• 专利附录
  • 专利说明
  • 权利要求
  • 类似技术
  • 同族专利
  • 引用文献
  • 法律状态
  • 优先权
    • 专利摘要:
    metal-intermetallic composite, method of manufacturing the same and articles comprising the same. The present invention relates to an article comprising a plurality of domains fused together, the domains comprising a core comprising a first metal, and a first layer disposed on the core, the first layer comprising a second metal, the first metal being chemically different from the second metal. here also described is a method comprising laminating a sheet in a rolling mill, the sheet comprising a first metal and having disposed on each opposite face of the sheet a first layer comprising a second metal, the second metal being chemically different from the first metal; cut the sheet into a plurality of sheets; stack the plurality of sheets; and laminate the stacked sheets in a laminator to form a piece of laminated metal.
    公开号:BR112014000971B1
    申请号:R112014000971-6
    申请日:2012-06-26
    公开日:2021-07-27
    发明作者:Randall V. Guest；Michael H. Johnson；Zhiyue Xu
    申请人:Baker Hughes Incorporated；
    IPC主号:
    专利说明:

    CROSS REFERENCE TO RELATED ORDERS
    [0001] This application claims the benefit of US Application No. 13/189150, filed July 22, 2011, which is incorporated herein by reference in its entirety. BACKGROUND 1. Field of Invention
    [0002] This description refers to metal-intermetallic composites, methods of manufacturing the same and articles comprising the same. 2. Description of Related Art
    [0003] In carrying out underground operations, such as, for example, oil and natural gas exploration, carbon dioxide capture, exploration and mining of minerals, such as iron, uranium, and the like, water exploration, and the like, it is often desirable to first drill a borehole that penetrates the formation.
    [0004] Once a borehole has been drilled, it is desirable that the borehole is completed before minerals, hydrocarbons and the like can be extracted from it. A finish involves the design, selection and installation of equipment and materials in or around the borehole to drive, pump or control the production or injection of fluids into the borehole. Once the borehole has been completed, the extraction of minerals, oil and gas, or water can begin.
    [0005] Sealing systems, such as gaskets, are commonly developed in a borehole as finishing equipment. Gaskets are often used to isolate portions of a borehole from each other. For example, gaskets are used to seal the annular crown between a pipe string and a wall (in the case of an unlined or open well) or casing tubes (in the case of a lined well) of the borehole, isolating the bore portion. drill hole above the gasket of the drill hole portion below the gasket.
    [0006] Seal systems that isolate a portion of the borehole from another portion of the borehole generally employ an expandable component and a support member. The support member protects the expandable component until the expandable component is expanded in the borehole to effect insulation. In order to expand the expandable component, it is desirable to first remove the support member. Removing the support member at the wrong speed could result in improper insulation of one part of the borehole from the other. Therefore, it is desirable to use a support member that can be removed in a controlled manner when desired. SUMMARY
    [0007] Here is described an article comprising a plurality of domains fused together, wherein the domains comprise a core comprising a first metal, and a first layer disposed on the core, the first layer comprising a second metal, the first metal being chemically different from the second metal, the article being used as a support element in a sealable system for oil exploration.
    [0008] Also described herein is an article comprising a plurality of domains fused together, wherein the domains comprise a fine-grained intermetallic alloy comprising a first metal and a second metal, wherein the domains comprise a gradient in composition between the first metal and the second metal, and where the first metal is chemically different from the second metal.
    [0009] Also described herein is a method comprising laminating a sheet in a laminator, the sheet comprising a first metal and having, disposed on each opposite face of the sheet, a first layer comprising a second metal, the second metal being chemically different of the first metal; cut the sheet into a plurality of sheets; stack the plurality of sheets; and laminate the stacked sheets in the laminator to form a piece of laminated metal.
