CN108642311B - Preparation method of magnesium alloy material - Google Patents

Preparation method of magnesium alloy material Download PDF

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CN108642311B
CN108642311B CN201810459250.XA CN201810459250A CN108642311B CN 108642311 B CN108642311 B CN 108642311B CN 201810459250 A CN201810459250 A CN 201810459250A CN 108642311 B CN108642311 B CN 108642311B
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magnesium alloy
magnesium
alloy material
production method
cleaning
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CN108642311A (en
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张建华
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Shandong Ruiye New Materials Co.,Ltd.
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Shandong Ruiye Flange Co ltd
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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
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C23/00—Alloys based on magnesium
    • C22C23/04—Alloys based on magnesium with zinc or cadmium as the next major constituent
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C10/00—Solid state diffusion of only metal elements or silicon into metallic material surfaces
    • C23C10/28—Solid state diffusion of only metal elements or silicon into metallic material surfaces using solids, e.g. powders, pastes
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/02—Pretreatment of the material to be coated
    • C23C14/028—Physical treatment to alter the texture of the substrate surface, e.g. grinding, polishing
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
    • C23C14/14—Metallic material, boron or silicon
    • C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
    • C23C14/24—Vacuum evaporation
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
    • C23C14/58—After-treatment
    • C23C14/5806—Thermal treatment

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  • Physics & Mathematics (AREA)
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Abstract

The invention discloses a preparation method of a novel magnesium alloy material, wherein a zinc film is plated on the surface of the magnesium alloy material to form a gradient structure, the production efficiency is high, and the corrosion resistance and the mechanical strength of the magnesium alloy are improved. The method combines vacuum coating and diffusion technologies, simplifies pretreatment procedures, and forms a process for completing pretreatment and diffusion coating at one time; the coating film is tightly combined with the magnesium substrate material, so that the diffusion layer is more uniform and consistent, the production efficiency is improved, the flow line production is facilitated, and the coating film has the advantages of no powder flying in a workplace and environmental protection. In addition, the alloy elements and the rare earth elements in the magnesium alloy material have synergistic effect, so that the mechanical property and the conductivity of the magnesium alloy material can be obviously improved, and the comprehensive performance of the magnesium alloy material is obviously improved.

Description

Preparation method of magnesium alloy material
Technical Field
The invention relates to the technical field of metal alloy preparation, in particular to a preparation method of a magnesium alloy material.
Background
The magnesium alloy material is an alloy formed by adding other elements based on magnesium. The method is characterized in that: the density is small (1.8 g/cm)3Left and right), high strength, large elastic modulus, good heat dissipation, good shock absorption, larger impact load bearing capacity than aluminum alloy, good organic matter and alkali corrosion resistance, and the main alloy elements comprise aluminum, zinc, manganese, cerium, thorium, a small amount of zirconium or cadmium, and the like. At present, the most widely used is magnesium-aluminum alloy, and then magnesium-manganese alloy and magnesium-zinc-zirconium alloy, which are mainly used in aviation, aerospace, transportation, chemical engineering, rocket and other industrial departments. Of the practical metals, magnesium is the lightest metal, and its specific gravity is about 2/3 for aluminum and 1/4 for iron.
The magnesium alloy material has wide application range, and the main application fields comprise:
1) aerospace industry, military industry, traffic (including automotive industry, aircraft industry, motorcycle industry, bicycle industry, etc.), 3C, etc.: the magnesium alloy has the characteristics of meeting the requirements of high-tech fields such as aerospace on noise absorption, shock absorption and radiation protection of light materials, greatly improving the aerodynamic performance of an aircraft and obviously reducing the structural weight. Magnesium alloy components are selected on fighter planes, bombers, helicopters, transporters, civil aircraft, airborne radars, ground-air missiles, carrier rockets, artificial satellites and flyers in China: one type of airplane selects 300-400 magnesium alloy components at most; the weight of one part is up to 300 kg; the maximum dimension of a member is 2m or more. In military industry, magnesium alloy plates are required to improve the strength of structural members, reduce the weight of equipment and improve the hit rate of weapons.
