• 专利附录
  • 专利说明
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    • 专利摘要:
    these are magnesium alloys suitable for use as corrosive downhole articles, where the alloys have a corrosion rate of at least 50 mg/cm²/day at 15% kcl at 93 °c and a proof strength 0.2% of at least 50mpa when tested using the astm b557-10 standard voltage test method. the invention also relates to methods for making the alloys, downhole tools comprising the alloys, and hydraulic fracturing methods using downhole tools.
    公开号:BR112017001189B1
    申请号:R112017001189-1
    申请日:2015-07-28
    公开日:2021-07-27
    发明作者:Timothy Wilks；Mark Turski
    申请人:Magnesium Elektron Limited；
    IPC主号:
    专利说明:

    [001] This invention relates to a magnesium alloy suitable for use as a corrosive downhole article, a method for manufacturing such an alloy, an article comprising the alloy and the use of the article. Fundamentals
    [002]The oil and gas industries use a technology known as hydraulic fracturing or "fracking". This typically involves pressurizing with water from a wellbore system in rocks that contain oil and/or gas in order to fracture the rocks to release the oil and/or gas.
    [003]To achieve this pressurization, valves can be used to separate different sections of a wellbore system. These valves are referred to as downhole valves, the term downhole being used in the context of the invention to refer to an article that is used in a well or wellbore.
    [004] One way to form such valves involves using balls of material known as frac balls to seal the parts of a wellbore. Fracture balls can be made from aluminum, magnesium, polymers or composites.
    [005] A problem with the use of frac balls relates to how they are removed once the frac operation has been completed in order to allow fluid to flow through the well or wellbore. One way to do this is to drill through the frac ball. However, this type of drilling process can hamper production as well as being expensive, difficult and therefore undesirable.
    [006] A proposed solution to this problem has been to form the fracturing sphere from a material that will dissolve or corrode under the conditions in the well or wellbore. One issue that must be considered with regard to such corrosive articles is ensuring that they are corrosive at a rate that allows them to remain usable for the period of time during which they are needed to perform their function, but that allows them to be corrosive. or dissolve later.
    [007] Degradable polymers have been used to provide a corrodible article for use in such methods. However, these polymers generally do not have particularly high mechanical strength.
    [008] An alternative corrosive article is described in U.S. Patent No. 8,425,651 in the name of Xu et. al. That document describes a powder metal composite comprising a nanomatrix, preferably made from Al or Ni or a combination thereof, in which a plurality of first particle, a plurality of second particle and a binding layer are dispersed. solid state. The first particle comprises Mg, Al, Zn or Mn, or a combination thereof, and the second particle comprises carbon nanoparticles. The composite can be produced by forming a powder mixture of the required components and then applying temperature and pressure to the powder to sinter and deform (but not melt) the composite to form a powder composite. One problem with such powder metallurgical methods is that they are complicated and expensive.
    [009] An additional corrosive article is described in U.S. Patent Application Publication No. 2012/0318513 in the name of Mazyar et. al. In that document, the corrosive article is described as having a corrosive core and a metallic layer covering the core. The core material is described as being a magnesium alloy. However, it appears that combining magnesium and one or more other materials in a form that is not an alloy is also intended to be covered by the use of the term "alloy" in Mazyar et. al. For example, this document refers to alloys of magnesium with tungsten, while it is actually not technically feasible to form an alloy of magnesium and tungsten. Similarly, Mazyer et. al. it also mentions magnesium powders coated with a metal oxide as being useful for forming the core, which again would not be magnesium "alloys". Thus, Mazyar et. al. seems to use the term "magnesium alloy" to mean any way in which magnesium and another metal are combined. The metallic layer is described as including aluminum or nickel.
    [010] A dissolvable downhole isolation device is described in US Patent Application Publication No. 2014/0124216 in the name of Halliburton Energy Services, Inc. Although there is a minimal description of how the device is manufactured, it appears that, again, a composite powder is formed instead of an "alloy". Furthermore, this document only mentions magnesium as one of a large list of components, with magnesium not being one of the preferred components. The device also requires the presence of an "electrolytic compound" that dissolves in the fluid in the well. Similarly, US Patent Application Publication No. 2014/0190705, also on behalf of Halliburton Energy Services, Inc., only mentions magnesium as one of a large list of components, with magnesium not being one of the preferred components . This document also requires the presence of an "electrolytic compound" that dissolves in the fluid at the bottom of the well.
