CN116689540A - A kind of high toughness reinforced aluminum-magnesium composite material and preparation method thereof - Google Patents

Abstract

The invention discloses a high-toughness reinforced aluminum-magnesium composite material and a preparation method thereof, and relates to the technical field of aluminum alloy. The preparation method comprises the steps of smelting a high-purity aluminum ingot, a pure magnesium ingot and a pure zinc ingot, regulating and controlling the content of each metal element to strengthen the performance of an aluminum-magnesium composite material, adding carbon-containing metal powder, carrying out electron beam irradiation-ultrasonic treatment, synthesizing a carbide reinforcing phase in situ, casting to form an ingot, carrying out hot extrusion-cold drawing treatment and heat treatment for multiple times to improve the strength and toughness of the aluminum-magnesium composite material, carrying out copper cladding and hydroxylation treatment, carrying out reaction on diethanolamine, boric acid, (3S, 4E, 6S) -4-ene-3, 6-octanediol, phosphorus trichloride, epichlorohydrin and hydrogen-terminated phenyl silicone oil to generate modified epoxy resin, forming a multi-position adsorption on a copper-clad aluminum-magnesium alloy wire to form a compact protective film, and forming a layer of hydrophobic net structure on the surface after coating and solidification to prevent water vapor with corrosive substances from contacting a surface coating.

Description

A kind of high toughness reinforced aluminum-magnesium composite material and preparation method thereof

technical field

The invention relates to the technical field of aluminum alloys, in particular to a high-toughness reinforced aluminum-magnesium composite material and a preparation method thereof.

Background technique

Aluminum-magnesium composite materials have low density, good corrosion resistance, high specific strength, and easy processing and molding, so that aluminum-magnesium composite products are widely used in marine environment, aviation, motor vehicles, cables and other fields. At present, aluminum-magnesium composite materials are mainly made of aluminum-magnesium alloy wires. The main process of domestic production is made by direct drawing, which cannot effectively control the growth of metal elements, thus affecting the performance of aluminum alloy wires. In addition, in coastal and inland hot and humid environments, because the environment contains harmful corrosive media such as chlorides and sulfides, aluminum-magnesium composites have strong corrosion sensitivity. Compared with other materials, the corrosion problem of aluminum-magnesium composite materials is more prominent, local areas will be eroded, the dense passivation film on the surface of aluminum-magnesium composite materials will be broken, and small holes developing inward will appear, which will affect its use.

Contents of the invention

The object of the present invention is to provide a high-toughness reinforced aluminum-magnesium composite material and a preparation method thereof, so as to solve the problems existing in the prior art.

In order to solve the above technical problems, the present invention provides the following technical proposal: a high-toughness reinforced aluminum-magnesium composite material, the high-toughness reinforced aluminum-magnesium composite material is smelted from high-purity aluminum ingots, pure magnesium ingots, and pure zinc ingots, and then added with Carbon metal powder, after electron beam irradiation and ultrasonic treatment, is made of aluminum-magnesium alloy melt, which is melted and cast into aluminum-magnesium alloy round ingots, and then processed by multiple hot extrusion-cold drawing and heat treatment to produce aluminum-magnesium alloy Alloy wire, and then covered and welded with copper strip to obtain copper-clad aluminum-magnesium alloy wire, which is prepared by hydroxylation treatment and coating.

Further, the coating includes a modified epoxy resin and a curing agent; the modified epoxy resin is prepared from diethanolamine, boric acid, (3S, 4E, 6S)-4-ene-3,6-octanediol , phosphorus trichloride, epichlorohydrin, and hydrogen-terminated phenyl silicone oil.

Further, a method for preparing a high-toughness reinforced aluminum-magnesium composite material includes the following preparation steps:

(1) Put the copper strip and aluminum-magnesium alloy wire with a thickness of 0.4-0.5mm and a width of 30-32mm into deionized water, acetone, absolute ethanol and deionized water in sequence, and after 500-600W ultrasonic cleaning for 20min, nitrogen gas Blow dry, carry out cladding welding simultaneously in the same direction on a cladding welding machine, stretch to a diameter of 0.04mm-6.0mm, and obtain copper-clad aluminum-magnesium alloy wire;

(2) Mix nitrogen-containing borate compound, hydrochloric acid with a mass fraction of 20%, and formaldehyde at a mass ratio of 1:0.1:0.5 to 1:0.1:1.1, heat up to 50°C, and add nitrogen-containing borate compound with a mass of 2.8 ~5.7 times the phosphite compound, after reacting for 2~4 hours, add toluene with 4~6 times the mass of the nitrogen-containing borate compound, stir at 60~80rpm for 1.5h, vacuum -0.06MPa, distill at 60°C for 4~5h Get intermediate A;

(3) Mix intermediate A, epichlorohydrin, and tetrabutylammonium bromide in a mass ratio of 1:10:0.07～1:16:0.07, heat up to 105～110°C, react for 5～7 hours, and cool to At room temperature, add a 40% sodium hydroxide solution with a mass fraction of 0.2 to 0.3 times the mass of intermediate A. After reacting for 2 to 3 hours, add deionized water to wash until the pH of the solution is 7, leave to separate and separate, take the organic phase, and vacuum Distill at -0.07MPa and 60°C for 3.5 to 4.5 hours to obtain epoxy resin;

