Amorphous alloy structure regulating agent, magnesium-based composite material using amorphous alloy structure regulating agent as reinforcing phase and soluble bridge plug using amorphous alloy structure regulating agent as reinforcing phase

Abstract

The invention belongs to the technical field of composite materials, and particularly relates to an amorphous alloy structure regulating agent, a magnesium-based composite material with the amorphous alloy structure regulating agent as a reinforcing phase and a preparation method of the magnesium-based composite material. In the preparation method, the core is that a magnesium-based amorphous alloy is divided into two parts, the surface of one part is coated with a zirconium oxide protective layer, and the other part is kept in an uncoated state; the two are sequentially introduced into a magnesium alloy matrix according to the proportion, and collaborative design and accurate matching of the mechanical property and the corrosion rate of the material can be realized by regulating and controlling the proportion of the coated amorphous and the uncoated amorphous. Meanwhile, according to the magnesium-based composite material provided by the invention, the key problems that the traditional degradable magnesium alloy is relatively low in strength and the degradation rate is difficult to regulate and control are synchronously solved, and integrated regulation and control of strength, plasticity and degradation performance are realized. In addition, the prepared magnesium-based composite material lays a key material foundation for manufacturing high-performance controllable degradation magnesium-based structural parts, and has important significance on promoting efficient development of shale oil and gas.

Description

Technical Field

[0001] This invention belongs to the field of composite material technology, specifically relating to amorphous alloy microstructure regulators and their magnesium-based composite materials as reinforcing phases and soluble bridge plugs. Background Technology

[0002] Magnesium alloys, as the most promising lightweight structural metals, are widely used in aerospace, transportation, and other fields due to their high specific strength, excellent damping properties, and good recyclability. In recent years, with the rapid development of unconventional energy extraction such as shale oil and gas, the application of magnesium alloys in soluble plugging tools has received considerable attention. Utilizing their self-dissolving properties in the downhole environment, tools such as bridge plugs can be self-dissolving after fracturing operations, eliminating the need for drilling and significantly improving extraction efficiency while reducing environmental impact, aligning with the development direction of green mining technologies.

[0003] However, the high chemical reactivity of magnesium alloys leads to their susceptibility to oxidation in Cl-containing alloys. - Corrosion rates in downhole environments are difficult to control stably and are easily affected by fluctuations in operating conditions, leading to unpredictable excessively fast or slow corrosion. Simultaneously, existing commercially available magnesium alloys generally have low strength, failing to meet the pressure-bearing performance requirements of soluble bridge plugs under high-pressure conditions. This bottleneck of insufficient strength and uncontrollable corrosion rates severely restricts the large-scale application of magnesium alloys in soluble bridge plugs. Amorphous alloy powder, as a novel material with a long-range disordered structure, possesses high strength, high hardness, and excellent corrosion resistance. Research shows that introducing an appropriate amount of amorphous alloy powder as a reinforcing phase into a magnesium matrix can simultaneously improve the material's mechanical properties and corrosion stability through load transfer strengthening and microstructure control.

[0004] Therefore, there is an urgent need to develop a new type of magnesium-based composite material based on amorphous alloy powder reinforcement. This material is expected to break through the technical bottlenecks of existing soluble magnesium alloys in terms of strength and corrosion control, and provide a more reliable material solution for the efficient development of shale oil and gas. It has important scientific research value and engineering application prospects. Summary of the Invention

[0005] Therefore, the first objective of this invention is to provide an amorphous alloy microstructure regulator and its preparation method, which aims to achieve synergistic regulation of the mechanical properties and corrosion rate of the composite material by introducing amorphous alloy powder with a ZrO2 coating onto the surface into a magnesium alloy.

[0006] The second objective of this invention is to provide a method for preparing magnesium-based composite materials using amorphous alloy microstructure regulators as reinforcing phases. By comparing the effects of amorphous alloy powders with different ZrO2 coating ratios on the overall performance of magnesium-based composite materials, this invention aims to overcome the bottleneck problem of insufficient strength and difficulty in controlling corrosion rate in traditional magnesium alloys, and to achieve synergistic control of the strength, plasticity, and corrosion resistance of magnesium alloys.

[0007] A third objective of this invention is to provide a soluble bridge plug prepared based on the above-mentioned magnesium-based composite material.

[0008] To achieve the objectives of the invention described above, the present invention adopts the following technical solution:

[0009] In a first aspect, the present invention provides a method for preparing an amorphous alloy microstructure regulator, comprising the following steps:

[0010] S11. Prepare micron-sized magnesium-based amorphous alloy powder, wherein the magnesium-based amorphous alloy is a MgCuYZn amorphous alloy with an atomic percentage composition of Mg. a Cu b Y c Zn d a, b, c, and d satisfy: a + b + c + d = 100, 40 ≤ a ≤ 70, 20 ≤ b ≤ 40, 1 ≤ c ≤ 20, and 1 ≤ d ≤ 20.

[0011] S12. Pre-treat the magnesium-based amorphous alloy powder;

[0012] S13. An atomic layer deposition system is used to deposit a zirconium oxide coating on the surface of the magnesium-based amorphous alloy powder to obtain magnesium-based amorphous alloy powder with a zirconium oxide coating on the surface.

[0013] The thickness of the zirconium oxide coating is 10–30 nm.