    [011]Although casting, forging and machining are described in Mazyar et. al., these are only mentioned in very general terms (eg method steps and heating temperatures are not indicated) and the structure of the resulting materials is not described. Furthermore, the preferred method of forming the corrosive article is to compress the powder into the desired shape, for example, by cold pressing using an isostatic press. As noted above, such powder metallurgical methods are complicated and expensive. Furthermore, the resulting powdered composites may have poor mechanical properties.
    [012] Thus, there is a need in the oil and gas industries to provide a corrosive article that provides the desired corrosion characteristics, while having improved mechanical properties, and at a lower cost than can actually be achieved . It is also advantageous for the corrosive article to have a relatively low density (eg compared to metals in general). This invention seeks to improve these problems. Declaration of invention
    [013] This invention relates to a magnesium alloy suitable for use as a corrosive downhole article, wherein the alloy has a corrosion rate of at least 50 mg/cm2/day in 15% KCl a 93°C and a 0.2% proof strength of at least 50MPa when tested using the ASTM B557-10 standard voltage test method.
    [014] In relation to this invention, the term "alloy" is used to mean a composition made by mixing and fusing two or more metallic elements, fusing, mixing and resolidifying these.
    [015]The term "rare earth metals" is used in connection with the invention to refer to the fifteen elements of lanthanides as well as Sc and Y.
    [016]The magnesium alloy preferably comprises one or more of Ni, Co, Ir, Au, Pd or Cu. In some embodiments, Ni is preferred. These metallic elements promote alloy corrosion. In all embodiments, the alloy preferably comprises one or more of Ni, Co, Ir, Au, Pd or Cu, more preferably Ni, in an amount between 0.01% and 15% by weight (% by weight weight) and, in some embodiments, more preferably between 0.1% and 10% by weight, even more preferably between 0.2% by weight and 8% by weight.
    [017] Particularly preferred combinations of metals in the magnesium alloy include Mg-Al-Zn-Mn, Mg-Al-Mn, Mg-Zn-Zr, Mg-Y-RE-Zr, Mg-Zn-Cu-Mn, Mg-Nd-Gd-Zr, Mg-Ag-RE-Zr, Mg-Zn-RE-Zr, Mg-Gd-Y-Zr, Mg-Al-Ca-Mn and Mg-Al-Sn-Zn-Mn. These additional elements can be included by forming a magnesium alloy with these elements and then adding to the molten alloy a corrosion promoting metallic element (ie, Ni, Co, Ir, Au, Pd and/or Cu).
    [018] In a first preferred embodiment, the magnesium alloy comprises (a) 0.01 to 10% by weight of one or more of Ni, Co, Ir, Au, Pd or Cu, (b) 1 to 10% in weight of Y, (c) 1 to 15% of at least one rare earth metal other than Y, and (d) 0 to 1% by weight of Zr.
    [019] In the first embodiment, the magnesium alloy comprises one or more rare earth metals other than Y in an amount of 1 to 15% by weight, more preferably in an amount of 1 to 10% by weight, even more preferably, in an amount of 1.5-5.0% by weight. A preferred rare earth metal other than Y is Nd. A particularly preferred amount of Nd in the alloy is from 1.7 to 2.5% by weight, more preferably from 2.0 to 2.3% by weight.
    [020] In the first embodiment, the magnesium alloy comprises Y in an amount of 1 to 10% by weight, preferably in an amount of 2.0 to 6.0% by weight, more preferably in an amount of 3.0 to 5.0% by weight, even more preferably in an amount of 3.3 to 4.3% by weight or 3.7 to 4.3% by weight.
    [021] In the first embodiment, the magnesium alloy comprises Zr in an amount of up to 1% by weight. In some embodiments, the magnesium alloy comprises Zr in an amount of 0.05 to 1.0% by weight, more preferably in an amount of 0.2 to 1.0% by weight, most preferably in an amount of 0.3 to 0.6% by weight. In some embodiments, the magnesium alloy comprises Zr in an amount of up to 0.6% by weight, preferably up to 0.3% by weight, more preferably up to 0.15% by weight. In some embodiments, the magnesium alloy is substantially free of Zr (for example, the magnesium alloy comprises less than 0.05% by weight of Zr).
    [022] For all modalities, preferably, the remainder of the alloy is magnesium and accidental impurities. It is preferred that the Mg content in the magnesium alloy is preferably at least 80% by weight, more preferably at least 85% by weight, most preferably at least 87% by weight.
