extruded compact metal powder

专利摘要:
ABSTRACT Patent of Invention: "METAL POWDER COMPACT EXTRUDED". The present invention relates to a compact metal powder is disclosed. The compact powder includes a substantially elongated cellular nanomatrix comprising a nanomatrix material. The compact powder also includes a plurality of substantially elongated dispersed particles comprising a particle core material comprising Mg, Al, Zn or Mn, or a combination thereof, dispersed in the cell nanomatrix. The compact powder additionally includes a bonding layer extending through the entire cellular nanomatrix between the dispersed particles, wherein the cellular nanomatrix and the dispersed particles are substantially elongated in a predetermined direction.
公开号:BR112014001741B1
申请号:R112014001741-7
申请日:2012-07-19
公开日:2020-12-01
发明作者:Zhiyue Xu
申请人:Baker Hughes Incorporated；
IPC主号:

专利说明:

[001] This application claims the benefit of United States Order No. 13/194361, filed on July 29, 2011, which is incorporated herein by reference in its entirety.
[002] This order contains subject matter related to the subject matter of copending orders, which are assigned to the same assignee of this order, Baker Hughes Incorporated of Houston, Texas. The orders listed below are hereby incorporated by reference in their entirety:
[003] United States Patent Application Serial No. 12 / 633,686, filed on December 8, 2009, entitled COATED METAL POWDER AND PRODUCTION METHOD OF THE SAME;
[004] United States Patent Application Serial No. 12 / 633,688 filed on December 8, 2009, entitled METHOD OF PRODUCTION OF A NANOMATRIC COMPACT POWDER METAL;
[005] United States Patent Application Serial No. 12 / 633,678, filed on December 8, 2009, entitled COMPOUND POWDER COMPOUND MATERIAL PROJECT;
[006] United States Patent Application Serial No. 12 / 633,683, filed on December 8, 2009, entitled TELESCOPIC UNIT WITH DISSOLVABLE BARRIER;
[007] United States Patent Application Serial No. 12 / 633,662, filed on December 8, 2009, entitled TOOL AND DISSOLUTION METHOD;
[008] United States Patent Application Serial No. 12 / 633,677, filed on December 8, 2009, entitled MULTI-COMPONENT DISAPPEARANCE RISK SPHERE AND METHOD FOR SAME PRODUCTION;
[009] United States Patent Application Serial No. 12 / 633,668, filed on December 8, 2009, entitled TOOL AND DISSOLUTION METHOD;
[0010] United States Patent Application Serial No. 12 / 633,682, filed on December 8, 2009, entitled NANOMATRIZ COMPACT POWDER METAL;
[0011] United States Patent Application Serial No. 12 / 913,310, filed on October 27, 2010, entitled NANOMATRIZ CARBON COMPOUND;
[0012] United States Patent Application Serial No. 12 / 847,594, filed on July 390, 2010, entitled NANOMATRIZ METAL COMPOSITE; and
[0013] United States Patent Application Document Number C & P4-52150-US, filed on the same date as this application, entitled METHOD OF PRODUCTION OF A METAL COMPACT POWDER. BACKGROUND
[0014] Oil and natural gas wells often use well bore components or tools that, due to their function, are only required to have limited service lives that are considerably shorter than the well's service life. After a service function of the component or tool is complete, they must be removed or arranged to recover the original size of the fluid path for use, including hydrocarbon production, CO2 sequestration, etc. The arrangement of components or tools was conventionally done by grinding or drilling the component or tool outside the well bore, which is generally time consuming and costly to operate.
[0015] In order to eliminate the need for milling or drilling operations, the removal of components or tools by dissolution or corrosion using controlled electrolytic materials having a cellular nanomatrix that can be selectively and controllably degraded or corroded in response to an environmental condition of the well bore, such as exposure to a predetermined well bore fluid, has been described in, for example, the related applications noted here.
[0016] Although these materials are very useful, further improvement of their strength, corrosion and productivity is very desirable. SUMMARY
[0017] An exemplary embodiment of a compact metal powder is revealed. The compact powder includes a substantially elongated cellular nanomatrix comprising a nanomatrix material. The compact powder also includes a plurality of substantially elongated dispersed particles comprising a particle core material comprising Mg, Al, Zn or Mn, or a combination thereof, dispersed in the cell nanomatrix. The compact powder additionally includes a bonding layer extending through the entire cellular nanomatrix between the dispersed particles, wherein the cellular nanomatrix and the dispersed particles are substantially elongated in a predetermined direction.
[0018] In another exemplary embodiment, a compact metal powder includes a substantially elongated cellular nanomatrix comprising a nanomatrix material. The compact powder also includes a plurality of substantially elongated dispersed particles comprising a particle core material comprising a metal having a standard oxidation potential less than Zn, ceramic, glass, or carbon, or a combination thereof, dispersed in the nanomatrix cell phone. The compact powder additionally includes a bonding layer that extends through the entire cellular nanomatrix between the dispersed particles, wherein the cellular nanomatrix and the dispersed particles are substantially elongated in a predetermined direction. BRIEF DESCRIPTION OF THE DRAWINGS
[0019] Referring now to the drawings in which similar elements are numbered similarly in the various Figures:
[0020] Figure 1 is a photomicrograph of a powder 10 as disclosed herein that was embedded in an epoxy specimen assembly material and sectioned;
[0021] Figure 2 is a schematic illustration of an exemplary embodiment of a powder particle 12 as it would appear in an exemplary sectional view represented by section 22 of Figure 1;
[0022] Figure 3 is a schematic illustration of a second exemplary embodiment of a powder particle 12 as it would appear in a second view in an exemplary section represented by section 2-2 of Figure 1;
[0023] Figure 4 is a schematic illustration of a third exemplary embodiment of a powder particle 12 as it would appear in a third exemplary sectional view represented by section 2-2 of Figure 1;
[0024] Figure 5 is a schematic illustration of a fourth exemplary embodiment of a powder particle 12 as it would appear in a fourth exemplary sectional view represented by section 2-2 of Figure 1;
[0025] Figure 6 is a schematic illustration of a second exemplary embodiment of a powder as disclosed here having a multimodal particle size distribution;
[0026] Figure 7 is a schematic illustration of a third exemplary embodiment of a powder as disclosed herein having a multimodal particle size distribution;
[0027] Figure 8 is a flow chart of an exemplary embodiment of a method of producing a powder as disclosed herein;
[0028] Figure 9 is a photomicrograph of an exemplary embodiment of a compact powder as disclosed herein;
[0029] Figure 10 is a schematic illustration of an exemplary embodiment of the compact powder of Figure 9 produced using a powder having particles coated with a single layer of powder as it would appear taken along the cut 10 - 10;
[0030] Figure 11 is a schematic illustration of an exemplary embodiment of a compact powder as disclosed herein having a homogeneous multimodal distribution of particle sizes;
[0031] Figure 12 is a schematic illustration of an exemplary embodiment of a compact powder as disclosed herein having a non-homogeneous multimodal particle size distribution;
[0032] Figure 13 is a schematic illustration of an exemplary embodiment of a compact powder as disclosed herein formed of a first powder and a second powder, and having a homogeneous multimodal distribution of particle sizes;
[0033] Figure 14 is a schematic illustration of an exemplary embodiment of a compact powder as disclosed herein, formed of a first powder and a second powder, and having a hand-homogeneous multimodal particle size distribution.
[0034] Figure 15 is a schematic illustration of another exemplary embodiment of the compact powder of Figure 9 produced using a powder having multilayer coated powder particles as it would appear taken along the cut 10 - 10;
[0035] Figure 16 is a schematic cross-sectional illustration of an exemplary embodiment of a precursor compact powder;
[0036] Figure 17 is a flow chart of an exemplary embodiment of a compact powder production method as disclosed herein;
[0037] Figure 18 is a flow chart of an exemplary embodiment of a method of producing a compact powder comprising substantially elongated powder particles, as disclosed herein;
[0038] Figure 19 is a photomicrograph of an exemplary embodiment of a compact powder comprising substantially elongated powder particles from a section parallel to the predetermined elongation direction, as disclosed herein;
[0039] Figure 20 is a photomicrograph of the compact powder of Figure 27 taken from a cross section to the predetermined stretching direction, as revealed here
[0040] Figure 21 is a schematic cross-sectional illustration of an exemplary embodiment of a compact powder comprising substantially elongated powder particles, as disclosed herein;
[0041] Figure 22 is a schematic cross-sectional illustration of another exemplary embodiment of a compact powder comprising substantially elongated powder particles, as disclosed herein;
[0042] Figure 23 is a schematic cross-sectional illustration of an extrusion mold and an exemplary embodiment of a compact powder forming method comprising substantially elongated powder particles of a powder;
[0043] Figure 24 is a schematic cross-sectional illustration of an extrusion mold and an exemplary embodiment of a compacting method comprising substantially elongated powder particles from an ingot;
[0044] Figure 25 is a graph of compressive stress as a function of stress illustrating the compressive strength of an exemplary embodiment of a compact powder comprising substantially elongated powder particles, as disclosed herein;
[0045] Figure 26 is a schematic cross-sectional illustration of an exemplary embodiment of compact powder articles comprising substantially elongated powder particles, as disclosed herein; and
[0046] Figure 27 is a schematic cross-sectional illustration of another exemplary embodiment of compact powder articles comprising substantially elongated powder particles, as disclosed herein. DETAILED DESCRIPTION
[0047] Lightweight, high strength metal materials and a method of producing these materials are revealed, which can be used in a wide variety of applications and application environments, including use in various well bore environments to produce various high strength, lightweight articles, including well bore articles, particularly tools or other downhole components, which can generally be described as controlled electrolytic materials, and which are selectively and controllably disposable, degradable, dissolvable, corrosive or, otherwise, characterized as being removable from the well bore. Many other applications for use on both durable and available or degradable articles are possible. In one embodiment, these high strength, selectively and controllably degradable, lightweight materials include sintered, fully dense post-compacts, formed of powder coated materials that include multiple lightweight particle cores, and core materials having several single-layer and multi-layer nano-scale coatings. In another embodiment, these materials include selectively and controllably degradable materials may include post-compacts that are not fully dense or non-sintered, or a combination thereof, formed from these coated powder materials. These post-compacts are characterized by a microstructure in which the compacted powder particles are substantially elongated in a predetermined direction to form substantially elongated powder particles, as described herein. The substantially elongated powder particles advantageously provide enhanced strength, including compressive strength, corrosion or dissolvability and productivity, as compared to similar post-compacts other than substantially elongated powder particles. These compact powders are produced from coated metallic powders that include several electrochemically active, high strength, light weight particle cores (for example, having relatively higher standard oxidation potentials), and core materials, such as electrochemically metals active, which are dispersed within a cellular nanomatrix formed from the various nano-scale metallic coating layers of metallic coating materials, and then subjected to substantial enough deformation to form substantially elongated dust particles, including particle cores and the metallic coating layers, and to make the metallic coating layers become discontinuous and oriented in the predetermined direction of elongation.
[0048] These improved materials are particularly useful in borehole applications. They provide a unique and advantageous combination of mechanical strength properties, such as compression and shear strength, low density, and selectable and controllable corrosion properties, particularly rapid and controlled dissolution in various well bore fluids, which are perfected over materials of cellular nanomatrix that do not have a microstructure with substantially elongated dust particles, as described herein. For example, the particle core and coating layers of these powders can be selected to provide sintered powders suitable for use as high-strength engineered materials having a compressive strength and shear strength comparable to several other engineered materials, including, carbon, stainless steels, alloy steels, but which also have a low density comparable to the various polymers, elastomers, porous low-density ceramics, and composite materials. As yet another example, these powders and compact materials can be configured to provide selectable and controllable degradation or disposition in response to a change in an environmental condition, such as a transition from a very low dissolution rate to a dissolution rate very fast in response to a change in a well hole property or condition next to an article formed from the compact, including a change of property in a well hole fluid that is in contact with the compact powder. The degradation characteristics or selectable and controllable disposition also describe allowing the dimensional stability and resistance of articles, such as well bore tools or other components, produced from these materials to be maintained until they are no longer needed, at which time a predetermined environmental condition, such as a borehole condition, including downhole fluid temperature, pressure or pH value, can be changed to promote its removal by rapid dissolution.
[0049] These powder coated and compact powder materials and designed materials and articles formed therefrom, as well as methods of producing them, are further described below.
[0050] Referring to Figures 1-5, a metallic powder 10 includes a plurality of metallic coated powder particles 12. The powder particles 12 can be formed to provide a powder 10, including free flowing powder, which can be spilled or otherwise arranged in all shapes and forms (not shown) having all shapes and sizes, and which can be used to form post-compact precursors 100 (Figure 16) and post-compact 200 (Figures 10-15), as described herein, which can be used as, or for use in the production, of various production articles, including various well bore tools and components.
