CN116287918B - Magnesium alloy soluble in chlorine-containing solution and preparation method and application thereof - Google Patents
Magnesium alloy soluble in chlorine-containing solution and preparation method and application thereof Download PDFInfo
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- CN116287918B CN116287918B CN202310524296.6A CN202310524296A CN116287918B CN 116287918 B CN116287918 B CN 116287918B CN 202310524296 A CN202310524296 A CN 202310524296A CN 116287918 B CN116287918 B CN 116287918B
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- 229910000861 Mg alloy Inorganic materials 0.000 title claims abstract description 115
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 title claims abstract description 74
- 239000000460 chlorine Substances 0.000 title claims abstract description 74
- 229910052801 chlorine Inorganic materials 0.000 title claims abstract description 74
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000011777 magnesium Substances 0.000 claims abstract description 61
- 239000012535 impurity Substances 0.000 claims abstract description 28
- 229910045601 alloy Inorganic materials 0.000 claims description 87
- 239000000956 alloy Substances 0.000 claims description 87
- 239000010949 copper Substances 0.000 claims description 42
- 238000001125 extrusion Methods 0.000 claims description 38
- 238000000034 method Methods 0.000 claims description 32
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 32
- 239000011701 zinc Substances 0.000 claims description 32
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 30
- 229910052749 magnesium Inorganic materials 0.000 claims description 30
- 229910052782 aluminium Inorganic materials 0.000 claims description 28
- 230000004907 flux Effects 0.000 claims description 28
- 238000001192 hot extrusion Methods 0.000 claims description 27
- 230000032683 aging Effects 0.000 claims description 26
- 229910052802 copper Inorganic materials 0.000 claims description 26
- 238000000265 homogenisation Methods 0.000 claims description 24
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 23
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 23
- 229910052684 Cerium Inorganic materials 0.000 claims description 22
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 22
- 229910052746 lanthanum Inorganic materials 0.000 claims description 22
- 230000008569 process Effects 0.000 claims description 22
- 239000000463 material Substances 0.000 claims description 18
- 229910052725 zinc Inorganic materials 0.000 claims description 16
- 150000002910 rare earth metals Chemical class 0.000 claims description 15
- 238000005266 casting Methods 0.000 claims description 14
- 238000007670 refining Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 10
- 239000007789 gas Substances 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 9
- 239000000314 lubricant Substances 0.000 claims description 9
- 238000004321 preservation Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 238000005303 weighing Methods 0.000 claims description 8
- 229910019083 Mg-Ni Inorganic materials 0.000 claims description 7
- 229910019403 Mg—Ni Inorganic materials 0.000 claims description 7
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 6
- 229910002804 graphite Inorganic materials 0.000 claims description 6
- 239000010439 graphite Substances 0.000 claims description 6
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052982 molybdenum disulfide Inorganic materials 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 5
- 239000003079 shale oil Substances 0.000 claims description 5
- 238000003723 Smelting Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 abstract description 10
- 238000010276 construction Methods 0.000 abstract description 4
- 239000003208 petroleum Substances 0.000 abstract description 4
- 239000000243 solution Substances 0.000 description 63
- 230000000052 comparative effect Effects 0.000 description 28
- 238000005728 strengthening Methods 0.000 description 19
- 238000004090 dissolution Methods 0.000 description 18
- 230000008018 melting Effects 0.000 description 18
- 238000002844 melting Methods 0.000 description 18
- 229910052759 nickel Inorganic materials 0.000 description 16
- 230000007797 corrosion Effects 0.000 description 12
- 238000005260 corrosion Methods 0.000 description 12
- 238000001514 detection method Methods 0.000 description 11
- 238000009749 continuous casting Methods 0.000 description 9
- 239000012530 fluid Substances 0.000 description 8
- 238000012797 qualification Methods 0.000 description 8
- 229910052688 Gadolinium Inorganic materials 0.000 description 6
- -1 aluminum rare earth Chemical class 0.000 description 6
- 239000000155 melt Substances 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 239000000523 sample Substances 0.000 description 4
- 238000011161 development Methods 0.000 description 3
- 230000018109 developmental process Effects 0.000 description 3
- 238000005553 drilling Methods 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 230000002829 reductive effect Effects 0.000 description 3
- 239000006104 solid solution Substances 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007922 dissolution test Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000005065 mining Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000035882 stress Effects 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229910004261 CaF 2 Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000002358 autolytic effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007872 degassing Methods 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 230000005496 eutectics Effects 0.000 description 1
- 239000012634 fragment Substances 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 230000000670 limiting effect Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
Classifications
-
- 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
- C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/006—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with use of an inert protective material including the use of an inert gas
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
- C22B9/00—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals
- C22B9/10—General processes of refining or remelting of metals; Apparatus for electroslag or arc remelting of metals with refining or fluxing agents; Use of materials therefor, e.g. slagging or scorifying agents
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P10/00—Technologies related to metal processing
- Y02P10/20—Recycling
Abstract
The invention discloses a magnesium alloy soluble in chlorine-containing solution, and a preparation method and application thereof, wherein the magnesium alloy comprises the following elements in percentage by mass: al:7.5% -12.0%, zn:0.6% -2.1%, ni:0.2% -0.8%, cu 1.2% -2.2%, la 1.2% -2.2%, ce 0.4% -0.8% and the balance of Mg and unavoidable impurity elements. The magnesium alloy which is soluble in chlorine-containing solution and prepared by the preparation method provided by the invention has the yield strength of more than or equal to 230MPa, the tensile strength of more than or equal to 330MPa, excellent mechanical properties, and can be dissolved in chloride ion solution within a certain concentration range, thereby being suitable for the field of petroleum exploitation and achieving the purposes of saving construction time, reducing exploitation cost and improving exploitation efficiency.
Description
Technical Field
The invention relates to a metal material and a processing technology, in particular to a magnesium alloy which is soluble in chlorine-containing solution, a preparation method and application thereof.
Background
Along with the exhaustion of traditional oil gas resources, shale oil gas gradually becomes an important direction for the development of the energy field in the current and future period, and has higher development prospect and economic value. According to statistics, the reserves of shale gas and shale oil in China are in the front of the world, and the future development prospect is wide. However, the related mining technology is still in the beginning price segment. Currently mainstream horizontal well exploitation commonly uses staged fracturing technology to realize the transformation of a plurality of strata simultaneously to improve single well productivity, thereby improving construction efficiency. One key component of this technology is fracturing tools, including temporary plugging balls, ball seats, bridge plugs, sliding sleeves, and the like. The tool needs to have solubility and good mechanical property in the fracturing process, and the good performance can directly influence the construction efficiency.
