CA3117106C - Nickel-containing high-toughness controllably degradable magnesium alloy material, preparation method therefor and use thereof - Google Patents
Nickel-containing high-toughness controllably degradable magnesium alloy material, preparation method therefor and use thereof Download PDFInfo
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- CA3117106C CA3117106C CA3117106A CA3117106A CA3117106C CA 3117106 C CA3117106 C CA 3117106C CA 3117106 A CA3117106 A CA 3117106A CA 3117106 A CA3117106 A CA 3117106A CA 3117106 C CA3117106 C CA 3117106C
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 189
- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 156
- 239000000956 alloy Substances 0.000 title claims abstract description 131
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 91
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 239000011777 magnesium Substances 0.000 claims abstract description 70
- 229910019758 Mg2Ni Inorganic materials 0.000 claims abstract description 61
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 34
- 239000012535 impurity Substances 0.000 claims abstract description 27
- 238000000034 method Methods 0.000 claims description 95
- 229910052749 magnesium Inorganic materials 0.000 claims description 42
- 238000001125 extrusion Methods 0.000 claims description 34
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 27
- 238000003723 Smelting Methods 0.000 claims description 27
- 238000005266 casting Methods 0.000 claims description 26
- 238000010438 heat treatment Methods 0.000 claims description 25
- 150000002910 rare earth metals Chemical class 0.000 claims description 24
- 229910000990 Ni alloy Inorganic materials 0.000 claims description 21
- 238000001816 cooling Methods 0.000 claims description 20
- 230000032683 aging Effects 0.000 claims description 19
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 18
- 229910000946 Y alloy Inorganic materials 0.000 claims description 18
- 238000000265 homogenisation Methods 0.000 claims description 17
- 239000007789 gas Substances 0.000 claims description 16
- 238000005275 alloying Methods 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 13
- 229910052727 yttrium Inorganic materials 0.000 claims description 13
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 11
- 229910000748 Gd alloy Inorganic materials 0.000 claims description 10
- 239000011261 inert gas Substances 0.000 claims description 10
- 239000002994 raw material Substances 0.000 claims description 10
- 229910052684 Cerium Inorganic materials 0.000 claims description 9
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 9
- 229910052691 Erbium Inorganic materials 0.000 claims description 9
- 229910052786 argon Inorganic materials 0.000 claims description 9
- ATTFYOXEMHAYAX-UHFFFAOYSA-N magnesium nickel Chemical compound [Mg].[Ni] ATTFYOXEMHAYAX-UHFFFAOYSA-N 0.000 claims description 9
- MIOQWPPQVGUZFD-UHFFFAOYSA-N magnesium yttrium Chemical compound [Mg].[Y] MIOQWPPQVGUZFD-UHFFFAOYSA-N 0.000 claims description 9
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 8
- 229910000636 Ce alloy Inorganic materials 0.000 claims description 8
- 229910001371 Er alloy Inorganic materials 0.000 claims description 8
- 229910000542 Sc alloy Inorganic materials 0.000 claims description 8
- IKBUJAGPKSFLPB-UHFFFAOYSA-N nickel yttrium Chemical compound [Ni].[Y] IKBUJAGPKSFLPB-UHFFFAOYSA-N 0.000 claims description 8
- 229910052706 scandium Inorganic materials 0.000 claims description 8
- DFIYZNMDLLCTMX-UHFFFAOYSA-N gadolinium magnesium Chemical compound [Mg].[Gd] DFIYZNMDLLCTMX-UHFFFAOYSA-N 0.000 claims description 7
- 238000002156 mixing Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 230000006698 induction Effects 0.000 claims description 5
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 5
- 229910000882 Ca alloy Inorganic materials 0.000 claims description 4
- 229910000640 Fe alloy Inorganic materials 0.000 claims description 4
- 229910018503 SF6 Inorganic materials 0.000 claims description 4
- 229910001297 Zn alloy Inorganic materials 0.000 claims description 4
- PGTXKIZLOWULDJ-UHFFFAOYSA-N [Mg].[Zn] Chemical compound [Mg].[Zn] PGTXKIZLOWULDJ-UHFFFAOYSA-N 0.000 claims description 4
- BBYGMOCGCCTLIV-UHFFFAOYSA-N [Sc].[Mg] Chemical compound [Sc].[Mg] BBYGMOCGCCTLIV-UHFFFAOYSA-N 0.000 claims description 4
- 239000012267 brine Substances 0.000 claims description 4
- ZFXVRMSLJDYJCH-UHFFFAOYSA-N calcium magnesium Chemical compound [Mg].[Ca] ZFXVRMSLJDYJCH-UHFFFAOYSA-N 0.000 claims description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 4
- 239000001569 carbon dioxide Substances 0.000 claims description 4
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 4
- RRTQFNGJENAXJJ-UHFFFAOYSA-N cerium magnesium Chemical compound [Mg].[Ce] RRTQFNGJENAXJJ-UHFFFAOYSA-N 0.000 claims description 4
- WITQLILIVJASEQ-UHFFFAOYSA-N cerium nickel Chemical compound [Ni].[Ce] WITQLILIVJASEQ-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 4
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 4
- OZCSIGAAICFSHZ-UHFFFAOYSA-N erbium magnesium Chemical compound [Mg].[Er] OZCSIGAAICFSHZ-UHFFFAOYSA-N 0.000 claims description 4
- KIPOFIHPOLEEOP-UHFFFAOYSA-N erbium nickel Chemical compound [Ni].[Er] KIPOFIHPOLEEOP-UHFFFAOYSA-N 0.000 claims description 4
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 4
- 239000001307 helium Substances 0.000 claims description 4
- 229910052734 helium Inorganic materials 0.000 claims description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- MHKWSJBPFXBFMX-UHFFFAOYSA-N iron magnesium Chemical compound [Mg].[Fe] MHKWSJBPFXBFMX-UHFFFAOYSA-N 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- XTOHTGPYKSWPDX-UHFFFAOYSA-N nickel scandium Chemical compound [Sc].[Ni] XTOHTGPYKSWPDX-UHFFFAOYSA-N 0.000 claims description 4
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 claims description 4
- 238000010791 quenching Methods 0.000 claims description 4
- 230000000171 quenching effect Effects 0.000 claims description 4
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 4
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 claims description 4
- SFZCNBIFKDRMGX-UHFFFAOYSA-N sulfur hexafluoride Chemical compound FS(F)(F)(F)(F)F SFZCNBIFKDRMGX-UHFFFAOYSA-N 0.000 claims description 4
- 229960000909 sulfur hexafluoride Drugs 0.000 claims description 4
- CVLNPENSSAFKOZ-UHFFFAOYSA-N gadolinium nickel Chemical compound [Ni].[Gd] CVLNPENSSAFKOZ-UHFFFAOYSA-N 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 18
- 238000010276 construction Methods 0.000 description 11
- 239000000243 solution Substances 0.000 description 8
- 239000000463 material Substances 0.000 description 7
- 239000003208 petroleum Substances 0.000 description 7
- 238000005553 drilling Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 5
- 238000012856 packing Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011159 matrix material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000000903 blocking effect Effects 0.000 description 2
- 238000007796 conventional method Methods 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- -1 for example Chemical compound 0.000 description 2
- 239000012634 fragment Substances 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 238000003801 milling Methods 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 239000003129 oil well Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000002679 ablation Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000002301 combined effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000005674 electromagnetic induction Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 230000008676 import Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000012768 molten material Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000003209 petroleum derivative Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 230000001131 transforming effect Effects 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
-
- 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
Abstract
The present disclosure provides a nickel-containing high-toughness controllably degradable magnesium alloy material, a preparation method therefor and use thereof, and relates to the technical field of magnesium alloys. The magnesium alloy material comprises the following components in percentage by mass: 0.3 to 8.5% of Ni, 0.5 to 28% of RE, with the balance being Mg and unavoidable impurities. RE represents rare earth elements. By adding Ni and RE elements to introduce an Mg12RENi-type long-period phase, an Mg2Ni phase and an MgxREy phase, the magnesium alloy material provided by the present disclosure significantly improves mechanical properties of the alloy material, the tensile strength being up to 510 MPa. At the same time, the presence of the Mg12RENi-type long-period phase and Mg2Ni phase enables the alloy material to be controllably degradable, and enables the degradation rate to be adjustable between 360 and 2400 mm/a. Downhole fracturing tools manufactured by using the magnesium alloy alleviates the technical problem existing in current downhole tools and satisfy the requirements in the field of oil and gas exploitation.
Description
Nickel-containing High-toughness Controllably Degradable Magnesium Alloy Material, Preparation Method therefor and Use thereof Technical Field The present disclosure relates to the technical field of magnesium alloy, in particular to a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, a preparation method therefor and use thereof.
Background Art With the rapid progress of economy, the petroleum problem in China has become one of the important problems with national concern. According to statistical data of the national statistical bureau, the net petroleum import in China is increasing continuously, and the dependency of petroleum in China on foreign countries directly breaks through 60% by 2015. According to international experience and opinion of people in authority, the dependency of petroleum in China on foreign countries must be kept below 60%.
China should reduce the dependency of petroleum on foreign countries, both from a strategic point of view and due to concerns about national safety and normal economic operation. Therefore, increasing the mining power of internal petroleum and improving the petroleum mining efficiency is an important measure for building powerful China, and it is urgent to explore new technologies and research and develop new materials.
China has abundant low-permeability oil and gas resources, and possesses great exploration and exploitation potential. The stable production and yield increase of future oil and gas production will depend on unconventional low-permeability oil and gas resources to a great extent. However, most of these unconventional oil and gas resources are distributed in strata with different depths, and the single-well productivity needs to be improved by simultaneously transforming a plurality of strata by adopting a multi-layer and multi-section fracturing technology, so that the yield of oil field and the construction efficiency are improved.
In multi-layer and multi-section fracturing, a packing tool (such as fracturing ball and bridge plug) needs to be used between layers and sections, so as to, after separation, Date Re9ue/Date Received 2021-07-12 carry out fracturing transformation layer by layer, and after the construction of all layers and all sections is completed, the packing tool is cleaned up from a wellbore, so as to break through a well and realize exploitation of oil and gas. However, most of the existing common packing tools are made of steel, and have the defects of difficult drilling and milling, 1 a Date Re9ue/Date Received 2021-07-12 long-time consumption, difficult removal of powders and fragments after drilling and so on, which greatly increases the construction period and cost.
Therefore, a light-weight fracturing ball capable of bearing a high pressure of fracturing construction and a high temperature of an oil well, and controllably and rapidly being corroded in the fluid environment of the oil well is researched, so that the construction cost and risk can be effectively reduced, the construction period can be shortened, and the construction efficiency can be improved.
Summary Object of the present disclosure include, for example, providing a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, so as to solve the technical problems that most of the existing common packing tools, made of steel, have the defects of difficult drilling and milling, long time consumption, difficult removal of powders and fragments after drilling and so on, which greatly increases the construction period and the cost.
The nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material provided in the present disclosure includes following components in percentage by mass: 0.3-8.5% of Ni, 0.5-28% of RE, and the balance of Mg and unavoidable impurities, wherein RE is a rare earth element, and Mg, Ni and RE form an Mgi2RENi-type long-period stacking ordered phase (i.e., Mg12NiRE-type long-period stacking ordered phase), an Mg2Ni phase and an MgxREy phase, wherein a volume fraction of the Mg12RENi-type long-period stacking ordered phase is 3-70%, a volume fraction of the Mg2Ni phase is 0_5-10%, a volume fraction of the MgxREy phase is 0.5-22%, and a value range of x:y is (3-12):1.
In one or more embodiments, the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material includes following components in percentage by mass: 0.5-8.0% of Ni, 1.5-20% of RE, and the balance of Mg and unavoidable impurities.
In one or more embodiments, the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material includes as-cast magnesium alloy, as-extruded magnesium alloy and aged magnesium alloy.
In one or more embodiments, the as-cast magnesium alloy includes an Mg12NiRE-type long-period stacking ordered phase, an Mg5RE phase and an Mg2Ni phase, wherein a volume fraction of the Mg12NiRE-type long-period stacking ordered phase is 3-65%, a volume fraction of the Mg2Ni phase is 0.5-6%, and a volume fraction of the Mg5RE phase is 0.5-15%.
In one or more embodiments, the as-extruded magnesium alloy includes an Mg12NiRE-type long-period stacking ordered phase, an Mg2Ni phase and an Mg5RE phase, wherein a volume fraction of the Mg12NiRE-type long-period stacking ordered phase is 4-70%, a volume fraction of the Mg2Ni phase is 1%-8%, and a volume fraction of the Mg5RE phase is 1-20%.
Background Art With the rapid progress of economy, the petroleum problem in China has become one of the important problems with national concern. According to statistical data of the national statistical bureau, the net petroleum import in China is increasing continuously, and the dependency of petroleum in China on foreign countries directly breaks through 60% by 2015. According to international experience and opinion of people in authority, the dependency of petroleum in China on foreign countries must be kept below 60%.
China should reduce the dependency of petroleum on foreign countries, both from a strategic point of view and due to concerns about national safety and normal economic operation. Therefore, increasing the mining power of internal petroleum and improving the petroleum mining efficiency is an important measure for building powerful China, and it is urgent to explore new technologies and research and develop new materials.
China has abundant low-permeability oil and gas resources, and possesses great exploration and exploitation potential. The stable production and yield increase of future oil and gas production will depend on unconventional low-permeability oil and gas resources to a great extent. However, most of these unconventional oil and gas resources are distributed in strata with different depths, and the single-well productivity needs to be improved by simultaneously transforming a plurality of strata by adopting a multi-layer and multi-section fracturing technology, so that the yield of oil field and the construction efficiency are improved.