[0051] Each of the powder coated metallic powder particles 12 of powder 10 includes a particle core 14 and a metallic coating layer 16 arranged on the particle core 14. The particle core 14 includes a core material 18. The material of core 18 can include any material suitable for forming the particle core 14 which provides powder particle 12 which can be sintered to form a high strength, light weight compact powder 200 having selectable and controllable dissolution characteristics. Suitable core materials include electrochemically active metals having a standard oxidation potential greater than or equal to that of Zn, including as Mg, Al, Mn or Zn, or a combination thereof. These electrochemically active metals are very reactive with a number of common well-bore fluids, which can be selectively determined or predetermined by selectively controlling the flow of fluids in or out of the well bore using conventional control devices and methods. These predetermined well bore fluids can include water, various aqueous solutions, including an aqueous salt solution or a brine, or various acids, or a combination thereof. Predetermined well-bore fluids can include any number of ionic fluids or highly polar fluids, such as those containing various chlorides. Examples include fluids comprising potassium chloride (KCl), hydrochloric acid (HCl), calcium chloride (CaCl2), calcium bromide (CaBr2), or zinc bromide (ZnBr2). Core material 18 may also include other metals that are less electrochemically active than Zn or non-metallic materials, or a combination thereof. Suitable non-metallic materials include ceramics, compounds, glass or carbon, or a combination thereof. Core material 18 can be selected to provide a high dissolution rate in a predetermined well bore fluid, but it can also be selected to provide a relatively low dissolution rate, including zero dissolution, where the dissolution of the nanomatrix causes the particle core 14 to be quickly indeterminate and released from the particle compact at the interface with the well bore fluid, such that the effective dissolution rate of particle compacts produced using particle cores 14 of these materials core 18 is high, even though the core material 18 itself may have a low dissolution rate, including core materials 20 which may be substantially insoluble in the well bore fluid.
[0052] With respect to electrochemically active metals as 18-core materials, including Mg, Al, Mn or Zn, these metals can be used as pure metals, or in any combination with each other, including various alloy combinations of these materials, including alloys binary, tertiary, or quaternary materials. These combinations can also include compounds from these materials. In addition, in addition to combinations with each other, the Mg, Al, Mn or Zn 18 core materials may also include other constituents, including various alloy additions, to alter one or more properties of the 14 particle cores, such as by enhancement resistance, lower density, or change in the dissolution characteristics of the core material 18.
[0053] Among these electrochemically active metals, Mg, either as a pure metal, or an alloy, or a composite material, is particularly useful, due to its low density, and ability to form high-strength alloys, as well as its high degree electromechanical activity, since they have a higher standard oxidation potential than Al, Mn or Zn. Mg alloys include all alloys that have Mg as an alloy constituent. Mg alloys combining other electrochemically active metals, as described herein, as alloy constituents, are particularly useful, including binary Mg-Zn, MgAl and Mg-Mn alloys, as well as Mg-Zn-Y and Mg tertiary alloys -Al-X, where X includes Zn, Mn, Si, Ca or Y, or a combination thereof. These Mg-Al-X alloys may include, by weight, up to about 85% Mg, up to about 15% Al, and up to about 5% X. The particle core 14 and core material 18, and particularly electrochemically active metals including Mg, Al, Mn or Zn, or combinations thereof, may also include a rare earth element or combination of rare earth elements. As used herein, rare earth elements include Sc, Y, La, Ce, Pr, Nd or Er, or a combination of rare earth elements. Where present, a rare earth element or combination of rare earth elements may be present, by weight, in an amount of about 5%, or less.
[0054] The particle core 14 and core material 18 have a melting temperature (TP). As used herein, TP includes the lowest temperature at which incipient melting or liquefaction, or other forms of partial melting, occur within the core material 18, regardless of whether the core material 18 comprises a pure metal, a multi-phase alloy having different melting temperatures, or a composite of materials having different melting temperatures.
[0055] Particle cores 14 can have any suitable particle size, or particle size ranges, or particle size distribution. For example, particle cores 14 can be selected to provide an average particle size that is represented by a normal or unimodal Gaussian-like distribution around a mean, as generally illustrated in Figure 1. In another example, the nuclei of particle 14 can be selected or mixed to provide a multimodal particle size distribution, including a plurality of average particle core sizes, such as, for example, a homogeneous bimodal distribution of average particle sizes, as illustrated generally and schematically in Figure 6. The selection of the particle core size distribution can be used to determine, for example, the particle size and interparticle spacing 15 of the particles 12 of powder 10. In an exemplary embodiment, the particle cores 14 may have a unimodal distribution and an average particle diameter of about 5 μm to about 300 μm, more particularly about 80 μm to about 120 μm, and even more particularly about 100 μm. In another exemplary embodiment, which may include a multimodal particle size distribution, particle cores 14 may have average particle diameters from about 50 nm to about 500 μm, more particularly about 500 nm to about 300 μm, and, even more particularly, about 5 μm to about 300 μm.
[0056] Particle cores 14 can have any suitable particle shape, including any regular or irregular geometric shape, or a combination thereof. In an exemplary embodiment, particle cores 14 are substantially spheroidal electrochemically active metal particles. In another exemplary embodiment, the particle cores 14 are ceramic particles of substantially irregular shape. In yet another exemplary embodiment, the particle cores 14 are carbon, or other nanotube structures, or cast glass microspheres.
[0057] Each of the metallic coated powder particles 12 of powder 10 also includes a metallic coating layer 16 which is arranged on the particle core 14. The metallic coating layer 16 includes a metallic coating material 20. The coating material metallic 20 gives the particles of powder 12 and powder 10 their metallic nature. The metallic coating layer 16 is a nanoscale coating layer. In an exemplary embodiment, the metallic coating layer 16 can have a thickness of about 25 nm to about 2500 nm. The thickness of the metal cladding layer 16 may vary on the surface of the particle core 14, but preferably it will have a substantially uniform thickness on the surface of the particle core 14. The metal cladding layer 16 may include a single layer, as illustrated in Figure 2, or a plurality of layers as a multilayer coating structure, as shown in Figures 3-5 for up to four layers. In a single layer coating, or in each of the layers of a multilayer coating, the metal coating layer 16 can include a single constituent chemical element or compound, or can include a plurality of chemical elements or compounds. Where a layer includes a plurality of chemical constituents or compounds, they can have all forms of homogeneous or heterogeneous distributions, including a homogeneous or heterogeneous distribution of metallurgical phases. This can include a graduated distribution where the relative amounts of constituents or chemical compounds vary according to respective constituent profiles across the thickness of the layer. In both the single layer and multilayer coating 16, each of the respective layers, or combinations thereof, can be used to provide a predetermined property to the powder particle 12 or a sintered compact powder formed therefrom. For example, the predetermined property can include the bond strength of the metallurgical bond between the particle core 14 and the coating material 20; the interdiffusion characteristics between the particle core 14 and the metallic coating layer 16, including any interdiffusion between the layers of a multilayer coating layer 16; the interdiffusion characteristics between the various layers of a multilayer coating layer 16; the interdiffusion characteristics between the metallic coating layer 16 of a powder particle and that of an adjacent powder particle 12; the bond strength of the metallurgical bond between the metallic coating layers of adjacent sintered powder particles 12, including the outermost layers of multilayer coating layers; and the electrochemical activity of the coating layer 16.
[0058] The metal cladding layer 16 and cladding material 20 have a melting temperature (TC). As used herein, TC includes the lowest temperature at which incipient melting or liquefaction, or other forms of partial melting, occur within the coating material 20, regardless of whether the coating material 20 comprises a pure metal, an alloy with phases multiple, each having different melting temperatures, or a compound, including a compound comprising a plurality of layers of coating material having different melting temperatures.
[0059] The metallic coating material 20 can include any suitable metallic coating material 20 which provides a sinterizable outer surface 21 which is configured to be sintered to an adjacent powder particle 12 which also has a metallic coating layer 16 and outer surface sinterizable 21. In powders 10 which also include second or additional (coated or uncoated) particles 32, as described herein, the sinterizable outer surface 21 of the metallic coating layer 16 is also configured to be sintered to a sinterable outer surface 21 of seconds particles 32. In an exemplary embodiment, powder particles 12 are sinterizable at a predetermined sintering temperature (TS) which is a function of core material 18 and coating material 20, such that sintering of compact powder 200 is performed entirely in the solid state, and where TS is less than TP and TC. The sintering of the solid state limits the interactions of particle core 14 / metallic coating layer 16 to the processes of diffusion of solid state and metallurgical transport phenomenon, and limits the growth of, and provides control over the resulting interface between them. In contrast, for example, the introduction of liquid phase sintering would provide rapid interdiffusion of particle core materials 14 / metal cladding layer 16, and make it difficult to limit the growth of, and provide control over, the resulting interface between them, and thereby interferes with the formation of the desirable microstructure of compact particle 200, as described herein.
[0060] In an exemplary embodiment, core material 18 will be selected to provide a chemical core composition, and coating material 20 will be selected to provide a chemical coating composition, and these chemical compositions will also be selected to differ from each other . In another exemplary embodiment, core material 18 will be selected to provide a chemical core composition, and coating material 20 will be selected to provide a chemical coating composition, and these chemical compositions will also be selected to differ from each other in their interface. . Differences in the chemical compositions of coating material 20 and core material 18 can be selected to provide different dissolution rates, and selectable and controllable dissolution of post-compacts 200 incorporating them, making them selectively and controllably dissolvable. This includes dissolution rates that differ in response to a changed condition in well theft, including an indirect or direct change in a well bore fluid. In an exemplary embodiment, a compact powder 200 formed of powder 10 having chemical compositions of core material 18 and coating material 20 that make compact 200 is selectably dissolvable in a well bore fluid in response to a changed well bore condition. which includes a change in temperature, change in pressure, change in flow rate, change in pH, or change in the chemical composition of well bore fluid, or a combination of these. The selectable dissolution response to the changed condition may result from current chemical reactions or processes that promote different dissolution rates, but also involve changes in the dissolution response that are associated with physical reactions or processes, such as changes in pressure or flow rate of the well bore fluid.
[0061] In an exemplary embodiment of a powder 10, the particle core 14 includes Mg, Al, Mn or Zn, or a combination thereof, as core material 18, and, more particularly, can include pure Mg and alloys of Mg, and the metallic coating layer 16 includes Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re, or Ni, or an oxide, nitride or carbide, intermetallic, or a ceramic thereof, or a combination of any of the materials mentioned above as coating material 20.
[0062] In another exemplary powder embodiment 10, the particle core 14 includes Mg, Al, Mn or Zn, or a combination thereof, as core material 18, and, more particularly, can include pure Mg and Mg alloys , and the metal cladding layer 16 includes a single Al or Ni layer, or a combination thereof, as cladding material 20, as shown in Figure 2. Where the metal cladding layer 16 includes a combination of two or more constituents , such as Al and Ni, the combination may include several graduated codeposited structures of these materials where the amount of each constituent, and, consequently, the composition of the layer, varies through the thickness of the layer, as also illustrated in Figure 2.
[0063] In yet another exemplary embodiment, the particle core 14 includes Mg, Al, Mn or Zn, or a combination thereof, as core material 18, and, more particularly, can include pure Mg and Mg alloys, and the coating layer 16 includes two layers as core material 20, as shown in Figure 3. The first layer 22 is arranged on the surface of the particle core 14, and includes Al or Ni, or a combination thereof, as described herein. The second layer 24 is arranged on the surface of the first layer, and includes Al, Zn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or a combination thereof, and the first layer has a chemical composition that is different from the chemical composition of the second layer. In general, the first layer 22 will be selected to provide a strong metallurgical bond to the particle core 14, and to limit the interdiffusion between the particle core 14 and the coating layer 16, particularly the first layer 22. The second layer 24 can be selected to increase the strength of the metallic coating layer 16, or to provide a strong metallurgical bond, and to promote sintering with the second layer 24 of adjacent powder particles 12, or both. In an exemplary embodiment, the respective layers of metallic coating layer 16 can be selected to promote the selective and controllable dissolution of coating layer 16 in response to a change in well hole property, including well hole fluid, as described here. However, this is only exemplary and it will be appreciated that another selection criterion for the various layers can also be employed. For example, any of the respective layers can be selected to promote the selective and controllable dissolution of the coating layer 16 in response to a change in a well hole property, including the well hole fluid, as described herein. Exemplary embodiments of two-layer metallic coating layers 16 for use in particle cores 14 comprising Mg include first / second layer combinations comprising Al / Ni and Al / W.