[0014] Preferably, the specific process for preparing micron-sized magnesium-based amorphous alloy powder in step S11 includes:

[0015] The MgCuYZn amorphous alloy strip was ball-milled at a speed of 150–250 rpm for 1–3 hours to obtain MgCuYZn amorphous alloy powder with a particle size of 10–25 μm. The ball milling was carried out using zirconia balls as the milling medium, and the ratio of the zirconia balls to the MgCuYZn amorphous alloy strip was 20–40:1. 1–5 wt% anhydrous ethanol was added as a grinding aid during the ball milling process, and the ball milling was carried out in a vacuum environment.

[0016] Preferably, the specific process of pretreating the magnesium-based amorphous alloy powder in step S12 includes:

[0017] The MgCuYZn amorphous alloy powder was placed in a centrifuge tube, acetone was added, and the mixture was treated under ultrasonic conditions for 30 min. After centrifugation, the supernatant was discarded. Then anhydrous ethanol was added, and the mixture was treated under ultrasonic conditions for 30 min. After centrifugation, the supernatant was discarded. The cleaned amorphous alloy powder was dried in a vacuum drying oven at 60°C for 2 h.

[0018] The ultrasonic conditions are: ultrasonic frequency of 80 kHz and power density of 0.8 W / cm². 2 The time is 1 minute.

[0019] Preferably, the specific steps for depositing a zirconium oxide coating on the surface of the magnesium-based amorphous alloy powder using an atomic layer deposition system in step S13 to obtain magnesium-based amorphous alloy powder with a zirconium oxide coating are as follows:

[0020] The pretreated MgCuYZn amorphous alloy powder was spread evenly in a sample boat, which was then placed in the isothermal zone of the atomic layer deposition system reaction chamber. Vacuum treatment was performed, and after treatment, the sample stage vibration device and deposition operation were activated. 200 ALD cycles were run for deposition. After deposition, the reaction chamber was cooled to below 80°C under a continuous N2 flow to obtain MgCuYZn amorphous alloy powder with a zirconia coating. The zirconia-coated MgCuYZn amorphous alloy powder was then heated to 250°C at a rate of 2°C / min under N2 protection and held for 1 hour for annealing. After annealing, it was dry-ground at 100 rpm for 5 minutes to obtain magnesium-based amorphous alloy powder with a zirconia coating.

[0021] More preferably, the materials, cleaning, parameter settings, and ALD cycle deposition operations of the atomic layer deposition system are as follows:

[0022] Materials prepared: MgCuYZn amorphous alloy powder, tetra(dimethylamino)zirconium, and deionized water;

[0023] First, the ALD reaction chamber was heated to 200°C and purged with nitrogen for 30 minutes. Then, it was treated with O2 plasma at 100W for 10 minutes to clean the atomic layer deposition system. Next, the ALD reaction chamber temperature was set to 160°C, the tetrakis(dimethylamino)zirconium source bottle temperature to 75°C, the gas delivery pipeline temperature to 100°C, and the deionized water source bottle temperature to 25°C. The basic vacuum level of the atomic layer deposition system was evacuated to <1.0 × 10⁻⁶. -4 The working pressure was stabilized at 1.0 Torr by introducing N2, the vibration frequency was 30 Hz, and the amplitude was 2 mm. Finally, 200 ALD cycles were performed for deposition. The steps of a complete ALD cycle are as follows:

[0024] Tetra(dimethylamino)zirconium pulse: Tetra(dimethylamino)zirconium vapor is introduced into the ALD reaction chamber for a pulse duration of 1 second;

[0025] First N2 purging: Introduce high-purity N2 and purge for 40 seconds;

[0026] Deionized water pulse: Water vapor is introduced into the ALD reaction chamber for 1 second;

[0027] Second N2 purging: Introduce N2 again and purge for 40 seconds.

[0028] Secondly, the present invention also provides a method for preparing a magnesium-based composite material, wherein the amorphous alloy microstructure regulator prepared by the above method is used as a reinforcing phase, and Mg-6Al is used as a matrix to prepare the magnesium-based composite material. The preparation steps are as follows:

[0029] S21. Melt the base magnesium to obtain a magnesium-based melt, and stir in the magnesium-based melt to add preheated pure aluminum, uncoated amorphous alloy powder and amorphous alloy microstructure regulator to obtain an alloy melt.

[0030] S22. The alloy melt is poured and cooled to form a magnesium-based composite material.

[0031] Preferably, the specific steps for obtaining a magnesium-based melt by melting the magnesium matrix in step S21, and for adding preheated pure aluminum, uncoated amorphous alloy powder, and amorphous alloy microstructure modifier to the magnesium-based melt to obtain an alloy melt are as follows: Commercial pure magnesium with a purity of not less than 99.95% is placed in a crucible-type resistance furnace and gradually heated to 720°C under a mixed protective gas atmosphere of CO2 and SF6 with a volume fraction ratio of 99:1, and held until completely melted to obtain a magnesium-based melt. Preheated commercial pure aluminum with a purity of not less than 99.90% is added to the magnesium-based melt at 720°C and held for 20 minutes to ensure complete melting. Then, preheated uncoated amorphous alloy powder is added and held for 10 minutes. Finally, when the temperature gradually decreases and stabilizes at 670°C, preheated amorphous alloy microstructure modifier is added and held for 5 minutes to finally obtain the alloy melt. The preheating treatment is preheating at 200°C for 1 minute. h; The entire addition process in step S21 needs to be carried out in ultrasonic stirring, and the ultrasonic power is 600-1000 W; The specific steps in step S22 to pour the alloy melt and cool it to obtain the magnesium-based composite material include: immediately pouring the alloy melt after stirring and heat preservation into a metal mold to achieve rapid solidification and obtain the magnesium-based composite material.