In multi-layer and multi-section fracturing, a packing tool (such as fracturing ball and bridge plug) needs to be used between layers and sections, so as to, after separation, Date Re9ue/Date Received 2021-07-12 carry out fracturing transformation layer by layer, and after the construction of all layers and all sections is completed, the packing tool is cleaned up from a wellbore, so as to break through a well and realize exploitation of oil and gas. However, most of the existing common packing tools are made of steel, and have the defects of difficult drilling and milling, 1 a Date Re9ue/Date Received 2021-07-12 long-time consumption, difficult removal of powders and fragments after drilling and so on, which greatly increases the construction period and cost.
Therefore, a light-weight fracturing ball capable of bearing a high pressure of fracturing construction and a high temperature of an oil well, and controllably and rapidly being corroded in the fluid environment of the oil well is researched, so that the construction cost and risk can be effectively reduced, the construction period can be shortened, and the construction efficiency can be improved.
Summary Object of the present disclosure include, for example, providing a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, so as to solve the technical problems that most of the existing common packing tools, made of steel, have the defects of difficult drilling and milling, long time consumption, difficult removal of powders and fragments after drilling and so on, which greatly increases the construction period and the cost.
The nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material provided in the present disclosure includes following components in percentage by mass: 0.3-8.5% of Ni, 0.5-28% of RE, and the balance of Mg and unavoidable impurities, wherein RE is a rare earth element, and Mg, Ni and RE form an Mgi2RENi-type long-period stacking ordered phase (i.e., Mg12NiRE-type long-period stacking ordered phase), an Mg2Ni phase and an MgxREy phase, wherein a volume fraction of the Mg12RENi-type long-period stacking ordered phase is 3-70%, a volume fraction of the Mg2Ni phase is 0_5-10%, a volume fraction of the MgxREy phase is 0.5-22%, and a value range of x:y is (3-12):1.
In one or more embodiments, the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material includes following components in percentage by mass: 0.5-8.0% of Ni, 1.5-20% of RE, and the balance of Mg and unavoidable impurities.
In one or more embodiments, the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material includes as-cast magnesium alloy, as-extruded magnesium alloy and aged magnesium alloy.
In one or more embodiments, the as-cast magnesium alloy includes an Mg12NiRE-type long-period stacking ordered phase, an Mg5RE phase and an Mg2Ni phase, wherein a volume fraction of the Mg12NiRE-type long-period stacking ordered phase is 3-65%, a volume fraction of the Mg2Ni phase is 0.5-6%, and a volume fraction of the Mg5RE phase is 0.5-15%.
In one or more embodiments, the as-extruded magnesium alloy includes an Mg12NiRE-type long-period stacking ordered phase, an Mg2Ni phase and an Mg5RE phase, wherein a volume fraction of the Mg12NiRE-type long-period stacking ordered phase is 4-70%, a volume fraction of the Mg2Ni phase is 1%-8%, and a volume fraction of the Mg5RE phase is 1-20%.
2 0PI21300392CA
Date Re9ue/Date Received 2021-04-20 In one or more embodiments, the aged magnesium alloy includes an Mg12N1RE-type long-period stacking ordered phase, an Mg2Ni phase and an MgxREy phase, wherein a volume fraction of the Mg12NiRE-type long-period stacking ordered phase is 4-70%, a volume fraction of the Mg2Ni phase is 2-10%, and a volume fraction of the MgxREy phase is 2-22%, wherein a value range of x:y is 3:1-12:1.
In one or more embodiments, the RE is at least one selected from the group consisting of Gd, Y, Er, Dy, Ce and Sc.
In one or more embodiments, the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material includes following components in percentage by mass: 0.3-8.5% of Ni, 0.5-28% of RE, 0.03-10% of M, and the balance of Mg and unavoidable impurities, wherein M
is an element capable of alloying with magnesium.
In one or more embodiments, the content of the unavoidable impurities, in percentage by mass, is not higher than 0.2% in the magnesium alloy material.
In one or more embodiments, M is at least one of Fe, Cu and Mn.
Object of the present disclosure include, for example, providing a method for preparing a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, including the following step:
uniformly mixing a nickel source, a magnesium source and a rare earth source, and carrying out alloying treatment to obtain the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material.
In one or more embodiments, the nickel source is selected from elemental nickel and/or nickel alloy.
In one or more embodiments, the nickel alloy is at least one selected from the group consisting of magnesium-nickel alloy, nickel-yttrium alloy and zinc-nickel alloy.
In one or more embodiments, the magnesium source is selected from elemental magnesium and/or magnesium alloy.
In one or more embodiments, the magnesium alloy is at least one selected from the group consisting of magnesium-gadolinium alloy, magnesium-yttrium alloy, magnesium-zinc alloy, magnesium-nickel alloy, magnesium-calcium alloy and magnesium-iron alloy.
In one or more embodiments, the rare earth source includes elemental rare earth and/or rare earth intermediate alloy.
In one or more embodiments, the elemental rare earth includes at least one selected from the group consisting of gadolinium, yttrium, erbium, dysprosium, cerium and scandium.
In one or more embodiments, the rare earth intermediate alloy includes at least one selected from the group consisting of magnesium-gadolinium alloy,
Date Re9ue/Date Received 2021-04-20 In one or more embodiments, the aged magnesium alloy includes an Mg12N1RE-type long-period stacking ordered phase, an Mg2Ni phase and an MgxREy phase, wherein a volume fraction of the Mg12NiRE-type long-period stacking ordered phase is 4-70%, a volume fraction of the Mg2Ni phase is 2-10%, and a volume fraction of the MgxREy phase is 2-22%, wherein a value range of x:y is 3:1-12:1.
In one or more embodiments, the RE is at least one selected from the group consisting of Gd, Y, Er, Dy, Ce and Sc.
In one or more embodiments, the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material includes following components in percentage by mass: 0.3-8.5% of Ni, 0.5-28% of RE, 0.03-10% of M, and the balance of Mg and unavoidable impurities, wherein M
is an element capable of alloying with magnesium.
In one or more embodiments, the content of the unavoidable impurities, in percentage by mass, is not higher than 0.2% in the magnesium alloy material.
In one or more embodiments, M is at least one of Fe, Cu and Mn.
Object of the present disclosure include, for example, providing a method for preparing a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, including the following step:
uniformly mixing a nickel source, a magnesium source and a rare earth source, and carrying out alloying treatment to obtain the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material.
In one or more embodiments, the nickel source is selected from elemental nickel and/or nickel alloy.
In one or more embodiments, the nickel alloy is at least one selected from the group consisting of magnesium-nickel alloy, nickel-yttrium alloy and zinc-nickel alloy.
In one or more embodiments, the magnesium source is selected from elemental magnesium and/or magnesium alloy.
In one or more embodiments, the magnesium alloy is at least one selected from the group consisting of magnesium-gadolinium alloy, magnesium-yttrium alloy, magnesium-zinc alloy, magnesium-nickel alloy, magnesium-calcium alloy and magnesium-iron alloy.
In one or more embodiments, the rare earth source includes elemental rare earth and/or rare earth intermediate alloy.
In one or more embodiments, the elemental rare earth includes at least one selected from the group consisting of gadolinium, yttrium, erbium, dysprosium, cerium and scandium.
In one or more embodiments, the rare earth intermediate alloy includes at least one selected from the group consisting of magnesium-gadolinium alloy,
3 0PI21300392CA
Date Re9ue/Date Received 2021-04-20 magnesium-yttrium alloy, magnesium-erbium alloy, magnesium-cerium alloy, magnesium-scandium alloy, nickel-yttrium alloy, nickel-gadolinium alloy, nickel-erbium alloy, nickel-cerium alloy and nickel-scandium alloy.
In one or more embodiments, the alloying treatment includes a smelting and casting method and a powder alloying method.
In one or more embodiments, the alloying treatment is carried out by adopting the smelting and casting method.
In one or more embodiments, the smelting and casting method includes following steps:
(a) casting: uniformly mixing a nickel source, a magnesium source and a rare earth source, and carrying out smelting and casting to obtain a magnesium alloy ingot; and (b) heat treatment: carrying out, in sequence, homogenization treatment and extrusion heat deformation treatment on the magnesium alloy ingot, to obtain the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material.
In one or more embodiments, the step (b) also includes an aging heat treatment step, wherein the aging heat treatment step is carried out after the extrusion heat deformation treatment.
In one or more embodiments, in the step (a), when the smelting and casting is carried out, the temperature is first increased to 690-800 C and maintained, the raw materials are stirred to enable them to melt completely, then the temperature is reduced to 630-680 C and maintained for 20-120 min, and after cooling, the magnesium alloy ingot is obtained.
In one or more embodiments, an inert gas is used during the smelting and casting for protection.
In one or more embodiments, the inert gas is at least one selected from the group consisting of helium, argon, carbon dioxide and sulfur hexafluoride, for example, argon. In one or more embodiments, a cooling method is at least one selected from the group consisting of brine bath, water quenching, furnace cooling and air cooling.
In one or more embodiments, smelting is carried out using a resistance furnace or a line frequency induction furnace.
In one or more embodiments, in the step (a), the nickel source, the rare earth source and the magnesium source are accurately weighed according to formula requirements, and uniformly mixed.
In one or more embodiments, in the step (b), the homogenization treatment is carried out at a temperature of 400-550 C for 4-40 h.
In one or more embodiments, in the step (b), an extrusion ratio in the extrusion heat deformation treatment is 8-40.
Date Re9ue/Date Received 2021-04-20 magnesium-yttrium alloy, magnesium-erbium alloy, magnesium-cerium alloy, magnesium-scandium alloy, nickel-yttrium alloy, nickel-gadolinium alloy, nickel-erbium alloy, nickel-cerium alloy and nickel-scandium alloy.
In one or more embodiments, the alloying treatment includes a smelting and casting method and a powder alloying method.
In one or more embodiments, the alloying treatment is carried out by adopting the smelting and casting method.
In one or more embodiments, the smelting and casting method includes following steps:
(a) casting: uniformly mixing a nickel source, a magnesium source and a rare earth source, and carrying out smelting and casting to obtain a magnesium alloy ingot; and (b) heat treatment: carrying out, in sequence, homogenization treatment and extrusion heat deformation treatment on the magnesium alloy ingot, to obtain the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material.
In one or more embodiments, the step (b) also includes an aging heat treatment step, wherein the aging heat treatment step is carried out after the extrusion heat deformation treatment.
In one or more embodiments, in the step (a), when the smelting and casting is carried out, the temperature is first increased to 690-800 C and maintained, the raw materials are stirred to enable them to melt completely, then the temperature is reduced to 630-680 C and maintained for 20-120 min, and after cooling, the magnesium alloy ingot is obtained.
In one or more embodiments, an inert gas is used during the smelting and casting for protection.
In one or more embodiments, the inert gas is at least one selected from the group consisting of helium, argon, carbon dioxide and sulfur hexafluoride, for example, argon. In one or more embodiments, a cooling method is at least one selected from the group consisting of brine bath, water quenching, furnace cooling and air cooling.
In one or more embodiments, smelting is carried out using a resistance furnace or a line frequency induction furnace.
In one or more embodiments, in the step (a), the nickel source, the rare earth source and the magnesium source are accurately weighed according to formula requirements, and uniformly mixed.
In one or more embodiments, in the step (b), the homogenization treatment is carried out at a temperature of 400-550 C for 4-40 h.
In one or more embodiments, in the step (b), an extrusion ratio in the extrusion heat deformation treatment is 8-40.
4 0PI21300392CA
Date Re9ue/Date Received 2021-04-20 In one or more embodiments, the extrusion heat deformation treatment is carried out at a temperature of 360-480 C.
In one or more embodiments, in the step (b), the aging heat treatment is carried out at a temperature of 150-250 C for 12-120 h.
In one or more embodiments, in the step (b), the aging heat treatment is carried out at a temperature of 180-220 C for 15-60 h.
Object of the present disclosure include, for example, providing use of a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material in the field of oil and gas exploitation.
The present disclosure at least has following beneficial effects:
(1) The nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material provided in the present disclosure takes magnesium as a base material, and the Mg12RENi-type long-period stacking ordered phase, the Mg2Ni phase and the Mg,REy phase are formed by adding Ni and RE, so that the tensile strength and plasticity of the alloy material are remarkably improved;
meanwhile, a quite large electronegativity difference exists between the Mg12RENi-type long-period stacking ordered phase and the Mg2Ni phase, and the magnesium matrix, and a large number of micro-batteries are formed, so that the generated nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material can be rapidly decomposed, and the downhole fracturing tool made of this magnesium alloy material can effectively meet the requirements of the field of oil and gas exploitation.
(2) When applied to the field of oil and gas exploitation, the controllably degradable alloy material provided in the present disclosure can be degraded completely downhole after accomplishing a task, and discharged through a pipe-line, without problems of easy blocking or jam, thus leaving out the drilling and grinding recycling process, reducing the engineering degree of difficulty, and improving the construction efficiency.
***
Various other aspects of the invention are defined with reference to the following preferred embodiments [1] to [30].
