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    • 专利摘要:
    powder metal composite of nanomatrix. the present invention relates to a powdered metal composite. the powdered metal composite includes a substantially continuous cellular nanomatrix that comprises a nanomatrix material. the compact material also includes a plurality of dispersed particles comprising a particle core material comprising mg, al, zn or mn, or a combination thereof, dispersed in the nanomatrix, wherein the dispersed particle core material comprises a plurality of distributed carbon nano-particles, and a layer and bond that extends throughout the nanomatrix between the dispersed particles. powdered metal compounds from the nanomatrix are uniquely lightweight, high strength materials that also provide singularly selectable and controllable corrosion properties, including very fast corrosion rates, useful for the production of a wide variety of degradable or disposable articles, including various tools and downhole components.
    公开号:BR112013010133B1
    申请号:R112013010133-4
    申请日:2011-10-27
    公开日:2020-02-11
    发明作者:Zhiyue Xu；Soma Chakraborty；Gaurav Agrawal
    申请人:Baker Hughes Incorporated；
    IPC主号:
    专利说明:

    OF METAL IN NANOWIATRIZ PO.
    CROSS REFERENCE TO RELATED PATENT APPLICATIONS
    The present patent application claims the benefit of U.S. Patent Application 5. 12/913321, filed on October 27, 2010, which is hereby incorporated as a reference title in its entirety.
    The present patent application contains the object related to the object of the following copending patent applications: U.S. Patent Applications Serial Numbers 12,633,682; 12 / 633,686; 12 / 633,688; 12 / 633,678;
    12 / 633,683; 12 / 633,662; 12 / 633,677; and 12 / 633,668, all of which were deposited on December 8, 2009; 12 / 847,594 that was filed on July 30, 2010, Attorney Document Number OMS4-48966-US filed on the same date as this patent application, which are assigned to the same assignee of the present patent application, Baker Hughes 15 Incorporated de Houston, Texas; and which are incorporated herein by reference in their entirety.
    BACKGROUND
    Oil and natural gas wells often use components or tools from the well bore which, due to their function, need only have limited service lives that are considerably shorter than the life of the well. After the utility function of a component or tool is completed, it must be removed or discarded in order to recover the original size of the fluid passage for use, including hydrocarbon production, CO 2 sequestration, etc. The disposal of the 25 components or tools has been carried out conventionally through milling or perforation removal of the component or tool out of the well bore, which are generally time-consuming and expensive operations.
    In order to eliminate the need for milling or drilling operations, the removal of components or tools by dissolving degradable polylactic polymers when using various fluids from the well bore has been proposed. However, these polymers generally do not have mechanical resistance.
    2/53 unique, fracture resistance and other mechanical properties necessary to perform the functions of the well bore components or tools in the well bore operating temperature range, therefore, their application has been limited.
    Other degradable materials have been proposed, including certain degradable metal alloys formed by certain reactive metals in a larger portion, such as aluminum, in conjunction with other alloy constituents in a smaller portion, such as gallium, indium, bismuth , tin and mixtures and combinations thereof, and without excluding certain secondary alloying elements, such as zinc, copper, silver, cadmium, lead, and mixtures and combinations thereof. These materials can be formed by melting the constituent powders and then solidifying the melt to form the alloy. They can also be formed by using powder metallurgy through pressing, compression, sintering, and others, from a powder mixture of a reactive metal and another constituent of the alloy in the mentioned amounts. These materials include many combinations that use metals, such as lead, cadmium, and others, which may not be suitable for release into the environment in conjunction with the degradation of the material. In addition, their formation may involve several melting phenomena that result in alloy structures that are dictated by the phase equilibria and the solidification characteristics of the respective alloy constituents, and that may not result in ideal or desirable alloy microstructures, properties mechanical or dissolving characteristics.
    Therefore, the development of materials that can be used to form well hole components and tools that have the necessary mechanical properties to perform their intended function and then removed from the well hole through controlled dissolution when using well hole fluids is very desirable.
    SUMMARY
    An exemplary embodiment of a powdered metal composite is presented. The powdered metal composite includes a cell nanomatrix
    3/53 substantially continuous home comprising a nanomatrix material. The compact material also includes a plurality of dispersed particles which comprise a particle core material comprising Mg, Al, Zn or Mn, or a combination thereof, dispersed in the nanomatrix, wherein the dispersed particle core material comprises a plurality of distributed carbon nanoparticles, and a bonding layer that extends across the nanomatrix between the scattered particles.
    Another exemplary embodiment of a powdered metal composite is also presented. The powdered metal composite includes a substantially continuous cellular nanomatrix that comprises a nanomatrix material. The compact material also includes a plurality of dispersed particles that comprise a particle core material that comprises a metal that has a lower standard oxidation potential than Zn, ceramic, glass or carbon, or a combination thereof, dispersed in the nanomatrix, and the core material of the dispersed particles comprises a plurality of distributed carbon nanoparticles and a bonding layer that extends throughout the nanomatrix between the dispersed particles.
    BRIEF DESCRIPTION OF THE DRAWINGS
    With reference now to the drawings in which the identical elements are numbered identically in the various figures:
    FIG. 1 is a microphotograph of a powder 10 as indicated herein that has been embedded in an epoxy specimen assembly material and sectioned;
    FIG. 2 is a schematic illustration of an exemplary embodiment of a powder particle 12 as it should appear in an exemplary view of the section represented by section 2-2 of FIG. 1;
    FIG. 3 is a schematic illustration of a second exemplary embodiment of a powder particle 12 as it should appear in a second exemplary view of the section represented by section 2-2 of FIG. 1;
    FIG. 4 is a schematic illustration of a third modali
    4/53 example of a dust particle 12 as it should appear in a third example view of the section represented by section 2-2 of FIG. 1;
    FIG. 5 is a schematic illustration of a fourth exemplary embodiment of a powder particle 12 as it should appear in a fourth exemplary view of the section represented by section 2-2 of FIG. 1;
    FIG. 6 is a schematic illustration of a second exemplary embodiment of a powder as indicated herein that has a multimodal particle size distribution;
    FIG. 7 is a schematic illustration of a third exemplary embodiment of a powder as indicated herein that has a multimodal particle size distribution;
    FIG. 8 is a flow chart of an exemplary embodiment of a powder production method as indicated herein;
    FIG. 9 is a microphotograph of an exemplary embodiment of a compact powder material as indicated herein;
    FIG. 10 is a schematic diagram of the illustration of an exemplary embodiment of the compact powder material of FIG. 9 produced when using a powder that has powder particles coated with a single layer as it should appear taken throughout section 10-10;
    FIG. 11 is a schematic illustration of an exemplary embodiment of a compact powder material as indicated herein that has a homogeneous multimodal particle size distribution;
    FIG. 12 is a schematic illustration of an exemplary embodiment of a compact powder material as indicated herein that has an inhomogeneous multimodal particle size distribution;
    FIG. 13 is a schematic illustration of an exemplary embodiment of a compact powder material as indicated herein formed from a first powder and a second powder and which has a homogeneous multimodal particle size distribution;
    FIG. 14 is a schematic illustration of a modality and
    5/53 xemplifier of a compact powder material as indicated herein formed from a first powder and a second powder and which has a non-homogeneous multimodal particle size distribution;
    FIG. 15 is a schematic diagram of the illustration of another exemplary embodiment of the compact powder material of FIG. 9 produced by using a powder that has multilayer coated powder particles as it should appear taken throughout section 10-10;
    FIG. 16 is a schematic cross-sectional illustration of an exemplary embodiment of a compact precursor powder material;
    and FIG. 17 is a flow chart of an exemplary embodiment of a method of producing a compact powder material as indicated herein.
    DETAILED DESCRIPTION
    High strength, lightweight metal materials are featured that can be used in a wide variety of applications and application environments, including use in various well bore environments to make various well bore tools or other well bore components lightweight, high strength and selective and controllably disposable or degradable, as well as many other applications for use in durable and disposable or degradable articles. These lightweight, high strength and selective and controllably degradable materials include compact, fully dense sintered materials formed from powder coated materials that include multiple lightweight particle cores and core materials that have multiple single layer nanoscale coatings. and multilayered. These compact powder materials are made from coated metal powders that include multiple particle cores and electrochemically active core materials (for example, which have relatively high standard oxidation potentials) light weight and high strength, such as electrochemically active metals , which are dispersed as particles dispersed within a cellular nanomatrix formed from the various layers of metallic nanocaps
    6/53 shedding of metallic lining materials, and are particularly useful in borehole applications. The core material of the dispersed particles also includes a plurality of distributed carbon nanoparticles. These compact powder materials provide a unique and advantageous combination of mechanical strength properties, such as compression and shear strength, low density and selectable and controllable corrosion properties, particularly fast and controlled dissolution in various well-hole fluids. For example, the particle core and coating layers of these powders can be selected to provide sintered compact powder materials suitable for use as high-strength designed materials that have a compressive strength and shear strength comparable to many other materials designed, including carbon, stainless steel and steel alloys, but which also have a low density compared to various polymers, elastomers, low-density porous ceramics and composite materials. As yet another example, these powders and compact powder materials can be configured to provide selectable and controllable degradation or disposal in response to a change in an ambient condition, such as a transition from a very low rate of dissolution to a speed very rapid dissolution in response to a change in a well hole property or condition close to an article formed from the compact material, including a change of property in a well hole fluid that is in contact with the compact material in powder. The selectable and controllable degradation or disposal characteristics described also allow for dimensional stability and resistance of articles, such as tools or other well bore components, made from these materials to be maintained until they are no longer needed, when then a predetermined ambient condition, such as a well hole condition, including temperature, pressure or pH value of the well hole fluid, can be changed to promote its removal by rapid dissolution. These powder coated materials and compact powder materials and projected materials formed from them,
    7/53 as well as the production methods thereof, are described below. The distributed carbon nanoparticles provide more reinforcement of the core material of the dispersed particles, thereby giving greater resistance to the compact powder material compared, for example, to the compact powder materials that have dispersed particle cores that do not include them. In addition, the density of certain distributed carbon nanoparticles may be lower than that of the core materials of the dispersed metal particles, thereby allowing compact powder materials with a lower density, in comparison, for example, to compact materials powder that have dispersed particle cores that do not include them. Thus, the use of carbon nanoparticles distributed in compact composite materials of nanomatrix metal can provide materials that have even higher relationships between strength and weight than compact nanomatrix metal materials that do not include distributed carbon nanoparticles. .
    With reference to FIGURES 1-5, a metallic powder 10 includes a plurality of metallic coated powder particles 12. The powder particles 12 can be formed to provide a powder, including a free flowing powder, which can be poured or otherwise disposed of. in all manner of shapes or molds (not shown) that have all manner of shapes and sizes and that can be used to form the precursor compact powder materials 100 (FIG. 16) and 200 compact powder materials (FIGURESFIGURES ΙΟΙ 5), as described herein, which can be used as, or for use in the manufacture of, various articles of manufacture, including various well bore tools and components 10.
