CN111041309B - Soluble magnesium-based alloy and preparation method thereof - Google Patents
Soluble magnesium-based alloy and preparation method thereof Download PDFInfo
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- 239000000956 alloy Substances 0.000 title claims abstract description 111
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 104
- 239000011777 magnesium Substances 0.000 title claims abstract description 92
- 229910052749 magnesium Inorganic materials 0.000 title claims abstract description 83
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 238000002360 preparation method Methods 0.000 title abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 25
- 229910052791 calcium Inorganic materials 0.000 claims abstract description 23
- 229910052692 Dysprosium Inorganic materials 0.000 claims abstract description 20
- 229910052751 metal Inorganic materials 0.000 claims abstract description 18
- 239000002184 metal Substances 0.000 claims abstract description 18
- 229910052758 niobium Inorganic materials 0.000 claims abstract description 15
- 229910052733 gallium Inorganic materials 0.000 claims abstract description 13
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000003723 Smelting Methods 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000007789 gas Substances 0.000 claims description 29
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 24
- 238000005245 sintering Methods 0.000 claims description 24
- 238000010438 heat treatment Methods 0.000 claims description 22
- 238000001125 extrusion Methods 0.000 claims description 20
- 238000000151 deposition Methods 0.000 claims description 17
- 238000003756 stirring Methods 0.000 claims description 17
- 229910019064 Mg-Si Inorganic materials 0.000 claims description 16
- 229910019406 Mg—Si Inorganic materials 0.000 claims description 16
- 230000032683 aging Effects 0.000 claims description 15
- 238000003754 machining Methods 0.000 claims description 15
- 239000010955 niobium Substances 0.000 claims description 15
- 229910019068 Mg—Ge Inorganic materials 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 14
- 229910052786 argon Inorganic materials 0.000 claims description 12
- 229910000861 Mg alloy Inorganic materials 0.000 claims description 11
- 230000001681 protective effect Effects 0.000 claims description 11
- 238000005266 casting Methods 0.000 claims description 10
- 229910052748 manganese Inorganic materials 0.000 claims description 10
- 239000011572 manganese Substances 0.000 claims description 10
- 150000002739 metals Chemical class 0.000 claims description 10
- 238000000889 atomisation Methods 0.000 claims description 9
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000000265 homogenisation Methods 0.000 claims description 9
- 239000000155 melt Substances 0.000 claims description 8
- 238000003801 milling Methods 0.000 claims description 8
- 230000008569 process Effects 0.000 claims description 7
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 6
- 239000011261 inert gas Substances 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 claims description 6
- 238000002844 melting Methods 0.000 claims description 6
- 230000008018 melting Effects 0.000 claims description 6
- 239000002245 particle Substances 0.000 claims description 6
- 239000002994 raw material Substances 0.000 claims description 6
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 5
- 238000004663 powder metallurgy Methods 0.000 claims description 5
- 238000003825 pressing Methods 0.000 claims description 5
- 238000012545 processing Methods 0.000 claims description 5
- 238000007493 shaping process Methods 0.000 claims description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 4
- 235000012438 extruded product Nutrition 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 239000000203 mixture Substances 0.000 claims description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 2
- 239000001569 carbon dioxide Substances 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 claims description 2
- 238000011084 recovery Methods 0.000 claims 1
- 238000004090 dissolution Methods 0.000 abstract description 19
- 229910052755 nonmetal Inorganic materials 0.000 abstract description 3
- 239000008151 electrolyte solution Substances 0.000 abstract description 2
- 239000011575 calcium Substances 0.000 description 16
- 239000000243 solution Substances 0.000 description 15
- 238000005516 engineering process Methods 0.000 description 12
- 239000003921 oil Substances 0.000 description 11
- 238000005553 drilling Methods 0.000 description 7
- 230000001965 increasing effect Effects 0.000 description 7
- -1 Ga is 1.5% Substances 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000006056 electrooxidation reaction Methods 0.000 description 3
- 230000004927 fusion Effects 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 238000012827 research and development Methods 0.000 description 3
- 238000005204 segregation Methods 0.000 description 3
- 238000009718 spray deposition Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000807 Ga alloy Inorganic materials 0.000 description 1
- 229910000645 Hg alloy Inorganic materials 0.000 description 1
- 229910001257 Nb alloy Inorganic materials 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003129 oil well Substances 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 230000002035 prolonged effect Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 230000011218 segmentation Effects 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000035882 stress Effects 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
-
- 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
- C22C1/03—Making non-ferrous alloys by melting using master alloys
-
- 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
-
- 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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Mechanical Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Geology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Physics & Mathematics (AREA)
- Mining & Mineral Resources (AREA)
- Thermal Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Fluid Mechanics (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geochemistry & Mineralogy (AREA)
- Powder Metallurgy (AREA)
Abstract
The invention relates to the field of metal smelting, and discloses a soluble magnesium-based alloy and a preparation method thereof, wherein the soluble magnesium-based alloy comprises the following components in percentage by weight: mn: 0.1-0.3%, Ca: 0.5 to 1.5%, Nb: 0.5-2%, Ge: 1-3%, Si: 0.1-0.3%, Hg: 1.4 to 1.9%, Ga: 0.9-1.5%, Dy: 0.3-0.5% and the balance of Mg; wherein the Ga/Hg ratio in the magnesium-based alloy is 0.45-1.1. Compared with the prior art, the fracturing ball prepared from the magnesium-based alloy prepared by the method has high toughness, good plasticity and strong pressure bearing capacity, the dissolution rate in an electrolyte solution meets the requirement, and the problems that the fracturing ball made of metal or nonmetal materials cannot be dissolved by itself and is difficult to flow back in the prior art are solved.