[0032] Thirdly, the present invention also provides a magnesium-based composite material, which is obtained by the preparation method of a magnesium-based composite material mentioned above. The chemical composition of the magnesium-based composite material is Mg-6Al-4MgCuYZn, wherein the content of the amorphous alloy structure regulator is 4wt%, the content of pure aluminum is 6wt%, and the content of pure magnesium is 90wt%. At the same time, the mass percentage of amorphous alloy powder with ZrO2 coating on the surface to uncoated amorphous alloy powder in the 4wt% MgCuYZn is 7-9:3-1.

[0033] Preferably, when the mass percentage of ZrO2-coated amorphous alloy powder in 4wt% MgCuYZn to uncoated amorphous alloy powder is 9:1, the ultimate tensile strength, elongation, and corrosion rate of the magnesium-based composite material are 260 MPa, 9.8%, and 254 mm / year, respectively.

[0034] Fourthly, the present invention also provides a soluble bridge plug, which includes a bridge plug body and a sealing structure, an anchoring structure and a bore structure disposed on the bridge plug body, wherein the entire or part of the bridge plug body is made of the magnesium-based composite material prepared above.

[0035] The beneficial effects of this invention are:

[0036] 1. This invention effectively isolates a portion of MgCuYZn amorphous alloy powder from direct contact with the high-temperature magnesium melt during subsequent smelting by coating a dense zirconium oxide layer onto its surface. This coating layer acts as a thermal barrier and diffusion barrier, significantly suppressing the atomic rearrangement and crystallization tendency of the amorphous phase at high temperatures, allowing this reinforcing phase to remain in the composite material with a complete amorphous structure. Amorphous alloys, due to their long-range disordered structure, possess strength, hardness, and elastic limits far exceeding those of traditional crystalline alloys. Therefore, as a high-performance reinforcing phase, they significantly improve the strength, stiffness, and load-bearing capacity of the composite material, thereby significantly enhancing its mechanical properties. On one hand, MgCuYZn amorphous alloy powder, as a rigid reinforcement, efficiently transfers and bears external loads from the softer magnesium matrix through a robust interface, greatly improving the material's mechanical properties. Simultaneously, the dispersed amorphous phase effectively hinders the coarsening of magnesium grains and acts as a heterogeneous nucleation substrate, pinning grain boundaries and refining grains. On the other hand, its uniformly distributed inert interface can alter the corrosion path, causing corrosion to shift from localized pitting to uniform dissolution.

[0037] 2. The uncoated amorphous alloy powder in this invention will inevitably crystallize during the melting process, transforming into a crystalline phase containing various intermetallic compounds. These crystalline phases, especially the high-potential-difference second phases such as Mg₂Cu and MgZn₂, have a significant electrochemical potential difference with the magnesium matrix, thus forming a large number of uniformly distributed micro-electrical couples within the composite material. These micro-electrical couples can effectively promote the anodic dissolution process of the magnesium matrix at the interface through an electrochemical driving mechanism, thereby actively guiding and accelerating the overall corrosion process of the composite material. This transforms the material degradation mode from the common localized pitting corrosion of magnesium alloys to a more uniform overall degradation, thereby achieving effective promotion and precise control of the degradation rate.

[0038] 3. This invention introduces two powders with opposing functions—anti-crystallization / reinforcing coated powder and corrosion-promoting / sacrificial uncoated powder—into a magnesium alloy in a specific ratio to prepare a magnesium-based composite material. By precisely controlling the ratio of the two powders, the synergistic design and linear control of the two key indicators of the final composite material's mechanical properties and corrosion rate can be achieved. Detailed Implementation

[0039] The technical solutions in the embodiments of the present invention will be clearly and completely described below. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0040] This invention discloses a method for preparing an amorphous alloy microstructure regulator, comprising the following steps:

[0041] S11. Preparation of micron-sized magnesium-based amorphous alloy powder;

[0042] S12. Pretreatment of magnesium-based amorphous alloy powder;

[0043] S13. A zirconium oxide coating is deposited on the surface of magnesium-based amorphous alloy powder using an atomic layer deposition system to obtain magnesium-based amorphous alloy powder with a zirconium oxide coating on the surface.

[0044] First, the magnesium-based amorphous alloy in step S11 is a MgCuYZn amorphous alloy, with an atomic percentage composition of Mg. a Cu b Y c Zn d Let a, b, c, and d satisfy: a + b + c + d = 100, 40 ≤ a ≤ 70, 20 ≤ b ≤ 40, 1 ≤ c ≤ 20, and 1 ≤ d ≤ 20. For example, a magnesium-based amorphous alloy is Mg... 65 Cu 20 Y 10 Zn5, Mg 70 Cu 15 Y 10 Zn5, Mg 58 Cu 25 Y 10Zn7. Of course, the values ​​of a, b, c, and d can also be other values, and this invention does not limit them. Secondly, the specific operation steps for preparing micron-sized magnesium-based amorphous alloy powder in step S11 are as follows: at a rotation speed of 150-250 rpm, the MgCuYZn amorphous alloy strip is placed in a mechanical ball mill and ball-milled for 1-3 hours to obtain MgCuYZn amorphous alloy powder; wherein, zirconia balls are used as the ball milling medium, the ratio of zirconia balls to MgCuYZn amorphous alloy strip is 20-40:1, 1-5 wt% anhydrous ethanol is added as a grinding aid during the ball milling process, and the ball milling is carried out in a vacuum environment.

