality of metal coating layers 40, first metal particles 22 and second particles 32, such as by CIP, HIP or dynamic forging. In one embodiment, the powder mixture may be compacted without sintering such that the microstructure comprises mechanical bonds between first metal particles 22, second particles 32 and metal coating layers 40 formed by deformation during compaction. The chemical composition of the network 56 may be different than that of metal coating material due to diffusion effects associated with the sintering. Powder metal compact 110 also includes matrix 52 that comprise first metal particles 22. Network 56 and matrix 52 correspond to and are formed from the plurality of metal coating layers 40 and first metal particles 22, respectively, as they are sintered together. The chemical composition of matrix 52 may also be different than that of first metal particles 22 due to diffusion effects associated with sintering. The method may also include forming an article 200 from the powder compact 110 by any suitable forming method as disclosed herein.
In one embodiment, the article 200 includes a selectively degradable article 210. In another embodiment, the article 200 includes a selectively degradable downhole article 220. In yet another embodiment, the selectively degradable downhole article 220 comprises a selectively degradable flow inhibition tool 230 or component 240. In still further embodiments, the selectively degradable flow inhibition tool 230 or component 240 comprises a frac plug, bridge plug, wiper plug, shear out plug, debris barrier, atmospheric chamber disc, swabbing element protector, sealbore protector, screen protector, beaded screen protector, screen basepipe plug, drill in stim liner plug, inflow control device plug, flapper valve, gaslift valve, transmatic plug, float shoe, dart, diverter ball, shifting/setting ball, ball seat, plug seat, dart seat, sleeve, teleperf disk, direct connect disk, drill-in liner disk, fluid loss control flapper, shear pin, screw, bolt, or cement plug.
An example of the lightweight, high strength, selectively degradable composite material 100 and powder mixture 10 used to form it is described below and illustrated in
In another embodiment, a different mixture of the particles described above having a reduced amount of first metal particles 22 and increased amount of second particles 32 was compacted under similar temperature and pressure conditions to form a powder compact 110 having the microstructure 50 shown in
The terms “a” and “an” herein do not denote a limitation of quantity, but rather denote the presence of at least one of the referenced items. 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., includes the degree of error associated with measurement of the particular quantity). Furthermore, unless otherwise limited all ranges disclosed herein are inclusive and combinable (e.g., ranges of “up to about 25 weight percent (wt. %), more particularly about 5 wt. % to about 20 wt. % and even more particularly about 10 wt. % to about 15 wt. %” are inclusive of the endpoints and all intermediate values of the ranges, e.g., “about 5 wt. % to about 25 wt. %, about 5 wt. % to about 15 wt. %”, etc.). The use of “about” in conjunction with a listing of constituents of an alloy composition is applied to all of the listed constituents, and in conjunction with a range to both endpoints of the range. Finally, unless defined otherwise, technical and scientific terms used herein have the same meaning as is commonly understood by one of skill in the art to which this invention belongs. The suffix “(s)” as used herein is intended to include both the singular and the plural of the term that it modifies, thereby including one or more of that term (e.g., the metal(s) includes one or more metals). Reference throughout the specification to “one embodiment”, “another embodiment”, “an embodiment”, and so forth, means that a particular element (e.g., feature, structure, and/or characteristic) described in connection with the embodiment is included in at least one embodiment described herein, and may or may not be present in other embodiments.
It is to be understood that the use of “comprising” in conjunction with the alloy compositions described herein specifically discloses and includes the embodiments wherein the alloy compositions “consist essentially of” the named components (i.e., contain the named components and no other components that significantly adversely affect the basic and novel features disclosed), and embodiments wherein the alloy compositions “consist of” the named components (i.e., contain only the named components except for contaminants which are naturally and inevitably present in each of the named components).
While one or more embodiments have been shown and described, modifications and substitutions may be made thereto without departing from the spirit and scope of the invention. Accordingly, it is to be understood that the present invention has been described by way of illustrations and not limitation.
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