2) The national defense industry field: because magnesium and magnesium alloy are impact-resistant, if magnesium alloy with corrosion resistance equivalent to that of aluminum alloy can be developed, the magnesium alloy has wide application prospect in various military fields such as weapons and the like. Such as magnesium powder for lighting bullets, high specific strength magnesium alloy bullet-stock materials for armor-piercing bullets, and parts such as tactical aviation missile cabin sections, aileron skins, siding and radars, magnesium alloy cross beams for satellites, camera frames and shells and the like which can be manufactured by using wrought magnesium alloys.
3) The field of automobile industry: the magnesium alloy automobile parts have low density, the weight of the whole automobile can be reduced, and the fuel consumption is indirectly reduced; the specific strength of magnesium is higher than that of aluminum alloy and steel, the specific rigidity is close to that of the aluminum alloy and steel, and the magnesium can bear certain load; the magnesium has good castability and dimensional stability, is easy to process and has low rejection rate; magnesium has a high damping coefficient, the damping capacity is greater than that of aluminum alloy and cast iron, and the magnesium can reduce noise when used for a shell, can reduce vibration when used for a seat and a rim, and improves the safety and the comfort of an automobile. At present, automobile instruments, seat frames, components of a direction control system, engine covers, gearboxes, intake manifolds, hubs, engines and safety components are all applied to magnesium alloy die-casting products.
However, magnesium alloy materials are generally low in absolute strength and cannot withstand physical damage of high strength; the chemical property is more active and is easy to corrode under the corrosion of rainwater, chemical substances and the like; the above disadvantages greatly limit the application of magnesium alloys, and therefore, the coating is often applied to the surface of magnesium metal to improve the corrosion resistance and mechanical strength.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to provide a preparation method of a novel magnesium alloy material, wherein a zinc film is plated on the surface of the magnesium alloy material to form a gradient structure, the production efficiency is high, and the corrosion resistance and the mechanical strength of the magnesium alloy are improved.
The invention provides a preparation method of a magnesium alloy material, which at least comprises the following components in percentage by mass:
B：3.4-5.1％
Mo：0.02-0.05％
Ni：3.0-3.2％
Sn：0.3-0.4％
Al：2-2.5％
Zn：1-5％
Sc：1.5-6％，
the balance of Mg and inevitable impurities;
wherein, the mass percentage of the element B can be 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4.0%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5.0%, 5.1% or any value in the range, which is not listed herein because of space limitation.
The mass percentage of the Mo element may be 0.02%, 0.025%, 0.03%, 0.035%, 0.04%, 0.045%, 0.05% or any value within the range, which is not listed herein due to space limitation.
The mass percentage of the Ni element may be 3.0%, 3.01%, 3.02%, 3.03%, 3.04%, 3.05%, 3.06%, 3.07%, 3.08%, 3.09%, 3.10%, 3.11%, 3.12%, 3.13%, 3.14%, 3.15%, 3.16%, 3.17%, 3.18%, 3.19%, 3.2%, or any value within the range, which is not listed herein because of space limitation.
The mass percentage of Sn element may be 0.3%, 0.31%, 0.32%, 0.33%, 0.34%, 0.35%, 0.36%, 0.37%, 0.38%, 0.39%, 0.4% or any value within the range, which is not listed herein due to space limitation.
The mass percentage of Al element may be 2%, 2.05%, 2.1%, 2.15%, 2.2%, 2.25%, 2.3%, 2.35%, 2.4%, 2.45%, 2.5% or any value within the range, which is not listed herein due to space limitation.