Description
Technical Field
The invention relates to the field of metal smelting, in particular to a soluble magnesium-based alloy and a preparation method thereof.
Background
In recent years, the low-permeability unconventional oil gas resources are newly increased and proved to reach 70% in oil gas reserves in China, the proportion of low permeability in oil gas yield in China is continuously increased in the future, and the stable yield and the yield increase of the oil gas yield are more dependent on the low-permeability unconventional oil gas resources. In the underground layered staged fracturing, a temporary plugging tool is required to be used for packing intervals, and after construction is completed, the temporary plugging tool needs to be removed.
One of the key components of the horizontal well staged fracturing technology is a fracturing ball, which is a main factor for determining whether fracturing is successful. At present, the main problems of the fracturing ball are as follows: the fracturing balls made of metal or nonmetal materials cannot be dissolved, and after fracturing operation is completed, the fracturing balls must be drained back out of a wellhead or ground by a drilling and milling tool. The flowback or drilling and milling of the fracturing balls not only increases the complexity of the fracturing process, but also prolongs the operation time, and seriously affects the production efficiency of the fracturing operation. In particular, in recent years, in order to improve the yield increasing effect of oil wells, the number of fracturing sections of horizontal wells is increased, fracturing balls which need to be drained or drilled and milled after fracturing operation are increased, the fracturing operation time is prolonged, and the production efficiency is reduced. The flowback or drilling and milling of the fracturing balls can greatly limit the popularization and application of the staged fracturing technology of the horizontal well, and is a problem to be solved urgently by the staged fracturing technology of the horizontal well.
Based on this, degradable materials need to be introduced into the tool, so that the temporary plugging workpiece is dissolved in the underground, the drilling and grinding process can be omitted, the engineering risk is reduced, the construction efficiency is improved, and the damage of drilling cuttings to a reservoir stratum is avoided. The magnesium metal has active chemical property, easy corrosion, small density and high specific strength, and is an ideal material for manufacturing the workpiece.
In 1 month 2012, Baker Hughes company (Baker chemical) in the united states proposed a controllable electrochemical corrosion material (CEM-Controlled electrochemical corrosion materials for short) based on the electrochemical corrosion characteristics of magnesium alloy, developed a soluble ball with a dissolution rate of 10mg · cm-2 · h-1, and successfully used for staged fracturing of horizontal wells. In 2013, the Shantou company (SANTROL) in the United states increased the soluble sealing balls in the product series through research and development. When the fracturing layer is provided with a perforation section and a separate-layer fracturing technology is needed in the fracturing process, the soluble fracturing balls play a role in temporarily plugging the perforations. The soluble fracturing ball can replace a standard RCN spherical fracturing ball used traditionally in oil fields, and the biggest advantage of the fracturing ball is that the fracturing ball is dissolved after effective plugging. Therefore, the soluble fracturing ball can solve the problems of flowback or drilling and milling of the fracturing ball, has the advantages of high fracturing operation efficiency, low cost and the like, and is particularly suitable for multi-section fracturing operation of a horizontal well. However, the foreign soluble fracturing ball technology is still in the technical blockade stage, and the domestic related technology is backward, so that the application of the stable and high-quality fracturing ball in the horizontal well staged fracturing technology cannot be efficiently realized. Therefore, in order to break through foreign technology blockages and promote the research and development and application of the horizontal well staged fracturing technology in China, the research and development of a high-end soluble fracturing ball for the horizontal well staged fracturing technology is urgently needed.
Disclosure of Invention
The purpose of the invention is as follows: aiming at the problems in the prior art, the invention provides a soluble magnesium-based alloy and a preparation method thereof, wherein a fracturing ball prepared from the magnesium-based alloy prepared by the method has high toughness, good plasticity and strong pressure bearing capacity, the dissolution rate in an electrolyte solution meets the requirement, and the problems that the fracturing ball prepared from a metal or non-metal material in the prior art cannot be dissolved by itself and is difficult to flow back are solved.
The technical scheme is as follows: the invention provides a soluble magnesium-based alloy which comprises the following components in percentage by weight: mn: 0.1-0.3%, Ca: 0.5 to 1.5%, Nb: 0.5-2%, Ge: 1-3%, Si: 0.1-0.3%, Hg: 1.4 to 1.9%, Ga: 0.9-1.5%, Dy: 0.3-0.5% and the balance of Mg; wherein the Ga/Hg ratio in the magnesium-based alloy is 0.45-1.1.
The invention also provides a preparation method of the soluble magnesium-based alloy, which comprises the following steps: s1: taking pure metals of raw materials Mg, Mn and Nb according to the proportion, preparing intermediate alloys of Mg-Ca, Mg-Si, Mg-Hg, Mg-Dy, Mg-Ge and Mg-Ga with powder particles of 20-200 mu m by adopting a powder metallurgy method, and drying all the raw materials; s2: smelting: under a protective atmosphere, firstly melting pure magnesium, then adding pure metals of Mn and Nb at 680-720 ℃, uniformly stirring, keeping the temperature for 25-35 min, adding intermediate alloys of Mg-Ca, Mg-Si, Mg-Hg, Mg-Dy, Mg-Ge and Mg-Ga, uniformly stirring, keeping the temperature for 25-35 min, and heating to 730-740 ℃; introducing air pressure of 0.12-0.5 MPa and flow rate of 0.01-0.2 m into the melt3Introducing argon into the alloy melt, stirring the mixture until the alloy is uniform, then cooling the alloy melt to 680-720 ℃, and preserving the temperature for 10-20 min; s3: casting: casting the molten metal smelted in the step S2 into a mould to form a cast ingot; s4: homogenizing heat treatment: carrying out homogenizing heat treatment on the ingot obtained in the step S3 at 380-420 ℃ for 18-30 hours, and then cooling along with the furnace; s5: extruding: extruding the cast ingot subjected to the homogenization heat treatment obtained in the step S4 into a blank at the temperature of 350-380 ℃, wherein the extrusion ratio is 4-20, and the extrusion speed is 2-20 m/min; s6: aging treatment: aging the blank obtained in the step S5; s7: machining and forming: and machining and shaping the blank obtained in the step S6.
