CN111748752B - Magnesium-based amorphous alloy for fracturing ball and preparation method of fracturing ball - Google Patents
Magnesium-based amorphous alloy for fracturing ball and preparation method of fracturing ball Download PDFInfo
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- 239000011777 magnesium Substances 0.000 title claims abstract description 64
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 43
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 43
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title abstract description 14
- 239000000956 alloy Substances 0.000 claims abstract description 43
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 38
- 239000010949 copper Substances 0.000 claims abstract description 22
- 238000004381 surface treatment Methods 0.000 claims abstract description 14
- 229910052802 copper Inorganic materials 0.000 claims abstract description 12
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims abstract description 4
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 4
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 4
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 4
- 229910052709 silver Inorganic materials 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 3
- 238000000034 method Methods 0.000 claims description 27
- 238000001816 cooling Methods 0.000 claims description 18
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 238000003723 Smelting Methods 0.000 claims description 15
- 230000035939 shock Effects 0.000 claims description 15
- 239000002131 composite material Substances 0.000 claims description 12
- 230000006698 induction Effects 0.000 claims description 12
- 238000005480 shot peening Methods 0.000 claims description 11
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 238000005266 casting Methods 0.000 claims description 7
- 238000002844 melting Methods 0.000 claims description 7
- 230000008018 melting Effects 0.000 claims description 7
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 4
- 239000004615 ingredient Substances 0.000 claims description 4
- 238000003754 machining Methods 0.000 claims description 4
- 238000007712 rapid solidification Methods 0.000 claims description 4
- 238000005728 strengthening Methods 0.000 claims description 4
- 229910001208 Crucible steel Inorganic materials 0.000 claims description 2
- 241001062472 Stokellia anisodon Species 0.000 claims 1
- 239000002994 raw material Substances 0.000 claims 1
- 238000004090 dissolution Methods 0.000 abstract description 12
- 229910000861 Mg alloy Inorganic materials 0.000 abstract description 7
- 238000010276 construction Methods 0.000 abstract description 5
- 238000005422 blasting Methods 0.000 description 9
- 239000007789 gas Substances 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 238000009718 spray deposition Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000001125 extrusion Methods 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000005300 metallic glass Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/005—Amorphous alloys with Mg as the major constituent
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- 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
- C22C1/11—Making amorphous alloys
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
- C22C45/001—Amorphous alloys with Cu as the major constituent
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- 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
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- 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
- C22F1/08—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of copper or alloys based thereon
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- 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
- C22F3/00—Changing the physical structure of non-ferrous metals or alloys by special physical methods, e.g. treatment with neutrons
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- E—FIXED CONSTRUCTIONS
- E21—EARTH OR ROCK DRILLING; MINING
- E21B—EARTH OR ROCK DRILLING; OBTAINING OIL, GAS, WATER, SOLUBLE OR MELTABLE MATERIALS OR A SLURRY OF MINERALS FROM WELLS
- E21B43/00—Methods or apparatus for obtaining oil, gas, water, soluble or meltable materials or a slurry of minerals from wells
- E21B43/25—Methods for stimulating production
- E21B43/26—Methods for stimulating production by forming crevices or fractures
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Abstract
本发明属于镁合金材料制备及油气田开发领域，具体涉及一种压裂球用镁基非晶合金及压裂球的制备方法。本发明所述镁基非晶合金成分组元为MgxCuyRz，x,y,z为摩尔百分数，x+y+z＝100,60≤x≤80,15≤y≤45,3≤z≤30,R为Y、Ag、Ni、Nd、Si、Gd、Pd、Zn和Al中的一种或几种以上的组合，采用该合金制备的压裂球具有更高的抗压强度。铜元素的添加可以促进合金的溶解，通过表面处理在压裂球表面形成残余压应力场和塑性变形层，一方面提高球体的力学性能，另一方面提高比表面积和降低溶解激活能，促进合金的溶解；利用该可溶镁基非晶合金加工得到的压裂球，使用后可在井下顺利溶解，自行返排，提高施工效率。
The invention belongs to the field of magnesium alloy material preparation and oil and gas field development, and particularly relates to a magnesium-based amorphous alloy for fracturing balls and a preparation method of the fracturing ball. The magnesium-based amorphous alloy composition of the present invention is Mg x Cu y R z , x, y, z are mole percentages, x+y+z=100, 60≤x≤80, 15≤y≤45,3 ≤z≤30, R is one or more combinations of Y, Ag, Ni, Nd, Si, Gd, Pd, Zn and Al, and the fracturing ball prepared with this alloy has higher compressive strength . The addition of copper can promote the dissolution of the alloy, and form a residual compressive stress field and a plastic deformation layer on the surface of the fracturing ball through surface treatment. The fracturing balls processed by the soluble magnesium-based amorphous alloy can be smoothly dissolved in the well after use and flow back by themselves to improve the construction efficiency.
