COMPACT COMPOSITE ENGINEERING POWDER MATERIAL

专利摘要:
engineering powder composite material. The present invention relates to a dispersed particle cellular nanomatrix composite material, which is configured to be in contact with a fluid and configured to provide a selectable and controllable transition from a first resistance condition to a second resistance condition which is lower than a functional endurance threshold, or to provide a first weight loss value for a second weight loss value that is greater than a weight loss threshold, as a function of a time in contact with the fluid.
公开号:BR112012013673B1
申请号:R112012013673-9
申请日:2010-12-07
公开日:2021-06-01
发明作者:Zhiyue Xu；Gaurav Agrawal
申请人:Baker Hughes Incorporated；
IPC主号:

专利说明:

CROSS REFERENCE TO RELATED PATENT APPLICATIONS
[001] This patent application claims the benefit of the filing date of patent application serial number US 12/633,678, filed on December 8, 2009, entitled "ENGINEERED POWDER COMPACT COMPOSITE MATERIAL". BACKGROUND OF THE INVENTION
[002] Oil and natural gas wells often use wellbore or drill string components (tools), which, due to their function, need to have only a limited useful life which is considerably less than the useful life of the well. After the service function of the component or tool is exhausted, it must be removed or discarded to recover the original size of the fluid passage for use, including hydrocarbon production, CO2 sequestration, etc. Disposal of components or tools has been conventionally done by crushing or drilling the component or tool out of the wellbore, which are usually time-consuming and costly operations.
[003] To eliminate the need for crushing or drilling operations, it has been proposed to remove components or tools by dissolving degradable polylactic polymers using various wellbore fluids. However, these polymers generally do not have the mechanical strength, fracture toughness, and other mechanical properties necessary to perform the functions of wellbore components or tools over the entire wellbore operating temperature range, and therefore their application presents been limited.
[004] Other degradable materials have been proposed, including certain degradable metal alloys formed from certain metals reactive in a major part, such as aluminum, along with other alloy constituents in a minor part, such as gallium, indium, bismuth, tin and mixtures and combinations thereof, and not excluding certain secondary alloying elements, such as zinc, copper, silver, cadmium, lead, and mixtures and combinations thereof. These materials can be formed by melting powders from the constituents and then solidifying the molten material to form the alloy. They can also be formed using powder metallurgy by pressing, compacting, sintering, and similar procedures, a mixture of powders of a reactive metal and another alloy constituent in the amounts mentioned. These materials include many combinations that utilize metals, such as lead, cadmium, and the like, which may not be suitable for release to the environment in conjunction with material degradation. In addition, their formation may involve various melting phenomena that result in alloy structures that are dictated by the phase balances and solidification characteristics of the respective alloy constituents, and that may not result in optimal or desirable alloy microstructures, as well as their mechanical properties or dissolution characteristics.
[005] Therefore, the development of materials that can be used to form wellbore components and tools that have the necessary mechanical properties to perform their intended function, and then removed from the wellbore by controlled dissolution using wellbore fluids , it is very desirable. SUMMARY OF THE INVENTION
[006] An exemplary embodiment of an engineered composite material with cellular nanomatrix of dispersed particles is described. The engineered composite material with dispersed particle cellular nanomatrix is configured to contact a fluid and configured to provide a selectable and controllable transition from a first strength condition to a second strength condition that is lower than a limit of functional strength, or from a first weight loss value to a second weight loss value that is greater than a weight loss threshold, as a function of time in contact with the fluid. BRIEF DESCRIPTION OF THE DRAWINGS
[007] Referring now to the drawings in which similar elements are numbered similarly in the various Figures:
[008] Figure 1 is a photomicrograph of a powder 10 described herein that was embedded in an epoxy material for mounting a specimen and sectioned;
[009] 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 2-2 of Figure 1;
[0010] Figure 3 is a schematic illustration of a second exemplary embodiment of a powder particle 12 as it would appear in a second exemplary sectional view represented by section 2-2 of Figure 1;
[0011] 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;
[0012] Figure 5 is a schematic illustration of a fourth exemplary embodiment of a powder particle 12 as it would appear in an exemplary fourth sectional view represented by section 2-2 of Figure 1;
[0013] Figure 6 is a schematic illustration of a second exemplary embodiment of a powder described herein having a multimodal particle size distribution;
[0014] Figure 7 is a schematic illustration of a third exemplary embodiment of a powder described herein having a multimodal particle size distribution;
[0015] Figure 8 is a flowchart of an exemplary embodiment of a method for manufacturing a powder described herein:

[0016] Figure 9 is a photomicrograph of an exemplary embodiment of a powder compact described herein;
[0017] Figure 10 is a schematic illustration of an exemplary embodiment of the powder compact of Figure 9 manufactured using a powder having powder particles coated with a single layer as it would appear if captured along section 10-10;
[0018] Figure 11 is a schematic illustration of an exemplary embodiment of a powder compact described herein that exhibits a homogeneous multimodal distribution of particle sizes;
[0019] Figure 12 is a schematic illustration of an exemplary embodiment of a powder compact described herein that exhibits an inhomogeneous multimodal distribution of particle sizes;
[0020] Figure 13 is a schematic illustration of an exemplary embodiment of a powder compact described herein formed from a first powder and a second powder, and having a homogeneous multimodal distribution of particle sizes;
[0021] Figure 14 is a schematic illustration of an exemplary embodiment of a powder compact described herein formed from a first powder and a second powder, and having an inhomogeneous multimodal distribution of particle sizes;
[0022] Figure 15 is a schematic illustration of another exemplary embodiment of the powder compact of Figure 9 manufactured using a powder having powder particles coated with multiple layers as would appear if captured along section 10-10;
[0023] Figure 16 is a schematic cross-sectional illustration of an exemplary embodiment of a precursor powder compact;
[0024] Figure 17 is a flowchart of an exemplary embodiment of a method for manufacturing a powder compact described herein:

[0025] Figure 18 is a table describing the particle core and metallic coating layer configurations for powder particles and powders used to manufacture exemplary embodiments of test powder compacts as described herein:

[0026] Figure 19 is a plot of the compressive strength of the powder compacts of Figure 18 dried and in an aqueous solution comprising 3% KCl;
[0027] Figure 20 is a plot of the corrosion rate (ROC) of the powder compacts of Figure 18 in an aqueous solution comprising 3% KCl at 93 oC (200 oF) and at room temperature;
[0028] Figure 21 is a plot of the ROC of the powder compacts of Figure 18 in 15% HCl;
[0029] Figure 22 is a schematic illustration of a change in a property of a powder compact described herein as a function of time and a change in the environmental condition of the powder compact;
[0030] Figure 23 is an electron photomicrograph of a fracture surface of a powder compact formed from a pure Mg powder;
[0031] Figure 24 is an electron photomicrograph of a fracture surface of an exemplary embodiment of a metal powder compact described herein; and
[0032] Figure 25 is a plot of the compressive strength of a powder compact as a function of the amount of a constituent (Al2O3) of the cellular nanomatrix. DETAILED DESCRIPTION OF THE INVENTION
[0033] High-strength lightweight metallic materials that can be used in a wide range of applications and application environments are described, including use in various downhole environments to manufacture various lightweight, high-strength, disposable, downhole tools or selectable and controllable degradable or other downhole components, as well as many other applications for use in durable and also disposable or degradable articles. These lightweight, high-strength, selectable and controllable degradable materials include fully dense sintered powder compacts formed from coated powder materials that include multiple light particle cores and core materials that feature multiple coatings at scale on the scale. single-layer and multi-layer. These powder compacts are manufactured from coated metallic powders that include various electrochemically active high strength light particle core and core materials (eg, having relatively higher standard oxidation potentials), such as electrochemically active metals. , which are dispersed within a cellular nanomatrix formed from several nanoscale metallic coating layers of metallic coating materials, and are particularly useful in wellbore applications. These powder compacts provide a unique and advantageous combination of mechanical strength properties such as compressive and shear strength, low density and selectable and controllable corrosion properties, particularly fast and controlled dissolution in various wellbore fluids. For example, the particle core and coating layers of these powders can be selected to produce sintered powder compacts suitable for use as high strength engineered materials that exhibit compressive strength and shear strength comparable to many other engineered materials, including carbon steels, stainless steels and alloy steels, but which also have a low density comparable to various polymers, elastomers, porous low density ceramics and composite materials. As yet another example, these powders and powder compact materials can be configured to provide selectable or controllable degradation or disposal in response to a change in an environmental condition, such as a transition from a very slow dissolution rate to a very slow dissolution rate. of very rapid dissolution in response to a change in a property or condition of a wellbore close to an article formed from the compact, including a property change in a wellbore fluid that comes in contact with the powder compact . The selectable or controllable degradation or disposal characteristics described also enable the dimensional stability and strength of items, such as tools or other wellbore components, manufactured from these materials, to be maintained until they are no longer needed, and in this At this time a predetermined environmental condition, such as a wellbore condition, including the temperature, pressure, or pH value of the wellbore fluid, can be changed to promote its removal by rapid dissolution. These powder coated and compact powder materials and the engineered materials formed from them, as well as the methods for making them, are further described below.
[0034] Referring to Figures 1-5, a metallic powder 10 includes a plurality of coated metallic powder particles 12. The powder particles 12 can be formed to produce a powder 10, including a free-flowing powder, which can be poured or otherwise arranged in any shapes or molds (not shown), having any shapes and sizes and which can be used to model compacts of powder precursors 100 (Figure 16) and powder compounds 200 (Figures 10-15), such as described herein, which can be used or for use in the fabrication of various fabricated articles, including various wellbore tools and components.
[0035] Each of the powder coated metal powder particles 12 10 includes a particle core 14 and a metal coating layer 16 disposed over the particle core 14. The particle core 14 includes a core material 18. The core material 18 can include any material suitable for forming the core of the particle 14 which produces the powder particle 12 which can be sintered to form a high strength lightweight powder compact 200 having selectable and controllable dissolution characteristics. Suitable core materials include electrochemically active metals that exhibit standard oxidation potential greater than or equal to that of Zn, including Mg, Al, Mn or Zn or a combination thereof. These electrochemically active metals are very reactive with many common wellbore fluids, including many ionic fluids or highly polar fluids such as those that contain many chlorides. Examples include fluids comprising potassium chloride (KCl), hydrochloric acid (HCl), calcium chloride (CaCl2), calcium bromide (CaBr2) or zinc bromide (ZnBr2). The core material 18 can 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, composites, glass or carbon, or a combination thereof. The core material 18 can be selected to provide a high dissolution rate in a predetermined wellbore fluid, but can also be selected to provide a relatively low dissolution rate, including zero dissolution, where dissolution of the material from the nanomatrix does. with the particle core 14 being rapidly weakened and released from the particle compact at the wellbore fluid interface, such that an effective rate of dissolution of particle compacts manufactured using particle cores 14 of these core materials 18 is high, even though the core 18 material itself may have a low dissolution rate, including core 20 materials that may be insoluble in the wellbore fluid.
[0036] As for electrochemically active metals as core materials 18, including Mg, Al, Mn or Zn, these metals can be used as pure metals or in any combination with each other, including various combinations of alloys of these materials, including binary alloys, ternary or quaternary of these materials. These combinations can also include composites of these materials. Furthermore, in addition to combinations with each other, the Mg, Al, Mn or Zn core materials 18 may also include other constituents, including various alloying additions, to alter one or more properties of the particle cores 14, such as improving the strength, lower density or change the dissolution characteristics of the core material 18.
[0037] Among electrochemically active metals, Mg, as a pure metal or an alloy or a composite material, is particularly useful because of its low density and ability to form high strength alloys, as well as its high degree of electrochemical activity, as it has a higher standard oxidation potential than Al, Mn or Zn. Mg alloys include all alloys that have Mg as a constituent of the alloy. Mg alloys that combine other electrochemically active metals as described herein as an alloy constituent are particularly useful, including Mg-Zn, Mg-Al and Mg-Mn binary alloys, as well as Mg-Zn-ternary alloys. Y and Mg-Al-X, where X includes Zn, Mn, Si, Ca or Y, or a combination of them. These Mg-Al-X alloys can include, by weight, up to about 85% Mg, up to about 15% Al and up to about 5% X. 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. When present, a rare-earth element or combination of rare-earth elements may be present in an amount of about 5% by weight or less.
[0038] The particle core 14 and the core material 18 have a melting temperature (TP). As used herein, the term TP includes the lowest temperature at which incipient melting or liquidation or other forms of partial melting occur within core material 18, regardless of whether core material 18 comprises a pure metal, an alloy. with multiple phases with different melting temperatures or composite materials with different melting temperatures.
[0039] The particle cores 14 may have any suitable particle size or particle size range or particle size distribution. For example, particle nuclei 14 can be selected to provide an average particle size that is represented by a unimodal normal or Gaussian-type distribution around a mean, as illustrated generally in Figure 1. In another example, the nuclei of particles 14 can be selected or mixed to provide a multimodal particle size distribution, including a plurality of mean core particle sizes, such as, for example, homogeneous bimodal distribution of mean particle sizes, as illustrated generally in Figure 6. Selecting the particle size distribution of the core can be used to determine, for example, the particle size and interparticle spacing 15 of the particles 12 of the powder 10. In an exemplary embodiment, the particle cores 14 may have a distribution. unimodal 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.
[0040] The particle cores 14 may have any suitable particle shape, including any regular or irregular geometric shape, or any combination thereof. In an exemplary embodiment, the particle cores 14 are substantially spheroidal electrochemically active metallic particles. In another exemplary embodiment, the particle cores 14 are substantially irregularly shaped ceramic particles. In yet another exemplary embodiment, the particle cores 14 are carbon or other nanotubular structures or hollow glass microspheres.
[0041] Each of the powder coated metallic powder particles 12 of the powder 10 also includes a metallic coating layer 16 which is disposed on the core of the particle 14. The metallic coating layer 16 includes a metallic coating material 20. metallic coating 20 gives the powder particles 12 and the powder 10 their metallic nature. Metallic coating layer 16 is a nanoscale coating layer. In an exemplary embodiment, metallic coating layer 16 can have a thickness of from about 25 nm to about 2,500 nm. The thickness of the metallic coating layer 16 may vary over the core surface of the particle 14, but will preferably be of substantially uniform thickness over the surface of the core of the particle 14. The metallic coating layer 16 may include a single layer, as illustrated. in Figure 2, or a plurality of layers as a multi-layer coating structure as illustrated in Figures 3-5 for up to four layers. In a single-layer coating, or in each of the layers of a multi-layer coating, metallic coating layer 16 can include a single constituent chemical element or compound, or it can include a plurality of chemical elements or compounds. When a layer includes a plurality of chemical constituents or compounds, they can have any homogeneous or heterogeneous distribution, including a homogeneous or heterogeneous distribution of metallurgical phases. This can include a flat distribution in which the relative amounts of the constituents or chemical compounds vary according to the respective profiles of the constituents across the thickness of the layer. In single-layer and multi-layer coatings, each of the respective layers, or combinations thereof, can be used to provide a predetermined property for the powder particle 12 or a sintered powder compact formed therefrom. For example, the predetermined property may include the cohesive 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 multi-layer 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 cohesive strength of the metallurgical bond between the metallic coating layers of adjacent sintered powder particles 12, including the outermost ones of multi-layer coating layers; and the electrochemical activity of the coating layer 16.
[0042] The metallic coating layer 16 and the coating material have a melting temperature (TC). As used herein, the term TC includes the lowest temperature at which incipient melting or liquidation 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 multiples. phases each with different melting temperatures or a composite with different melting temperatures.
[0043] The metallic coating material 20 can include any metallic coating material 20 that provides a sinterable outer surface 21 that is configured to be sintered to an adjacent powder particle 12 that also has a metallic coating layer 16 and a sinterable outer surface 21. In powders 10 which also include a second particle 32 or additional particles (coated or uncoated) 32, as described herein, the sinterable outer surface 21 of metallic coating layer 16 is also configured to be sintered to a surface sinterable external 21 of the second particles 32. In an exemplary embodiment, the powder particles 12 are sintered at a predetermined sintering temperature (TS) which is a function of the core material 18 and the coating material 20 such that the - terization of the powder compact 200 is carried out entirely in solid state, and where TS is less than TP and TC. Solid state sintering limits particle core 14 interactions with coating layer 16 to solid state diffusion processes and metallurgical transport phenomena, and limits the growth of the resulting interface between them and provides control over it. In contrast, for example, liquid phase introduction and sintering would provide rapid inter-diffusion of the core materials of particle 14/metal coating layer 16, and makes it difficult to limit the growth of the resulting interface between them and provide control over it, and therefore, it interferes with the formation of the desirable microstructure of the particulate compact 200, as described herein.
[0044] In an exemplary embodiment, core material 18 should be selected to provide a chemical composition of the core, and coating material 20 should be selected to provide a chemical composition of the coating, and these chemical compositions should also be selected to differ from each other. In another exemplary embodiment, core material 18 should be selected to provide a chemical composition of the core, and coating material 20 should be selected to provide a chemical composition of the coating, and these chemical compositions should also be selected to differ from each other. in its interface. Differences in the chemical compositions of the coating material 20 and the core material 18 can be selected to provide different selectable and controllable dissolution and dissolution rates of powder compacts 200 that incorporate them making them selectable and controllable dissolvable. This includes dissolution rates that differ in response to a changed condition in the wellbore, including an indirect or direct change in a wellbore fluid. In an exemplary embodiment, a powder compact 200 formed from the powder 10 having chemical compositions of the core material 18 and the coating material 20, which produce the compact 200, is selectably dissolvable in a bore fluid of wellbore in response to a changed wellbore condition that includes a change in temperature, change in pressure, change in flow rate, change in pH, or change in the chemical composition of the wellbore fluid, or a combination of these. The selectable dissolution response to the changed condition can result from actual chemical reactions or processes that promote different dissolution rates, but it also encompasses changes in the dilution response that are associated with physical reactions or processes, such as changes in the pressure or flow of the fluid in the well hole.