    Each of the metallic powder coated particles 12 of the powder 10 includes a particle core 14 and a metallic coating layer 16 arranged on the particle core 14. The particle core 14 includes a core material 18. The core material 18 can include any material suitable for forming the particle core 14 which provides the powder particle 12 which can be sintered to form a lightweight, high strength 200 compact powder material which has dissolving characteristics if
    8/53 selectable and controllable. Suitable core materials include electrochemically active metals that have a standard oxidation potential greater than or equal to that of Zn, including as Mg, Al, Mn or Zn or a combination thereof. These electrochemically active metals are very reactive with a number of common well-hole fluids, including any number of ionic fluids or highly polar fluids, such as those containing various chlorides. Examples include fluids comprising potassium chloride (KCI), hydrochloric acid (HCI), calcium chloride (CaCl 2 ), calcium bromide (CaBr 2 ) or zinc bromide (ZnBr 2 ). Core material 18 may also include other metals that are less electrochemically active than Zn or non-metallic materials, or a combination thereof. Suitable non-metallic materials include ceramics, composites or glass. Core material 18 includes a plurality of distributed carbon nanoparticles 90 as described herein. As used herein, at least some of the powder particles 12 of the powder 10 will include the particle cores 14 which have the core material 18 which includes a plurality of distributed carbon nanoparticles 90. Thus, a plurality of carbon nanoparticles distributed particles 90 may be present in each of the powder particles 12, or only in a portion of the powder particles 12. Furthermore, although in one embodiment the powder particles 12 that include the distributed carbon nanoparticles 90 include a plurality of them , it is also possible to distribute a single carbon nanoparticle 90 within the particle core 14. Core material 18 can be selected to provide a high rate of dissolution in a predetermined well bore fluid, but it can also be selected to provide a relatively low dissolution rate, including zero dissolution, where the nanomat material dissolves riz causes the particle core 14 to be rapidly weakened and released from the compact particle material at the interface with the well bore fluid, such that the effective rate of dissolution of the compact particle materials obtained when using the particle cores 14 of these 18 core materials are high, even though the ma itself
    Core material 18/53 may have a low dissolution rate, including core materials 20 which may be substantially insoluble in the well hole fluid.
    With respect to electrochemically active metals such as 18 core materials, including Mg, Al, Mn or Zn, these metals can be used as pure metals or in any combination with each other, including various combinations of alloys of these materials , including binary, tertiary or quaternary alloys of these materials. These combinations can also include composites of these materials. In addition, in addition to combinations of each other, Mg, Al, Mn or Zn core materials 18 may also include other constituents, including various splicing additions, to alter one or more properties of particle cores 14, such as such as improving strength, lowering density, or changing the dissolution characteristics of the core material 18.
    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, since 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. Magnesium alloys that combine other electrochemically active metals, as described herein, as constituents of the alloy, are in particular useful, including the binary Mg-Zn, Mg-AI and Mg-Mn alloys, as well as the tertiary Mg alloys -Zn-Y and Mg-AI-X, where X includes Zn, Mn, Si, Ca or Y, or a combination thereof. Such Mg-AI-X alloys can include, by weight, up to about 85% Mg, up to about 15% Al and up to about 5% X. The particle core 14 and the core material 18, and in particular electrochemically active metals including Mg, Al, Mn or Zn, or combinations thereof, may also include a terrarara element or a combination of rare earth elements. As used herein, rare earth elements include Sc, Y, La, Ce, Pr, Nd or Er, or a combination of rare earth elements. Where present, one he
    10/53 rare earth elements or combinations of rare earth elements may be present, by weight, in an amount of about 5% or less.
    The particle core 14 and the core material 18, including the distributed carbon nanoparticles 90, have a melting temperature (Tp). As used herein, T P includes the lowest temperature at which incipient melting or liquidation or other forms of partial melting occur within the core material 18, regardless of whether the core material 18 comprises a pure metal, an alloy with multiple phases that have different melting temperatures or a composite of materials that have different melting temperatures.
    Particle cores 14 can have any particle size or particle size range or appropriate particle size distribution. For example, particle cores 14 can be selected so as to provide an average particle size that is represented by a normal or Gauss-like unimodal distribution around an average or medium, as illustrated generally in FIG. 1. In another example, particle cores 14 can be selected or mixed to provide a multimodal particle size distribution, including a plurality of average particle core sizes, such as, for example, a homogeneous bimodal size distribution particle averages, as illustrated generally and schematically in FIG. 6. The selection of the particle size distribution can be used to determine, for example, the particle size and the interparticle spacing 15 of the particles 12 of the powder 10. In an exemplary embodiment, the particle cores 14 can have a unimodal distribution and an average particle diameter of about 5 pm to about 300 pm, more particularly from about 80 pm to about 120 pm, and even more particularly about 100 pm.
    The particle cores 14 can have any suitable particle shape, including any regular or irregular geometric shape, or a combination thereof. In an exemplary embodiment, particle cores 14 are electrochemically active metal particles
    11/53 substantially spheroidal. In another exemplary embodiment, particle cores 14 are ceramic particles, including ceramic particles of regular and irregular shapes. In yet another exemplary embodiment, the particle cores 14 are hollow glass microspheres.
    The particle cores 14 of metallic coated powder particles 12 of the powder 10 also include a plurality of distributed carbon nanoparticles 90 dispersed within the core material 18. The distributed carbon nanoparticles 90 may include carbon nanoparticles of any suitable allotrope. Suitable allotropes include diamond (nanodiamond) nanoparticles; graphite, including various graphenes; fullerenes, including multiple buckyballs, sets of buckyballs, nanobuds or nanotubes, and including single-walled or multi-walled nanotubes; amorphous carbon; glassy carbon; carbon nano-foam; lonsdaleite; or chaoita, or a combination of them. The distributed carbon nanoparticles 90 can have any suitable nanoparticle shape or size. As used herein, a nanoparticle can include several regular and irregular particle shapes, including planar, spheroidal, ellipsoidal and tubular or cylindrical shapes, having at least a particle size of about 100 nm or less, and more particularly at least one particle size between about 0.1 nm and about 100 nm, and more particularly about 1.0 nm to about 100 nm. The distributed carbon nanoparticles 90 may also include metallized nanoparticles that have a metal disposed therein, such as, for example, a metal layer disposed on an outer surface of the carbon nanoparticle. Suitable carbon nanoparticles include several graphenes; fullerenes or nanodiamonds, or a combination thereof. Suitable fullerenes can include buckyballs, sets of buckyballs, buckeypapers, nanobuds or nanotubes, including single-walled nanotubes and multi-walled nanotubes. Fullerenes can also include three-dimensional polymers of any of the above elements. Suitable fullerenes can also
    12/53 may also include metallopherenes, or those fullerenes that encompass various metals or metal ions.
    Fullerenes in the form of substantially spheroidal hollow polyhedra or buckyballs, as indicated herein, can include any of the known hollow cage-type allotropic forms of carbon that have a polyhedral structure. Buckyballs can include, for example, about 20 to about 100 carbon atoms. For example, C60 is a fullerene that has 60 carbon atoms and a high symmetry (D 5h ), and a relatively common commercially available fullerene. Exemplary fullerenes include, for example, C30, C32, C34, C38, C40, C42, C44, C46, C48, Cso, CS2, C60, C70, C76, or C84 and others, or combinations thereof. Buckuballs or sets of buckyballs can include any size or diameter of sphere, including substantially spheroidal configurations that have any number of carbon atoms.
    Nanotubes are tubular or cylindrical carbon based structures that have open or closed ends, which can be inorganic or made entirely or partially of carbon, and can also include other elements such as metals or metalloids. Both single-walled and multi-walled nanotubes are substantially cylindrical and can have any predetermined tube length or tube diameter, or combinations thereof. Multi-walled nanotubes can have any predetermined number of walls.
    Nanographite is a graphite plate-type agglomerate, in which a stacked structure of one or more layers of graphite, which has a two-dimensional structure of the fused hexagonal ring type with an extended, relocated π-electron system, in layers and weakly linked together through a π-π stacking interaction. Graphene in general, and including nanographene, can be a single sheet or several sheets of graphite that have nanoscale dimensions, such as an average particle size of (larger mean size) less than about, for example, 500 nm in the , or in other modalities may have a larger average size of more than about 1 pm. The nanographene can be prepared
    13/53 by the nanografite exfoliation or can be subjected to a catalytic bond disruption of a series of carbon-carbon bonds in a carbon nanotube to form a nanographene ribbon by an unfolding process, followed by the nanographene derivatization to prepare , for example, nanographene oxide. Graphene nanoparticles can be of any suitable predetermined planar size, including any predetermined length or predetermined width, and can thus include any predetermined number of carbon atoms.
    The nanodiamonds employed here may be from a natural source, such as a by-product of milling or other processing of natural diamonds, or may be synthetic, prepared by any appropriate commercial method such as, but not limited to, high temperature and high pressure (HPHT), explosive shock (also known as detonation, abbreviated as DTD), chemical vapor deposition (CVD), physical vapor deposition (PVD), ultrasonic cavitation, and others. Nanodiamonds can be used as received, or can be classified and cleaned by various methods to remove contaminants and non-diamond carbon phases that may be present, such as amorphous carbon waste or graphite. Nanodiamonds can be monocrystalline or polycrystalline. Nanodiamonds can include several regular and irregular shapes, including substantially spheroidal shapes. Nanodiamonds can be monodispersed, where all particles are the same size with little variation, or polydispersed, where particles have a range of sizes and are averaged. Polydispersed nanodiamonds are generally used. The medium-sized nanodiamonds of die-facing particles can be used, and in this way the particle size distribution of the nanodiamonds can be unimodal (showing a single distribution), bimodal showing two distributions, or multimodal, showing more than one particle size distribution , as described here.
    The carbon nanoparticles distributed 90 can be distributed both homogeneously and heterogeneously within the naked material
    14/53 cleo 18. For example, in an exemplary embodiment of a homogeneous distribution, a plurality of carbon nanoparticles of the same type, including those that have the same size and shape, can be distributed or evenly dispersed within each nucleus of particle 14 and throughout the core material 18 thereof. In another exemplary embodiment of a heterogeneous distribution, a plurality of different types of carbon nanoparticles, including those having a different size, shape, or both, can be distributed uniformly or non-uniformly within each of the particle cores. 14 and throughout the core material 18 thereof. In another exemplary embodiment of a heterogeneous distribution, the distributed carbon nanoparticles 90 can preferably be distributed (for example, in a higher volumetric concentration), for example, around a periphery of the particle nucleus 14, or towards the interior of the particle core 14.
    The distributed carbon nanoparticles 90 can be used in any appropriate relative amount of the particle core 14 into which they are distributed, whether by weight, volume or percentage of atom. In an exemplary embodiment, the distributed carbon nanoparticles 92 can include about 20 percent or less by weight, and more particularly about 10 percent or less by weight, and even more particularly about 5 percent or less by weight.