In the exploitation process of petroleum or shale gas, the well needs to be sealed to generate pressure after well completion, shale is fractured, and oil gas is oozed out. The normal downhole temperature is between 100 ℃ and 150 ℃, the fracturing tool and the fracturing fluid enter the well at the same time, the fracturing fluid is not high in temperature, the initial temperature is approximately below 50 ℃, the fracturing operation is carried out for a plurality of hours, the temperature is below 90 ℃, and the fracturing tool cannot be dissolved. In order to ensure that the fracturing tool has better dissolution performance, the concentration of chloride ions in the fracturing fluid can be adjusted to accelerate corrosion. Therefore, developing a soluble magnesium alloy that can be used in solutions of different chloride ion concentrations has very broad prospects.
The information disclosed in this background section is only for enhancement of understanding of the general background of the invention and should not be taken as an acknowledgement or any form of suggestion that this information forms the prior art already known to a person of ordinary skill in the art.
Disclosure of Invention
The invention aims to provide a magnesium alloy which can be dissolved in chlorine-containing solution, can be automatically dissolved in petroleum underground, has higher strength and plasticity, can omit drilling, grinding and recycling processes, reduces engineering risks, improves construction efficiency, and can also avoid damage of drill cuttings and circulating liquid to a reservoir.
To achieve the above object, an embodiment of the present invention provides a magnesium alloy soluble in a chlorine-containing solution, the magnesium alloy including the following elements in mass percent: al:7.5% -12.0%, zn:0.6% -2.1%, ni:0.2% -0.8%, 1.2% -2.2% Cu, 1.2% -2.2% La, 0.4% -0.8% Ce, and the balance of Mg and unavoidable impurity elements.
In another aspect of the present invention, there is provided a method for preparing a magnesium alloy soluble in a chlorine-containing solution, comprising the steps of:
a. weighing magnesium ingots, zinc ingots, aluminum ingots, red copper, mg-Ni intermediate alloy, mg-La intermediate alloy and Mg-Ce intermediate alloy according to the mass percentage of the magnesium alloy;
b. after the magnesium ingot is heated to be molten under the coverage of RJ-2 flux, sequentially adding Mg-Ni intermediate alloy, aluminum ingot, zinc ingot, red copper, mg-La intermediate alloy and Mg-Ce intermediate alloy, and after adding the rare earth intermediate alloy, covering RJ-5 to reduce burning loss;
c. refining and casting into cast ingots by using RJ-5 flux and protective atmosphere after all materials are melted;
d. and carrying out homogenization treatment on the cast ingot, and then carrying out hot extrusion to form bars, and carrying out aging treatment.
In one or more embodiments of the present invention, in the step a, the mass percentage of Ni in the Mg-Ni intermediate alloy is (20-80)%, the mass percentage of La in the Mg-La intermediate alloy is (30-40)%, and the mass percentage of Ce in the Mg-Ce intermediate alloy is (30-40)%.
In one or more embodiments of the present invention, the amount of the RJ-5 flux in the steps b and c is (2 to 4)% of the total weight of the magnesium ingot, the zinc ingot, the aluminum ingot, the red copper, the Mg-Ni master alloy, the Mg-La master alloy and the Mg-Ce master alloy; and/or, the protective atmosphere in the step c is nitrogen or argon.
In one or more embodiments of the present invention, in the step c, after all materials are melted, the melt is refined for 30-40min at 750±5 ℃, then is left for 0-30min, and is cast into a semi-continuous ingot at 740-750 ℃ while keeping the temperature at 740-750 ℃ during the standing process.
In one or more embodiments of the present invention, in the step c, when the electromagnetic semi-continuous casting system is used to cast the semi-continuous ingot at 740-750 ℃, the electromagnetic system is used to stir the mixed melt and the ingot with electromagnetic frequency (20-40) Hz and current (90-130) a until the ingot is completed.
In one or more embodiments of the present invention, in the step d, the ingot is homogenized, specifically, the ingot is placed in a heating furnace, and then two-stage homogenization is performed, where the homogenization conditions are: (250-350) DEG C (2-5) h+ (380-420) DEG C (8-16) h.
In one or more embodiments of the present invention, in the step d, the ingot blank is hot extruded into a bar, specifically, the ingot blank is heat-preserved for (4-6) h at (320-380) DEG C, then hot extruded on a horizontal extruder, the extrusion outlet speed is (0.5-2) mm/s, the temperature of an extrusion barrel and a die during hot extrusion is (320-380) DEG C, and the extrusion ratio is (7-25): 1; water-based graphite or molybdenum disulfide is used as a lubricant in the extrusion process.
In one or more embodiments of the present invention, in the step d, the aging treatment is specifically to take a bar, and treat (22-32) h at (150-200) °c.
In another aspect, the invention provides an application of a preparation method of magnesium alloy soluble in chlorine-containing solution in preparation of fracturing tools for shale oil and gas exploitation.
The advantages and beneficial effects of the embodiment of the invention are that:
1. compared with the prior art, the rare earth elements La and Ce are added into the magnesium alloy, so that not only can the hydrogen be removed, but also the porosity of the cast ingot is reduced, the overall flaw detection qualification rate of the cast ingot is improved, and the yield of the cast ingot is also improved.
2. After the dummy ingot head and tail are removed from the ingot, the quality of the surface of the residual ingot can be improved.
3. The magnesium alloy provided by the invention has better self-dissolving performance in solutions with different chloride ion concentrations.
4. The preparation process is simple and easy, the rare earth elements are all cheap rare earth, the preparation cost is low, and the preparation process is suitable for industrial production.
Drawings
FIG. 1 is an engineering stress strain diagram of magnesium alloys soluble in chlorine-containing solutions according to examples 1 to 6 of the present invention;
FIG. 2 is an engineering stress strain diagram of magnesium alloys soluble in chlorine-containing solutions according to comparative examples 1 to 5 in the present invention.
Detailed Description
The following detailed description of embodiments of the invention is, therefore, to be taken in conjunction with the accompanying drawings, and it is to be understood that the scope of the invention is not limited to the specific embodiments.