[0064] In yet another embodiment, the particle core 14 includes Mg, Al, Mn or Zn, or a combination thereof, as core material 18, and, more particularly, can include pure Mg and Mg alloys, and the Coating layer 16 includes three layers, as shown in Figure 4. The first layer 22 is arranged on the particle core 14, and can include Al or Ni, or a combination thereof. The second layer 24 is arranged on the first layer 22, and may include Al, Zn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or an oxide, nitride, carbide, intermetallic, or ceramics thereof, or a combination of any of the aforementioned second layer materials. The third layer 26 is arranged on the second layer 24, and can include Al, Mn, Fe, Co, Ni, or a combination thereof. In a three-layer configuration, the composition of adjacent layers is different, such that the first layer has a chemical composition that is different from the second layer, and the second layer has a chemical composition that is different from the third layer. In an exemplary embodiment, the first layer 22 can be selected to provide a strong metallurgical bond to the particle core 14, and to limit the interdiffusion between the particle core 14 and the coating layer 16, particularly the first layer 22. The second layer 24 can be selected to increase the strength of the metal cladding layer 16, or to limit the interdiffusion between the particle core 14, or the first layer 22 and third or outer layer 26, or to promote adhesion to a strong metallurgical bond between the third layer 26 and the first layer 22, or any combination thereof. The third layer 26 can be selected to provide a strong metallurgical bond and promote sintering with the third layer 26 of adjacent dust particles 12. However, this is only exemplary, and it will be appreciated that another selection criterion for the various layers can also be employee. For example, any of the respective layers can be selected to promote the selective and controllable dissolution of the coating layer 16 in response to a change in a well hole property, including the well hole fluid, as described herein. An exemplary embodiment of a three-layer coating layer for use in the particle cores comprising Mg includes first / second / third layer combinations comprising Al / Al2O3 / Al.
[0065] In yet another embodiment, the particle core 14 includes Mg, Al, Mn or Zn, or a combination thereof, as core material 18, and, more particularly, can include pure Mg and Mg alloys, and the coating layer 16 includes four layers, as shown in Figure 5. In the four-layer configuration, the first layer 22 can include Al or Ni, or a combination thereof, as described herein. The second layer 24 may include Al, Zn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or an oxide, nitride, carbide, intermetallic, or wax thereof, or a combination of the aforementioned second layer materials. The third layer 26 may also include Al, Zn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or an oxide, nitride, carbide, intermetallic, or wax thereof, or a combination of any of the aforementioned third layer materials. The fourth layer 28 can include Al, Mn, Fe, Co, Ni, or a combination thereof. In a four-layer configuration, the chemical composition of adjacent layers is different, such that the chemical composition of the first layer 22 is different from the chemical composition of the second layer 24, the chemical composition of the second layer 24 is different from the chemical composition of the third layer 26, and the chemical composition of third layer 26 is different from the chemical composition of fourth layer 28. In an exemplary embodiment, the selection of the various layers will be similar to that described for the above three-layer configuration with respect to the inner layers ( first) and external (fourth), with the second and third layers available to provide enhanced interlayer adhesion, total metallic coating layer strength 16, limited interlayer diffusion, or selectable and controllable dissolution, or a combination of these. However, this is only exemplary, and it will be appreciated that another selection criterion for the various layers can also be employed. For example, any of the respective layers can be selected to promote the selective and controllable dissolution of the coating layer 16 in response to a change in a well hole property, including the well hole fluid, as described herein.
[0066] The thickness of the various layers in multilayer configurations can be distributed among the various layers in any way, considering that the sum of the layer thicknesses provides a layer of 16 nanoscale coating, including layer thicknesses, as here described. In one embodiment, the first layer 22 and the outer layer (24, 26, or 28 depending on the number of layers) can be thicker than other layers, where present, due to the desire to provide sufficient material to promote the desired bonding of the first layer 22 with the particle core 14, or the bonding of the outer layers of adjacent powder particles 12, during sintering compact powder 200.
[0067] Powder 10 can also include an additional or second powder 30 interspersed in the plurality of powder particles 12, as shown in Figure 7. In an exemplary embodiment, the second powder 30 includes a plurality of second powder particles 32. These second powder particles 32 can be selected to change a physical, chemical, mechanical, or other property of a powder particle compact 200 formed of powder 10 and second powder 30, or a combination of such properties. In an exemplary embodiment, the change of ownership may include an increase in the compressive strength of powder compact 200 formed of powder 10 and second powder 30. In another exemplary embodiment, the second powder 30 can be selected to promote selective and controllable dissolution in compact particle 200 formed of powder 10 and second powder 30 in response to a change in a well bore property, including well bore fluid, as described herein. The second powder particles 32 can be uncoated or coated with a metallic coating layer 36. When coated, including the single layer or multilayer coatings, the coating layer 36 of the second powder particles 32 can comprise the same coating material 40 as coating material 20 of dust particles 12, or coating material 40 may be different. The second powder particles 32 (uncoated), or particle cores 34, can include any suitable material to provide the desired benefit, including any metals. In an exemplary embodiment, when coated powder particles 12 comprising Mg, Al, Mn or Zn, or a combination thereof, are employed, suitable second powder particles 32 may include Ni, W, Cu, Co or Fe, or a combination of the same. Since the second powder particles 32 will also be configured for solid state sintering on powder particles 12 at the predetermined sintering temperature (TS), the particle cores 34 will have a melting temperature TAP, and any coating layers 36 will have a second melting temperature TAC, where TS is less than TAP and TAC. It will also be appreciated that the second powder 30 is not limited to an additional powder particle type 32 (i.e., a second powder particle), but can include a plurality of additional powder particles 32 (i.e., second, third, fourth, etc. types of additional dust particles 32) in any number.
[0068] Referring to Figure 8, an exemplary embodiment of a method 300 of producing a metallic powder 10 is disclosed. Method 300 includes forming 310 of a plurality of particle cores 14, as described herein. Method 300 also includes deposition 320 of a metallic coating layer 16 on each of the plurality of particle cores 14. Deposition 320 is the process by which coating layer 16 is arranged on particle core 14, as described herein.
[0069] The formation 310 of the particle cores 14 can be carried out by any suitable method for forming a plurality of particle cores 14 of the desired core material 18, which essentially comprises powder formation methods of core material 18. Methods Suitable dust formation methods include mechanical methods; including machining, grinding, impaction and other mechanical methods for forming metal dust; chemical methods, including chemical decomposition, precipitation of a liquid or gas, reactive solid solid synthesis, and other chemical dusting methods; atomization methods, including gas atomization, liquid and water atomization, centrifugal atomization, plasma atomization, and other atomization methods for forming a powder; and various methods of evaporation and condensation. In an exemplary embodiment, particle cores 14 comprising Mg can be manufactured using an atomization method, such as vacuum spray formation, or inert gas spray formation.
[0070] Deposition 320 of metallic coating layers 16 on the plurality of particle cores 14 can be performed using any suitable deposition method, including various thin film deposition methods, such as, for example, chemical vapor deposition methods , and physical vapor deposition methods. In an exemplary embodiment, deposition 320 of metallic coating layers 16 is carried out using deposition of chemical fluidized bed vapor (FBCVD). Deposition 320 of the metallic coating layers 16 by FBCVD includes flow of a reactive fluid as a coating medium that includes the desired metallic coating material 20 through a fluidized particle core bed 14 in a reactor vessel under suitable conditions, including conditions of temperature, pressure and flow rate and the like, sufficient to induce a chemical reaction of the coating medium to produce the desired metallic coating material 20, and includes its deposition on the surface of the particle cores 14 to form coated powder particles 12. The reactive fluid selected will depend on the desired metallic coating material 20, and will typically comprise an organometallic compound that includes the metallic material to be deposited, such as tetracarbonyl nickel (Ni (CO) 4), tungsten hexafluoride (WF6), and aluminum triethyl (C6H15Al), which is transported in a carrier fluid, such as helium or argon gas. The reactive fluid, including the carrier fluid, causes at least a portion of the plurality of particle cores 14 to be suspended in the fluid, thereby enabling the total surface of the suspended particle cores 14 to be exposed to the reactive fluid, including , for example, a desired organometallic constituent, and enabling the deposition of metallic coating material 20 and the coating layer 16 on the total surfaces of the particle cores 14, such that they become enclosed, forming coated particles 12 having layers of metal cladding 16, as described herein. As also described herein, each metallic coating layer 16 can include a plurality of coating layers. The coating material 20 can be deposited in multiple layers to form a multilayer metallic coating layer 16 by repeating the deposition step 320 described above, and changing the reactive fluid 330 to provide the desired metallic coating material 20 for each subsequent layer, where each subsequent layer is deposited on the outer surface of the particle cores 14 that already include any previously deposited coating layer, or layers that make up the metallic coating layer 16. The metallic coating materials 20 of the respective layers (e.g. 22, 24, 26, 28, etc.) can be different from each other, and the differences can be provided by using different reactive media which are configured to produce the desired metallic coating layers 16 on the particle cores 14 in the fluidized bed reactor.
[0071] As shown in Figures 1 and 9, the particle core 14 and core material 18, and the metallic coating layer 16 and the coating material 20, can be selected to provide powder particles 12 and a powder 10 that it is configured by compacting and sintering to provide a compact powder 200 that is high strength, light weight (i.e., having a relatively low density), and is selectively and controllably removable from a well bore in response to a change in a well-bore property, including being selectively and controllably dissolvable in an appropriate well-bore fluid, including various well-bore fluids, as disclosed herein. The compact powder 200 includes a substantially continuous cellular nanomatrix 216 of a nanomatrix material 220 having a plurality of dispersed particles 214 dispersed throughout the entire cellular nanomatrix 216. The substantially continuous cellular nanomatrix 216 and nanomatrix material 220 formed of metallic coating layers sintered 16 is formed by compacting and sintering the plurality of metallic coating layers 16 of the plurality of powder particles 12. The chemical composition of nanomatrix material 220 may be different from that of coating material 20 due to the diffusion effects associated with the sintering, as described here. The compact powder metal 200 also includes a plurality of dispersed particles 214 comprising particle core material 218. The scattered particle cores 214 and core material 218 correspond to and are formed from the plurality of particle cores 14 and the core material 18 of the plurality of powder particles 12 depending on the metallic coating layers 16 are sintered together to form nanomatrix 216. The chemical composition of core material 218 may be different from that of core material 18 due to the diffusion effects associated with sintering, as described here.
[0072] As used herein, the use of the term substantially continuous cellular nanomatrix 216 does not connote the major constituent of the compact, but preferably refers to the minority of constituents or constituents, whether by weight or by volume. This is distinguished from many matrix composite materials where the matrix comprises the majority of constituents by weight or volume. The use of the term substantially continuous cellular nanomatrix is intended to describe the extensive, regular, continuous and interconnected nature of the distribution of nanomatrix material 220 within compact 200. As used herein, "substantially continuous" describes the extent of the nanomatrix material through all the compact powder 200 such that it extends between and surrounds substantially all of the dispersed particles 214. Substantially continuous is used to indicate that complete continuity and regular order of the nanomatrix around each dispersed particle 214 is not required. For example, defects in the coating layer 16 on the particle core 14 in some powder particles 12 can cause particle cores 14 to bond during compacting sintering 200, thereby causing localized discontinuities to result within the nanomatrix. cell 216, even though in the other portions of the compact powder, the nanomatrix is substantially continuous and exhibits the structure described herein. As used herein, "cell" is used to indicate that the nanomatrix defines a network of interconnected, usually repetitive compartments, or cells of nanomatrix material 220 that envelop and also interconnect dispersed particles 214. As used herein, "nanomatrix" is used to describe the size and scale of the matrix, particularly the thickness of the matrix between adjacent dispersed particles 214. The metallic coating layers that are sintered together to form the nanomatrix are nanoscale thick coating layers. Since nanomatrix in many locations, other than the intersection of more than two dispersed particles 214, generally comprise the interdiffusion and bonding of two layers of coating 16 of adjacent powder particles 12 having nanoscale thicknesses, the matrix formed also it has a nanoscale thickness (for example, approximately twice the thickness of the coating layer, as described herein), and is thus described as a nanomatrix. Additionally, the use of the term dispersed particles 214 does not connote the minor constituent of compact 200, but preferably refers to the majority of constituents or constituents, whether by weight or by volume. The use of the term dispersed particle is intended to convey the discontinuous and discrete distribution of particle core material 218 within compact 200.