[0045] 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 may include pure Mg and Mg alloys, and 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 thereof, or a combination of any of the aforementioned materials as coating material 20.
[0046] In another exemplary embodiment of powder 10, particle core 14 includes Mg, Al, Mn or Zn, or a combination thereof, as core material 18, and more particularly may include Mg and Mg alloys, and the layer of metallic coating 16 includes a single layer of Al or Ni, or a combination thereof, as coating material 20, as illustrated in Figure 2. When metallic coating layer 16 includes a combination of two or more constituents, such as Al and Ni, the combination can include several leveled or co-deposited structures of these materials, where the amount of each constituent, and thus the layer composition, varies across the layer thickness, as also illustrated in Figure 2.
[0047] In yet another exemplary embodiment, the core of particle 14 includes Mg, Al, Mn or Zn, or a combination thereof, as core material 18, and more particularly may include pure Mg and Mg alloys, and the layer of Coating 16 includes two layers as coating material 20, as illustrated in Figure 3. First layer 22 is disposed on the surface of particle core 14 and includes Al or Ni, or a combination thereof, as described herein. The second layer 24 is disposed 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, first layer 22 should be selected to provide a strong metallurgical bond to particle core 14 and to limit interdiffusion between particle core 14 and coating layer 16, particularly first layer 22. Second layer 24 may be selected to increase the strength of the metallic coating layer 16, or to provide a strong metallurgical bond and 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 selective and controllable dissolution of coating layer 16 in response to a change in a wellbore property, including the wellbore fluid. well, as described here. However, this is only an example and it should be appreciated that other selection criteria for the various layers can also be used. For example, any one of the respective layers can be selected to promote selective and controllable dissolution of casing layer 16 in response to a change in a wellbore property, including wellbore fluid, as described herein. Exemplary embodiments of a two-layer metallic coating layer 16 for use over particle cores 14 comprising Mg include combinations of first/second layers comprising Al/Ni and Al/W.
[0048] 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 may include pure Mg and Mg alloys, and the coating layer 16 includes three layers, as illustrated in Figure 4. First layer 22 is disposed over the core of particle 14 and may include Al or Ni, or a combination thereof. The second layer 24 is disposed over 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 or a carbide thereof, or a combination of any of the aforementioned second layer materials. Third layer 26 is disposed over second layer 24 and may 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, first layer 22 may be selected to provide a strong metallurgical bond to particle core 14 and to limit interdiffusion between particle core 14 and coating layer 16, particularly first layer 22 The second layer 24 can be selected to increase the strength of the metallic coating layer 16, or to limit interdiffusion between the particle core 14 or the first layer 22 and the outer layer or third layer 26, or to promote adhesion and 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 or adjacent particles 12. However, this is only exemplary and other selection criteria for the various layers should also be considered. can be employed. For example, any one of the respective layers can be selected to promote selective and controllable dissolution of casing layer 16 in response to a change in a wellbore property, including wellbore fluid, as described herein. An exemplary embodiment of a three-layer coating layer for use over particle cores, which comprises Mg, includes combinations of first/second/third layers comprising Al/Al2O3/Al.
[0049] In yet another embodiment, the particle core includes Mg, Al, Mn, or Zn, or a combination thereof, as core material 18, and more particularly may include pure Mg or Mg alloys, and the coating layer 16 includes four layers as illustrated in Figure 5. In the four layer configuration, first layer 22 may 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 or carbide thereof, or a combination of the aforementioned materials of the second layer . 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 or carbide thereof, or a combination of the aforementioned materials of the third layer. The fourth layer 28 can include Al, Mn, Fe, Co, Ni or a combination thereof. In the 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 the third layer 26 is different from the chemical composition of the fourth layer 28. In an exemplary embodiment, the selection of the various layers will be similar to that described for the three-layer configuration above with respect to the inner (first) layer and the outer (fourth) layer, with the second and third layers being available to provide increased adhesion between layers, strength of the entire melic coating layer (16), limited diffusion between layers or selectable and controllable dissolution, or a combination thereof. However, this is just an example and it should be appreciated that other selection criteria for the various layers can also be used. For example, any one of the respective layers can be selected to promote selective and controllable dissolution of casing layer 16 in response to a change in a wellbore property, including wellbore fluid, as described herein.
[0050] The thickness of the various layers in multi-layer configurations can be proportionally apportioned between the various layers in any way, as long as the sound of the layer thicknesses produces a coating layer16 on a nanometric scale, including the layer thicknesses, as described here. In one embodiment, the first layer 22 and outer layer (24, 26 or 28 depending on the number of layers) may be thicker than the other layers, when present, due to the desire to provide sufficient material to promote the desired adhesion of the first layer 22 with particle core 14, or adhering outer layers of adjacent powder particles 12, during sintering of powder compact 200.
[0051] The powder 10 may also include an additional powder or second powder 30 interspersed with the plurality of powder particles 12, as illustrated 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 compact of powder particles 200 formed from powder 10 and second powder 30, or a combination of these properties. In an exemplary embodiment, the property change can include an increase in the compressive strength of powder compact 200 formed from powder 10 and second powder 30. In another exemplary embodiment, second powder 30 can be selected to promote dissolution selective and controllable of a powder compact 200 formed from powder 10 and second powder 30 in response to a change in a wellbore property, including wellbore fluid, as described herein. The second powder particles 32 can be uncoated or coated with a metallic coating layer 36. When coated, including single-layer or multi-layer coatings, the coating layer 36 of the second powder particles 32 can comprise the same coating material 40 that the coating material 20 of the powder particles 12, or the coating material 40 may be different. The second powder particles 32 (uncoated) or particle cores 34 can include any material suitable to provide the desired benefit, including many 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 them. As the second powder particles 32 will also be configured for solid state sintering to the powder particles 12 at the predetermined sintering temperature (TS), the particle cores 34 will have a melting temperature of TAP and any coating layers 36 will have a second temperature merger TAC, where TS is less than TAP and TAC. It should also be appreciated that the second powder 30 is not limited to one type of additional powder particle 32 (i.e., a second powder particle), but may include a plurality of additional powder particles 32 (i.e., second, third, fourth, etc. additional 32 dust particle types) in any number.
[0052] Referring to Figure 8, an exemplary embodiment of a method 300 for manufacturing a metallic powder 10 is described. Method 300 includes forming a plurality of particle cores 14 as described herein. Method 300 also includes depositing a metallic coating layer 320 onto each of the plurality of particle cores 14. Deposition 320 is the process by which coating layer 16 is disposed over particle core 14 as described above.
[0053] The formation 310 of the particle cores 14 may be carried out by any suitable method to form a plurality of particle cores 14 of the desired core material 18, which essentially comprises methods for forming a powder of the core material 18. The methods Appropriate powder formation methods include mechanical methods, including machining, crushing, impacting and other mechanical methods to form the metallic powder; chemical methods, including chemical decomposition, precipitation from a liquid or gas, reactive solid/solid synthesis, and other chemical methods to form powders; atomization methods, including gas atomization, liquid and water atomization, centrifugal atomization, plasma atomization and other methods of atomization to form a powder; and various methods of evaporation and condensation. In an exemplary embodiment, the Mg-comprising particle cores 14 can be fabricated using an atomization method, such as vacuum spray formation or inert gas spray formation.
[0054] The deposition 320 of metallic coating layers 16 onto 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 deposition methods of vapor and physical vapor deposition. In an exemplary embodiment, deposition 320 of metallic coating layers 16 is performed using fluidized bed chemical vapor deposition (FBCVD). The deposition 320 of metallic coating layers 16 by FBCVB includes flowing a reactive fluid as a coating medium that includes the desired metallic coating material 20 through a bed of fluidized particle cores 14 in a reactor tank under appropriate conditions, including conditions of temperature, pressure and flow, and the like, sufficient to induce a chemical reaction of the coating medium to produce the desired coating material 20 and induce its deposition on the surface of the particle cores 14 to form the coated powder particles 12. The reactive fluid selected will depend on the desired metallic coating material 20, and would typically comprise an organometallic compound that includes the metallic material to be deposited, such as nickel carbonyl (Ni(CO)4), hexafluoro- tungsten rectum (WF6), and aluminum triethyl (C6H15Al), which is transported in a carrier fluid such as helium or argon gas. The reactive fluid, including carrier fluid, causes at least a portion of the plurality of particle cores 14 to be suspended in the fluid, thereby allowing the entire surface of the suspended particle cores 14 to be exposed to the reactive fluid, including, for example, a desired organometallic constituent, and allowing the deposition of the metallic coating material 20 and the coating layer 16 onto the entire surfaces of the particle cores 14 such that they are surrounded, forming coated particles 12 which exhibit metallic coating layers 16 as described herein. As also described herein, each metallic cladding layer 16 may include a plurality of cladding layers. The coating material 20 may be deposited in multiple layers to form a multilayer metallic coating layer 16 by repeating the depositing step 320 described above and exchanging (330) the reactive fluid to produce 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 which already include any previously deposited coating layers that constitute 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 produced by using different reactive means which are configured to produce the desired metallic coating layers 16 on the particle cores 14 in the fluidized bed reactor .
[0055] As illustrated in Figures 1 and 9, the particle core 14 and the core material 18 and the metallic coating layer 16 and the coating material 20 can be selected to produce powder particles 12 and a powder 10 that is configured for compaction and sintering to produce a powder compact 200 that is light (i.e., having a relatively low density), high strength, and is selectable and controllably removable from a wellbore in response to a change in a property of the wellbore, including the fact that it is selectable and controllable dissolvable in an appropriate polebore fluid, including various wellbore fluids described herein. The powder compact 200 includes a substantially continuous cellular nanomatrix 216 and nanomatrix material 220 which has a plurality of dispersed particles 214 dispersed throughout the entire cellular nanomatrix 216. The substantially continuous cellular nanomatrix 216, and the nanomatrix 220 material formed of sintered metallic coating layers 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 the material of nanomatrix 200 may be different from that of the coating material 20 due to diffusion effects associated with sintering as described herein. Metal powder compact 200 also includes a plurality of dispersed particles 214 comprising particle core material 218. Dispersed particle cores 214 and core material 218 correspond to and are formed from the plurality of particle cores 14 and of the core material 18 of the plurality of powder particles 12 as the metallic coating layers 16 are sintered together to form the nanomatrix 216. The chemical composition of the core material 218 may differ from that of the core material 18 due to diffusion effects associated with sintering as described herein.