The RJ-2 flux in the embodiment of the invention can protect magnesium melt in the process of melting magnesium ingot, and reduce burning loss. The RJ-5 flux is suitable for rare earth magnesium alloy, is mainly used as a Jin Fu cover, has refining purposes, and has strong diffusion performance, surface tension and chemical stability. The melting point and specific gravity of the alloy are lower than those of magnesium alloy, and the alloy is scattered on the magnesium alloy, so that the alloy has the effect of isolating the melt from air, and the oxidation and combustion of metal in the smelting process are reduced. Its main component is MgCl 2 、KCl、BaCl 2 、CaF 2 、CaCl 2 NaCl, mgO, insoluble matter and H 2 O。
Magnesium ingots, zinc ingots, aluminum ingots, red copper and intermediate alloys employed in the examples of the present invention all contain a small amount of unavoidable impurities.
The purity of the argon adopted in the embodiment of the invention is more than or equal to 99 percent.
In the embodiment of the invention, the magnesium alloy cast ingot is extruded after two-stage homogenization treatment to obtain the extrusion rod, and the extrusion rod is subjected to aging strengthening treatment and is subjected to dissolution test. The dissolution rate V in the dissolution test was calculated as v= (M1-M2)/(s×t), where M1, M2 are the mass of the sample before and after the soak test, S is the surface area of the soaked sample, and T is the soak time.
The following description of the preferred embodiments of the present invention is provided in connection with the detailed description, but it should be understood that the description is merely for the purpose of further illustrating the features and advantages of the invention and is not a limitation of the claims of the invention. Throughout the specification and claims, unless explicitly stated otherwise, the term "comprise" or variations thereof such as "comprises" or "comprising", etc. will be understood to include the stated element or component without excluding other elements or components.
The embodiment provides a magnesium alloy which is soluble in chlorine-containing solution, wherein the mass percentages of the elements are as follows:
Al：7.5%~12.0%，Zn：0.6%~2.1%，Ni：0.2% -0.8%, 1.2% -2.2% of Cu, 1.3% -2.2% of La, 0.4% -0.8% of Ce and the balance of Mg and unavoidable impurity elements. Based on AZ91 magnesium alloy, la and Ce rare earth elements are added to modify the magnesium alloy, and a high-melting-point high-thermal-stability aluminum rare earth phase is formed in the magnesium alloy. Mg due to the relatively low melting point of aluminum rare earth 17 Al 12 The precipitation of phase has inhibiting effect, and Mg is changed 17 Al 12 The shape and distribution of the magnesium alloy matrix are increased, and the functions of strengthening the matrix and refining the structure are achieved.
Further preferably, the mass percentages of the respective elements in the magnesium alloy soluble in the chlorine-containing solution are as follows: al:7.5%, zn:0.6%, ni:0.4%, cu:1.2%, la:1.8%, ce:0.6% of Mg and the balance of unavoidable impurity elements. By adding a certain mass percent of rare earth elements, the magnesium alloy can be self-dissolved in a solution with the mass percent of chloride ions being more than 1.4% within the temperature range of (45-93) DEG C at a higher dissolution rate. Therefore, the concentration of chloride ions in the fracturing fluid can be regulated to promote the fracturing tool made of the magnesium alloy which is soluble in the chlorine-containing solution by mass percent, so that the corrosion speed is increased, and the exploitation efficiency is improved.
Further preferably, the mass percentages of the respective elements in the magnesium alloy soluble in the chlorine-containing solution are as follows:
9.2% of Al, 0.6% of Zn, 1.6% of La, 0.5% of Ce, 1.4% of Cu, 0.3% of Ni and the balance of Mg and unavoidable impurities. In the present invention, ni may combine with Mg to form Mg 2 Ni phase, mg 2 The Ni phase can accelerate the corrosion of the magnesium alloy, thereby improving the corrosion rate of the alloy. Ni can also combine with Al to form Al 3 Ni 2 A phase distributed in Mg 17 Al 12 In the phase, not only Mg is reduced 17 Al 12 The corrosion barrier function of the phase promotes the stripping of corrosion products in the degradation process, and refines the matrix alloy grains, thereby improving the mechanical property.
Further preferably, the mass percentages of the respective elements in the magnesium alloy soluble in the chlorine-containing solution are as follows:
10.5% of Al, 2.0% of Zn, 2.2% of La, 0.8% of Ce, 2.2% of Cu, 0.2% of Ni and the balance of Mg and unavoidable impurities. In the invention, the addition of trace Zn can improve the solid solution strengthening and precipitation strengthening effects of the magnesium alloy, thereby further improving the performance of the magnesium alloy.
Further preferably, the mass percentages of the respective elements in the magnesium alloy soluble in the chlorine-containing solution are as follows:
9.5% of Al, 1.6% of Zn, 1.9% of La, 0.6% of Ce, 2.0% of Cu, 0.2% of Ni and the balance of Mg and unavoidable impurities. In the invention, al is utilized to generate solid solution strengthening effect on the magnesium alloy, thereby improving the strength of the magnesium alloy. In addition, because the solid solubility of La and Ce in magnesium is extremely low, crystal grains and reticular eutectic can be refined, and the precipitation strengthening effect can be exerted, so that the mechanical property is improved. The addition of the rare earth elements Ce and La with different proportions not only can play roles in removing impurities and hydrogen, but also can further improve the casting, wear resistance and corrosion resistance of the magnesium alloy.
Further preferably, the mass percentages of the respective elements in the magnesium alloy soluble in the chlorine-containing solution are as follows:
8.5% of Al, 1.6% of Zn, 1.6% of La, 0.5% of Ce, 2.0% of Cu, 0.2% of Ni and the balance of Mg and unavoidable impurities. In the present invention, cu element can combine with Mg to form Mg 2 Cu phase, mg due to micro-galvanic corrosion 2 The Cu phase accelerates the corrosion rate of the magnesium alloy.
Further preferably, the mass percentages of the respective elements in the magnesium alloy soluble in the chlorine-containing solution are as follows:
12.0% of Al, 2.1% of Zn, 1.3% of La, 0.4% of Ce, 1.8% of Cu, 0.8% of Ni and the balance of Mg and unavoidable impurities. The Zn is used for generating solid solution strengthening effect on the magnesium alloy, so that the strength of the magnesium alloy is improved.
