WO2020082781A1 - 含镍高强韧可控降解镁合金材料及其制备方法和应用 - Google Patents

含镍高强韧可控降解镁合金材料及其制备方法和应用 Download PDF

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WO2020082781A1
WO2020082781A1 PCT/CN2019/094183 CN2019094183W WO2020082781A1 WO 2020082781 A1 WO2020082781 A1 WO 2020082781A1 CN 2019094183 W CN2019094183 W CN 2019094183W WO 2020082781 A1 WO2020082781 A1 WO 2020082781A1
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phase
nickel
magnesium
alloy
magnesium alloy
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PCT/CN2019/094183
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English (en)
French (fr)
Inventor
王敬丰
高诗情
刘世杰
王奎
潘复生
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重庆大学
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Priority to US16/966,882 priority Critical patent/US20210040593A1/en
Priority to CA3117106A priority patent/CA3117106C/en
Publication of WO2020082781A1 publication Critical patent/WO2020082781A1/zh

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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/06—Alloys based on magnesium with a rare earth metal as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D7/00—Casting ingots, e.g. from ferrous metals
    • B22D7/005—Casting ingots, e.g. from ferrous metals from non-ferrous metals
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
    • C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
    • C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon

Definitions

  • the present disclosure relates to the technical field of magnesium alloys, and in particular, to a nickel-containing high-strength and controllable degradable magnesium alloy material, and a preparation method and application thereof.
  • China's oil problem has become one of the important issues of national concern. According to the statistics of the National Bureau of Statistics, China's net oil imports continue to increase, and by 2015 China's dependence on foreign oil directly broke through 60%. According to international experience and the opinions of authoritative persons, CNPC's foreign dependency must be kept below 60%. Whether it is from a strategic perspective or out of consideration for national security and the normal operation of the economy, China should reduce its foreign dependence on oil. Therefore, intensifying the exploitation of domestic oil and improving the efficiency of oil extraction is an important measure for China's strong country to rejuvenate the country, and it is urgent to explore new technologies and develop new materials.
  • packer tools (such as fracturing balls and bridge plugs) should be used to separate the layers and perform fracturing reconstruction layer by layer. After all layers are completed, the packer tools should be discharged out of the wellbore, Open wells to realize oil and gas production.
  • packer tools are now made of steel, which has the disadvantages of drilling and milling, long time consumption, post-drilling powder, and difficult return of fragments, which greatly increases the construction cycle and cost.
  • the objectives of the present disclosure include, for example, to provide a nickel-containing high-strength and controllable degradable magnesium alloy material to alleviate that most commonly used packing tools are currently made of steel, which has difficulties in drilling and milling, takes a long time, and powders and fragments after drilling are not easy Shortcomings such as flowback greatly increase the technical problems of construction cycle and cost.
  • the nickel-containing high-strength and controllable degradable magnesium alloy material provided by the present disclosure includes the following components in mass percentage: Ni: 0.3 to 8.5%, RE: 0.5 to 28%, the balance is Mg and inevitable impurities; , RE is a rare earth element, Mg, Ni and RE form Mg 12 RENi type long period phase, Mg 2 Ni phase and Mg x RE y phase; the volume fraction of the Mg 12 RENi type long period phase is 3 to 70%, Mg 2 The volume fraction of the Ni phase is 0.5 to 10%, the volume fraction of the Mg x RE y phase is 0.5 to 22%, and the value range of x: y is (3 to 12): 1.
  • the nickel-containing high-strength controllable degradable magnesium alloy material includes the following components in terms of mass percentage: Ni is 0.5-8.0%, RE is 1.5-20%, and the balance is Mg And inevitable impurities.
  • the nickel-containing high-strength controllable degradable magnesium alloy material includes a cast magnesium alloy, an extruded magnesium alloy, and an aging magnesium alloy.
  • the as-cast magnesium alloy includes an Mg 12 NiRE type long-period phase, Mg 5 RE phase and Mg 2 Ni phase, and the volume fraction of the Mg 12 NiRE-type long cycle phase is 3 ⁇ 65%, the volume fraction of the Mg 2 Ni phase is 0.5-6%, and the volume fraction of the Mg 5 RE phase is 0.5-15%.
  • the extruded magnesium alloy includes an Mg 12 NiRE type long-period phase, Mg 2 Ni phase and Mg 5 RE phase, and the volume fraction of the Mg 12 NiRE type long-period phase
  • the volume fraction is 4 to 70%
  • the volume fraction of the Mg 2 Ni phase is 1% to 8%
  • the volume fraction of the Mg 5 RE phase is 1 to 20%.
  • the aged magnesium alloy includes Mg 12 NiRE type long-period phase, Mg 2 Ni phase and Mg x RE y phase, and the volume fraction of the Mg 12 NiRE type long-period phase is 4 ⁇ 70%, the volume fraction of the Mg 2 Ni phase is 2-10%, and the volume fraction of the Mg x RE y phase is 2-22%, where the value range of x: y is (3-12): 1.
  • the RE is selected from at least one of Gd, Y, Er, Dy, Ce, and Sc.
  • the nickel-containing high-strength controllable degradable magnesium alloy material includes the following components in terms of mass percentage: Ni: 0.3 to 8.5%, RE: 0.5 to 28%, M: 0.03 to 10%, the balance is Mg and inevitable impurities; among them, M is an element that can alloy with magnesium.
  • the mass percentage of inevitable impurities in the magnesium alloy material is not higher than 0.2%.
  • M is at least one of Fe, Cu, and Mn.
  • the purpose of the present disclosure includes, for example, to provide a method for preparing a nickel-containing high-strength and controllable degradable magnesium alloy material, which includes the steps of: uniformly mixing a nickel source, a magnesium source, and a rare earth source, and performing alloying treatment to obtain nickel-containing high strength Tough and controlled degradation of magnesium alloy materials.
  • the nickel source is selected from elemental nickel and / or nickel alloys.
  • the nickel alloy is selected from at least one of a magnesium-nickel alloy, a nickel-yttrium alloy, or a zinc-nickel alloy.
  • the magnesium source is selected from elemental magnesium and / or magnesium alloys.
  • the magnesium alloy is selected from at least one of magnesium gadolinium alloy, magnesium yttrium alloy, magnesium zinc alloy, magnesium nickel alloy, magnesium calcium alloy, or magnesium iron alloy.
  • the rare earth source includes a rare earth element and / or a rare earth intermediate alloy.
  • the rare earth element includes at least one of gadolinium, yttrium, erbium, dysprosium, cerium, and scandium.
  • the rare earth master alloy includes magnesium gadolinium alloy, magnesium yttrium alloy, magnesium erbium alloy, magnesium cerium alloy, magnesium scandium alloy, nickel yttrium alloy, nickel gadolinium alloy, nickel erbium alloy, nickel cerium At least one of alloys and nickel-scandium alloys.
  • the alloying treatment includes a smelting casting method and a powder alloy method.
  • the smelting casting method is used for alloying.
  • the smelting casting method includes the following steps:
  • step (b) further includes an aging heat treatment step, and the aging heat treatment step is provided after the extrusion heat deformation treatment.
  • step (a) when smelting and casting is performed, the temperature is first raised to 690-800 ° C, and the material is melted by heat preservation and stirring, and then the temperature is reduced to 630-680 ° C, and the heat preservation is 20-120min After cooling, a magnesium alloy ingot is obtained.
  • inert gas protection is used during smelting and casting.
  • the inert gas is selected from at least one of helium, argon, carbon dioxide, and sulfur hexafluoride, for example, argon.
  • the cooling method is selected from at least one of brine bath, water quenching, furnace cooling, or air cooling.
  • resistance furnace or power frequency induction circuit smelting is used.
  • step (a) the nickel source, rare earth source, and magnesium source are accurately weighed and mixed according to the requirements of the recipe.
  • the temperature for homogenization treatment is 400-550 ° C., and the time is 4-40 hours.
  • step (b) the extrusion ratio during the extrusion deformation process is 8-40.
  • the temperature at which the extrusion treatment is performed is 360-480 ° C.
  • the temperature for performing the aging heat treatment is 150 to 250 ° C., and the time is 12 to 120 h.
  • step (b) the temperature for performing the aging heat treatment is 180 to 220 ° C., and the time is 15 to 60 h.
  • the purpose of the present disclosure includes, for example, to provide the application of nickel-containing high-strength and controllable degradable magnesium alloy materials in the field of oil and gas development.
  • the nickel-containing high-strength and controllable degradable magnesium alloy material provided by the present disclosure uses magnesium as the base material, and by adding Ni and RE, the Mg 12 RENi type long-period phase, Mg 2 Ni phase and Mg x RE y phase are formed, thereby Significantly improve the tensile strength and plasticity of the alloy material; at the same time, there is a large electron negative difference between the Mg 12 RENi type long-period phase and the Mg 2 Ni phase and the magnesium matrix, forming a large number of micro-batteries, which makes the resulting nickel-containing high strength
  • the tough and controllable degradable magnesium alloy material can be quickly decomposed, and the downhole fracturing tool made of the magnesium alloy material can effectively meet the needs in the field of oil and gas development.