The mass percentage of Zn element may be 1%, 1.2%, 1.4%, 1.6%, 1.8%, 2%, 2.2%, 2.4%, 2.6%, 2.8%, 3%, 3.2%, 3.4%, 3.6%, 3.8%, 4%, 4.2%, 4.4%, 4.6%, 4.8%, or 5% or any value within the range, which is not listed herein because of space limitation.
The mass percentage of the Sc element may be 1.5%, 1.6%, 1.7%, 1.8%, 1.9%, 2%, 2.1%, 2.2%, 2.3%, 2.4%, 2.5%, 2.6%, 2.7%, 2.8%, 2.9%, 3%, 3.1%, 3.2%, 3.3%, 3.4%, 3.5%, 3.6%, 3.7%, 3.8%, 3.9%, 4%, 4.1%, 4.2%, 4.3%, 4.4%, 4.5%, 4.6%, 4.7%, 4.8%, 4.9%, 5%, 5.1%, 5.2%, 5.3%, 5.4%, 5.5%, 5.6%, 5.7%, 5.8%, 5.9%, 6% or any value within the range, as long as the space is not limited thereto.
The preparation method of the magnesium alloy material at least comprises the following steps:
(1) mixing the raw materials and then carrying out ball milling to obtain powder; then, vacuum induction melting is carried out at 1050-;
(2) mechanically polishing the surface of the magnesium alloy, then grinding the surface on water sand paper to remove surface impurities, then ultrasonically cleaning the surface in an alcohol/ketone solution, and air-drying the surface to obtain a magnesium base material;
(3) putting a magnesium base material and a high-purity zinc target material into a vacuum tank, and plating a zinc film on the surface of the magnesium base material by adopting a vacuum evaporation method;
(4) annealing treatment is carried out for 3-4h under the conditions of 700-730 ℃ (for example, 700 ℃, 702 ℃, 704 ℃, 706 ℃, 708 ℃, 710 ℃, 712 ℃, 714 ℃, 716 ℃, 718 ℃, 720 ℃, 722 ℃, 724 ℃, 726 ℃, 728 ℃, 730 ℃ or any value in the range, which is not listed for reasons of space limitation), and then the magnesium alloy material is obtained by cleaning with a water-based cleaning agent.
Preferably, in the step (1), the ball milling is carried out by a mechanical ball milling method;
preferably, the particle size of the powder is less than or equal to 18nm, and may be, for example, 17nm, 16nm, 15nm, 14nm, 13nm, 12nm, 11nm, 10nm, 9nm, 8nm, 7nm, 6nm, 5nm, 4nm, 3nm, 2nm, 1nm or any value within the range, which is not listed herein due to space limitation;
preferably, the deslagging agent is a composite deslagging agent with silicate as a main component.
Preferably, in the step (2), the magnesium alloy is polished to a surface roughness Ra of 0.8 μm or less, such as 0.7 μm, 0.6 μm, 0.5 μm, 0.4 μm, 0.3 μm, 0.2 μm, 0.1 μm or any value in the range, which is not listed herein due to space limitation;
preferably, the model of the water sand paper is 800# -2000#, and may be 800#, 900#, 1000#, 1100#, 1200#, 1300#, 1400#, 1500#, 1600#, 1700#, 1800#, 1900# or 2000 #;
preferably, the alcohol solution is a methanol and/or ethanol solution;
preferably, the ketone solution is an acetone solution;
preferably, the ultrasonic cleaning time is 1-3min, for example, 1min, 1.2min, 1.4min, 1.6min, 1.8min, 2min, 2.2min, 2.4min, 2.6min, 2.8min, 3min or any value in the range, which is not listed herein due to space limitation.
Preferably, in the step (3), the pressure in the vacuum tank is less than or equal to 6 × 10 during vacuum evaporation-3Pa, for example, may be 5 × 10-3Pa、4×10-3Pa、3×10-3Pa、2×10-3Pa、1×10-3Pa or any value in the range, which is not listed any more due to space limitation;
preferably, during vacuum evaporation, the temperature in the vacuum tank is 350-;
preferably, the thickness of the zinc film is 2-16 μm, and may be, for example, 2 μm, 3 μm, 4 μm, 5 μm, 6 μm, 7 μm, 8 μm, 9 μm, 10 μm, 11 μm, 12 μm, 13 μm, 14 μm, 15 μm, 16 μm or any value within the range, which is not listed herein due to space limitation.