Date Recue/Date Received 2023-07-28 [1] A
method for preparing a magnesium alloy material which is a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, said magnesium alloy material comprising following components in percentage by mass:
0.3% to 8.5% of Ni, 0.5% to 28% of RE, and a balance of Mg and unavoidable impurities, wherein RE is at least one rare earth element, and Mg, Ni and RE form an Mg12RENi long-period stacking ordered phase, an Mg2Ni phase and an Mg,REy phase; wherein a volume fraction of the Mg12RENi long-period stacking ordered phase is 3% to 70%, a volume fraction of the Mg2Ni phase is 0.5% to 10%, a volume fraction of the Mg,REy phase is 0.5 to 22%, and a value range of x:y is 3:1 to 12:1;
said method comprising the following steps of (i) uniformly mixing a nickel source, a magnesium source and at least one rare earth element source, and (ii) carrying out an alloying treatment by a smelting and casting method, to provide the magnesium alloy material; and wherein the smelting and casting method comprises:
(a) a casting step, after step (i) mentioned above, carrying out a smelting and casting comprising firstly increasing temperature to 690 C to 800 C, maintaining the temperature at 690 C to 800 C and stirring raw materials until said raw materials completely melt, reducing temperature to 630 C to 680 C and maintaining for 20 min to 120 min, and then cooling to provide a magnesium alloy ingot; and (b) a heat treatment comprising carrying out a homogenization treatment, an extrusion heat deformation treatment and an aging heat treatment on the magnesium alloy ingot in sequence to provide the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material.
5a Date Recue/Date Received 2023-07-28 [2] The method according to [1], wherein the magnesium alloy material comprises following components in percentage by mass:
0.5% to 8.0% of Ni, 1.5% to 20% of RE, a balance of Mg and unavoidable impurities.
[3] The method according to [1], wherein the magnesium alloy material comprises at least one of an as-cast magnesium alloy, an as-extruded magnesium alloy and an aged magnesium alloy.
[4] The method according to [3], wherein the as-cast magnesium alloy comprises the Mg12RENi long-period stacking ordered phase, the Mg5RE phase and the Mg2Ni phase, wherein the volume fraction of the Mg12RENi long-period stacking ordered phase is 3% to 65%, the volume fraction of the Mg2Ni phase is 0.5% to 6%, and the volume fraction of the Mg5RE phase is 0.5% to 15%.
Date Re9ue/Date Received 2021-04-20 In one or more embodiments, the extrusion heat deformation treatment is carried out at a temperature of 360-480 C.
In one or more embodiments, in the step (b), the aging heat treatment is carried out at a temperature of 150-250 C for 12-120 h.
In one or more embodiments, in the step (b), the aging heat treatment is carried out at a temperature of 180-220 C for 15-60 h.
Object of the present disclosure include, for example, providing use of a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material in the field of oil and gas exploitation.
The present disclosure at least has following beneficial effects:
(1) The nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material provided in the present disclosure takes magnesium as a base material, and the Mg12RENi-type long-period stacking ordered phase, the Mg2Ni phase and the Mg,REy phase are formed by adding Ni and RE, so that the tensile strength and plasticity of the alloy material are remarkably improved;
meanwhile, a quite large electronegativity difference exists between the Mg12RENi-type long-period stacking ordered phase and the Mg2Ni phase, and the magnesium matrix, and a large number of micro-batteries are formed, so that the generated nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material can be rapidly decomposed, and the downhole fracturing tool made of this magnesium alloy material can effectively meet the requirements of the field of oil and gas exploitation.
(2) When applied to the field of oil and gas exploitation, the controllably degradable alloy material provided in the present disclosure can be degraded completely downhole after accomplishing a task, and discharged through a pipe-line, without problems of easy blocking or jam, thus leaving out the drilling and grinding recycling process, reducing the engineering degree of difficulty, and improving the construction efficiency.
***
Various other aspects of the invention are defined with reference to the following preferred embodiments [1] to [30].
Date Recue/Date Received 2023-07-28 [1] A
method for preparing a magnesium alloy material which is a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, said magnesium alloy material comprising following components in percentage by mass:
0.3% to 8.5% of Ni, 0.5% to 28% of RE, and a balance of Mg and unavoidable impurities, wherein RE is at least one rare earth element, and Mg, Ni and RE form an Mg12RENi long-period stacking ordered phase, an Mg2Ni phase and an Mg,REy phase; wherein a volume fraction of the Mg12RENi long-period stacking ordered phase is 3% to 70%, a volume fraction of the Mg2Ni phase is 0.5% to 10%, a volume fraction of the Mg,REy phase is 0.5 to 22%, and a value range of x:y is 3:1 to 12:1;
said method comprising the following steps of (i) uniformly mixing a nickel source, a magnesium source and at least one rare earth element source, and (ii) carrying out an alloying treatment by a smelting and casting method, to provide the magnesium alloy material; and wherein the smelting and casting method comprises:
(a) a casting step, after step (i) mentioned above, carrying out a smelting and casting comprising firstly increasing temperature to 690 C to 800 C, maintaining the temperature at 690 C to 800 C and stirring raw materials until said raw materials completely melt, reducing temperature to 630 C to 680 C and maintaining for 20 min to 120 min, and then cooling to provide a magnesium alloy ingot; and (b) a heat treatment comprising carrying out a homogenization treatment, an extrusion heat deformation treatment and an aging heat treatment on the magnesium alloy ingot in sequence to provide the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material.
5a Date Recue/Date Received 2023-07-28 [2] The method according to [1], wherein the magnesium alloy material comprises following components in percentage by mass:
0.5% to 8.0% of Ni, 1.5% to 20% of RE, a balance of Mg and unavoidable impurities.
[3] The method according to [1], wherein the magnesium alloy material comprises at least one of an as-cast magnesium alloy, an as-extruded magnesium alloy and an aged magnesium alloy.
[4] The method according to [3], wherein the as-cast magnesium alloy comprises the Mg12RENi long-period stacking ordered phase, the Mg5RE phase and the Mg2Ni phase, wherein the volume fraction of the Mg12RENi long-period stacking ordered phase is 3% to 65%, the volume fraction of the Mg2Ni phase is 0.5% to 6%, and the volume fraction of the Mg5RE phase is 0.5% to 15%.
[5] The method according to [3], wherein the as-cast magnesium alloy comprises the Mg12RENi long-period stacking ordered phase, the Mg2Ni phase and the Mg5RE phase, wherein the volume fraction of the Mg12RENi long-period stacking ordered phase is 4% to 70%, the volume fraction of the Mg2Ni phase is 1% to 8%, and the volume fraction of the Mg5RE phase is 1% to 20%.
[6] The method according to [3], wherein the as-cast magnesium alloy comprises the Mg12RENi long-period stacking ordered phase, the Mg2Ni phase and the MgxREy phase, wherein the volume fraction of the Mg12RENi long-period stacking ordered phase is 4% to 70%, the volume fraction of the Mg2Ni phase is 2% to 10%, and the volume fraction of the Mg,REy phase is 2% to 22%.
[7] The method according to any one of [1] to [6], wherein the RE is at least one selected from the group consisting of Gd, Y, Er, Dy, Ce and Sc.
[8] The method according to [7], wherein the content of the unavoidable impurities, in percentage by mass, is not higher than 0.2% in the magnesium alloy material.
5b Date Recue/Date Received 2023-07-28
5b Date Recue/Date Received 2023-07-28
[9] The method according to [7] , wherein the magnesium alloy material further comprises a component M which is at least one element capable of alloying with magnesium, and wherein the magnesium alloy material comprises following components in percentage by mass:
0.3% to 8.5% of Ni, 0.5% to 28% of RE, 0.03% to 10% of the component M, and a balance of Mg and unavoidable impurities.
0.3% to 8.5% of Ni, 0.5% to 28% of RE, 0.03% to 10% of the component M, and a balance of Mg and unavoidable impurities.
[10] The method according to [9], wherein the content of the unavoidable impurities, in percentage by mass, is not higher than 0.2% in the magnesium alloy material.
[11] The method according to [9] or [10] , wherein component M is selected from the group consisting of Fe, Cu and Mn.
[12] The method according to any one of [1] to [11] , wherein the nickel source is selected from the group consisting of elemental nickel, nickel alloy and mixtures thereof.
[13] The method according to [12] , wherein the nickel alloy is at least one selected from the group consisting of magnesium-nickel alloy, nickel-yttrium alloy and zinc-nickel alloy.
[14] The method according to [11] , wherein the magnesium source is selected from the group consisting of elemental magnesium, magnesium alloy and mixtures thereof.
[16] The method according to [14] , wherein the magnesium alloy is at least one selected from the group consisting of magnesium-gadolinium alloy, magnesium-yttrium alloy, magnesium-zinc alloy, magnesium-nickel alloy, magnesium-calcium alloy and magnesium-iron alloy.
[16] The method according to [11] , wherein the at least one rare earth element source comprises elemental rare earth and/or rare earth intermediate alloy.
5c Date Recue/Date Received 2023-07-28 [17] The method according to [16], wherein the elemental rare earth comprises at least one selected from the group consisting of gadolinium, yttrium, erbium, dysprosium, cerium and scandium.
[18] The method according to [16], wherein the rare earth intermediate alloy comprises at least one selected from the group consisting of magnesium-gadolinium alloy, magnesium-yttrium alloy, magnesium-erbium alloy, magnesium-cerium alloy, magnesium-scandium alloy, nickel-yttri urn alloy, nickel-gadolini urn alloy, nickel-erbium alloy, nickel-cerium alloy and nickel-scandium alloy.
[19] The method according to [11], wherein the aging heat treatment is carried out at a temperature of 150 C to 250 C for 12 h to 120 h.
[20] The method according to [11] or [19], wherein the aging heat treatment is carried out at a temperature of 180 C to 220 C for 15 h to 60 h.
[21] The method according to [11], wherein the cooling is obtained by a cooling method which is at least one selected from the group consisting of brine bath, water quenching, furnace cooling and air cooling.
[22] The method according to any one of [11] to [21], wherein an inert gas is used during the smelting and casting for protection.
[23] The method according to [22], wherein the inert gas is at least one selected from the group consisting of helium, argon, carbon dioxide and sulfur hexafluoride.
[24] The method according to [23], wherein the inert gas is argon.
[25] The method according to any one of [11] to [24], wherein the smelting is carried out using a resistance furnace or a line frequency induction furnace.
[26] The method according to any one of [11] to [25], wherein in the step (b), the homogenization treatment is carried out at a temperature of 400 C to 550 C for 4h to 40h.
[27] The method according to [26], wherein in the step (b), the extrusion heat deformation treatment is carried out at an extrusion ratio of 8 to 40.
5d Date Recue/Date Received 2023-07-28 [28] The method according to [27], wherein the extrusion heat deformation treatment is carried out at a temperature of 360 C to 480 C.
[29] A magnesium alloy material which is a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, obtained from the method defined in any one of [1] to [28].
[30] A use of the magnesium alloy material as defined in [29] in a field of oil and gas exploitation.
Detailed Description of Embodiments Embodiments of the present disclosure will be described in detail below in combination with examples, while a person skilled in the art would understand that the following examples are merely used for illustrating the present disclosure, but should not be considered as limitation on the scope of the present disclosure. If no specific conditions are specified in the examples, they are carried out under normal conditions or conditions recommended by manufacturers. If manufacturers of reagents or apparatuses used are not specified, they are all conventional products commercially available.
According to one aspect of the present disclosure, the present disclosure provides a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, including following components in percentage by mass:
0.3-8.5% of Ni, 0.5-28% of RE, and the balance of Mg and unavoidable impurities, wherein RE is a rare earth element, and Mg, Ni 5e Date Recue/Date Received 2023-07-28 and RE mainly form an Mg12RENi-type long-period stacking ordered phase, an Mg2Ni phase and an MgxREy phase.
A volume fraction of the Mg12RENi-type long-period stacking ordered phase is 3-70%, a volume fraction of the Mg2Ni phase is 0.5-10%, and a volume fraction of the MgxREy phase is 0.5-22%.
In one or more embodiments, the content of the unavoidable impurities in the magnesium alloy material, in percentage by mass, is not higher than 0.2%.
In one or more embodiments, the long-period stacking ordered phase (LPSO), a new reinforcing phase in magnesium alloy, is formed by periodic changes in atomic position or chemical composition in a crystal structure, and the long-period structure is divided into two aspects, namely, stacking order and chemical composition order, and the Mg12RENi-type long-period stacking ordered phase in one or more embodiments is a result of combined effect of both stacking order and chemical composition order.
In the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material provided in the present disclosure, a typical but non-limited content of Ni (nickel), in percentage by mass, is, for example, 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%.
In the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material provided in the present disclosure, a typical but non-limited content of RE, in percentage by mass, is, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25% or 28%.
In one or more embodiments, the volume fraction of the Mgi2REN1-type long-period stacking ordered phase is 3-70%, the volume fraction of the Mg5RE phase is 0.5-20%, the volume fraction of the Mg2Ni phase is 0.5-10%, the volume fraction of the MgxREy phase is 0.5-22%, and a value range of x:y is (3-12):1 (i.e., 3:1-12:1).
By setting the volume fraction of the Mg12RENi-type long-period stacking ordered phase to be 3-70%, the volume fraction of the Mg2Ni phase to be 0.5-10%, and the volume fraction of the MgxREy phase to be 0.5-22%, the Mg12RENi-type long-period stacking ordered phase and the MgxREy phase remarkably improve the tensile strength of the alloy material, and enable the alloy to maintain certain plasticity; and meanwhile, a relatively large potential difference exists between the Mg12RENi-type long-period stacking ordered phase and the Mg2Ni phase, and the magnesium matrix, and a large number of micro-batteries are formed, so that the generated alloy material can be rapidly decomposed, which effectively meets the requirements of the field of oil and gas exploitation on downhole tool materials.