  • controllable degradable alloy material provided by the present disclosure When used in the field of oil and gas exploration, it can be completely degraded downhole after completion of the task and discharged through the pipeline, and there is no problem of easy jam and blockage, thereby eliminating drilling and grinding recovery Process, reduce engineering difficulty and improve construction efficiency.
  • the present disclosure provides a nickel-containing high-strength and controllable degradable magnesium alloy material, including the following components in mass percent: Ni: 0.3 to 8.5%, RE: 0.5 to 28%, and more The amount is Mg and unavoidable impurities; among them, RE is a rare earth element, and Mg, Ni and RE mainly form Mg 12 RENi type long-period phase, Mg 2 Ni phase and Mg x RE y phase.
  • the volume fraction of the Mg 12 RENi type long-period phase is 3 to 70%, the volume fraction of the Mg 2 Ni phase is 0.5 to 10%, and the volume fraction of the Mg x RE y phase is 0.5 to 22%.
  • the mass percentage of inevitable impurities in the magnesium alloy material is not higher than 0.2%.
  • the long-period phase is a new reinforced phase in magnesium alloys formed by periodic changes in atomic position or chemical composition in a crystal structure.
  • the structure is divided into two aspects: stacking order and chemical composition order.
  • the Mg 12 RENi type long-period phase is the result of the combined action of stacking order and chemical composition order.
  • the typical but non-limiting mass percentage content of Ni is 0.3%, 0.5%, 0.8%, 1%, 1.2%, 1.5 %, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 4%, 4.2%, 4.5%, 4.8%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% or 8.5%.
  • the typical but non-limiting mass percentage of RE is 0.5%, 1%, 2%, 3%, 4%, 5%, 8 %, 10%, 12%, 15%, 18%, 20%, 22%, 25% or 28%.
  • the volume fraction of the Mg 12 RENi long-period phase is 3 to 70%
  • the volume fraction of the Mg 5 RE phase is 0.5 to 20%
  • the volume fraction of the Mg 2 Ni phase is 0.5 to 10 %
  • the volume fraction of the Mg x RE y phase is 0.5 to 22%
  • the value range of x: y is (3 to 12): 1.
  • the Mg 12 RENi-type long-period phase and Mg x RE y phase significantly improve the tensile strength of the alloy material and keep the alloy a certain plasticity; at the same time, Mg 12 RENi-type long-period phase and Mg 2 Ni phase exist between the magnesium matrix
  • the large potential difference forms a large number of micro-batteries, so that the resulting alloy material can be quickly decomposed, effectively meeting the needs of downhole tool materials in the field of oil and gas development.
  • the typical but non-limiting volume fraction of Mg 12 RENi type long-period phase in nickel-containing high-strength and controllable degradable magnesium alloy materials is 3%, 4%, 5%, 8 %, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70%;
  • Mg 2 Ni Typical but non-limiting volume fractions of the phase are 0.5%, 1%, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%;
  • Mg x RE Typical but non-limiting volume fraction of phase y is 0.5, 1%, 2%, 5%, 8%, 10%, 12%, 15%, 18%, 20% or 22%; typical of x: y But non-limiting values are 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1, 10: 1, 11: 1, or 12: 1.
  • the nickel-containing high-strength and controllable degradable magnesium alloy material provided by the present disclosure is based on magnesium, and by adding Ni and RE, a Mg 12 RENi type long-period phase and a Mg x RE y phase are formed, thereby significantly improving the tensile strength of the alloy material Strength; At the same time, Mg 12 RENi type long-period phase and Mg 2 Ni phase have a large electronegativity difference with the magnesium matrix, forming a large number of micro-batteries, so that the resulting nickel-containing high-strength and controllable degradable magnesium alloy material can be quickly decomposed
  • the downhole fracturing tool made of the magnesium alloy material can effectively meet the needs in the field of oil and gas development.
  • controllable degradable alloy material provided by the present disclosure when used in the field of oil and gas exploration, it can be completely degraded downhole after completion of the task and discharged through the pipeline, without the problem of easy jam and blockage, thereby eliminating the drilling and recovery process , Reduce engineering difficulty and improve construction efficiency.
  • Ni when the nickel-containing high-strength and controllable degradable magnesium alloy material, Ni is 0.5-7.5%, RE is 1.5-19%; Mg 12 RENi type long-period phase volume fraction When the volume fraction of the Mg 5 RE phase is 1 to 15%, and the volume fraction of the Mg 2 Ni phase is 1 to 5%.
  • the nickel-containing high-strength and controllable degradable magnesium alloy material has a tensile strength of 325-505 MPa at room temperature, a yield strength of 156-415 MPa, an elongation of 6.0-21.8%, and a decomposition rate of 3.5wt% KCl solution at 90 ° C It is 363mm / a ⁇ 2500mm / a.
  • the nickel-containing high-strength and controllable degradable magnesium alloy material includes a cast magnesium alloy, an extruded magnesium alloy, and an aged magnesium alloy.
  • Mg, Ni, and RE mainly form an Mg 12 RENi type long-period phase, Mg 2 Ni phase, and Mg 5 RE phase, and the Mg 12 NiRE
  • the volume fraction of the long-period phase is 3 to 65%
  • the volume fraction of the Mg 2 Ni phase is 0.5 to 6%
  • the volume fraction of the Mg 5 RE phase is 0.5 to 15%.
  • the typical but non-limiting volume fraction of the Mg 12 NiRE type long-period phase is 3%, 4%, 5%, 8%, 10 %, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, or 65%; typical but non-limiting Mg 2 Ni phase
  • the non-limiting volume fraction is 0.5%, 0.8%, 1%, 2%, 5%, 8%, 10%, 12% or 15%.
  • Mg, Ni, and RE mainly form an Mg 12 RENi type long-period phase, Mg 2 Ni phase, and Mg 5 RE phase, and Mg 12 NiRE type
  • the volume fraction of the long-period phase is 4 to 70%
  • the volume fraction of the Mg 2 Ni phase is 1% to 8%
  • the volume fraction of the Mg 5 RE phase is 1 to 20%;
  • the typical but non-limiting volume fraction of the Mg 12 NiRE type long-period phase is 4%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70%; typical but not limited to Mg 2 Ni phase
  • the volume fraction of sex is 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5% or 8% ;
  • the typical but non-limiting volume fraction of the Mg 5 RE phase is 1%, 2%, 5%, 8%, 10%, 12%, 15%, 18% or 20%.
  • Mg 12 NiRE type long period phase volume fraction phase volume fraction is 4 ⁇ 70%
  • Mg 2 Ni phase volume fraction is 2% ⁇ 10%
  • the typical but non-limiting volume fraction of the Mg 12 NiRE type long-period phase is 4%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70%; typical but not limited to Mg 2 Ni phase
  • the volume fraction of sex is 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 9% or 10% ;
  • Typical but non-limiting volume fractions of the Mg x RE y phase such as 2%, 5%, 8%, 10%, 12%, 15%, 18%, 20% or 22%, where x: y is typical However, non-limiting values are 3: 1, 4: 1, 5: 1, 6: 1, 7: 1, 8: 1, 9: 1, 10: 1, 11: 1, or 12: 1.
  • RE is
  • the nickel-containing high-strength controllable degradable magnesium alloy material includes the following components in mass percentage: Ni: 0.3 to 8.5%, RE: 0.5 to 28%, M: 0.03 ⁇ 10%, the balance is Mg and inevitable impurities; among them, M is an element that can be alloyed with magnesium.
  • typical but non-limiting mass percentages of Ni are 0.3%, 0.5%, 0.8%, 1%, 1.2 %, 1.5%, 1.8%, 2%, 2.2%, 2.5%, 2.8%, 3%, 3.2%, 3.5%, 4%, 4.2%, 4.5%, 4.8%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8% or 8.5%;
  • the typical but non-limiting mass percentage of RE is 0.5%, 1%, 2%, 3%, 4%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25% or 28%;
  • typical but non-limiting mass percentages of M are 0.03%, 0.05%, 0.08%, 0.1%, 0.15% , 0.2%, 0.5%, 0.8%, 1%, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%.
  • M includes but is not limited to at least one of Fe, Cu, and Mn.
  • the present disclosure provides the preparation method of the above-mentioned nickel-containing high-strength and controllable degradable magnesium alloy material, including the following steps:
  • the nickel source, the magnesium source and the rare earth source are uniformly mixed and alloyed to obtain a nickel-containing high-strength and controllable degradable magnesium alloy material.
  • the preparation method of the nickel-containing high-strength and controllable degradable magnesium alloy material provided by the present disclosure is simple in process, convenient in operation, easy to carry out industrialized large-scale production, and reduces costs.
  • the alloying treatment includes a smelting casting method and a powder alloy method.
  • the nickel source is selected from elemental nickel and / or nickel alloys.
  • the nickel alloy is selected from one or more of magnesium nickel alloy, nickel yttrium alloy, or zinc nickel alloy.
  • the magnesium source is selected from elemental magnesium and / or magnesium alloys.
  • the magnesium alloy is selected from one or more of magnesium gadolinium alloy, magnesium yttrium alloy, magnesium zinc alloy, magnesium nickel alloy, magnesium calcium alloy or magnesium iron alloy.
  • the rare earth source includes rare earth elements and / or rare earth master alloys.
  • the rare earth element includes one or more of gadolinium, yttrium, erbium, dysprosium, cerium, and scandium.