[0045] In step S12, the purpose is to pretreat the surface of the magnesium-based amorphous alloy powder. Specifically, this involves cleaning the magnesium-based amorphous alloy powder with an organic solvent, ultrasonication, and drying. The specific operation process is as follows: Place the MgCuYZn amorphous alloy powder in a centrifuge tube, add acetone, treat under ultrasonic conditions for 30 minutes, centrifuge, and discard the supernatant; then add anhydrous ethanol, treat under ultrasonic conditions for 30 minutes, centrifuge, and discard the supernatant; dry the cleaned amorphous alloy powder in a vacuum drying oven at 60°C for 2 hours; wherein the ultrasonic conditions are an ultrasonic frequency of 80 kHz and a power density of 0.8 W / cm³. 2 The time is 1 minute.

[0046] In step S13, an atomic layer deposition system is used to deposit a zirconium oxide coating on the surface of magnesium-based amorphous alloy powder, resulting in magnesium-based amorphous alloy powder with a zirconium oxide coating. The specific process includes: spreading the pretreated MgCuYZn amorphous alloy powder evenly in a sample boat; placing the sample boat into the isothermal zone of the atomic layer deposition system's reaction chamber; and evacuating the vacuum to a base pressure <1.0 × 10⁻⁶. -4 Torr, N2 was introduced to stabilize the working pressure at 1.0 Torr. After the treatment, the sample stage vibration device with a frequency of 30 Hz and an amplitude of 2 mm was turned on and the deposition operation was carried out. 200 ALD cycles were run to deposit zirconia with a thickness of 20 nm. After deposition, the reaction chamber was cooled to below 80°C under a continuous flow of N2 to obtain MgCuYZn amorphous alloy powder with a zirconia coating on the surface. The MgCuYZn amorphous alloy powder with the zirconia coating was heated to 250°C at 2°C / min under N2 protection and held for 1 h for annealing. After annealing, it was dry ground at 100 rpm for 5 min to obtain magnesium-based amorphous alloy powder with a zirconia coating on the surface.

[0047] It should be noted that the materials, cleaning, parameter settings, and ALD cycle deposition operations of the atomic layer deposition system are as follows:

[0048] Materials preparation: MgCuYZn amorphous alloy powder as the matrix material, tetra(dimethylamino)zirconium (TDMAZr) as the precursor and deionized water.

[0049] Cleaning: First, the ALD reaction chamber is heated to 200°C and purged with nitrogen for 30 minutes to remove air and moisture from the reaction chamber and provide a clean, dry, and inert environment for subsequent processing. Then, O2 plasma treatment is performed at a power of 100W for 10 minutes to utilize the high activity of oxygen plasma to decompose and remove any organic contaminants that may remain on the inner wall of the reaction chamber and on the sample stage, thereby further improving the cleanliness of the system.

[0050] Parameter settings: The reaction chamber temperature is 160°C, which is the base temperature for deposition and affects precursor adsorption, reaction kinetics, and film quality; the TDMAZr source bottle temperature is 75°C, used to provide sufficient precursor vapor pressure to ensure effective pulse transport; the gas delivery pipeline temperature is 100°C to prevent precursor condensation during transport; the deionized water source bottle temperature is 25°C to keep deionized water in a liquid state, providing water vapor pulses through evaporation; finally, 200 ALD cycles are performed for deposition. A complete ALD cycle operation is as follows:

[0051] TDMAZr pulse: TDMAZr vapor is introduced into the reaction chamber for 1 second to allow the precursor to fully react with the powder surface.

[0052] First N2 purging: High-purity N2 is introduced and purged for 40 seconds to remove excess precursors and reaction byproducts.

[0053] Deionized water pulse: Water vapor is introduced into the reaction chamber for 1 second to complete the hydrolysis reaction and generate ZrO2.

[0054] Second N2 purging: Introduce N2 again and purge for 40 seconds to prepare the clean surface for the next cycle.

[0055] Therefore, based on the preparation method provided above, the present invention further obtains an amorphous alloy microstructure regulator product, wherein the magnesium-based amorphous alloy powder has an average particle size of 10-25 μm and a zirconium oxide coating with a thickness of 10-30 nm is formed on its surface.

[0056] Furthermore, this invention also provides a method for preparing a magnesium-based composite material, wherein the method uses an amorphous alloy microstructure regulator as a reinforcing phase to prepare a Mg-6Al-4MgCuYZn magnesium-based composite material, specifically including the following steps:

[0057] S21. Melt the base magnesium to obtain a magnesium-based melt, stir and add preheated pure aluminum, uncoated amorphous alloy powder and amorphous alloy microstructure regulator to the magnesium-based melt to obtain an alloy melt.

[0058] S22. The alloy melt is poured and cooled to form a magnesium-based composite material.