    [023] A particularly preferred composition of the first embodiment is a magnesium alloy comprising 3.3 to 4.3% by weight of Y, 0.2 to 1.0% by weight of Zr, 2.0 to 2.5 % by weight of Nd and optionally 0.3 to 1.0% by weight of other rare earths with Ni as the element metal. An alternative preferred composition of the first embodiment is a magnesium alloy comprising 3.3 to 4.3% by weight of Y, up to 0.2% by weight of Zr, 1.7 to 2.5% by weight of Nd and optionally 0.3 to 1.0% by weight of other rare earths with Ni as the element metal.
    [024] In the first embodiment, the magnesium alloy preferably comprises Ni in an amount between 0.01% and 10% by weight, more preferably between 0.1% and 8% by weight, even more preferably between 0.2% by weight and 7% by weight. Another particularly preferred composition is a magnesium alloy comprising 3.3 to 4.3% by weight of Y, 0.2 to 1.0% by weight of Zr, 2.0 to 2.5% by weight of Nd and 0.2 to 7% by weight of Ni. A particularly preferred alternative composition is a magnesium alloy comprising 3.3 to 4.3% by weight of Y, 0.2% by weight or less of Zr, 1.7 to 2.5% by weight of Nd and 0 .2 to 7% by weight of Ni. It is preferable that the remainder of the alloy be magnesium and accidental impurities.
    [025] In a second preferred embodiment, the magnesium alloy comprises (a) 0.01 to 10% by weight of one or more of Ni, Co, Ir, Au, Pd or Cu, (b) 1 to 15% in weight of Al, (c) 0.1 to 1% Mn, and (d) optionally one or more of Ca, Sn and Zn.
    [026] In the second embodiment, the magnesium alloy comprises 1 to 15% by weight of Al, preferably 2 to 12% by weight of Al, more preferably 2.5 to 10% by weight of Al.
    [027] In the second embodiment, the magnesium alloy comprises 0.1 to 1% by weight of Mn, preferably 0.1 to 0.8% by weight of Mn, more preferably 0.2 to 0.6% by weight of Mn.
    [028] In the second embodiment, the magnesium alloy optionally comprises one or more of Ca, Sn and Zn. When the alloy comprises Sn, it is preferably in an amount of 2 to 6% by weight, more preferably 3 to 5% by weight. When the alloy comprises Zn, it is preferably in an amount of from 0.1 to 3% by weight, more preferably from 0.2 to 2.5% by weight. In some embodiments, the alloy comprises both Sn and Zn. When the alloy comprises Ca, it is preferably in an amount of 1 to 10% by weight, more preferably 2 to 6% by weight.
    [029] In the second embodiment, the magnesium alloy preferably comprises Ni in an amount between 0.01% and 10% by weight, more preferably between 0.01% and 5% by weight, even more preferably between 0.1% by weight and 3% by weight.
    [030] In a third preferred embodiment, the magnesium alloy comprises (a) 0.01 to 15% by weight of one or more of Ni, Co, Ir, Au, Pd or Cu, (b) 1 to 9% in weight Zn and (c) optionally one or More of Mn and Zr.
    [031] In the third embodiment, the magnesium alloy comprises 1 to 9% by weight Zn, preferably 5 to 8% by weight Zn, more preferably 6 to 7% by weight Zn.
    [032] In the third embodiment, when the alloy comprises Mn, it is preferably in an amount of 0.1 to 1% by weight, more preferably 0.5 to 1.0% by weight, even more preferably from 0.7 to 0.9% by weight.
    [033] In the third embodiment, the magnesium alloy preferably comprises Ni in an amount between 0.01% and 10% by weight, more preferably between 0.01% and 7% by weight, even more preferably between 0.1% by weight and 5% by weight.
    [034] In the third embodiment, the magnesium alloy may also comprise Cu, preferably in an amount of 0.1 to 5% by weight, more preferably 0.5 to 3% by weight, even more preferably 1 at 2% by weight. In some embodiments, the alloy comprises Mn and Cu.
    [035] In the third embodiment, when the magnesium alloy comprises Zr, it is preferably in an amount of up to 1% by weight, more preferably in an amount of 0.05 to 1.0% by weight, even more preferably, in an amount of 0.2 to 1.0% by weight, more preferably in an amount of 0.3 to 0.7% by weight.