Preferably, in the step (4), the water-based cleaning agent comprises a surfactant and an auxiliary agent;
preferably, the surfactant is a nonionic surfactant and/or an anionic surfactant;
preferably, the auxiliary agent comprises any one or a combination of at least two of a builder, a corrosion inhibitor, a stabilizer, a defoamer or a solubilizer;
preferably, the cleaning is ultrasonic cleaning and/or mechanical cleaning, more preferably ultrasonic cleaning.
Preferably, the magnesium alloy material at least comprises the following components in percentage by mass:
B：3.4-5.1％
Mo：0.02-0.05％
Ni：3.0-3.2％
Sn：0.3-0.4％
Al：2-2.5％
Zn：1-5％
Sc：1.5-6％，
the balance of Mg and inevitable impurities;
the preparation method of the magnesium alloy material at least comprises the following steps:
(1) mixing the raw materials, and then carrying out mechanical ball milling to obtain powder, wherein the particle size of the powder is less than or equal to 18 nm; then carrying out vacuum induction melting at 1050-;
(2) mechanically polishing the surface of the magnesium alloy, then grinding the magnesium alloy on 800-2000 # waterproof abrasive paper until the surface roughness Ra is less than or equal to 0.8 mu m, removing surface impurities, then ultrasonically cleaning the magnesium alloy in a methanol and/or acetone solution for 1-3min, and air-drying to obtain a magnesium base material;
(3) putting magnesium base material and high-purity zinc target material into vacuum tank, plating zinc film with thickness of 2-16 μm on the surface of magnesium base material by vacuum evaporation method, wherein the pressure in vacuum tank is less than or equal to 6 × 10-3Pa, the temperature is 350-450 ℃;
(4) annealing treatment is carried out for 3-4h at the temperature of 700-.
In the invention, the alloy elements and the rare earth elements in the magnesium alloy material have synergistic effect, so that the mechanical property of the magnesium alloy material can be obviously improved, wherein the yield strength and the tensile strength are respectively improved. The grain refinement in the step (1) can further improve the strength and the conductivity, and a magnesium alloy material with an ultrafine microstructure is formed. And (3) polishing and grinding the surface of the magnesium alloy in the step (2) so that the galvanized film can better penetrate into the magnesium base material in the next step. When the step (3) is carried out, the zinc coating film of the magnesium substrate is subjected to vacuum evaporation and diffusion in a heating state, so that the production efficiency of the preparation of the gradient alloy is effectively improved. The annealing process in the step (4) can further diffuse zinc atoms in the vacuum galvanizing layer on the surface of the magnesium matrix into the surface layer of the magnesium matrix to form a diffusion layer, thereby improving the surface electrode potential of the magnesium matrix, enhancing the binding force of the zinc layer and the magnesium matrix, and limiting the duration to effectively avoid that magnesium atom crystal grains are too large and influence the mechanical property of the magnesium matrix. The magnesium alloy material prepared by the method has the advantages that the formed coating is not easy to separate from the magnesium metal or magnesium alloy matrix.
Compared with the prior art, the invention has at least the following beneficial effects:
the invention aims to provide a preparation method of a novel magnesium alloy material, wherein a zinc film is plated on the surface of the magnesium alloy material to form a gradient structure, the production efficiency is high, and the corrosion resistance and the mechanical strength of the magnesium alloy are improved. The method combines vacuum coating and diffusion technologies, simplifies pretreatment procedures, and forms a process for completing pretreatment and diffusion coating at one time; the coating film is tightly combined with the magnesium substrate material, so that the diffusion is more uniform and consistent, the production efficiency is improved, the flow line production is facilitated, and the coating film has the advantages of no powder flying in a workplace and environmental protection. In addition, the alloy elements and the rare earth elements in the magnesium alloy material have synergistic effect, so that the mechanical property and the conductivity of the magnesium alloy material can be obviously improved, and the comprehensive performance of the magnesium alloy material is obviously improved.