In one or more embodiments, in the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, a typical but non-limited volume fraction of the Mg12RENi-type long-period stacking Date Re9ue/Date Received 2021-04-20 ordered phase is, for example, 3%, 4%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70%; a typical but non-limited volume fraction of the Mg2Ni phase is, for example, 0.5%, 1%, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%; a typical but non-limited volume fraction of the MgxREy phase is, for example, 0.5%, 1%, 2%, 5%, 8%, 10%, 12%, 15%, 18%, 20% or 22%; and a typical but non-limited numerical value of x:y is 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 high-toughness, controllably degradable magnesium alloy material provided in the present disclosure takes magnesium as a base material, and the Mg12RENi-type long-period stacking ordered phase and the MgxREy phase are formed by adding Ni and RE, so that the tensile strength of the alloy material is remarkably improved;
meanwhile, a quite large electronegativity difference exists between the Mg12RENI-type long-period stacking ordered phase and the Mg2Ni phase, and the magnesium matrix, and a large number of micro-batteries are formed, so that the generated nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material can be rapidly decomposed, and the downhole fracturing tool made of this magnesium alloy material can effectively meet the requirements of the field of oil and gas exploitation.
Besides, when applied to the field of oil and gas exploitation, the controllably degradable alloy material provided in the present disclosure can be degraded completely downhole after accomplishing a task, and discharged through a pipe-line, without problems of easy blocking or jam, thus leaving out the drilling and grinding recycling process, reducing the engineering degree of difficulty, and improving the construction efficiency.
In one or more embodiments of the present disclosure, when Ni is 0.5-7.5%
and RE is 1.5-19%, in the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material; and the volume fraction of the Mg12RENi-type long-period stacking ordered phase is 4.8-65%, the volume fraction of the Mg5RE phase is 1-15%, and the volume fraction of the Mg2Ni phase is 1-5%, the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material has the tensile strength of 325-505 MPa, the yield strength of 156-415 MPa, and the elongation of 6.0-21.8% at room temperature, and the decomposition rate of 363 mmia - 2500 rnm/a in a 3.5wt% KCI solution at 90 C.
In one or more embodiments of the present disclosure, the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material includes as-cast magnesium alloy, as-extruded magnesium alloy and aged magnesium alloy.
In one or more embodiments of the present disclosure, in the as-cast magnesium alloy, Mg, Ni and RE mainly form an Mgi2RENi-type long-period stacking ordered phase, an Mg2Ni phase and an Mg5RE phase, wherein a volume fraction of the Mgi2NiRE-type long-period stacking ordered phase is 3-65%, a volume fraction of the Mg2Ni phase is 0.5-6%, and a volume fraction of the Mg5RE phase is 0.5-15%.
Date Re9ue/Date Received 2021-04-20 In one or more embodiments of the present disclosure, in the as-cast magnesium alloy, a typical but non-limited volume fraction of the Mg12N1RE-type long-period stacking ordered phase is, for example, 3%, 4%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60% or 65%; a typical but non-limited volume fraction of the Mg2Ni phase is, for example, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%
or 6%; and a typical but non-limited volume fraction of the Mg5RE phase is, for example, 0.5%, 0.8%, 1%, 2%, 5%, 8%, 10%, 12% or 15%.
In one or more embodiments of the present disclosure, in the as-extruded magnesium alloy, Mg, Ni and RE mainly form an Mgi2RENi-type long-period stacking ordered phase, an Mg2Ni phase and an Mg5RE phase, wherein a volume fraction of the Mg12NiRE-type long-period stacking ordered phase is 4-70%, a volume fraction of the Mg2Ni phase is 1%-8%, and a volume fraction of the Mg5RE phase is 1-20%.
In one or more embodiments of the present disclosure, in the as-extruded magnesium alloy, a typical but non-limited volume fraction of the Mg12NiRE-type long-period stacking ordered phase is, for example, 4%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70%; a typical but non-limited volume fraction of the Mg2Ni phase is, for example, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5% or 8%; and a typical but non-limited volume fraction of the Mg5RE
phase is, for example, 1%, 2%, 5%, 8%, 10%, 12%, 15%, 18% or 20%.
In one or more embodiments of the present disclosure, in the aged magnesium alloy, Mg, Ni and RE mainly form an Mg12RENi-type long-period stacking ordered phase, an Mg2Ni phase and MgxREy phase (x:y=(3-12):1), wherein a volume fraction of the Mg12NiRE-type long-period stacking ordered phase is 4-70%, a volume fraction of the Mg2Ni phase is 2%-10%, and a volume fraction of the Mg5RE phase is 2-22%.
In one or more embodiments of the present disclosure, in the aged magnesium alloy, a typical but non-limited volume fraction of the Mg12NiRE-type long-period stacking ordered phase is, for example, 4%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70%; a typical but non-limited volume fraction of the Mg2Ni phase is, for example, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 9% or 10%; a typical but non-limited volume fraction of the MgxREy phase is, for example, 2%, 5%, 8%, 10%, 12%, 15%, 18%, 20% or 22%, wherein a typical but non-limited numerical value of x:y is, for example, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1 or 12:1.
In one or more embodiments of the present disclosure, RE is one or more selected from the group consisting of Gd, Y, Er, Dy, Ce and Sc.
In one or more embodiments of the present disclosure, the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material includes following components in percentage by mass: 0.3-8.5% of Ni, 0.5-28% of RE, 0.03-10% of M, and the balance of Mg and unavoidable impurities, wherein M is an element capable of alloying with magnesium.
Date Re9ue/Date Received 2021-04-20 In one or more embodiments of the present disclosure, in the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, a typical but non-limited percentage by mass of Ni is, for example, 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%; a typical but non-limited percentage by mass of RE is, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25% or 28%; and a typical but non-limited percentage by mass of M is, for example, 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%.
In one or more embodiments of the present disclosure, M includes, but is not limited to at least one of Fe, Cu and Mn.
According to a second aspect of the present disclosure, the present disclosure provides a method for preparing the above nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, including the following step:
uniformly mixing a nickel source, a magnesium source and a rare earth source, and carrying out alloying treatment to obtain the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material.
The method for preparing a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material provided in the present disclosure is simple in process and convenient in operation, facilitates large-scale industrial production, and reduces the cost.
In one or more embodiments of the present disclosure, the alloying treatment includes a smelting and casting method and a powder alloying method.
In one or more embodiments of the present disclosure, the nickel source is selected from elemental nickel and/or nickel alloy.
In one or more embodiments of the present disclosure, the nickel alloy is one or more selected from the group consisting of magnesium-nickel alloy, nickel-yttrium alloy and zinc-nickel alloy.
In one or more embodiments of the present disclosure, the magnesium source is selected from elemental magnesium and/or magnesium alloy.
In one or more embodiments of the present disclosure, the magnesium alloy is one or more selected from the group consisting of magnesium-gadolinium alloy, magnesium-yttrium alloy, magnesium-zinc alloy, magnesium-nickel alloy, magnesium-calcium alloy and magnesium-iron alloy.
In one or more embodiments of the present disclosure, the rare earth source includes elemental rare earth and/or rare earth intermediate alloy.
Date Re9ue/Date Received 2021-04-20 In one or more embodiments of the present disclosure, the elemental rare earth includes one or more selected from the group consisting of gadolinium, yttrium, erbium, dysprosium, cerium and scandium.
In one or more embodiments of the present disclosure, the rare earth intermediate alloy includes at least one selected from the group consisting of 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 alloy and nickel-scandium alloy.
In one or more embodiments of the present disclosure, the alloying treatment is carried out by adopting the smelting and casting method, including following steps:
(a) casting: uniformly mixing a nickel source, a magnesium source and a rare earth source, and carrying out smelting and casting to obtain a magnesium alloy ingot; and (b) heat treatment: carrying out, in sequence, homogenization treatment and extrusion heat deformation treatment on the magnesium alloy ingot to obtain the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material.
In the method for preparing a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material provided in the present disclosure, by carrying out casting and heat treatment in sequence, Mg, Ni and RE in the prepared alloy material form the Mg12NiRE-type long-period stacking ordered phase, the MgxREy phase and the Mg2Ni phase, not only the tensile strength and plasticity of the alloy material are remarkably improved, but also a large number of micro-batteries are formed in the alloy material, so that the generated nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material can be rapidly decomposed, and a downhole fracturing tool made of this magnesium alloy material can be completely degraded downhole, so that the engineering difficulty is reduced, and the construction efficiency is improved.
In one or more embodiments of the present disclosure, the step (b) also includes an aging heat treatment step, which is carried out after the extrusion heat deformation treatment, wherein the comprehensive performance of the nickel-containing, high-strength and high-toughness, alloy material is more excellent by carrying out the aging heat treatment step.
In one or more embodiments of the present disclosure, in the step (a), when the smelting and casting is carried out, the temperature is first increased to 690-800 C and maintained, the raw materials are stirred to enable them to melt completely, then the temperature is reduced to 630-680 C and maintained for 20-120 min, and after cooling, the magnesium alloy ingot is obtained.
Date Re9ue/Date Received 2021-04-20 In one or more typical but non-limited embodiments of the present disclosure, in the step (a), the temperature after the smelting is, for example, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790 or 800 C.
In one or more embodiments of the present disclosure, during smelting and casting, after all the raw materials melt, a typical but non-limited temperature after temperature reduction is, for example, 630, 635, 640, 645, 650, 655, 660, 665, 670, 675 or 680 C; and the temperature is kept for, for example, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 110 or 120 min after temperature reduction.
In one or more embodiments of the present disclosure, the smelting is carried out using a resistance furnace or a line frequency induction furnace.
In one or more embodiments of the present disclosure, at least one cooling method of brine bath, water bath, water quenching or air cooling is used for cooling.
In one or more embodiments of the present disclosure, in the step (a), the nickel source, the rare earth source and the magnesium source are accurately weighed according to formula requirements, and uniformly mixed.
In one or more embodiments of the present disclosure, the inert gas is used during smelting and casting for protection, wherein the inert gas includes, but is not limited to, helium, argon, carbon dioxide and sulfur hexafluoride, for example, argon.
In one or more embodiments of the present disclosure, in the step (b), the homogenization treatment is carried out at a temperature of 400-550 C for 4-40 h.
In one or more typical but non-limited embodiments of the present disclosure, the homogenization treatment is carried out, for example, at a temperature of 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540 or 550 C; and the homogenization treatment is carried out, for example, for 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35 or 40 h.
In one or more embodiments of the present disclosure, the extrusion heat deformation treatment is carried out at an extrusion ratio of 8-40.
In one or more typical but non-limited embodiments of the present disclosure, the extrusion ratio 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 01 40.
In one or more embodiments of the present disclosure, the extrusion heat deformation treatment is carried out at a temperature of 360-480 C.
In one or more typical but non-limited embodiments of the present disclosure, the extrusion heat deformation treatment is carried out at, for example, a temperature of 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460,470 or 480 C.
11. 0PI21300392CA
Date Re9ue/Date Received 2021-04-20 In one or more embodiments of the present disclosure, in the step (b), the aging heat treatment is carried out at a temperature of 150-250 C for 12-120 h.
In one or more typical but non-limited embodiments of the present disclosure, the aging heat treatment is carried out at, for example, a temperature of 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 230, 240 or 250 C; and the aging heat treatment is carried out, for example, for 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 120 h.
According to a third aspect of the present disclosure, the present disclosure provides use of the above nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material in the field of oil and gas exploitation.
The technical solutions provided in the present disclosure are further described below in connection with embodiments and comparison examples.
Example 1 The present example provides a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, including following components in percentage by mass: 6.9% of Ni, 18% of Y, and the balance of Mg and unavoidable impurities, wherein Mg, Ni and Y form an Mg12YNi-type long-period stacking ordered phase, an Mg5Y phase and an Mg2Ni phase, a volume fraction of the Mgi2YNi-type long-period stacking ordered phase is 66%, a volume fraction of the Mg5Y phase is 4%, and a volume fraction of the Mg2Ni phase is 2%.
A method for preparing a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material provided in the present example includes following steps:
(1) accurately blending materials according to formula amounts, wherein a nickel source, a yttrium source and a magnesium source are added in forms of magnesium-yttrium alloy and nickel-yttrium alloy, respectively;
(2) casting: smelting using a resistance furnace or a line frequency induction furnace, wherein argon is used as a protective gas in the smelting process, increasing the temperature to 770 C and maintaining the temperature, stirring the raw materials by electromagnetic induction so that components are homogeneous and raw materials melt fully, reducing the temperature to 655 C after the raw materials melt completely, standing and maintaining the temperature for 25 min, taking out the molten materials to undergo salt bath water cooling to obtain an alloy ingot; and (3) heat treatment: carrying out homogenization treatment, extrusion heat deformation treatment and aging heat treatment on the magnesium alloy ingot in sequence, and air-cooling the magnesium alloy ingot to room temperature to obtain the nickel-containing, high-strength and high-toughness, controllably Date Re9ue/Date Received 2021-04-20 degradable magnesium alloy material, wherein the homogenization treatment is carried out at a temperature of 500 C for 10 h; and the extrusion deformation is carried out at a temperature of 400 C, and an extrusion ratio is 11.