The common magnesium alloy has the weaknesses of low strength, difficult deformation, poor corrosion resistance, low use temperature and the like. The magnesium alloy is added with a proper amount of rare earth elements, so that the magnesium alloy has the function of modifying and refining tissues, and simultaneously has the functions of removing impurities and degassing, thereby improving the casting, wear resistance and corrosion resistance of the magnesium alloy. However, because the melting point of the rare earth element is greatly higher than that of the magnesium element, the rare earth metal is difficult to be melted when being directly added into the magnesium alloy in smelting, and the rare earth metal can only be added into the magnesium intermediate alloy. In addition, because the sensitivity of rare earth magnesium alloy to impurities is higher than that of conventional magnesium alloy, rare earth reacts with impurities to generate high-density compounds and precipitate, and the rare earth elements are easy to be rapidly lost although the materials can be purified. Therefore, it is necessary to use a raw material having a low impurity element content by appropriately restricting the harmful impurity element of the raw material. The invention adopts Mg-Ni, mg-La, mg-Ce, magnesium ingots, aluminum ingots, zinc ingots and red copper as raw materials, wherein the purity of the magnesium ingots, the aluminum ingots, the zinc ingots and the red copper is more than or equal to 99.9 percent.
The embodiment also provides an application of the magnesium alloy which is soluble in the chlorine-containing solution in preparing a fracturing tool for shale oil and gas exploitation.
In order to better embody the salient features of the present invention, a further description will be given below with reference to specific preparation examples.
The homogenization treatment adopted in the embodiment of the invention is mainly used for guaranteeing the homogenization of the ingot blank and facilitating the hot extrusion forming process. And the subsequent aging treatment is to increase the hardness and strength of the alloy bar. In addition, the addition of the rare earth elements not only plays a role in removing hydrogen, but also reduces the loose degree of the cast ingot, improves the overall flaw detection qualification rate of the cast ingot, and improves the yield of the cast ingot accordingly, especially after the cast ingot removes the dummy ingot head and tail, the surface quality of the residual cast ingot is high, and the flaw detection qualification rate is more than 95%.
Example 1
The magnesium alloy which is soluble in chlorine-containing solution and prepared in the embodiment consists of the following elements in percentage by mass: 7.5% of Al, 0.6% of Zn, 1.8% of La, 0.6% of Ce, 1.2% of Cu and 0.4% of Ni, and the balance of Mg and unavoidable impurities.
The preparation method of the magnesium alloy soluble in the chlorine-containing solution in the embodiment specifically comprises the following steps:
a. according to the mass percentages of magnesium ingots, zinc ingots, aluminum ingots, red copper, mg-20% Ni intermediate alloy, mg-30% La intermediate alloy and Mg-30% Ce intermediate alloy which are soluble in chlorine-containing solution, weighing RJ-5 flux accounting for 2% of the total weight of the materials.
b. And (3) adding the magnesium ingot covered with the RJ-2 flux into a resistance furnace for melting, and setting the melting temperature to be 750 ℃. Sequentially adding Mg-20% Ni intermediate alloy, aluminum ingot, zinc ingot, red copper, mg-30% La intermediate alloy and Mg-30% Ce intermediate alloy, and covering RJ-5 after adding rare earth intermediate alloy to reduce burning loss.
c. After all materials are melted, refining is carried out for 30min at 750 ℃ by using RJ-5 flux under the protection of nitrogen, then standing is carried out for 20min, the temperature is kept at 740 ℃ in the standing process, and after the standing is finished, semi-continuous cast ingots are cast at 740 ℃. An electromagnetic semi-continuous casting system is used for obtaining an ingot, an electromagnetic system is used for simultaneously carrying out electromagnetic stirring on the mixed melt and the ingot with the electromagnetic frequency of (20-40) Hz and the current of (90-130) A until the casting is completed.
d. Homogenizing: placing the magnesium alloy cast ingot into a heating furnace, and then performing double-stage homogenization treatment; the two-stage homogenization treatment conditions are 250 ℃ multiplied by 3h+380 ℃ multiplied by 14h;
hot extrusion: carrying out heat preservation on the ingot blank with the oxide skin removed for 4 hours at 300 ℃, then carrying out hot extrusion on a horizontal extruder, wherein the extrusion outlet speed is 1mm/s, the temperature of an extrusion cylinder and a die is 320 ℃ during hot extrusion, the extrusion ratio is 17:1, and water-based graphite is used as a lubricant during extrusion;
aging treatment: and (3) carrying out ageing strengthening treatment on the bar, wherein the ageing strengthening treatment condition is 180 ℃ for 28 hours, so that the strength of the bar is further improved, and the soluble magnesium alloy is obtained.
Example 2
The magnesium alloy which is soluble in chlorine-containing solution and prepared in the embodiment consists of the following elements in percentage by mass: al 9.2%, zn 0.6%, la 1.6%, ce 0.5%, cu 1.4% and Ni 0.3%, the balance being Mg and unavoidable impurities.
The preparation method of the magnesium alloy soluble in the chlorine-containing solution in the embodiment specifically comprises the following steps:
a. according to the mass percentages of magnesium ingots, zinc ingots, aluminum ingots, red copper, mg-20% Ni intermediate alloy, mg-30% La intermediate alloy and Mg-30% Ce intermediate alloy which are soluble in chlorine-containing solution, weighing RJ-5 flux accounting for 3% of the total weight of the materials.
b. And (3) adding the magnesium ingot covered with the RJ-2 flux into a resistance furnace for melting, and setting the melting temperature to be 750 ℃. Sequentially adding Mg-20% Ni intermediate alloy, aluminum ingot, zinc ingot, red copper, mg-30% La intermediate alloy and Mg-30% Ce intermediate alloy, and covering RJ-5 after adding rare earth intermediate alloy to reduce burning loss.
c. After all materials are melted, refining is carried out for 35min at 750 ℃ by using RJ-5 flux under the protection of nitrogen, then standing is carried out for 30min, the temperature is kept at 750 ℃ in the standing process, and after the standing is finished, semicontinuous cast ingots are cast at 750 ℃. An electromagnetic semi-continuous casting system is used for obtaining cast ingots, an electromagnetic system is used for simultaneously carrying out electromagnetic stirring on a melt and the cast ingots until casting is completed, wherein the electromagnetic frequency is (20-40) Hz, and the current is (90-130) A.
d. Homogenizing: placing the magnesium alloy cast ingot into a heating furnace, and then performing double-stage homogenization treatment; the two-stage homogenization treatment conditions are 300 ℃ multiplied by 4h+400 ℃ multiplied by 10h;
hot extrusion: carrying out heat preservation on the ingot blank for 5h at 350 ℃, and then carrying out hot extrusion on a horizontal extruder, wherein the extrusion outlet speed is 0.5mm/s, and the extrusion ratio of an extrusion cylinder to a die is 17:1 when the hot extrusion is carried out at 350 ℃; molybdenum disulfide is used as a lubricant in the extrusion process;
aging treatment: and (3) carrying out ageing strengthening treatment on the bar, wherein the ageing strengthening treatment condition is 190 ℃ for 26 hours, so as to further improve the strength of the bar and obtain the soluble magnesium alloy.
