CN111041310B - Magnesium alloy for fracturing ball and preparation method thereof - Google Patents
Magnesium alloy for fracturing ball and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/02—Alloys based on magnesium with aluminium as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/02—Making non-ferrous alloys by melting
- C22C1/03—Making non-ferrous alloys by melting using master alloys
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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
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C23/00—Alloys based on magnesium
- C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/06—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of magnesium or alloys based thereon
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- E—FIXED CONSTRUCTIONS
- E21—EARTH DRILLING; MINING
- E21B—EARTH DRILLING, e.g. DEEP 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
Abstract
The invention relates to the field of metal smelting, and discloses a magnesium alloy for fracturing balls and a preparation method thereof, wherein the soluble magnesium-based alloy comprises the following components in percentage by weight: al: 6-16%, Zn: 1.0-6.5%, Fe: 0.1-5.0%, Cu: 0.1-7.0%, Ni: 0.1-7.5%, Ca: 0.1-8.0%, Y: 0.1-1.5 percent, and the balance of Mg. 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 magnesium alloy for fracturing balls 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.
Chinese patent 101177752 proposes a magnesium-zinc-rare earth alloy containing 4.5% of zinc and a preparation method thereof, in particular to a magnesium-based alloy added with heavy rare earth yttrium or gadolinium and light rare earth lanthanum or neodymium in a magnesium-zinc-rare earth system and a preparation method thereof. The magnesium-zinc-rare earth alloy added with four rare earths provided by the invention is respectively MG-4.5WT% ZN- (0.2WT% -2 WT%) LA; MG4.5WT% ZN- (0.2WT% -2 WT%) ND; MG-4.5WT% ZN- (0.2WT% -4.8 WT%) GD and MG-4.5WT% ZN- (0.2WT% -2.8 WT%) Y, can solve the problems of few kinds of magnesium-zinc-rare earth alloy and poor selective utilization or substitution utilization of rare earth resources. However, the yield strength is 200MPa or less.
In 1 month 2012, Baker Hughes, United states of America, Becker Hours, 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 10 mg-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: 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 fracturing balls made of metal or nonmetal materials in the prior art cannot be dissolved by self and are 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: al: 6-16%, Zn: 1.0-6.5%, Fe: 0.1-5.0%, Cu: 0.1-7.0%, Ni: 0.1-7.5%, Ca: 0.1-8.0%, Y: 0.1-1.5 percent, and the balance of Mg.
The invention also provides a preparation method of the soluble magnesium-based alloy, which comprises the following steps: s1: taking pure metals of Mg, Cu, Ni and Zn as raw materials according to the proportion, and preparing Mg-Al, Mg-Ca, Mg-Y and FeCl with powder particles of 20-200 mu m by adopting a powder metallurgy method3Intermediate alloy, and drying all raw materials; s2: smelting: under a protective atmosphere, firstly melting pure magnesium, then adding pure metals of Cu, Ni and Zn at 700-720 ℃, uniformly stirring, keeping the temperature for 10-30 min, and adding Mg-Al, Mg-Ca and FeCl3The intermediate alloy is stirred uniformly and then is kept at the temperature for 10-20 min, the temperature is reduced to 670-680 ℃, the Mg-Y intermediate alloy is added, the temperature is kept for 3-5 min after the stirring is uniform, and the temperature is increased to 690-700 ℃; introducing air pressure of 0.1-0.5 MPa and flow rate of 0.01-0.2 m into the melt3Argon is introduced for 3-5 min while stirring until the alloy is uniform, then the temperature of the alloy melt is reduced to 670-680 ℃, and the temperature is kept for 5-20 min; s3: casting: pouring molten metal smelted in the step S2 into a mold while stirring to form a cast ingot; s4: homogenizing heat treatment: carrying out homogenization heat treatment on the cast ingot obtained in the step S3 at the temperature of 360-440 ℃ for 15-40 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 340-430 ℃, wherein the extrusion ratio is 3-25, 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 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.
preferably, the temperature of the aging treatment is 110-140 ℃, and the time is 10-48 hours.
Preferably, in the S1, the pure metals of Mg, Cu, Ni and Zn and the Mg-Al, Mg-Ca, Mg-Y, 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 magnesium alloy powder, mixing magnesium powder, copper powder, nickel powder, zinc powder, Mg-Al, Mg-Ca and Mg-Y, FeCl3Fully mixing the master alloy powder according to the proportion under the protection of inert gas; s2: pre-pressing: pre-pressing and forming the mixed powder under the pressure of 70-150 MPa; s3, sintering: sintering the pre-pressed and formed material at 500-600 ℃, applying pressure of 150-245 MPa in the sintering process, sintering for 1-3.5 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 particle size of the magnesium powder is 50-80 um, and the copper powder, the nickel powder, the zinc powder and the Mg-Al, Mg-Ca and Mg-Y, FeCl are adopted3The granularity of the master alloy powder is 5-10 um.