Description
Technical Field
The invention belongs to the field of magnesium alloy material preparation and oil-gas field development, and particularly relates to a magnesium-based amorphous alloy for a fracturing ball and a preparation method of the fracturing ball.
Background
With the increasing development of oil and gas reserves in China, the proportion of the reserves of low-permeability unconventional oil and gas resources is continuously increased. In order to obtain relatively stable oil and gas yield, the multi-layer multi-stage fracturing process is widely applied to low-permeability unconventional oil and gas wells. In the underground layered staged fracturing, temporary plugging tools are required to be adopted to plug intervals, and the temporary plugging tools are removed in time after construction is completed. At present, most of tools of the type are made of steel, high polymer, ceramic or crystalline magnesium alloy materials, and have the following characteristics:
(1) the steel has the defects of high density, slow dissolution rate, difficult flowback and the like;
(2) the polymer and ceramic materials have the advantage of low density, but the compressive strength can not meet the standard of fracturing, and the risk of deforming and clamping the shell exists in the underground high-temperature and high-pressure environment;
(3) the crystalline magnesium alloy material has the advantages of low density, high dissolution rate, easy processing and the like, and becomes one of the materials for preparing the soluble fracturing ball. Chinese patent (publication No. CN105908037B, published 2018.09.04) discloses a magnesium alloy for manufacturing soluble fracturing balls and a preparation method thereof; chinese patent publication No. CN105908038B, publication No. 2018.09.04, discloses a soluble alloy for use in making fracture parting tools; chinese patent publication No. CN204492756U, published 2015.07.22 discloses a soluble ball seat and a fracturing ball for a pitching sliding sleeve; chinese patent (publication No. CN107099712B, bulletin day 2019.01.04) discloses a soluble magnesium alloy composite material fracturing ball and a preparation method thereof; chinese patent (publication No. CN105950930B, bulletin No. 2018.02.06) discloses a soluble extrusion magnesium alloy and a preparation method thereof; chinese patent (publication No. CN105177383B, bulletin No. 2017.10.31) discloses a magnesium-based composite material containing iron and a preparation method and application thereof; chinese patent (publication No. CN107675055B, published 2019.03.26) discloses a preparation method of a high pressure-resistant degradable magnesium-based composite material; chinese patent publication No. CN107385245B, published 2019.06.18, discloses a method for manufacturing soluble alloy fracturing balls for oil and gas exploitation; however, the above patents all adopt crystalline alloy materials or composite materials using magnesium as a main element, and have insufficient compressive strength and limited bearing capacity in extreme environments such as high temperature and high pressure.
Therefore, the development of a high compressive strength, degradable, lightweight fracturing ball is urgently needed. After fracturing is finished, the solvent is injected to be completely or partially dissolved, and a channel is opened, so that the requirements of fracturing and flowback construction are met.
Disclosure of Invention
The purpose of the invention is: the temporary plugging tool is manufactured by utilizing the high-strength degradable characteristic of the magnesium-based amorphous alloy, is automatically dissolved by a solvent after fracturing to lose efficacy, smoothly realizes flowback, omits a drilling and grinding recovery process, reduces engineering risks and improves the exploitation efficiency.