Example 3
The magnesium alloy which is soluble in chlorine-containing solution and prepared in the embodiment consists of the following elements in percentage by mass: 10.3% of Al, 2.0% of Zn, 2.2% of La, 0.8% of Ce, 2.2% of Cu and 0.2% of Ni, and the balance of Mg and unavoidable impurities.
The preparation method of the magnesium alloy soluble in the chlorine-containing solution in the embodiment specifically comprises the following steps:
a. according to the mass percentages of magnesium ingots, zinc ingots, aluminum ingots, red copper, mg-20% Ni intermediate alloy, mg-30% La intermediate alloy and Mg-30% Ce intermediate alloy which are soluble in chlorine-containing solution, weighing RJ-5 flux accounting for 4% of the total weight of the materials.
b. And (3) adding the magnesium ingot covered with the RJ-2 flux into a resistance furnace for melting, and setting the melting temperature to be 750 ℃. Sequentially adding Mg-20% Ni intermediate alloy, aluminum ingot, zinc ingot, red copper, mg-30% La intermediate alloy and Mg-30% Ce intermediate alloy, and covering RJ-5 after adding rare earth intermediate alloy to reduce burning loss.
c, after all materials are melted, refining for 40min at 750 ℃ by using RJ-5 flux under the protection of argon, and casting into semicontinuous ingots. An electromagnetic semi-continuous casting system is used for obtaining an ingot, an electromagnetic system is used for simultaneously carrying out electromagnetic stirring on the mixed melt and the ingot with the electromagnetic frequency of (20-40) Hz and the current of (90-130) A until the casting is completed.
d. Homogenizing: placing the magnesium alloy cast ingot into a heating furnace, and then performing double-stage homogenization treatment; the two-stage homogenization treatment conditions are 350 ℃ multiplied by 2h+420 ℃ multiplied by 10h;
hot extrusion: carrying out heat preservation on the ingot blank for 6 hours at 320 ℃, and then carrying out hot extrusion on a horizontal extruder, wherein the extrusion outlet speed is 2mm/s, and the extrusion ratio of an extrusion cylinder to a die is 7:1 at 320 ℃ during hot extrusion; water-based graphite is used as a lubricant in the extrusion process;
aging treatment: and (3) carrying out ageing strengthening treatment on the bar, wherein the ageing strengthening treatment condition is 190 ℃ for 26 hours, so as to further improve the strength of the bar and obtain the soluble magnesium alloy.
Example 4
The magnesium alloy which is soluble in chlorine-containing solution and prepared in the embodiment consists of the following elements in percentage by mass: al 9.5%, zn 1.6%, la 1.9%, ce 0.6%, cu 2.0% and Ni 0.2%, the balance being Mg and unavoidable impurities.
The preparation method of the magnesium alloy soluble in the chlorine-containing solution in the embodiment specifically comprises the following steps:
a. according to the mass percentages of magnesium ingots, zinc ingots, aluminum ingots, red copper, mg-80% Ni intermediate alloy, mg-40% La intermediate alloy and Mg-40% Ce intermediate alloy which are soluble in chlorine-containing solution, weighing RJ-5 flux accounting for 3% of the total weight of the materials.
b. And (3) adding the magnesium ingot covered with the RJ-2 flux into a resistance furnace for melting, and setting the melting temperature to be 750 ℃. Sequentially adding Mg-80% Ni intermediate alloy, aluminum ingot, zinc ingot, red copper, mg-40% La intermediate alloy and Mg-40% Ce intermediate alloy, and covering RJ-5 after adding rare earth intermediate alloy to reduce burning loss.
c. After all materials are melted, refining is carried out for 30min at 750 ℃ by using RJ-5 flux under the protection of argon, then standing is carried out for 20min, the temperature is kept at 750 ℃ in the standing process, and after the standing is finished, a semicontinuous ingot is cast at 750 ℃. An electromagnetic semi-continuous casting system is used for obtaining cast ingots, an electromagnetic system is used for simultaneously carrying out electromagnetic stirring on a melt and the cast ingots until casting is completed, wherein the electromagnetic frequency is (20-40) Hz, and the current is (90-130) A.
d. Homogenizing: placing the magnesium alloy cast ingot into a heating furnace, and then performing double-stage homogenization treatment; the two-stage homogenization treatment conditions are 350 ℃ multiplied by 2h+420 ℃ multiplied by 10h;
hot extrusion: carrying out heat preservation on the ingot blank for 6h at 350 ℃, and then carrying out hot extrusion on a horizontal extruder, wherein the extrusion outlet speed is 2mm/s, and the extrusion ratio of an extrusion cylinder to a die is 17:1 at the temperature of 350 ℃ during hot extrusion; water-based graphite is used as a lubricant in the extrusion process;
aging treatment: and (3) carrying out ageing strengthening treatment on the bar, wherein the ageing strengthening treatment condition is 180 ℃ for 28 hours, so that the strength of the bar is further improved, and the soluble magnesium alloy is obtained.
Example 5
The magnesium alloy which is soluble in chlorine-containing solution and prepared in the embodiment consists of the following elements in percentage by mass: 8.5% of Al, 1.6% of Zn, 1.6% of La, 0.5% of Ce, 2.0% of Cu and 0.2% of Ni, and the balance of Mg and unavoidable impurities.