[0059] In step S21, the specific steps for melting the base magnesium to obtain a magnesium-based melt, and adding preheated pure aluminum, uncoated amorphous alloy powder, and amorphous alloy microstructure modifier to the magnesium-based melt to obtain an alloy melt are as follows: Commercial pure magnesium with a purity of not less than 99.95% is placed in a crucible-type resistance furnace, and the temperature is gradually raised to 720°C and held until completely melted under a mixed protective gas atmosphere of CO2 and SF6 with a volume fraction ratio of 99:1 to obtain a magnesium-based melt. At 720°C, preheated commercial pure aluminum with a purity of not less than 99.90% is added to the magnesium-based melt and held for 20 minutes to ensure complete melting. Then, preheated uncoated amorphous alloy powder is added and held for 10 minutes. Finally, when the temperature gradually decreases and stabilizes at 670°C, preheated amorphous alloy microstructure modifier is added and held for 5 minutes to finally obtain the alloy melt.

[0060] In step S22, the alloy melt after stirring and heat preservation is immediately poured into a metal mold to achieve rapid solidification and obtain a magnesium-based composite material.

[0061] It should be noted that before placing commercial pure magnesium in a crucible-type resistance furnace, an angle grinder is needed to remove the oxide film on the surface of the pure magnesium; the preheating process for pure aluminum, uncoated amorphous alloy powder and reinforcing phase is to preheat at 200℃ for 1 hour; the entire addition process in step S21 needs to be carried out in ultrasonic stirring, wherein the stirring is carried out by ultrasonic stirring to stir the magnesium-based melt so that the alloying elements are evenly distributed in the magnesium melt, and the ultrasonic power of ultrasonic stirring is 600-1000W.

[0062] Based on the above-mentioned preparation method of magnesium-based composite materials, the present invention also provides a magnesium-based composite material with the chemical composition of Mg-6Al-4MgCuYZn, wherein the content of amorphous alloy structure regulator is 4wt%, the content of pure aluminum is 6wt%, and the content of pure magnesium is 90wt%; at the same time, the mass percentage of amorphous alloy powder with ZrO2 coating on the surface to uncoated amorphous alloy powder in the 4wt% MgCuYZn is 7-9:3-1.

[0063] In a preferred embodiment of the present invention, when the mass percentage of ZrO2-coated amorphous alloy powder in 4wt% MgCuYZn to that in uncoated amorphous alloy powder is 9:1, the ultimate tensile strength, elongation and corrosion rate of the magnesium-based composite material are 260 MPa, 9.8% and 254 mm / year, respectively.

[0064] Therefore, the present invention also provides a soluble bridge plug, which includes a bridge plug body and a sealing structure, an anchoring structure and a bore structure disposed on the bridge plug body, wherein the entire or part of the bridge plug body is made of the magnesium-based composite material mentioned above.

[0065] Next, the present invention will illustrate, through the following embodiments and comparative examples, that the content of amorphous alloy microstructure modifiers as reinforcing phases has a significant impact on the mechanical properties of magnesium-based composite materials.

[0066] Example 1

[0067] A magnesium-based composite material has the chemical composition Mg-6Al-4MgCuYZn, wherein the mass percentage of ZrO2-coated amorphous alloy powder to uncoated amorphous alloy powder in 4 wt% MgCuYZn is 9:1. Therefore, the preparation of this magnesium-based composite material requires first obtaining an amorphous alloy microstructure regulator, and then using the amorphous alloy microstructure regulator as a reinforcing phase to prepare its magnesium-based composite material for soluble bridge plugs.

[0068] First step: Preparation of amorphous alloy microstructure regulator.

[0069] S11. Preparation of micron-sized magnesium-based amorphous alloy powder: The MgCuYZn amorphous alloy strip was placed in a mechanical ball mill and ball-milled for 2 hours at a speed of 200 rpm to obtain MgCuYZn amorphous alloy powder with a particle size of 20 μm. Zirconia balls were used as the ball milling medium, and the ratio of zirconia balls to MgCuYZn amorphous alloy strips was 30:1. 3 wt% anhydrous ethanol was added as a grinding aid during the ball milling process, and the ball milling was carried out in a vacuum environment.

[0070] S12. Pretreatment of magnesium-based amorphous alloy powder: Place MgCuYZn amorphous alloy powder in a centrifuge tube, add acetone, treat under ultrasonic conditions for 30 min, centrifuge and discard the supernatant; then add anhydrous ethanol, treat under ultrasonic conditions for 30 min, centrifuge and discard the supernatant; place the cleaned MgCuYZn amorphous alloy powder in a vacuum drying oven at 60℃ for 2 h; wherein the ultrasonic conditions are an ultrasonic frequency of 80 kHz and a power density of 0.8 W / cm³. 2 The time is 1 minute.

[0071] S13. A zirconium oxide coating is deposited on the surface of magnesium-based amorphous alloy powder using an atomic layer deposition system to obtain magnesium-based amorphous alloy powder with a zirconium oxide coating: The pretreated MgCuYZn amorphous alloy powder is spread evenly in a sample boat, which is then placed in the isothermal zone of the atomic layer deposition system reaction chamber, and a vacuum is drawn until the base pressure is <1.0×10⁻⁶. -4 Torr, N2 was introduced to stabilize the working pressure at 1.0 Torr. After the treatment, the sample stage vibration device with a frequency of 30 Hz and an amplitude of 2 mm was turned on and the deposition operation was carried out. 200 ALD cycles were run to deposit zirconia with a thickness of 20 nm. After deposition, the reaction chamber was cooled to below 80°C under a continuous flow of N2 to obtain MgCuYZn amorphous alloy powder with a zirconia coating on the surface. The MgCuYZn amorphous alloy powder with the zirconia coating was heated to 250°C at 2°C / min under N2 protection and held for 1 h for annealing. After annealing, it was dry ground at 100 rpm for 5 min to obtain magnesium-based amorphous alloy powder with a zirconia coating on the surface.