Drawings
Fig. 1 is a cross-sectional SEM image of a magnesium alloy material produced in example 1 of the present invention;
fig. 2 is a scanning map of a spectral surface of a magnesium alloy material produced in example 1 of the present invention.
Detailed Description
The invention will be further described with reference to the following figures and specific examples, which are not intended to limit the invention in any way.
Example 1
In this embodiment, the magnesium alloy material at least comprises the following components in percentage by mass:
B：3.4％
Mo：0.02％
Ni：3.0％
Sn：0.3％
Al：2％
Zn：1％
Sc：1.5％，
the balance of Mg and inevitable impurities;
the preparation method of the magnesium alloy material at least comprises the following steps:
(1) mixing the raw materials, and then carrying out mechanical ball milling to obtain powder, wherein the particle size of the powder is less than 18 nm; then vacuum induction melting is carried out at 1050 ℃, after the metal is melted, a composite slag removing agent with silicate as the main component is added, and the magnesium alloy is obtained after stirring and cooling;
(2) mechanically polishing the surface of the magnesium alloy, then grinding the magnesium alloy on 800# waterproof abrasive paper until the surface roughness Ra is less than or equal to 0.8 mu m, removing surface impurities, then ultrasonically cleaning the magnesium alloy in a methanol and acetone solution for 1min, and air-drying to obtain a magnesium base material;
(3) putting magnesium base material and high-purity zinc target material into vacuum tank, plating zinc film with thickness of 2 μm on the surface of magnesium base material by vacuum evaporation method, wherein the pressure in vacuum tank is less than or equal to 6 × 10 during vacuum evaporation-3Pa, the temperature is 350 ℃;
(4) annealing treatment is carried out for 3-4h at 700 ℃, and then ultrasonic cleaning and/or mechanical cleaning is carried out by using a water-based cleaning agent to obtain the magnesium alloy material.
The magnesium alloy material is subjected to electron microscope scanning and energy spectrum surface scanning to observe the appearance of a diffusion layer of the section of the magnesium alloy material. As shown in FIG. 1, the cross-sectional morphology of the sample is observed by a scanning electron microscope (model S4800), and it can be seen that a significant gradient layer is formed from the surface layer to the matrix of the cross-section of the sample I, and the surface layer has a uniform and dense zinc film; as shown in fig. 2, when the cross section of the sample is observed by scanning the energy spectrum plane, the zinc content in the sample is gradually reduced from the surface layer to the inside along with the increase of the depth, and a gradient diffusion layer can be obtained.
Example 2
In this embodiment, the magnesium alloy material at least comprises the following components in percentage by mass:
B：5.1％
Mo：0.05％
Ni：3.2％
Sn：0.4％
Al：2.5％
Zn：5％
Sc：6％，
the balance of Mg and inevitable impurities;
the preparation method of the magnesium alloy material at least comprises the following steps:
(1) mixing the raw materials, and then carrying out mechanical ball milling to obtain powder, wherein the particle size of the powder is equal to 18 nm; then vacuum induction melting is carried out at 1090 ℃, after the metal is melted, a composite slag removing agent with silicate as the main component is added, and the magnesium alloy is obtained after stirring and cooling;
(2) mechanically polishing the surface of the magnesium alloy, then grinding the magnesium alloy on 2000# waterproof abrasive paper until the surface roughness Ra is less than or equal to 0.8 mu m, removing surface impurities, then ultrasonically cleaning the magnesium alloy in a methanol solution for 3min, and air-drying to obtain a magnesium base material;
(3) putting magnesium base material and high-purity zinc target material into vacuum tank, coating zinc film with thickness of 16 μm on the surface of magnesium base material by vacuum evaporation method, wherein the pressure in vacuum tank is less than or equal to 6 × 10 during vacuum evaporation-3Pa, the temperature is 450 ℃;
(4) annealing treatment is carried out for 3-4h at the temperature of 730 ℃, and then ultrasonic cleaning and/or mechanical cleaning is carried out by using a water-based cleaning agent to obtain the magnesium alloy material.