    Each of the metallic coated powder particles 12 of the powder 10 also includes a metallic coating layer 16 which is arranged on the particle core 14. The metallic coating layer 16 includes a metallic coating material 20. The metallic coating material 20 gives powder particles 12 and powder 10 their metallic nature. The metallic coating layer 16 is a nanoscale coating layer. In an exemplary embodiment, the metallic coating layer 16 can have a thickness of about 25 nm to about 2500 nm. The thickness of the metal cladding layer 16 can vary on the surface of the particle core 14, but should preferably have a substantially uniform thickness on the surface of the particle core
    15/53
    14. The metal cladding layer 16 may include a single layer, as illustrated in FIG. 2, or a plurality of layers as a multilayer coating structure, as illustrated in FIGURES 3-5 for up to four layers. In a single layer coating, or in each layer of a multilayer coating, the metal coating layer 16 may include a single constituent chemical element or compound, or it may include a plurality of chemical elements or compounds. Where a layer includes a plurality of chemical constituents or compounds, they can have any form of homogeneous or heterogeneous distributions, including a homogeneous or heterogeneous distribution of metallurgical phases. This can include a graduated distribution in which the relative amounts of constituents or chemical compounds vary according to the respective constituent profiles through the thickness of the layer. In both single and multi-layer coatings 16, each of the respective layers, or combinations thereof, can be used to provide a predetermined property to the powder particle 12 or a sintered powder compact material formed from the same. For example, the predetermined property can include the bond strength of the metallurgical bond between the particle core 14 and the coating material 20; the interdiffusion characteristics between the particle core 14 and the metallic coating layer 16, including any interdiffusion between the layers of a multilayer coating layer 16; the interdiffusion characteristics between the various layers of a multilayer coating layer 16; the interdiffusion characteristics between the metallic coating layer 16 of a powder particle and that of an adjacent powder particle 12; the bond strength of the metallurgical bond between the metallic coating layers of the adjacent sintered powder particles 12, including the outermost layers of multilayer coating layers; and the electrochemical activity of the coating layer 16.
    The metallic coating layer 16 and the coating material 20 have a melting temperature (T c ). As used herein, the
    16/53
    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 multiple phases, each with different melting temperatures or a composite, which includes a compound comprising a plurality of layers of coating material having different melting temperatures.
    The metallic coating material 20 can include any suitable metallic coating material 20 that provides a sinterable outer surface 21 which is configured to be sintered to an adjacent powder particle 12 which also has a metallic coating layer 16 and sinterable outer surface 21. In powders 10 which also include additional second particles (coated or uncoated) 32, as described herein, the sinterizable outer surface 21 of the metallic coating layer 16 is also configured to be sintered to a sinterable outer surface 21 of second particles 32. In an exemplary embodiment, the powder particles 12 are sinterizable at a predetermined sintering temperature (T s ) which is a function of the core material 18 and the coating material 20, such that the sintering of the compact powder material 200 is performed entirely in the solid state and where T s is less than T P and T c . Sintering in the solid state limits interactions between the 14 / particle core and the metallic cladding layer for solid-state diffusion processes and metallurgical transport phenomena and limits the growth of and provides control over the resulting interface between them . On the other hand, for example, the introduction of liquid phase sintering should provide for the rapid interdiffusion of the coating materials from layer 16 of the particle core 14 / metal coating layer and makes it difficult to limit the growth of and the provision of control over the resulting interface between them, and thereby interferes with the formation of the desirable microstructure of the compact particle material 200 as described herein.
    In an exemplary embodiment, the core material 18
    17/53 will be selected to provide a chemical composition of the core and coating material 20 will be selected to provide a chemical coating composition and these chemical compositions will also be selected to differ from each other. In another exemplary embodiment, core material 18 will be selected to provide a chemical composition of the core and coating material 20 will be selected to provide a chemical coating composition, and these chemical compositions will also be selected to differ from each other in your interface. Differences in the chemical compositions of coating material 20 and core material 18, including distributed carbon nanoparticles 90, can be selected to provide different dissolution rates and the selectable and controllable dissolution of the compact powder materials 200 incorporating the same and make them selectively and controllably dissolvable. This includes dissolution rates that differ in response to an altered well hole condition, including an indirect or direct change in a fluid from the well hole. In an exemplary embodiment, a compact powder material 200 formed from powder 10 that has chemical compositions of core material 18 and coating material 20 that make compact material 200 selectively dissolvable in a well bore fluid in response to an altered well hole condition that includes a change in temperature, a change in pressure, a change in flow, a change in pH or a change in the chemical composition of the fluid from the well hole, or a combination thereof. The response of the selectable dissolution to the altered condition may result from actual chemical reactions or processes that promote different dissolution rates, but it also encompasses the changes in the dissolution response that are associated with the physical reactions or processes, such as changes in pressure or fluid flow from the well bore.
    In an exemplary embodiment of a powder 10, the particle core 14 includes Mg, Al, Mn or Zn, or a combination thereof, as core material 18, and more particularly can include pure Mg and Mg alloys, and the layer metal cladding 16 includes Al, Zn, Mn, Mg, Mo, W,
    18/53
    Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or an oxide, nitride or carbide thereof, or a combination of any of the materials mentioned above as coating material 20.
    In another exemplary embodiment of powder 10, the particle core 14 includes Mg, Al, Mn or Zn, or a combination thereof, as core material 18, and more particularly can include pure Mg and Mg alloys, and the layer Metallic coating 16 includes a single layer of Al or Ni, or a combination thereof, as coating material 20, as illustrated in FIG. 2. Where the metallic cladding layer 16 includes a combination of two or more constituents, such as Al and Ni, the combination may include several graduated or codeposited structures of these materials where the quantity of each constituent, and thus the composition of the layer, varies through the thickness of the layer, also as illustrated in FIG. 2.
    In yet another exemplary embodiment, the particle core 14 includes Mg, Al, Mn or Zn, or a combination thereof, as core material 18, and more particularly can include pure Mg and Mg alloys, and the coating layer 16 includes two layers as core material 20, as illustrated in FIG. 3. The first layer 22 is disposed on the surface of the particle core 14 and includes Al or Ni, or a combination thereof, as described herein. The second layer 24 is arranged on the surface of the first layer and includes Al, Zn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or a combination thereof, and the first layer has a chemical composition that is different from the chemical composition of the second layer. In general, the first layer 22 should be selected to provide a strong metallurgical bond to the particle core 14 to limit the interdiffusion between the particle core 14 and the coating layer 16, in particular the first layer 22. The second layer 24 can be selected to increase the strength of the metallic coating layer 16, or to provide a strong metallurgical bond and promote sintering with the second layer 24 of adjacent powder particles 12, or both. In an exemplifying modality, the respective layers of the ca
    19/53 metallic coating layer 16 can be selected to promote selective and controllable dissolution of coating layer 16 in response to a change in a well hole property, including the well hole fluid, as described herein. However, this is only an example and it should be appreciated that other selection criteria for the various layers can also be employed. For example, some of the respective layers may be selected to promote the selective and controllable dissolution of the coating layer 16 in response to a change in a well hole property, including the well hole fluid, as described herein. Exemplary embodiments of a two-layer metallic coating layer 16 for use in particle cores 14 comprising Mg include combinations of the first and second layers comprising Al / Ni and Al / W.
    In yet another embodiment, the particle core 14 includes Mg, Al, Mn or Zn, or a combination thereof, as core material 18, and more particularly can include pure Mg and Mg alloys, and the coating layer 16 includes three layers, as illustrated in FIG. 4. The first layer 22 is arranged on the particle core 14 and can include Al or Ni, or a combination thereof. The second layer 24 is arranged 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 carbide of themselves, or a combination of any of the above mentioned second layer materials. The third layer 26 is disposed on the second layer 24 and can include Al, Mn, Fe, Co, Ni or a combination thereof. In a three-layer configuration, the composition of adjacent layers is different, such that the first layer has a chemical composition that is different from the second layer, and the second layer has a chemical composition that is different from the third layer. In an exemplary embodiment, the first layer 22 can be selected to provide a strong metallurgical bond to the particle core 14 and to the interdiffusion of the boundary between the core 14 and coating layer 16 of the particle, in particular first layer 22. The second layer 24 can be selected for
    20/53 to increase the strength of the metal cladding layer 16, or to limit the interdiffusion between the particle core 14 or the first layer 22 and third outer 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 of the adjacent powder particles 12. However, this is only an example and it should be appreciated that other selection criteria for the various layers can also be employed. For example, some of the respective layers may be selected to promote the selective and controllable dissolution of the coating layer 16 in response to a change in a well hole property, including the well hole fluid, as described herein. An exemplary embodiment of a three-layer coating layer for use in the particle cores comprising Mg includes combinations of the first, second and third layers comprising AI / AI 2 O 3 / AI.
    In yet another embodiment, the particle core 14 includes Mg, Al, Mn or Zn, or a combination thereof, as core material 18, and more particularly can include pure Mg and Mg alloys, and the coating layer 16 includes four layers, as illustrated in FIG. 5. In the four-layer configuration, the 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, a nitride, a carbide thereof, or a combination of the materials of the second layer mentioned above. 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 any one of the above mentioned third layer materials. The fourth layer 28 may include Al, Mn, Fe, Co, Ni or a combination thereof in the four-layer configuration, in which the chemical composition of the adjacent layers is different, such that the chemical composition of the first layer 22 is different the chemical composition of the second
    21/53 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) and outer (fourth) layers, with the second and third layers available to provide enhanced interlayer adhesion, overall strength of the coating layer metallic 16, limited interlayer diffusion or selectable and controllable dissolution, or a combination thereof. However, this is only an example and it should be appreciated that other selection criteria for the various layers can also be employed. For example, any of the respective layers can be selected to promote the selective and controllable dissolution of the coating layer 16 in response to a change in a well hole property, including the well hole fluid, as described herein.
    The thickness of the various layers in multi-layer configurations can be apportioned among the various layers in any way as long as the sum of the layer thicknesses provide a nanoscale coating layer 16, including layer thicknesses as described herein. In one embodiment, the first layer 22 and the outer layer (24, 26, or 28 depending on the number of layers) can be thicker than other layers, where present, due to the desire to provide sufficient material to promote the desired bond of the first layer 22 with the particle core 14, or the bonding of the outer layers of the adjacent powder particles 12, during the sintering of the compact powder material 200.
    The powder 10 can also include an additional second powder 30 interspersed in the plurality of powder particle 12, as illustrated in FIG. 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 alter a physical, chemical, mechanical or
    22/53 other than a compact powder particle material 200 formed from powder 10 and the second powder 30, or a combination of such properties. In an exemplary embodiment, the change in property may include an increase in the compressive strength of the compact powder material 200 formed from powder 10 and the second powder 30. In another exemplary embodiment, the second powder 30 can be selected to promote selective and controllable dissolution in the compact particle material 200 formed from powder 10 and second powder 30 in response to a change in a well hole property, including the well hole 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 multilayer coatings, the coating layer 36 of the second powder particles 32 can comprise the same material coating material 40 that the coating material 20 of the powder particles 12, or the coating material 40 may be different. Second powder particles 32 (uncoated) or particle cores 34 can include any material suitable for providing the desired benefit, including many metals. The core material, the second powder particles 32 (uncoated) or the particle cores 34 can also include a plurality of second dispersed carbon particles 92 as described herein. The second distributed carbon nanoparticles 92 may be any of those described herein, and may be the same nanoparticles and the same distribution as the first carbon nanoparticles, or different nanoparticles, or a different distribution, or both. Analogous to the first carbon nanoparticles 90, the second carbon nanoparticles 92 can also include a metal layer 93 arranged thereon. The composition of the metal layer 93 can be selected to include the same composition as the second core material 38 to improve the mixing of the second carbon nanoparticles 92 in the melt, or it can be selected to have a composition that is different from the second carbon material. core 38, and can be selected to alloy and mix with the second core material
    23/53
    38, or to avoid mixing and alloying with the second core material 38, for example. The metal layer 93 can also be disposed on the second carbon nanoparticle 92 by any appropriate method, including various methods of chemical or physical deposition, and more particularly including plating, chemical vapor deposition methods or physical deposition methods of steam, and even more particularly through various FBCVD methods. In an exemplary embodiment, when coated powder particles 12 comprising Al, Mn or Zn, or a combination thereof, the appropriate second powder particles 32 may include Ni, W, Cu, Co or Fe, or a combination of them, since the second powder particles 32 will also be configured for solid state sintering for the powder particles 12 at the predetermined sintering temperature (TS), the particle cores 34, including all the second distributed carbon nanoparticles 92, will have a melting temperature T A p and any of the coating layers 36 will have a second melting temperature T A c, where Ts is less than T A p and T A c- It should also be appreciated that the second powder 30 is not limited to an additional powder particle type 32 (i.e., a second dust particle), but can include a plurality of additional particles 32 (i.e., second, third, fourth, etc.). , additional powder particle types 32) in any number, each of which may also include second distributed carbon nanoparticles 92.