[0073] Compact powder 200 can be of any desired shape or size, including that of a cylindrical ingot or bar that can be machined or otherwise used to form useful articles of manufacture, including various well-hole tools and components . The pressing used to form precursor compact powder 100 and sintering and pressing processes used to form compact powder 200 and deform the powder particles 12, including particle cores 14 and coating layers 16, to provide the overall density and macroscopic shape and size compact powder 200 as well as its microstructure. The compact powder microstructure 200 includes an equiaxed configuration of dispersed particles 214 which are dispersed throughout and embedded within the substantially continuous cellular nanomatrix 216 of the sintered coating layers. This microstructure is somewhat analogous to an equiaxed grain microstructure with a continuous grain boundary phase, except that it does not require the use of alloy constituents having thermodynamic phase equilibrium properties that are capable of producing such a structure. Preferably, this dispersed structure of equiaxed particle and cell nanomatrix 216 of sintered metal coating layers 16 can be produced using constituents where thermodynamic phase equilibrium conditions would not produce an equiaxed structure. The equiaxed morphology of the scattered particles 214 and the cellular network 216 of particle layers result from sintering and deformation of the dust particles 12 as they are compacted and interdiffused, and deform to fill the interparticle spaces 15 (Figure 1). Sintering temperatures and pressures can be selected to ensure that the compact density 200 reaches substantially the total theoretical density.
[0074] In an exemplary embodiment as shown in Figures 1 and 9, dispersed particles 214 are formed from particle cores 14 dispersed in the cellular nanomatrix 216 of sintered metal coating layers 16, and nanomatrix 216 includes a solid state metallurgical bond 217 or bonding layer 219, as schematically illustrated in Figure 10, extending between dispersed particles 214 through the entire cell nanomatrix 216 that is formed at a sintering temperature (TS), where TS is less than TC and TP. As indicated, the solid state metallurgical bond 217 is formed in the solid state by solid state interdiffusion between the coating layers 16 of adjacent powder particles 12 which are compressed in touch contact during the compacting and sintering processes used to form compact powder 200, as described herein. As such, the sintered coating layers 16 of cellular nanomatrix 216 include a solid state bonding layer 219 that has a thickness (t) defined by the extent of the interdiffusion of the coating material 20 of the coating layers 16, which in turn , will be defined by the nature of the coating layers 16, 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 sintering and compacting conditions , including the sintering time, temperature and pressure used to form a 200 compact powder.
[0075] As the nanomatrix 216 is formed, including bond 217 and bond layer 219, the chemical composition or phase distribution, or both, of the metal coating layers 16, may change. The nanomatrix 216 also has a melting temperature (TM). As used herein, TM includes the lowest temperature at which incipient melting or liquefaction, or other forms of partial melting, will occur within nanomatrix 216, regardless of whether nanomatrix material 220 comprises a pure metal, a multiphase alloy, each having different melting temperatures or a compound, including a compound comprising a plurality of layers of various coating materials having different melting temperatures, or a combination thereof, or otherwise. As dispersed particles 214 and particle core material 218 are formed in conjunction with nanomatrix 216, diffusion of constituents of metallic coating layers 16 within particle cores 14 is also possible, which can result in changes in chemical composition or phase distribution, or both, of particle cores 14. As a result, dispersed particles 214 and particle core materials 218 may have a melting temperature (TDP) that is different from TP. As used herein, TDP includes the lowest temperature at which incipient melting or liquefaction, or other forms of partial melting, will occur within the dispersed particles 214, regardless of whether particle core material 218 comprises a pure metal, an alloy with phases multiple, each having different melting temperatures or a compound, or otherwise. In one embodiment, compact powder 200 is formed at a sintering temperature (TS), where TS is less than TC, TP, TM and TDP, and sintering is carried out entirely in the solid state, resulting in a state bonding layer solid. In another exemplary embodiment, compact powder 200 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 sintering includes limited or partial melting in the interior of compact powder 200, as described herein, and additionally includes sintering of liquid state or liquid phase, resulting in a bonding layer that is at least partially fused 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 that includes cell nanomatrix 216 and dispersed particles 214. For example, localized liquefaction or fusion may be allowed occur, for example, within all or a portion of nanomatrix 216, considering that the morphology of cell nanomatrix 216 / dispersed particle 214 is preserved, such as by selection of particle cores 14, TS and tS that do not provide complete fusion of particle cores. Similarly, localized liquefaction may be allowed to occur, for example, within all or a portion of the dispersed particles 214, considering that the morphology of the cell nanomatrix 216 / dispersed particle 214 is preserved, such as by selecting the metallic coating layers 16 , TS and tS that do not provide complete melting of the coating layer or layers 16. The melting of the metallic coating layers 16 can, for example, occur during sintering along the interface of the metal layer 16 / particle core 14, or along of the interface between adjacent layers of multilayer coating layers 16. It will be appreciated that combinations of TS and tS that exceed the predetermined values may result in other microstructures, such as an equilibrium fusion / resolving microstructure if, for example, both nanomatrix 216 (i.e., combination of metallic coating layers 16) and dispersed particles 214 (i.e., particle cores 14) are fused, thus allowing rapid interdiffusion of these materials.
[0076] The dispersed particles 214 can comprise any of the materials described herein for particle cores 14, even though the chemical composition of dispersed particles 214 may be different due to the diffusion effects, as described herein. In an exemplary embodiment, dispersed particles 214 are formed of particle cores 14 comprising materials having a standard oxidation potential greater than, or equal to Zn, including Mg, Al, Zn or Mn, or a combination thereof, may include various binary, tertiary and quaternary alloys, or other combinations of these constituents, as disclosed herein, together with the particle cores 14. Of these materials, those having dispersed particles 214 comprising Mg and the nanomatrix 216 formed from the metallic coating materials 16 described here are particularly useful. The scattered particles 214 and Mg, Al, Zn or Mn particle core material 218, or a combination thereof, may also include a rare earth element, or a combination of rare earth elements, as disclosed herein, together with 14 particle cores.
[0077] In another exemplary embodiment, dispersed particles 214 are formed from particle cores 14 comprising metals that are less electrochemically active than Zn, or non-metallic materials. Suitable non-metallic materials include ceramics, glass (for example, cast glass microspheres) or carbon, or a combination thereof, as described herein.
[0078] The dispersed particles 214 of compact powder 200 can have any suitable particle size, including the average particle sizes described herein for particle cores 14.
[0079] The dispersed particles 214 can have any suitable shape depending on the shape selected for particle cores 14 and powder particles 12, as well as the method used to sinter and compact powder 10. In an exemplary embodiment, powder particles 12 can be spheroidal or substantially spheroidal, and the dispersed particles 214 may include an equiaxed particle configuration, as described herein.
[0080] The nature of the dispersion of dispersed particles 214 can be affected by the selection of powder 10 or powders 10 used to produce particle compact 200. In an exemplary embodiment, a powder 10 having a unimodal distribution of powder particle sizes 12 can be selected to form compact powder 200, and will produce a substantially homogeneous unimodal dispersion of particle sizes of dispersed particles 214 within cell nanomatrix 216, as generally illustrated in Figure 9. In another exemplary embodiment, a plurality of powders 10 having a plurality of powder particles with particle cores 14 that have the same core materials 18 and different core sizes, and the same coating material 20, can be selected and uniformly mixed, as described herein, to provide a powder 10 having a multimodal distribution homogeneous powder particle sizes 12, and can be used to form compact powder 200 having a multimodal dispersion the homogeneous particle size of dispersed particles 214 within cell nanomatrix 216, as schematically illustrated in Figures 6 and 11. Similarly, in yet another exemplary embodiment, a plurality of powders 10 having a plurality of particle cores 14 that may have the same core materials 18 and different core sizes, and the same coating material 20, can be selected and distributed in a non-uniform manner to provide a non-homogeneous multimodal distribution of powder particle sizes, and can be used to form compact powder 200 having a non-homogeneous multimodal dispersion of particle sizes of dispersed particles 214 within cell nanomatrix 216, as illustrated schematically in Figure 12. The selection of the particle size distribution can be used to determine, for example, the particle size and interparticle spacing of the scattered particles 214 inside the cellular nanomatrix 216 of compact powders 200 produced from powder 10.
[0081] As generally illustrated in Figures 7 and 13, compact metal powder 200 can also be formed using coated metal powder 10 and an additional or second powder 30, as described herein. The use of an additional powder 30 provides a compact powder 200 which also includes a plurality of second dispersed particles 234, as described herein, which are dispersed within the nanomatrix 216, and are also dispersed with respect to the dispersed particles 214. The second particles Dispersed 234 can be formed of second coated or uncoated powder particles 32, as described herein. In an exemplary embodiment, the second coated powder particles 32 can be coated with a coating layer 36 which is the same as the coating layer 16 of powder particles 12, such that the coating layers 36 also contribute to nanomatrix 216 In another exemplary embodiment, the second particles of powder 232 may be uncoated, such that the second dispersed particles 234 are embedded within nanomatrix 216. As disclosed herein, powder 10 and additional powder 30 can be mixed to form a homogeneous dispersion dispersed particles 214 and second dispersed particles 234, as shown in Figure 13, or to form a non-homogeneous dispersion of these particles, as shown in Figure 14. The second dispersed particles 234 can be formed of any suitable additional powder 30 which is different from powder 10, or due to a compositional difference in particle core 34, or coating layer 36, or both, and may to include any of the materials disclosed herein for use as second powder 30 which are different from powder 10 which is selected to form compact powder 200. In an exemplary embodiment, the second dispersed particles 234 may include Fe, Ni, Co or Cu, or oxides , nitrides, carbides, intermetallic, or ceramic thereof, or a combination of any of the materials mentioned above.
[0082] Nanomatrix 216 is a cellular network of substantially continuous metallic coating layers 16, which are sintered together. The thickness of nanomatrix 216 will depend on the nature of the powder 10 or powders 10 used to form compact powder 200, as well as the incorporation of any second powder 30, particularly the thicknesses of the coating layers associated with these particles. In an exemplary embodiment, the thickness of nanomatrix 216 is substantially uniform across the entire compact powder microstructure 200, and comprises about twice the thickness of the coating layers 16 of powder particles 12. In another exemplary embodiment, the cellular network 216 has a substantially uniform average thickness between dispersed particles 214 of about 50 nm to about 5000 nm.
[0083] Nanomatrix 216 is formed by sintering the metallic coating layers 16 of particles adjacent to each other by interdiffusion and creating a bonding layer 219, as described herein. The metal cladding layers 16 can be single-layer or multilayer structures, and they can be selected to promote or inhibit diffusion, or both, within the layer, or between the layers of the metal cladding layer 16, or between the metal cladding 16 and particle core 14, or between metal cladding layer 16 and metal cladding layer 16 of an adjacent powder particle, the interdiffusion extent of metal cladding layers 16 during sintering may be limited or extensive, depending coating thicknesses, coating material, or selected materials, sintering conditions and other factors. Given the potential complexity of interdiffusion and interaction of constituents, the description of the resulting chemical composition of nanomatrix 216 and nanomatrix material 220 can be simply understood to be a combination of the constituents of coating layers 16 which may also include one or more particulate constituents dispersed particles 214, depending on the extent of interdiffusion, if any, that occurs between dispersed particles 214 and nanomatrix 216. Similarly, the chemical composition of dispersed particles 214 and particle core material 218 can simply be understood to be a combination of the constituents of particle core 14 which may also include one or more constituents of nanomatrix 216 and nanomatrix material 220, depending on the extent of interdiffusion, if any, that occurs between the dispersed particles 214 and nanomatrix 216.