    [00010] Here also a method is described which comprises arranging, on a pipe column, a sealing system, the sealing system comprising an expandable component and a support member, wherein the support member comprises a plurality of fused domains therebetween, wherein the domains comprise a core comprising a first metal, and a first layer disposed on the core, the first layer comprising a second metal, the first metal being chemically different from the second metal; introduce the pipe string into a well; and dissolve the supporting member. BRIEF DESCRIPTION OF THE DRAWINGS
    [00011] For a detailed understanding of the present description, reference will be made to the following detailed description of the preferred embodiment, taken in conjunction with the accompanying drawings, in which like elements have been given equal numerals and in which: Figure 1 is a representation of a system an exemplary prior art seal; and Figure 2 is a representation of an exemplary microstructure that is present in the article. DETAILED DESCRIPTION
    [00012] The invention will now be described more fully below with reference to the accompanying drawings, in which various embodiments are shown. This invention can, however, be embodied in many different forms, and should not be construed as limited to the embodiments presented herein. Preferably, these embodiments are provided so that this description is complete, and that it fully conveys the scope of the invention to those skilled in the art. Equal reference numerals refer to similar elements throughout.
    [00013] It will be understood that when an element is referred to as being "in" another element, it may be directly on top of the other element or intermediate elements may be present between them. In contrast, when an element is referred to as being "directly in" another element, there will be no intermediate elements present. As used herein, the term "and/or" includes any or all combinations of one or more of the associated listed items.
    [00014] It will be understood that although the terms "first", "second", "third", etc. can be used here to describe various elements, components, regions, domains, layers and/or sections, these elements, components, regions, domains, layers and/or sections shall not be limited by these terms. These terms are only used to distinguish an element, component, region, domain, layer or section from another element, component, region, domain, layer or section. Thus, "a first element", "component, "region", "domain", "layer" or "section" discussed below could be called a second element, component, region, domain, layer or section without departing from the teachings here.
    [00015] The terminology used here is for the purpose of describing specific embodiments only and is not intended to be limiting. As used here, the singular forms "a" and "the" are intended to include the plural forms as well, unless the context clearly indicates otherwise. It will be further understood that the terms "comprises" and/or "comprising", or "includes" and/or "including", when used in this specification, specify the presence of features, regions, integers, steps, operations, elements and/ or components shown, but do not preclude the presence or addition of one or more features, regions, integers, steps, operations, elements, components and/or groups thereof.
    [00016] Unless otherwise defined, all terms (including technical and scientific terms) used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this description belongs. It will be further understood that terms, such as those defined in commonly used dictionaries, are to be interpreted as having a meaning that is consistent with their meaning in the context of the relevant technique and the present description, and will not be interpreted in an idealized or overly formal sense. itself as expressly defined here.
    [00017] Exemplary embodiments are described here with reference to cross-sectional illustrations which are schematic illustrations of idealized embodiments. Thus, variations in the form of illustrations should be expected as a result of, for example, manufacturing techniques and/or tolerances. Thus, embodiments described herein should not be construed as limited to region-specific shapes as illustrated here, but should include deviations in shapes that result, for example, from fabrication. For example, a region illustrated or depicted as flat may typically have rough and/or non-linear features. Furthermore, the pointed angles that are illustrated can be rounded. Thus, the regions illustrated in the figures are schematic in nature and their shapes are not intended to illustrate the precise shape of a region and are not intended to limit the scope of the present claims.
    [00018] The transition term "comprising" comprises the transition terms "consisting of" and "consisting essentially of".
    [00019] All "inclusive" numeric ranges included here are interchangeable and comprise parameters and all numeric values that fall between the parameters.
    [00020] As used herein, a "borehole" can be any type of borehole in an earth formation, such as a well, including but not limited to a production well, a non-production well, a an experimental well, an exploratory well, a well for storage or capture, and the like. Drillholes can be vertical, horizontal, some angle between vertical and horizontal, offset and unoffset, and combinations thereof, for example a vertical drillhole with a non-vertical component.
    [00021] The term "support member" refers to a device that supports the expandable member and the column of tubes. The "support member" may also function to protect, guard and/or shield the expandable component from damage prior to removal.
    [00022] The term "expandable", as used in "expandable component", can encompass a variety of means by which expansion can occur. Expansion can occur, for example, through expansion, inflation via pressure, thermal expansion, and the like, or a combination thereof. Some expandable components can be actuated by hydraulic pressure transmitted or through the piping diameter, ring gear, or a control line. Other expandable components can be actuated via an electrical line deployed from the borehole surface. Additionally, some expandable components employing materials that respond to fluids from the surrounding borehole and borehole have been used to form a seal.