[0072] The materials, cleaning, parameter settings, and ALD cycle deposition operations of the atomic layer deposition system are as follows:

[0073] Prepare the following materials: MgCuYZn amorphous alloy powder, TDMAZr, and deionized water;

[0074] First, the ALD reaction chamber was heated to 200°C and purged with nitrogen for 30 minutes. Then, it underwent O2 plasma treatment at 100W for 10 minutes to clean the atomic layer deposition system. Next, the ALD reaction chamber temperature was set to 160°C, the TDMAZr source bottle temperature to 75°C, the gas delivery pipe temperature to 100°C, and the deionized water source bottle temperature to 25°C. Finally, 200 ALD cycles were performed for deposition. The steps for one complete ALD cycle are as follows:

[0075] Tetra(dimethylamino)zirconium pulse: TDMAZr vapor is introduced into the ALD reaction chamber for 1 second;

[0076] First N2 purging: Introduce high-purity N2 and purge for 40 seconds;

[0077] Deionized water pulse: Water vapor is introduced into the ALD reaction chamber for 1 second;

[0078] Second N2 purging: Introduce N2 again and purge for 40 seconds.

[0079] The second step: preparation of magnesium-based composite materials.

[0080] Before melting, the oxide film on the surface of the pure magnesium matrix was removed using an angle grinder. Pure aluminum, amorphous alloy powder, and the prepared amorphous alloy microstructure modifier were preheated in a drying oven at 200°C for 1 hour. Commercial pure magnesium with a purity of not less than 99.95% was placed in a crucible-type resistance furnace and gradually heated to 720°C under a protective atmosphere of a mixed protective gas atmosphere of CO2 and SF6 with a volume fraction ratio of 99:1, and held until completely melted to obtain a magnesium-based melt. At 720°C, preheated commercial pure aluminum with a purity of not less than 99.90% was added to the magnesium-based melt and held for 20 minutes to ensure complete melting. Then, preheated amorphous alloy powder was added and held for 10 minutes. Finally, when the temperature gradually decreased and stabilized at 670°C, preheated amorphous alloy microstructure modifier was added and held for 5 minutes. The entire addition process must be carried out under ultrasonic stirring with an ultrasonic power of 700W. Finally, the alloy melt after stirring and heat preservation is immediately poured into a metal mold to achieve rapid solidification and obtain a cast magnesium-based composite material.

[0081] Example 2

[0082] The preparation method in this embodiment is the same as that in Example 1, except that:

[0083] A magnesium-based composite material with the chemical composition of Mg-6Al-4MgCuYZn, wherein the mass percentage of amorphous alloy powder coated with ZrO2 and uncoated amorphous alloy powder in 4wt% MgCuYZn is 7:3.

[0084] In step S11 of the first stage, the MgCuYZn amorphous alloy strip is placed in a mechanical ball mill and ball-milled for 1 hour at a speed of 150 rpm to obtain MgCuYZn amorphous alloy powder with a particle size of 25 μm, thus preparing micron-sized magnesium-based amorphous alloy powder. Among them, zirconia balls are used as the ball milling medium, the ratio of zirconia balls to MgCuYZn amorphous alloy strip is 20:1, 1 wt% anhydrous ethanol is added as a grinding aid during the ball milling process, and the ball milling is carried out in a vacuum environment.

[0085] The ultrasonic power in the second stage is 600W.

[0086] Example 3

[0087] The preparation method in this embodiment is the same as that in Example 1, except that:

[0088] A magnesium-based composite material has the chemical composition Mg-6Al-4MgCuYZn, wherein the mass percentage of amorphous alloy powder coated with ZrO2 and uncoated amorphous alloy powder in 4wt% MgCuYZn is 8:2.

[0089] In step S11 of the first stage, the MgCuYZn amorphous alloy strip is placed in a mechanical ball mill and ball-milled for 3 hours at a speed of 250 rpm to obtain MgCuYZn amorphous alloy powder with a particle size of 10 μm, thus preparing micron-sized magnesium-based amorphous alloy powder. Among them, zirconia balls are used as the ball milling medium, the ratio of zirconia balls to MgCuYZn amorphous alloy strip is 40:1, 5 wt% anhydrous ethanol is added as a grinding aid during the ball milling process, and the ball milling is carried out in a vacuum environment.

[0090] The ultrasonic power in the second stage is 1000W.

[0091] Comparative Example 1

[0092] Unlike Example 1, the magnesium-based composite material for the soluble bridge plug does not introduce any surface-state magnesium-based amorphous alloy powder as a reinforcing phase during the smelting process. Instead, Mg-6Al magnesium alloy material is prepared directly from pure magnesium and pure aluminum.

[0093] Comparative Example 2

[0094] Unlike Example 1, the mass ratio of the ZrO2-coated amorphous alloy powder to the uncoated amorphous alloy powder added to the magnesium-based composite material for the soluble bridge plug is 10:0, that is, all 4wt% of MgCuYZn is a ZrO2-coated amorphous alloy microstructure regulator.