Preferably, in the S2, the protective atmosphere is CO2And SF6The proportion of the mixed gas is 200-400: 1; or, the protective atmosphere is Ar and SF6Mixed gas of (2) in a ratio of 200-400: 1; or, the protective atmosphere is N2And SF6The proportion of the mixed gas is 200-400: 1.
preferably, in the step S6, the temperature of the aging treatment is 100-120 ℃ and the time is 5-24 hours.
Preferably, in the S1, the pure metals of Mg, Mn, Cu, Ni and Ga and the Mg-Ca, Mg-Si, Mg-Hg, Mg-Ce and FeCl3The purities of the intermediate alloys are all more than or equal to 99.9 percent.
The invention also provides a preparation method of the soluble magnesium-based alloy, which comprises the following steps: s1: milling: preparing required magnesium alloy powder, and fully mixing magnesium powder, manganese powder, niobium powder and intermediate alloy powder of Mg-Ca, Mg-Si, Mg-Hg, Mg-Dy, Mg-Ge and Mg-Ga according to the proportion under the protection of inert gas; s2: pre-pressing: prepressing and forming the mixed powder under the pressure of 80-120 MPa; s3, sintering: sintering the pre-pressed and formed material at 520-580 ℃, applying pressure of 160-240 MPa in the sintering process, sintering time of 1.6-2.3 h, introducing inert gas for protection, and cooling along with a furnace after sintering to obtain a soluble magnesium-based alloy material; s4: machining and forming: and processing and shaping the soluble magnesium-based alloy material in a sintering blank machine.
Preferably, the granularity of the magnesium powder is 50-80 um, and the granularity of the manganese powder, the niobium powder and the intermediate alloy powder of Mg-Ca, Mg-Si, Mg-Hg, Mg-Dy, Mg-Ge and Mg-Ga is 5-10 um.
Preferably, the magnesium powder, the manganese powder, the copper powder, the nickel powder and Mg-Ca, Mg-Si, Mg-Hg, Mg-Ce, Mg-Ga and FeCl3The purity of the master alloy powder is more than or equal to 99.9 percent.
Preferably, in the S1 and the S3, the inert gas is CO2And SF6The proportion of the mixed gas is 200-400: 1; or, Ar and SF6The proportion of the mixed gas is 200-400: 1; or, N2And SF6The proportion of the mixed gas is 200-400: 1.
the invention also provides a preparation method of the soluble magnesium-based alloy, which comprises the following steps: s1: smelting the required magnesium alloy solution: under a protective atmosphere, firstly melting pure magnesium, adding pure metals of Mn and Nb at 700-740 ℃, uniformly stirring, keeping the temperature for 25-35 min, adding intermediate alloys of Mg-Ca, Mg-Si, Mg-Hg, Mg-Dy, Mg-Ge and Mg-Ga, uniformly stirring, keeping the temperature for 25-35 min, and keeping the temperature for 730-750 ℃; introducing argon into the melt, introducing the argon while stirring until the alloy is uniform, then reducing the temperature of the alloy melt to 720-730 ℃, and preserving the temperature for 15-20 min; s2: atomization and deposition: atomizing the alloy solution in the S1, and depositing to obtain a deposition blank; the atomization pressure during atomization deposition is 0.4-1.5 MPa, the atomization gas is argon, nitrogen or carbon dioxide, and the deposition distance is 0.5-1.2 m; s3: extruding: extruding the deposition blank at 350-380 ℃ to obtain an extruded product, wherein the extrusion ratio is 5-15, and the extrusion speed is 2-20 m/min; s4: aging treatment: aging the extruded article; s5: machining and forming: and machining and forming the aged product.
Preferably, in the step S4, the temperature during the aging treatment is 100 to 120 ℃ and the time is 5 to 40 hours.
The invention also provides application of the soluble magnesium-based alloy in the soluble alloy fracturing ball for oil and gas exploitation.
Has the advantages that: (1) in the formula of the soluble magnesium-based alloy, the content of total alloy elements is low, segregation is weakened during solidification, the components are more uniform, no serious side reaction is caused, and polarization is slight.
(2) The mercury and the gallium contained in the formula of the soluble magnesium-based alloy are high hydrogen evolution overpotential elements, so that the electrochemical performance of the alloy can be improved, the stability of the magnesium alloy is improved, the hydrogen evolution reaction is inhibited, and the safety is improved; gallium in the formula is non-toxic, replaces a part of mercury, improves the working environment and improves the personal safety.
(4) In the formula of the soluble magnesium-based alloy, the main phase of the alloy is α -Mg solid solution and Mg distributed in grain boundaries3Hg phase and NbCa GP zone, the mechanical property of the alloy is increased along with the increase of Hg content, but the elongation is not influenced.
(5) In the preparation method of the soluble magnesium-based alloy, the temperature of homogenization heat treatment is 380-420 ℃, the time is 18-30 hours, and furnace cooling is carried out. Gross variation of as-cast conditionCrystalline Mg3The Hg phase is unstable and, after homogenization heat treatment, Mg3Hg is eliminated and dissolved into the matrix; after homogenization treatment, the crystal grains are equiaxed, the crystal boundary is fine, clear and straight, and Mg with the size of about 0.5-1.5 mu m is distributed in the matrix3Hg phase, evenly distributed in crystal boundary and crystal; hg, Nb and Ga alloy elements have serious segregation in the casting state, and Hg, Nb and Ga are uniformly distributed and segregation phenomenon is reduced after homogenization heat treatment; homogenizing heat treatment to make coarse Mg3Hg phase is dissolved, so that alloy elements are uniformly distributed, stress concentration is weakened, and subsequent plastic processing is facilitated; the homogenization heat treatment can improve the corrosion resistance of the alloy, decompose eutectic structures and reduce the number of the micro-couples.