The technical scheme of the invention is as follows:
a high strength degradable magnesium-based amorphous alloy fracturing ball is characterized in that:
it is made of Mg-base amorphous alloy and its component is MgxCuyRzX, Y and z are mole percentages, x + Y + z is 100, x is more than or equal to 60 and less than or equal to 80, Y is more than or equal to 15 and less than or equal to 45, z is more than or equal to 3 and less than or equal to 30, and R is one or the combination of more than one of Y, Ag, Ni, Nd, Si, Gd, Pd, Zn and Al.
A preparation method of a high-strength degradable magnesium-based amorphous alloy fracturing ball is characterized by comprising the following steps:
1. ingredients
According to MgxCuyRzMg, Cu and R elements are respectively weighed according to target components, and the mass percent purity of each element is not lower than 99%.
2 melting alloy ingot
Putting Cu and R elements into a vacuum arc furnace for smelting, uniformly smelting in an argon protective atmosphere with the mass percent purity of 99.99%, and taking out a Cu-R master alloy ingot after cooling; putting the Mg and Cu-R master alloy ingots into a vacuum induction furnace for smelting, uniformly smelting in an argon protective atmosphere with the mass percentage purity of 99.99%, and taking out the Mg-Cu-R master alloy ingots after cooling;
3 casting of bulk amorphous alloy
Putting the Mg-Cu-R master alloy ingot obtained in the step 2 into an induction furnace of a rapid solidification device for heating and melting, carrying out spray casting or casting on the ingot into a water-cooled copper mold, and cooling to obtain MgxCuyRzA bulk amorphous alloy ingot. The cooling speed of the water-cooling copper mold is 10-105K/s, the vacuum degree of the induction furnace is less than or equal to 1 multiplied by 10-1Pa。
4 machining and forming
Mixing Mg obtained in the step 3xCuyRzThe bulk amorphous alloy ingot is machined to form a ball.
5 surface treatment
And (4) carrying out surface treatment on the spherical object obtained in the step (4) by adopting a laser shock peening process, a shot blasting process or a composite process of the two processes. Wherein the laser power density of the laser shock peening process is 1-20 GW/cm2The overlapping rate of the light spots is 12-70%, and the impact frequency is 1-3 times; the shot medium of the shot peening strengthening process is cast steel shot, glass shot or ceramic shot, the shot peening strength is 0.03-0.2A, and the coverage rate is 100-300%; the processing sequence of the composite process is laser shock and shot blasting or shot blasting and laser shock. And performing surface treatment to obtain the high-strength degradable magnesium-based amorphous alloy fracturing ball.
The invention has the advantages that:
first, the magnesium-based amorphous alloy has mechanical properties, such as high fracture strength, which are incomparable with those of the common magnesium-based crystalline alloy. The compression strength of the amorphous Mg-Cu-Zn-Y can reach 880MPa, which is about 2-3 times of that of the crystalline alloy. The fracturing ball prepared from the alloy has higher compressive strength.
Secondly, the addition of copper can promote the dissolution of the alloy.
And thirdly, a residual compressive stress field and a plastic deformation layer are formed on the surface of the fracturing ball through surface treatment, so that the mechanical property of the ball is improved, the specific surface area is improved, the dissolution activation energy is reduced, and the dissolution of the alloy is promoted.
The fracturing ball processed by the soluble magnesium-based amorphous alloy can be smoothly dissolved in the well after being used, and can automatically flow back, so that the construction efficiency is improved.
Drawings
Four Mg pieces in the example of FIG. 165Cu20Zn5Y10Room temperature compressive strength bar chart of bulk amorphous alloy sample
Mg in FIG. 2 example65Cu20Zn5Y10Dissolution rate of bulk amorphous alloy fracturing balls in 3% KCl aqueous solution
Detailed Description
A high strength degradable magnesium-based amorphous alloy fracturing ball is characterized in that:
it is made of magnesium-based non-magnesiumA crystal alloy having a composition consisting of MgxCuyRzX, Y and z are mole percentages, x + Y + z is 100, x is more than or equal to 60 and less than or equal to 80, Y is more than or equal to 15 and less than or equal to 45, z is more than or equal to 3 and less than or equal to 30, and R is one or the combination of more than one of Y, Ag, Ni, Nd, Si, Gd, Pd, Zn and Al.