    [036] It is preferable that the corrosion promoting metallic element (i.e. Ni, Co, Ir, Au, Pd and/or Cu) has a solubility of at least 0.1% by weight in molten magnesium at 850 °C. Preferably, the metal corrosion promoting element has a solubility of at least 0.5% by weight in molten magnesium at 850°C, more preferably at least 1% by weight. In some embodiments, it is preferred that the metallic corrosion promoting element has a solubility of at least 1% by weight in the molten magnesium alloy to which it must be added at 850°C. With respect to molten material, the term "solubility" is used to mean that the corrosion-promoting metallic element dissolves in the molten magnesium or magnesium alloy.
    [037] Preferably, the metallic corrosion promoting element has a solubility of less than 0.1% by weight, more preferably less than 0.01% by weight, in solid magnesium at 25 °C. In some embodiments, it is preferable that the metallic corrosion promoting element has a solubility of less than 0.1% by weight, more preferably less than 0.01% by weight, in the solid magnesium alloy to which it is to be added at 25°C. °C. In relation to solid material, the term "solubility" is used to mean that the atoms of the corrosion-promoting metallic element are randomly distributed throughout the alloy in a single phase (ie, rather than forming a separate phase).
    [038] The magnesium alloy preferably has a corrosion rate of at least 50 mg/cm2/day, preferably at least 75 mg/cm2/day, even more preferably at least 100 mg/cm2/day day in 3% KCl at 38°C (100F). It is preferred that the magnesium alloy has a corrosion rate of at least 75 mg/cm2/day, preferably at least 250 mg/cm2/day, even more preferably at least 500 mg/cm2/day, in 15% KCl at 93°C (200F). It is preferred that the corrosion rate, in 3% KCl at 38°C or in 15% KCl at 93°C (200F), is less than 15,000 mg/cm2/day.
    [039] It is preferable that the magnesium alloy has a 0.2% proof strength of at least 75 MPa, more preferably at least 100 MPa, even more preferably at least 150 MPa, when tested with use of the ASTM B557-10 standard strain test method. It is preferred that the 0.2% proof strength be less than 700 MPa. The proof strength of a material is the stress at which the material's stress changes from elastic deformation to plastic deformation, causing the material to deform permanently.
    [040] It is preferable that the 0.2% proof strength of the magnesium alloy, when one or more of Ni, Co, Ir, Au, Pd or Cu has been added, is at least 80%, more preferably At least 90% of the proof strength of 0.2% of the base alloy. The term "base alloy" is used to mean the magnesium alloy without having added one or more of Ni, Co, Ir, Au, Pd or Cu. Even more preferably, the 0.2% proof strength of the magnesium alloy when Ni has been added is at least 80%, more preferably at least 90%, the 0.2% proof strength of the base alloy. .
    [041] This invention also relates to a corrosive downhole article, such as a downhole tool, which comprises the magnesium alloy described above. In some embodiments, the corrosive downhole article is a frac ball, plug, packer, or tool assembly. The fracturing ball is preferably substantially spherical in shape. In some embodiments, the frac ball consists essentially of the magnesium alloy described above.
    [042] This invention also relates to a method for producing a magnesium alloy suitable for use as a corrosive downhole article comprising the steps of: a) melting magnesium or a magnesium alloy; b) adding one or more of Ni, Co, Ir, Au, Pd or Cu to the molten magnesium or magnesium alloy such that one or more of Ni, Co, Ir, Au, Pd or Cu fuse; c) mixing the resulting molten magnesium alloy; and d) melting the magnesium alloy.
    [043] Preferably, the method is to produce a magnesium alloy as defined above. It is preferable that the melting step is carried out at a temperature of 650 °C (i.e. the melting point of pure magnesium) or more, preferably less than 1090 °C (the boiling point of pure magnesium). A preferred temperature range is 650°C to 850°C, more preferably 700°C to 800°C, most preferably about 750°C.
    [044]The casting step typically involves pouring the molten magnesium alloy into a mold and then allowing it to cool and solidify. The mold can be a die mold, permanent mold, sand mold, investment mold, direct cold casting (DC) mold, or other mold.
    [045]After step (c), the method may comprise one or more of the following additional steps: (d) extrusion, (e) forging, (f) rolling, (g) machining.