    With respect to FIG. 8, an exemplary embodiment of a method 300 of producing a metallic powder 10 is shown. Method 300 includes the formation 310 of a plurality of particle cores 14, including distributed carbon nanoparticles 90, as described herein. Method 300 also includes depositing 320 of a metallic coating layer 16 on each core of the plurality of particle cores 14. Deposition 320 is the process by which coating layer 16 is arranged on particle core 14 such as described here.
    The formation 310 of the particle cores 14 can be performed by any appropriate method for the formation of a plurality of numbers
    Particle oils 14 of the desired core material 18, which essentially comprise methods of forming a powder of core material 18. Suitable powder forming methods include mechanical methods; including machining, milling, impaction and other mechanical methods for forming metal powder; chemical methods, including chemical decomposition, precipitation of a liquid or gas, reactive solid-solid synthesis and other chemical powder formation methods; atomization methods, including gas atomization, liquid and water atomization, centrifugal atomization, plasma atomization and other atomization methods for the formation of a powder; and various methods of evaporation and condensation.
    The distributed carbon nanoparticles 90 can be dispersed within the particle cores 14 and the core material 18 by any appropriate method of distribution or dispersion that is compatible with the particle nucleus forming method 14. In an exemplary embodiment, particle cores 14 comprising Mg can be manufactured using an atomization method, such as vacuum spray formation or inert gas spray formation. The distributed carbon nanoparticles 90 can be distributed within a melting mass of the core material 18 prior to atomization to form particle nuclei 14, such as when using various mixing methods to add the carbon 90 nanoparticles to the melting mass. . In an exemplary embodiment, the carbon nanoparticles 90 may include a layer of metal 91 disposed over them. The composition of the metal layer 91 can be selected to include the same composition as the core material 18 to improve the mixing of the carbon nanoparticles 90 m to the melt mass, or can be selected to have a composition that is different from the core material 18, and can be selected for alloying and mixing with core material 18, or to avoid mixing and alloying with core material 18, for example. The metal layer 91 can be arranged on the carbon nanoparticles 90 by any appropriate method,
    25/53 including various methods of chemical or physical deposition, and more particularly including plating, chemical vapor deposition methods of physical vapor deposition, and even more particularly by means of various FBCVD methods.
    Deposition 320 of the metallic coating layers 16 on the plurality of particle cores 14 can be performed using any appropriate deposition method, including various thin film deposition methods, such as, for example, chemical vapor deposition methods and of physical vapor deposition. In an exemplary embodiment, the deposition 320 of the metallic coating layers 16 is performed using chemical fluidized bed vapor deposition (FBCVD). Deposition 320 of the metallic coating layers 16 by FBCVD includes the flow of 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 vessel under appropriate conditions , including conditions of temperature, pressure and flow, and still others, sufficient to induce a chemical reaction of the coating medium to produce the desired metallic coating material 20 and induce its deposition on the surface of the particle cores 14 to form the particles powder coatings 12. The reactive fluid selected will depend on the desired metallic coating material 20, and will typically comprise an organometallic compound that includes the metallic material to be deposited, such as nickel tetracarbonyl (Ni (CO) 4 ), tungsten hexafluoride ( WF 6 ), and triethyl aluminum (C 6 H 15 AI), which is transported in a fluid carrier pain, such as helium or argon gas. The reactive fluid, including the carrier fluid, causes at least a portion of the plurality of particle numbers 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, example, a desired organometallic constituent, and allowing deposition of the metallic coating material 20 and the coating layer 16 on all surfaces of the particle cores 14 in such a way that each is closed, forming the particles
    Coated 26/53 12 having metallic coating layers 16, as described herein. Also as described herein, each metallic coating layer 16 can include a plurality of coating layers. The coating material 20 can be deposited in multiple layers to form a multilayer metallic coating layer 16 by repeating the deposition step 320 described above and changing the reactive fluid 330 to provide the desired metallic coating material 20 for each layer subsequent layer, where each subsequent layer is deposited on the outer surface of the particle cores 14 which already include any previously deposited coating layer or layers that make up the metallic coating layer 16. The metallic coating materials 20 of the respective layers (for example, 22, 24, 26, 28, etc.) can be different from each other, and the differences can be provided by using different reactive media that are configured to produce the desired metallic coating layers 16 on the particle cores 14 in the reactor. fluidized bed.
    As illustrated in FIGURES 1 and 9, particle core 14 and core material 18, including distributed carbon nanoparticles 90, and metallic coating layer 16 and coating material 20, can be selected to provide the particles of powder 12 and a powder 10 which is configured for compaction and sintering to obtain a compact powder material 200 that is lightweight (that is, with a relatively low density), high strength and is selectively and controllably removable from a well bore in response to a change in a well bore property, including the fact that it is selectively and controllably dissolvable in an appropriate well bore fluid, including various well bore fluids as indicated herein. The compact powder material 200 includes a substantially continuous cellular nanomatrix 216 of a nanomatrix material 220 that has a plurality of dispersed particles 214 that are dispersed throughout the cellular nanomatrix 216. The substantially continuous nanomatrix 216 and the nanomatrix material 220 formed of sintered metal cladding layers 16 is formed by the compac
    27/53 removal and sintering of the plurality of metallic coating layers 16 of the plurality of powder particles 12. The chemical composition of nanomatrix material 220 may be different from that of coating material 20 due to the diffusion effects associated with sintering such as described here. The powdered metal compound 200 also includes a plurality of dispersed particles 214 comprising the particle core material 218. The scattered particle cores 214 and the core material 218 correspond to and are formed from the plurality of particle cores 14 and the core material 18 of the plurality of powder particles 12, since the metallic coating layers 16 are sintered together to form the nanomatrix 216. The chemical composition of the core material 218 may be different from that of the core material 18 due to the diffusion effects associated with sintering as described herein. The distributed carbon nanoparticles 290 are distributed within the dispersed particles 214 as described herein, and all dispersed particles 214, or only a portion thereof, may be included, as described herein. The distributed carbon nanoparticles 290 formed from the carbon nanoparticles 90 that have a metal layer 91 disposed on them can retain all or a portion of that layer in the compact material as distributed carbon nanoparticles 291.
    As used herein, the use of the term substantially continuous cellular nanomatrix 216 does not connote the major constituent of the compact powder material, but instead refers to the constituent or secondary constituents, by weight or by volume. This is distinct from most matrix composite materials where the matrix comprises the main constituent by weight or by volume. The use of the term substantially continuous cellular nanomatrix lends itself to describe the extensive, regular, continuous and interconnected nature of the distribution of nanomatrix material 220 within the compact powder material 200. As used herein, substantially continuous describes the extent of the material of the nanomatrix throughout the compact powder material 200 in such a way that it extends between and substantially envelops all dispersed particles 214. Substantial28 / 53 continuous mind is used to indicate that the complete continuity and regular order of the nanomatrix around each dispersed particle 214 are not required. For example, defects in the coating layer 16 over the particle core 14 in some powder particles 12 can cause the particle cores 14 to bond during the sintering of the compact powder material 200, thereby causing localized discontinuities within the cell nanomatrix 216, even if in the other portions of the compact powder material the nanomatrix is substantially continuous and exhibits the structure described here. As used herein, cell is used to indicate that the nanomatrix defines a network of generally repeated compartments or cells interconnected from nanomatrix material 220 that encompass and also interconnect dispersed particles 214. As used herein, nanomatrix is used to describe the size or scale of the matrix, in particular the thickness of the matrix between adjacent dispersed particles 214. The metallic coating layers that are sintered together to form the nanomatrix are themselves nanoscale thickness coating layers. Since the nanomatrix in most locations, with the exception of the intersection of more than two dispersed particles 214, generally comprises interdiffusion and a bonding of two two layers of coating 16 of adjacent powder particles 12 that have nanoscale thicknesses, the The matrix formed also has a nanoscale thickness (for example, about twice the coating thickness of the layer as described herein) and is thus described as a nanomatrix. In addition, the use of the term dispersed particles 214 25 does not connote the secondary constituent of the compact powder material 200, but instead refers to the main constituent or constituents, by weight or by volume. The use of the term dispersed particle refers to the conduct of the discontinuous and distinct distribution of the particle core material 218 within the compact powder material 200.
    The compact powder material 200 can be of any desired shape or size, including that of a cylindrical billet or bar that can be machined or used to form useful articles of manufacture.
    29/53 ration, including various tools and well hole components. Pressing is used to form the precursor powder compact material 100 and the sintering and compression processes are used to form the powder compact material 200 and deform the powder particles 12, including the particle cores 14 and the coating layers 16 to obtain the total density and the desired macroscopic shape and size of the compact powder material 200 as well as its microstructure. The microstructure of the compact powder material 200 includes the configuration of equidistant axes of the dispersed particles 214, including the distributed carbon nanoparticles 290, which are dispersed throughout and embedded within the substantially continuous cellular nanomatrix 216 of the sintered coating layers. This microstructure is somewhat analogous to a grain microstructure of equidistant axes with a continuous grain boundary phase, except that it does not require the use of alloy constituents that have thermodynamic phase equilibrium properties that can produce such a structure. Instead, this scattered particle structure of equidistant axes and the cellular nanomatrix 216 of the sintered metal cladding layers 16 can be produced by using constituents in which the conditions of equilibrium of thermodynamic phases should not produce an equidistant axis structure. The morphology of equidistant axes of the scattered particles 214 and the cellular network 216 of the particle layers results from the sintering and deformation of the dust particles 12, as they are compacted and inter-diffuse and deform to fill the interparticle spaces 15 (FIG. 1 ). Sintering temperatures and pressures can be selected to ensure that the density of the compact powder material 200 reaches substantially complete theoretical density.
    In an exemplary embodiment as illustrated in FIGURES 1 and 9, dispersed particles 214 are formed from particle cores 14 dispersed in cell nanomatrix 216 of sintered metal coating layers 16, and nanomatrix 216 includes a metallurgical bond 217, such as a solid-state metallurgical bond, or bond layer 219, as illustrated schematically in FIG. 10, what if
    30/53 tends between the scattered particles 214 throughout the cell nanomatrix 216 which is formed at a sintering temperature (T s ), where T s is less than T c and T P. As indicated, the metallurgical bond 217 is formed by a controlled interdiffusion between the coating layers 16 of adjacent powder particles 12 which are compressed to a touch contact during the compacting and sintering processes used to form the compact powder material 200 , as described here. In one embodiment, this can include a solid state metallurgical bond 217 formed in the solid state by interdiffusion of solid state between the coating layers 16 of the adjacent powder particles 12 which are compressed to a touch contact during the compacting and sintering processes used to form the compact powder material 200, as described herein. In this way, the sintered coating layers 16 of the cellular nanomatrix 216 include a bonding layer 219 that has a thickness (t) defined by the extent of the interdiffusion of the coating materials 20 of the metallic coating layers 16, which, in turn, will be defined by the nature of the coating layers 16, including whether they are single layer or multilayer coating layers, or have been selected to promote or limit such interdiffusion, and other factors, as described herein, as well as sintering conditions and compaction, including sintering time, temperature and pressure used to form the compact powder material 200.