Similarly to the above example 1, the magnesium alloy material is subjected to electron microscope scanning and energy spectrum surface scanning to observe the appearance of the diffusion layer of the gradient alloy section, and it can be observed through a scanning electron microscope (S4800 type) that an obvious gradient layer is formed from the surface layer to the matrix of the sample section, and a uniform and dense zinc layer is formed on the surface layer; and the fact that the zinc content of the sample is gradually reduced along with the increase of the depth from the surface layer to the inside of the cross section of the sample can be observed through energy spectrum surface scanning, and a gradient diffusion layer can be obtained.
Example 3
In this embodiment, the magnesium alloy material at least comprises the following components in percentage by mass:
B：4.3％
Mo：0.035％
Ni：3.1％
Sn：0.35％
Al：2.25％
Zn：3％
Sc：3.75％，
the balance of Mg and inevitable impurities;
the preparation method of the magnesium alloy material at least comprises the following steps:
(1) mixing the raw materials, and then carrying out mechanical ball milling to obtain powder, wherein the particle size of the powder is less than 18 nm; then vacuum induction melting is carried out at 1070 ℃, after the metal is melted, a composite slag removing agent with silicate as the main component is added, and the magnesium alloy is obtained after stirring and cooling;
(2) mechanically polishing the surface of the magnesium alloy, then grinding the magnesium alloy on 1400# waterproof abrasive paper until the surface roughness Ra is less than or equal to 0.8 mu m, removing surface impurities, then carrying out ultrasonic cleaning in an acetone solution for 2min, and air-drying to obtain a magnesium base material;
(3) putting magnesium base material and high-purity zinc target material into vacuum tank, plating zinc film with thickness of 9 μm on the surface of magnesium base material by vacuum evaporation method, wherein the pressure in vacuum tank is less than or equal to 6 × 10 during vacuum evaporation-3Pa, the temperature is 400 ℃;
(4) annealing treatment is carried out for 3.5h at 715 ℃, and then ultrasonic cleaning and/or mechanical cleaning is carried out by using a water-based cleaning agent to obtain the magnesium alloy material.
The magnesium alloy material is also subjected to electron microscope scanning and energy spectrum surface scanning to observe the appearance of a diffusion layer of the gradient alloy section, and a scanning electron microscope (S4800 type) can also be used for observing that an obvious gradient layer is formed from the surface layer to a matrix of the sample section, and a uniform and compact zinc layer is formed on the surface layer; and the fact that the zinc content of the sample is gradually reduced along with the increase of the depth from the surface layer to the inside of the cross section of the sample can be observed through energy spectrum surface scanning, and a gradient diffusion layer can be obtained.