The preparation method of the magnesium alloy soluble in the chlorine-containing solution in the embodiment specifically comprises the following steps:
a. according to the mass percentages of magnesium ingots, zinc ingots, aluminum ingots, red copper, mg-20% Ni intermediate alloy, mg-30% La intermediate alloy and Mg-30% Ce intermediate alloy which are soluble in chlorine-containing solution, weighing RJ-5 flux accounting for 2% of the total weight of the materials.
b. And (3) adding the magnesium ingot covered with the RJ-2 flux into a resistance furnace for melting, and setting the melting temperature to be 750 ℃. Sequentially adding Mg-20% Ni intermediate alloy, aluminum ingot, zinc ingot, mg-50% Cu intermediate alloy, mg-30% La intermediate alloy and Mg-30% Ce intermediate alloy, and covering RJ-5 after adding the rare earth intermediate alloy to reduce burning loss.
c. After all materials are melted, refining is carried out for 40min at 750 ℃ by using RJ-5 flux under the protection of nitrogen, then standing is carried out for 30min, and the temperature is kept at 750 ℃ in the standing process; after the standing, casting into semi-continuous cast ingots at 750 ℃. An electromagnetic semi-continuous casting system is used for obtaining cast ingots, an electromagnetic system is used for simultaneously carrying out electromagnetic stirring on a melt and the cast ingots until casting is completed, wherein the electromagnetic frequency is (20-40) Hz, and the current is (90-130) A.
d. Homogenizing: placing the magnesium alloy cast ingot into a heating furnace, and then performing double-stage homogenization treatment; the two-stage homogenization treatment conditions are 250 ℃ multiplied by 2 hours and 420 ℃ multiplied by 10 hours;
hot extrusion: carrying out heat preservation on the ingot blank for 5h at 380 ℃, then carrying out hot extrusion on a horizontal extruder, wherein the extrusion outlet speed is 1mm/s, and the extrusion ratio of an extrusion cylinder to a die is 25:1 at 380 ℃ during hot extrusion; molybdenum disulfide is used as a lubricant in the extrusion process;
aging treatment: and (3) carrying out ageing strengthening treatment on the bar under the condition of 200 ℃ for 22 hours to further improve the strength of the bar, so as to obtain the soluble magnesium alloy.
Example 6
The magnesium alloy which is soluble in chlorine-containing solution and prepared in the embodiment consists of the following elements in percentage by mass: 12.0% of Al, 2.1% of Zn, 1.3% of La, 0.4% of Ce, 1.8% of Cu and 0.8% of Ni, and the balance of Mg and unavoidable impurities.
The preparation method of the magnesium alloy soluble in the chlorine-containing solution in the embodiment specifically comprises the following steps:
a. according to the mass percentages of magnesium ingots, zinc ingots, aluminum ingots, red copper, mg-20% Ni intermediate alloy, mg-30% La intermediate alloy and Mg-30% Ce intermediate alloy which are soluble in chlorine-containing solution, weighing RJ-5 flux accounting for 4% of the total weight of the materials.
b. And (3) adding the magnesium ingot covered with the RJ-2 flux into a resistance furnace for melting, and setting the melting temperature to be 750 ℃. Sequentially adding Mg-20% Ni intermediate alloy, aluminum ingot, zinc ingot, red copper, mg-30% La intermediate alloy and Mg-30% Ce intermediate alloy, and covering RJ-5 after adding rare earth intermediate alloy to reduce burning loss.
c. After all materials are melted, refining is carried out for 40min at 750 ℃ by using RJ-5 flux under the protection of nitrogen at the same time, and then semi-continuous cast ingots are cast at 750 ℃. An electromagnetic semi-continuous casting system is used for obtaining cast ingots, an electromagnetic system is used for simultaneously carrying out electromagnetic stirring on a melt and the cast ingots until casting is completed, wherein the electromagnetic frequency is (20-40) Hz, and the current is (90-130) A.
d. Homogenizing: placing the magnesium alloy cast ingot into a heating furnace, and then performing double-stage homogenization treatment; the two-stage homogenization treatment conditions are 350 ℃ multiplied by 4h+420 ℃ multiplied by 8h;
hot extrusion: carrying out heat preservation on the ingot blank for 4h at 350 ℃, and then carrying out hot extrusion on a horizontal extruder, wherein the extrusion outlet speed is 0.5mm/s, and the extrusion ratio of an extrusion cylinder to a die is 7:1 when the hot extrusion is carried out at 350 ℃; molybdenum disulfide is used as a lubricant in the extrusion process;
aging treatment: and (3) carrying out ageing strengthening treatment on the bar, wherein the ageing strengthening treatment condition is 190 ℃ for 26 hours, so as to further improve the strength of the bar and obtain the soluble magnesium alloy.
Comparative example 1
The magnesium alloy prepared in the comparative example 1 consists of the following elements in percentage by mass: 9.5% of Al, 1.6% of Zn, 2.0% of Cu, 0.2% of Ni, and the balance of Mg and unavoidable impurities.
The preparation method is the same as in example 4.
Comparative example 2
The magnesium alloy prepared in the comparative example 2 consists of the following elements in percentage by mass: 9.5% of Al, 1.4% of Zn, 1.9% of La, 0.6% of Ce, and the balance of Mg and unavoidable impurities.
The preparation method is the same as in example 4.
Comparative example 3
The magnesium alloy prepared in the comparative example 3 consists of the following elements in percentage by mass: 8.5% of Al, 1.6% of Zn, 1.6% of La, 0.5% of Gd, 2.0% of Cu, 0.2% of Ni and the balance of Mg and unavoidable impurities.
The preparation method is the same as in example 5, wherein the Gd element is added by using Mg-30% Gd intermediate alloy.
Comparative example 4
The magnesium alloy prepared in the comparative example 4 consists of the following elements in percentage by mass: 8.5% of Al, 1.6% of Zn, 1.6% of Gd, 0.5% of Ce, 2.0% of Cu, 0.2% of Ni and the balance of Mg and unavoidable impurities. Wherein the Gd element is added by using Mg-30% Gd intermediate alloy.
The preparation method is the same as in example 5, wherein the addition of Gd element uses Mg-30% Gd intermediate alloy, and the influence of Gd and La elements on the performance is compared.
Comparative example 5
The magnesium alloy prepared in the comparative example 5 consists of the following elements in percentage by mass: 9.5% of Al, 1.6% of Zn, 1.6% of La, 0.5% of Ce, 2.0% of Cu, 0.2% of Ni and the balance of Mg and unavoidable impurities.
The preparation method of this comparative example 5 was the same as in example 4 except that the aging treatment was not performed in this comparative example.
Flaw detection was performed on the ingots obtained in step c of examples 1 to 6 and comparative examples 1 to 5 using an electromagnetic semi-continuous casting system, and the flaw detection yields obtained and the mechanical properties at room temperature of the chlorine-containing solution-soluble magnesium alloys prepared in examples 1 to 6 and comparative examples 1 to 5 are shown in Table 1.