[0056] As used herein, the use of the term "substantially continuous cellular nanomatrix 216" does not connote the major constituent of the powder compact, but rather refers to the minor constituent or constituents, either by weight or by volume. This is distinguished from most composite matrix materials in which the matrix comprises the major constituent by weight or by volume. The use of the term "substantially continuous cellular nanomatrix" is intended to describe the extended, smooth, continuous and interconnected nature of the material distribution of the nanomatrix 220 within the powder compact 200. As used herein, the term "substantially continuous" describes the extent of the material of the nanomatrix in the entire powder compact 200 such that it extends between and envelopes substantially all of the dispersed particles 214. "Substantially continuous" is used to indicate the complete continuity and regular order of the nanomatrix around each particle scattered 214 are not necessary. For example, defects in coating layer 16 over particle core 13 in the same powder particles 12 can cause bridging of particle cores 14 during sintering of powder compact 200, thereby causing resulting localized discontinuities within the cellular nanomatrix 216, although in other parts of the powder compact the nanomatrix is substantially continuous and exhibits the structure described herein. As used herein, the term "cellular" is used to indicate that the nanomatrix defines a network of generally repetitive interconnected compartments or cells of the material of the nanomatrix 220 that encompass and also interconnect the dispersed particles 214. As used herein, the term " nanomatrix" is used to describe the size or 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 themselves coating layers with thickness on the nanometric scale. tric. As the nanomatrix in most places, other than the intersection of more than two dispersed particles 214, generally comprises the interdiffusion and joining of more than two dispersed particles 214, it generally comprises the interscattering and joining of two coating layers 16 of adjacent powder particles 12, which have thicknesses on the nanometer scale, the formed matrix also has a thickness on the nanometer scale (for example, approximately twice the thickness of the coating layer, as described herein), and thus being described as one in the - nomatrix. Furthermore, the use of the term "dispersed particles 214" does not connote the minor constituent of powder compact 220, but rather refers to the major constituent or constituents, either by weight or by volume. The use of the term "dispersed particle" is intended to convey discontinuous and distinct distribution of the core material of particle 218 within the powder compact 200.
[0057] The powder compact 200 can be of any desired shape or size, including an ingot or cylindrical stick shape that can be machined or otherwise used to form useful manufactured articles, including various wellbore tools and components. The pressing used to form the precursor powder compact 100 and the sintering and pressing processes used to form the powder compact 200 deform the powder particles 12, including particle cores 14 and coating layers 16, to produce full density and the desired macroscopic shape and size of the powder compact 200, as well as its microstructure. The microstructure of the powder compact 200 includes an equiaxial configuration of dispersed particles 214 that are dispersed and embedded widely within the substantially continuous cellular nanomatrix 216 of sintered coating layers. This microstructure is somewhat analogous to an equiaxial grain microstructure with a continuous grain boundary phase, except that it does not require the use of alloy constituents that exhibit thermodynamic phase equilibrium properties that are capable of producing such a structure. Instead, this equiaxial and nanomatrix dispersed particle structure 216 of sintered metallic coating layers 16 can be produced using constituents in which thermodynamic phase equilibrium conditions would not produce an equiaxial structure. The equiaxed morphology of the dispersed particles 214 and the cellular matrix 216 of particle layers results from the sintering and deformation of the powder particles 12 as they are compacted and inter-diffuse and deform to fill the spaces between particles 15 (Figure 1). Sintering temperatures and pressures can be selected to ensure that the compact powder 200 density reaches substantially full theoretical density.
[0058] In an exemplary embodiment, as illustrated in Figures 1 and 9, the dispersed particles 214 are formed from the particle cores 14 dispersed in the cellular nanomatrix 216 of the sintered metallic coating layers 16, and the nanomatrix 216 includes a metallurgical bond solid state 217 or bonded layer 219, as illustrated schematically in Figure 10, extending between the dispersed particles 214 in the entire cellular nanomatrix 216 which is formed at a sintering temperature (TS) where TS is less than TP and TC. as indicated, the solid state metallurgical bond is formed in the solid state by solid state interdiffusion between coating layers 16 of adjacent powder particles 12 which are compressed by contacting during the compaction and sintering processes used to form the compact of 200 powder as described above. Thus, the sintered coating layers 16 of the cellular nanomatrix 216 include a solid state bonding layer 219 having a thickness (t) defined by the extent of interdiffusion of materials from the coating 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-layer or multi-layer coating layers, whether they have been selected to promote or limit such interdiffusion, and other factors, including the time, temperature and pressure of the sintering used to form powder compact 200.
[0059] As the nanomatrix 216 is formed, including the bond 217 and the bonding layer 219, the chemical composition or phase distribution, or both, of the metallic coating layers 16 may change. Nanomatrix 216 also features a melting temperature (TM). As used herein, the term TM includes the lowest temperature at which incipient melting or liquidation or other forms of partial melting occur within the nanomatrix 216, regardless of whether the material 220 of the nanomatrix comprises a pure metal, a multiphase alloy, each having different melting temperatures or a composite, including a composite comprising a plurality of layers of various coating materials having different melting temperatures, or a combination thereof, or otherwise. As dispersed particles 214 and particle core materials 218 are formed together with nanomatrix 216, diffusion of metallic coating layer constituents 216 into particle cores 14 is also possible, which may also be possible. result in changes in the chemical composition or phase distribution, or both, of particle cores 14. As a result, the dispersed particles 214 and particle core materials 218 may have a melting temperature (TDP) that is different from TP. As used herein, the term TDP includes the lowest temperature at which incipient melting or liquidation or other forms of partial melting occur within dispersed particles 214, regardless of whether the core material of particle 218 comprises a pure metal, a alloy with multiple phases each with different melting temperatures or a composite, or differently. The 200 powder compact is formed at a temperature (TS) where TS is less than TC, TP, TM and TDP.
[0060] The dispersed particles 214 may comprise any of the materials described herein for particle cores 14, although the chemical composition of the dispersed particles 214 may be different due to diffusion effects as described herein. In an exemplary embodiment, the dispersed particles 214 are formed from particle cores 14 that comprise materials that exhibit a standard oxidation potential greater than or equal to Zn, including Mg, Al, Zn, or Mn, or a combination thereof, and may include various binary, ternary and quaternary alloys or other combinations of these constituents, as described herein, together with particle cores 14. Among these materials, those having dispersed particles 214 comprising Mg and nanomatrix 216 formed from materials coatings 16 described herein are particularly useful. The dispersed particles 214 and the core material of particles 218 of Mg, Al, Zn or Mn, or a combination thereof, may also include a rare-earth element, or a combination of rare-earth elements, as described herein, together. with the 14 particle nuclei.
[0061] 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, glasses (eg, glass microspheres) or carbon, or a combination thereof, as described herein.
[0062] The dispersed particles 214 of the powder compact 200 may have any suitable particle size, including the average particle sizes described herein for the particle cores 14.
[0063] The dispersed particles 214 can have any suitable shape depending on the shape selected for the particle cores 14 and the powder particles 12, as well as the method used to sinter and compact the powder 10. In an exemplary embodiment, the powder particles 12 can be spheroidal or substantially spheroidal and dispersed particles 214 can include an equiaxed particle configuration, as described herein.
[0064] The nature of the dispersed particle dispersion 214 can be affected by the selection of powder 10 or powders 10 used to produce the particle compact 200. In an exemplary embodiment, a powder 10 that exhibits a unimodal powder particle size distribution 12 can be selected to form a powder compact 200 and will produce a substantially homogeneous unimodal dispersion of particle sizes of dispersed particles 214 within the cellular nanomatrix 216, as illustrated generally in Figure 9. In another exemplary embodiment, a plurality of powders 10 which present a plurality of powder particles with particle cores 14 which have the same materials as the cores 18 and different sizes of the cores and the same coating material 20 can be selected and uniformly mixed as described herein to produce a powder 10 which has a homogeneous unimodal distribution of powder particle sizes 12, and can be used to form the powder compact 200 which exhibits a homogeneous multimodal dispersion of particle sizes of dispersed particles 214 within the cellular nanomatrix 216, as illustrated schematically in Figures 6 and 11. Similarly, in yet another exemplary embodiment, a plurality of powders 10 which exhibit a plurality of particle cores 14 which can have the same materials as core 18 and different core sizes and the same coating material 20 can be selected and distributed in an uneven manner to produce an inhomogeneous multimodal distribution of powder particle sizes. , and can be used to form the powder compact 200 which exhibits an inhomogeneous multimodal dispersion of particle sizes of dispersed particles 214 within the cellular nanomatrix 216, as illustrated schematically in Figure 12. Selection of the core particle size distribution can be used to determine, for example, particle size and space between particles of the dispersed particles 214 within the cellular nanomatrix 216 of powder compacts 200 manufactured from the powder 10.
[0065] As illustrated generally in Figures 7 and 13, the metal powder compact 200 may also be formed using the coated metal powder 10 and a second powder or additional powder 30, as described herein. The use of an additional powder 30 produces a powder compact 200 which also includes a plurality of second dispersed particles 234, as described herein, which are dispersed within the nanomatrix 216 and are dispersed also with respect to the dispersed particles 214. The second dispersed particles 214. 234 can be formed from coated or uncoated second powder particles 32 as described herein. In an exemplary embodiment, the second coated powder particles 32 may be coated with a coating layer 36 which is the same as coating layer 16 of the powder particles 12 such that coating layers 36 also contribute to the nanomatrix 216 In another exemplary embodiment, the second powder particles 232 can be uncoated, such that the dispersed second particles 234 are embedded within the nanomatrix 216. As described herein, the powder 10 and the additional powder 30 can be mixed to form a homogeneous dispersion of dispersed particles 214 and second dispersed particles 234, as illustrated in Figure 13, or to form an inhomogeneous dispersion of these particles, as illustrated in Figure 14. Second dispersed particles 234 can be formed from any suitable additional powder 30 which is different from powder 10, either due to a compositional difference in the core of the particle 34, or in the coating layer 36, or both, and can include any of the materials described herein for use as second powder 30 that are different from powder 10 that is selected to form powder compact 200. In an exemplary embodiment, dispersed second particles 234 can include Fe , Ni, Co or Cu, or their oxides, nitrides or carbides, or a combination of any of the aforementioned materials.
[0066] The nanomatrix 216 is a substantially continuous cellular network of metallic coating layers 16 that are sintered together. The thickness of nanomatrix 216 will depend on the nature of the powder 10 or powders 10 used to form the powder compact 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 the nanomatrix 216 is substantially uniform over the entire microstructure of the powder compact 200 and comprises about twice the thickness of the coating layers 16 of the powder particles 12. In another exemplary embodiment, the cellular network 216 exhibits a substantially uniform average thickness between the dispersed particles 214 from about 50 nm to about 5,000 µm.
[0067] The nanomatrix 216 is formed by sintering the metallic coating layers 16 of particles adjacent to one another by interdiffusion and creating bonding layer 219, as described herein. The metallic coating layers 16 can be single-layer or multi-layer structures, and they can be selected to promote or inhibit diffusion, or both, within the layer or between the layers of the metallic coating layer 16, or between the coating layer 16 and the core of the particle 14, or between the metallic coating layer 16 and the metallic coating layer 16 of an adjacent powder particle, and the extent of interdiffusion of metallic coating layers 16 during sintering may be limited or extensive depending on coating thicknesses, selected coating material or materials, sintering conditions, and other factors. Given the potential complexity of interdiffusion and interaction of the constituents, the description of the resulting chemical composition of the nanomatrix 216 and the material of the nanomatrix 220 can be understood simply as being a combination of the constituents of the coating layers 16 which may also include one or more constituents of dispersed particles 214, depending on the extent of interdiffusion, if any, that occurs between the dispersed particles 214 and the nanomatrix 216. Similarly, the chemical composition of the dispersed particles 214 and the core material of the particle 218 can be understood simply to be a combination of the core constituents of the particle 14 which may also include one or more constituents of the nanomatrix 216 and the material of the nanomatrix 220, depending on the extent of interdiffusion, if any, that occurs between the dispersed particles 214 and the nanomatrix 216.
[0068] In an exemplary embodiment, the nanomatrix 220 material has a chemical composition and the 218 particle core material has a different chemical composition than the 220 nanomatrix material, and the 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 fast dissolution rate, in response to a controlled change in a wellbore property or condition near the compact 200 , including a property change in a wellbore fluid that contacts the powder compact 200, as described herein. Nanomatrix 216 can be formed from powder particles 12 having a single coating layer or multiple coating layers 16. This design flexibility provides a large number of material combinations, particularly in the case of multi-layer coating layers 16 , which can be used to individualize the cellular nanomatrix 216 and the material composition of the nanomatrix 220 by controlling the interaction of the constituents of the coating layers, both within a 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 modalities that demonstrate this flexibility are provided below.