(6) The soluble magnesium-based alloy material has the hardness of 50-70 HV and the density of 1.74-2.15 g/cm3The dissolution rate in a normal-temperature 3% KCl solution is 10-40 mg-cm-2·h-1The dissolution rate in a 3% KCl solution at about 90 ℃ is 20-160 mg-cm-2·h-1The fracturing ball prepared in the staged fracturing technology of the horizontal well can bear 160-340 MPa of pressure, and the performance of the fracturing ball exceeds the level of the prior art.
(7) According to the preparation method of the soluble magnesium-based alloy, other elements such as manganese, calcium, silicon and the like are added into the magnesium alloy consisting of magnesium, mercury and gallium, so that the strength of magnesium is improved, the dissolution rate of the magnesium alloy can be controlled, and the synergy of the mechanical property and the degradation rate of the magnesium alloy is achieved;
(8) the fracturing ball prepared from the soluble magnesium-based alloy prepared by the preparation method has high degradability, is very suitable for underground use, is hopeful to realize the breakthrough of the deep processing field of the magnesium-based alloy, and can generate powerful promotion effect on the improvement of the technology and equipment level of the deep processing field of the magnesium-based alloy;
(9) the fracturing ball made of the soluble magnesium-based alloy prepared by the preparation method can overcome the defects of difficult drilling and milling, long time consumption, difficult flowback of drilled and removed powder and fragments and the like in the traditional material fracturing operation process, greatly improve the operation efficiency and reduce the unconventional oil and gas resource exploitation operation cost.
(10) Different methods are adopted according to different purposes: method one (fusion casting method): the fusion casting method has the advantages of large alloy structure, uneven components, weak alloy mechanical property and high dissolution speed, and is suitable for a working environment at 60-90 ℃; method two (powder metallurgy): the structure is fine, the components are easy to control and uniform, the mechanical property is good, and the device is suitable for low-temperature (less than 60 ℃) and high-temperature (higher than 90 ℃) operating environments; method three (spray deposition method): fine structure, uniform components, good mechanical property, lower cost than the second method, and is suitable for low-temperature (less than 60 ℃) and high-temperature (higher than 90 ℃) operating environments.
(11) In the first method (fusion casting method), each intermediate alloy is prepared by a powder metallurgy method, and the powder particles are 20-200 mu m, so that the components of the melt are more uniform, the agglomeration of alloy elements in the melt is weakened, and the solid structure with more uniform components is obtained. The uniformity of the components is improved, and the mechanical property and the electrochemical property are both beneficial.
Drawings
FIG. 1 is a photograph (top left and top right) of a soluble magnesium-based alloy prepared by the method of embodiment 1 and a structural picture thereof (bottom left: 200 times magnification of metallographic microscope, bottom right: 200 times magnification of metallographic microscope);
fig. 2 is a photograph (upper left and lower left) of a soluble magnesium-based alloy prepared by the method of embodiment 4 or embodiment 7 and a structural picture thereof (right: metallographic microscope magnification 200 times).
Detailed Description
The present invention will be described in detail with reference to the accompanying drawings.
Embodiment 1:
the embodiment provides a soluble magnesium-based alloy for preparing fracturing balls for oil and gas exploitation, which comprises the following components in percentage by weight: mn: 0.2%, Ca: 1%, Nb: 1%, Ge: 2%, Si: 0.2%, Hg: 1.6%, Ga: 1.0%, Dy: 0.4%, Mg: 92.6 percent; wherein the Ga/Hg ratio is 0.63.
The preparation method of the soluble magnesium-based alloy comprises the following steps:
firstly, pure metals of raw materials Mg, Mn and Nb are taken according to the proportion, and intermediate alloys of Mg-Ca, Mg-Si, Mg-Hg, Mg-Dy, Mg-Ge and Mg-Ga with powder particles of 20-200 mu m prepared by a powder metallurgy method are taken, and all the raw materials are dried.
S1: smelting: in CO2And SF6Under the mixed gas atmosphere with the proportion of 300:1, firstly melting pure magnesium, then adding pure metals of Mn and Nb with the purity of more than or equal to 99.9% at 690 ℃, uniformly stirring, keeping the temperature for 30min, adding intermediate alloys of Mg-Ca, Mg-Si, Mg-Hg, Mg-Dy, Mg-Ge and Mg-Ga with the purity of more than or equal to 99.9%, uniformly stirring, keeping the temperature for 30min, and heating to 735 ℃; introducing 0.3MPa and 0.05m into the melt3Introducing argon into the alloy melt, stirring the mixture until the alloy is uniform, then reducing the temperature of the alloy melt to 700 ℃, and keeping the temperature for 15 min;
s2: casting: and casting the molten metal smelted in the step S1 into a mold to form an ingot.
S3: homogenizing heat treatment: homogenizing and heat-treating the ingot obtained in the step S2 at 400 ℃ for 25 hours, and then cooling along with the furnace;
s4: extruding: extruding the cast ingot subjected to the homogenizing heat treatment obtained in the step S3 into a blank at 360 ℃; the extrusion ratio was 10 and the extrusion speed was 10 m/min.
S5: aging treatment: the billet obtained in S4 was aged at 110 ℃ for 15 hours.