Example 4
In this embodiment, the magnesium alloy material at least comprises the following components in percentage by mass:
B：4.2％
Mo：0.04％
Ni：3.05％
Sn：0.32％
Al：2.4％
Zn：2.5％
Sc：3％，
the balance of Mg and inevitable impurities;
the preparation method of the magnesium alloy material at least comprises the following steps:
(1) mixing the raw materials, and then carrying out mechanical ball milling to obtain powder, wherein the particle size of the powder is equal to 18 nm; then vacuum induction melting is carried out at 1080 ℃, after the metal is melted, a composite slag removing agent with silicate as the main component is added, and the magnesium alloy is obtained after stirring and cooling;
(2) mechanically polishing the surface of the magnesium alloy, then grinding the magnesium alloy on 1000# waterproof abrasive paper until the surface roughness Ra is less than or equal to 0.8 mu m, removing surface impurities, then carrying out ultrasonic cleaning in a methanol and acetone solution for 2min, and air-drying to obtain a magnesium base material;
(3) putting magnesium base material and high-purity zinc target material into vacuum tank, plating zinc film with thickness of 10 μm on the surface of magnesium base material by vacuum evaporation method, wherein the pressure in vacuum tank is less than or equal to 6 × 10 during vacuum evaporation-3Pa, temperature 325 ℃;
(4) annealing treatment is carried out for 3.2h at 710 ℃, and then ultrasonic cleaning and/or mechanical cleaning are carried out by using a water-based cleaning agent to obtain the magnesium alloy material.
The magnesium alloy material is also subjected to electron microscope scanning and energy spectrum surface scanning to observe the diffusion layer of the gradient alloy, and the obvious gradient layer is observed from the surface layer to the matrix of the sample section through a scanning electron microscope (S4800 type), and a uniform and compact zinc layer is formed on the surface layer; and the fact that the zinc content of the sample is gradually reduced along with the increase of the depth from the surface layer to the inside of the cross section of the sample can be observed through energy spectrum surface scanning, and a gradient diffusion layer can be obtained.
Comparative example 1
The same as example 1 except that the percentage by mass of the element B was 1%.
Comparative example 2
The same as example 1 except that the percentage by mass of the element B was 10%.
Comparative example 3
The same procedure as in example 1 was repeated, except that the content of Mo was 1% by mass.
Comparative example 4
The same procedure as in example 1 was repeated except that Mo was not added.
Comparative example 5
The same procedure as in example 1 was repeated, except that the Ni element was 1% by mass.
Comparative example 6
The same procedure as in example 1 was repeated, except that the Ni element was contained in an amount of 10% by mass.
Comparative example 7
The same procedure as in example 1 was repeated, except that the Sn element was 1% by mass.
Comparative example 8
The same procedure as in example 1 was repeated, except that the Sn element content was 0.1% by mass.
Comparative example 9
The same procedure as in example 1 was repeated, except that the Al element was 0.1% by mass.
Comparative example 10
The same procedure as in example 1 was repeated, except that the Al element was 8% by mass.
Comparative example 11
The same procedure as in example 1 was repeated, except that the amount of Zn element was 0.1% by mass.
Comparative example 12
The same as example 1 was repeated, except that the Zn element was 10% by mass.
Comparative example 13
The procedure was repeated as in example 1 except that the content of Sc was 0.1% by mass.
Comparative example 14
The same as in example 1 was repeated, except that the content of Sc was 10% by mass.
Comparative example 15
The procedure of example 1 was repeated, except that the thickness of the zinc film in step (3) was 0.1. mu.m.
Comparative example 16
The procedure of example 1 was repeated, except that the thickness of the zinc film in step (3) was 20 μm.
Comparative example 17
The same procedure as in example 1 was repeated except that the annealing temperature in step (4) was 600 ℃.
Comparative example 18
The same procedure as in example 1 was repeated except that the annealing temperature in step (4) was 800 ℃.