  • the rare earth master alloy includes magnesium gadolinium alloy, magnesium yttrium alloy, magnesium erbium alloy, magnesium cerium alloy, magnesium scandium alloy, nickel yttrium alloy, nickel gadolinium alloy, nickel erbium alloy, nickel At least one of cerium alloy and nickel-scandium alloy.
  • the alloying treatment by the smelting casting method includes the following steps:
  • the preparation method of nickel-containing high-strength and controllable degradable magnesium alloy material makes Mg, Ni and RE in the prepared alloy material form Mg 12 NiRE type long-period phase, Mg x RE y by casting and heat treatment in sequence Phase and Mg 2 Ni phase, not only significantly improve the tensile strength and plasticity of the alloy material; but also form a large number of micro-batteries in the alloy material, so that the generated nickel-containing high-strength and controllable degradable magnesium alloy material can be quickly decomposed.
  • the downhole fracturing tool made of materials can be completely degraded downhole, thereby reducing the engineering difficulty and improving the construction efficiency.
  • an aging heat treatment step is further included.
  • the aging heat treatment step is provided after the extrusion heat deformation treatment, and the aging heat treatment step is performed to make the nickel-containing high strength and toughness.
  • the overall performance of alloy materials is more excellent.
  • step (a) when smelting and casting is performed, the temperature is first increased to 690-800 ° C, and the temperature is kept and stirred to completely melt the raw materials, and then the temperature is reduced to 630-680 ° C to keep warm 20 ⁇ 120min. After cooling, a magnesium alloy ingot is obtained.
  • the temperature after smelting is, for example, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780 , 790 or 800 °C.
  • the typical but non-limiting temperature after cooling is 630, 635, 640, 645, 650, 655, 660, 665 , 670, 675, or 680 ° C; the holding time after cooling is 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 110, or 120 min.
  • resistance furnace or power frequency induction circuit melting is used.
  • At least one cooling method of brine bath, water bath, water quenching or air cooling is used for cooling.
  • step (a) the nickel source, the rare earth source, and the magnesium source are accurately weighed and mixed according to the requirements of the recipe.
  • inert gas is used for smelting and casting.
  • the inert gas includes but is not limited to helium, argon, carbon dioxide, and sulfur hexafluoride, such as argon.
  • the temperature for homogenization treatment is 400 to 550 ° C., and the time is 4 to 40 h.
  • the temperature of the homogenization treatment is 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540, or 550 ° C; the time for homogenization treatment is 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35, or 40h.
  • the extrusion ratio during the extrusion deformation process is 8-40.
  • the extrusion is, for example, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 20, 22, 24 , 25, 26, 27, 28, 30, 32, 35, 38 or 40.
  • the temperature at which the extrusion deformation process is performed is 360-480 ° C.
  • the temperature of the extrusion deformation treatment is, for example, 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460, 470 or 480 °C.
  • the temperature at which the aging heat treatment is performed is 150 to 250 ° C., and the time is 12 to 120 h.
  • the temperature of the aging heat treatment is, for example, 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210 , 215, 220, 230, 240 or 250 °C; the aging heat treatment time is 12, 13, 14, 15, 16, 17, 18, 19, 20, 22, 25, 28, 30, 35, 40, 45, 50, 55, 60, 70, 80, 90, 100, 110 or 120h.
  • the present disclosure provides the application of the above-mentioned nickel-containing high-strength controllable degradable magnesium alloy material in the field of oil and gas development.
  • This embodiment provides a nickel-containing high-strength and controllable degradable magnesium alloy material, including the following components in mass percentage: Ni: 6.9%, Y: 18%, the balance is Mg and inevitable impurities; wherein, Mg, Ni and Y form Mg 12 YNi type long period phase, Mg 5 Y phase and Mg 2 Ni phase, the volume fraction of Mg 12 YNi type long period phase is 66%, the volume fraction of Mg 5 Y phase is 4%, Mg 2 The volume fraction of the Ni phase is 2%.
  • the magnesium alloy ingots are subjected to homogenization treatment, extrusion heat deformation treatment and aging heat treatment in sequence, and air-cooled to room temperature, that is, nickel-containing high-strength and controllable degradable magnesium alloy material is prepared; the homogenization treatment temperature is 500 °C, time 10h; extrusion deformation temperature 400 °C, extrusion ratio 11.
  • This embodiment provides a nickel-containing high-strength and controllable degradable magnesium alloy material, including the following components in mass percentage: Ni: 2.3%, Y: 5.3%, the balance is Mg and inevitable impurities, the balance It is Mg and inevitable impurities; among them, Mg, Ni and Y form Mg 12 YNi-type long-period phase, Mg 5 Y phase and Mg 2 Ni phase, the volume fraction of Mg 12 YNi-type long-period phase is 23%, Mg 5 The volume fraction of the Y phase is 6%, and the volume fraction of the Mg 2 Ni phase is 1.8%.
  • the preparation method of the degradable magnesium alloy material provided in this embodiment is the same as the preparation method of Embodiment 1, and will not be repeated here.
  • This embodiment provides a nickel-containing high-strength and controllable degradable magnesium alloy material, including the following components in terms of mass percentage: Gd: 8.5%, Y: 4.5%, Ni: 0.5%, Mn: 0.8%, balance Mg and unavoidable impurities; among them, Mg, Gd, Y and Ni form Mg 12 YNi type long-period phase, Mg 12 GdNi type long-period phase, Mg 5 Gd phase, Mg 5 Y phase and Mg 2 Ni phase, where The volume fraction of the two long-period phases is 15%, the volume fraction of the Mg 5 Gd phase and the Mg 5 Y phase is 12%, and the volume fraction of the Mg 2 Ni phase is 1.2%.
  • the preparation method of the degradable magnesium alloy material provided in this example is different from the preparation method provided in Example 1 in that the temperature of the homogenization treatment is 540 ° C and the time is 4h; the extrusion deformation temperature is 450 ° C and the extrusion The ratio is 11; the aging heat treatment temperature is 200 ° C. and the time is 50 h.
  • the other steps are the same as the preparation method in Example 1, and are not repeated here.
  • This embodiment provides a nickel-containing high-strength and controllable degradable magnesium alloy material, including the following components in mass percentage: Gd: 4%, Er: 4%, Ni: 0.8%, the balance is Mg and inevitable Impurities; among them, Mg, Gd, Er and Ni form Mg 12 GdNi type long-period phase, Mg 12 ErNi type long-period phase, Mg 5 Gd phase, Mg 5 Er phase and Mg 2 Ni phase, of which two long-period phases The volume fraction of is 10.5%, the volume fraction of Mg 5 Gd phase and Mg 5 Er phase is 8%, and the volume fraction of Mg 2 Ni phase is 1.2%.
  • the preparation method of the degradable magnesium alloy material provided in this example is different from the preparation method provided in Example 1 in that the temperature of the homogenization treatment is 450 ° C and the time is 12h; the extrusion deformation temperature is 450 ° C and the extrusion The ratio is 28, and the other steps are the same as the preparation method in Example 1, which will not be repeated here.
  • This embodiment provides a nickel-containing high-strength and controllable degradable magnesium alloy material, including the following components in mass percentage: Dy: 19%, Ni: 2.9%, the balance is Mg and inevitable impurities; wherein, Mg, Ni and Dy form the Mg 12 DyNi-type long-period phase, Mg 5 Dy phase and Mg 2 Ni phase, wherein the volume fraction of the Mg 12 DyNi-type long-period phase is 24% and the volume fraction of the Mg 5 Dy phase is 11% , The volume fraction of the Mg 2 Ni phase is 1.5%.
  • the preparation method of the degradable magnesium alloy material provided in this example is different from the preparation method provided in Example 1 in that the homogenization treatment temperature is 540 ° C and the time is 6h; the extrusion deformation temperature is 360 ° C and the extrusion The ratio is 28; the aging heat treatment temperature is 200 ° C. and the time is 60 h.
  • the other steps are the same as the preparation method in Example 1, and are not repeated here.
  • This embodiment provides a nickel-containing high-strength and controllable degradable magnesium alloy material, including the following components in terms of mass percentage: Ce: 1%, Zr: 0.5%, Ni: 1%, the balance is Mg and inevitable Impurities; among them, Mg, Ni, Ce and Zr form Mg 12 CeNi type long-period phase, Mg 12 ZrNi type long-period phase, Mg 5 Zr phase, Mg 5 Ce phase and Mg 2 Ni phase, of which, the long-period phase The volume fraction was 4.8%, the volume fraction of the Mg 5 Zr phase and the Mg 5 Ce phase was 2%, and the volume fraction of the Mg 2 Ni phase was 4%.
  • the preparation method of the degradable magnesium alloy material provided in this example is the same as the preparation method provided in Example 4, and details are not described herein again.
  • This embodiment provides a nickel-containing high-strength and controllable degradable magnesium alloy material, including the following components in mass percentage: Er: 6%, Ni: 7.5%, the balance is Mg and inevitable impurities; wherein, Mg, Er and Ni form Mg 12 ErNi type long-period phase, Mg 5 Er phase and Mg 2 Ni phase, the volume fraction of Mg 12 ErNi-type long-period phase is 65%, the volume fraction of Mg 5 Er phase is 3%, Mg 2 The volume fraction of the Ni phase is 5%.