S6: machining and forming: and machining and shaping the blank obtained in the step S5.
The structure photo of the soluble magnesium-based alloy prepared by the method is shown in figure 1, and the soluble magnesium-based alloy is thick in structure and poor in mechanical property.
Embodiment 2:
this embodiment is substantially the same as embodiment 1 except that (1) when the homogenization heat treatment is performed at S3, the heat treatment temperature is 380 ℃ and the treatment time is 30 hours; (2) the extrusion ratio at the time of extrusion at S4 was 5; (3) in the components of the soluble magnesium-based alloy, Ga is 1.5%, Mg: 92.1 percent; wherein the Ga/Hg ratio is 0.94.
Otherwise, this embodiment is identical to embodiment 1, and will not be described herein.
Embodiment 3:
this embodiment is substantially the same as embodiment 1 except that (1) in the homogenization heat treatment of S3, the heat treatment temperature is 420 ℃ and the treatment time is 20 hours; (2) the extrusion ratio at the time of extrusion at S4 was 15; (3) in the components of the soluble magnesium-based alloy, Hg is 1.5 percent; ga 1.5%, Mg: 92.2 percent; wherein the Ga/Hg ratio is 1.1.
Otherwise, this embodiment is identical to embodiment 1, and will not be described herein.
The dissolution rate in a normal temperature 3% KCl solution, the dissolution rate in a 3% KCl solution at about 90 ℃, and the pressure parameters that the horizontal well staged fracturing sphere can withstand of the soluble magnesium-based alloy prepared in the above embodiments 1 to 3 are as follows.
TABLE 1
As can be seen from Table 1, the dissolving rate of the segmented fracturing ball in 3% KCl solution at normal temperature and 90 ℃ is high, the mechanical property is good, and the using requirement of the segmented fracturing ball can be met.
Embodiment 4:
the embodiment provides a soluble magnesium-based alloy for preparing fracturing balls for oil and gas exploitation, which comprises the following components in percentage by weight: mn: 0.1%, Ca: 1.5%, Nb: 2%, Ge: 3%, Si: 0.2%, Hg: 1.8%, Ga: 1.44%, Dy: 0.3%, Mg: 89.96 percent; wherein the Ga/Hg ratio is 0.8.
The preparation method of the soluble magnesium-based alloy comprises the following steps:
s1: milling: preparing the required magnesium alloy powder, namely mixing magnesium powder with the granularity of 50-80 mu m and the purity of more than or equal to 99.9 percent, manganese powder with the granularity of 5-10 mu m and the purity of more than or equal to 99.9 percent, niobium powder and intermediate alloy powder of Mg-Ca, Mg-Si, Mg-Hg, Mg-Dy, Mg-Ge and Mg-Ga according to the proportion in CO2And SF6The mixed gas with the proportion of 300:1 is fully mixed under the protection of the mixed gas;
s2: pre-pressing: prepressing and forming the mixed powder under the pressure of 100 MPa;
s3, sintering: sintering the pre-pressed material at 560 ℃, wherein the pressure applied in the sintering process is 200MPa, the sintering time is 2h, and introducing CO2And SF6Under the protection of mixed gas with the proportion of 300:1, cooling along with a furnace after sintering to obtain a soluble magnesium-based alloy material;
s4: machining and forming: the soluble magnesium-based alloy material is processed and formed in a sintering blank machine.
The structure photo of the soluble magnesium-based alloy prepared by the method is shown in figure 2, the structure is refined, the structure is not oriented, and the performance is uniform.
Embodiment 5:
this embodiment is substantially the same as embodiment 4 except that (1) the sintering temperature is 580 ℃ and the sintering time is 1.8 hours at the time of sintering in S3; (2) in the components of the soluble magnesium-based alloy, Ga is 0.9%, Mg: 89.42 percent; wherein the Ga/Hg ratio is 0.5.
Otherwise, this embodiment is completely the same as embodiment 4, and will not be described herein.
Embodiment 6:
this embodiment is substantially the same as embodiment 4 except that (1) the sintering temperature is 520 ℃ and the sintering time is 2.3 hours at the time of sintering in S3; (2) in the components of the soluble magnesium-based alloy, Hg is 1.4 percent; ga 1.2%, Mg: 89.5 percent; wherein the Ga/Hg ratio is 0.86.
Otherwise, this embodiment is completely the same as embodiment 4, and will not be described herein.
The dissolution rate in a normal temperature 3% KCl solution, the dissolution rate in a 3% KCl solution at about 90 ℃, and the pressure parameters that the horizontal well staged fracturing sphere can withstand of the soluble magnesium-based alloy prepared in the above embodiments 4 to 6 are as follows 2.
TABLE 2
As can be seen from Table 2, the dissolution rate is reduced as compared with Table 1, because the amount of coarse second phases in the alloy is reduced, the number of microcells formed is reduced, and the corrosion resistance is improved. But the mechanical property is improved compared with that of the material shown in the table 1, and the fine grain strengthening effect is obvious due to the tissue refinement, so that the mechanical property of the material is improved.
Embodiment 7:
the embodiment provides a soluble magnesium-based alloy for preparing fracturing balls for oil and gas exploitation, which comprises the following components in percentage by weight: mn: 0.3%, Ca: 0.5%, Nb: 0.5%, Ge: 1%, Si: 0.2%, Hg: 1.5%, Ga: 1.5%, Dy: 0.5%, Mg: 94 percent; wherein the Ga/Hg ratio is 1.