    [046]It is preferable that step (a) comprises the melting of a magnesium alloy. Preferably, the magnesium alloy of step (a) comprises one or more of Al, Zn, Mn, Zr, Y, rare earth metals, Cu, Nd, Gd, Ca, Sn and/or Ag. particularly preferred ones for step (a) include Mg-Al-Zn-Mn, Mg-Al-Mn, Mg-Zn-Zr, Mg-Y-RE-Zr, Mg-Zn-Cu-Mn, Mg-Nd-Gd -Zr, Mg-Ag-RE-Zr, Mg-Zn-RE-Zr, Mg-Gd-Y-Zr, Mg-Al-Ca-Mn and Mg-Al-Sn-Zn-Mn. As noted above, these additional elements can be included by forming a magnesium alloy with these elements, and then adding the corrosion-promoting metallic element to the cast alloy.
    [047] In a first preferred embodiment, the magnesium alloy comprises 1 to 10% by weight of Y, 1 to 15% by weight of rare earths other than Y and up to 1% by weight of Zr. A particularly preferred magnesium alloy comprises 3.3 to 4.3% by weight of Y, up to 1% by weight of Zr, 2.0 to 2.5% by weight of Nd and optionally 0.3 to 1.0% by weight of rare earths. In such an alloy, Zr may be present in an amount of 0.05 to 1.0% by weight, or the alloy may comprise less than 0.05% by weight of Zr. Preferably, Ni is added in an amount between 0.2% and 7% by weight. It is preferable that the remainder of the alloy be magnesium and accidental impurities.
    [048] In a second preferred embodiment, the magnesium alloy comprises 1 to 15% by weight of Al and up to 2% by weight in total of Zn and/or Mn. The alloy preferably comprises 2 to 12% by weight of Al. Preferably, the alloy comprises 0.2 to 1.2% by weight in total Zn and/or Mn. Preferably, Ni is added in an amount of 0.1 to 3% by weight.
    [049] In a third preferred embodiment, the magnesium alloy comprises 1 to 9% by weight of Zn and optionally one or more of Mn and Zr. The alloy preferably comprises 5 to 8% by weight of Zn. Preferably, Ni is added in an amount of 0.1 to 5% by weight.
    [050] The composition of the magnesium alloy, in particular, of the first and third modalities, can be adapted to achieve a desired corrosion rate that stays in a specific range. The desired corrosion rate at 15% KCl at 93°C can be in any of the following particular ranges: 50 to 100 mg/cm2/day; 100 to 250 mg/cm2/day; 250 to 500 mg/cm2/day; 500 to 1000 mg/cm2/day; 1,000 to 3,000 mg/cm2/day; 3,000 to 4,000 mg/cm2/day; 4,000 to 5,000 mg/cm2/day; 5,000 to 10,000 mg/cm2/day; 10,000 to 15,000 mg/cm2/day.
    [051] The method of the invention can also comprise the adaptation compositions of magnesium alloys, in particular, of the first and third modalities, so that the cast magnesium alloys reach the desired corrosion rates in KCl at 15% at 93 ° C that are in at least two of the following ranging from: 50 to 100 mg/cm2/day; 100 to 250 mg/cm2/day; 250 to 500 mg/cm2/day; 500 to 1000 mg/cm2/day; 1000 to 3000 mg/cm2/day; 3000 to 4000 mg/cm2/day; 4,000 to 5,000 mg/cm2/day; 5,000 to 10,000 mg/cm2/day; and 10,000 to 15,000 mg/cm2/day.
    [052] It is preferable that the corrosion promoting metallic element (i.e. Ni, Co, Ir, Au, Pd and/or Cu) has a solubility of at least 0.1% by weight in molten magnesium at 850 °C. Preferably, the metal corrosion promoting element has a solubility of at least 0.5% by weight in molten magnesium at 850°C, more preferably at least 1% by weight. In some embodiments, it is preferable that the metallic corrosion promoting element has a solubility of at least 1% by weight in the molten magnesium or magnesium alloy to which it is added.
    [053] Preferably, the corrosion promoting metallic element (ie Ni, Co, Ir, Au, Pd and/or Cu) has a solubility of less than 0.1% by weight, more preferably less than 0.01% by weight in solid magnesium at 25°C. In some embodiments, it is preferable that the corrosion promoting metallic element has a solubility of less than 0.1% by weight, more preferably less than 0.01% by weight, in the molten magnesium or magnesium alloy to which a once cooled to 25°C and solidified.