Example 2 The present example provides a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, including following components in percentage by mass: 2.3% of Ni, 5.3% of Y, and the balance of Mg and unavoidable impurities, wherein Mg, Ni and Y form an Mg12YNi-type long-period stacking ordered phase, an Mg5Y phase and an Mg2Ni phase, a volume fraction of the Mg12YNI-type long-period stacking ordered phase is 23%, a volume fraction of the Mg5Y phase is 6%, and a volume fraction of the Mg2Ni phase is 1.8%.
A method for preparing a degradable magnesium alloy material provided in the present example is the same as that of Example 1, and unnecessary details will not be given herein.
Example 3 The present example provides a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, including following components in percentage by mass: 8.5% of Gd, 4.5% of Y, 0.5 % of Ni, 0.8% of Mn, and the balance of Mg and unavoidable impurities, wherein Mg, Gd, Y and Ni form an Mg12YNi-type long-period stacking ordered phase, an Mg12GdNi-type long-period stacking ordered phase, an Mg5Gd phase, an Mg5Y phase and an Mg2Ni phase, and wherein a volume fraction of the two long-period stacking ordered phases is 15%, a volume fraction of the Mg5Gd phase and the Mg5Y phase is 12%, and a volume fraction of the Mg2Ni phase is 1.2%.
A method for preparing a degradable magnesium alloy material provided in the present example is different from the preparation method provided in Example 1 in that the homogenization treatment is carried out at a temperature of 540 C for 4 h; the extrusion deformation is carried out at a temperature of 450 C, and an extrusion ratio is 11; and the aging heat treatment is carried out at a temperature of 200 C for 50 h. All of other steps are the same as those in the preparation method in Example 1, and unnecessary details will not be given herein.
Example 4 The present example provides a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, including following components in percentage by mass: 4% of Gd, 4% of Er, 0.8% of Ni, and the balance of Mg and unavoidable impurities, wherein Mg, Gd, Er and Ni form an Mg12GdNi-type long-period stacking ordered phase, an Mg12ErNi-type long-period stacking ordered phase, an Mg5Gd phase, an Mg5Er phase and an Mg2Ni phase, and wherein a volume fraction of the two long-period Date Re9ue/Date Received 2021-04-20 stacking ordered phases is 10.5%, a volume fraction of the Mg5Gd phase and the Mg5Er phase is 8%, and a volume fraction of the Mg2Ni phase is 1.2%.
A method for preparing a degradable magnesium alloy material provided in the present example is different from the preparation method provided in Example 1 in that the homogenization treatment is carried out at a temperature of 450 C for 12 h; and the extrusion deformation is carried out at a temperature of 450 C, and an extrusion ratio is 28. All of other steps are the same as those in the preparation method in Example 1, and unnecessary details will not be given herein.
Example 5 The present example provides a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, including following components in percentage by mass: 19% of Dy, 2.9% of Ni, and the balance of Mg and unavoidable impurities, wherein Mg, Ni and Dy form an Mg12DyNi-type long-period stacking ordered phase, an Mg5Dy phase and an Mg2Ni phase, and wherein a volume fraction of the Mgi2DyNi-type long-period stacking ordered phase is 24%, a volume fraction of the Mg5Dy phase is 11%, and a volume fraction of the Mg2Ni phase is 1.5%.
A method for preparing a degradable magnesium alloy material provided in the present example is different from the preparation method provided in Example 1 in that the homogenization treatment is carried out at a temperature of 540 C for 6 h; the extrusion deformation is carried out at a temperature of 360 C, and an extrusion ratio is 28; and the aging heat treatment is carried out at a temperature of 200 C for 60 h. All of other steps are the same as those in the preparation method in Example 1, and unnecessary details will not be given herein.
Example 6 The present example provides a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, including following components in percentage by mass: 1% of Ce, 0.5% of Zr, 1% of Ni, and the balance of Mg and unavoidable impurities, wherein Mg, Ni, Ce and Zr form an Mg12CeNi-type long-period stacking ordered phase, an Mg12ZrNi-type long-period stacking ordered phase, an Mg5Zr phase, an Mg5Ce phase and an Mg2Ni phase, and wherein a volume fraction of the long-period stacking ordered phases is 4.8%, a volume fraction of the Mg5Zr phase and the Mg5Ce phase is 2%, and a volume fraction of the Mg2Ni phase is 4%.
A method for preparing a degradable magnesium alloy material provided in the present example is the same as the preparation method provided in Example 4, and unnecessary details will not be given herein.
Example 7 The present example provides a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, including following components in percentage by mass: 6% of Er, 7.5% of Ni, and the balance of Mg and unavoidable impurities, wherein Mg, Er and Ni form an Date Re9ue/Date Received 2021-04-20 Mgi2ErNi-type long-period stacking ordered phase, an Mg5Er phase and an Mg2Ni phase, and wherein a volume fraction of the Mg12ErNi-type long-period stacking ordered phase is 65%, a volume fraction of the Mg5Er phase is 3%, and a volume fraction of the Mg2Ni phase is 5%.
A method for preparing a degradable magnesium alloy material provided in the present example is different from the preparation method provided in Example 1 in that the homogenization treatment is carried out at a temperature of 500 C for 10 h; and the extrusion deformation is carried out at a temperature of 400 C, and an extrusion ratio is 11. All of other steps are the same as those in the preparation method in Example 1, and unnecessary details will not be given herein.
Example 8 The present example provides a controllably degradable magnesium alloy material, including following components in percentage by mass: 8.0% of Gd, 5.0% of Y, 1.5% of Ni, 0.8% of Mn, and the balance of Mg and unavoidable impurities, wherein Mg, Gd, Y and Ni form Mg12GdNi type and Mg12GdY-type long-period stacking ordered phases and Mg24Y5 and Mg5Gd phases, and wherein a volume fraction of the Mg12GdNi-type and Mgi2GdY-type long-period stacking ordered phases is 20%, a volume fraction of the Mg24Y5 and Mg5Gd phases is 12%, and a volume fraction of the Mg2Ni phase is 2%.
A method for preparing the degradable magnesium alloy material provided in the present example is different from the preparation method provided in Example 1 in that the homogenization treatment is carried out at a temperature of 540 C for 4 h; the extrusion deformation is carried out at a temperature of 400 C, and an extrusion ratio is 11; and the aging heat treatment is carried out at a temperature of 200 C for 50 h. All of other steps are the same as those in the preparation method in Example 1, and unnecessary details will not be given herein.
In the above Examples 1-8, contents of the unavoidable impurities in the magnesium alloy material are all less than 0.2%.
Comparative Example 1 The present comparative example provides a magnesium alloy material, which is different from Example 1 in that no Ni is contained, and that the magnesium-yttrium alloy is prepared according to a conventional method.
Comparative Example 2 The present comparative example provides a magnesium alloy material, which is different from Example 1 in that no Y is contained, and that the magnesium-nickel alloy is prepared according to a conventional method.
Comparative Example 3 The present comparative example provides a magnesium alloy material, which is different from Example 1 in that Ni is 0.1% in percentage by mass. A
[16] The method according to [14] , wherein the magnesium alloy is at least one selected from the group consisting of magnesium-gadolinium alloy, magnesium-yttrium alloy, magnesium-zinc alloy, magnesium-nickel alloy, magnesium-calcium alloy and magnesium-iron alloy.
[16] The method according to [11] , wherein the at least one rare earth element source comprises elemental rare earth and/or rare earth intermediate alloy.
5c Date Recue/Date Received 2023-07-28 [17] The method according to [16], wherein the elemental rare earth comprises at least one selected from the group consisting of gadolinium, yttrium, erbium, dysprosium, cerium and scandium.
[18] The method according to [16], wherein the rare earth intermediate alloy comprises at least one selected from the group consisting of magnesium-gadolinium alloy, magnesium-yttrium alloy, magnesium-erbium alloy, magnesium-cerium alloy, magnesium-scandium alloy, nickel-yttri urn alloy, nickel-gadolini urn alloy, nickel-erbium alloy, nickel-cerium alloy and nickel-scandium alloy.
[19] The method according to [11], wherein the aging heat treatment is carried out at a temperature of 150 C to 250 C for 12 h to 120 h.
[20] The method according to [11] or [19], wherein the aging heat treatment is carried out at a temperature of 180 C to 220 C for 15 h to 60 h.
[21] The method according to [11], wherein the cooling is obtained by a cooling method which is at least one selected from the group consisting of brine bath, water quenching, furnace cooling and air cooling.
[22] The method according to any one of [11] to [21], wherein an inert gas is used during the smelting and casting for protection.
[23] The method according to [22], wherein the inert gas is at least one selected from the group consisting of helium, argon, carbon dioxide and sulfur hexafluoride.
[24] The method according to [23], wherein the inert gas is argon.
[25] The method according to any one of [11] to [24], wherein the smelting is carried out using a resistance furnace or a line frequency induction furnace.
[26] The method according to any one of [11] to [25], wherein in the step (b), the homogenization treatment is carried out at a temperature of 400 C to 550 C for 4h to 40h.
[27] The method according to [26], wherein in the step (b), the extrusion heat deformation treatment is carried out at an extrusion ratio of 8 to 40.
5d Date Recue/Date Received 2023-07-28 [28] The method according to [27], wherein the extrusion heat deformation treatment is carried out at a temperature of 360 C to 480 C.
[29] A magnesium alloy material which is a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, obtained from the method defined in any one of [1] to [28].
[30] A use of the magnesium alloy material as defined in [29] in a field of oil and gas exploitation.
Detailed Description of Embodiments Embodiments of the present disclosure will be described in detail below in combination with examples, while a person skilled in the art would understand that the following examples are merely used for illustrating the present disclosure, but should not be considered as limitation on the scope of the present disclosure. If no specific conditions are specified in the examples, they are carried out under normal conditions or conditions recommended by manufacturers. If manufacturers of reagents or apparatuses used are not specified, they are all conventional products commercially available.
According to one aspect of the present disclosure, the present disclosure provides a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, including following components in percentage by mass:
0.3-8.5% of Ni, 0.5-28% of RE, and the balance of Mg and unavoidable impurities, wherein RE is a rare earth element, and Mg, Ni 5e Date Recue/Date Received 2023-07-28 and RE mainly form an Mg12RENi-type long-period stacking ordered phase, an Mg2Ni phase and an MgxREy phase.
A volume fraction of the Mg12RENi-type long-period stacking ordered phase is 3-70%, a volume fraction of the Mg2Ni phase is 0.5-10%, and a volume fraction of the MgxREy phase is 0.5-22%.
In one or more embodiments, the content of the unavoidable impurities in the magnesium alloy material, in percentage by mass, is not higher than 0.2%.
In one or more embodiments, the long-period stacking ordered phase (LPSO), a new reinforcing phase in magnesium alloy, is formed by periodic changes in atomic position or chemical composition in a crystal structure, and the long-period structure is divided into two aspects, namely, stacking order and chemical composition order, and the Mg12RENi-type long-period stacking ordered phase in one or more embodiments is a result of combined effect of both stacking order and chemical composition order.
In the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material provided in the present disclosure, a typical but non-limited content of Ni (nickel), in percentage by mass, is, for example, 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%.
In the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material provided in the present disclosure, a typical but non-limited content of RE, in percentage by mass, is, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25% or 28%.
In one or more embodiments, the volume fraction of the Mgi2REN1-type long-period stacking ordered phase is 3-70%, the volume fraction of the Mg5RE phase is 0.5-20%, the volume fraction of the Mg2Ni phase is 0.5-10%, the volume fraction of the MgxREy phase is 0.5-22%, and a value range of x:y is (3-12):1 (i.e., 3:1-12:1).
By setting the volume fraction of the Mg12RENi-type long-period stacking ordered phase to be 3-70%, the volume fraction of the Mg2Ni phase to be 0.5-10%, and the volume fraction of the MgxREy phase to be 0.5-22%, the Mg12RENi-type long-period stacking ordered phase and the MgxREy phase remarkably improve the tensile strength of the alloy material, and enable the alloy to maintain certain plasticity; and meanwhile, a relatively large potential difference exists between the Mg12RENi-type long-period stacking ordered phase and the Mg2Ni phase, and the magnesium matrix, and a large number of micro-batteries are formed, so that the generated alloy material can be rapidly decomposed, which effectively meets the requirements of the field of oil and gas exploitation on downhole tool materials.
In one or more embodiments, in the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, a typical but non-limited volume fraction of the Mg12RENi-type long-period stacking Date Re9ue/Date Received 2021-04-20 ordered phase is, for example, 3%, 4%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70%; a typical but non-limited volume fraction of the Mg2Ni phase is, for example, 0.5%, 1%, 1.5%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9% or 10%; a typical but non-limited volume fraction of the MgxREy phase is, for example, 0.5%, 1%, 2%, 5%, 8%, 10%, 12%, 15%, 18%, 20% or 22%; and a typical but non-limited numerical value of x:y is 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 high-toughness, controllably degradable magnesium alloy material provided in the present disclosure takes magnesium as a base material, and the Mg12RENi-type long-period stacking ordered phase and the MgxREy phase are formed by adding Ni and RE, so that the tensile strength of the alloy material is remarkably improved;
meanwhile, a quite large electronegativity difference exists between the Mg12RENI-type long-period stacking ordered phase and the Mg2Ni phase, and the magnesium matrix, and a large number of micro-batteries are formed, so that the generated nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material can be rapidly decomposed, and the downhole fracturing tool made of this magnesium alloy material can effectively meet the requirements of the field of oil and gas exploitation.
Besides, when applied to the field of oil and gas exploitation, the controllably degradable alloy material provided in the present disclosure can be degraded completely downhole after accomplishing a task, and discharged through a pipe-line, without problems of easy blocking or jam, thus leaving out the drilling and grinding recycling process, reducing the engineering degree of difficulty, and improving the construction efficiency.