The preparation method of the soluble magnesium-based alloy comprises the following steps:
s1: smelting the required magnesium alloy solution: under a protective atmosphere, firstly melting pure magnesium, then adding pure metals of Mn and Nb at 720 ℃, uniformly stirring, keeping the temperature for 30min, adding intermediate alloys of Mg-Ca, Mg-Si, Mg-Hg, Mg-Dy, Mg-Ge and Mg-Ga, uniformly stirring, keeping the temperature for 30min, and heating to 740 ℃; introducing argon into the melt, stirring while introducing the argon until the alloy is uniform, then reducing the temperature of the alloy melt to 740 ℃, and keeping the temperature for 15 min;
s2: atomization and deposition: atomizing the alloy solution in the S1 under the condition that the argon pressure is 1.0MPa, and then depositing under the condition that the deposition distance is 1.0m to obtain a deposition blank;
s3: extruding: extruding the deposition blank under the conditions that the extrusion temperature is 370 ℃, the extrusion ratio is 10 and the extrusion speed is 10m/min to obtain an extruded product;
s4: aging treatment: aging the extruded product at 110 deg.C for 20 hr;
s5: machining and forming: and machining and forming the aged product.
Embodiment 8:
this embodiment is substantially the same as embodiment 7 except that (1) the extrusion ratio is 5 when extruding at S3; (2) in the components of the soluble magnesium-based alloy, Hg is 1.9%, Ga is 0.9%, Mg: 93.8 percent; wherein the Ga/Hg ratio is 0.47.
Otherwise, this embodiment is completely the same as embodiment 7, and will not be described herein.
Embodiment 9:
this embodiment is substantially the same as embodiment 7 except that (1) the extrusion ratio is 15 at the time of extrusion at S3; (2) in the components of the soluble magnesium-based alloy, Hg is 1.9%, Ga is 1.2%, Mg: 94.1 percent; wherein the Ga/Hg ratio is 0.63.
Otherwise, this embodiment is completely the same as embodiment 7, and will not be described herein.
The dissolution rate in normal temperature 3% KCl solution, the dissolution rate in 3% KCl solution at about 90 ℃, and the pressure parameters that the horizontal well staged fracturing sphere can withstand of the soluble magnesium-based alloy prepared in embodiments 7 to 9 above are as follows in table 3.
TABLE 3
| Dissolution Rate in 3% KCl solution at Normal temperature (mg. cm)-2·h-1） | Dissolution Rate in 3% KCl solution at about 90 ℃ (mg. cm)-2·h-1） | Pressure (MPa) that horizontal well segmentation fracturing ball can bear | |
| Embodiment 7 | 0.92 | 25.89 | 261 |
| Embodiment 8 | 0.68 | 21.05 | 259 |
| Embodiment 9 | 0.87 | 23.62 | 258 |
As can be seen from Table 3, the mechanical properties are better than those of Table 1 and equivalent to those of Table 2, and the fine-grain strengthening effect is obvious because the spray deposition effectively refines the structure. The dissolution rate is comparable to table 2 and better than table 1, since the tissue is uniform and the coarse second phases capable of forming microcells are reduced, the dissolution rate is lower than table 1. Alloys prepared by spray deposition may contain voids that accelerate dissolution of the alloy, but are detrimental to mechanical properties.
The above embodiments are merely illustrative of the technical concepts and features of the present invention, and the purpose of the embodiments is to enable those skilled in the art to understand the contents of the present invention and implement the present invention, and not to limit the protection scope of the present invention. All equivalent changes and modifications made according to the spirit of the present invention should be covered within the protection scope of the present invention.
Claims (10)
1. A soluble magnesium-based alloy is characterized by comprising the following components in percentage by weight: mn: 0.1-0.3%, Ca: 0.5 to 1.5%, Nb: 0.5-2%, Ge: 1-3%, Si: 0.1-0.3%, Hg: 1.4 to 1.9%, Ga: 0.9-1.5%, Dy: 0.3-0.5% and the balance of Mg; wherein the Ga/Hg ratio in the magnesium-based alloy is 0.45-1.1.
2. A method of making a soluble magnesium based alloy as claimed in claim 1 comprising the steps of:
s1: taking pure metals of raw materials Mg, Mn and Nb according to the proportion, and intermediate alloys of Mg-Ca, Mg-Si, Mg-Hg, Mg-Dy, Mg-Ge and Mg-Ga with powder particles of 20-200 mu m prepared by a powder metallurgy method, and drying all the raw materials;
s2: smelting: under a protective atmosphere, firstly melting pure magnesium, then adding pure metals of Mn and Nb at 680-720 ℃, and uniformly stirringThen preserving heat for 25-35 min, adding intermediate alloys of Mg-Ca, Mg-Si, Mg-Hg, Mg-Dy, Mg-Ge and Mg-Ga, stirring uniformly, preserving heat for 25-35 min, and heating to 730-740 ℃; introducing air pressure of 0.12-0.5 MPa and flow rate of 0.01-0.2 m into the melt3Introducing argon into the alloy melt, stirring the mixture until the alloy is uniform, then cooling the alloy melt to 680-720 ℃, and preserving the temperature for 10-20 min;
s3: casting: casting the molten metal smelted in the step S2 into a mould to form a cast ingot;
s4: homogenizing heat treatment: carrying out homogenizing heat treatment on the ingot obtained in the step S3 at 380-420 ℃ for 18-30 hours, and then cooling along with the furnace;
s5: extruding: extruding the cast ingot subjected to the homogenization heat treatment obtained in the step S4 into a blank at the temperature of 350-380 ℃, wherein the extrusion ratio is 4-20, and the extrusion speed is 2-20 m/min;
s6: aging treatment: aging the blank obtained in the step S5;
s7: machining and forming: and machining and shaping the blank obtained in the step S6.