    When nanomatrix 216 is formed, including bond 217 and bond layer 219, the distribution of the chemical composition or phase, or both, of the metal coating layers 16 can change. Nanomatrix 216 also has a melting temperature (T M ). As used herein, T M includes the lowest temperature at which incipient fusion or liquidation or other forms of partial fusion will occur within nanomatrix 216, regardless of whether nanomatrix material 220 comprises a pure metal, an alloy with multiple phases each of which has different melting temperatures or a composite, including a composite comprising a plurality of layers of various coating materials that have
    31/53 different melting temperatures, or a combination thereof, or others. Since dispersed particles 214 and particle core materials 218 are formed together with nanomatrix 216, diffusion of the constituents of the metallic coating layers 16 into particle cores 14 is also possible, which can result in changes in distribution of the chemical composition or phase, or both, of the particle cores 14. As a result, dispersed particles 214 and particle core materials 218, including distributed carbon nanoparticles 290, may have a melting temperature ( T D p) which is different from T P. As used herein, T DP includes the lowest temperature at which incipient fusion or liquidation or other forms of partial fusion will occur within the dispersed particles 214, regardless of whether the particle core material 218 comprises a pure metal, a alloy with multiple phases each of which has different melting temperatures or a composite, or others. In an exemplary embodiment, the compact powder material 200 is formed at a sintering temperature (Ts), where T s is less than T c , T P , T M and T DP , and sintering is executed entirely in solid state, resulting in a solid state bonding layer. In another example, the compact powder material 200 is formed at a sintering temperature (T s ), where T s is greater than or equal to one or more of T c , T P , T M or T DP and sintering includes limited or partial melting within the compact powder material 200 as described herein, and may also include sintering of liquid or liquid phase, resulting in a bonding layer that is at least partially melted and re-consolidated. In this modality, the combination of a predetermined Ts and a predetermined sintering time (t s ) will be selected to preserve the desired microstructure that includes cell nanomatrix 216 and dispersed particles 214. For example, localized liquidation may be allowed or fusion, for example, within all or a portion of nanomatrix 216, as long as the morphology of cell nanomatrix 216 / dispersed particle 214 is preserved, such as when selecting particle cores 14, Ts et s that do not provide
    32/53 the complete fusion of the particle nuclei. Similarly, localized liquidation may be allowed to occur, for example, within all or a portion of the dispersed particles 214 as long as the cell morphology of the cell nanomatrix 216 / dispersed particle 214 is preserved, such as when selecting metallic coating layers. 16, Ts et s that do not provide complete melting of the coating layer or layers 16. The melting of the metallic coating layers 16 can, for example, occur during sintering along the interface between the metallic layer 16 and the particle core 14, or along the interface between adjacent layers of the multilayer coating layers16. It should be appreciated that combinations of T s et s that exceed predetermined values can result in other microstructures, such as an equilibrium fusion / resolidation microstructure if, for example, both nanomatrix 216 (ie, the combination of layers of metal cladding 16) and dispersed particles 214 (i.e., particle cores 14) are melted, thereby allowing the rapid interdiffusion of these materials.
    The dispersed particles 214 can comprise any of the materials described herein for the particle cores 14, even though the chemical composition of the dispersed particles 214 may be different due to the diffusion effects as described herein. In an exemplary embodiment, dispersed particles 214 are formed from particle cores 14 which comprise materials that have a standard oxidation potential greater than or equal to that of Zn, including Mg, Al, Zn or Mn, or a combination of they may include various binary, tertiary and quaternary alloys or other combinations of these constituents as indicated here together with particle cores 14. Of those materials, those having dispersed particles 214 include Mg and nanomatrix 216 formed from the materials of metallic cladding 16 described herein are particularly useful. The scattered particles 214 and the particle core material 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 herein indicated in conjunction with numbers 33/53 particle oils 14.
    In another exemplary embodiment, dispersed particles 214 are formed from particle cores 14 that comprise metals that are less electrochemically active than Zn or non-metallic materials. Suitable non-metallic materials include ceramics, glass (e.g., hollow glass microspheres) or carbon, or a combination thereof, as described herein.
    The dispersed particles 214 of the compact powder material 200 can have any appropriate particle size, including the average particle sizes described herein for the particle cores 14.
    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 compress the powder 10. In an exemplary embodiment, the powder particles 12 can be spheroidal or substantially spheroidal and dispersed particles 214 may include a particle configuration of equidistant axes as described herein.
    The dispersion nature of the dispersed particles 214 can be affected by the selection of the powder 10 or the powders 10 used to produce the particle material 200. In an exemplary embodiment, a powder 10 that has a unimodal distribution of powder particle sizes 12 can be selected to form the compact powder material 200 and produce a substantially homogeneous unimodal dispersion of particle sizes of the dispersed particles 214 within cell nanomatrix 216, as generally illustrated in FIG. 9. In another exemplary embodiment, a plurality of powders 10 that have a plurality of powder particles with particle cores 14 that have the same core materials 18 and different core sizes and the same coating material 20 can be selected and mixed uniformly as described herein to obtain a powder 10 which has a homogeneous multimodal distribution of powder particle sizes 12, and can be used to form the compact powder material 200 which has a homogeneous multimodal dispersion of ta
    34/53 particles particles of the scattered particles 214 within the cell nanomatrix 216, as schematically illustrated in FIGURES 6 and 11. Similarly, in yet another exemplary embodiment, a plurality of powders 10 having a plurality of particle cores 14 that can have the same core materials 18 and different core sizes and the same coating material 20 can be selected and distributed in a non-uniform manner to provide an inhomogeneous multimodal distribution of powder particle sizes, and can be used to form the compact powder material 200 which has an inhomogeneous multimodal dispersion of particle sizes of the dispersed particles 214 within the cellular nanomatrix 216, as illustrated schematically in FIG. 12. The selection of the particle size distribution can be used to determine, for example, the particle size and the interparticle spacing of the dispersed particles 214 within the cell nanomatrix 216 of the compact powder materials 200 produced from the powder 10 .
    As generally illustrated in FIGURES 7 and 13, the powdered metal composite 200 can also be formed by using coated metal powder 10 and an additional second powder 30, as described herein. The use of an additional powder 30 provides a compact powder material 200 which also includes a plurality of second dispersed particles 234, as described herein, which are dispersed within nanomatrix 216 and are also dispersed with respect to dispersed particles 214. The second dispersed particles 234 can be formed from the second coated or uncoated powder particles 32, as described herein, and may also include the second distributed carbon nanoparticles 92, as described herein. In an exemplary embodiment, the second coated powder particles 32 can be coated with a coating layer 36 which is the same as the coating layer 16 of the powder particles 12, in such a way that the coating layers 36 also contribute to the nanomatrix 216. In another exemplary embodiment, the second particles of powder 232 may be uncoated in such a way that the second dispersed particles 234 are embedded within the nanoma
    35/53 root 216. The second distributed carbon nanoparticles 292 can be distributed within the second dispersed particles 234 as described herein, and can be included in all second dispersed particles 234, or only a portion thereof, as described herein . The second distributed carbon nanoparticles 292 formed from the second carbon nanoparticles 92 which have a metal layer 83 disposed on them can retain all or a portion of that layer in the compact material as second distributed carbon nanoparticles 293. As indicated here , powder 10 and additional powder 30 can be mixed to form a homogeneous dispersion of dispersed particles 214 and second dispersed particles 234, as illustrated in FIG. 13, or to form a non-homogeneous dispersion of these particles, as illustrated in FIG. 14. The second dispersed particles 234 can be formed from any appropriate additional powder 30 which is different from powder 10, due to a compositional difference in particle core 34, or in coating layer 36, or both, and may include any of the materials indicated herein for use as a second powder 30 which are different from the powder 10 which is selected to form the compact powder material 200. In an exemplary embodiment, the second dispersed particles 234 can include Fe, Ni, Co or Cu , or the oxides, nitrides or carbides thereof, or a combination of any of the materials mentioned above.
    Nanomatrix 216 is a substantially continuous cellular network of metallic coating layers 16 that are sintered together. The thickness of the nanomatrix 216 will depend on the nature of the powder 10 or powders 10 used to form the compact powder material 200, as well as the incorporation of any second powder 30, in particular the thicknesses of the coating layers associated with these particles. In an exemplary embodiment, the thickness of nanomatrix 216 is substantially uniform throughout the microstructure of the compact powder material 200 and comprises about twice the thickness of the coating layers 16 of the powder particles 12. In another exemplary embodiment, the mesh
    Cell 36/53 216 has a substantially uniform average thickness between the scattered particles 214 of about 50 nm to about 5,000 nm.
    Nanomatrix 216 is formed by sintering the metallic coating layers 16 of the adjacent particles together by interdiffusion and creating the bonding layer 219 as described herein. The metallic cladding layers 16 can be single-layer or multilayered structures, and can be selected to promote or inhibit diffusion, or both, within the layer or between the layers of the metallic cladding layer 16, or between the layer of metal cladding 16 and particle core 14, or between metal cladding layer 16 and metal cladding layer 16 of an adjacent powder particle, the extent of interdiffusion of metal cladding layers 16 during sintering can be limited or extensive depending on coating thicknesses, selected coating material or materials, sintering conditions and other factors. Due to the potential complexity of interdiffusion and interaction of constituents, the description of the chemical composition of the resulting nanomatrix 216 and material 220 of the nanomatrix can simply be understood as a combination of the constituents of the coating layers 16 which may also include one or more constituents of the scattered particles 214, depending on the extent of interdiffusion, if any, that occurs between scattered particles 214 and nanomatrix 216. Similarly, the chemical composition of scattered particles 214 and particle core material 218 can simply be understood as a combination of the constituents of the particle core 14 which may also include one or more constituents of the nanomatrix 216 and the material 220 of the nanomatrix, depending on the extent of the interdiffusion, if any, that occurs between the dispersed particles 214 and the nanomatrix 216.
    In an exemplary embodiment, material 220 of the nanomatrix has a chemical composition and material 218 of the particle core has a chemical composition that is different from that of material 220 of the nanomatrix, and differences in chemical compositions can be configured to provide a selectable and controllable dissolution rate, including a selectable transition from a very low dissolution rate to a very rapid dissolution rate, in response to a controlled change in a well hole property or condition close to the compact material 200, including a change of property in a fluid from the well bore that comes in contact with the compact powder material 200, as described herein. Nanomatrix 216 can be formed from powder particles 12 which have single-layer and multi-layer coating layers 16. This design flexibility provides a large number of material combinations, particularly in the case of multiple coating layers layers 16, which can be used to adapt the cell nanomatrix 216 and the composition of material nanomatrix 220 by controlling the interaction of the constituents of the coating layer, both within a given layer, as well as between a layer of coating 16 and the particle core 14 with which it is associated or a coating layer 16 of an adjacent powder particle 12. Various exemplary embodiments that demonstrate this flexibility are provided below.