    [00023] Here an article is described for a sealing system comprising a plurality of multilayer metal domains that may comprise particles. In an exemplary embodiment, the article is a support member for a sealing system that is used in underground boreholes. Each domain comprises a metallic core which comprises a first metal. A first layer comprising a second metal is disposed on the metal core. The first layer may have disposed therein an optional second layer comprising a third metal. These multi-layered metallic domains will each function as a galvanic cell when exposed to borehole fluids. In one embodiment, these multilayer metallic domains are fabricated into a support member for a sealing system that can be dissolved in a controlled manner (when exposed to borehole fluids) to expose an expandable component to borehole fluids. surrounding survey. The fluids surrounding the borehole cause them to expand to form a seal which insulates one portion of the borehole from the other portion of the borehole.
    [00024] Also described herein is a method of fabricating a support member comprising the plurality of fused multilayer metal domains which may comprise sheets or blades. The method comprises fabricating a sheet from the first metal and arranging on opposite surfaces of the sheet a layer of a second metal. An optional third layer of metal can then be disposed on opposite surfaces of the sheet. The sheet is then cut into several smaller sheets, which are stacked on top of each other to form a pile. The stack is laminated until it is reduced to a thickness that is a fraction of the original thickness of the stacked sheets. The first multilayer sheet is again cut into several sheets, which are stacked on top of each other and subjected to lamination to produce a second multilayer sheet. The process of forming sheets, cutting and stacking them, and then laminating them is repeated several times to produce a final sheet. The final sheet is then cut, stacked as before, and forged into a desired shape (hereafter referred to as an "article").
    [00025] Figure 1 is a representation of an exemplary sealing system 100. The sealing system 100 is arranged around a column of tubes 102 and comprises an expandable member 104 and a support member 106. The support member 106 sustains the expandable member 104 during the introduction of the string of tubes 102 into the reservoir and prevents the expandable member 104 from being degraded before the point at which it is to be used.
    [00026] When the pipe string 102 has reached the point in the well in which it will be used, the support member 106 will be removed from the sealing system 100 and the expandable component 104 will undergo expansion to isolate one portion of the well from the other portion of the well.
    [00027] In order to effect the desired use of the expandable member 104, the removal of the support member 106 has to be carried out under controlled conditions. Therefore, a support member 106 made of a material that can be removed in a controlled manner so that expansion of the expandable member 104 can be brought about in the desired time to insulate one portion of the well from the other is desirable.
    [00028] In an exemplary embodiment, the support member 106 is fabricated by stacking several multilayer metal sheets and repeatedly passing these sheets through a rolling mill. With each "pass" through the laminator, the pile thickness is reduced by about 15 to about 30% of the original pile thickness. A "pass"', as defined here, is the process by which the original pile is reduced in thickness by about 15 to about 30% of the original pile thickness. A pass can involve multiple trips between laminators. In one embodiment, the stack thickness is reduced by about 20 to about 28% of the original stack thickness. In another embodiment, the stack thickness is reduced by about 22 to about 26% of the original stack thickness.
    [00029] In general, it is desirable to conduct numerous passes through the laminator in order to reduce the thickness of the original sheet by about 1/8 to about 1/15 of its original thickness, specifically by about 1/10 to about 1 /13 of its original thickness. The number of passes conducted during lamination is from about 2 to about 15, specifically from about 3 to about 14 and more specifically from about 5 to about 10.
    [00030] The lamination process can be a cold lamination process or a hot lamination process. Cold rolling processes are generally conducted below the metal's recrystallization temperature, while hot rolling processes are generally conducted at a temperature above the metal's recrystallization temperature. The recrystallization temperature under consideration would be that for the metal or alloy having the highest recrystallization temperature of all metals in the article. In an exemplary embodiment, the lamination process is a hot lamination process. The lamination process is generally conducted at a temperature of about 150 to about 450°C. In an exemplary embodiment, the lamination process is generally conducted at a temperature of from about 400 to about 437°C.
    [00031] The process of forming multilayer sheets that are repeatedly laminated, cut and stacked produces a structure comprising fine grain structure, including interspersed domains of a first and a second metal and combinations thereof. The structure of the domains in the article is similar to that which would be obtained from the sintering of individual particles, each of which comprises a core and a plurality of layers disposed over this core to begin with. In other words, the product comprises multi-structured domains that come into contact with each other. The multilayer domains in the article come into contact with each other and present interstices located between these domains. In one embodiment, these domains are merged with each other. Domains can have gradients in composition between the second metal and the third metal as well as between the first metal and the third metal.