[0069] As illustrated in Figure 10, in an exemplary embodiment, the powder compact 200 is formed from powder particles 12, where the coating layer 16 comprises a single layer, and the resulting nanomatrix 216 between adjacent ones of the plurality of dispersed particles 214 comprises the single metallic coating layer 16 of one powder particle 12, a bonding layer 219 and the single coating layer 16 of another one of adjacent powder particles 12 . The thickness (t) of the bonding layer 219 is determined by the extent of interdiffusion between the single metallic coating layers 16, and may comprise the entire thickness of the nanomatrix 216 or only a portion of it. In an exemplary embodiment of powder compact 200 formed using a single-layer powder 10, powder compact 200 may include dispersed particles 214 comprising Mg, Al, Zn or Mn, or a combination thereof, as described herein, and the nanomatrix 216 may include 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 materials. aforementioned, including combinations in which the material of nanomatrix 220 of cellular nanomatrix 216, including bonding layer 219, has a chemical composition and core material 218 of dispersed particles 214 has a different chemical composition than the chemical composition of material of 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 property of a wellbore, including a wellbore fluid of the well, as described here. In another exemplary embodiment of a powder compact 200 formed from a powder 10 having a single coating layer configuration, the dispersed particles 214 include Mg, Al, Zn or Mn, or a combination thereof, and the cellular nanomatrix 216 includes Al or Ni, or a combination of them.
[0070] As illustrated in Figure 15, in another exemplary embodiment, the powder compact 200 is formed from powder particles 12 in which the coating layer 16 comprises a multi-layer coating layer 16 having a plurality of layers of coating, and the resulting nanomatrix 216 between adjacent ones of the plurality of dispersed particles 214 comprises the plurality of layers (t) comprising the coating layer 16 of a particle 12, a joining layer 219, and the plurality of layers comprising the coating layer 16 of another of the powder particles 12. In Figure 15, this is illustrated with a two-layer metal coating layer 16, but it is to be understood that the plurality of layers of the multi-layer metal coating layer 16 may include any desired number of layers. The thickness (t) of the bonding layer 219 is again determined by the extent of interdiffusion between the plurality of layers of the respective coating layers 16, and may comprise the entire thickness of the nanomatrix 216 or only a part of it. In this embodiment, the plurality of layers comprising each coating layer 16 can be used to control the interdiffusion and formation of the bonding layer 219 and the thickness (t).
[0071] In an exemplary embodiment of a powder compact 200 manufactured using the powder particles 12 with multi-layer coating layers 16, the compact includes dispersed particles 214 comprising Mg, Al, Zn or Mn, or a combination thereof, as herein described, and the nanomatrix 216 comprises a cellular network of coating layers with two sintered layers 16, as illustrated in Figure 3, comprising first layers 22 which are disposed over the dispersed particles 214 and second layers 24 which are disposed over the first layers 22. 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 them. In these configurations, the dispersed particle 214 and multilayer coating layer 16 materials used to form the nanomatrix 216 are selected such that the chemical compositions of adjacent materials are different (e.g., dispersed particle/first layer and first layer/second layer).
[0072] In another exemplary embodiment of a powder compact 220 manufactured using powder particles 12 with multi-layer coating layers 16, the compact includes dispersed particles 214 comprising Mg, Al, Zn or Man, or a combination thereof, as herein described, and the nanomatrix 216 comprises a cellular network of sintered three-layer metallic coating layers 16, as illustrated in Figure 4, comprising first layers 22 which are disposed over the dispersed particles 214, the second layers 24 which are disposed over the first layers 22, and third layers 26 which overlay second layers 24. 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, or carbide thereof, or a combination of any of the above-mentioned 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 the powder compact 200 manufactured using the powders with two coating layers, but should also be extended to include the material used for the third coating layer.
[0073] In yet another exemplary embodiment of a powder compact 200 manufactured using powder particles 12 with multi-layer coating layers 16, the compact includes dispersed particles 214 comprising Mg, Al, Zn or Mn, or a combination thereof, such as described herein, and the nanomatrix 216 comprises a cellular network of four sintered coating layers 16, comprising first layers 22 which are disposed over the dispersed particles 214; second layers 24 which are disposed on top of first layers 22; the third layers 26 which are disposed on the second layers 24; and fourth layers 28 which are disposed on top of third layers 26. 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, or carbide thereof, or a combination of either the above-mentioned second layer materials; the third layers include 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 them. materials of the aforementioned third layers; 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 herein for powder compacts 200 manufactured using powder with two coating layers, but should also be extended to include the material used for the third and fourth coating layers.
[0074] In another exemplary embodiment of a powder compact 200, the dispersed particles 214 comprise a metal that has an oxidation pattern potential less 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 ceramic, glass or carbon shapes, or a combination thereof. Furthermore, in powder compacts 200 that include dispersed particles 214 that comprise these metals or non-metallic materials, nanomatrix 216 may include 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 materials, as nanomatrix 220 material.
Referring to Figure 16, the sintered powder compact 200 may comprise a sintered precursor powder compact 100 that includes a plurality of mechanically bonded deformed powder particles as described herein. The precursor powder compact 100 can be formed by compacting the powder 10 to the point where the powder particles 12 are pressed together, thereby deforming them and forming mechanical bonds between particles or other bonds 110 associated with this sufficient deformation. to cause the deformed powder particles 12 to adhere to each other and form a green powder compact having a green density less than the theoretical density of a fully dense compact 10, in part due to the spaces 15 between particles. Compaction can be carried out, for example, by isostatically pressing the powder 10 at room temperature to produce the deformation of the bond between particles of powder particles 12 necessary to form the powder precursor compact 100.
[0076] The sintered and forged powder compacts 200 that include dispersed particles 214 and comprise Mg, and the nanomatrix 216 comprises various nanomatrix materials, as described herein, have been shown to have an excellent combination of mechanical strength and low density that exemplify lightweight materials of high strength described here. Examples of powder compacts 200 having dispersed pure Mg particles 214 and various nanomatrices 216 formed from powders 10 having pure Mg particle cores 14 and multiple layers of single-layer and multi-layer 16 pure Mg metallic coating layers include Al, Ni, W, or Al2O3, or a combination of them, and which were manufactured using method 400 described herein, are listed in a table in Figure 18. These 200 powder compacts have undergone various mechanical and other tests, including density testing, and its degradation behavior of mechanical properties, were also characterized as described herein. The results indicate that these materials can be configured to provide a wide range of selectable and controllable corrosion or dissolution behaviors from very low corrosion rates to extremely high corrosion rates, particularly corrosion rates that are lower and higher than than those of powder compacts that do not incorporate the cellular nanomatrix, such as a compact formed from pure Mg powder through the same compaction and sintering processes compared to those that include dispersed particles of pure Mg in the various cellular nanomatrixes described here. These powder compacts 200 can also be configured to provide substantially improved properties compared to powder compacts formed from pure Mg particles that do not include the nanoscale coatings described herein. For example, referring to Figures 18 and 19, powder compacts 200 including dispersed particles 214 comprising Mg and nanomatrix 216 comprising various materials of nanomatrix 220 described herein demonstrated room temperature compressive strengths of at least about 255 MPa (37 ksi), and demonstrated compressive strengths at room temperature greater than about 345 MPa (50 ksi), either in the dry state or immersed in a 3% KCl solution at 93 oC (200 oF). In contrast, powder compacts formed from pure Mg powders exhibit a compressive strength of about 138 MPa (20 ksi) or less. The strength of the powdered metal compact 200 of the nanomatrix can be further improved by optimizing the powder 10, particularly the weight percentage of the nanoscale metal coating layers 16 that are used to form the cellular nanomatrix 216. For example, Figure 25 illustrates the effect of varying the percentage by weight (% by weight), i.e., the thickness, of an alumina coating on the compressive strength at room temperature of a powder compact 20 with a cellular nanomatrix 216 formed to from coated powder particles 12 which include a 16 multilayer metallic coating layer (Al/Al2O3/Al) over cores of pure Mg particles 14. In this example, the optimum strength is achieved at 4% by weight of alumina, which represents a 21% increase compared to that of 0% by weight of alumina.
[0077] Powder compacts 200 comprising dispersed particles 214 that include Mg and nano-matrix 216 that includes various nano-matrix materials, as described herein, also demonstrated room temperature shear strength of at least about 138 MPa (20 ksi). This contrasts with powder compacts formed from pure Mg powders which exhibit room temperature shear strengths of about 55 MPa (8 ksi).
[0078] Powder compacts 200 of the types described herein are capable of achieving an actual density substantially equal to the predetermined theoretical density of a compact material based on the composition of powder 10, including the relative amounts of the constituents of the particle cores 14 and the layer of metallic coating 16, and are described herein also as being completely dense powder compacts. Powder compacts 200 comprising dispersed particles that include Mg and the nanomatrix 216 that includes various materials of the nanomatrix, as described herein, demonstrated actual densities of about 1.738 g/cm3 to about 2.50 g/cm3, which are substantially equal to the predetermined theoretical densities, differing by at most 4% from the predetermined theoretical densities.
[0079] The powder compounds 200 described herein may be configured to be selectively and controllably dissolvable in a wellbore fluid in response to a changed condition in a wellbore. Examples of the changed condition that can be exploited to produce selectable and controllable dissolution capacity include a change in temperature, change in pressure, change in flow rate, change in pH or change in the chemical composition of the wellbore fluid, or combinations thereof . An example of a changed condition comprising a change in temperature includes a change in downhole fluid temperature. For example, referring to Figures 18 and 20, powder compacts 200 comprising dispersed particles 214 that include Mg and the cellular nanomatrix 216 that includes various nanomatrix materials, as described herein, exhibit relatively low corrosion rates in a solution of 3% KCl at room temperature, in ranges between about 0 and about 11 mg/cm2/h compared to relatively high corrosion rates at 93 oC (200 oF), which are in the range between about 1 and about 246 mg/cm2/h, depending on the different coating layers 16 at the nanometer scale. An example of a changed condition comprising a change in chemical composition includes a change in a chloride ion concentration or pH value, or both, of the wellbore fluid. For example, referring to Figures 18 and 21, powder compacts 200 comprising dispersed particles 214 that include Mg and nanomatrix 216 that includes various nanoscale coatings described herein demonstrate corrosion rates on 15% HCl that remain. in the range between about 4,750 mg/cm2/h and about 7,432 mg/cm2/h. Therefore, selectable and controllable dissolution in response to a changed wellbore condition, namely the change in wellbore fluid chemical composition from KCl to HCl, can be used to achieve a characteristic response as illustrated in Figure 22, illustrates that at a predetermined critical service time (CST), a changed condition can be imposed on the powder compact 200 as it is applied in a given application, such as a wellbore environment, which causes a controllable change in a property of the powder compact 200 in response to a changed condition in the environment in which it is applied. For example, at a predetermined critical service time (CST), changing a wellbore fluid that is in contact with the powder compact 200 from a first fluid (eg KCl) that provides a first corrosion rate and a weight loss or associated strength as a function of time for a second wellbore fluid (eg, HCl) that provides a second associated corrosion rate and weight loss and associated strength as a function of time, where the associated corrosion rate to the first fluid is much less than the corrosion rate associated with the second fluid. This characteristic response to a change in wellbore fluid conditions can be used, for example, to associate the critical service time with a dimension loss limit or a minimum strength required for a specific application, such that, when a tool or wellbore fluid component formed from the powder compact 200 described herein is no longer required in wellbore service (e.g., time critical service (CST)) the condition of the bottom of the (eg the chloride ion concentration of the wellbore fluid can be changed to cause rapid dissolution of the powder compact 200 and its removal from the wellbore. In the example described