    [054]The metallic corrosion promoting element is one or more of Ni, Co, Ir, Au, Pd or Cu. In some embodiments, Ni is preferred. With respect to the compositions of the first preferred embodiment, the corrosion-promoting metallic element is preferably added in an amount between 0.01% and 10% by weight, more preferably between 0.1% and 8% by weight, even more preferably between 0.2% and 7% by weight. With respect to the compositions of the second preferred embodiment, the metallic corrosion promoting element is preferably added in an amount between 0.01% and 15% by weight, more preferably between 0.01% and 5% by weight, even more preferably, between 0.1% and 3%% by weight. With respect to the compositions of the third preferred embodiment, the corrosion-promoting metallic element is preferably added in an amount between 0.01% and 10% by weight, more preferably 0.01% and 7% by weight, further more preferably between 0.1% and 5% by weight.
    [055] A particularly preferred first embodiment of the method comprises the melting in step (a) of a magnesium alloy comprising 3.3 to 4.3% by weight of Y, 0.2 to 1.0% by weight of Zr , 2.0 to 2.5% by weight of Nd and optionally 0.3 to 1.0% by weight of rare earths and add in step (b) Ni as the corrosion promoting metallic element. It is preferable that in step (b) Ni is added in an amount between 0.01% and 10% by weight, more preferably between 0.1% by weight and 8% by weight.
    [056] This invention also relates to a magnesium alloy suitable for use as a corrosive downhole article that can be obtained by the method described above.
    [057] Furthermore, this invention relates to a magnesium alloy as described above for use as a corrosive downhole article.
    [058] This invention also relates to a method of hydraulic fracturing which comprises using a corrosive downhole article comprising the magnesium alloy as described above, or a downhole tool as described above. Preferably, the method comprises forming an at least partial seal in a wellbore with the corrosive downhole article. The method may then comprise removing the at least partial seal, allowing the downhole corrosive article to corrode. Such corrosion can occur at a desired rate with certain alloy compositions of the disclosure as discussed above. It is preferred that the corrosive downhole article be a frac ball, plug, packer or tool assembly. The fracturing ball is preferably substantially spherical in shape. In some embodiments, the frac ball consists essentially of the magnesium alloy described above.
    [059] This invention will be further described with reference to the following figures which are not intended to limit the scope of the claimed invention, in which:
    [060]the figure shows a microstructure of sample DF9905D of example 1;
    [061] Figure 2 shows a graph of % loss in test stress against the addition of Ni (% by weight) for the alloys of examples 3A, 3B and 3C;
    [062] Figure 3 shows a graph of test stress against the addition of Ni (% by weight) for the alloys of examples 3A, 3B and 3C; and
    [063] Figure 4 shows a graph of the corrosion rate against the addition of Ni (% by weight) for the alloys of examples 3a, 3B and 3C; Examples Example 1 - magnesium aluminum alloy
    [064] A base magnesium alloy consisting of the commercial alloy AZ80A which has a typical chemical composition of 8.5% by weight of Al, 0.5% by weight of Zn and 0.3% by weight of Mn, was melted by heating to 750°C and nickel was added in amounts ranging from 0.01% by weight to 1% by weight. The product was then converted into an ingot and extruded into a rod.
    [065] In order to simulate the mild and extreme corrosion performance in a well, the material was corrosion tested by measuring the weight loss in a 3% by weight aqueous solution of potassium chloride at a constant temperature of 38 °C (100F) and 15% by weight of aqueous potassium chloride solution at a constant temperature of 93°C (200F).
    [066]Corrosion rates are shown in Table 1 below. The samples comprise the standard alloy (ie AZ80A without added nickel) and two samples with different amounts of added nickel. Table 1

    [067]The data in Table 1 clearly shows the increased corrosion level achieved in the samples to which nickel was added, with a higher nickel content resulting in a higher corrosion rate.
    [068]The mechanical properties of the samples were also tested using standard stress tests (ie ASTM B557-10), and the results are shown in Table 2 below.
    Table 2
    [069] Figure 1 shows a microstructure of sample DF9905D (i.e. 0.61% nickel by weight). The dark area of the microstructure, marked "1", is the α-Mg phase (ie, the phase comprising magnesium in solid solution with the other alloying elements). The light area of the microstructure, the example of which is marked "2", is the phase comprising the corrosion promoting element (ie nickel in this case) and magnesium. Example 2 - Magnesium and Yttrium Rare Earth Alloy
    [070] The process of example 1 was repeated, but with the base magnesium alloy AZ80A being replaced by the commercial Elektron 43 alloy. An alloy WE43C with a composition of 3.7a 4.3% by weight of Y was used 0.2 to 1.0% by weight of Zr, 2.0 to 2.5% by weight of Nd and 0.3 to 1.0% by weight of rare earths.