Preferably, the magnesium powder, the copper powder, the nickel powder, the zinc powder and the Mg-Al, Mg-Ca, Mg-Y, 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, and then adding pure metals of Cu, Ni and Zn and FeCl at 720-740 DEG C3Uniformly stirring the intermediate alloy, keeping the temperature for 20-35 min, adding the intermediate alloy of Mg-Al, Mg-Ca and Mg-Y, uniformly stirring, and keeping the temperature for 10-20 min; introducing into the meltIntroducing argon, stirring until the alloy is uniform, then raising the temperature of the alloy melt to 740-750 ℃, and preserving the temperature for 5-10 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 0.2-2 MPa, the atomization gas is argon, nitrogen or carbon dioxide, and the deposition distance is 0.1-1.5 m; s3: extruding: extruding the deposition blank at 350-420 ℃ to obtain an extruded product, wherein the extrusion ratio is 2-30, and the extrusion speed is 1-20 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 100-120 ℃ and the time is 5-48 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 total alloy element content is high, the mass fraction is 10-40%, a large amount of strengthening phases can be formed, and the optimization and improvement of the mechanical property of the alloy are facilitated.
(2) The nickel and the copper contained in the formula of the soluble magnesium-based alloy are high hydrogen evolution overpotential elements, a large amount of second phases can be formed, and the second phases and the magnesium-based alloy form a micro-couple pair, so that the dissolution of the alloy is facilitated. The dissolution rate can be controlled by controlling the content and distribution of the over-potential elements with high hydrogen evolution. .
(3) 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. The as-cast coarse structure is unstable, and after the homogenization heat treatment, the coarse second phase is dissolved into the matrix, so that the element distribution is more uniform; the Cu and Ni alloy elements have serious segregation in the casting state, and the Cu and Ni are uniformly distributed and the segregation phenomenon is weakened after the homogenization heat treatment; the stress concentration is weakened, and the subsequent plastic processing is facilitated; the homogenization heat treatment is beneficial to the formation of a second phase which is uniformly mixed, the number of couple pairs is increased, and the dissolution speed of the alloy is improved.
(4) In the preparation method of the soluble magnesium-based alloy, argon is introduced while stirring is carried out during smelting, the concentration of impurity gas atoms in an argon bubble blown into a melt is low, the impurity gas atoms in the melt are diffused into the argon bubble due to concentration gradient and then float out of the melt along with the argon bubble, so that the effect of removing the impurity gas is achieved; in addition, the blown-in argon bubbles have higher surface energy under the action of the gravity of the melt, can automatically capture metal and nonmetal inclusion particles in the upward floating process, bring the impurity particles to the surface of the melt, enter a slagging layer and achieve the aim of removing the metal and nonmetal inclusion particles.
(5) In the preparation method of the soluble magnesium-based alloy, during casting, molten metal is stirred and cast into a mold to form an ingot; the melt components are more uniform in a mode of stirring and casting, and the performance balance of each part of the final cast ingot is ensured.
(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 copper/nickel/calcium yttrium and the like are added into the magnesium alloy consisting of magnesium, aluminum and zinc, 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 50-90 ℃; method two (powder metallurgy) and method three (spray deposition): the structure is fine, the components are uniform, the mechanical property is good, and the method is suitable for Chinese mild and high-temperature (60-150 ℃) operation environments.
(11) All the intermediate alloys in the first method (the fusion casting method) are 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 favorably obtained. The uniformity of the components is improved, and the mechanical property and the electrochemical property are both beneficial.
Detailed Description
The present invention will be described in detail with reference to the following embodiments.
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: al: 10%, Zn: 4%, Fe: 3%, Cu: 3%, Ni: 3%, Ca: 4%, Y: 0.5%, Mg: 72.5 percent.
The preparation method of the soluble magnesium-based alloy comprises the following steps:
firstly, pure metals of Mg, Cu, Ni and Zn as raw materials are taken according to the mixture ratio, and Mg-Al, Mg-Ca, Mg-Y and FeCl with the powder particles of 20-200 mu m prepared by adopting a powder metallurgy method3Intermediate alloying, and drying all raw materials.