A preparation method of a high-strength degradable magnesium-based amorphous alloy fracturing ball is characterized by comprising the following steps:
1. ingredients
According to MgxCuyRzMg, Cu and R elements are respectively weighed according to target components, and the mass percent purity of each element is not lower than 99%.
2 melting alloy ingot
Putting Cu and R elements into a vacuum arc furnace for smelting, uniformly smelting in an argon protective atmosphere with the mass percent purity of 99.99%, and taking out a Cu-R master alloy ingot after cooling; putting the Mg and Cu-R master alloy ingots into a vacuum induction furnace for smelting, uniformly smelting in an argon protective atmosphere with the mass percentage purity of 99.99%, and taking out the Mg-Cu-R master alloy ingots after cooling;
3 casting of bulk amorphous alloy
Putting the Mg-Cu-R master alloy ingot obtained in the step 2 into an induction furnace of a rapid solidification device for heating and melting, carrying out spray casting or casting on the ingot into a water-cooled copper mold, and cooling to obtain MgxCuyRzA bulk amorphous alloy ingot. The cooling speed of the water-cooling copper mold is 10-105K/s, the vacuum degree of the induction furnace is less than or equal to 1 multiplied by 10-1Pa。
4 machining and forming
Mixing Mg obtained in the step 3xCuyRzThe bulk amorphous alloy ingot is machined to form a ball.
5 surface treatment
And (4) carrying out surface treatment on the spherical object obtained in the step (4) by adopting a laser shock peening process, a shot blasting process or a composite process of the two processes. Wherein the laser power density of the laser shock peening process is 1-20 GW/cm2The overlapping rate of the light spots is 12-70%, and the impact frequency is 1-3 times; the shot medium of the shot peening strengthening process is cast steelShot, glass shot or ceramic shot, wherein the shot blasting strength is 0.03-0.2A, and the coverage rate is 100-300%; the processing sequence of the composite process is laser shock and shot blasting or shot blasting and laser shock. And performing surface treatment to obtain the high-strength degradable magnesium-based amorphous alloy fracturing ball.
The working principle of the invention is as follows:
amorphous alloys, also known as metallic glasses, are a general term for a class of metallic materials characterized by long-range disorder and short-range order of atoms. The magnesium-based amorphous alloy has mechanical properties, such as high breaking strength, which are incomparable with those of the common magnesium-based crystalline alloy. The compression strength of the amorphous Mg-Cu-Zn-Y can reach 880MPa, which is about 2-3 times of that of the crystalline alloy. The fracturing ball prepared from the alloy has higher compressive strength. Meanwhile, the addition of Cu element can promote the dissolution of the alloy. In addition, a residual compressive stress field and a plastic deformation layer are formed on the surface of the fracturing ball through surface treatment, so that the mechanical property of the ball is improved, the specific surface area is improved, the dissolution activation energy is reduced, and the dissolution of the alloy is promoted. The fracturing ball processed by the soluble magnesium-based amorphous alloy can be smoothly dissolved in the well after being used, and can automatically flow back, so that the construction efficiency is improved.
Example 1
In this embodiment, a high-strength degradable magnesium-based amorphous alloy fracturing ball is made of Mg65Cu20Zn5Y10Magnesium-based amorphous alloy. The preparation method of the fracturing ball comprises the following steps:
1. ingredients
According to Mg65Cu20Zn5Y10Mg, Cu and R elements are respectively weighed according to target components, and the mass percent purity of each element is more than 99.0%.