above, the powder compact 200 is dissolvable selectable at a rate in the range between about 0 and about 7,000 mg/cm2/h. This response range provides, for example, the ability to remove a sphere with a diameter of 7.62 cm (3 in) formed of this material from a hole of well changing the fluid at the bottom of the well in less than an hour. The selectable and controllable dissolution behavior described above, coupled with the excellent strength and low density property described herein, define a new nanomatrix engineering material with dispersed particles that is configured to contact a fluid and to provide a transition selectable and controllable from a first strength condition to a second strength condition that is lower than a functional strength threshold, or a first weight loss value to a second weight loss value that is greater than one weight loss limit, as a function of time in contact with the fluid. The dispersed particles/nanomatrix composite is characteristic of the powder compacts described herein, and includes a cellular nanomatrix 216 of nanomatrix material 220, a plurality of dispersed particles 214, including the core material of particles 218 which is dispersed within the matrix. Nanomatrix 216 is characterized by a solid state bonding layer 219 that spans the entire nanomatrix. The fluid contact time described above may include the critical service time (CST) as described above. The CST can include a predetermined time that is desired or required to dissolve a predetermined portion of the powder compact 200 that is in contact with the fluid. The CST may also include a time corresponding to a change in the property of the engineering material or fluid, or a combination thereof. In the case of an engineering material property change, the change may include a change in an engineering material temperature. In the event that there is a change in fluid property, the change may include changing a fluid temperature, pressure, flow, chemical composition or pH, or a combination of these. engineering or fluid, or a combination thereof, can be individualized to the desired STD characteristic response, including the rate of change of the specific property (eg weight loss, strength loss) both prior to CST (eg Stage 1) as well as after CST (eg Stage 2), as illustrated in Figure 22.
[0080] Referring to Figure 17, a method 400 for manufacturing a powder compact 200 is illustrated. Method 400 includes forming (410) a coated metallic powder 10 comprising powder particles 12 having particle cores 14 with nanoscale metallic coating layers 16 disposed thereon, wherein the metallic coating layers 16 have a chemical composition and the cores of the particles 14 have a chemical composition different from the chemical composition different from the chemical composition of the metallic coating material 16. Method 400 also includes forming (420) a powder compact by applying a predetermined temperature and a predetermined pressure to the coated powder particles , sufficient to sinter them by solid phase sintering of the coating layers of the plurality of the coated powder particles 12 to form a substantially continuous cellular nanomatrix 216 of a material of the nanomatrix 220 and a plurality of dispersed particles 214 within the nanomatrix 216, such as described here.
[0081] The formation (410) of coated metallic powder 10 comprising powder particles 12 having particle cores 14 with nanoscale metallic coating layers 16 disposed over them, can be performed by any suitable method. In an exemplary embodiment, formation 410 includes applying metallic coating layers 16, as described above, to particle cores 14, as described herein, using fluidized bed chemical vapor deposition (FBCVD) as described herein. Applying metallic coating layers 16 may include applying metallic coating layers 16 in a single layer or applying metallic coating layers 16 in multi-layers as described herein. Applying metallic coating layers 16 can also include controlling the thickness of the individual layers as they are being applied, as well as controlling the overall thickness of metallic coating layers 16. The particle cores 14 can be formed as described herein.
[0082] Formation 420 of powder compact 200 may include any suitable method to form a fully dense compact of powder 10. In an exemplary embodiment, formation 420 includes dynamic forging a precursor powder compact with green density 100 to apply a predetermined temperature and a predetermined pressure sufficient to sinter and deform the powder particles and form a completely dense nanomatrix 216 and arranged particles 214 as described herein. The term "dynamic forging", as used herein, means the dynamic application of a charge at a temperature and for an appropriate time sufficient to promote sintering of adjacent metallic coating layers 16 of powder particles 12, and may preferably include the application of a dynamic forging charge at a predetermined charge rate for a time and at a temperature sufficient to form a fully dense, sintered powder 200 compact. In an exemplary embodiment, dynamic forging includes: (1) heating a powder precursor or green state compact 100 to a predetermined solid state sintering temperature, such as, for example, a temperature sufficient to promote interdiffusion between metallic coating layers 16 of adjacent powder particles 12; (2) maintain the precursor powder compact 100 at the sintering temperature for a predetermined residence time, such as, for example, a time sufficient to ensure substantial uniformity of sintering temperature across the entire precursor compact 100; (3) forging the precursor powder compact 100 to full density, such as, for example, applying a predetermined forging pressure according to a program or rate of increment sufficient to quickly reach full density, while maintaining the compact at predetermined sintering temperature; and (4) cool the compact to room temperature. The predetermined pressure and predetermined temperature applied during formation 420 should include a sintering temperature, TS, and a forging pressure, PF, as described herein, which will ensure the solid state sintering and deformation of the powder particles. 12, to form the fully dense powder compact 200, including bond 217 and bond layer 219 in the solid state. The steps of heating and maintaining the precursor powder compact 100 at the predetermined sintering temperature for the predetermined time may include any appropriate combination of temperature and time, and will depend, for example, on the powder 10 selected, including the materials used for the particle core 14 ee for metallic coating layer 16, the size of the precursor powder compact 100, the heating method used, and other factors influencing the time required to reach the desired temperature and temperature uniformity within the compact of precursor powder 100. In the forging step, the predetermined pressure may include any appropriate pressure and pressure application schedule or rate of pressure increase sufficient to achieve a fully dense powder compact 200, and will depend, for example, on the properties of the material of the selected powder particles 12, including temperature-dependent clamping/deformation characteristics ( eg bond/strain rate characteristics), metallurgical and phase equilibrium thermodynamic characteristics, displacement dynamics, and other material properties. For example, the dynamic forging maximum forging pressure and forging program (ie, pressure increment rates that correspond to the clamping rates employed) can be used to individualize the mechanical strength and stiffness of the powder compact. The maximum forging pressure and the rate of forging increment (ie strain rate) is the pressure just below the crack pressure, ie when dynamic recovery processes are unable to alleviate the formation work in the microstructure of the compact without the formation of a crack or the compact. For example, for applications that require a powder compact that has relatively higher strength and lower stiffness, relatively higher forging pressures and higher increment rates can be used. If a relatively higher rigidity of the powder compact is required, relatively lower pressures and forging increment rates can be used.
[0083] For certain exemplary embodiments of powders 10 described herein and precursor compacts 100 of sufficient size to form wellbore tools and components, predetermined residence times of from about 1 to about 5 hours can be used. The predetermined sintering temperature, TS, will preferably be selected, as described herein, to prevent melting of the particle cores 14 and metallic coating layers 16 as they are transformed during method 400 to produce the dispersed particles 214 and the nanomatrix 216. In these embodiments, dynamic forging can include the application of a forging pressure, such as dynamic pressing to a maximum pressure of about 552 MPa (80 ksi) at a pressure increment rate of about 3 .45 MPa (0.5 ksi) to about 13.8 MPa (2 ksi)/second.
[0084] In an exemplary embodiment in which the particle cores 14 included Mg, and the metallic coating layer 16 included several single-layer or multi-layer coating layers as described herein, such as various single-layer and multi-layer coatings comprising Al, dynamic forging was carried out by sintering at a TS temperature of about 450 oC to about 470 oC for up to about 1 hour without the application of forging pressure, and then a dynamic forging by application of isostatic pressures at increment rates from 3.45 MPa (0.5 ksi) to about 13.8 MPa (2 ksi)/second up to a maximum pressure, PS, of about 207 MPa (30 ksi) 414 MPa (60 ksi), which resulted in forging cycles from 15 seconds to about 120 seconds. The short duration of the forging cycle is a significant advantage as it limits interdiffusion, including interdiffusion within a given metallic coating layer 16, interdiffusion between adjacent metallic coating layers 16, and interdiffusion between metallic coating layers 16 and the particle cores 14, to that necessary to form the metallurgical bond 217 and the bonding layer 219, while maintaining the desirable shape of the equiaxed dispersed particle with the integrity of the reinforcing phase of the cell nanomatrix 216. Dynamic forging is much shorter than the forming cycles and sintering times for conventional powder compact forming processes such as hot isostatic pressing (HIP), pressure assisted sintering or diffusion sintering.
[0085] Method 400 may also optionally include forming 430 a powder precursor compact by compacting the plurality of coated powder particles 12 sufficiently to deform the particles and form bonds between particles and form the powder precursor compact 100 prior to forming 420 of the compact of powder. Compaction can include pressing, such as isostatic pressing, of the plurality of powder particles 12 at room temperature to form powder precursor compact 100. Compaction 430 can be carried out at room temperature. In an exemplary embodiment, powder 12 can include particle cores 14 comprising Mg, and formation 430 of the powder precursor compact 430 can be carried out at room temperature at an isostatic pressure of from about 69 MPa (10 ksi) to about 414 MPa (60 ksi).
[0086] Method 400 may also optionally include intermixing 440 a second powder 30 into powder 10, as described herein, prior to formation 420 of the powder compact, or the formation 430 of the precursor powder compact.
[0087] Without wishing to be bound by theory, powder compacts 200 are formed from powder particles 12 which include a particle core 14 and an associated core material 18, as well as a metallic coating layer 16 and a material of associated metallic coating 20, to form a substantially continuous three-dimensional cellular nanomatrix 216 which includes a material of the nanomatrix 220 formed by sintering, and the associated diffusion bonding of respective coating layers 16, which includes a plurality of dispersed particles 214 of the core materials. of particle 218. This unique structure can include metastable combinations of materials that would be very difficult or impossible to form by solidification from a melt having the same relative amounts of 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 wellbore fluid environment, where the predetermined fluid can a commonly used wellbore fluid which is injected into the wellbore or extracted from the wellbore. As should be further understood from the description provided herein, the controlled dissolution of the nanomatrix exposes the dispersed particles of core materials. The core materials of the particles can also be selected to also provide selectable and controllable dissolution in the wellbore fluid. Alternatively, they can also be selected to provide a specific mechanical property, such as compressive strength or shear strength, for the powder compact 200, without necessarily providing selectable and controlled dissolution of the core materials themselves, as dissolution The selectable and controlled nanomatrix material surrounding these particles will necessarily release them so that they are driven away by the fluid from the wellbore. The microstructural morphology of the substantially continuous cellular nanomatrix 216, which can be selected to provide a phase-enhancing material with dispersed particles 214, which can be selected to produce equiaxed dispersed particles 214, gives the powder compacts better mechanical properties , including compressive strength and shear strength, as the resulting morphology of the nanomatrix/dispersed particles can be manipulated to provide reinforcement through processes that are similar to traditional reinforcement mechanisms, such as grain size reduction, solution hardening through use of impurity atoms, precipitation or age hardening and work/force hardening mechanisms. The nanomatrix/scattered particles structure tends to limit the displacement motion due to the numerous interfaces of the particle nanomatrix, as well as the interfaces between distinct layers within the nanomatrix material, as described here. This is exemplified in the fracture behavior of these materials, as illustrated in Figures 23 and 24. In Figure 23, a powder compact 200 manufactured using uncoated pure Mg powder and subjected to shear stress sufficient to induce damage demonstrated intergranular fracture. In contrast, in Figure 24, a powder compact 200 fabricated using powder particles 12 which have particle cores 14 of pure Mg powder to form dispersed particles 214 and metallic coating layers 16, which includes Al to form nanomatrix 216 , and subjected to a shear stress sufficient to induce damage, demonstrated transgranular fracture and a substantially higher fracture stress as described herein. Due to the fact that these materials have a high strength characteristic, 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 would otherwise not provide the necessary strength characteristics for use in desired applications, including wellbore tools and components.
[0088] Although one or more embodiments have been illustrated and described, modifications and substitutions can be made thereto without departing from the spirit and scope of the invention. Accordingly, it is to be understood that the present invention has been described by way of illustration and not limitation.