In one or more embodiments of the present disclosure, when Ni is 0.5-7.5%
and RE is 1.5-19%, in the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material; and the volume fraction of the Mg12RENi-type long-period stacking ordered phase is 4.8-65%, the volume fraction of the Mg5RE phase is 1-15%, and the volume fraction of the Mg2Ni phase is 1-5%, the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material has the tensile strength of 325-505 MPa, the yield strength of 156-415 MPa, and the elongation of 6.0-21.8% at room temperature, and the decomposition rate of 363 mmia - 2500 rnm/a in a 3.5wt% KCI solution at 90 C.
In one or more embodiments of the present disclosure, the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material includes as-cast magnesium alloy, as-extruded magnesium alloy and aged magnesium alloy.
In one or more embodiments of the present disclosure, in the as-cast magnesium alloy, Mg, Ni and RE mainly form an Mgi2RENi-type long-period stacking ordered phase, an Mg2Ni phase and an Mg5RE phase, wherein a volume fraction of the Mgi2NiRE-type long-period stacking ordered phase is 3-65%, a volume fraction of the Mg2Ni phase is 0.5-6%, and a volume fraction of the Mg5RE phase is 0.5-15%.
Date Re9ue/Date Received 2021-04-20 In one or more embodiments of the present disclosure, in the as-cast magnesium alloy, a typical but non-limited volume fraction of the Mg12N1RE-type long-period stacking ordered phase is, for example, 3%, 4%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60% or 65%; a typical but non-limited volume fraction of the Mg2Ni phase is, for example, 0.5%, 0.8%, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%
or 6%; and a typical but non-limited volume fraction of the Mg5RE phase is, for example, 0.5%, 0.8%, 1%, 2%, 5%, 8%, 10%, 12% or 15%.
In one or more embodiments of the present disclosure, in the as-extruded magnesium alloy, Mg, Ni and RE mainly form an Mgi2RENi-type long-period stacking ordered phase, an Mg2Ni phase and an Mg5RE phase, wherein a volume fraction of the Mg12NiRE-type long-period stacking ordered phase is 4-70%, a volume fraction of the Mg2Ni phase is 1%-8%, and a volume fraction of the Mg5RE phase is 1-20%.
In one or more embodiments of the present disclosure, in the as-extruded magnesium alloy, a typical but non-limited volume fraction of the Mg12NiRE-type long-period stacking ordered phase is, for example, 4%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70%; a typical but non-limited volume fraction of the Mg2Ni phase is, for example, 1%, 1.5%, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5% or 8%; and a typical but non-limited volume fraction of the Mg5RE
phase is, for example, 1%, 2%, 5%, 8%, 10%, 12%, 15%, 18% or 20%.
In one or more embodiments of the present disclosure, in the aged magnesium alloy, Mg, Ni and RE mainly form an Mg12RENi-type long-period stacking ordered phase, an Mg2Ni phase and MgxREy phase (x:y=(3-12):1), wherein a volume fraction of the Mg12NiRE-type long-period stacking ordered phase is 4-70%, a volume fraction of the Mg2Ni phase is 2%-10%, and a volume fraction of the Mg5RE phase is 2-22%.
In one or more embodiments of the present disclosure, in the aged magnesium alloy, a typical but non-limited volume fraction of the Mg12NiRE-type long-period stacking ordered phase is, for example, 4%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 25%, 30%, 35%, 40%, 45%, 50%, 55%, 60%, 65% or 70%; a typical but non-limited volume fraction of the Mg2Ni phase is, for example, 2%, 2.5%, 3%, 3.5%, 4%, 4.5%, 5%, 5.5%, 6%, 6.5%, 7%, 7.5%, 8%, 9% or 10%; a typical but non-limited volume fraction of the MgxREy phase is, for example, 2%, 5%, 8%, 10%, 12%, 15%, 18%, 20% or 22%, wherein a typical but non-limited numerical value of x:y is, for example, 3:1, 4:1, 5:1, 6:1, 7:1, 8:1, 9:1, 10:1, 11:1 or 12:1.
In one or more embodiments of the present disclosure, RE is one or more selected from the group consisting of Gd, Y, Er, Dy, Ce and Sc.
In one or more embodiments of the present disclosure, the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material includes following components in percentage by mass: 0.3-8.5% of Ni, 0.5-28% of RE, 0.03-10% of M, and the balance of Mg and unavoidable impurities, wherein M is an element capable of alloying with magnesium.
Date Re9ue/Date Received 2021-04-20 In one or more embodiments of the present disclosure, in the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, a typical but non-limited percentage by mass of Ni is, for example, 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%; a typical but non-limited percentage by mass of RE is, for example, 0.5%, 1%, 2%, 3%, 4%, 5%, 8%, 10%, 12%, 15%, 18%, 20%, 22%, 25% or 28%; and a typical but non-limited percentage by mass of M is, for example, 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%.
In one or more embodiments of the present disclosure, M includes, but is not limited to at least one of Fe, Cu and Mn.
According to a second aspect of the present disclosure, the present disclosure provides a method for preparing the above nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, including the following step:
uniformly mixing a nickel source, a magnesium source and a rare earth source, and carrying out alloying treatment to obtain the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material.
The method for preparing a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material provided in the present disclosure is simple in process and convenient in operation, facilitates large-scale industrial production, and reduces the cost.
In one or more embodiments of the present disclosure, the alloying treatment includes a smelting and casting method and a powder alloying method.
In one or more embodiments of the present disclosure, the nickel source is selected from elemental nickel and/or nickel alloy.
In one or more embodiments of the present disclosure, the nickel alloy is one or more selected from the group consisting of magnesium-nickel alloy, nickel-yttrium alloy and zinc-nickel alloy.
In one or more embodiments of the present disclosure, the magnesium source is selected from elemental magnesium and/or magnesium alloy.
In one or more embodiments of the present disclosure, the magnesium alloy is one or more selected from the group consisting of magnesium-gadolinium alloy, magnesium-yttrium alloy, magnesium-zinc alloy, magnesium-nickel alloy, magnesium-calcium alloy and magnesium-iron alloy.
In one or more embodiments of the present disclosure, the rare earth source includes elemental rare earth and/or rare earth intermediate alloy.
Date Re9ue/Date Received 2021-04-20 In one or more embodiments of the present disclosure, the elemental rare earth includes one or more selected from the group consisting of gadolinium, yttrium, erbium, dysprosium, cerium and scandium.
In one or more embodiments of the present disclosure, the rare earth intermediate alloy includes at least one selected from the group consisting of 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 alloy and nickel-scandium alloy.
In one or more embodiments of the present disclosure, the alloying treatment is carried out by adopting the smelting and casting method, including following steps:
(a) casting: uniformly mixing a nickel source, a magnesium source and a rare earth source, and carrying out smelting and casting to obtain a magnesium alloy ingot; and (b) heat treatment: carrying out, in sequence, homogenization treatment and extrusion heat deformation treatment on the magnesium alloy ingot to obtain the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material.
In the method for preparing a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material provided in the present disclosure, by carrying out casting and heat treatment in sequence, Mg, Ni and RE in the prepared alloy material form the Mg12NiRE-type long-period stacking ordered phase, the MgxREy phase and the Mg2Ni phase, not only the tensile strength and plasticity of the alloy material are remarkably improved, but also a large number of micro-batteries are formed in the alloy material, so that the generated nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material can be rapidly decomposed, and a downhole fracturing tool made of this magnesium alloy material can be completely degraded downhole, so that the engineering difficulty is reduced, and the construction efficiency is improved.
In one or more embodiments of the present disclosure, the step (b) also includes an aging heat treatment step, which is carried out after the extrusion heat deformation treatment, wherein the comprehensive performance of the nickel-containing, high-strength and high-toughness, alloy material is more excellent by carrying out the aging heat treatment step.
In one or more embodiments of the present disclosure, in the step (a), when the smelting and casting is carried out, the temperature is first increased to 690-800 C and maintained, the raw materials are stirred to enable them to melt completely, then the temperature is reduced to 630-680 C and maintained for 20-120 min, and after cooling, the magnesium alloy ingot is obtained.
Date Re9ue/Date Received 2021-04-20 In one or more typical but non-limited embodiments of the present disclosure, in the step (a), the temperature after the smelting is, for example, 690, 700, 710, 720, 730, 740, 750, 760, 770, 780, 790 or 800 C.
In one or more embodiments of the present disclosure, during smelting and casting, after all the raw materials melt, a typical but non-limited temperature after temperature reduction is, for example, 630, 635, 640, 645, 650, 655, 660, 665, 670, 675 or 680 C; and the temperature is kept for, for example, 20, 25, 30, 35, 40, 45, 50, 60, 70, 80, 90, 100, 110 or 120 min after temperature reduction.
In one or more embodiments of the present disclosure, the smelting is carried out using a resistance furnace or a line frequency induction furnace.
In one or more embodiments of the present disclosure, at least one cooling method of brine bath, water bath, water quenching or air cooling is used for cooling.
In one or more embodiments of the present disclosure, in the step (a), the nickel source, the rare earth source and the magnesium source are accurately weighed according to formula requirements, and uniformly mixed.
In one or more embodiments of the present disclosure, the inert gas is used during smelting and casting for protection, wherein the inert gas includes, but is not limited to, helium, argon, carbon dioxide and sulfur hexafluoride, for example, argon.
In one or more embodiments of the present disclosure, in the step (b), the homogenization treatment is carried out at a temperature of 400-550 C for 4-40 h.
In one or more typical but non-limited embodiments of the present disclosure, the homogenization treatment is carried out, for example, at a temperature of 400, 410, 420, 430, 440, 450, 460, 470, 480, 490, 500, 510, 520, 530, 540 or 550 C; and the homogenization treatment is carried out, for example, for 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 20, 25, 30, 35 or 40 h.
In one or more embodiments of the present disclosure, the extrusion heat deformation treatment is carried out at an extrusion ratio of 8-40.
In one or more typical but non-limited embodiments of the present disclosure, the extrusion ratio 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 01 40.
In one or more embodiments of the present disclosure, the extrusion heat deformation treatment is carried out at a temperature of 360-480 C.
In one or more typical but non-limited embodiments of the present disclosure, the extrusion heat deformation treatment is carried out at, for example, a temperature of 360, 370, 380, 390, 400, 410, 420, 430, 440, 450, 460,470 or 480 C.
11. 0PI21300392CA
Date Re9ue/Date Received 2021-04-20 In one or more embodiments of the present disclosure, in the step (b), the aging heat treatment is carried out at a temperature of 150-250 C for 12-120 h.
In one or more typical but non-limited embodiments of the present disclosure, the aging heat treatment is carried out at, for example, a temperature of 150, 155, 160, 165, 170, 175, 180, 185, 190, 195, 200, 205, 210, 215, 220, 230, 240 or 250 C; and the aging heat treatment is carried out, for example, for 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 120 h.
According to a third aspect of the present disclosure, the present disclosure provides use of the above nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material in the field of oil and gas exploitation.
The technical solutions provided in the present disclosure are further described below in connection with embodiments and comparison examples.
Example 1 The present example provides a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, including following components in percentage by mass: 6.9% of Ni, 18% of Y, and the balance of Mg and unavoidable impurities, wherein Mg, Ni and Y form an Mg12YNi-type long-period stacking ordered phase, an Mg5Y phase and an Mg2Ni phase, a volume fraction of the Mgi2YNi-type long-period stacking ordered phase is 66%, a volume fraction of the Mg5Y phase is 4%, and a volume fraction of the Mg2Ni phase is 2%.
A method for preparing a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material provided in the present example includes following steps:
(1) accurately blending materials according to formula amounts, wherein a nickel source, a yttrium source and a magnesium source are added in forms of magnesium-yttrium alloy and nickel-yttrium alloy, respectively;
(2) casting: smelting using a resistance furnace or a line frequency induction furnace, wherein argon is used as a protective gas in the smelting process, increasing the temperature to 770 C and maintaining the temperature, stirring the raw materials by electromagnetic induction so that components are homogeneous and raw materials melt fully, reducing the temperature to 655 C after the raw materials melt completely, standing and maintaining the temperature for 25 min, taking out the molten materials to undergo salt bath water cooling to obtain an alloy ingot; and (3) heat treatment: carrying out homogenization treatment, extrusion heat deformation treatment and aging heat treatment on the magnesium alloy ingot in sequence, and air-cooling the magnesium alloy ingot to room temperature to obtain the nickel-containing, high-strength and high-toughness, controllably Date Re9ue/Date Received 2021-04-20 degradable magnesium alloy material, wherein the homogenization treatment is carried out at a temperature of 500 C for 10 h; and the extrusion deformation is carried out at a temperature of 400 C, and an extrusion ratio is 11.
Example 2 The present example provides a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, including following components in percentage by mass: 2.3% of Ni, 5.3% of Y, and the balance of Mg and unavoidable impurities, wherein Mg, Ni and Y form an Mg12YNi-type long-period stacking ordered phase, an Mg5Y phase and an Mg2Ni phase, a volume fraction of the Mg12YNI-type long-period stacking ordered phase is 23%, a volume fraction of the Mg5Y phase is 6%, and a volume fraction of the Mg2Ni phase is 1.8%.
A method for preparing a degradable magnesium alloy material provided in the present example is the same as that of Example 1, and unnecessary details will not be given herein.