[0084] In an exemplary embodiment, nanomatrix material 220 has a chemical composition, and particle core material 218 has a chemical composition that is different from that of nanomatrix material 220, and differences in chemical compositions can 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 well hole property or condition close to compact 200, including a change of ownership in a well bore fluid that is in contact with compact powder 200, as described here. Nanomatrix 216 can be formed of powder particles 12 having a single layer and multilayer coating layers 16. This design flexibility provides a large number of material combinations, particularly in the case of multilayer coating layers 16, which can be used to house the cell nanomatrix 216 and nanomatrix material composition 220 by controlling the interaction of the constituents of the coating layer, both within a given layer, as well as between a coating layer 16 and the particle core 14 with which it is associated with, or a coating layer 16 of an adjacent powder particle 12. Several exemplary embodiments that demonstrate this flexibility are provided below.
[0085] As shown in Figure 10, in an exemplary embodiment, compact powder 200 is formed of powder particles 12 where the coating layer 16 comprises a single layer, and the resulting nanomatrix 216 between adjacent nano matrices of the plurality of dispersed particles 214 comprises the single metallic coating layer 16 of a powder particle 12, a bonding layer 219 and the single coating layer 16 of another coating layer of the adjacent powder particles 12. The thickness (t) of the bonding layer 219 it is determined by the extent of interdiffusion between the unique metallic coating layers 16, and may involve the full thickness of nanomatrix 216, or only a portion thereof. In an exemplary embodiment of compact powder 200 formed using a single layer powder 10, compact powder 200 may include dispersed particles 214 comprising Mg, Al, Zn or Mn, or a combination thereof, as described herein, and nanomatrix 216 may include Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or an oxide, carbide, nitride, intermetallic, or wax thereof, or a combination of any of the materials mentioned above, including combinations where nanomatrix material 220 of cellular nanomatrix 216, including binding layer 219, has a chemical composition and core material 218 of dispersed particles 214 has a chemical composition that is different from the chemical composition of material nanomatrix 216. The difference in chemical composition of nanomatrix material 220 and core material 218 can be used to provide selectable and controllable dissolution in response to a change in a well bore property, including a well hole, as described here. In a further exemplary embodiment of a compact powder 200 formed of a powder 10 having a single coating layer configuration, dispersed particles 214 include Mg, Al, Zn or Mn, or a combination thereof, and cell nanomatrix 216 includes Al or Ni, or a combination thereof.
[0086] As shown in Figure 15, in another exemplary embodiment, compact powder 200 is formed of powder particles 12 where the coating layer 16 comprises a multilayer coating layer 16 having a plurality of coating layers, and the nanomatrix The resulting 216 between adjacent nano matrices of the plurality of dispersed particles 214 comprises the plurality of layers (t) comprising the coating layer 16 of one particle 12, a bonding layer 219, and the plurality of layers comprising coating layer 16 of another one of the powder particles 12. In Figure 15, this is illustrated with a two-layer metallic coating layer 16, but it will be understood that the plurality of multilayer metallic coating layer layers 16 can include any desired number of layers. The thickness (t) of the bonding layer 219 is again determined by the extent of the interdiffusion between the plurality of layers of the respective coating layers 16, and may involve the total thickness of nanomatrix 216, or only a portion thereof. In this embodiment, the plurality of layers comprising each coating layer 16 can be used to control the interdiffusion and formation of bond layer 219 and thickness (t).
[0087] In an exemplary embodiment of a compact powder 200 produced using powder particles 12 with multilayer coating layers 16, the compact includes dispersed particles 214 comprising Mg, Al, Zn or Mn, or a combination thereof, as described herein , and nanomatrix 216 comprises a cellular network of two-layer sintered coating layers 16, as shown in Figure 3, comprising first layers 22 which are arranged in the dispersed particles 214, and second layers 24 which are arranged in the first layers 22. The first layers 22 include Al or Ni, or a combination thereof, and second layers 24 include Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or a combination of the same. In these configurations, dispersed particle materials 214 and multilayer coating layer 16 used to form nanomatrix 216 are selected so that the chemical compositions of adjacent materials are different (e.g., dispersed particle / first layer and first layer / second layer).
[0088] In another exemplary embodiment of a compact powder 200 produced using powder particles 12 with multilayer coating layers 16, the compact includes dispersed particles 214 comprising Mg, Al, Zn or Mn, or a combination thereof, as described herein. , and nanomatrix 216 comprises a cellular network of sintered three-layer metallic coating layers 16, as shown in Figure 4, comprising first layers 22 which are arranged in the dispersed particles 214, second layers 24 which are arranged in the first layers 22, and third layers 26 which are arranged in second layers 24. The first layers 22 include Al or Ni, or a combination thereof; the second layers 24 include Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or an oxide, nitride, carbide, intermetallic, or wax thereof, or a combination of any of the aforementioned second layer materials; and the third layers include Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or a combination thereof. The selection of materials is analogous to the selection considerations described herein for compact powder 200 produced using two-layer powder coating layers, but it must also be extended to include the material used for the third coating layer.
[0089] In yet another exemplary embodiment of a compact powder 200 produced using powder particles 12 with multilayer coating layers 16, the compact includes dispersed particles 214 comprising Mg, Al, Zn or Mn, or a combination thereof, as herein described, and nanomatrix 216 comprises a cellular network of sintered four-layer coating layers 16 comprising first layers 22 which are arranged in dispersed particles 214; the second layers 24 which are arranged in the first layers 22; the third layers 26 which are arranged in the second layers 24 and the fourth layers 28 which are arranged in the third layers 26. The first layers 22 include Al or Ni, or a combination thereof; second layers 24 include Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or an oxide, nitride, carbide, intermetallic, or wax thereof, or a combination any of the materials of the second layer mentioned above; the third layers include Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or an oxide, nitride, carbide, intermetallic, or wax thereof, or a combination any of the aforementioned third layer materials; and the fourth layers include Al, Mn, Fe, Co or Ni, or a combination thereof. The selection of materials is analogous to the selection considerations described here for compact powders 200 produced using two-layer powder coating layers, but it must also be extended to include the material used for the third and fourth coating layers.
[0090] In another exemplary embodiment of a compact powder 200, the dispersed particles 214 comprise a metal having a lower standard oxidation potential than Zn, or a non-metallic material, or a combination thereof, as described herein, and the nanomatrix 216 comprises a cellular network of sintered metallic coating layers 16. Suitable non-metallic materials include various ceramics, glass or carbon forms, or a combination thereof. Additionally, in compact powders 200 that include dispersed particles 214 comprising these metals or non-metallic materials, nanomatrix 216 can include Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or an oxide, carbide, nitride, intermetallic, or ceramic thereof, or a combination of any of the materials mentioned above as nanomatrix material 220.
[0091] Referring to Figure 16, sintered compact powder 200 may comprise a sintered precursor compact powder 100 that includes a plurality of mechanically bonded, deformed powder particles, as described herein. The precursor compact powder 100 can be formed by compacting the powder 10 to the point that the powder particles 12 are pressed together, thereby deforming them and forming interparticle mechanics or other connections 110 associated with this deformation, sufficient to make with which the deformed powder particles 12 adhere to each other and form a compact powder in the green state having a green density that is less than the theoretical density of a fully dense powder compact 10, due in part to the interparticle spaces 15. Compaction can be carried out, for example, by isostatically pressing powder 10 at room temperature to provide the deformation and interparticle bonding of powder particles 12 necessary to form precursor compact powder 100.
[0092] The sintered and forged compact powders 200 that include dispersed particles 214 comprising Mg and nanomatrix 216 comprising various nanomatrix materials, as described herein, demonstrated an excellent combination of mechanical strength and low density that exemplifies high strength materials, of weight take here revealed. Examples of compact powders 200 having dispersed particles of pure Mg 214 and several nano matrices 216 formed of powders 10 having pure Mg particle cores 14 and several metallic and unique multilayer coating layers 16 that include Al, Ni, W or Al2O3 , or a combination thereof, and which were produced using method 400 disclosed herein, include Al, Ni + Al, W + Al and Al + Al2O3 + Al. These compact powders 200 were subjected to various mechanical tests and other tests, including density test, and their dissolution, and the degradation behavior of mechanical property was also characterized as disclosed herein. The results indicate that these materials can be configured to provide a wide range of selectable and controllable corrosion or dissolution behavior from very low corrosion rates to extremely high corrosion rates, particularly corrosion rates that are both lower and higher than those of compact powders that do not incorporate the cellular nanomatrix, such as a compact formed of pure Mg powder through the same compaction and sintering processes, compared to those that include dispersed particles of pure Mg in the various cell nano matrices described here. These compact powders 200 can also be configured to provide substantially enhanced properties as compared to compact powders formed from pure Mg particles that do not include the nanoscale coatings described herein. For example, compact powders 200 which include dispersed particles 214 comprising Mg and nanomatrix 216 comprising various nanomatrix materials 220 described herein have demonstrated compressive strengths at room temperature of at least about 37 ksi, and have additionally demonstrated compressive strengths at room temperature in excess of about 50 ksi, both dried and immersed in a 3% KCl solution at 200 ° F. In contrast, compact powders formed from pure Mg powders have a compressive strength of about 20 ksi or less. The strength of the nanomatrix 200 compact metal can be further improved by optimizing the powder 10, particularly the weight percentage of the nano scale 16 metal coating layers that are used to form the cell nanomatrix 216. For example, the variation of percentage by weight (weight%), that is, of alumina coating effects, the compressive strength at room temperature of a compact powder 200 of a cellular nanomatrix 216 formed of coated powder particles 12 that includes a multilayer metallic coating layer 16 (Al / Al2O3 / Al) in pure Mg 14 particle cores. In this example, optimum strength is achieved at 4 weight% alumina, which represents a 21% increase as compared to that of 0 weight% alumina.
[0093] Compact powders 200 comprising dispersed particles 214 that include Mg and nanomatrix 216 that includes various nanomatrix materials, as described herein, also demonstrated shear strength at room temperature of at least about 20 ksi. This is in contrast to compact powders formed from pure Mg powders that have shear strengths at an ambient temperature of about 8 ksi.
[0094] Compact powders 200 of the type disclosed herein are capable of reaching a current density that is substantially equal to the predetermined theoretical density of a compact material based on powder composition 10, including relative amounts of particle constituents of particles 14 and the metallic coating layer 16, and are also described herein as being fully dense compact powders. Compact powders 200 comprising dispersed particles that include Mg and nanomatrix 216 that include various nanomatrix materials, as described herein, have demonstrated current densities of about 1.738 g / cm3 to about 2.50 g / cm3, which are substantially equal to the densities predetermined theoretical differences, differing by at least 4% from the predetermined theoretical densities.