S1: smelting: in CO2And SF6Under the mixed gas atmosphere with the ratio of 300:1, firstly melting pure magnesium, then adding pure metals of Cu, Ni and Zn with the purity of more than or equal to 99.9 percent at 710 ℃, uniformly stirring, keeping the temperature for 25min, and adding Mg-Al, Mg-Ca and FeCl with the purity of more than or equal to 99.9 percent3The intermediate alloy is stirred uniformly and then is kept at the temperature for 15min, the temperature is reduced to 675 ℃, the Mg-Y intermediate alloy is added, the temperature is kept for 4min after the stirring is uniform, and the temperature is increased to 695 ℃; introducing 0.3MPa and 0.1m into the melt3Argon gas is introduced for 4min, the mixture is stirred while the argon gas is introduced until the alloy is uniform, then the temperature of the alloy melt is reduced to 675 ℃, and the temperature is kept for 15 min;
s2: casting: and (4) casting the molten metal smelted in the step (S1) into a mold while stirring 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 380 ℃; the extrusion ratio was 10 and the extrusion speed was 10 m/min.
S5: aging treatment: the billet obtained in S4 was aged at 120 ℃ for 25 hours.
S6: machining and forming: and machining and shaping the blank obtained in the step S5.
Embodiment 2:
this embodiment is substantially the same as embodiment 1 except that (1) in the homogenization heat treatment of S3, the heat treatment temperature is 400 ℃ 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, Y: 1.5%, Mg: 71.5 percent.
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 370 ℃ and the treatment time is 40 hours; (2) the extrusion ratio at the time of extrusion at S4 was 5; (3) in the components of the soluble magnesium-based alloy, Y: 1%, Mg: 72 percent. .
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: al: 16%, Zn: 1%, Fe: 0.5%, Cu: 7%, Ni: 0.5%, Ca: 8%, Y: 0.1%, Mg: 66.9 percent.
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 um and the purity of more than or equal to 99.9 percent, copper powder, nickel powder and zinc powder with the granularity of 5-10 um and the purity of more than or equal to 99.9 percent, and Mg-Al, Mg-Ca and Mg-Y, FeCl3The master alloy powder is mixed in CO according to the proportion2And 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.
Embodiment 5:
this embodiment is substantially the same as embodiment 4 except that (1) the sintering temperature is 600 ℃ and the sintering time is 1 hour in the sintering at S3; (2) in the components of the soluble magnesium-based alloy, Y is 1 percent, Mg: 66 percent.
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 500 ℃ and the sintering time is 3 hours at the time of sintering at S3; (2) in the components of the soluble magnesium-based alloy, Y is 1.5%, Mg: 65.5 percent.
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: al: 7%, Zn: 6%, Fe: 5%, Cu: 0.5%, Ni: 7%, Ca: 0.5%, Y: 1%, Mg: 73 percent.
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, and then adding pure metals of Cu, Ni and Zn and FeCl at 730 DEG C3Stirring the intermediate alloy uniformly, keeping the temperature for 30min, adding the intermediate alloy of Mg-Al, Mg-Ca and Mg-Y, stirring uniformly, and keeping the temperature for 15 min; introducing argon into the melt, stirring while introducing argon until the alloy is uniform, and melting the alloyReducing the body temperature to 745 ℃, and keeping the temperature for 10 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 30 at the time of extrusion at S3; (2) in the components of the soluble magnesium-based alloy, Y is 0.4%, Mg: 73.6 percent.
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 5 when extruding at S3; (2) in the components of the soluble magnesium-based alloy, Y is 1.5%, Mg: 72.5.