The results of the performance tests are shown in Table 1, and it can be seen from Table 1 that the magnesium alloy materials obtained in examples 1-4 prepared by the preparation method of the present invention have relative density of 99.2-99.4%, tensile strength of 610-760MPa, electrical conductivity of more than 80%, yield strength of about 230MPa, self-corrosion potential of about-0.5V, and self-corrosion current density of 1 × 10-6A/cm2-8×10-6A/cm2Left and right, interface bonding strength is 12-16N; in contrast to the comparative examples, some of the performance metrics were comparable to those of examples 1-4 (e.g., relative density, tensile strength, interfacial bond strength, conductivity, etc., of some of the comparative examples), and some were 1-2 orders of magnitude different (e.g., self-corrosion current density). However, in summary, of the seven performance indexes tested, comparative examples 1 to 18 cannot achieve the same performance index
Levels of examples 1-4. Therefore, the novel magnesium alloy material prepared by the preparation method of the invention has the advantages of zinc-plated film on the surface, gradient structure formation, high production efficiency and improvement of corrosion resistance and mechanical strength of the magnesium alloy material. In addition, the alloy elements and the rare earth elements in the magnesium alloy material have synergistic effect, the mechanical property and the conductivity of the magnesium alloy material can be obviously improved, the comprehensive performance of the magnesium alloy material is obviously improved, and the problems that the conventional magnesium alloy material is generally low in absolute strength and cannot withstand high-strength physical damage are solved; the chemical property is more active, and the corrosion is easy under the corrosion of rainwater, chemical substances and the like, so that the popularization is high, and the economic prospect is wide.
Table 1 results of performance testing
Figure BDA0001660470450000131
Figure BDA0001660470450000141
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
The invention is not the best known technology.

Claims (14)

1. The preparation method of the magnesium alloy material is characterized by comprising the following components in percentage by mass:
B：3.4-5.1％
Mo：0.02-0.05％
Ni：3.0-3.2％
Sn：0.3-0.4％
Al：2-2.5％
Zn：1-5％
Sc：1.5-6％，
the balance of Mg and inevitable impurities;
the preparation method of the magnesium alloy material at least comprises the following steps:
(1) mixing the raw materials and then carrying out ball milling to obtain powder; then carrying out vacuum induction melting at 1050-;
(2) mechanically polishing the surface of the magnesium alloy, then grinding the surface of the magnesium alloy on water sand paper to remove surface impurities, then carrying out ultrasonic cleaning in an alcohol solution and/or a ketone solution, and air-drying to obtain a magnesium base material;
(3) putting a magnesium base material and a high-purity zinc target material into a vacuum tank, plating a zinc film on the surface of the magnesium base material by adopting a vacuum evaporation method, wherein the pressure in the vacuum tank is less than or equal to 6 × 10-3Pa, the temperature is 350-450 ℃;
(4) annealing treatment is carried out for 3-4h at the temperature of 700-.
2. The method according to claim 1, wherein in the step (1), the ball milling is performed by a mechanical ball milling method.
3. The production method according to claim 1 or 2, wherein in the step (1), the particle size of the powder is 18nm or less.
4. The production method according to claim 1 or 2, wherein in the step (1), the slag remover is a composite slag remover containing silicate as a main component.
5. The production method according to claim 1 or 2, wherein in the step (2), the magnesium alloy is ground to a surface roughness Ra of 0.8 μm or less.
6. The method according to claim 1 or 2, wherein in the step (2), the type of the waterproof abrasive paper is 800# -2000 #.
7. The method according to claim 1 or 2, wherein in the step (2), the alcohol solution is a methanol and/or ethanol solution.
8. The production method according to claim 1 or 2, wherein in the step (2), the ketone solution is an acetone solution.
9. The production method according to claim 1 or 2, wherein in the step (2), the time of the ultrasonic cleaning is 1 to 3 min.
10. The production method according to claim 1 or 2, wherein in the step (3), the thickness of the zinc film is 2 to 16 μm.
11. The production method according to claim 1 or 2, wherein in the step (4), the water-based cleaning agent comprises a surfactant and an auxiliary agent.
12. The method according to claim 11, wherein in the step (4), the surfactant is a nonionic surfactant and/or an anionic surfactant.
13. The method according to claim 11, wherein in the step (4), the auxiliary agent comprises any one or a combination of at least two of a builder, a corrosion inhibitor, a stabilizer, a defoamer or a solubilizer.
14. The production method according to claim 1 or 2, wherein in the step (4), the cleaning is ultrasonic cleaning and/or mechanical cleaning.
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