    [00032] In one embodiment, the domains may alternatively also comprise a fine-grained alloy rich in small domains of intermetallic compounds between the first metal and the second metal, the first metal and the third metal and the second metal and the third metal, without any layer between these respective metals. The presence of a fine-grained alloy results in numerous advantages. Fine-grained alloys with concentration gradients produce effective galvanic cells. These structures produce an improvement in strength due to fine grain sizes and dense intergranular regions over other structures that contain layered domains.
    [00033] Figure 2 is a representation of an exemplary microstructure for articles manufactured by the method described here. Figure 2 depicts the microstructure of an exemplary article 200 comprising domains 202 described herein. As can be seen in Figure 2, each domain comprises core 204 comprising the first metal, first layer 206 comprising second metal, and optional third layer 208 comprising third metal. As noted above, some domains may comprise a fine-grained alloy that comprises an intermetallic compound.
    [00034] The core can have an average domain size of about 44 to about 1400 micrometers. In an exemplary embodiment, the core can have an average domain size from about 63 to about 105 micrometers. The average domain size is a radius of rotation.
    [00035] The core with the first layer in it can have an average domain size of about 45.1 to about 1445 micrometers. In an exemplary embodiment, the core with the first layer disposed thereon can have an average domain size of from about 64.6 to about 108 micrometers.
    [00036] The core with the first and second layers disposed on it can have an average domain size of about 45 to 1600 micrometers. In an exemplary embodiment, the core with the first and second layers disposed thereon can have an average domain size of from about 65 to about 110 micrometers.
    [00037] In one embodiment, in a method of manufacturing the support member, a sheet comprising a first metal is coated on its opposite faces with a layer of a second metal. The sheet may have an original thickness of from about 0.05 to about 0.20 centimeters, specifically from about 0.08 to about 0.18 centimeters, and more specifically from about 0.1 to about 0.15 centimeters. Each second metal layer can have a thickness of from about 0.005 centimeters to about 0.02 centimeters, specifically from about 0.003 to about 0.015 centimeters, and more specifically from about 0.001 centimeters to about 0.013 centimeters. An optional third layer of metal may be disposed on opposite faces of the sheet to contact the second layer of metal. The thickness of each third metal layer can be equal to the thickness of each second metal layer.
    [00038] The first metal is generally present in an amount of from about 60 to about 95 percent by weight (% by weight) based on the total weight of the article. An exemplary amount of the first metal is from about 90 to about 92 percent by weight based on the total weight of the article.
    [00039] The second metal is generally present in an amount of from about 5 to about 40 percent by weight based on the total weight of the article. An exemplary amount of the second metal is from about 8 to about 10 percent by weight based on the total weight of the article.
    [00040] The third metal is generally present in an amount of from about 0.0001 to about 3 percent by weight based on the total weight of the article. An exemplary amount of the third metal is from about 0.01 to about 0.1 weight percent based on the total weight of the article.
    [00041] In one embodiment, the second metal layer can be disposed on the sheet by means of techniques involving vapor deposition. Examples of suitable techniques for disposing the second layer include chemical vapor deposition or physical deposition.
    [00042] Chemical vapor deposition includes atmospheric chemical vapor deposition, low pressure chemical vapor deposition, ultra high vacuum chemical vapor deposition, aerosol assisted vapor deposition, chemical deposition in vapor phase of direct liquid injection, microwave plasma assisted chemical vapor deposition, plasma activated chemical vapor deposition, atomic layer chemical vapor deposition, hot wire chemical vapor deposition ( hot filament), metalorganic chemical vapor deposition, chemical vapor deposition of combustion, vapor phase epitaxy, rapid thermal chemical vapor deposition, physicochemical hybrid vapor deposition, or a combination comprising at least one of the above processes. If combinations of the above chemical vapor deposition processes are used, they can be employed simultaneously or sequentially.
    [00043] Physical vapor deposition includes cathodic arc deposition, electron beam physical vapor deposition, evaporative deposition, pulsed laser deposition, spray deposition or a combination comprising at least one of the processes above. If combinations of the above physical vapor deposition processes are used, they can be employed simultaneously or sequentially. Combinations of physical vapor deposition processes and chemical vapor deposition processes can also be used.