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 normal temperature 3% KCl solution （mg·cm-2·h-1） | Dissolution rate in 3% KCl solution at about 90 deg.C （mg·cm-2·h-1） | The segmented fracturing ball of the horizontal well can bear Pressure (MPa) | |
| Implementation method Formula 7 | 52.6 | 146.4 | —— |
| Implementation method Formula 8 | 57.4 | 154.8 | 414 |
| Implementation method Formula 9 | 55.81 | 147 | 420 |
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 (8)
1. A method of preparing a soluble magnesium based alloy comprising the following components in weight percent: al: 6-16%, Zn: 1.0-6.5%, Fe: 0.1-5.0%, Cu: 0.1-7.0%, Ni: 0.1-7.5%, Ca: 0.1-8.0%, Y: 0.1-1.5% and the balance of Mg; the preparation method is characterized by comprising the following steps:
s1: taking pure metals of Mg, Cu, Ni and Zn as raw materials according to the proportion, and preparing Mg-Al, Mg-Ca, Mg-Y and FeCl with powder particles of 20-200 mu m by adopting a powder metallurgy method3Intermediate alloy, and drying all raw materials;
s2: smelting: under a protective atmosphere, firstly melting pure magnesium, then adding pure metals of Cu, Ni and Zn at 700-720 ℃, uniformly stirring, keeping the temperature for 10-30 min, and adding Mg-Al, Mg-Ca and FeCl3The intermediate alloy is stirred uniformly and then is kept at the temperature for 10-20 min, the temperature is reduced to 670-680 ℃, the Mg-Y intermediate alloy is added, the temperature is kept for 3-5 min after the stirring is uniform, and the temperature is increased to 690-700 ℃; introducing air pressure of 0.1-0.5 MPa and flow rate of 0.01-0.2 m into the melt3Argon is introduced for 3-5 min, stirring is carried out while the argon is introduced until the alloy is uniform, then the temperature of the alloy melt is reduced to 670-680 ℃, and the temperature is kept for 5-20 min;
s3: casting: pouring molten metal smelted in the step S2 into a mold while stirring to form a cast ingot;
s4: homogenizing heat treatment: carrying out homogenization heat treatment on the cast ingot obtained in the step S3 at the temperature of 360-440 ℃ for 15-40 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 340-430 ℃, wherein the extrusion ratio is 3-25, 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.
2. The method of claim 1A method for preparing a soluble magnesium-based alloy, characterized in that in S2, the 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.
3. the method of claim 1 or 2, wherein the aging treatment is performed at a temperature of 110 to 140 ℃ for 10 to 48 hours in the step S6.
4. A method of preparing a soluble magnesium based alloy comprising the following components in weight percent: al: 6-16%, Zn: 1.0-6.5%, Fe: 0.1-5.0%, Cu: 0.1-7.0%, Ni: 0.1-7.5%, Ca: 0.1-8.0%, Y: 0.1-1.5% and the balance of Mg; the preparation method is characterized by comprising the following steps:
s1: milling: preparing magnesium alloy powder, mixing magnesium powder, copper powder, nickel powder, zinc powder, Mg-Al, Mg-Ca and Mg-Y, FeCl3Fully mixing the master alloy powder according to the proportion under the protection of inert gas;
wherein the granularity of the magnesium powder is 40-70 um, and the copper powder, the nickel powder, the zinc powder and the Mg-Al, Mg-Ca and Mg-Y, FeCl are used as raw materials3The granularity of the master alloy powder is 5-10 um;
s2: pre-pressing: pre-pressing and forming the mixed powder under the pressure of 70-150 MPa;
s3, sintering: sintering the pre-pressed and formed material at 500-600 ℃, applying pressure of 150-245 MPa in the sintering process, sintering for 1-3.5 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.
5. The method of claim 4, 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.
6. a method of preparing a soluble magnesium based alloy comprising the following components in weight percent: al: 6-16%, Zn: 1.0-6.5%, Fe: 0.1-5.0%, Cu: 0.1-7.0%, Ni: 0.1-7.5%, Ca: 0.1-8.0%, Y: 0.1-1.5% and the balance of Mg; the preparation method is characterized by comprising the following steps:
s1: smelting the required magnesium alloy solution: under a protective atmosphere, firstly melting pure magnesium, and then adding pure metals of Cu, Ni and Zn and FeCl at 720-740 DEG C3Uniformly stirring the intermediate alloy, keeping the temperature for 20-35 min, adding the intermediate alloy of Mg-Al, Mg-Ca and Mg-Y, uniformly stirring, and keeping the temperature for 10-20 min; introducing argon into the melt, stirring while introducing the argon until the alloy is uniform, then heating the alloy melt to 740-750 ℃, and preserving the temperature for 5-10 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 0.2-2 MPa, the atomization gas is argon, nitrogen or carbon dioxide, and the deposition distance is 0.1-1.5 m;
s3: extruding: extruding the deposition blank at 350-420 ℃ to obtain an extruded product, wherein the extrusion ratio is 2-30, and the extrusion speed is 1-20 m/min;
s4: aging treatment: aging the extruded article;
s5: machining and forming: and machining and forming the aged product.
7. The method of claim 6, wherein the aging treatment is performed at 100 to 120 ℃ for 5 to 48 hours in S4.
8. Use of the soluble magnesium-based alloy prepared by the method for preparing the soluble magnesium-based alloy according to any one of claims 1 to 3, 4 to 5, or 6 to 7 in a soluble alloy fracturing ball for oil and gas exploitation.
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