    As illustrated in FIG. 10, in an exemplary embodiment, the compact powder material 200 is formed from the powder particles where the coating layer 16 comprises a single layer, and the resulting nanomatrix 216 between adjacent particles of the plurality of dispersed particles 214 comprises the individual metallic coating layer 16 of one particle 12, a bonding layer 219 and individual coating layer 25 of another of the adjacent powder particles
    12. The thickness (t) of the bonding layer 219 is determined by the extent of the interdiffusion between the individual metallic cladding layers 16, and can encompass the entire thickness of the nanomatrix 216 or only a portion thereof in an exemplary embodiment of the compact material in powder 30 200 formed when using a single layer powder 10, the compact powder material 200 may include dispersed particles 214 comprising Mg, Al, Zn or Mn, or a combination thereof, as described herein, and nano38 / Matrix 216 may include Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or an oxide, carbide or nitride thereof, or a combination of any one of the aforementioned materials, including combinations in which the nanomatrix material 220 of the cell nanomatrix 216, including the bond layer 219, has a chemical composition and the material
    218 of the core of the dispersed particles 214 has a chemical composition that is different from the chemical composition of material 216 of the nanomatrix. The difference in chemical composition of nanomatrix material 220 and core material 218 can be used to provide selectable and controllable dissolution in response to a change in a well hole property, including a well hole fluid, such as as described here. In another exemplary embodiment of a compact powder material 200 formed from a powder 10 having an individual coating layer configuration, the dispersed particles 214 include Mg, Al, Zn or Mn, or a combination thereof, and cell nanomatrix 216 includes Al or Ni, or a combination thereof.
    As illustrated in FIG. 15, in another exemplary embodiment, the compact powder material 200 is formed from the powder particles 12 wherein the coating layer 16 comprises a multilayer coating layer 20 having a plurality of coating layers, and the resulting nanomatrix 216 between adjacent particles of the plurality of dispersed particles 214 comprises the plurality of layers (t) comprising the coating layer 16 of a particle 12, a bonding layer 219, and the plurality of layers comprising 25 the layer coating 16 of another of the powder particles 12. In FIG. 15, this is illustrated with a two-layer metal cladding layer 16, but it should be understood that the plurality of layers of the multilayer metal cladding layer 16 can include any desired number of layers. The thickness (t) of the connecting layer 30 219 is determined again by the extent of the interdiffusion between the plurality of layers of the respective coating layers 16, and can encompass the entire thickness of the nanomatrix 216 or only a portion
    39/53 of the same. In this embodiment, the plurality of layers comprising each coating layer 16 can be used to control the interdiffusion and the formation of the bonding layer 219 and the thickness (t).
    In an exemplary embodiment of a compact powder material 200 produced by using powder particles 12 with multilayer coating layers 16, the compact material includes dispersed particles 214 comprising Mg, Al, Zn or Mn, or a combination of themselves, as described herein, and nanomatrix 216 comprises a cellular network of two-layer sintered coating layers 16, as shown in FIG. 3, which comprises the first layers 22 which are arranged on the dispersed particles 214 and the second layers 24 which are arranged on the first layers 22. The first layers 22 include Al or Ni, or a combination thereof, and the second layers 24 include Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or a combination thereof. In these configurations, the materials of the dispersed particles 214 and the multilayer coating layer 16 used to form the nanomatrix 216 are selected so that the chemical compositions of the adjacent materials are different (for example, dispersed particle / first layer and first layer / second layer).
    In another exemplary embodiment of a compact powder material 200 produced by using powder particles 12 with multilayer coating layers 16, the compact material includes dispersed particles 214 comprising Mg, Al, Zn or Mn, or a combination thereof, as described herein, and nanomatrix 216 comprises a cellular network of sintered three-layer metallic coating layers 16, as shown in FIG. 4, comprising the first layers 22 which are arranged on the scattered particles 214; the second layers 26 which are arranged on the first layers 22; the third layers 26 which are arranged on the second layers 24 and the fourth layers 28 which are arranged on the third layers 26. The first layers 22 include Al or Ni, or a combination thereof; second layers 24 include Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca,
    40/53
    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 here for the compact powder material 200 produced when using two-layer coating layer powders, but should also be extended to include the material used for the third coating layer.
    In yet another exemplary embodiment of a compact powder material 200 produced using powder particles 12 with multilayer coating layers 16, the compact material includes dispersed particles 214 comprising Mg, Al, Zn or Mn, or a combination thereof, as described herein, and nanomatrix 216 comprises a cellular network of sintered four-layer coating layers 16 comprising the first layers 22 which are arranged on the dispersed particles 214; the second layers 24 which are arranged on the first layers 22; the third layers 26 which are arranged on the second layers 24 and the fourth layers 28 which are arranged on the third layers 26. The first layers 22 include Al or Ni, or a combination thereof; second layers 24 include Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or an oxide, nitride or carbide thereof, or a combination of any one of the aforementioned 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 the aforementioned third layer materials; and the fourth layers include Al, Mn, Fe, Co or Ni, or a combination thereof. The selection of materials is analogous to the selection considerations described here for compact powder materials 200 produced when using two-layer coating layer powders, but should also be extended to include the material used for the third and fourth layers of coating.
    41/53
    In another exemplary embodiment of a compact powder material 200, the dispersed particles 214 comprise a metal that has a lower standard oxidation potential than that of Zn or a non-metallic material, or a combination thereof, as described herein, and nanomatrix 216 comprises a cellular network of sintered metallic coating layers 16. Suitable non-metallic materials include various ceramics, glass or carbon forms, or a combination thereof. In addition, in compact powder materials 200 which include dispersed particles 214 comprising such 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, carbide or nitride thereof, or a combination of any of the materials mentioned above as material 220 of the nanomatrix.
    With reference to FIG. 16, the sintered powder compact material 200 may comprise a sintered precursor powder compact material 100 which includes a plurality of deformed mechanically bonded powder particles as described herein. The precursor powder compact material 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 or other interparticle connections 110 associated with such deformation sufficient to make that the deformed powder particles 12 are adhered to each other and form a compact powder material in a green state that has a green density that is less than the theoretical density of a fully dense compact powder material 10, due in part to interparticle spaces 15. Compaction can be carried out, for example, by isostatically compressing powder 10 at room temperature to provide the deformation and interparticle bonding of the powder particles 12 necessary to form the precursor powder compact material 100.
    Sintered and forged compact powder materials 200 including dispersed particles 214 comprising Mg and nanomatrix 216 comprising various materials of the nanomatrix as described herein
    42/53 demonstrated an excellent combination of mechanical strength and low density that exemplify the high strength and light weight materials presented here. These materials can be configured to provide a wide range of corrosion or selectable and controllable dissolving behavior from very low corrosion rates to extremely high corrosion rates, in particular the corrosion rates that are both lower and higher than those of compact powder materials that do not incorporate the cellular nanomatrix, such as a compact material formed from pure Mg powder through the same compacting and sintering processes compared to those that include dispersed pure Mg particles in the various cellular nanostructures described herein. These compact powder materials 200 can also be configured to provide substantially enhanced properties compared to compact powder materials formed from the pure Mg particles that do not include the nanoscale coatings described herein. For example, compact powder materials 200 which include dispersed particles 214 comprising Mg and nanomatrix 216 comprising various materials 220 of the nanomatrix described herein exhibited compressive strength at room temperature of at least about 37 ksi, and demonstrated other strengths to compression at room temperature above about 50 ksi, both dry and immersed in a 3% KCI solution at 200 ° F. The incorporation of distributed carbon nanoparticles, such as distributed carbon nanoparticles 90, should further increase the compressive strength values of these compact powder materials 200. On the other hand, compact powder materials formed from Mg powders pure have a compressive strength of about 20 ksi or less. The strength of the powder metal composite 200 of the nanomatrix can be further improved by optimizing the powder 10, in particular the weight percentage of the metal nanoscale coating layers 16 that are used to form the cellular nanomatrix 216. For example, with the variation of the percentage by weight (% by weight), that is, the thickness, of an alumina coating, the compressive strength at ambient temperature of a material is varied
    43/53 al compact powder 200 of a cellular nanomatrix 216 formed from the coated powder particles 12 which include a multilayer metallic coating layer (AI / AI 2 O 3 / AI) 16 in the nuclei of pure Mg particles 14. In this example, the ideal strength is obtained at 4% by weight of alumina, which represents an increase of 21% compared to that of 0% by weight of alumina.
    Compact powder materials 200 comprising dispersed particles 214 including Mg and nanomatrix 216 which includes various nanomatrix materials as described herein also exhibited a shear strength at room temperature of at least about 20 ksi. This is different from the case with compact powder materials formed from pure Mg powders that have shear strengths at an ambient temperature of about 8 ksi. The incorporation of distributed carbon nanoparticles 90 should further increase the values of shear strength at room temperature of these compact powder materials 200.
    The compact powder materials 200 of the types presented here can achieve an actual density that is substantially equal to the predetermined theoretical density of a compact material based on the composition of the powder 10, including relative amounts of particle core constituents 14 and the metallic coating layer 16, and are also described herein as being fully dense compact powder materials. Compact powder materials 200 comprising dispersed particles including Mg and nanomatrix 216 which includes various materials of the nanomatrix as described herein exhibited actual densities of about 1.738 g / cm 3 to about 2.50 g / cm 3 , which they are substantially equal to the predetermined theoretical densities, differing by a maximum of 4% from the predetermined theoretical densities. The incorporation of distributed carbon nanoparticles 92, including those having a lower density, including a density of about 1.3 to about 1.4 g / cm 3 , will reduce these densities by an amount that depends on the relative quantities of the 92 used carbon nanoparticles distributed.