[0095] Comparative Example 3

[0096] Unlike Example 1, the mass ratio of the amorphous alloy powder with ZrO2 coating to the uncoated amorphous alloy powder added to the magnesium-based composite material for the soluble bridge plug is 0:10, that is, all 4wt% of MgCuYZn is amorphous powder without ZrO2 coating.

[0097] Mechanical and corrosion properties of the magnesium-based composite materials for soluble bridge plugs prepared according to the preparation methods of Examples 1-3 and Comparative Examples 1-3 were tested. Mechanical property testing: Tensile tests were conducted using an electronic universal testing machine at a strain rate of 1 mm / min. Corrosion property testing: The corrosion test environment was a 3% KCl solution at a temperature of 50°C. To enhance the reliability of the experimental results, each sample was tested five times. The obtained test data are recorded in Table 1.

[0098] Table 1 Performance test results of magnesium-based composite materials for soluble bridge plugs

[0099]

[0100] As shown in Table 1, this invention introduces both magnesium-based amorphous alloy powder coated with ZrO2 and uncoated magnesium-based amorphous alloy powder into the magnesium alloy matrix. Through these two functional reinforcing phases, a magnesium-based composite material with both high strength and controllable degradation behavior was successfully prepared. By adjusting the mass ratio of the two powders, the mechanical properties and corrosion rate of the composite material were synergistically optimized.

[0101] It was also observed that when 4wt% MgCuYZn powder with a ZrO2 coating was combined with uncoated amorphous alloy powder at a mass ratio of 9:1, the magnesium-based composite material exhibited the best performance in terms of ultimate tensile strength and corrosion rate. This is because the ZrO2-coated amorphous alloy acts as a high-strength inert framework, dominating mechanical strengthening; while the uncoated amorphous alloy crystallizes during the smelting process, serving as a controllable corrosion trigger point and guiding the corrosion from localized pitting to a uniform morphology.

[0102] Comparative experiments confirmed the necessity of dual-state combination: adding only an amorphous alloy with a ZrO2 coating on the surface can improve strength, but the corrosion rate is low; adding only an uncoated amorphous alloy loses the high strength characteristics of amorphous alloys, has limited strength improvement, and leads to an overall high corrosion rate; while the magnesium alloy matrix without adding any surface-state amorphous alloy has the lowest and uncontrollable performance.

[0103] Therefore, only by combining two types of amorphous powders with different surface states can we simultaneously achieve a significant improvement in mechanical properties and an active design that transforms the corrosion mode from uncontrolled pitting corrosion to controllable uniform corrosion. This effectively breaks through the two major technical bottlenecks of insufficient mechanical strength and uncontrollable degradation behavior that have long existed in traditional biodegradable magnesium alloys, providing a new paradigm for the application of magnesium alloys in the field of precision degradation.

[0104] The above description is merely a preferred embodiment of the present invention and is not intended to limit the scope of protection of the present invention. Any modifications, equivalent substitutions, improvements, etc., made within the spirit and principles of the present invention should be included within the scope of protection of the present invention.

Claims

1. A method for preparing an amorphous alloy microstructure regulator, characterized in that, Includes the following steps: S11. Prepare micron-sized magnesium-based amorphous alloy powder, wherein the magnesium-based amorphous alloy is a MgCuYZn amorphous alloy with an atomic percentage composition of Mg. a Cu b Y c Zn d a, b, c, and d satisfy: a + b + c + d = 100, 40 ≤ a ≤ 70, 20 ≤ b ≤ 40, 1 ≤ c ≤ 20, and 1 ≤ d ≤ 20. S12. Pre-treat the magnesium-based amorphous alloy powder; S13. An atomic layer deposition system is used to deposit a zirconium oxide coating on the surface of the magnesium-based amorphous alloy powder to obtain magnesium-based amorphous alloy powder with a zirconium oxide coating on the surface. The thickness of the zirconium oxide coating is 10–30 nm.

2. The method for preparing an amorphous alloy microstructure regulator according to claim 1, characterized in that, The specific process for preparing micron-sized magnesium-based amorphous alloy powder in step S11 includes: The MgCuYZn amorphous alloy strip was ball-milled at a speed of 150–250 rpm for 1–3 hours to obtain MgCuYZn amorphous alloy powder with a particle size of 10–25 μm. The ball milling was carried out using zirconia balls as the milling medium, and the ratio of the zirconia balls to the MgCuYZn amorphous alloy strip was 20–40:

1. 1–5 wt% anhydrous ethanol was added as a grinding aid during the ball milling process, and the ball milling was carried out in a vacuum environment.

3. The method for preparing an amorphous alloy microstructure regulator according to claim 1, characterized in that, The specific process of pretreating the magnesium-based amorphous alloy powder in step S12 includes: The MgCuYZn amorphous alloy powder was placed in a centrifuge tube, acetone was added, and the mixture was treated under ultrasonic conditions for 30 min. After centrifugation, the supernatant was discarded. Then anhydrous ethanol was added, and the mixture was treated under ultrasonic conditions for 30 min. After centrifugation, the supernatant was discarded. The cleaned amorphous alloy powder was dried in a vacuum drying oven at 60°C for 2 h. The ultrasonic conditions are: ultrasonic frequency of 80 kHz and power density of 0.8 W / cm². 2 The time is 1 minute.