[0095] Compact powders 200, as disclosed herein, can be configured to be selectively and controllably dissolvable in a well bore fluid in response to a changed condition in a well bore. Examples of the changed condition that can be exploited to provide selectable and controllable dissolvability include a change in temperature, change in pressure, change in flow rate, change in pH, or change in the chemical composition of well bore fluid, or a combination of these . An example of a changed condition comprising a change in temperature includes a change in the fluid temperature of the well bore. For example, compact powders 200 comprising dispersed particles 214 that include Mg and cellular nanomatrix 216 that includes various nanomatrix materials, as described herein, have relatively low corrosion rates in a 3% KCl solution at room temperature, which varies from about 0 to about 11 mg / cm2 / hour, as compared to relatively high corrosion rates at 200 ° F ranging from about 1 to about 246 mg / cm2 / hour, depending on the different nanoscale coating layers 16. 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 well bore fluid. For example, compact powders 200 comprising dispersed particles 214 that include Mg and nanomatrix 216 that include various nanoscale coatings, described herein, demonstrated corrosion rates at 15% HCl in the range of about 4750 mg / cm2 / hour at about 7432 mg / cm2 / hour. In this way, selectable and controllable dissolvability in response to a changed well hole condition, namely the change in the chemical composition of the well hole fluid from KCl to HCl, can be used to achieve a characteristic response such that in a predetermined critical service time (CST), a changed condition can be imposed under compact 200 as it is applied to a given application, such as a well bore environment, which causes a controllable change in a compact powder property 200 in response to a changed condition in the environment in which it is applied. For example, CST pre-determined which changes a well-hole fluid that is in contact with compact powder 200 from a first fluid (eg KCl) that provides a first corrosion rate and an associated weight loss, or resistance as a function of time to a second wellbore fluid (eg, HCl) that provides a second rate of corrosion and associated weight loss, and resistance as a function of time, in which the rate of corrosion associated with the first fluid is much less than the corrosion rate associated with the second fluid. This characteristic response to a change in well-hole fluid conditions can be used, for example, to associate critical service time with a size loss limit, or the minimum resistance required for a particular application, such that when a well hole tool or component formed from compact powder 200, as disclosed herein, is no longer needed in service at the well hole (for example, CST), the condition in the well hole (for example, the chloride ion concentration of the borehole fluid) can be changed to cause the quick dissolution of compact powder 200 and its removal from the borehole. In the example described above, compact powder 200 is selectively dissolvable at a rate ranging from about 0 to about 7000 mg / cm2 / hour. This response range provides, for example, the ability to remove a 3 inch diameter sphere formed from this material from a well bore by changing the well bore fluid in less than an hour. The selectable and controllable dissolvability behavior described above, coupled with the excellent strength and low density properties described here above, define a new dispersed particle-designed nanomaterial material that is configured to contact a fluid, and configured to provide a selectable transition and controllable from one of a first resistance condition to a second resistance condition that is lower than a functional resistance limit, or a first amount of weight loss to a second amount of weight loss that is greater than one weight loss limit, as a function of time in contact with the fluid. The dispersed particle-nanomatrix compound is characteristic of the compact powders 200 described herein, and includes a cellular nanomatrix 216 of nanomatrix material 220, a plurality of dispersed particles 214 including particle core material 218 that is dispersed within the matrix. The nanomatrix 216 is characterized by a solid state bonding layer 219 that extends through the entire nanomatrix. The time in contact with the fluid described above may include the CST, as described above. The CST can include a predetermined time that is desired or required to dissolve a predetermined portion of the compact powder 200 that is in contact with the fluid. The CST can also include a time corresponding to a change in the property of the designed material or the fluid, or a combination of them. In the case of a change in ownership of the projected material, the change may include a change in a temperature of the projected material. In the case where there is a change in the fluid's property, the change may include a change in a fluid temperature, pressure, flow rate, chemical composition or pH, or a combination thereof. Both the projected material and the change in property of the projected material or the fluid, or a combination thereof, can be housed to provide the desired CST response characteristic, including the rate of change of the particular property (for example, weight loss , loss of resistance) both before CST (for example, Stage 1) and after CST (for example, Stage 2).
[0096] Referring to Figure 17, a method 400 of producing a compact powder 200. Method 400 includes formation 410 of a coated metal powder 10 comprising powder particles 12 having particle cores 14 with metallic nano coating layers scale 16 arranged therein, where the metallic coating layers 16 have a chemical composition, and the particle cores 14 have a chemical composition that is different from the chemical composition of the metallic coating material 16. Method 400 also includes formation 420 of a compact powder by applying a predetermined temperature, and a predetermined pressure to the coated powder particles sufficient to sinter them by solid phase sintering of the coated layers of the plurality of coated particle powders 12, to form a nanomatrix substantially continuous cell surface 216 of a nanomatrix material 220, and a plurality of dispersed particles 214 dispersed within nanomatrix 216, as described here.
[0097] Formation 410 of coated metal powder 10 comprising powder particles 12 having particle cores 14 with nanoscale metal coating layers 16 arranged therein can be carried out by any suitable method. In an exemplary embodiment, formation 410 includes application of the metallic coating layers 16, as described herein, to particle cores 14, as described herein, using fluidized bed chemical vapor deposition (FBCVD), as described herein. The application of the metallic coating layers 16 can include application of metallic single layer coating layers 16, or metallic multilayer coating layers 16, as described herein. The application of the metallic coating layers 16 can also include controlling the thickness of the individual layers as they are being applied, as well as controlling the total thickness of the metallic coating layers 16. The particle cores 14 can be formed, as described herein.
[0098] Formation 420 of compact powder 200 can include any suitable method of forming a compact of fully dense powder 10. In an exemplary embodiment, formation 420 includes dynamic forging of a precursor compact powder of green density 100 to apply a temperature predetermined pressure and a predetermined pressure sufficient to sinter and deform the powder particles, and form a fully dense nanomatrix 216 and dispersed particles 214, as described herein. The dynamic forge, as used herein, means dynamic application of a charge at temperature and for a time sufficient to promote the sintering of the metallic coating layers 16 of adjacent dust particles 12, and may preferably include application of a forge charge. dynamic at a predetermined loading rate for a time, and at a temperature sufficient to form a sintered, fully dense 200 compact powder. In an exemplary embodiment, the dynamic forge includes: 1) heating a precursor or compact state powder green 100 at a predetermined solid phase sintering temperature, such as, for example, a temperature sufficient to promote interdiffusion between metallic coating layers 16 of adjacent powder particles 12; 2) retention of the precursor compact powder 100 at the sintering temperature for a predetermined retention time, such as, for example, a time sufficient to ensure substantial uniformity of the sintering temperature throughout the entire precursor compact 100; 3) forging the precursor compact powder 100 to full density, such as, for example, by applying a predetermined forging pressure according to a predetermined pressure table, or sufficient ramp rate to quickly reach full density, while retaining the compact at the predetermined sintering temperature; and 4) cooling the compact to room temperature. The predetermined pressure and predetermined temperature applied during formation 420 will include a sintering temperature, TS, and the forging pressure, PF, as described herein, which will ensure sintering and solid state deformation of the powder particles 12 to form fully dense compact powder 200, including solid state bond 217 and bond layer 219. The steps of heating and retaining the precursor compact powder 100 at the predetermined sintering temperature for the predetermined time can include any suitable combination of temperature and time, and will depend, for example, on the powder 10 selected, including the materials used for the particle core 14 and metallic coating layer 16, the size of the precursor compact powder 100, the heating method used, and other factors influencing the time required to reach the desired temperature and temperature uniformity inside the precursor compact powder 100. In the forging stage, the pre-pressure The termination can include any suitable pressure and pressure application table, or pressure ramp rate sufficient to achieve a fully dense compact powder 200, and will depend, for example, on the material properties of the selected powder particles 12, including stress characteristics dependent on temperature / stress (eg stress / stress rate characteristics), interdiffusion characteristics and metallurgical thermodynamics and phase balance, displacement dynamics and other material properties. For example, the maximum dynamic forging pressure and the forging table (that is, the pressure ramp rates that correspond to the stress rates employed) can be used to provide the mechanical strength and hardness of the compact. The maximum forging pressure and forging ramp rate (ie stress rate) is the pressure immediately below the compact's fracture pressure, that is, where dynamic recovery processes are unable to relieve stress energy in the compact's microstructure without the formation of a fracture in the compact. For example, for applications that require a compact powder that has relatively higher strength and lower hardness, relatively higher forging pressures and ramp rates can be used. If relatively higher hardness of the compact is required, relatively lower forging pressures and ramp rates can be used.
[0099] For certain exemplary embodiments of powders 10 described herein and compact precursors 100 of a size sufficient to form many well bore tools and components, predetermined retention times of about 1 to about 5 hours can be used. The predetermined sintering temperature, TS, will preferably be selected, as described herein, to avoid melting any particle cores 14 and metallic coating layers 16 as they are transformed during method 400 to provide dispersed particles 214 and nanomatrix 216. For these embodiments, the dynamic forge may include applying a forge pressure, such as by dynamic pressing to a maximum of about 80 ksi at a pressure ramp rate of about 0.5 to about 2 ksi / second .
[00100] In an exemplary embodiment where the particle cores 14 include Mg, and the metallic coating layer 16 includes multiple layers of multilayer and single layer coating, as described herein, such as several multilayer and single bed coatings comprising Al, the dynamic forging was carried out by sintering at a temperature, TS, from about 450 ° C to about 470 ° C for up to about 1 hour without applying a forge pressure, followed by dynamic forging by applying pressures isostatic at ramp rates between about 0.5 to about 2 ksi / second at maximum pressure, Ps, from about 30 ksi to about 60 ksi, which results in forging cycles from 15 seconds to about 120 seconds . The short duration of the forging cycle is a significant advantage as its interdiffusion limit, including interdiffusion within a given metallic cladding layer 16, interdiffusion between adjacent metallic cladding layers 16, and interdiffusion between metallic cladding layers 16 and particle cores 14, those necessary to form metallurgical bond 217 and bond layer 219, while also maintaining the desired dispersed particle shape equiaxied 214 with the integrity of the strengthening phase of the cell nanomatrix 216. The duration of the dynamic forging cycle is much shorter than the forming cycles and sintering times required for conventional compacting processes, such as hot isostatic pressure (HIP), pressure-assisted sintering, or diffusion sintering.
[00101] Method 400 may also optionally include formation 430 of a precursor compact powder by compacting the plurality of coated powder particles 12 sufficiently to deform the particles and form interparticle bonds between them, and to form the precursor compact powder 100 prior to 420 formation of compact powder. Compaction can include pressing, such as isostatic pressing, of the plurality of powder particles 12 at room temperature to form precursor compact powder 100. Compaction 430 can be carried out at room temperature. In an exemplary embodiment, powder 10 may include particle cores 14 comprising Mg, and the formation of the precursor compact powder 430 may be carried out at room temperature at an isostatic pressure of about 10 ksi to about 60 ksi.
[00102] Method 400 may optionally also include intermix 440 of a second powder 30 in powder 10, as described herein, prior to formation 420 of the compact powder, or formation 430 of the precursor compact powder.
[00103] Without being bound by theory, compact powders 200 are formed of coated powder particles 12 which include a particle core 14 and associated core material 18, as well as a metallic coating layer 16 and an associated metallic coating material 20 to form a substantially continuous three-dimensional cell nanomatrix 216, which includes a sintering material nanomatrix 220, and the associated diffusion bond of the respective coating layers 16 which include a plurality of dispersed particles 214 of the particle core material 218. This unique structure can include metastable combinations of materials that would be very difficult or impossible to form by solidifying a melt having the same relative amounts as the constituent materials. Coating layers and associated coating materials can be selected to provide selectable and controllable dissolution in a predetermined fluid environment, such as a well bore environment, where the predetermined fluid can be a well bore fluid commonly used that is either injected into the well bore, or extracted from the well bore. As will be further understood from the description here, the controlled dissolution of the nanomatrix exposes the dispersed particles of the core materials. Particle core materials can also be selected to also provide selectable and controllable dissolution in the well bore fluid. Alternatively, they can also be selected to provide a particular mechanical property, such as compressive strength or shear strength, to compact 200, without necessarily providing selectable and controlled dissolution of the core materials, since the selectable and controlled dissolution of the material nanomatrix that surrounds these particles necessarily release them so that they are transported away by the well bore fluid. The microstructural morphology of the substantially continuous cellular nanomatrix 216, which can be selected to provide a strengthening phase material, with dispersed particles 214, which can be selected to provide equiaxed dispersed particles 214, provides these compact powders with enhanced mechanical properties, including strength compressive strength and shear resistance, since the morphology resulting from the nanomatrix / dispersed particles can be manipulated to provide strengthening through processes that are comparable to traditional strengthening mechanisms, such as reducing grain size, hardening the solution through the use of atoms impurity, precipitation or age hardening and operating resistance / hardening mechanisms. The dispersed nanomatrix / particle structure tends to limit the displacement movement due to the numerous particle nanomatrix interfaces, as well as interfaces between discrete layers within the nanomatrix material, as described herein. This is exemplified by the fracture behavior of these materials. A compact powder 200 produced using pure uncoated Mg powder, and subjected to sufficient shear stress to induce failure, demonstrates intergranular fracture. In contrast, a compact powder 200 produced using powder particles 12 having pure Mg powder particle cores 14 to form dispersed particles 214, and metallic coating layers 16 that include Al to form nanomatrix 216 and subjected to sufficient shear stress to induce failure, they demonstrate transgranular fracture and substantially higher fracture stress, as described here. Because these materials have high strength characteristics, the core material and coating material can be selected to use low density materials, or other low density materials, such as low density metals, ceramics, glass or carbon, which, otherwise, they would not provide the strength characteristics necessary for use in the desired applications, including well hole tools and components.