  • the preparation method of the degradable magnesium alloy material provided in this example is different from the preparation method provided in Example 1 in that the homogenization treatment temperature is 500 ° C and the time is 10 hours; the extrusion deformation temperature is 400 ° C and the extrusion The ratio is 11, and the other steps are the same as the preparation method in Example 1, which will not be repeated here.
  • This embodiment provides a controllable degradable magnesium alloy material, including the following components in mass percentage: Gd: 8.0%, Y: 5.0%, Ni: 1.5%, Mn: 0.8%, the balance is Mg and not Impurities to be avoided; among them, Mg, Gd, Y and Ni form Mg 12 GdNi type and Mg 12 GdY type long period phases and Mg 24 Y 5 and Mg 5 Gd phases, Mg 12 GdNi type and Mg 12 GdY type long period phases The volume fraction is 20%, the volume fraction of the Mg 24 Y 5 and Mg 5 Gd phases is 12%, and the volume fraction of the Mg 2 Ni phase is 2%.
  • the preparation method of the degradable magnesium alloy material provided in this example is different from the preparation method provided in Example 1 in that the homogenization treatment temperature is 540 ° C and the time is 4h; the extrusion deformation temperature is 400 ° C and the extrusion The ratio is 11; the aging temperature is 200 ° C. and the time is 50 h.
  • the other steps are the same as the preparation method in Example 1, and are not repeated here.
  • the content of inevitable impurities in the magnesium alloy material is all 0.2% or less.
  • This comparative example provides a magnesium alloy material, which differs from Example 1 in that it does not contain Ni, and the magnesium yttrium alloy is prepared according to a conventional method.
  • This comparative example provides a magnesium alloy material, which differs from Example 1 in that it does not contain Y, and the magnesium-nickel alloy is prepared according to a conventional method.
  • This comparative example provides a magnesium alloy material, which is different from Example 1 in that the mass percentage of Ni is 0.1%, and the preparation method thereof is the same as that in Example 1, which will not be repeated here.
  • This comparative example provides a magnesium alloy material, which is different from Example 1 in that the mass percentage of Ni is 10%, and the preparation method thereof is the same as that in Example 1, which will not be repeated here.
  • This comparative example provides a magnesium alloy material, which is different from Example 1 in that the mass percentage of Y is 0.1%, and the preparation method is the same as that in Example 1, which will not be repeated here.
  • This comparative example provides a magnesium alloy material, which is different from Example 1 in that the mass percentage of Y is 25%, and the preparation method is the same as that in Example 1, which will not be repeated here.
  • the tensile strength, yield strength, elongation and corrosion rate of the magnesium alloy materials provided in Examples 1 to 7 were measured respectively, in which the tensile strength, yield strength and elongation were measured at room temperature, and the test direction of tensile strength was extrusion In the pressing direction (0 °), the stretching speed is 2 mm / min; the corrosion rate is measured in a KCl solution with a concentration of 3.5 wt% at 90 ° C. The results are shown in Table 1.
  • the nickel-containing high-strength and controllable degradable magnesium alloy materials provided in Examples 1-7 have a tensile strength of 267-505 MPa at room temperature, a yield strength of 156-415 MPa, and an elongation of 6.0-21.8 %
  • the decomposition rate in 3.5wt% KCl solution at 90 ° C is 363mm / a ⁇ 2100mm / a, which shows that the magnesium alloy material provided by the present disclosure, by adding a specific content of nickel and rare earth elements using magnesium as a matrix material, makes The mechanical properties of magnesium alloy materials have been significantly improved, and the degradation rate can meet the requirements for the use of downhole tool self-ablation in the field of oil and gas.
  • the present disclosure provides a method for preparing nickel-containing high-strength and controllable degradable magnesium alloy materials, which can be carried out in batches in industry.
  • the process is simple, the operation is convenient, it is easy to carry out industrialized mass production, and the production cost is reduced.