权利要求:
Claims (11)
[0001]
1. Engineered composite material (200) with dispersed particle cellular nanomatrix, characterized by the fact that: it is configured for contact with a fluid and provides a selectable and controllable transition from a first strength condition to a second strength condition, which is lower than a functional endurance limit, or from a first weight loss value to a second weight loss value, which is greater than a weight loss limit, as a function of a time in contact with the fluid , and comprises a substantially continuous cellular nanomatrix (216) of a nanomatrix material (220), a plurality of dispersed particles (214) comprising a core material of the particles (218) dispersed within the nanomatrix (216) and a bonding layer. in metallic solid state (219), which spans the entire cellular nanomatrix (220), the dispersed particles (214) comprise Mg, Zn or Mn, or a combination thereof, and the cellular nanomatrix (2 16) comprises Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re, or Ni, or a combination of any of the aforementioned materials, and the nanomatrix (216) shows a chemical composition and the dispersed particles (214) have a chemical composition that is different from the chemical composition of the nanomatrix (216), and the time in contact with the fluid comprises a time required to dissolve a part of the nanomatrix in contact with the fluid .
[0002]
2. Engineering material, according to claim 1, characterized in that the cell nanomatrix (216) has an average thickness of 50 nm to 5,000 μm.
[0003]
3. Engineering material according to claim 1, characterized in that the dispersed particles (214) comprise Mg, and the composite material (200) of the dispersed particle nanomatrix has a compressive strength at room temperature of at least 255 MPa (37 ksi).
[0004]
4. Engineering material according to claim 1, characterized in that the dispersed particles (214) comprise Mg, and the composite material (200) of the dispersed particle nanomatrix has a shear strength of at least 138 MPa ( 20 ksi).
[0005]
5. Engineering material according to claim 1, characterized in that the composite material (200) of the cellular nanomatrix of dispersed particles comprises a powder compact that has a predetermined theoretical density and an actual density that is substantially equal to the predetermined theoretical density.
[0006]
6. Engineering material according to claim 1, characterized in that the dispersed particles (214) comprise Mg, and the composite material (200) of the cellular nanomatrix of dispersed particles has a density of 1.738 g/cm3 to 2 .50 g/cm3.
[0007]
7. Engineering material according to claim 1, characterized in that the particle core material (218) comprises Mg, and the powder compact is selectably dissolvable at a rate of 0 to 7,000 mg /cm2/h of the powder compact.
[0008]
8. Engineering material, according to claim 1, characterized in that the fluid is a wellbore fluid.
[0009]
9. Engineering material, according to claim 8, characterized in that the wellbore fluid comprises KCl, HCl, CaBr2, or ZnBr2, or a combination of them.
[0010]
10. Engineering material, according to claim 1, characterized in that the cellular nanomatrix between those adjacent to the plurality of dispersed particles comprises a single metallic coating layer of one particle, a bonding layer and a single coating layer metallic of another.
[0011]
11. Engineering material according to claim 1, characterized in that the cellular nanomatrix among those adjacent to the plurality of dispersed particles comprises a one-particle multilayer metallic coating layer, a bonding layer and a metallic coating layer multilayer from another.