Example 3 The present example provides a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, including following components in percentage by mass: 8.5% of Gd, 4.5% of Y, 0.5 % of Ni, 0.8% of Mn, and the balance of Mg and unavoidable impurities, wherein Mg, Gd, Y and Ni form an Mg12YNi-type long-period stacking ordered phase, an Mg12GdNi-type long-period stacking ordered phase, an Mg5Gd phase, an Mg5Y phase and an Mg2Ni phase, and wherein a volume fraction of the two long-period stacking ordered phases is 15%, a volume fraction of the Mg5Gd phase and the Mg5Y phase is 12%, and a volume fraction of the Mg2Ni phase is 1.2%.
A method for preparing a degradable magnesium alloy material provided in the present example is different from the preparation method provided in Example 1 in that the homogenization treatment is carried out at a temperature of 540 C for 4 h; the extrusion deformation is carried out at a temperature of 450 C, and an extrusion ratio is 11; and the aging heat treatment is carried out at a temperature of 200 C for 50 h. All of other steps are the same as those in the preparation method in Example 1, and unnecessary details will not be given herein.
Example 4 The present example provides a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, including following components in percentage by mass: 4% of Gd, 4% of Er, 0.8% of Ni, and the balance of Mg and unavoidable impurities, wherein Mg, Gd, Er and Ni form an Mg12GdNi-type long-period stacking ordered phase, an Mg12ErNi-type long-period stacking ordered phase, an Mg5Gd phase, an Mg5Er phase and an Mg2Ni phase, and wherein a volume fraction of the two long-period Date Re9ue/Date Received 2021-04-20 stacking ordered phases is 10.5%, a volume fraction of the Mg5Gd phase and the Mg5Er phase is 8%, and a volume fraction of the Mg2Ni phase is 1.2%.
A method for preparing a degradable magnesium alloy material provided in the present example is different from the preparation method provided in Example 1 in that the homogenization treatment is carried out at a temperature of 450 C for 12 h; and the extrusion deformation is carried out at a temperature of 450 C, and an extrusion ratio is 28. All of other steps are the same as those in the preparation method in Example 1, and unnecessary details will not be given herein.
Example 5 The present example provides a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, including following components in percentage by mass: 19% of Dy, 2.9% of Ni, and the balance of Mg and unavoidable impurities, wherein Mg, Ni and Dy form an Mg12DyNi-type long-period stacking ordered phase, an Mg5Dy phase and an Mg2Ni phase, and wherein a volume fraction of the Mgi2DyNi-type long-period stacking ordered phase is 24%, a volume fraction of the Mg5Dy phase is 11%, and a volume fraction of the Mg2Ni phase is 1.5%.
A method for preparing a degradable magnesium alloy material provided in the present example is different from the preparation method provided in Example 1 in that the homogenization treatment is carried out at a temperature of 540 C for 6 h; the extrusion deformation is carried out at a temperature of 360 C, and an extrusion ratio is 28; and the aging heat treatment is carried out at a temperature of 200 C for 60 h. All of other steps are the same as those in the preparation method in Example 1, and unnecessary details will not be given herein.
Example 6 The present example provides a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, including following components in percentage by mass: 1% of Ce, 0.5% of Zr, 1% of Ni, and the balance of Mg and unavoidable impurities, wherein Mg, Ni, Ce and Zr form an Mg12CeNi-type long-period stacking ordered phase, an Mg12ZrNi-type long-period stacking ordered phase, an Mg5Zr phase, an Mg5Ce phase and an Mg2Ni phase, and wherein a volume fraction of the long-period stacking ordered phases is 4.8%, a volume fraction of the Mg5Zr phase and the Mg5Ce phase is 2%, and a volume fraction of the Mg2Ni phase is 4%.
A method for preparing a degradable magnesium alloy material provided in the present example is the same as the preparation method provided in Example 4, and unnecessary details will not be given herein.
Example 7 The present example provides a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, including following components in percentage by mass: 6% of Er, 7.5% of Ni, and the balance of Mg and unavoidable impurities, wherein Mg, Er and Ni form an Date Re9ue/Date Received 2021-04-20 Mgi2ErNi-type long-period stacking ordered phase, an Mg5Er phase and an Mg2Ni phase, and wherein a volume fraction of the Mg12ErNi-type long-period stacking ordered phase is 65%, a volume fraction of the Mg5Er phase is 3%, and a volume fraction of the Mg2Ni phase is 5%.
A method for preparing a degradable magnesium alloy material provided in the present example is different from the preparation method provided in Example 1 in that the homogenization treatment is carried out at a temperature of 500 C for 10 h; and the extrusion deformation is carried out at a temperature of 400 C, and an extrusion ratio is 11. All of other steps are the same as those in the preparation method in Example 1, and unnecessary details will not be given herein.
Example 8 The present example provides a controllably degradable magnesium alloy material, including following components in percentage by mass: 8.0% of Gd, 5.0% of Y, 1.5% of Ni, 0.8% of Mn, and the balance of Mg and unavoidable impurities, wherein Mg, Gd, Y and Ni form Mg12GdNi type and Mg12GdY-type long-period stacking ordered phases and Mg24Y5 and Mg5Gd phases, and wherein a volume fraction of the Mg12GdNi-type and Mgi2GdY-type long-period stacking ordered phases is 20%, a volume fraction of the Mg24Y5 and Mg5Gd phases is 12%, and a volume fraction of the Mg2Ni phase is 2%.
A method for preparing the degradable magnesium alloy material provided in the present example is different from the preparation method provided in Example 1 in that the homogenization treatment is carried out at a temperature of 540 C for 4 h; the extrusion deformation is carried out at a temperature of 400 C, and an extrusion ratio is 11; and the aging heat treatment is carried out at a temperature of 200 C for 50 h. All of other steps are the same as those in the preparation method in Example 1, and unnecessary details will not be given herein.
In the above Examples 1-8, contents of the unavoidable impurities in the magnesium alloy material are all less than 0.2%.
Comparative Example 1 The present comparative example provides a magnesium alloy material, which is different from Example 1 in that no Ni is contained, and that the magnesium-yttrium alloy is prepared according to a conventional method.
Comparative Example 2 The present comparative example provides a magnesium alloy material, which is different from Example 1 in that no Y is contained, and that the magnesium-nickel alloy is prepared according to a conventional method.
Comparative Example 3 The present comparative example provides a magnesium alloy material, which is different from Example 1 in that Ni is 0.1% in percentage by mass. A
15 0PI21300392CA
Date Re9ue/Date Received 2021-04-20 method for preparing the magnesium alloy material is the same as that in Example 1, and unnecessary details will not be given herein.
Comparative Example 4 The present comparative example provides a magnesium alloy material, which is different from Example 1 in that Ni is 10 % in percentage by mass. A
method for preparing the magnesium alloy material is the same as that in Example 1, and unnecessary details will not be given herein.
Comparative Example 5 The present comparative example provides a magnesium alloy material, which is different from Example 1 in that Y is 0.1 % in percentage by mass. A
method for preparing the magnesium alloy material is the same as that in Example 1, and unnecessary details will not be given herein.
Comparative Example 6 The present comparative example provides a magnesium alloy material, which is different from Example 1 in that Y is 25% in percentage by mass. A
method for preparing the magnesium alloy material is the same as that in Example 1, and unnecessary details will not be given herein.
Test Example 1 The magnesium alloy materials provided in Examples 1-7 are respectively measured for tensile strength, yield strength, elongation and corrosion rate, wherein the tensile strength, the yield strength and the elongation are measured at room temperature, a test direction of the tensile strength is an extrusion direction (0 ), a tensile speed is 2 mm/min, and a corrosion rate is measured at 90 C in a 3.5wt% KCl solution. Results are shown in Table 1.
Table 1 Table of Property Data of Magnesium Alloy Materials Tensile Group Strength Yield Strength Elongation Corrosion Rate (MPa) (MPa) (`%) (mm a) Example 1 445 345 11.3 1800 Example 2 404 313 8.9 834 Example 3 402 298 10.8 407 Example 4 409 187 20.1 635 Example 5 325 156 21.8 785 Example 6 267 185 21 363 Example 7 355 282 17 2100 Example 8 505 415 6.0 1300 Comparative 410 315 2 10 Example 1 Comparative Example 2 Date Re9ue/Date Received 2021-04-20 Comparative 425 320 3.5 98 Example 3 Comparative Example 4 Comparative 168 85 5.3 1850 Example 5 Comparative Example 6 Notes: "-" indicates that the material is brittle, which has an extremely low elongation and cannot be put into use.
It can be seen from Table 1 that the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy materials provided in Examples 1-7 have the tensile strength of 267-505 MPa, the yield strength of 156-415 MPa, and the elongation of 6.0-21.8% at room temperature, and has the decomposition rate of 363 mm/a - 2100 mm/a in a 3.5wt% KCI
solution at 90 C, which indicates that the magnesium alloy material provided in the present disclosure has remarkably improved mechanical properties by adding specific contents of nickel and rare earth element to magnesium acting as a base material, and the degradation rate of the magnesium alloy material can meet the use requirement of self-ablation of downhole tools in the field of petroleum and natural gas.
Finally, it should be noted that the various embodiments above are merely used for illustrating the technical solutions of the present disclosure, rather than limiting the present disclosure; although the detailed description is made to the present disclosure with reference to various preceding embodiments, those ordinarily skilled in the art should understand that they still could modify the technical solutions recited in various preceding embodiments, or make equivalent substitutions to some or all of the technical features therein; and these modifications or substitutions do not make the corresponding technical solutions essentially depart from the scope of the technical solutions of various embodiments of the present disclosure.
Industrial Applicability The method for preparing a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material provided in the present disclosure can be carried out in batch in industry and is simple in process, convenient in operation, facilitates large-scale industrial production, and reduces the production cost, the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material prepared with this method has remarkably improved tensile strength and plasticity of alloy materials and other advantages, moreover, the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material prepared with this method can be rapidly decomposed, and the downhole fracturing tools made of this magnesium alloy material can effectively meet requirements in the field of oil and gas exploitation.
Date Re9ue/Date Received 2021-04-20
Date Re9ue/Date Received 2021-04-20 method for preparing the magnesium alloy material is the same as that in Example 1, and unnecessary details will not be given herein.
Comparative Example 4 The present comparative example provides a magnesium alloy material, which is different from Example 1 in that Ni is 10 % in percentage by mass. A
method for preparing the magnesium alloy material is the same as that in Example 1, and unnecessary details will not be given herein.
Comparative Example 5 The present comparative example provides a magnesium alloy material, which is different from Example 1 in that Y is 0.1 % in percentage by mass. A
method for preparing the magnesium alloy material is the same as that in Example 1, and unnecessary details will not be given herein.
Comparative Example 6 The present comparative example provides a magnesium alloy material, which is different from Example 1 in that Y is 25% in percentage by mass. A
method for preparing the magnesium alloy material is the same as that in Example 1, and unnecessary details will not be given herein.
Test Example 1 The magnesium alloy materials provided in Examples 1-7 are respectively measured for tensile strength, yield strength, elongation and corrosion rate, wherein the tensile strength, the yield strength and the elongation are measured at room temperature, a test direction of the tensile strength is an extrusion direction (0 ), a tensile speed is 2 mm/min, and a corrosion rate is measured at 90 C in a 3.5wt% KCl solution. Results are shown in Table 1.
Table 1 Table of Property Data of Magnesium Alloy Materials Tensile Group Strength Yield Strength Elongation Corrosion Rate (MPa) (MPa) (`%) (mm a) Example 1 445 345 11.3 1800 Example 2 404 313 8.9 834 Example 3 402 298 10.8 407 Example 4 409 187 20.1 635 Example 5 325 156 21.8 785 Example 6 267 185 21 363 Example 7 355 282 17 2100 Example 8 505 415 6.0 1300 Comparative 410 315 2 10 Example 1 Comparative Example 2 Date Re9ue/Date Received 2021-04-20 Comparative 425 320 3.5 98 Example 3 Comparative Example 4 Comparative 168 85 5.3 1850 Example 5 Comparative Example 6 Notes: "-" indicates that the material is brittle, which has an extremely low elongation and cannot be put into use.
It can be seen from Table 1 that the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy materials provided in Examples 1-7 have the tensile strength of 267-505 MPa, the yield strength of 156-415 MPa, and the elongation of 6.0-21.8% at room temperature, and has the decomposition rate of 363 mm/a - 2100 mm/a in a 3.5wt% KCI
solution at 90 C, which indicates that the magnesium alloy material provided in the present disclosure has remarkably improved mechanical properties by adding specific contents of nickel and rare earth element to magnesium acting as a base material, and the degradation rate of the magnesium alloy material can meet the use requirement of self-ablation of downhole tools in the field of petroleum and natural gas.
Finally, it should be noted that the various embodiments above are merely used for illustrating the technical solutions of the present disclosure, rather than limiting the present disclosure; although the detailed description is made to the present disclosure with reference to various preceding embodiments, those ordinarily skilled in the art should understand that they still could modify the technical solutions recited in various preceding embodiments, or make equivalent substitutions to some or all of the technical features therein; and these modifications or substitutions do not make the corresponding technical solutions essentially depart from the scope of the technical solutions of various embodiments of the present disclosure.
Industrial Applicability The method for preparing a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material provided in the present disclosure can be carried out in batch in industry and is simple in process, convenient in operation, facilitates large-scale industrial production, and reduces the production cost, the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material prepared with this method has remarkably improved tensile strength and plasticity of alloy materials and other advantages, moreover, the nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material prepared with this method can be rapidly decomposed, and the downhole fracturing tools made of this magnesium alloy material can effectively meet requirements in the field of oil and gas exploitation.