    44/53
    The compact powder materials 200 as indicated herein can be configured to be selectively and controllably dissolvable in a well hole fluid in response to an altered condition in a well hole. Examples of the altered condition that can be exploited to provide a selectable and controllable dissolving capacity include a change in temperature, a change in pressure, a change in flow, a change in pH or a change in the chemical composition of the fluid from the well bore , or a combination thereof. An example of an altered condition comprising a change in temperature includes a change in the fluid temperature of the well bore. Compact powder materials 200 comprising dispersed particles 214 which include Mg and cellular nanomatrix 216 which includes various materials of the nanomatrix as described herein have relatively low corrosion rates in a 3% KCI solution at room temperature ranging from about 0 to about 11 mg / cm 2 / h compared to relatively high corrosion rates at 200 ° F ranging from about 1 to about 246 mg / cm 2 / h depending on the different nanoscale coating layers 16 . An example of a changed condition comprising a change in chemical composition includes a change in a concentration of the chloride ions or in the pH value, or both, of the fluid from the well bore. For example, compact powder materials 200 comprising dispersed particles 214 that include Mg and nanomatrix 216 that include various nanoscale coatings described herein exhibit corrosion rates in 15% HCI ranging from about 4,750 mg / cm 2 / there is about 7,432 mg / cm 2 / h. In this way, the selectable and controllable dissolution capacity in response to an altered well hole condition, that is, the change in the chemical composition of the well hole fluid from KCI to HCI, can be used to obtain a characteristic response in a such that at a predetermined critical service time (CST) selected an altered condition can be imposed on the compact powder material 200 while it is applied in a given application, such as a well bore environment, which causes a controllable change in a property of 200 compact powder material
    45/53 in response to an altered condition in the environment in which it is applied. For example, to a predetermined CST that changes a fluid from the well bore that comes in contact with the compact powder material 200 of a first fluid (eg KCI) that provides a first rate of corrosion and an associated weight loss as a function of time to a second well hole fluid (eg HCI) that provides a second rate of corrosion and associated weight loss as a function of time, where the rate of corrosion associated with the first fluid is much lower than the rate of corrosion associated with the second fluid. This characteristic response to a change in the fluid conditions of the well bore can be used, for example, to associate critical service time with a size loss limit or minimum resistance required for a particular application, such that, when a tool or a well hole component formed from the compact powder material 200 as indicated here is no longer needed in the well hole service (eg CST) the condition in the well hole (eg the concentration of chloride ions in the well hole fluid) can be changed to cause the powder compact 200 to rapidly dissolve and remove it from the well hole. In the example described above, the compact powder material 200 is selectively dissolvable at a rate ranging from about 0 to about 7,000 mg / cm / h. This response range provides, for example, the ability to remove a 3-inch diameter sphere formed from that material from a well bore by changing fluid from the well bore in less than an hour. The behavior of the selectable and controllable dissolving capacity described above, coupled with the excellent strength and low density properties described here, defines a new designed dispersed particle nanomatrix material that is configured for contact with a fluid and configured to provide a transition selectable and controllable from one of a first resistance condition to a second resistance condition that is lower than a functional resistance limit, or a first quantity for a second amount of weight loss that is greater than a weight loss as a function of
    46/53 weight loss in contact with the fluid. The dispersed particle nanomatrix composite is characteristic of the compact powder materials 200 described herein and includes a cellular nanomatrix 216 of material 220 of the nanomatrix, a plurality of dispersed particles 214 including material 218 of the particle core that is dispersed within the matrix. Nanomatrix 216 is characterized by a bonding layer 219, such as a solid state bonding layer, which extends throughout the nanomatrix. The time in contact with the fluid described above can include the CST as described above. The CST may include a predetermined time that is desired or required to dissolve a predetermined portion of the compact powder material 200 that is in contact with the fluid. The CST may also include a time that corresponds to a change in the property of the designed material or the fluid, or a combination thereof in the event of a change in the property of the designed material, the change may include a change in a temperature of the projected material. In the event that there is a change in the fluid's property, the change may include a change in a temperature, pressure, flow rate, chemical composition or pH of the fluid, or a combination of these. Both the projected material and the change in property of the projected material or the fluid, or a combination thereof, can be adapted to provide the desired CST response characteristic, including the rate of change of the particular property (for example, loss of weight loss resistance) before CST and after CST.
    With reference to FIG. 17, it is a method 400 of producing a compact powder material 200. Method 400 includes the formation 410 of a coated metallic powder 10 comprising powder particles 12 having particle cores 14 with metallic coating layers nanoscale 16 arranged thereon, where the metallic coating layers 16 have a chemical composition and the particle cores 14 have a chemical composition that is different from the chemical composition of the metallic coating material 16. Method 400 also includes the formation 420 of a compact powder material by applying a predetermined temperature and a predetermined pressure to the dust particles
    47/53 coated enough to sinter them by solid phase sintering the coated layers of the plurality of coated particle powders 12 to form a substantially continuous cellular nanomatrix 216 of a material 220 of the nanomatrix and a plurality of dispersed particles 214 dispersed within of nanomatrix 216 as described herein.
    The formation 410 of the coated metallic powder 10 comprising the powder particles 12 having the particle cores 14 with the nanoscale metallic coating layers 16 arranged thereon can be carried out by any appropriate method. In an exemplary embodiment, formation 410 includes applying the metallic coating layers 16, as described herein, to the particle cores 14, as described herein, when using chemical fluidized bed vapor deposition (FBCVD) as herein described. The application of the metallic coating layers 16 may include the application of the single layer metallic coating layers 16 or the multilayer metallic coating layers 16 as described herein. The application of the metallic coating layers 16 can also include controlling the thickness of the individual layers while they are being applied, as well as controlling the total thickness of the metallic coating layers 16. The particle cores 14 can be formed as described herein. .
    The formation 420 of the compact powder material 200 may include any appropriate method of forming a compact powder material totally dense 10. In an exemplary embodiment, the formation 420 includes the dynamic forging of a compact precursor powder material of green density 100 for applying a predetermined temperature and a predetermined pressure sufficient to sinter and deform the powder particles and form a fully dense nanomatrix 216 and dispersed particles 214 as described herein. The dynamic forge as used herein means the dynamic application of a load at a temperature and for a time sufficient to sinter the metallic coating layers 16 of the adjacent dust particles 12, and may preferably include the application of a load of dynamic forging at a predetermined load rate
    48/53 swims for a time and at a temperature sufficient to form a sintered and fully dense 200 compact powder material. In an exemplary embodiment, the dynamic forge includes: 1) heating a precursor or green state compact material 100 to a predetermined solid-phase sintering temperature such as, for example, a temperature sufficient to promote interdiffusion between the metal coating layers 16 of the adjacent powder particles 12; 2) maintaining the compact precursor powder material 100 at the sintering temperature for a predetermined retention time such as, for example, sufficient time to ensure substantial uniformity of the sintering temperature throughout the compact precursor material 100; 3) the forging of the precursor powder compact material 100 to full density such as, for example, when applying a predetermined forging pressure according to a pressure schedule or a predetermined ramp rate sufficient to quickly reach the total density while the compact material is kept at the predetermined sintering temperature; and 4) cooling the compact material to room temperature. The predetermined pressure and predetermined temperature applied during formation 420 will include a sintering temperature, Ts, and a forging pressure, Pf, as described herein, which will ensure sintering, such as solid state sintering, and the deformation of the powder particles 12 to form the fully dense powder compact material 200, including the bond 217, as a solid state bond, and the bond layer 219. The heating and maintenance steps of the precursor powder compact material 100 at the predetermined sintering temperature for the predetermined time can 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 and the metal coating layer 16, of the size of the precursor powder compact material 100, the heating method used and other factors influencing the time nec necessary to achieve the desired temperature and temperature uniformity within the precursor 100 compact powder material. In the forging stage, the pressure
    The predetermined 49/53 can include any pressure programming and application of appropriate pressure or pressure ramp rate sufficient to obtain a fully dense compact powder material 200, and will depend, for example, on the material properties of the selected powder particles 12 , including temperature-dependent stress / stress characteristics (eg stress / solicitation rate characteristics), interdiffusion and metallurgical thermodynamics and phase balance characteristics, displacement dynamics and other material properties. For example, the maximum forge pressure of the dynamic forge and the forge schedule (that is, the pressure ramp rates that correspond to the stress rates employed) can be used to adapt the mechanical strength and hardness of the compact powder material . The forge pressure and the maximum forge ramp rate (ie the stress rate) is the pressure immediately below the crack pressure of the compact material, that is, where the dynamic recovery processes fail to relieve the stress energy in the microstructure of the compact material without the formation of a crack in the compact material. For example, for applications that require a compact powder material that has relatively higher strength and lower hardness, forging pressures and relatively higher ramp rates can be used. If a relatively higher hardness of the compact powder material is required, forging pressures and relatively lower ramp rates can be used.
    For certain exemplary embodiments of the powders 10 described herein and the compact precursor materials 100 of a size sufficient to form many tools and well bore components, predetermined retention times of about 1 to about 5 hours can be used. The predetermined sintering temperature, TS, will preferably be selected as described herein to avoid melting the particle cores 14, including the distributed carbon nanoparticles 90, or the metallic coating layers 16, as they are transformed during the method 400 to provide the dispersed particles 214 and the nanomatrix 216. For these modalities, the dynamic forge may include aa
    50/53 forging pressure, such as dynamic compression up to a maximum of about 80 ksi at a pressure ramp rate of about 0.5 to about 2 ksi / s.
    In an exemplary embodiment where the particle cores 14 include Mg and the metallic coating layer 16 includes several layers of single layer and multilayer coating as described herein, such as several single layer and multilayer coatings that comprise Al, the dynamic forge was carried out by sintering at a temperature, T s , from about 450 ° C to about 470 ° C for up to about 1 hour without applying a forge pressure, followed by the dynamic forge by application of isostatic pressures at ramp rates between about 0.5 and about 2 ksi / s a maximum pressure, Ps, from about 30 ksi to about 60 ksi, which resulted in forging cycles of 15 seconds at about 120 seconds. The forging cycle can be affected depending on the amount of distributed carbon nanoparticles 90 included in the particle cores 14, since the incorporation of the nanoparticles can change the dynamic response of the dust particles 12 during the forging, as well as by limitation (for example, example, reduction) of the associated displacement and sliding movement mechanisms. The short duration of the forging cycle is a significant advantage, as it limits interdiffusion, including interdiffusion within a certain layer of metallic cladding 16, interdiffusion between adjacent metal cladding layers 16 and interdiffusion between layers of metallic cladding 16 and particle cores 14, and that necessary to form the metallurgical bond 217 and bonding layer 219, while also maintaining the shape of the scattered particle of equidistant axes 214 with the integrity of the reinforcing phase of the cell nanomatrix 216. A the dynamic forging cycle duration is much shorter than the forming cycles and the sintering times required for conventional compact powder forming processes, such as hot isostatic compression (HIP), pressure-assisted sintering or diffusion sintering.
    Method 400 can also optionally include training
    51/53
    430 of a precursor powder compact material by compacting the plurality of coated powder particles 12 sufficiently to deform the particles and form interparticle bonds between them and formation of the precursor powder compact material 100 before formation 420 of the compact powder material . Compaction can include compression, such as isostatic compression, of the plurality of powder particles 12 at room temperature to form the precursor powder compact material 100. Compaction 430 can be carried out at room temperature. In an exemplary embodiment, powder 10 can include particle cores 14 comprising Mg and formation 430 of the precursor powder compact material can be carried out at room temperature at an isostatic pressure of about 10 ksi to about 60 ksi.
    Method 400 may also optionally include mixing 440 of a second powder 30 into powder 10 as described herein before formation 420 of the compact powder material, or formation 430 of the precursor powder compact material.
    Without being bound by theory, compact powder materials 200 are formed from the coated powder particles 12 include a particle core 14 and the associated core material 18 as well as a metallic coating layer 16 and an associated metallic coating material to form a substantially continuous three-dimensional cellular nanomatrix 216 that includes a material 220 of the nanomatrix formed by sintering 20 and the associated diffusion bonding of the respective coating layers 16 that includes a plurality of dispersed particles 214 of the particle core materials 218. That structure singular can include metastable combinations of materials that must be very difficult or impossible to form by solidifying a melt that has the same relative quantities as the constituent materials. Coating layers and associated coating materials can be selected to provide selectable and controllable dissolution in a predetermined fluid environment, such as a well hole environment, where the predetermined fluid can be a generally used well hole fluid
    52/53 that is injected into the well hole or extracted from the well hole. As should be understood from the present description, the controlled dissolution of the nanomatrix exposes the dispersed particles of the core materials. The particle core materials can also be selected to also provide selectable and controllable dissolution in the well hole fluid. Alternatively, they can also be selected to provide a particular mechanical property, such as compressive strength or shear strength, to the compact powder material 200, without necessarily providing the selectable and controlled dissolution of the core materials themselves, since the selectable and controlled dissolution of the nanomatrix material that surrounds these particles will necessarily release them so that they are carried away by the fluid from the well bore. The microstructural morphology of the substantially continuous cell nanomatrix 216, which can be selected to provide a phase reinforcing material, with dispersed particles 214, which can be selected to provide dispersed particles with equidistant axes 214, provides these compact powder materials with enhanced mechanical properties, including compressive strength and shear strength, as the morphology of those of the nanomatrix / dispersed particles can be manipulated to provide reinforcement through processes that are similar to traditional reinforcement mechanisms, such as reducing grain size, solution hardening through the use of impurity atoms, precipitation or chronological hardening and work strengthening / hardening mechanisms. The structure of the nanomatrix / scattered particles tends to limit the displacement movement due to the interfaces of the nanomatrix of numerous particles, the interfaces between different layers within the material of the nanomatrix the incorporation of distributed carbon nanoparticles 90 or second distributed carbon nanoparticles 92, as described herein. The fracture behavior of compact powder materials of these materials can demonstrate an intergranular fracture in response to sufficient shear stresses to induce failure. On the other hand, the compact powder materials 200 produced when using
    53/53 powder particles 12 which have the pure Mg powder particle cores 14 to form the dispersed particles 214 and the metal coating layers 16 which includes Al to form the nanomatrix 216 and subjected to a sufficient shear stress to induce the transgranular fracture shown in the failure and a substantially higher fracture stress as described herein. Due to the fact that these materials have high strength characteristics, the core material and the coating material can be selected to use low density materials or other low density materials, such as metals, ceramics or low density glass, which otherwise they must not provide the strength characteristics necessary for use in the desired applications, including tools and borehole components.