2 melting alloy ingot
Putting Cu, Zn and Y elements into a vacuum arc furnace for smelting, uniformly smelting in an argon protective atmosphere with the mass percent purity of 99.99%, and taking out a Cu-Zn-Y master alloy ingot after cooling; putting the Mg and Cu-Zn-Y master alloy ingot into a vacuum induction furnace for smelting, uniformly smelting in an argon protective atmosphere with the mass percentage purity of 99.99 percent, and taking out the Mg-Cu-Zn-Y master alloy ingot after cooling;
3 casting of bulk amorphous alloy
Putting the Mg-Cu-Zn-Y master alloy ingot obtained in the step 2 into an induction furnace of a rapid solidification device for heating and melting, carrying out spray casting or casting on the ingot into a water-cooled copper mold, and cooling to obtain MgxCuyRzA bulk amorphous alloy ingot. The cooling rate of the water-cooled copper mold is 103K/s, the vacuum degree of the induction furnace is less than or equal to 1 multiplied by 10-1Pa。
4 machining and forming
Mixing Mg obtained in step 2.365Cu20Zn5Y10The bulk amorphous alloy ingot was machined to form a 20mm diameter sphere.
5 surface treatment
And (4) carrying out surface treatment on the spherical object obtained in the step (4) by adopting a composite process consisting of a laser shock peening process and a shot blasting process. Wherein the laser power density of the laser shock peening process is 10GW/cm2The overlapping rate of the light spots is 50 percent, and the impact frequency is 1 time; the shot medium of the shot peening strengthening process is glass shot, the shot peening strength is 0.08A, and the coverage rate is 100 percent; the processing sequence of the composite process is laser shock and shot blasting. And performing surface treatment to obtain the high-strength degradable magnesium-based amorphous alloy fracturing ball.
Measured by X-ray diffraction, Mg65Cu20Zn5Y10The bulk amorphous alloy ingot is of an amorphous structure. The average value of the room-temperature compressive strength of the alloy was 446MPa (see FIG. 1). The average dissolution rate of the fracturing balls in a 3% KCl aqueous solution at 50 ℃ is 11.5mg/cm2Absolute reaction temperature, average dissolution rate in aqueous 3% KCl solution at 80 ℃ of 31.9mg/cm2H (see FIG. 2).
Claims (4)
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0361136A1 (en) * | 1988-09-05 | 1990-04-04 | Yoshida Kogyo K.K. | High strength magnesium-based alloys |
| CN101575686A (en) * | 2009-06-22 | 2009-11-11 | 北京科技大学 | Magnesium-based block amorphous metal base in-situ composite material |
| CN102304676A (en) * | 2011-09-21 | 2012-01-04 | 镇江忆诺唯记忆合金有限公司 | Quaternary magnesium-based amorphous alloy |
| CN103173699A (en) * | 2013-03-22 | 2013-06-26 | 哈尔滨工程大学 | Zn-containing Mg-Cu-Gd bulk amorphous alloy and preparation method thereof |
| CN104178663A (en) * | 2013-05-27 | 2014-12-03 | 中国科学院金属研究所 | Aluminum-based alloy material for preparing disintegration fracturing balls and preparation method thereof |
| CN109797361A (en) * | 2019-03-05 | 2019-05-24 | 北京科技大学 | A kind of preparation method of solvable Mg alloy surface high corrosion resistant coating |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0361136A1 (en) * | 1988-09-05 | 1990-04-04 | Yoshida Kogyo K.K. | High strength magnesium-based alloys |
| CN101575686A (en) * | 2009-06-22 | 2009-11-11 | 北京科技大学 | Magnesium-based block amorphous metal base in-situ composite material |
| CN102304676A (en) * | 2011-09-21 | 2012-01-04 | 镇江忆诺唯记忆合金有限公司 | Quaternary magnesium-based amorphous alloy |
| CN103173699A (en) * | 2013-03-22 | 2013-06-26 | 哈尔滨工程大学 | Zn-containing Mg-Cu-Gd bulk amorphous alloy and preparation method thereof |
| CN104178663A (en) * | 2013-05-27 | 2014-12-03 | 中国科学院金属研究所 | Aluminum-based alloy material for preparing disintegration fracturing balls and preparation method thereof |
| CN109797361A (en) * | 2019-03-05 | 2019-05-24 | 北京科技大学 | A kind of preparation method of solvable Mg alloy surface high corrosion resistant coating |
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