[00104] Referring to Figure 18, a method 500 of producing selectively corrosive articles 502 from the materials described herein, including powders 10, precursor compact powders 100, and compact powders 200, is disclosed. Method 500 includes forming 510 of a powder 10 comprising a plurality of metal powder particles 12, each metal powder particle comprising a nanoscale metal coating layer 16 arranged in a particle core 14, as described herein. Method 500 also includes forming 520 of a compact powder 522 of the powder particles 10, wherein the powder particles 512 of the compact powder 522 are substantially elongated in a predetermined direction 524 to form substantially elongated powder particles 512. In a In this embodiment, the coating layers 516 of the substantially elongated particles 512 are substantially discontinuous in the predetermined direction 524. By substantially discontinuous, it is significant that the elongated coating layers 516 and elongated particle cores 514 can be elongated, including being thinned, to the point that the elongated coating layers 516 (lighter particle phase), elongated particle cores 514 (darker phase), or a combination thereof, become separated or fractured or otherwise discontinuous in the pre- determined 524, or stretching direction, as shown in Figure 19, which is a photomicrograph of a cross section of a powder compact 522 parallel to the predetermined direction 524. Figure 19 reveals the substantially discontinuous nature of the coating layers 516 along the predetermined direction 524. This microstructure of articles 502, having this substantially discontinuous coating layer structure 16, can it may also be described, alternatively, as an extruded structure comprising a matrix of particle core material 18 having particles uniformly dispersed from the coating layer 16 dispersed therein. The coating layers 516 can also retain some continuity, such that they can be substantially continuous perpendicular to the predetermined direction 524, similar to the microstructure shown in Figure 9. However, Figure 20, which is a photomicrograph of a cross section of a compact powder 522 approximately perpendicular or transversal to the predetermined direction 524, reveals that the coating layers 516 can also be substantially discontinuous perpendicular to the predetermined direction 524. The nature of the elongated metal layers 516, including whether they are substantially continuous or discontinuous , and both the predetermined direction 524, or in a transversal direction thereto, will generally be determined by the amount of deformation or elongation afforded to compact 522, including the reduction ratio employed, with higher elongation ratios resulting in more deformation , resulting in an elongated discontinuous metallic layer 516 in the direction the predetermined, or transversal to this, or both.
[00105] It will be understood that while the structure described above has been described with reference to the substantially elongated particles 512, that the compact powder 522 comprises a plurality of substantially elongated particles 512 which are joined together, as described herein, to form a network of substantially elongated interconnected particles 512 that define a substantially elongated cellular nanomatrix 616 comprising a network of interconnected elongated cells of nanomatrix material 616 having a plurality of substantially elongated dispersed particle nuclei 614 of nucleus material 618 arranged within the cells. Depending on the amount of deformation allowed to form elongated particles 512, the elongated coating layers and the nanomatrix can be substantially continuous in the predetermined direction 524, as shown in Figure 21, or substantially discontinuous, as shown in Figure 22.
[00106] Referring again to Figures 18 and 23, the formation 520 of the compact powder 522 of the powder particles 12 can be carried out by directly extruding 530 of a powder 10 comprising a plurality of powder particles 12. The extrusion 530 can be performed by forcing powder 10 and powder particles 12 through an extrusion mold 526, as shown schematically in Figure 23 to cause the consolidation and elongation of elongated particles 512 and formation of compact powder 522. Compact powder 522 can be consolidated to substantially total theoretical density based on the composition of the powder 10 employed, or less than the total theoretical density, including any predetermined percentage of the theoretical density, including about 40 percent to about 100 percent of the theoretical density, and, more particularly, about 60 percent to about 98 percent of theoretical density, and, more particularly, about 75 percent to about 95 percent of theoretical density. Additionally, compact powder 522 can be sintered such that the elongated particles 512 are bonded together with metallic or chemical bonds, and are characterized by interdiffusion between adjacent particles 512, including their adjacent elongated metal layers 516, or can be non-sintered, such that the extrusion is carried out at an ambient temperature, and the elongated particles 512 are bonded together with mechanical bonds and intermixing associated with mechanical deformation and elongation of the elongated particles 512.
[00107] Sintering can be performed by heating the extrudate. In one embodiment, heating can be performed during extrusion by preheating the particles before extrusion, or alternatively, heating them during extrusion using a heating device 536, or a combination thereof. In another embodiment, sintering can be carried out by heating the extrudate after extrusion using any suitable heating device. In yet another embodiment, sintering can be carried out by heating the particles before, or heating the extrudate during or after extrusion, or any combination of the above. Heating can be carried out at any suitable temperature, and will generally be selected to be lower than a critical recrystallization temperature, and, more particularly, below a dynamic recrystallization temperature, of the elongated particles 512, in order to maintain operation and avoid grain recovery and growth within the deformed microstructure. However, in certain embodiments, heating can be carried out at a temperature that is higher than a dynamic recrystallization temperature of an alloy formed by melting having the same total composition as the constituents, considering that it does not result in current recrystallization of the microstructure. comprising the substantially elongated grains. Without being bound by theory, this may be related to the particle core / structure of the nanomatrix, in which the constituents of the coating layer are distributed like the nanomatrix having dispersed particles, preferably than an alloy microstructure formed by melting where the constituents comprising the coating layers can all be distributed differently due to the solubility of the coating layer material in the particle core material. This may also result because the process of hardening the dynamic deformation occurs more quickly than that of dynamic recrystallization, such that the strength of the material preferably increases rather than decreases even though the formation 520 is carried out above the recrystallization temperature of an alloy formed by fusion having the same amounts of constituents. The critical recrystallization temperature will depend on the amount of deformation introduced and other factors. In certain embodiments, including compact powders 522 formed of powder particles 12 comprising several Mg or Mg 14 particle cores, heating during formation 520 can be carried out at a forming temperature of about 300 ° F to about 1000 ° F, and, more particularly, about 300 ° F to about 800 ° F, and, even more particularly, about 500 ° F to about 800 ° F. In certain other embodiments, the formation can be carried out at a temperature, which is less than a melting temperature of the compact powder, such as extruded, and which can include a temperature which is less than TC, TP, TM or TDP as described here. In other embodiments, the formation can be carried out at a temperature that is about 20 ° C to about 300 ° C below the melting temperature of the compact.
[00108] In one embodiment, extrusion 530 can be performed according to a predetermined reduction ratio. Any suitable predetermined reduction ratio can be employed, which, in one embodiment, can comprise a ratio of an initial thickness (ti) of the particles to a final thickness (tf), or ti / tf, and, in other embodiments, it can comprise a ratio of an initial length (li) of the particles to a final length (lf), or li / lf. In one embodiment, the ratio can be about 5 to about 2000, and, more particularly, it can be about 50 to about 2000, and, even more particularly, about 50 to about 1000. Alternatively, in other embodiments , the reduction ratio can be expressed as an initial thickness (ti) of the extrusion mold cavity to a final thickness (tf), or ti / tf, and in another embodiment, it can comprise a ratio of an initial cross-sectional area (ai) from the mold cavity to an area of final cross section (af), or ai / af.
[00109] Referring to Figures 18 and 24, while formation 520 of compact powder 522 can be performed by directly extruding 530 of powder 10 as described above, in other embodiments, formation 520 of compact powder 522 may include compaction 540 of powder 10 and powder particles 12 in an ingot 542, and deformation 550 of the ingot 542, to provide a compact powder 522 having elongated powder particles 512, as described herein. Ingot 542 may include a precursor compact powder 100 or a compact powder 200, as described herein, which may be formed by compaction 540, according to the methods described herein, including cold pressing (uniaxial pressing), isostatic hot pressing, cold isostatic pressing, extrusion, cold rolling formation, hot rolling formation, or forging, to form ingot 542. In one embodiment, extrusion 540 compaction may include a sufficient reduction ratio, as described herein, to consolidating the powder particles 12 and forming the ingot 542 without substantially elongated powder particles 512 formation. This may include extrusion at lower reduction ratios than those effective to form elongated particles 512, such as reduction ratios less than about 50, and in other embodiments, less than about 5. In another embodiment, the extraction compaction 540 to form ingot 542 may be sufficient to form partially substantially elongated powder particles 512. This may include extrusion at reduction ratios greater than or equal to those effective to form elongated particles 512, such as reduction ratios greater than or equal to about 50, and, in other embodiments , greater than or equal to about 5, where the deformation associated with compaction 540 is followed by additional deformation associated with deformation 550 of ingot 542.
[00110] Deformation 550 of ingot 542 can be performed by any suitable deformation method. Suitable deformation methods can include extrusion, hot rolling, cold rolling, drawing or stamping, or a combination thereof, for example. The formation 550 of the ingot 542 can also be carried out according to a predetermined reduction ratio, including the predetermined reduction ratios described herein.
[00111] In certain embodiments, compact powders 522 having substantially elongated powder particles 512 formed according to method 500, as described herein, have a strength, particularly a final compressive strength, which is greater than the precursor compact powder 100, or compact powder 200 formed using the same powder particles. For example, +100 mesh spherical powder particles 12 having a pure Mg particle core 14 and a coating layer 16 comprising, by particle weight, a 9% pure Al layer disposed in the particle core, followed by a layer of 4% alumina disposed in pure Al and a layer of 4% Al disposed in alumina exhibited a final compressive strength greater than ingots 542 comprising precursor compact powders 100 and compact powders 200 described herein, including those formed by dynamic forging , as described herein, which generally has an equiaxed arrangement of cell nanomatrix 216 and dispersed particles 214. In one embodiment, compact powders 522 having substantially elongated powder particles 512 of Mg / Al / Al2O3 / Al, as described, have an elastic modulus up to about 5.1 x106 psi, and final compressive strengths greater than about 50 ksi, and, more particularly, greater than about 60 ksi, and, even more particularly, up to about 76 k itself, as shown in Figure 25, as well as compressive performance resistances up to about 46 ksi. These compact powders 522 also exhibit higher rates of corrosion in predetermined well bore fluids than ingots 542 comprising precursor compact powders 100 and compact powders 200, described herein. In one embodiment, compact powders 522 having substantially elongated powder particles 512 of Mg / Al / Al2O3 / Al, as described, have corrosion rates in a 3% aqueous solution of potassium chloride in water at 200 ° F up to about of 2.1 mg / cm2 / hour, as compared to a compact 200 corrosion rate of the same powder of about 0.2 mg / cm2 / hour. In another embodiment, compact powders 522 having substantially elongated powder particles 512 of Mg / Al / Al2O3 / Al, as described, have corrosion rates of 5-15% by volume of HCl greater than about 7,000 mg / cm2 / hour, including a corrosion rate greater than about 11,000 in 15% HCl.
[00112] The 500 method described can be used to form various alloys, as described herein, in various forms, including ingots, bars, rods, plates, tubulars, plates, wires, and other forms of stock, which can in turn , be used to form a wide variety of articles 502, particularly a wide variety of downhole articles 580, and, more particularly, various tools and downhole components. As shown in Figures 26 and 27, exemplary embodiments include several balls 582, including several diverter balls; 584 plugs, including various cylindrical and disk-shaped plugs; tubular 586; gloves 588, including gloves 588 used to provide multiple seats 590, such as a ball seat 592 and the like, for downhole use and application to a well hole 594. Articles 580 can be designed to be used anywhere at the bottom of the well, including inside the tubular metal housing 596, or inside the cement liner 598, or inside the well hole 600, and can be used permanently, or can be designated to be selectively removable, as described herein, in response to a predetermined well bore condition, such as exposure to a predetermined temperature, or predetermined well bore fluid.
[00113] While one or more embodiments have been shown and described, modifications and substitutions can be made to these without departing from the spirit and scope of the invention. Consequently, it is to be understood that the present invention has been described by way of illustration and not limitation.