    Although one or more modalities have been shown and described, modifications and substitutions can be made to them without departing from the character and scope of the invention. Therefore, it should be understood that the present invention has been described by way of illustration and not by way of limitation.
    权利要求:
    Claims (38)
    [1]
    1. Powder metal composite, characterized by comprising: a continuous cellular nanomatrix that comprises a nanomatrix material;
    a plurality of dispersed particles (12) comprising a particle core material (18) comprising Mg, Al, Zn or Mn, or a combination thereof, dispersed in the cellular nanomatrix, wherein the core material (18) of the dispersed particles comprise a plurality of distributed carbon nanoparticles (90); and a bonding layer that extends throughout the cellular nanomatrix between the dispersed particles.
    [2]
    2. Powdered metal composite according to claim 1, characterized in that the bonding layer comprises a solid state bonding layer.
    [3]
    3. Powdered metal composite according to claim 2, characterized by the fact that the material of the nanomatrix has a melting temperature (TM), the material of the particle core (18) has a melting temperature (TDP) ; wherein the compact material is sinterable in a solid state at a sintering temperature (TS), and TS is less than TM and Tdp.
    [4]
    Powdered metal composite according to claim 1, characterized in that the bonding layer comprises a partially melted and resolidified bonding layer.
    [5]
    5. Powdered metal composite according to claim 1, characterized in that the material of the particle core (18) comprises Mg-Zn, Mg-Zn, Mg-Al, Mg-Mn, or Mg-Zn -Y.
    [6]
    6. Powdered metal composite according to claim 1, characterized in that the core material (18) comprises an Mg-Al-X alloy, where X comprises Zn, Mn, Si, Ca or Y , or a combination of these.
    [7]
    7. Powdered metal composite according to claim 6, characterized in that the Mg-Al-X alloy comprises, by weight,
    Petition 870180041212, of 05/17/2018, p. 4/14
    2/7 up to 85% Mg, up to 15% Al and up to 5% X.
    [8]
    8. Powdered metal composite according to claim 1, characterized by the fact that the dispersed particles further comprise a rare earth element.
    [9]
    Powdered metal composite according to claim 1, characterized in that the dispersed particles have an average particle size from 5 pm to 300 pm.
    [10]
    10. Powdered metal composite according to claim 1, characterized in that the dispersion of dispersed particles comprises a homogeneous dispersion within the cellular nanomatrix.
    [11]
    A powdered metal composite according to claim 1, characterized in that the dispersion of dispersed particles comprises a multi-modal distribution of particle sizes within the cell nanomatrix.
    [12]
    12. Powdered metal composite according to claim 1, characterized in that the dispersed particles have a particle shape of equidistant axes.
    [13]
    13. Powdered metal composite according to claim 1, characterized in that it also comprises a plurality of second dispersed particles, wherein the second dispersed particles are also dispersed within the cellular nanomatrix and with respect to the dispersed particles.
    [14]
    14. Powdered metal composite according to claim 13, characterized in that the second dispersed particles comprise Fe, Ni, Co or Cu, or the oxides, nitrides or carbides thereof, or a combination of any of the materials mentioned above.
    [15]
    15. Powdered metal composite according to claim 1, characterized by the fact that the material of the nanomatrix comprises Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or an oxide, carbide or nitride thereof, or a combination of any of the materials mentioned above, and in which the nanomatrix material has a composition
    Petition 870180041212, of 05/17/2018, p. 5/14
    3/7 chemical tion and the material of the particle core (18) has a chemical composition that is different from the chemical composition of the nanomatrix material.
    [16]
    16. Powdered metal composite according to claim 1, characterized by the fact that the cell nanomatrix has an average thickness of 50 nm to 5,000 nm.
    [17]
    17. Powdered metal composite according to claim 1, characterized in that the compact material is formed from a sintered powder that comprises a plurality of powder particles (12), wherein each powder particle has a particle core (14) which, upon sintering, comprises a dispersed particle and a single metallic coating layer (16) disposed thereon, and in which the cellular nanomatrix between adjacent particles of the plurality of particles (12) dispersed it comprises the single metallic coating layer (16) of a powder particle, the bonding layer and the single metallic coating layer (16) of another of the powder particles.
    [18]
    A powdered metal composite according to claim 17, characterized in that the dispersed particles comprise Mg and the cellular nanomatrix comprises Al or Ni, or a combination thereof.
    [19]
    19. Powdered metal composite according to claim 1, characterized in that the compact material is formed from a sintered powder comprising a plurality of powder particles (12), where each powder particle has a particle core (14) which, upon sintering, comprises a dispersed particle and a plurality of metallic coating layers disposed on it, and in which the cellular nanomatrix between adjacent particles of the plurality of dispersed particles (12) comprises the the plurality of metallic coating layers of one powder particle, the bonding layer and the plurality of metallic coating layers of another of the powder particles, and the adjacent layers of the plurality of metallic coating layers have different chemical compositions.
    [20]
    20. Powdered metal composite according to claim
    Petition 870180041212, of 05/17/2018, p. 6/14
    4/7
    19, characterized by the fact that the plurality of layers comprises a first layer that is arranged on the particle core (14) and a second layer that is arranged on the first layer.
    [21]
    21. Powdered metal composite according to claim
    20, characterized by the fact that the dispersed particles comprise Mg and the first layer comprises Al or Ni, or a combination thereof, and the second layer comprises Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or a combination thereof, wherein the first layer has a chemical composition that is different from a chemical composition of the second layer.
    [22]
    22. Powdered metal composite according to claim
    21, characterized by the fact that the metal powder is according to claim 18, which further comprises a third layer which is arranged on the second layer.
    [23]
    23. Powdered metal composite according to claim
    22, characterized by the fact that the first layer comprises Al or Ni, or a combination thereof, the second layer comprises Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or an oxide, nitride or carbide thereof, or a combination of any of the materials of the second layer mentioned above, and the third layer comprises Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or a combination thereof, wherein the second layer has a chemical composition that is different from a chemical composition of the third layer.
    [24]
    24. Powdered metal composite according to claim
    23, characterized by the fact that it also comprises a fourth layer that is arranged on the third layer.
    [25]
    25. Powdered metal composite according to claim
    24, characterized by the fact that the first layer comprises Al or Ni, or a combination thereof, the second layer comprises Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or an oxide, nitride or carbide thereof, or a combination of any
    Petition 870180041212, of 05/17/2018, p. 7/14
    5/7 of the materials of the aforementioned second layer, the third layer comprises Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or an oxide, a nitride or a carbide thereof, or a combination of any of the above mentioned third layer materials, and the fourth layer comprises Al, Mn, Fe, Co or Ni, or a combination thereof, wherein the second layer has a chemical composition it is different from a chemical composition of the third layer and the third layer has a chemical composition that is different from a chemical composition of the third layer.
    [26]
    26. Powdered metal composite according to claim 1, characterized by the fact that carbon nanoparticles comprise graphene, fullerene or nanodiamond nanoparticles, or a combination thereof.
    [27]
    27. Powdered metal composite according to claim 26, characterized in that the core material (18) comprises fullerene, and fullerene comprises a single-walled nanotube, a multi-walled nanotube, buckyball or a cluster of buckyballs, or a combination of them.
    [28]
    28. Powdered metal composite according to claim 26, characterized in that the distributed carbon nanoparticles (90) have at least a dimension of 0.1 nm to 100 nm.
    [29]
    29. Powdered metal composite according to claim 26, characterized by the fact that the carbon nanoparticles are homogeneously dispersed within the dispersed particles.
    [30]
    30. Powdered metal composite according to claim 26, characterized by the fact that the carbon nanoparticles are heterogeneously dispersed within the dispersed particles.
    [31]
    31. Powdered metal composite according to claim 30, characterized by the fact that carbon nanoparticles are dispersed close to a periphery of the dispersed particles.
    [32]
    32. Powdered metal composite, characterized by comprising:
    Petition 870180041212, of 05/17/2018, p. 8/14
    6/7 a continuous cellular nanomatrix that comprises a nanomatrix material;
    a plurality of dispersed particles (12) that comprise a particle core material (18) that comprises a metal that has a lower standard oxidation potential than Zn, ceramic, glass, or carbon, or a combination of themselves, dispersed in the cellular nanomatrix, wherein the core material (18) of the dispersed particles comprises a plurality of distributed carbon nanoparticles (90); and a bonding layer that extends throughout the cellular nanomatrix between the dispersed particles.
    [33]
    33. Powdered metal composite according to claim 32, characterized in that the material of the nanomatrix comprises Al, Zn, Mn, Mg, Mo, W, Cu, Fe, Si, Ca, Co, Ta, Re or Ni, or an oxide, carbide or nitride thereof, or a combination of any of the materials mentioned above, where the nanomatrix material has a chemical composition and the core material (18) has a chemical composition that is different from the chemical composition of the nanomatrix material.
    [34]
    34. Powdered metal composite according to claim 32, characterized by the fact that carbon nanoparticles comprise graphene, fullerene or nanodiamond nanoparticles, or a combination thereof.
    [35]
    35. Powdered metal composite according to claim 34, characterized in that the core material (18) comprises fullerene, and fullerene comprises a single-walled nanotube, a multi-walled nanotube, buckyball or a cluster of buckyballs, or a combination of them.
    [36]
    36. Powdered metal composite according to claim 32, characterized in that the bonding layer comprises a solid-state bonding layer.
    [37]
    37. Powdered metal composite according to claim 36, characterized in that the material of the nanomatrix has a melting temperature (TM), the material of the particle core (18) has a temperature
    Petition 870180041212, of 05/17/2018, p. 9/14
    7/7 melting time (Tdp); wherein the compact material is sinterable in a solid state at a sintering temperature (Ts), and Ts is less than Tm and Tdp.
    [38]
    38. Powdered metal composite according to claim
    5 32, characterized by the fact that the bonding layer comprises a partially melted and solidified bonding layer.
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    法律状态:
    2018-02-20| B06A| Patent application procedure suspended [chapter 6.1 patent gazette]|
    2019-12-10| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2020-02-11| 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 27/10/2011, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US12/913,321|US9090955B2|2010-10-27|2010-10-27|Nanomatrix powder metal composite|
    US12/913,321|2010-10-27|
    PCT/US2011/058099|WO2012058433A2|2010-10-27|2011-10-27|Nanomatrix powder metal composite|
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