    [071]Corrosion rates are shown in Table 3 below. The samples comprise the standard alloy (ie WE43C without added nickel) and five samples with different amounts of added nickel.

    [072]The data in Table 3 clearly show the increased corrosion level achieved in the samples to which nickel was added, with a higher nickel content resulting in a higher corrosion rate.
    [073]The mechanical properties of these samples were also tested using standard stress tests, and the results are shown in Table 4 below.
    Table 4
    [074] The data in Table 4 show that the alloys of the invention have improved mechanical properties, in particular, proof strength of 0.2%, when compared to prior art compositions. Example 3A - magnesium and aluminum alloys
    [075]Other magnesium alloy compositions were prepared by combining the components in the amounts listed in Table 5 below (the balance being magnesium). These compositions were then melted by heating to 750 °C. The product was then converted into an ingot and extruded into a rod.

    Table 5
    [076]The mechanical properties of these samples were also tested using the same standardized stress tests, and the results are shown in Table 6 below. Alloy class: Mg-AI

    Table 6
    [077]These data show that the addition of nickel to these magnesium and aluminum alloys significantly increases the corrosion rate of the alloys. Advantageously, for these alloys, this increase in corrosion rate is provided while maintaining the mechanical properties of the alloy (as exemplified by the 0.2% proof strength). Thus, the alloys tested in this example may find use as components in downhole tools due to their combination of high corrosion rates and good mechanical properties. Example 3B - rare earth alloys of yttrium and magnesium
    [078]Other magnesium alloy compositions were prepared by combining the components in the amounts listed in Table 7 below. These compositions were then melted by heating to 750 °C. The product was then converted into an ingot and extruded into a rod.

    [079]The mechanical properties of these samples were tested using standard stress tests, and the results are shown in Table 8 below.
    Table 8
    [080]These data show that, as for magnesium and aluminum alloys, the addition of nickel to these rare earth magnesium and yttrium alloys significantly increases the corrosion rate of the alloy. Advantageously, for these alloys, this increase in corrosion rate is provided while maintaining the mechanical properties of the alloy (as exemplified by the 0.2% proof strength). However, in addition to these advantageous properties, for these alloys, the increase in corrosion rate is substantially proportional to the amount of nickel added. This can provide the additional feature that the corrosion rate of these alloys is therefore "adjustable" and alloys with specific desirable corrosion rates, or specific corrosion rate ranges, can be produced. Thus, the alloys tested in this example can be used as components in downhole tools due to their combination of high corrosion rates and good mechanical properties. Example 3C - magnesium and zinc alloys
    [081] Magnesium alloy compositions were prepared by combining the components in the amounts listed in Table 9 below. These compositions were then melted by heating to 750°C. The product was then converted into one. ingot and extruded into a rod.
    Table 9
    [082]The mechanical properties of these samples were tested using standard stress tests, and the results are shown in Table 10 below.
    Table 10
    [083]These data show that, as for magnesium and aluminum alloys and magnesium, yttrium and rare earth alloys, the addition of nickel to these magnesium and zinc alloys significantly increases their corrosion rate. Alloys of magnesium and zinc are known in the art to have high strength values and it is shown in the disclosure that the addition of nickel also increases their corrosion rate. However, the data demonstrates that the mechanical properties of these alloys (as exemplified by the 0.2% proof strength) decrease with increasing nickel content.
    [084] This example shows that not all magnesium alloys provide the necessary mechanical strength for certain uses of the invention when nickel is added and that it is, in fact, difficult to predict how the properties of a given alloy will change when an element promoting corrosion, such as nickel, is added.
    [085] In figures 2, 3 and 4, the mechanical properties of the alloys of examples 3A, 3B and 3C against the addition of Ni (% by weight) were plotted.
    [086] Figure 2 shows that, in particular, for the magnesium and zinc alloys of example 3C ("Zn-Mg", where zinc is the main reinforcing element), between 20% and 40% of the strength is lost when nickel is added. In contrast, the strength of magnesium and aluminum ("Mg-Al") and magnesium, yttrium and rare earth (Mg-Y-RE) alloys (examples 3a and 3B) is maintained. Figure 3 is a graph showing the absolute proof values (MPa) against the addition of Ni (% by weight).
    [087] Figure 4 is a graph of the corrosion rate against the addition of Ni (% by weight). For magnesium, yttrium and rare earth alloys, a line was drawn through the data points that demonstrate the correlation between corrosion rate and Ni addition for these alloys. This shows that magnesium, yttrium and rare earth alloys can advantageously be adapted to achieve a specific desired corrosion rate or range of corrosion rates.