权利要求:
Claims (27)
[0001]
1. Compact powder metal (200) characterized by comprising: a substantially elongated cellular nanomatrix (216) comprising a nanomatrix material (220); a plurality of substantially elongated dispersed particles (214) comprising a particulate core material (218) comprising Mg, Al, Zn or Mn, or a combination thereof, dispersed in the cellular nanomatrix (216); and a solid state bonding layer (219) formed by solid-state bonding that extends across the entire cell nanomatrix (216) between adjacent dispersed particles, wherein the cell nanomatrix (216) and the dispersed particles are substantially elongated in a predetermined direction to a point where the cell nanomatrix (216), dispersed particles and the solid state bonding layer (219) are substantially continuous in the predetermined direction or to a point where the nanomatrix and the dispersed particles are they separate, break or are otherwise substantially discontinuous in the predetermined direction.
[0002]
2. Compact powder metal (200) according to claim 1, characterized by the fact that the substantially elongated nanomatrix and the dispersed particles exhibit a predetermined reduction ratio.
[0003]
3. Compact powder metal (200) according to claim 2, characterized by the fact that the predetermined reduction ratio is from 5 to 2000.
[0004]
4. Compact powder metal (200) according to claim 3, characterized by the fact that the predetermined reduction ratio is from 50 to 1000.
[0005]
5. Compact powder metal (200) according to claim 1, characterized by the fact that the particulate core material comprises Mg-Zn, Mg-Zn, Mg-Al, Mg-Mn, Mg-Zn-Y , or an Mg-Al-X alloy, wherein X comprises Zn, Mn, Si, Ca or Y, or a combination thereof.
[0006]
6. Compact powder metal (200) according to claim 1, characterized in that the dispersed particles additionally comprise a rare earth element.
[0007]
7. Compact powder metal (200) according to claim 1, characterized in that the compact powder is formed from a compact precursor that has dispersed particles with an average particle size from 50 nm to 500 μm.
[0008]
Compact metal powder (200) according to claim 1, characterized in that the dispersion of dispersed particles comprises a substantially homogeneous dispersion within the cellular nanomatrix (216).
[0009]
Compact metal powder (200) according to claim 1, characterized in that the dispersion of dispersed particles comprises a multimodal distribution of particle sizes within the cell nanomatrix (216).
[0010]
Compact metal powder (200) according to claim 1, characterized in that it further comprises a plurality of second substantially elongated dispersed particles, wherein the second dispersed particles are also dispersed within the cellular nanomatrix (216) and in relation to the dispersed particles, and in which the second dispersed particles comprise Fe, Ni, Co or Cu, or oxides, nitrides, carbides, intermetallic or ceramics thereof, or a combination of any of the materials previously mentioned.
[0011]
11. Compact powder metal (200) according to claim 1, characterized by the fact that the nanomatrix material (220) comprises Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or an oxide, carbide, nitride, intermetallic or ceramic of the same, or a combination of any of the materials mentioned above, in which the nanomatrix material (220) has a chemical composition and the material particulate core (218) has a chemical composition that is different from the chemical composition of the nanomatrix material (220).
[0012]
Compact metal powder (200) according to claim 1, characterized in that the particulate core material (218) comprises pure Mg and has a final compressive strength of at least 50 ksi.
[0013]
13. Compact powder metal (200) according to claim 1, characterized in that the compact is formed from a sintered powder comprising a plurality of powder particles, each powder particle having a particulate core which, after sintering, comprises a dispersed particle and a single metallic coating layer located on it and where the cellular nanomatrix (216) between adjacent nanomatrices of the plurality of dispersed particles (214) comprises the unique metallic coating layer of a powder particle, the bonding layer (219) and the unique metallic coating layer of another of the powder particles.
[0014]
14. Compact powder metal (200) according to claim 13, characterized in that the dispersed particles comprise Mg and the cellular nanomatrix (216) comprises Al or Ni, or a combination thereof.
[0015]
15. Compact powder metal (200), characterized by comprising: a substantially elongated cellular nanomatrix (216) comprising a nanomatrix material (220); a plurality of substantially elongated dispersed particles (214) comprising a particulate core material (218) comprising Mg, Al, Zn or Mn, or a combination thereof, dispersed in the cellular nanomatrix (216); and a bonding layer (219) that extends throughout the cellular nanomatrix (216) between the dispersed particles, in which the cellular nanomatrix (216) and the dispersed particles are substantially elongated in a predetermined direction and in which the nanomatrix and the scattered particles are elongated in the predetermined direction to the point where the nanomatrix and the scattered particles become separated, broken or otherwise substantially discontinuous in the predetermined direction.
[0016]
16. Compact powder metal (200) according to claim 15, characterized in that the substantially discontinuous nanomatrix and the dispersed particles comprise substantially discontinuous chains of nanomatrix material (220) and particulate core material (218) , respectively, oriented in the predetermined direction.
[0017]
17. Compact powder metal (200), characterized by comprising: a substantially elongated cellular nanomatrix (216) comprising a nanomatrix material (220); a plurality of substantially elongated dispersed particles (214) comprising a particulate core material (218) comprising Mg, Al, Zn or Mn, or a combination thereof, dispersed in the cellular nanomatrix (216); and a bonding layer (219) that extends across the cell nanomatrix (216) between the dispersed particles, wherein the cell nanomatrix (216) and the dispersed particles are substantially elongated in a predetermined direction, and where the compact is formed from a sintered powder comprising a plurality of powder particles, each powder particle having a particle core which, after sintering, comprises a dispersed particle and a plurality of metallic coating layers located thereon, and in that the cellular nanomatrix (216) between adjacent cellular nanomatrixes of the plurality of dispersed particles (214) comprises the plurality of metallic coating layers of a powder particle, the bonding layer (219) and plurality of metallic coating layers of other particles powder particles, and wherein cellular nanomatrixes adjacent to the plurality of metallic coating layers have different chemical compositions.
[0018]
18. Compact powder metal (200) according to claim 17, characterized in that the plurality of layers comprises a first layer (22) that is located on the particulate core and a second layer (24) that is located on the first layer (22).
[0019]
19. Compact powder metal (200) according to claim 18, characterized in that the dispersed particles comprise Mg and the first layer (22) comprises Al or Ni, or a combination thereof, and the second layer ( 24) comprises Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or a combination thereof, in which the first layer (22) has a chemical composition that it is different from the chemical composition of the second layer (24).
[0020]
20. Compact powder metal (200) according to claim 19, characterized in that it further comprises a third layer (26) which is located on the second layer (24).
[0021]
21. Compact powder metal (200) according to claim 20, characterized in that the first layer (22) comprises Al or Ni, or a combination thereof, the second layer (24) comprises Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or an oxide, nitride, carbide, intermetallic or ceramic thereof, or a combination of any of the materials of the second layer ( 24) previously mentioned and the third layer (26) comprises Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or a combination thereof, in which the second layer (24) has a chemical composition that is different from the chemical composition of the third layer (26).
[0022]
22. Compact powder metal (200) according to claim 21, characterized in that it further comprises a fourth layer (28) which is located on the third layer (26).
[0023]
23. Compact powder metal (200) according to claim 22, characterized in that the first layer (22) comprises Al or Ni, or a combination thereof, the second layer (24) comprises Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or an oxide, nitride, carbide, intermetallic or ceramic thereof, or a combination of any of the materials of the second layer ( 24) previously mentioned, the third layer (26) comprises Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or an oxide, nitride or carbide thereof, or a combination of any of the aforementioned third layer materials (26), and the fourth layer (28) comprises Al, Mn, Fe, Co or Ni, or a combination thereof, wherein the second layer (24) has a chemical composition that is different from the chemical composition of the third layer (26) and the third layer (26) has a chemical composition that is different from the chemical composition of the fourth layer (28).
[0024]
24. Compact powder metal (200) characterized by comprising: a substantially elongated cellular nanomatrix (216) comprising a nanomatrix material (220); a plurality of substantially elongated dispersed particles (214) comprising a particulate core material (218) comprising a metal that has a lower standard oxidation potential than Zn, ceramic, glass, or carbon, or a combination thereof , dispersed in the cellular nanomatrix (216); and a solid state bonding layer (219) formed by solid-state bonding that extends across the entire cell nanomatrix (216) between adjacent dispersed particles, wherein the cell nanomatrix (216) and the dispersed particles are substantially elongated in a predetermined direction to the point where the cell nanomatrix (216), scattered particles and solid state bonding layer (219) are substantially continuous in the predetermined direction.
[0025]
25. Compact powder metal (200) according to claim 24, characterized by the fact that the nanomatrix material (220) comprises Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or an oxide, carbide, nitride, intermetallic or ceramic of the same, or a combination of any of the materials mentioned above, in which the nanomatrix material (220) has a chemical composition and the material the core has a chemical composition that is different from the chemical composition of the nanomatrix material (220).
[0026]
26. Compact powder metal (200), characterized by comprising: a substantially elongated cellular nanomatrix (216) comprising a nanomatrix material (220); a plurality of substantially elongated dispersed particles (214) comprising a particulate core material (218) comprising a metal that has a lower standard oxidation potential than Zn, ceramic, glass or carbon, or a combination thereof, dispersed in the cellular nanomatrix (216); and a bonding layer (219) that extends throughout the cellular nanomatrix (216) between the dispersed particles, in which the cellular nanomatrix (216) and the dispersed particles are substantially elongated in a predetermined direction, in which the nanomatrix and the scattered particles are elongated in the predetermined direction to a point where the nanomatrix and the scattered particles become separated, broken or otherwise substantially discontinuous in the predetermined direction.
[0027]
27. Compact powder metal (200) according to claim 26, characterized in that the substantially discontinuous nanomatrix and the dispersed particles comprise substantially discontinuous chains of nanomatrix material (220) and particulate core material (218) , respectively, oriented in the predetermined direction.

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同族专利:

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公开号 | 公开日

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CN103688012B|2017-07-28|

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AP2014007388A0|2014-01-31|

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BR112014001741A2|2017-02-21|

---

AU2012290576B2|2016-12-08|

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US9243475B2|2016-01-26|

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AU2012290576A1|2014-01-16|

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WO2013019421A3|2013-04-18|

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US20130025409A1|2013-01-31|

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WO2013019421A2|2013-02-07|

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EP2737156A2|2014-06-04|

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CA2841132A1|2013-02-07|

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CN103688012A|2014-03-26|

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EP2737156A4|2016-01-20|

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CA2841132C|2016-09-13|

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法律状态:
2018-12-11| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|

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2019-10-29| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

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2020-05-26| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|

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2020-09-01| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

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2020-12-01| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 19/07/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

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申请号 | 申请日 | 专利标题

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US13/194,361|US9243475B2|2009-12-08|2011-07-29|Extruded powder metal compact|

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US13/194,361|2011-07-29|

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PCT/US2012/047379|WO2013019421A2|2011-07-29|2012-07-19|Extruded powder metal compact|

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