  • Nickel high-strength and controlled-degradable magnesium alloy material has the advantages of significantly improving the tensile strength and plasticity of the alloy material, and the nickel-containing high-strength and controllable degradable magnesium alloy material prepared by this method can be quickly decomposed.
  • the completed downhole fracturing tool can effectively meet the needs of the oil and gas development field.

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Abstract

本公开提供了一种含镍高强韧可控降解镁合金材料及其制备方法和应用，涉及镁合金技术领域，镁合金材料包括按质量百分比计的如下组分：Ni:0.3～8.5％，RE:0.5～28％，余量为Mg及不可避免的杂质；RE为稀土元素。本公开提供的镁合金材料通过添加Ni和RE元素，引入Mg 12RENi型长周期相、Mg 2Ni相及Mg xRE y相，显著提高了合金材料力学性能，抗拉强度最高可达510MPa；同时Mg 12RENi型长周期相及Mg 2Ni相的存在使得合金材料能够可控降解，实现降解速率在360～2400mm/a间可调。利用该镁合金制作得到的井下压裂工具，缓解了目前井下工具存在的技术问题，满足了油气开发领域的需求。

Description

含镍高强韧可控降解镁合金材料及其制备方法和应用
相关申请的交叉引用
本公开要求于2018年10月23日提交中国专利局的申请号为201811237934.1、名称为“含镍高强韧可控降解镁合金材料及其制备方法和应用”的中国专利申请的优先权，其全部内容通过引用结合在本公开中。
技术领域
本公开涉及镁合金技术领域，尤其是涉及一种含镍高强韧可控降解镁合金材料及其制备方法和应用。
背景技术
随着经济的飞速发展，我国的石油问题已经成为举国关注的重要问题之一。根据国家统计局的统计数据，我国的石油净进口量不断增涨，到2015年中国石油对外的依存度直接冲破了60％。根据国际经验和权威人士的意见，中国石油对外依存度必须保持在60％以下。无论是从战略角度出发，还是出于对国家安全和经济正常运行的考虑，中国都应该减少石油的对外依存度。所以，加大对内石油的开采力度，提高石油开采效率是我国强国兴邦的重要措施，亟待探索新技术和研发新材料。
中国低渗透油气资源丰富，具有很大的勘探开发潜力。未来油气产量的稳产、增产将很大程度依赖于低渗透非常规油气资源。但是这些非常规油气资源大多分布于不同深度的地层中，需要采用多层多段压裂技术实现同时对多个地层的改造来提高单井产能，从而提高油田产量和施工效率。
多层多段压裂中，层段间需使用封隔工具(如压裂球、桥塞)分隔后逐层进行压裂改造，待所有层段施工完成后再将封隔工具返排出井筒，以便打通井道实现油、气的开采。然而现在常用封隔工具大多由钢材制得，存在钻铣困难、耗时长、钻后粉末、碎块不易返排等缺点，极大增加了施工周期和成本。
因此，研制一种能构承受压裂施工的高压和油井高温的，并在油井流体环境下能可控地进行快速腐蚀的轻质压裂球，可以有效地降低施工成本和风险，缩短施工周期，提高施工效率。
发明内容
本公开的目的包括，例如，提供一种含镍高强韧可控降解镁合金材料，以缓解现在常用封隔工具大多由钢材制得，存在钻铣困难、耗时长、钻后粉末、碎块不易返排等缺点，极大增加了施工周期和成本的技术问题。
本公开提供的含镍高强韧可控降解镁合金材料，包括按质量百分比计的如下组分：Ni:0.3～8.5％，RE:0.5～28％，余量为Mg及不可避免的杂质；其中，RE为稀土元素，Mg、Ni和RE形成Mg 12RENi型长周期相、Mg 2Ni相和Mg xRE y相；所述Mg 12RENi型长周期相的体积分数为3～70％，Mg 2Ni相的体积分数为0.5～10％，Mg xRE y相的体积分数为0.5～22％，x:y的取值范围为(3～12):1。
在一种或多种实施方式中，所述含镍高强韧可控降解镁合金材料包括按质量百分比计的如下组分：Ni为0.5～8.0％，RE为1.5～20％，余量为Mg及不可避免的杂质。
在一种或多种实施方式中，所述含镍高强韧可控降解镁合金材料包括铸态镁合金、挤压态镁合金和时效态镁合金。
在一种或多种实施方式中，所述铸态镁合金包括Mg 12NiRE型长周期相和Mg 5RE相及Mg 2Ni相，所述Mg 12NiRE型长周期相的体积分数为3～65％，Mg 2Ni相的体积分数为0.5～6％，Mg 5RE相的体积分数为0.5～15％。
在一种或多种实施方式中，所述挤压态镁合金包括Mg 12NiRE型长周期相和Mg 2Ni相及Mg 5RE相，所述Mg 12NiRE型长周期相的体积分数相的体积分数为4～70％，Mg 2Ni相的体积分数为1％～8％，Mg 5RE相的体积分数为1～20％。
在一种或多种实施方式中，所述时效态镁合金包括Mg 12NiRE型长周期相和Mg 2Ni相及Mg xRE y相，所述Mg 12NiRE型长周期相的体积分数为4～70％，Mg 2Ni相的体积分数为2～10％，Mg xRE y相的体积分数为2～22％，其中x:y的取值范围为(3～12):1。
在一种或多种实施方式中，所述RE选自Gd、Y、Er、Dy、Ce和Sc中的至少一种。
在一种或多种实施方式中，所述含镍高强韧可控降解镁合金材料包括按质量百分比计的如下组分：Ni:0.3～8.5％，RE:0.5～28％，M:0.03～10％，余量为Mg及不可避免的杂质；其中，M为能与镁发生合金化的元素。
在一种或多种实施方式中，不可避免的杂质在镁合金材料中的质量百分含量不高于0.2％。
在一种或多种实施方式中，M为Fe、Cu和Mn中的至少一种。
本公开的目的包括，例如，提供一种含镍高强韧可控降解镁合金材料的制备方法，包括如下步骤：将镍源、镁源和稀土源混合均匀，进行合金化处理，得到含镍高强韧可控降解镁合金材料。
在一种或多种实施方式中，所述镍源选自镍单质和/或镍合金。
在一种或多种实施方式中，所述镍合金选自镁镍合金、镍钇合金或锌镍合金中的至少一种。
在一种或多种实施方式中，所述镁源选自镁单质和/或镁合金。
在一种或多种实施方式中，所述镁合金选自镁钆合金、镁钇合金、镁锌合金、镁镍合金、镁钙合金或镁铁合金中的至少一种。
在一种或多种实施方式中，所述稀土源包括稀土单质和/或稀土中间合金。
在一种或多种实施方式中，所述稀土单质包括钆、钇、铒、镝、铈和钪中的至少一种。
在一种或多种实施方式中，所述稀土中间合金包括镁钆合金、镁钇合金、镁铒合金、镁铈合金、镁钪合金、镍钇合金、镍钆合金、镍铒合金、镍铈合金和镍钪合金中的至少一种。
在一种或多种实施方式中，所述合金化处理包括熔炼铸造法和粉末合金法。
在一种或多种实施方式中，采用熔炼铸造法进行合金化处理。
在一种或多种实施方式中，所述熔炼铸造法包括如下步骤：
(a)铸造：将镍源、镁源和稀土源混合均匀，进行熔炼铸造，得到镁合金铸锭；
(b)热处理：将镁合金铸锭依次进行均匀化处理和挤压热变形处理，即制得含镍高强韧可控降解镁合金材料。
在一种或多种实施方式中，步骤(b)中还包括时效热处理步骤，所述时效热处理步骤设置于所述挤压热变形处理之后。
在一种或多种实施方式中，在步骤(a)中，进行熔炼铸造时，先升温至690～800℃，保温并搅拌使原料全部熔化，再降温至630～680℃，保温20～120min，冷却后，得到镁合金铸锭。
在一种或多种实施方式中，熔炼铸造时采用惰性气体保护。
在一种或多种实施方式中，所述惰性气体选自氦气、氩气、二氧化碳和六氟化硫中的至少一种，例如，氩气。在一种或多种实施方式中，冷却方式选自盐水浴、水淬、炉冷或空冷中的至少一种。
在一种或多种实施方式中，采用电阻炉或工频感应路熔炼。
在一种或多种实施方式中，在步骤(a)中，按照配方要求精确称取镍源、稀土源和镁源混合均匀。
在一种或多种实施方式中，在步骤(b)中，进行均匀化处理的温度为400～550℃，时间为4～40h。
在一种或多种实施方式中，在步骤(b)中，进行挤压变形处理时的挤压比为8～40。
在一种或多种实施方式中，进行挤压变形处理的温度为360～480℃。
在一种或多种实施方式中，在步骤(b)中，进行时效热处理的温度为150～250℃，时间为12～120h。
在一种或多种实施方式中，在步骤(b)中，进行时效热处理的温度为180～220℃，时间为15～60h。
本公开的目的包括，例如，提供含镍高强韧可控降解镁合金材料在油气开发领域中的应用。
本申请的有益效果至少包括：
(1)本公开提供的含镍高强韧可控降解镁合金材料以镁为基础材料，通过加入Ni和RE，形成Mg 12RENi型长周期相、Mg 2Ni相和Mg xRE y相，从而显著提高了合金材料的抗拉强度和塑性；同时Mg 12RENi型长周期相及Mg 2Ni相，与镁基体之间存在很大电负差，形成大量微电池，从而使得生成的含镍高强韧可控降解镁合金材料能够快速分解，利用该镁合金材料制成的井下压裂工具，能够有效满足油气开发领域的需求。
(2)本公开提供的可控降解合金材料在油气开采领域中应用时，在完成任务后能够在井下完全降解，通过管道排出，不存在易卡涩、堵塞问题，从而省去了钻磨回收工序，降低工程难度，提高施工效率。
具体实施方式
下面将结合实施例对本公开的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本公开，而不应视为限制本公开的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售购买获得的常规产品。
根据本公开的一个方面，本公开提供了一种含镍高强韧可控降解镁合金材料，包括按质量百分计的如下组分：Ni:0.3～8.5％，RE:0.5～28％，余量为Mg及不可避免的杂质；其中，RE为稀土元素，Mg、Ni和RE主要形成Mg 12RENi型长周期相、Mg 2Ni相和Mg xRE y相。