3. The soluble magnesium-based alloy according to claim 2, wherein in said S2 said protective atmosphere is CO2And SF6The proportion of the mixed gas is 200-400: 1;
or, the protective atmosphere is Ar and SF6The proportion of the mixed gas is 200-400: 1;
or, the protective atmosphere is N2And SF6The proportion of the mixed gas is 200-400: 1.
4. a soluble magnesium-based alloy according to claim 2 or 3, wherein said aging treatment in S6 is carried out at a temperature of 100 to 120 ℃ for a period of 5 to 24 hours.
5. A method of making a soluble magnesium based alloy as claimed in claim 1 comprising the steps of:
s1: milling: preparing required magnesium alloy powder, and fully mixing magnesium powder, manganese powder, niobium powder and intermediate alloy powder of Mg-Ca, Mg-Si, Mg-Hg, Mg-Dy, Mg-Ge and Mg-Ga according to the proportion under the protection of inert gas;
s2: pre-pressing: prepressing and forming the mixed powder under the pressure of 80-120 MPa;
s3, sintering: sintering the pre-pressed and formed material at 520-580 ℃, applying pressure of 160-240 MPa in the sintering process, sintering time of 1.6-2.3 h, introducing inert gas for protection, and cooling along with a furnace after sintering to obtain a soluble magnesium-based alloy material;
s4: machining and forming: and processing and shaping the soluble magnesium-based alloy material in a sintering blank machine.
6. The soluble magnesium-based alloy according to claim 5, wherein said magnesium powder has a particle size of 50-80 um, and said manganese powder, niobium powder and said Mg-Ca, Mg-Si, Mg-Hg, Mg-Dy, Mg-Ge, Mg-Ga master alloy powder each have a particle size of 5-10 um.
7. The soluble magnesium-based alloy according to claim 5 or 6, wherein in said S1 and said S3, said inert gas is CO2And SF6The proportion of the mixed gas is 200-400: 1;
or, Ar and SF6The proportion of the mixed gas is 200-400: 1;
or, N2And SF6The proportion of the mixed gas is 200-400: 1.
8. a method of making a soluble magnesium based alloy as claimed in claim 1 comprising the steps of:
s1: smelting the required magnesium alloy solution: under a protective atmosphere, firstly melting pure magnesium, then adding pure metals of Mn and Nb at 700-740 ℃, uniformly stirring, keeping the temperature for 25-35 min, adding intermediate alloys of Mg-Ca, Mg-Si, Mg-Hg, Mg-Dy, Mg-Ge and Mg-Ga, uniformly stirring, keeping the temperature for 25-35 min, and heating to 730-750 ℃; introducing argon into the melt, introducing the argon while stirring until the alloy is uniform, then reducing the temperature of the alloy melt to 720-730 ℃, and preserving the temperature for 15-20 min;
s2: atomization and deposition: atomizing the alloy solution in the S1, and depositing to obtain a deposition blank; the atomization pressure during atomization deposition is 0.4-1.5 MPa, the atomization gas is argon, nitrogen or carbon dioxide, and the deposition distance is 0.5-1.2 m;
s3: extruding: extruding the deposition blank at 350-380 ℃ to obtain an extruded product, wherein the extrusion ratio is 5-15, and the extrusion speed is 2-20 m/min;
s4: aging treatment: aging the extruded article;
s5: machining and forming: and machining and forming the aged product.
9. The soluble magnesium-based alloy according to claim 8, wherein said aging treatment in S4 is performed at a temperature of 100 to 120 ℃ for 5 to 40 hours.
10. Use of the soluble magnesium-based alloy of claim 1 in a soluble alloy fracturing ball for oil and gas recovery.
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Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009068132A1 (en) * | 2007-11-28 | 2009-06-04 | Daimler Ag | Motor block having molded cylinder sleeves comprising a plurality of material layers and method for producing the cylinder sleeves |
| CN101623699A (en) * | 2008-07-08 | 2010-01-13 | 山西银光华盛镁业股份有限公司 | Method for producing magnesium alloy anode plate of torpedo battery |
| CN101624661A (en) * | 2008-07-08 | 2010-01-13 | 山西银光华盛镁业股份有限公司 | Method for fusion casting of mercury-containing anode magnesium alloy of torpedo battery |
| CN104004950A (en) * | 2014-06-05 | 2014-08-27 | 宁波高新区融创新材料科技有限公司 | Easily-soluble magnesium alloy material as well as production method and application thereof |
| CN104651691A (en) * | 2015-02-06 | 2015-05-27 | 宁波高新区融创新材料科技有限公司 | Rapidly degradable magnesium alloy material as well as manufacturing method and application thereof |
| CN105624499A (en) * | 2014-10-29 | 2016-06-01 | 中国石油化工股份有限公司 | Rapidly corroded magnesium-base alloy material and preparation method thereof |
| CN105755338A (en) * | 2014-12-15 | 2016-07-13 | 中国电子科技集团公司第十八研究所 | Preparation method for magnesium alloy negative electrode material used for seawater battery |
| CN105908038A (en) * | 2016-06-24 | 2016-08-31 | 中国石油集团川庆钻探工程有限公司长庆井下技术作业公司 | Soluble alloy used for manufacturing fracture separating tool and preparation method of soluble alloy |