    权利要求:
    Claims (15)
    [0001]
    1. Magnesium alloy suitable for use as a corrosive downhole article, CHARACTERIZED by the fact that the magnesium alloy comprises: a) 0.01 to 10% by weight of one or more of Ni, Co, Ir, Au, Pd or Cu, b) 1 to 10% by weight of Y, c) 1 to 15% by weight of at least one rare earth metal other than Y, and d) 0 to 1% by weight of Zr, and magnesium in an amount of at least 80% by weight, wherein the magnesium alloy has a corrosion rate of at least 50 mg/cm2/day at 15% KCl at 93°C and a proof strength of 0.2% of at least 50MPa when tested using the ASTM B557-10 Standard Voltage Test Method.
    [0002]
    2. Magnesium alloy according to claim 1, CHARACTERIZED by the fact that the magnesium alloy has a corrosion rate of at least 75 mg/cm2/day in 15% KCl at 93 °C.
    [0003]
    3. Magnesium alloy according to claim 1 or 2, CHARACTERIZED by the fact that the magnesium alloy has a 0.2% proof strength of at least 150 MPa when tested using the ASTM standard tensile test method B557-10.
    [0004]
    4. Magnesium alloy according to any one of claims 1 to 3, CHARACTERIZED by the fact that the magnesium alloy comprises 0.1 to 8% by weight of Ni.
    [0005]
    5. Magnesium alloy according to any one of claims 1 to 4, CHARACTERIZED by the fact that the magnesium alloy comprises Y in an amount of 2.0 to 6.0% by weight.
    [0006]
    6. Magnesium alloy according to claim 5, CHARACTERIZED by the fact that the magnesium alloy comprises Y in an amount of 3.0 to 5.0% by weight.
    [0007]
    7. Magnesium alloy according to any one of claims 1 to 6, CHARACTERIZED by the fact that the magnesium alloy comprises at least one rare earth metal other than Y in an amount of 1.5 to 5.0% in Weight.
    [0008]
    8. Magnesium alloy according to any one of claims 1 to 7, CHARACTERIZED by the fact that at least one rare earth metal other than Y is Nd.
    [0009]
    9. Magnesium alloy according to claim 8, CHARACTERIZED by the fact that the magnesium alloy comprises Nd in an amount of 1.7 to 2.5% by weight.
    [0010]
    10. Magnesium alloy according to any one of claims 1 to 9, CHARACTERIZED by the fact that the magnesium alloy comprises Zr in an amount of up to 0.3% by weight.
    [0011]
    11. Magnesium alloy according to claim 1, CHARACTERIZED by the fact that the magnesium alloy comprises 3.3 to 4.3% by weight of Y, up to 0.2% by weight of Zr and 1.7 to 2.5% by weight of Nd and optionally 0.3 to 1.0% by weight of other rare earths.
    [0012]
    12. Magnesium alloy according to any one of claims 1 to 11, CHARACTERIZED by the fact that the proof strength of 0.2% of the magnesium alloy when one or more of Ni, Ir, Au, Pd or Cu was added is at least 80% of the 0.2% proof strength of the base alloy.
    [0013]
    13. Magnesium alloy according to any one of claims 1 to 12, CHARACTERIZED by the fact that the corrosive downhole article is a downhole tool.
    [0014]
    14. Magnesium alloy according to claim 13, CHARACTERIZED by the fact that the downhole tool is a frac ball, plug, packer or tool assembly.
    [0015]
    15. Method for hydraulic fracturing, CHARACTERIZED by the fact that it comprises the use of a downhole tool, as defined in claim 14.
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    法律状态:
    2019-08-27| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-03-23| B07A| Application suspended after technical examination (opinion) [chapter 7.1 patent gazette]|
    2021-06-29| 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 28/07/2015, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    GBGB1413327.6A|GB201413327D0|2014-07-28|2014-07-28|Corrodible downhole article|
    GB1413327.6|2014-07-28|
    PCT/GB2015/052169|WO2016016628A2|2014-07-28|2015-07-28|Corrodible downhole article|BR122021010481-6A| BR122021010481B1|2014-07-28|2015-07-28|MAGNESIUM ALLOY SUITABLE FOR USE AS A CORROSIBLE WELLBOARD ARTICLE AND METHOD FOR HYDRAULIC FRACTURING|
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