所述Mg 12RENi型长周期相的体积分数为3～70％，Mg 2Ni相的体积分数为0.5～10％，Mg xRE y相的体积分数为0.5～22％。
在一种或多种实施方式中，不可避免的杂质在镁合金材料中的质量百分含量不高于0.2％。
在一种或多种实施方式中，长周期相(LPSO)是镁合金中一种新的增强相，是在一种晶体结构中出现原子位置或化学成分的周期性变化而形成的，长周期结构分为堆垛有序和化学成分有序两个方面，在一种或多种实施方式中的Mg 12RENi型长周期相是堆垛有序和化学成分有序两方面共同作用的结果。
在本公开提供的含镍高强韧可控降解镁合金材料中，Ni(镍)的典型但非限制性的质量百分含量如为0.3％、0.5％、0.8％、1％、1.2％、1.5％、1.8％、2％、2.2％、2.5％、2.8％、3％、3.2％、3.5％、4％、4.2％、4.5％、4.8％、5％、5.5％、6％、6.5％、7％、7.5％、8％或8.5％。
在本公开提供的含镍高强韧可控降解镁合金材料中，RE的典型但非限制性的质量百分含量如为0.5％、1％、2％、3％、4％、5％、8％、10％、12％、15％、18％、20％、22％、25％或28％。
在一种或多种实施方式中，Mg 12RENi型长周期相的体积分数为3～70％，Mg 5RE相的体积分数为0.5～20％，Mg 2Ni相的体积分数为0.5～10％，Mg xRE y相的体积分数为0.5～22％，x:y的取值范围为(3～12):1。
通过将Mg 12RENi型长周期相的体积分数设置为3～70％，Mg 2Ni相的体积分数设置为0.5～10％，Mg xRE y相的体积分数设置为0.5～22％，使Mg 12RENi型长周期相及Mg xRE y相，显著提高合金材料的抗拉强度，并使合金保持一定的塑性；同时Mg 12RENi型长周期相及Mg 2Ni相，与镁基体之间存在较大的电势差，形成大量微电池，使得生成的合金材料能够快速分解，有效满足了油气开发领域对井下工具材料的需求。
在一种或多种实施方式中，含镍高强韧可控降解镁合金材料中，Mg 12RENi型长周期相的典型但非限制性的体积分数如为3％、4％、5％、8％、10％、12％、15％、18％、20％、25％、30％、35％、40％、45％、50％、55％、60％、65％或70％；Mg 2Ni相的典型但非限制性的体积分数为0.5％、1％、1.5％、2％、3％、4％、5％、6％、7％、8％、9％或10％；Mg xRE y相的典型但非限制性的体积分数如为0.5、1％、2％、5％、8％、10％、12％、15％、18％、20％或22％；x:y的典型但非限制性的数值为3:1、4:1、5:1、6:1、7:1、8:1、9:1、10:1、11:1或12:1。
本公开提供的含镍高强韧可控降解镁合金材料以镁为基础材料，通过加入Ni和RE，形成Mg 12RENi型长周期相和Mg xRE y相，从而显著提高了合金材料的抗拉强度；同时Mg 12RENi型长周期相及Mg 2Ni相，与镁基体之间存在很大电负差，形成大量微电池，从而使得生成的含镍高强韧可控降解镁合金材料能够快速分解，利用该镁合金材料制成的井下压裂工具，能够有效满足油气开发领域的需求。
另外，本公开提供的可控降解合金材料在油气开采领域中应用时，在完成任务后能够在井下完全降解，通过管道排出，不存在易卡涩、堵塞问题，从而省去了钻磨回收工序，降低工程难度，提高施工效率。
在本公开的一种或多种实施方式中，当含镍高强韧可控降解镁合金材料中，Ni为0.5～7.5％，RE为1.5～19％；Mg 12RENi型长周期相的体积分数为4.8～65％，Mg 5RE相的体积分数为1～15％，Mg 2Ni相的体积分数为1～5％时。
含镍高强韧可控降解镁合金材料在室温下的抗拉强度为325～505MPa，屈服强度为156～415MPa，延伸率为6.0～21.8％，在90℃，3.5wt％KCl溶液中的分解速率是363mm/a～2500mm/a。
在本公开的一种或多种实施方式中，含镍高强韧可控降解镁合金材料包括铸态镁合金、挤压态镁合金和时效态镁合金。
在本公开的一种或多种实施方式中，铸态镁合金中，Mg、Ni和RE主要形成了Mg 12RENi型长周期相、Mg 2Ni相和Mg 5RE相，所述Mg 12NiRE型长周期相的体积分数为3～65％，Mg 2Ni相的体积分数为0.5～6％，Mg 5RE相的体积分数为0.5～15％。
在本公开的一种或多种实施方式中，铸态镁合金中，Mg 12NiRE型长周期相的典型但非限制性的体积分数如为3％、4％、5％、8％、10％、12％、15％、18％20％、25％、30％、35％、40％、45％、50％、55％、60％或65％；Mg 2Ni相的典型但非限制性的体积分数如为0.5％、0.8％、1％、1.5％、2％、2.5％、3％、3.5％、4％、4.5％、5％、5.5％或6％；Mg 5RE相的典型但非限制性的体积分数如为0.5％、0.8％、1％、2％、5％、8％、10％、12％或15％。
在本公开的一种或多种实施方式中，挤压态镁合金中，Mg、Ni和RE主要形成了Mg 12RENi型长周期相、Mg 2Ni相和Mg 5RE相，Mg 12NiRE型长周期相的体积分数相的体积分数为4～70％，Mg 2Ni相的体积分数为1％～8％，Mg 5RE相的体积分数为1～20％；
在本公开的一种或多种实施方式中，挤压态镁合金中，Mg 12NiRE型长周期相的典型但非限制性的体积分数如为4％、5％、8％、10％、12％、15％、18％20％、25％、30％、35％、40％、45％、50％、55％、60％、65％或70％；Mg 2Ni相的典型但非限制性的体积分数如为1％、1.5％、2％、2.5％、3％、3.5％、4％、4.5％、5％、5.5％、6％、6.5％、7％、7.5％或8％；Mg 5RE相的典型但非限制性的体积分数如为1％、2％、5％、8％、10％、12％、15％、18％或20％。
在本公开的一种或多种实施方式中，时效态镁合金中，Mg、Ni和RE主要形成了Mg 12RENi型长周期相、Mg 2Ni相和Mg xRE y相(x:y＝(3～12):1)，Mg 12NiRE型长周期相的体积分数相的体积分数为4～70％，Mg 2Ni相的体积分数为2％～10％，Mg 5RE相 的体积分数为2～22％。
在本公开的一种或多种实施方式中，挤压态镁合金中，Mg 12NiRE型长周期相的典型但非限制性的体积分数如为4％、5％、8％、10％、12％、15％、18％20％、25％、30％、35％、40％、45％、50％、55％、60％、65％或70％；Mg 2Ni相的典型但非限制性的体积分数如为2％、2.5％、3％、3.5％、4％、4.5％、5％、5.5％、6％、6.5％、7％、7.5％、8％、9％或10％；Mg xRE y相的典型但非限制性的体积分数如为2％、5％、8％、10％、12％、15％、18％、20％或22％，其中x:y的典型但非限制性的数值如为3:1、4:1、5:1、6:1、7:1、8:1、9:1、10:1、11:1或12:1。在本公开的一种或多种实施方式中，RE选自Gd、Y、Er、Dy、Ce、Sc中的一种或几种。
在本公开的一种或多种实施方式中，含镍高强韧可控降解镁合金材料包括按质量百分比计的如下组分：Ni:0.3～8.5％，RE:0.5～28％，M:0.03～10％，余量为Mg及不可避免的杂质；其中，M为能与镁发生合金化的元素。
在本公开的一种或多种实施方式中，含镍高强韧可控降解镁合金材料中，Ni的典型但非限制性的质量百分比如为0.3％、0.5％、0.8％、1％、1.2％、1.5％、1.8％、2％、2.2％、2.5％、2.8％、3％、3.2％、3.5％、4％、4.2％、4.5％、4.8％、5％、5.5％、6％、6.5％、7％、7.5％、8％或8.5％；RE的典型但非限制性的质量百分含量如为0.5％、1％、2％、3％、4％、5％、8％、10％、12％、15％、18％、20％、22％、25％或28％；M的典型但非限制性的质量百分比如为0.03％、0.05％、0.08％、0.1％、0.15％、0.2％、0.5％、0.8％、1％、1.5％、2％、3％、4％、5％、6％、7％、8％、9％或10％。
在本公开的一种或多种实施方式中，M包括但不限于Fe、Cu和Mn中的至少一种。
根据本公开的第二个方面，本公开提供了上述含镍高强韧可控降解镁合金材料的制备方法，包括如下步骤：
将镍源、镁源和稀土源混合均匀，进行合金化处理，得到含镍高强韧可控降解镁合金材料。
本公开提供的含镍高强韧可控降解镁合金材料的制备方法工艺简单，操作方便，易于进行工业化大生产，降低成本。
在本公开的一种或多种实施方式中，合金化处理包括熔炼铸造法和粉末合金法。
在本公开的一种或多种实施方式中，镍源选自镍单质和/或镍合金。
在本公开的一种或多种实施方式中，所述镍合金选自镁镍合金、镍钇合金或锌镍合金中一种或几种。
在本公开的一种或多种实施方式中，镁源选自镁单质和/或镁合金。
在本公开的一种或多种实施方式中，镁合金选自镁钆合金、镁钇合金、镁锌合金、镁镍合金、镁钙合金或镁铁合金中一种或几种。
在本公开的一种或多种实施方式中，稀土源包括稀土单质和/或稀土中间合金。
在本公开的一种或多种实施方式中，稀土单质包括钆、钇、铒、镝、铈和钪中的一种或几种。
在本公开的一种或多种实施方式中，稀土中间合金包括镁钆合金、镁钇合金、镁铒合金、镁铈合金、镁钪合金、镍钇合金、镍钆合金、镍铒合金、镍铈合金和镍钪合金中的至少一种。
在本公开的一种或多种实施方式中，采用熔炼铸造法进行合金化处理，包括如下步骤：
(a)铸造：将镍源、镁源和稀土源混合均匀，进行熔炼铸造，得到镁合金铸锭；
(b)热处理：将镁合金铸锭依次进行均匀化处理和挤压热变形处理，即制得含镍高强韧可控降解镁合金材料。
本公开提供的含镍高强韧可控降解镁合金材料的制备方法，通过依次进行铸造和热处理，使得制成的合金材料中Mg、Ni和RE形成Mg 12NiRE型长周期相、Mg xRE y相和Mg 2Ni相，不仅显著提高了合金材料的抗拉强度和塑性；而且合金材料中形成大量微电池，使得生成的含镍高强韧可控降解镁合金材料能够快速分解，利用该镁合金材料制成的井下压裂工具，能够在井下完全降解，从而降低了工程难度，提高了施工效率。