| CN105908037A (en) * | 2016-06-24 | 2016-08-31 | 中国石油集团川庆钻探工程有限公司长庆井下技术作业公司 | Magnesium alloy used for manufacturing soluble fracturing ball and preparing method of magnesium alloy |
| CN104087804B (en) * | 2014-07-28 | 2016-09-07 | 胡贤晨 | A kind of creep resistance Dow metal and preparation method thereof |
| CN105950930A (en) * | 2016-06-24 | 2016-09-21 | 中国石油集团川庆钻探工程有限公司长庆井下技术作业公司 | Soluble extrusion magnesium alloy and preparation method thereof |
| JP2017206757A (en) * | 2016-05-20 | 2017-11-24 | 不二ライトメタル株式会社 | Resolvable magnesium alloy |
| CN107385245A (en) * | 2017-06-09 | 2017-11-24 | 西安理工大学 | Manufacture method based on oil-gas mining with soluble alloy pressure break ball |
| CN107502802A (en) * | 2017-09-19 | 2017-12-22 | 西安理工大学 | Instrument magnesium alloy and preparation method thereof is temporarily blocked up in a kind of oil-gas mining |
| CN109694976A (en) * | 2019-03-13 | 2019-04-30 | 山东省科学院新材料研究所 | A kind of low cost soluble magnesium alloy and its preparation method and application |
| CN110106416A (en) * | 2019-05-24 | 2019-08-09 | 山东省科学院新材料研究所 | A kind of superhigh intensity can dissolve magnesium alloy and its preparation method and application |
| CN110129599A (en) * | 2019-06-11 | 2019-08-16 | 广东省材料与加工研究所 | Magnesium alloy materials, preparation method and application |
| CN110184518A (en) * | 2019-04-24 | 2019-08-30 | 北京易联结科技发展有限公司 | A kind of rapidly-soluble high-strength high-elongation ratio magnesium alloy and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170268088A1 (en) * | 2014-02-21 | 2017-09-21 | Terves Inc. | High Conductivity Magnesium Alloy |
-
2019
- 2019-12-08 CN CN201911246268.2A patent/CN111041309B/en active Active
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2009068132A1 (en) * | 2007-11-28 | 2009-06-04 | Daimler Ag | Motor block having molded cylinder sleeves comprising a plurality of material layers and method for producing the cylinder sleeves |
| CN101623699A (en) * | 2008-07-08 | 2010-01-13 | 山西银光华盛镁业股份有限公司 | Method for producing magnesium alloy anode plate of torpedo battery |
| CN101624661A (en) * | 2008-07-08 | 2010-01-13 | 山西银光华盛镁业股份有限公司 | Method for fusion casting of mercury-containing anode magnesium alloy of torpedo battery |
| CN104004950A (en) * | 2014-06-05 | 2014-08-27 | 宁波高新区融创新材料科技有限公司 | Easily-soluble magnesium alloy material as well as production method and application thereof |
| CN104087804B (en) * | 2014-07-28 | 2016-09-07 | 胡贤晨 | A kind of creep resistance Dow metal and preparation method thereof |
| CN105624499A (en) * | 2014-10-29 | 2016-06-01 | 中国石油化工股份有限公司 | Rapidly corroded magnesium-base alloy material and preparation method thereof |
| CN105755338A (en) * | 2014-12-15 | 2016-07-13 | 中国电子科技集团公司第十八研究所 | Preparation method for magnesium alloy negative electrode material used for seawater battery |
| CN104651691A (en) * | 2015-02-06 | 2015-05-27 | 宁波高新区融创新材料科技有限公司 | Rapidly degradable magnesium alloy material as well as manufacturing method and application thereof |
| JP2017206757A (en) * | 2016-05-20 | 2017-11-24 | 不二ライトメタル株式会社 | Resolvable magnesium alloy |
| CN105908037A (en) * | 2016-06-24 | 2016-08-31 | 中国石油集团川庆钻探工程有限公司长庆井下技术作业公司 | Magnesium alloy used for manufacturing soluble fracturing ball and preparing method of magnesium alloy |
| CN105950930A (en) * | 2016-06-24 | 2016-09-21 | 中国石油集团川庆钻探工程有限公司长庆井下技术作业公司 | Soluble extrusion magnesium alloy and preparation method thereof |
| CN105908038A (en) * | 2016-06-24 | 2016-08-31 | 中国石油集团川庆钻探工程有限公司长庆井下技术作业公司 | Soluble alloy used for manufacturing fracture separating tool and preparation method of soluble alloy |
| CN107385245A (en) * | 2017-06-09 | 2017-11-24 | 西安理工大学 | Manufacture method based on oil-gas mining with soluble alloy pressure break ball |
| CN107502802A (en) * | 2017-09-19 | 2017-12-22 | 西安理工大学 | Instrument magnesium alloy and preparation method thereof is temporarily blocked up in a kind of oil-gas mining |
| CN109694976A (en) * | 2019-03-13 | 2019-04-30 | 山东省科学院新材料研究所 | A kind of low cost soluble magnesium alloy and its preparation method and application |
| CN110184518A (en) * | 2019-04-24 | 2019-08-30 | 北京易联结科技发展有限公司 | A kind of rapidly-soluble high-strength high-elongation ratio magnesium alloy and preparation method thereof |
| CN110106416A (en) * | 2019-05-24 | 2019-08-09 | 山东省科学院新材料研究所 | A kind of superhigh intensity can dissolve magnesium alloy and its preparation method and application |
| CN110129599A (en) * | 2019-06-11 | 2019-08-16 | 广东省材料与加工研究所 | Magnesium alloy materials, preparation method and application |
Non-Patent Citations (4)
| Title |
|---|
| 井下暂堵工具用可溶镁合金研究;郭皓;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20180215;B019-565 * |
| 压裂分隔工具用可溶镁合金Mg-7A1-1Zn-1 Ni-1Cu的制备与性能;杨军;《有色金属工程》;20180630;第8卷(第3期);47-56 * |
| 可溶性镁合金的制备及其性能;姜倩等;《工程科学学报》;20180228;第40卷(第2期);192--199 * |
| 石油钻井用可溶性镁合金材料研究;李敏;《中国优秀硕士学位论文全文数据库 工程科技Ⅰ辑》;20180615;B022-72 * |
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