TABLE 1 mechanical Properties of magnesium alloys soluble in chlorine-containing solutions at Room temperature and percent of pass for flaw detection of ingots
To sum up, in example 4 and comparative examples 1-2, la and Ce rare earth elements were added to modify magnesium alloy during casting of magnesium alloy soluble in chlorine-containing solution, and high melting point and high thermal stability aluminum rare earth phase was formed in the magnesium alloy. Mg due to the relatively low melting point of aluminum rare earth 17 Al 12 The phase has inhibiting effect, and changes Mg 17 Al 12 The shape and distribution of the magnesium alloy matrix are increased, and the functions of strengthening the matrix and refining the structure are achieved. The magnesium alloy which is soluble in chlorine-containing solution and prepared by the preparation method provided by the invention has the yield strength of more than or equal to 230MPa, the tensile strength of more than or equal to 350MPa, the elongation of more than or equal to 11 percent and excellent mechanical properties.
Wherein, the addition ratio of La and Ce in example 5 is the same as that of La and Gd in comparative example 3, and Gd is used in place of La in comparative example 4, and the addition ratio of Gd and Ce is the same as that of example 5 and comparative example 3. As can be seen from the data in Table 1, the mechanical properties of comparative example 3 are lower than those of example 5, and the reason for this is that the content of the aluminum rare earth phase formed in example 5 is higher than that of comparative example 3, and the mechanical properties of comparative example 4 are close to those of example 5, but the preparation cost of example 5 is lower than that of comparative example 4.
In addition, after the rare earth element added in example 4 is removed in comparative example 1, the mechanical properties are lower than those of example 4, but the dissolution rate in chlorine-containing solution under different conditions is higher than that of example 4, and after the Cu and Ni elements in example 4 are removed in comparative example 2, the tensile strength and yield strength are both higher than those of example 4, but the dissolution rate in chlorine-containing solution under different conditions is far lower than that of example 4, and as can be seen from comparative examples 1-2 and example 4, the soluble magnesium alloy with excellent mechanical properties and controllable dissolution rate can be prepared through the ratio among elements.
The flaw detection qualification rate of the cast ingot refers to the qualification rate of the cast ingot obtained by performing full coverage scanning on the cast ingot along the length direction by adopting an ultrasonic flaw detector, wherein the minimum resolution of a probe is more than or equal to 2mm, when the wavelength is more than or equal to 5mm, the cast ingot is considered to be unqualified, and the unqualified cast ingot quantity is divided by the total detection quantity, namely the qualification rate. In summary, the magnesium alloy which is prepared by the preparation method and is soluble in chlorine-containing solution is subjected to flaw detection after an ingot is obtained by using an electromagnetic semi-continuous casting system, and the flaw detection qualification rate can reach more than 95%. Further, compared with comparative examples 1-2 and example 4, the addition of rare earth elements La and Ce can improve the solubility of magnesium alloy in chlorine-containing solutions with different concentrations, and simultaneously can greatly improve the internal tissue structure of the magnesium alloy, so that the magnesium alloy has higher flaw detection qualification rate.
The dissolution properties of the chlorine-containing solution-soluble magnesium alloys prepared in examples 1 to 6 and comparative examples 1 to 5 in the chlorine-containing solutions having simulated downhole temperatures of 93 ℃, 70 ℃, 50 ℃ and 45 ℃ respectively were tested, and the weight of the chlorine-containing solutions dissolved per hour in chlorine-containing solutions having different concentrations was recorded, and the test results are shown in tables 2, 3, 4 and 5. Wherein, the dissolution rate=weight difference before and after dissolution/(sample surface area×dissolution time), the chlorine-containing solutions of different concentrations are respectively 0.3%, 0.5%, 0.84%, 1.0% and 3% KCl solutions, and the mass fractions of the chloride ions thereof are respectively 0.14%, 0.24%, 0.4%, 0.48% and 1.4%.
TABLE 2 dissolution rates of chlorine-containing solutions at 93℃for magnesium alloys soluble in chlorine-containing solutions
TABLE 3 dissolution rates of chlorine-containing solutions at 70℃for magnesium alloys soluble in chlorine-containing solutions
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TABLE 4 dissolution rates of chlorine-containing solutions at 50℃for magnesium alloys soluble in chlorine-containing solutions
TABLE 5 dissolution rates of chlorine-containing solutions at 45℃for magnesium alloys soluble in chlorine-containing solutions
TABLE 6 solubility of 100 grams chlorine-containing solutions of different concentrations at different temperatures
TABLE 7 solubility of 100 grams chlorine-containing solutions of different concentrations at different temperatures
In the exploitation process of petroleum or shale gas, the well needs to be sealed to generate pressure after well completion, shale is fractured, and oil gas is oozed out. The normal underground temperature is between 100 ℃ and 150 ℃, the fracturing tool and the fracturing fluid enter the underground at the same time, the fracturing fluid is not high in temperature, the initial temperature is approximately below 50 ℃, the fracturing operation is carried out for several hours, the temperature is below 90 ℃, and the fracturing tool is not dissolved, so that the defects of difficult drilling and milling, long time consumption, difficult flowback of powder and fragments after drilling and the like are caused. Therefore, in order to obtain better dissolution performance of the fracturing tool, the concentration of chloride ions in the fracturing fluid can be regulated to accelerate or slow down the corrosion rate.
From the above data, it is understood that the fracturing tools prepared by using the magnesium alloy which is soluble in chlorine-containing solution and prepared in examples 1 and 2 have a concentration of more than 30 mg ∙ hours in high-concentration chloride ion solution at (45-93) -1 ∙cm -2 The above autolytic property. Especially in 3% KCl solution at 93 deg.C, the dissolution rate is fast, with a dissolution rate higher than 70 mg ∙ h -1 ∙cm -2 Therefore, the mass fraction of chloride ions in the fracturing fluid can be adjusted to be higher than 0.14% during downhole operation to accelerate the self-dissolution rate of the fracturing tool so as to extractHigh mining efficiency.
The foregoing examples are illustrative of the present invention and are not intended to be limiting, and any other modifications, substitutions, combinations, or simplifications made without departing from the spirit and principles of the invention are to be considered as equivalent substitutions within the scope of the invention.