在本公开的一种或多种实施方式中，在步骤(b)中，还包括时效热处理步骤，该时效热处理步骤设置于挤压热变形处理之后，通过进行时效热处理步骤，使得含镍高强韧合金材料的综合性能更加优异。
在本公开的一种或多种实施方式中，在步骤(a)中，进行熔炼铸造时，先升温至690～800℃，保温并搅拌使原料全部熔化，再降温至630～680℃，保温20～120min，冷却后，得到镁合金铸锭。
在公开的一种或多种典型但非限制性的实施方式中，在步骤(a)中，熔炼后的温度如为690、700、710、720、730、740、750、760、770、780、790或800℃。
在本公开的一种或多种实施方式中，在熔炼铸造时，原料全部融化后，降温后的典型但非限制性的温度如为630、635、640、645、650、655、660、665、670、675或680℃；降温后的保温时间如为20、25、30、35、40、45、50、60、70、80、90、100、110或120min。
在本公开的一种或多种实施方式中，采用电阻炉或工频感应路熔炼。
在本公开的一种或多种实施方式中，采用盐水浴、水浴、水淬或空冷中的至少一种冷却方式进行冷却。
在本公开的一种或多种实施方式中，在步骤(a)中，按照配方要求精确称取镍源、稀土源和镁源混合均匀。
在本公开的一种或多种实施方式中，熔炼铸造时采用惰性气体保护，该惰性气体包括但不限于氦气、氩气、二氧化碳和六氟化硫，例如氩气。
在本公开的一种或多种实施方式中，在步骤(b)中，进行均匀化处理的温度为400～550℃，时间为4～40h。
在本公开的一种或多种典型但非限制性的实施方式中，均匀化处理的温度如为400、410、420、430、440、450、460、470、480、490、500、510、520、530、540或550℃；均匀化处理的时间如为4、5、6、7、8、9、10、11、12、13、14、15、20、25、30、35或40h。
在本公开的一种或多种实施方式中，进行挤压变形处理时的挤压比为8～40。
在本公开的一种或多种典型但非限制性的实施方式中，挤压比如为8、9、10、11、12、13、14、15、16、17、18、20、22、24、25、26、27、28、30、32、35、38或40。
在本公开的一种或多种实施方式中，进行挤压变形处理的温度为360～480℃。
在本公开的一种或多种典型但非限制性的实施方式中，进行挤压变形处理的温度如为360、370、380、390、400、410、420、430、440、450、460、470或480℃。
在本公开的一种或多种实施方式中，在步骤(b)中，进行时效热处理的温度为150～250℃，时间为12～120h。
在本公开的一种或多种典型但非限制性的实施方式中，时效热处理的温度如为150、155、160、165、170、175、180、185、190、195、200、205、210、215、220、230、240或250℃；时效热处理的时间如为12、13、14、15、16、17、18、19、20、22、25、28、30、35、40、45、50、55、60、70、80、90、100、110或120h。
根据本公开的第三个方面，本公开提供了上述含镍高强韧可控降解镁合金材料在油气开发领域中的应用。
下面结合实施例和对比例对本公开提供的技术方案作进一步的描述。
实施例1
本实施例提供了一种含镍高强韧可控降解镁合金材料，包括按质量百分比计的如下组分：Ni:6.9％，Y:18％，余量为Mg及不可避免的杂质；其中，Mg、Ni和Y形成Mg 12YNi型长周期相、Mg 5Y相和Mg 2Ni相，Mg 12YNi型长周期相的体积分数为66％，Mg 5Y相的体积分数为4％，Mg 2Ni相的体积分数为2％。
本实施例提供的含镍高强韧可控降解镁合金材料的制备方法包括如下步骤：
(1)按照配方量精确配料；其中，镍源、钇源和镁源分别以镁钇合金和镍钇合金形式加入；
(2)铸造：采用电阻炉或工频感应炉熔炼，熔炼过程中采用氩气作为保护气体，升温至770℃保温并电磁感应搅拌使成分均匀且原料充分熔化，待原料全部熔化后降温至655℃静置保温25min，取出进行盐浴水冷获得合金铸锭；
(3)热处理：将镁合金铸锭依次进行均匀化处理、挤压热变形处理和时效热处理，空冷至室温，即制得含镍高强韧可控降解镁合金材料；其中均匀化处理的温度为500℃，时间为10h；挤压变形温度为400℃，挤压比为11。
实施例2
本实施例提供了一种含镍高强韧可控降解镁合金材料，包括按质量百分比计的如下组分：Ni:2.3％，Y:5.3％，余量为Mg及不可避免的杂质，余量为Mg及不可避免的杂质；其中，Mg、Ni和Y形成Mg 12YNi型长周期相、Mg 5Y相和Mg 2Ni相，Mg 12YNi型长周期相的体积分数为23％，Mg 5Y相的体积分数为6％，Mg 2Ni相的体积分数为1.8％。
本实施例提供的可降解镁合金材料的制备方法与实施例1的制备方法相同，在此不再赘述。
实施例3
本实施例提供了一种含镍高强韧可控降解镁合金材料，包括按质量百分比计的如下组分：Gd:8.5％，Y:4.5％，Ni:0.5％，Mn:0.8％，余量为Mg及不可避免的杂质；其中，Mg、Gd、Y和Ni形成Mg 12YNi型长周期相、Mg 12GdNi型长周期相、Mg 5Gd相、Mg 5Y相和Mg 2Ni相，其中两种长周期相的体积分数为15％，Mg 5Gd相和Mg 5Y相的体积分数为12％，Mg 2Ni相的体积分数为1.2％。
本实施例提供的可降解镁合金材料的制备方法与实施例1提供的制备方法的不同之处在于，均匀化处理的温度为540℃，时间为4h；挤压变形温度为450℃，挤压比为11；时效热处理温度为200℃，时间为50h，其它步骤均与实施例1中的制备方法相同，在此不再赘述。
实施例4
本实施例提供了一种含镍高强韧可控降解镁合金材料，包括按质量百分比计的如下组分：Gd:4％，Er:4％，Ni:0.8％，余量为Mg及不可避免的杂质；其中，Mg、Gd、Er和Ni形成Mg 12GdNi型长周期相、Mg 12ErNi型长周期相、Mg 5Gd相、Mg 5Er相和Mg 2Ni相， 其中两种长周期相的体积分数为10.5％，Mg 5Gd相、Mg 5Er相的体积分数为8％，Mg 2Ni相的体积分数为1.2％。
本实施例提供的可降解镁合金材料的制备方法与实施例1提供的制备方法的不同之处在于，均匀化处理的温度为450℃，时间为12h；挤压变形温度为450℃，挤压比为28，其它步骤均与实施例1中的制备方法相同，在此不再赘述。
实施例5
本实施例提供了一种含镍高强韧可控降解镁合金材料，包括按质量百分比计的如下组分：Dy:19％，Ni:2.9％，余量为Mg及不可避免的杂质；其中，Mg、Ni和Dy形成Mg 12DyNi型长周期相、Mg 5Dy相和Mg 2Ni相，其中，Mg 12DyNi型长周期相的体积分数为24％、Mg 5Dy相的体积分数为11％，Mg 2Ni相的体积分数为1.5％。
本实施例提供的可降解镁合金材料的制备方法与实施例1提供的制备方法的不同之处在于，均匀化处理的温度为540℃，时间为6h；挤压变形温度为360℃，挤压比为28；时效热处理温度为200℃，时间为60h，其它步骤均与实施例1中的制备方法相同，在此不再赘述。
实施例6
本实施例提供了一种含镍高强韧可控降解镁合金材料，包括按质量百分比计的如下组分：Ce:1％，Zr:0.5％，Ni:1％，余量为Mg及不可避免的杂质；其中，Mg、Ni、Ce和Zr形成Mg 12CeNi型长周期相、Mg 12ZrNi型长周期相、Mg 5Zr相、Mg 5Ce相和Mg 2Ni相，其中，长周期相的体积分数为4.8％、Mg 5Zr相和Mg 5Ce相的体积分数为2％，Mg 2Ni相的体积分数为4％。
本实施例提供的可降解镁合金材料的制备方法与实施例4提供的制备方法相同，在此不再赘述。
实施例7
本实施例提供了一种含镍高强韧可控降解镁合金材料，包括按质量百分比计的如下组分：Er:6％，Ni:7.5％，余量为Mg及不可避免的杂质；其中，Mg、Er和Ni形成Mg 12ErNi型长周期相、Mg 5Er相和Mg 2Ni相，Mg 12ErNi型长周期相的体积分数为65％，Mg 5Er相的体积分数为3％，Mg 2Ni相的体积分数为5％。
本实施例提供的可降解镁合金材料的制备方法与实施例1提供的制备方法的不同之处在于，均匀化处理的温度为500℃，时间为10h；挤压变形温度为400℃，挤压比为11，其它步骤均与实施例1中的制备方法相同，在此不再赘述。
实施例8
本实施例提供了一种可控降解镁合金材料，包括按质量百分比计的如下组分：Gd:8.0％，Y:5.0％，Ni:1.5％，Mn：0.8％，余量为Mg及不可避免的杂质；其中，Mg、Gd、Y和Ni形成Mg 12GdNi型和Mg 12GdY型长周期相及Mg 24Y 5和Mg 5Gd相，Mg 12GdNi型和Mg 12GdY型长周期相的体积分数为20％，Mg 24Y 5和Mg 5Gd相的体积分数为12％，Mg 2Ni相的体积分数为2％。
本实施例提供的可降解镁合金材料的制备方法与实施例1提供的制备方法的不同之处在于，均匀化处理的温度为540℃，时间为4h；挤压变形温度为400℃，挤压比为11；时效温度为200℃，时间为50h，其它步骤均与实施例1中的制备方法相同，在此不再赘述。
上述实施例1～8中，不可避免杂质在镁合金材料中的含量均为0.2％以下。
对比例1
本对比例提供了一种镁合金材料，其与实施例1的不同之处在于，不包含Ni，该镁钇合金按照常规方法制备而成。
对比例2
本对比例提供了一种镁合金材料，其与实施例1的不同之处在于，不包含Y，该镁镍合金按照常规方法制备而成。
对比例3
本对比例提供了一种镁合金材料，其与实施例1的不同之处在于，Ni的质量百分比为0.1％，其制备方法同实施例1，在此不再赘述。
对比例4
本对比例提供了一种镁合金材料，其与实施例1的不同之处在于，Ni的质量百分比为10％，其制备方法同实施例1，在此不再赘述。
对比例5
本对比例提供了一种镁合金材料，其与实施例1的不同之处在于，Y的质量百分比为0.1％，其制备方法同实施例1，在此不再赘述。
对比例6
本对比例提供了一种镁合金材料，其与实施例1的不同之处在于，Y的质量百分比为25％，其制备方法同实施例1，在此不再赘述。
试验例1
将实施例1～7提供的镁合金材料分别测定抗拉强度、屈服强度、延伸率和腐蚀速率，其中抗拉强度、屈服强度和延伸率在室温下进行测定，抗拉强度的测试方向为挤压方向(0°)，拉伸速度为2mm/min；腐蚀速率在90℃，浓度为3.5wt％的KCl溶液中进行测定，结果如表1所示。