Date Re9ue/Date Received 2021-04-20
Claims (30)
1. A
method for preparing a magnesium alloy material which is a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, said magnesium alloy material comprising following components in percentage by mass:
0.3% to 8.5% of Ni, 0.5% to 28% of RE, and a balance of Mg and unavoidable impurities, wherein RE is at least one rare earth element, and Mg, Ni and RE form an Mgi2RENi long-period stacking ordered phase, an Mg2Ni phase and an Mg,REy phase; wherein a volume fraction of the Mg12RENi long-period stacking ordered phase is 3% to 70%, a volume fraction of the Mg2Ni phase is 0.5% to 10%, a volume fraction of the Mg,REy phase is 0.5 to 22%, and a value range of x:y is 3:1 to 12:1;
said method comprising the following steps of (i) uniformly mixing a nickel source, a magnesium source and at least one rare earth element source, and (ii) carrying out an alloying treatment by a smelting and casting method, to provide the magnesium alloy material; and wherein the smelting and casting method comprises:
(a) a casting step, after step (i) mentioned above, carrying out a smelting and casting comprising firstly increasing temperature to 690 C to 800 C, maintaining the temperature at 690 C to 800 C and stirring raw materials until said raw materials completely melt, reducing temperature to 630 C to 680 C and maintaining for 20 min to 120 min, and then cooling to provide a magnesium alloy ingot; and (b) a heat treatment comprising carrying out a homogenization treatment, an extrusion heat deformation treatment and an aging heat treatment on the magnesium alloy ingot in sequence to provide the nickel-containing, high-Date Recue/Date Received 2023-07-28 strength and high-toughness, controllably degradable magnesium alloy material.
method for preparing a magnesium alloy material which is a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, said magnesium alloy material comprising following components in percentage by mass:
0.3% to 8.5% of Ni, 0.5% to 28% of RE, and a balance of Mg and unavoidable impurities, wherein RE is at least one rare earth element, and Mg, Ni and RE form an Mgi2RENi long-period stacking ordered phase, an Mg2Ni phase and an Mg,REy phase; wherein a volume fraction of the Mg12RENi long-period stacking ordered phase is 3% to 70%, a volume fraction of the Mg2Ni phase is 0.5% to 10%, a volume fraction of the Mg,REy phase is 0.5 to 22%, and a value range of x:y is 3:1 to 12:1;
said method comprising the following steps of (i) uniformly mixing a nickel source, a magnesium source and at least one rare earth element source, and (ii) carrying out an alloying treatment by a smelting and casting method, to provide the magnesium alloy material; and wherein the smelting and casting method comprises:
(a) a casting step, after step (i) mentioned above, carrying out a smelting and casting comprising firstly increasing temperature to 690 C to 800 C, maintaining the temperature at 690 C to 800 C and stirring raw materials until said raw materials completely melt, reducing temperature to 630 C to 680 C and maintaining for 20 min to 120 min, and then cooling to provide a magnesium alloy ingot; and (b) a heat treatment comprising carrying out a homogenization treatment, an extrusion heat deformation treatment and an aging heat treatment on the magnesium alloy ingot in sequence to provide the nickel-containing, high-Date Recue/Date Received 2023-07-28 strength and high-toughness, controllably degradable magnesium alloy material.
2. The method according to claim 1, wherein the magnesium alloy material comprises following components in percentage by mass:
0.5% to 8.0% of Ni, 1.5% to 20% of RE, a balance of Mg and unavoidable impurities.
0.5% to 8.0% of Ni, 1.5% to 20% of RE, a balance of Mg and unavoidable impurities.
3. The method according to claim 1, wherein the as-cast magnesium alloy comprises at least one of an as-cast magnesium alloy, an as-extruded magnesium alloy and an aged magnesium alloy.
4. The method according to claim 3, wherein the as-cast magnesium alloy comprises the Mgl2RENi long-period stacking ordered phase, the Mg5RE phase and the Mg2Ni phase, wherein the volume fraction of the Mg12RENi long-period stacking ordered phase is 3% to 65%, the volume fraction of the Mg2Ni phase is 0.5% to 6%, and the volume fraction of the Mg5RE phase is 0.5% to 15%.
5. The method according to claim 3, wherein the as-cast magnesium alloy comprises the Mgl2RENi long-period stacking ordered phase, the Mg2Ni phase and the Mg5RE phase, wherein the volume fraction of the Mg12RENi long-period stacking ordered phase is 4% to 70%, the volume fraction of the Mg2Ni phase is 1% to 8%, and the volume fraction of the Mg5RE phase is 1% to 20%.
6. The method according to claim 3, wherein the magnesium alloy material comprises the Mgi2RENi long-period stacking ordered phase, the Mg2Ni phase and the Mg,REy phase, wherein the volume fraction of the Mg12RENi long-period stacking ordered phase is 4% to 70%, the volume fraction of the Mg2Ni phase is 2% to 10%, and the volume fraction of the Mg,REy phase is 2% to 22%.
7. The method according to any one of claims 1 to 6, wherein the RE is at least one selected from the group consisting of Gd, Y, Er, Dy, Ce and Sc.
Date Recue/Date Received 2023-07-28
Date Recue/Date Received 2023-07-28
8. The method according to claim 7, wherein the content of the unavoidable impurities, in percentage by mass, is not higher than 0.2% in the magnesium alloy material.
9. The method according to claim 7, wherein the magnesium alloy material further comprises a component M which is at least one element capable of alloying with magnesium, and wherein the magnesium alloy material comprises following components in percentage by mass:
0.3% to 8.5% of Ni, 0.5% to 28% of RE, 0.03% to 10% of the component M, and a balance of Mg and unavoidable impurities.
0.3% to 8.5% of Ni, 0.5% to 28% of RE, 0.03% to 10% of the component M, and a balance of Mg and unavoidable impurities.
10. The method according to claim 9, wherein the content of the unavoidable impurities, in percentage by mass, is not higher than 0.2% in the magnesium alloy material.
11. The method according to claim 9 or 10, wherein component M is selected from the group consisting of Fe, Cu and Mn.
12. The method according to any one of claims 1 to 11, wherein the nickel source is selected from the group consisting of elemental nickel, nickel alloy and mixtures thereof.
13. The method according to claim 12, wherein the nickel alloy is at least one selected from the group consisting of magnesium-nickel alloy, nickel-yttrium alloy and zinc-nickel alloy.
14. The method according to claim 11, wherein the magnesium source is selected from the group consisting of elemental magnesium, magnesium alloy and mixtures thereof.
15. The method according to claim 14, wherein the magnesium alloy is at least one selected from the group consisting of magnesium-gadolinium alloy, magnesium-Date Recue/Date Received 2023-07-28 yttrium alloy, magnesium-zinc alloy, magnesium-nickel alloy, magnesium-calcium alloy and magnesium-iron alloy.
16. The method according to claim 11, wherein the at least one rare earth element source comprises elemental rare earth and/or rare earth intermediate alloy.
17. The method according to claim 16, wherein the elemental rare earth comprises at least one selected from the group consisting of gadolinium, yttrium, erbium, dysprosium, cerium and scandium.
18. The method according to claim 16, wherein the rare earth intermediate alloy comprises at least one selected from the group consisting of magnesium-gadolini um alloy, magnesium-yttrium alloy, magnesium-erbium alloy, magnesium-cerium alloy, magnesium-scandium alloy, nickel-yttrium alloy, nickel-gadolinium alloy, nickel-erbium alloy, nickel-cerium alloy and nickel-scandium alloy.
19. The method according to claim 11, wherein the aging heat treatment is carried out at a temperature of 150 C to 250 C for 12 h to 120 h.
20. The method according to claim 11 or 19, wherein the aging heat treatment is carried out at a temperature of 180 C to 220 C for 15 h to 60 h.
21. The method according to claim 11, wherein the cooling is obtained by a cooling method which is at least one selected from the group consisting of brine bath, water quenching, furnace cooling and air cooling.
22. The method according to any one of claims 11 to 21, wherein an inert gas is used during the smelting and casting for protection.
23. The method according to claim 22, wherein the inert gas is at least one selected from the group consisting of helium, argon, carbon dioxide and sulfur hexafluoride.
24. The method according to claim 23, wherein the inert gas is argon.
25. The method according to any one of claims 11 to 24, wherein the smelting is carried out using a resistance furnace or a line frequency induction furnace.
Date Recue/Date Received 2023-07-28
Date Recue/Date Received 2023-07-28
26. The method according to any one of claims 11 to 25, wherein in the step (b), the homogenization treatment is carried out at a temperature of 400 C to 550 C for 4h to 40h.
27. The method according to claim 26, wherein in the step (b), the extrusion heat deformation treatment is carried out at an extrusion ratio of 8 to 40.
28. The method according to claim 27, wherein the extrusion heat deformation treatment is carried out at a temperature of 360 C to 480 C.
29. A magnesium alloy material which is a nickel-containing, high-strength and high-toughness, controllably degradable magnesium alloy material, obtained from the method defined in any one of claims 1 to 28.
30. A use of the magnesium alloy material as defined in claim 29 in a field of oil and gas exploitation.
Date Recue/Date Received 2023-07-28
Date Recue/Date Received 2023-07-28
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811237934.1 | 2018-10-23 | ||
| CN201811237934.1A CN109295368B (en) | 2018-10-23 | 2018-10-23 | Nickel-containing high-toughness controllable degradation magnesium alloy material and preparation method and application thereof |
| PCT/CN2019/094183 WO2020082781A1 (en) | 2018-10-23 | 2019-07-01 | Nickel-containing high-toughness controllably degradable magnesium alloy material, preparation method therefor and use thereof |
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| CA3117106A1 CA3117106A1 (en) | 2020-04-30 |
| CA3117106C true CA3117106C (en) | 2024-01-23 |
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| US (1) | US20210040593A1 (en) |
| CN (1) | CN109295368B (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109295368B (en) * | 2018-10-23 | 2020-06-19 | 重庆大学 | Nickel-containing high-toughness controllable degradation magnesium alloy material and preparation method and application thereof |
| CN110106416B (en) * | 2019-05-24 | 2020-03-24 | 山东省科学院新材料研究所 | Ultrahigh-strength dissolvable magnesium alloy and preparation method and application thereof |
| CN110592518B (en) * | 2019-10-12 | 2021-12-31 | 中国石油化工股份有限公司 | Hard alloy coating capable of being completely dissolved in aqueous medium and preparation method and application thereof |
| WO2021102922A1 (en) * | 2019-11-29 | 2021-06-03 | 福建坤孚股份有限公司 | Preparation method for high-strength soluble magnesium alloy material |
| CN111139386B (en) * | 2019-11-29 | 2021-06-08 | 福建坤孚股份有限公司 | Preparation method of high-strength soluble magnesium alloy material |
| CN111304511B (en) * | 2020-03-27 | 2022-01-04 | 有研工程技术研究院有限公司 | Magnesium alloy material for oil and gas exploitation and preparation method and application thereof |
| US20230193109A1 (en) * | 2020-05-07 | 2023-06-22 | Kureha Corporation | Frac plug and method for manufacturing same, and method for sealing borehole |
| CN113061790B (en) * | 2021-03-16 | 2022-05-06 | 西安交通大学 | Mg-Zn-Ni ternary magnesium alloy material with wide corrosion rate range |
| CN113528917A (en) * | 2021-07-27 | 2021-10-22 | 重庆大学 | High-strength magnesium alloy with long-period phase and preparation method thereof |
| CN113718149B (en) * | 2021-08-06 | 2022-06-21 | 中北大学 | Preparation process of high-damping Mg-Ni-Y magnesium alloy |
| CN114134380A (en) * | 2021-11-30 | 2022-03-04 | 重庆大学 | High-strength high-damping Mg-Gd-Ni magnesium alloy and preparation method thereof |
| CN114574744B (en) * | 2022-03-04 | 2022-11-01 | 哈尔滨工业大学 | High-modulus magnesium alloy and preparation method thereof |
| CN114908280B (en) * | 2022-05-31 | 2022-11-22 | 重庆大学 | High-strength-toughness rapidly-degraded Mg-Er-Ni alloy for underground fracturing and preparation method thereof |
| CN115608994A (en) * | 2022-09-22 | 2023-01-17 | 哈尔滨理工大学 | Preparation and forming process of magnesium-based composite material lath |
| CN116043086B (en) * | 2022-12-19 | 2024-04-12 | 湖南稀土金属材料研究院有限责任公司 | Soluble magnesium alloy, preparation method and application thereof, and fracturing product |
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| JP4958267B2 (en) * | 2006-11-21 | 2012-06-20 | 株式会社神戸製鋼所 | Magnesium alloy material and method for producing the same |
| CN103981417B (en) * | 2014-05-28 | 2016-03-23 | 南京工程学院 | A kind of Biological magnesium alloy of LPSO structure of high-volume fractional and preparation method |
| CN104328320B (en) * | 2014-11-28 | 2017-01-04 | 重庆市科学技术研究院 | A kind of high-strength high-plasticity magnesium alloy |
| CN105316550B (en) * | 2015-03-12 | 2019-01-25 | 华东交通大学 | One kind high resistant damping magnesium alloy of phase containing long-periodic structure and preparation method thereof |
| CN109295368B (en) * | 2018-10-23 | 2020-06-19 | 重庆大学 | Nickel-containing high-toughness controllable degradation magnesium alloy material and preparation method and application thereof |
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| WO2020082781A1 (en) | 2020-04-30 |
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