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同族专利:

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公开号 | 公开日

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CN102781609B|2014-12-17|

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EP2509732B1|2019-11-27|

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AU2010328289B2|2014-09-11|

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US20110136707A1|2011-06-09|

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WO2011071910A3|2011-10-06|

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MY169475A|2019-04-12|

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CA2783346A1|2011-06-16|

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EP2509732A4|2015-09-23|

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WO2011071910A2|2011-06-16|

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AU2010328289A1|2012-06-07|

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BR112012013673A2|2016-04-19|

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CN102781609A|2012-11-14|

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EP2509732A2|2012-10-17|

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US9109429B2|2015-08-18|

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CA2783346C|2016-07-12|

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法律状态:
2017-08-22| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|

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2017-11-28| B09B| Patent application refused [chapter 9.2 patent gazette]|

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2018-02-14| B12B| Appeal against refusal [chapter 12.2 patent gazette]|

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2021-06-01| 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 07/12/2010, OBSERVADAS AS CONDICOES LEGAIS. PATENTE CONCEDIDA CONFORME ADI 5.529/DF |

优先权:

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申请号 | 申请日 | 专利标题

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US12/633,678|2009-12-08|

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US12/633,678|US9109429B2|2002-12-08|2009-12-08|Engineered powder compact composite material|

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PCT/US2010/059268|WO2011071910A2|2009-12-08|2010-12-07|Engineered powder compact composite material|

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