表1镁合金材料性能数据表
Figure PCTCN2019094183-appb-000001
注：“—”表示材料为脆性，延伸率极低无法投入使用。
从表1中可以看出，实施例1～7提供的含镍高强韧可控降解镁合金材料在室温下的抗拉强度为267～505MPa，屈服强度为156～415MPa，延伸率为6.0～21.8％，在90℃，3.5wt％KCl溶液中的分解速率是363mm/a～2100mm/a，这说明本公开提供的镁合金材料，通过以镁为基体材料加入特定含量的镍和稀土元素，使得镁合金材料的力学性能显著提升，降解速率能够满足石油天然气领域中井下工具自行消融的使用要求。
最后应说明的是：以上各实施例仅用以说明本公开的技术方案，而非对其限制；尽管参照前述各实施例对本公开进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分或者全部技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本公开各实施例技术方 案的范围。
工业实用性
本公开提供的一种含镍高强韧可控降解镁合金材料的制备方法能够在工业上批量进行，其工艺简单，操作方便，易于进行工业化大生产，降低生产成本，以及使用该方法制备的含镍高强韧可控降解镁合金材料具有显著提高的合金材料的抗拉强度和塑性等优点，并且使用该方法制备的含镍高强韧可控降解镁合金材料能够快速分解，利用该镁合金材料制成的井下压裂工具，能够有效满足油气开发领域的需求。

Claims (16)

  1. 一种含镍高强韧可控降解镁合金材料，包括按质量百分比计的如下组分：Ni:0.3～8.5％，RE:0.5～28％，余量为Mg及不可避免的杂质；其中，RE为稀土元素，Mg、Ni和RE主要形成了Mg 12RENi型长周期相、Mg 2Ni相和Mg xRE y相；所述Mg 12RENi型长周期相的体积分数为3～70％，Mg 2Ni相的体积分数为0.5～10％，Mg xRE y相的体积分数为0.5～22％，x:y的取值范围为(3～12):1。
  2. 根据权利要求1所述的含镍高强韧可控降解镁合金材料，其中，包括按质量百分比计的如下组分：Ni为0.5～8.0％，RE为1.5～20％，余量为Mg及不可避免的杂质；优选地，所述含镍高强韧可控降解镁合金材料包括铸态镁合金、挤压态镁合金和时效态镁合金；
    优选地，所述铸态镁合金包括Mg 12NiRE型长周期相和Mg 5RE相及Mg 2Ni相，所述Mg 12NiRE型长周期相的体积分数为3～65％，Mg 2Ni相的体积分数为0.5～6％，Mg 5RE相的体积分数为0.5～15％；
    优选地，所述挤压态镁合金包括Mg 12NiRE型长周期相和Mg 2Ni相及Mg 5RE相，所述Mg 12NiRE型长周期相的体积分数相的体积分数为4～70％，Mg 2Ni相的体积分数为1％～8％，Mg 5RE相的体积分数为1～20％；
    优选地，所述时效态镁合金包括Mg 12NiRE型长周期相和Mg 2Ni相及Mg xRE y相，所述Mg 12NiRE型长周期相的体积分数为4～70％，Mg 2Ni相的体积分数为2～10％，Mg xRE y相的体积分数为2～22％，其中x:y的取值范围为(3～12):1。
  3. 根据权利要求1或2所述的含镍高强韧可控降解镁合金材料，其中，所述RE选自Gd、Y、Er、Dy、Ce和Sc中的至少一种；
    优选地，所述含镍高强韧可控降解镁合金材料包括按质量百分比计的如下组分：Ni:0.3～8.5％，RE:0.5～28％，M:0.03～10％，余量为Mg及不可避免的杂质；
    其中，M为能与镁发生合金化的元素。
  4. 根据权利要求3所述的含镍高强韧可控降解镁合金材料，其中，不可避免的杂质在镁合金材料中的质量百分含量不高于0.2％。
  5. 根据权利要求3所述的含镍高强韧可控降解镁合金材料，其中，M为Fe、Cu和Mn中的至少一种。
  6. 根据权利要求1～5中任一项所述的含镍高强韧可控降解镁合金材料的制备方法，包括如下步骤：将镍源、镁源和稀土源混合均匀，进行合金化处理，得到含镍高强韧可控降解镁合金材料。
  7. 根据权利要求6所述的制备方法，其中，所述镍源选自镍单质和/或镍合金；
    优选地，所述镍合金选自镁镍合金、镍钇合金或锌镍合金中的至少一种；
    优选地，所述镁源选自镁单质和/或镁合金；
    优选地，所述镁合金选自镁钆合金、镁钇合金、镁锌合金、镁镍合金、镁钙合金或镁铁合金中的至少一种；
    优选地，所述稀土源包括稀土单质和/或稀土中间合金；
    优选地，所述稀土单质包括钆、钇、铒、镝、铈和钪中的至少一种；
    优选地，所述稀土中间合金包括镁钆合金、镁钇合金、镁铒合金、镁铈合金、镁钪合金、镍钇合金、镍钆合金、镍铒合金、镍铈合金和镍钪合金中的至少一种。
  8. 根据权利要求6所述的制备方法，其中，所述合金化处理包括熔炼铸造法和粉末合金法；
    优选地，采用熔炼铸造法进行合金化处理；
    优选地，所述熔炼铸造法包括如下步骤：
    (a)铸造：将镍源、镁源和稀土源混合均匀，进行熔炼铸造，得到镁合金铸锭；
    (b)热处理：将镁合金铸锭依次进行均匀化处理和挤压热变形处理，即制得含镍高强韧可控降解镁合金材料；
    优选地，步骤(b)中还包括时效热处理步骤，所述时效热处理步骤设置于所述挤压热变形处理之后。
  9. 根据权利要求8所述的制备方法，其中，在步骤(a)中，进行熔炼铸造时，先升温至690～800℃，保温并搅拌使原料全部熔化，再降温至630～680℃，保温20～120min，冷却后，得到镁合金铸锭；
    优选地，熔炼铸造时采用惰性气体保护；
    优选地，冷却方式选自盐水浴、水淬、炉冷或空冷中的至少一种。
  10. 根据权利要求9所述的制备方法，其中，所述惰性气体选自氦气、氩气、二氧化碳和六氟化硫中的至少一种。
  11. 根据权利要求9所述的制备方法，其中，所述惰性气体为氩气。
  12. 根据权利要求9所述的制备方法，其中，采用电阻炉或工频感应路熔炼。
  13. 根据权利要求6所述的制备方法，其中，在步骤(b)中，进行均匀化处理的温度为400～550℃，时间为4～40h；
    优选地，在步骤(b)中，进行挤压变形处理时的挤压比为8～40；优选地，进行挤压变形处理的温度为360～480℃。
  14. 根据权利要求6所述的制备方法，其中，进行时效热处理的温度为150～250℃，时间为12～120h。
  15. 根据权利要求6所述的制备方法，其中，进行时效热处理的温度为180～220℃，时间为15～60h。
  16. 根据权利要求1～5中任一项所述的含镍高强韧可控降解镁合金材料在油气开发领域中的应用。
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CN109295368B (zh) * 2018-10-23 2020-06-19 重庆大学 含镍高强韧可控降解镁合金材料及其制备方法和应用
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CN113528917A (zh) * 2021-07-27 2021-10-22 重庆大学 一种具有长周期相的高强度镁合金及其制备方法
CN113718149B (zh) * 2021-08-06 2022-06-21 中北大学 一种高阻尼Mg-Ni-Y镁合金的制备工艺
CN114134380A (zh) * 2021-11-30 2022-03-04 重庆大学 高强度高阻尼Mg-Gd-Ni镁合金及其制备方法
CN114574744B (zh) * 2022-03-04 2022-11-01 哈尔滨工业大学 一种高模量镁合金及其制备方法
CN114908280B (zh) * 2022-05-31 2022-11-22 重庆大学 一种井下压裂用高强韧快速降解Mg-Er-Ni合金及其制备方法
CN115608994A (zh) * 2022-09-22 2023-01-17 哈尔滨理工大学 一种镁基复合材料板条制备与成形工艺
CN116043086B (zh) * 2022-12-19 2024-04-12 湖南稀土金属材料研究院有限责任公司 可溶镁合金及其制备方法与应用、压裂制品

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008127639A (ja) * 2006-11-21 2008-06-05 Kobe Steel Ltd マグネシウム合金材およびその製造方法
CN103981417A (zh) * 2014-05-28 2014-08-13 南京工程学院 一种高体积分数的lpso结构的生物镁合金及制备方法
CN104328320A (zh) * 2014-11-28 2015-02-04 重庆市科学技术研究院 一种高强度高塑性镁合金
CN105316550A (zh) * 2015-03-12 2016-02-10 华东交通大学 一种含长周期结构相高阻尼镁合金及其制备方法
CN109295368A (zh) * 2018-10-23 2019-02-01 重庆大学 含镍高强韧可控降解镁合金材料及其制备方法和应用

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008127639A (ja) * 2006-11-21 2008-06-05 Kobe Steel Ltd マグネシウム合金材およびその製造方法
CN103981417A (zh) * 2014-05-28 2014-08-13 南京工程学院 一种高体积分数的lpso结构的生物镁合金及制备方法
CN104328320A (zh) * 2014-11-28 2015-02-04 重庆市科学技术研究院 一种高强度高塑性镁合金
CN105316550A (zh) * 2015-03-12 2016-02-10 华东交通大学 一种含长周期结构相高阻尼镁合金及其制备方法
CN109295368A (zh) * 2018-10-23 2019-02-01 重庆大学 含镍高强韧可控降解镁合金材料及其制备方法和应用

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