The foregoing descriptions of specific exemplary embodiments of the present invention are presented for purposes of illustration and description. It is not intended to limit the invention to the precise form disclosed, and obviously many modifications and variations are possible in light of the above teaching. The exemplary embodiments were chosen and described in order to explain the specific principles of the invention and its practical application to thereby enable one skilled in the art to make and utilize the invention in various exemplary embodiments and with various modifications as are suited to the particular use contemplated. It is intended that the scope of the invention be defined by the claims and their equivalents.
Claims (10)
1. A magnesium alloy soluble in a chlorine-containing solution, characterized in that the magnesium alloy consists of the following elements in mass percent: al:7.5% -12.0%, zn:0.6% -2.1%, ni:0.2% -0.8%, 1.2% -2.2% Cu, 1.2% -2.2% La, 0.4% -0.8% Ce and the balance of Mg and unavoidable impurity elements;
the preparation method of the magnesium alloy soluble in the chlorine-containing solution comprises the following steps:
a. weighing magnesium ingots, zinc ingots, aluminum ingots, red copper, mg-Ni intermediate alloy, mg-La intermediate alloy and Mg-Ce intermediate alloy according to the mass percentage of the magnesium alloy;
b. smelting magnesium ingots under the coverage of RJ-2 flux, after the magnesium ingots are melted, sequentially adding Mg-Ni intermediate alloy, aluminum ingots, zinc ingots, red copper, mg-La intermediate alloy and Mg-Ce intermediate alloy, and after adding rare earth intermediate alloy, covering RJ-5 to reduce burning loss;
c. refining and casting into cast ingots by using RJ-5 flux and protective atmosphere after all materials are melted;
d. after homogenizing the cast ingot, hot extruding the cast ingot into bars, performing aging treatment, homogenizing the cast ingot, specifically placing the cast ingot in a heating furnace, and then performing double-stage homogenizing treatment under the following conditions: the primary homogenization is carried out at the temperature of 250-350 ℃ for 2-5h, and the secondary homogenization is carried out at the temperature of 380-420 ℃ for 8-16h; carrying out hot extrusion on the ingot blank to form a bar, specifically carrying out heat preservation on the ingot blank for 4-6 hours at 300-350 ℃, then carrying out hot extrusion on a horizontal extruder, wherein the extrusion outlet speed is 0.5-2 mm/s, the temperature of an extrusion cylinder and a die during hot extrusion is 320-380 ℃, and the extrusion ratio is 7-25:1; in the extrusion process, water-based graphite or molybdenum disulfide is used as a lubricant, and the aging treatment process specifically refers to taking the bar and treating the bar at 150-200 ℃ for 22-32h.
2. A method for preparing a magnesium alloy soluble in a chlorine-containing solution as claimed in claim 1, comprising the steps of:
a. the magnesium alloy according to claim 1, wherein the magnesium alloy comprises magnesium ingots, zinc ingots, aluminum ingots, red copper, mg-Ni intermediate alloy, mg-La intermediate alloy and Mg-Ce intermediate alloy;
b. smelting magnesium ingots under the coverage of RJ-2 flux, after the magnesium ingots are melted, sequentially adding Mg-Ni intermediate alloy, aluminum ingots, zinc ingots, red copper, mg-La intermediate alloy and Mg-Ce intermediate alloy, and after adding rare earth intermediate alloy, covering RJ-5 to reduce burning loss;
c. refining and casting into cast ingots by using RJ-5 flux and protective atmosphere after all materials are melted;
d. and carrying out homogenization treatment on the cast ingot, and then carrying out hot extrusion to form bars, and carrying out aging treatment.
3. The method for preparing the magnesium alloy soluble in the chlorine-containing solution according to claim 2, wherein in the step a, the mass percentage of Ni in the Mg-Ni intermediate alloy is 20-80%, the mass percentage of La in the Mg-La intermediate alloy is 30-40%, and the mass percentage of Ce in the Mg-Ce intermediate alloy is 30-40%.
4. The method for preparing magnesium alloy soluble in chlorine-containing solution according to claim 2, wherein the amount of RJ-5 flux used in steps b and c is 2-4% of the total weight of magnesium ingot, zinc block, aluminum ingot, red copper, mg-Ni intermediate alloy, mg-La intermediate alloy and Mg-Ce intermediate alloy; and the protective atmosphere in the step c is nitrogen or argon.
5. The method for preparing a magnesium alloy soluble in a chlorine-containing solution according to claim 2, wherein in the step c, after all materials are melted, the mixed melt is refined for 30-40min at 750+ -5 ℃, then is left to stand for 0-30min, the temperature is maintained at 740-750 ℃ during the standing process, and a semi-continuous cast ingot is cast at 740-750 ℃.
6. The method for preparing a magnesium alloy soluble in a chlorine-containing solution according to claim 5, wherein in the step c, when the magnesium alloy is cast into a semi-continuous ingot at 740-750 ℃, an electromagnetic system is used to perform electromagnetic stirring on the mixed melt and the ingot with an electromagnetic frequency of 20-40Hz and an electric current of 90-130A until the ingot is completed.
7. The method for preparing magnesium alloy soluble in chlorine-containing solution according to claim 2, wherein in step d, the ingot is homogenized, in particular, the ingot is placed in a heating furnace, and then subjected to two-stage homogenization under the following conditions: the primary homogenization is carried out at the temperature of 250-350 ℃ for 2-5h, and the secondary homogenization is carried out at the temperature of 380-420 ℃ for 8-16h.
8. The method for preparing magnesium alloy soluble in chlorine-containing solution as claimed in claim 2, wherein in the step d, the ingot blank is hot extruded into bar, specifically, the ingot blank is subjected to heat preservation for 4-6 hours at 300-350 ℃, then hot extrusion is carried out on a horizontal extruder, the extrusion outlet speed is 0.5-2 mm/s, the temperature of an extrusion cylinder and a die during hot extrusion is 320-380 ℃, and the extrusion ratio is 7-25:1; water-based graphite or molybdenum disulfide is used as a lubricant in the extrusion process.
9. The method for preparing a magnesium alloy soluble in a chlorine-containing solution according to claim 7, wherein in the step d, the aging treatment is specifically performed by taking a bar and treating the bar at 150-200 ℃ for 22-32 hours.
10. Use of the magnesium alloy soluble in chlorine-containing solutions of claim 1 or the method of preparing magnesium alloy soluble in chlorine-containing solutions of any one of claims 2-9 in the preparation of fracturing tools for shale oil and gas exploitation.
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| CN116287918A (en) | 2023-06-23 |
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