    [00044] In another embodiment, the second metal layer can be disposed on the sheet by techniques involving electrolytic bathing, electroplating, dip coating or cold spraying. Combinations of such methods can also be used to apply the second layer to the sheet.
    [00045] The first metal and the second metal are selected in such a way that they can form a galvanic cell that corrodes in the presence of borehole fluids. In other words, if the first metal forms the anode of the galvanic cell, the second metal forms the cathode and vice versa. The first metal is different in composition from the second metal. The third metal is usually selected to control the corrosion rate of the galvanic cell.
    [00046] The first metal and the second metal may comprise transition metals, alkali metals, alkaline earth metals, or combinations thereof, provided that the first metal is not the same as the second metal. The first metal can comprise aluminum, magnesium, zinc, copper, iron, nickel, cobalt, or the like, or a combination comprising at least one of the above metals. The second metal may comprise aluminum, magnesium, zinc, copper, iron, nickel, cobalt, or the like, or a combination comprising at least one of the above metals, provided it is chemically different from the first metal. In one embodiment, the second metal is electrolytically different from the first metal.
    [00047] The third metal may comprise nickel, aluminum, magnesium, zinc, copper, iron, cobalt, or the like, or a combination comprising at least one of the above metals, provided that it is chemically different from the first metal. In one embodiment, the third metal is chemically different from the first metal and the second metal. In another embodiment, the third metal is electrolytically different from the first metal and the second metal.
    [00048] In an exemplary embodiment, the first metal comprises aluminum, while the second metal comprises magnesium. The third metal can comprise nickel.
    [00049] In another exemplary embodiment, the first metal comprises magnesium, while the second metal comprises aluminum. The third metal can comprise nickel.
    [00050] In one embodiment, the sheet obtained after being subjected to a reduction in thickness can be stacked and forged in a rolling mill into a piece of rolled metal. The sheet metal piece can then be extruded into a desired shape to form the desired article. In an exemplary embodiment, the sheet obtained after being subjected to a 2 to 5 pass reduction in thickness can be stacked and forged in a rolling mill into a piece of rolled metal. The sheet metal piece is then extruded into a final desired shape.
    [00051] In another embodiment, the sheet obtained after being subjected to a reduction in thickness can be stacked and forged in a rolling mill or in a press in a rounded material.
    [00052] The process is advantageous in that it can be conducted quickly compared to a comparative sintering process involving powders. It is also desirable because it does not involve the formation and pressing of metal powders, which can sometimes be difficult. The process described herein can be advantageously used to manufacture sheet metal for laminated tube, flat stamped items, billet materials for balls, and the like.
    [00053] Support members fabricated by this method are advantageous because their dissolution by borehole fluids can be controlled. This allows the expansion of the expandable component to be controlled as well.
    [00054] The article described here can be used as a support member for a sealing system for underground wells from which oil and natural gas are extracted. In one method of using the support member, it is disposed over an expandable member in a sealing system to support the expandable member until it is desired for the expandable member to expand and form a seal. When the pipe string with the sealing system is moved underground during oil exploration, the borehole fluids will interact with the support member by configuring a plurality of galvanic cells within the support member. The galvanic cells are operative causing eventual corrosion of the support member and exposure of the expandable component to borehole fluids. The expandable member expands to seal one portion of the borehole from another portion of the well.
    [00055] While the invention has been described in detail in connection with numerous embodiments, the invention is not limited to such described embodiments. Preferably, the invention may be modified to incorporate any number of variations, alterations, substitutions or equivalent provisions not heretofore described, but which are compatible with the scope of the invention. Additionally, while various embodiments of the invention have been described, it will be understood that aspects of the invention may include only some of the described embodiments. Accordingly, the invention is not to be seen as limited to the foregoing description, but is only limited by the scope of the appended claims.