4. The method for preparing an amorphous alloy microstructure regulator according to claim 1, characterized in that, The specific steps for depositing a zirconium oxide coating on the surface of the magnesium-based amorphous alloy powder using an atomic layer deposition system in step S13 to obtain magnesium-based amorphous alloy powder with a zirconium oxide coating are as follows: The pretreated MgCuYZn amorphous alloy powder was spread evenly in a sample boat, which was then placed in the isothermal zone of the atomic layer deposition system reaction chamber. Vacuum treatment was performed, and after treatment, the sample stage vibration device and deposition operation were activated. 200 ALD cycles were run for deposition. After deposition, the reaction chamber was cooled to below 80°C under a continuous N2 flow to obtain MgCuYZn amorphous alloy powder with a zirconia coating. The zirconia-coated MgCuYZn amorphous alloy powder was then heated to 250°C at a rate of 2°C / min under N2 protection and held for 1 hour for annealing. After annealing, it was dry-ground at 100 rpm for 5 minutes to obtain magnesium-based amorphous alloy powder with a zirconia coating.

5. The method for preparing an amorphous alloy microstructure regulator according to claim 4, characterized in that, The materials, cleaning, parameter settings, and ALD cycle deposition operations of the atomic layer deposition system are as follows: Materials prepared: MgCuYZn amorphous alloy powder, tetra(dimethylamino)zirconium, and deionized water; First, the ALD reaction chamber was heated to 200°C and purged with nitrogen for 30 minutes. Then, it was treated with O2 plasma at 100W for 10 minutes to clean the atomic layer deposition system. Next, the ALD reaction chamber temperature was set to 160°C, the tetrakis(dimethylamino)zirconium source bottle temperature to 75°C, the gas delivery pipeline temperature to 100°C, and the deionized water source bottle temperature to 25°C. The basic vacuum level of the atomic layer deposition system was evacuated to <1.0 × 10⁻⁶. -4 The working pressure was stabilized at 1.0 Torr by introducing N2, the vibration frequency was 30 Hz, and the amplitude was 2 mm. Finally, 200 ALD cycles were performed for deposition. The steps of a complete ALD cycle are as follows: Tetra(dimethylamino)zirconium pulse: Tetra(dimethylamino)zirconium vapor is introduced into the ALD reaction chamber for a pulse duration of 1 second; First N2 purging: Introduce high-purity N2 and purge for 40 seconds; Deionized water pulse: Water vapor is introduced into the ALD reaction chamber for 1 second; Second N2 purging: Introduce N2 again and purge for 40 seconds.

6. A method for preparing a magnesium-based composite material, characterized in that, Magnesium-based composite materials are prepared using the amorphous alloy microstructure regulator described in claim 5 as the reinforcing phase and Mg-6Al as the matrix. The preparation steps are as follows: S21. Melt the base magnesium to obtain a magnesium-based melt, and stir in the magnesium-based melt to add preheated pure aluminum, uncoated amorphous alloy powder and amorphous alloy microstructure regulator to obtain an alloy melt. S22. The alloy melt is poured and cooled to form a magnesium-based composite material.

7. The method for preparing a magnesium-based composite material according to claim 6, characterized in that, In step S21, the process of melting the base magnesium to obtain a magnesium-based melt, and then adding preheated pure aluminum, uncoated amorphous alloy powder, and an amorphous alloy microstructure modifier to the magnesium-based melt to obtain an alloy melt, involves the following steps: Commercially pure magnesium with a purity of not less than 99.95% is placed in a crucible-type resistance furnace and gradually heated to 720°C under a protective gas atmosphere of a CO2 to SF6 volume fraction ratio of 99:1, and held until completely melted to obtain the magnesium-based melt. Preheated commercially pure aluminum with a purity of not less than 99.90% is added to the magnesium-based melt at 720°C and held for 20 minutes to ensure complete melting. Then, preheated uncoated amorphous alloy powder is added and held for 10 minutes. Finally, when the temperature gradually decreases and stabilizes at 670°C, preheated amorphous alloy microstructure modifier is added and held for 5 minutes to obtain the final alloy melt. The preheating treatment involves preheating at 200°C for 1 minute. h; The entire addition process in step S21 needs to be carried out in ultrasonic stirring, and the ultrasonic power is 600-1000 W; The specific steps in step S22 to pour the alloy melt and cool it to obtain the magnesium-based composite material include: immediately pouring the alloy melt after stirring and heat preservation into a metal mold to achieve rapid solidification and obtain the magnesium-based composite material.

8. A magnesium-based composite material, characterized in that, The magnesium-based composite material is obtained according to any one of claims 6-7, wherein the chemical composition of the magnesium-based composite material is Mg-6Al-4MgCuYZn, wherein the content of the amorphous alloy structure regulator is 4wt%, the content of pure aluminum is 6wt%, and the content of pure magnesium is 90wt%; and the mass percentage of the amorphous alloy powder with ZrO2 coating on the surface to the uncoated amorphous alloy powder in the 4wt% MgCuYZn is 7-9:3-1.

9. The magnesium-based composite material according to claim 8, characterized in that, When the mass percentage of ZrO2-coated amorphous alloy powder in 4wt% MgCuYZn to uncoated amorphous alloy powder is 9:1, the ultimate tensile strength, elongation, and corrosion rate of the magnesium-based composite material are 260 MPa, 9.8%, and 254 mm / year, respectively.

10. A soluble bridge plug, characterized in that, It includes a bridge plug body and a sealing structure, an anchoring structure and a bore structure disposed on the bridge plug body, wherein the entire or part of the bridge plug body is made of the magnesium-based composite material as described in any one of claims 8-9.

Images