    权利要求:
    Claims (11)
    [0001]
    1. Article (200), characterized in that it comprises: a plurality of domains (202) fused together, wherein the domains (202) comprise: a core (204) comprising a first metal; wherein the first metal is aluminum, magnesium, zinc, copper, iron, nickel, cobalt, or a combination comprising at least one of these metals; a first layer (206) disposed on the core (204), the first layer (206) comprising a second metal, the first metal being chemically different from the second metal; wherein the second metal is aluminum, magnesium, zinc, copper, iron, nickel, cobalt or a combination comprising at least one of these metals; wherein the domains (202) comprise a gradient in composition between the first metal and the second metal; wherein the core (204) is in the form of a particle with a domain size of 44 to 1400 micrometers and wherein the plurality of domains (202) have interstices between them; a second layer (208) that is disposed over the first layer (206), wherein the second layer (208) comprises a third metal that is different from the first metal and the second metal; where the third metal is nickel, aluminum, zinc magnesium, copper, iron, cobalt or a combination thereof; where the third metal is present in an amount of 0.01 to 0.1% by weight, based on the total weight of the article; where the second metal is present in an amount of 8 to 10% by weight, based on the total weight of the article (200).
    [0002]
    2. Article (200), according to claim 1, characterized in that it is a support element in a sealable system (100) for oil exploration.
    [0003]
    3. Article (200) according to claim 1, characterized in that it is a drive ball for a borehole system.
    [0004]
    4. Article (200), according to claim 1, characterized in that the first metal is aluminum.
    [0005]
    5. Article (200), according to claim 1, characterized in that the first metal is magnesium.
    [0006]
    6. Article (200) according to claim 1, characterized in that the second metal is aluminum.
    [0007]
    7. Article (200), according to claim 1, characterized in that the second metal is magnesium.
    [0008]
    8. Article (200) according to claim 1, characterized in that it is manufactured by laminating a sheet comprising the first metal and coated on each of its opposite sides with a first layer comprising the second metal, cutting the laminated sheet into a plurality of sheets; stacking the plurality of sheets; re-laminating sheets stacked in the laminator; and repeatedly cutting, stacking, and rolling the stacked sheets.
    [0009]
    9. Article (200) characterized in that it comprises: a plurality of domains (202) fused together, wherein the domains (202) comprise: a fine-grained intermetallic alloy comprising a first metal, a second metal and a third metal; wherein the domains (202) comprise a gradient in composition between the first metal and the second metal; and wherein the first metal is chemically different from the second metal; wherein the first metal is aluminum or magnesium; wherein the second metal is aluminum or magnesium; wherein a core (204) of the domain comprises the first metal and is in the form of a particle with a domain size of 44 to 1400 micrometers, and wherein the plurality of domains (202) have interstices between them; where the third metal is different from the first and second metal; where the third metal is nickel, aluminum, zinc magnesium, copper, iron, cobalt or a combination thereof; where the third metal is present in an amount of 0.01 to 0.1% by weight, based on the total weight of the article; where the second metal is present in an amount of 8 to 10% by weight, based on the total weight of the article (200).
    [0010]
    10. Article (200) according to claim 9, characterized in that it is a support element in a sealable system (100) for oil exploration.
    [0011]
    11. Article (200) according to claim 9, characterized in that it is a drive ball for a borehole system.
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    同族专利:
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    US20200240232A1|2020-07-30|
    US20170266923A1|2017-09-21|
    CN103687924B|2017-02-22|
    US9707739B2|2017-07-18|
    MY173754A|2020-02-19|
    EP2734599B1|2020-10-21|
    BR112014000971A2|2017-02-21|
    US10697266B2|2020-06-30|
    EP2734599A2|2014-05-28|
    CN103687924A|2014-03-26|
    AU2012287461B2|2016-06-23|
    AP2014007358A0|2014-01-31|
    EP3093137A1|2016-11-16|
    EP2734599A4|2015-11-25|
    WO2013015928A3|2013-04-04|
    AU2016228209A1|2016-10-06|
    EP3093325A1|2016-11-16|
    CA2841068C|2017-03-21|
    WO2013015928A2|2013-01-31|
    AU2016228209B2|2017-09-07|
    CA2841068A1|2013-01-31|
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    法律状态:
    2018-04-03| B06F| Objections, documents and/or translations needed after an examination request according [chapter 6.6 patent gazette]|
    2019-07-30| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2020-10-06| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-05-11| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-07-27| 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 26/06/2012, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    US13/189,150|2011-07-22|
    US13/189,150|US9707739B2|2011-07-22|2011-07-22|Intermetallic metallic composite, method of manufacture thereof and articles comprising the same|
    PCT/US2012/044229|WO2013015928A2|2011-07-22|2012-06-26|Intermetallic metallic composite, method of manufacture thereof and articles comprising the same|
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