(4) Mix the epoxy resin and the platinum catalyst at a mass ratio of 1:0.001, stir evenly, and then raise the temperature to 80°C under the protection of nitrogen, and add 0.4 to 1.1 times the mass of the epoxy resin with a hydrogen-terminated phenyl silicone oil, After heat preservation reaction for 3-5 hours, vacuum degree -0.07MPa, distillation at 70°C for 2.0-2.5 hours to obtain modified epoxy resin; mix modified epoxy resin with ethylenediamine at a mass ratio of 30:1 to obtain a coating;

(5) Immerse the copper-clad aluminum-magnesium alloy wire in the mixed solution A and the mixed solution B in turn according to the material-to-liquid ratio of 1:20. After 400-600W ultrasonic vibration for 20 minutes, wash it with deionized water for 6 times, dry it with nitrogen, and apply Coating, curing to obtain a high-toughness reinforced aluminum-magnesium composite material with a diameter of 0.1-1.2mm.

Further, the preparation method of the aluminum-magnesium alloy wire described in step (1) is as follows: hot-extrude the aluminum-magnesium alloy round ingot at 400-450° C. at an extrusion speed of 0.8 mm/s, and cool in air to At room temperature, multi-pass cold drawing is carried out at 1.5-2.0mm/min. The diameter reduction of each cold drawing is 0.05-0.15mm. Extrude until fibers with a diameter of 5-8mm are obtained, put them into heat treatment furnaces at 450°C, 550°C, 750°C, and 950°C in sequence, keep them warm for 5-10 minutes, and cool to room temperature.

Further, the preparation method of the aluminum-magnesium alloy round ingot is as follows: melting high-purity aluminum ingots, pure magnesium ingots, and pure zinc ingots at 720-760°C to obtain a melt, adding 0.008-0.5 times the mass of the melt containing Carbon metal powder, evacuated to 0.005-0.05Pa, irradiated with an electron beam with a power of 15kW for 5-8 minutes, then ultrasonicated at 400-500W for 3 minutes, and repeated the above irradiation and ultrasonic for 2-3 times to obtain an aluminum-magnesium alloy melt; The magnesium alloy melt is cast at a casting temperature of 740-800°C and a casting speed of 23-33mm/min, and then annealed at 450-500°C for 18-22 hours to obtain an aluminum-magnesium alloy round ingot with a diameter of 15-30mm.

Further, the mass ratio of the high-purity aluminum ingot, pure magnesium ingot, and pure zinc ingot is 42:1:0.04 to 62:1:0.06; the mass ratio of chromium powder, carbon powder, and iron powder in the carbon-containing metal powder The ratio is 7:3:1.

Further, the preparation method of the nitrogen-containing borate compound in step (2) is: mix boric acid, diethanolamine, and xylene at a mass ratio of 1:3:1.0 to 1:4:1.25, and react at 160°C for 6 to 10 hours Finally, vacuum -0.08MPa, 75°C distillation for 1-2h, after washing with tetrahydrofuran for 4-6 times, vacuum -0.09MPa, 50°C distillation for 30-50min.

Further, the preparation method of the phosphite compound described in step (2) is: carbon tetrachloride, (3S,4E,6S)-4-ene-3,6-octanediol, phosphorus trichloride Mix at a ratio of 10:1.5:1~13:2.2:1, stir at 60~80rpm for 2~3h, wash with ethyl acetate, saturated aqueous solution of sodium bicarbonate, and deionized water for 3 times in sequence, separate the organic phase, add organic Anhydrous magnesium sulfate with a phase mass of 0.5 to 0.8 times, dried for 1 hour, filtered, vacuum degree -0.08MPa, 50°C distillation for 3 to 4 hours.

Further, the mass ratio of concentrated sulfuric acid and hydrogen peroxide in the mixed solution A described in step (5) is 14:1.

Further, the mass ratio of ammonia water and hydrogen peroxide in the mixed solution B described in step (5) is 4.5:1.

Compared with the prior art, the beneficial effects achieved by the present invention are:

In the present invention, by regulating the content of aluminum, magnesium and other tough chemical components, smelting and forming aluminum-magnesium alloy melt, adding carbon-containing metal powder, using electron beam irradiation, carbon powder and surrounding metal elements synthesize carbides in situ, and assisted by ultrasonic Next, the internal air and air bubbles are discharged, and the carbides are evenly dispersed in the melt, which is beneficial to refine the grains, eliminate the dendrites in the structure, and improve the strength of the aluminum-magnesium composite material during the casting and drawing process; then the aluminum Magnesium alloy melt is melted and cast into ingots, and its internal structure is excellent. After annealing, through multiple hot extrusion-cold drawing treatments, high-strength aluminum-magnesium alloy wires with fine grains, uniform diameters, and smooth surfaces are obtained, and then combined with The copper strip is clad and welded, and after multi-pass stretching, the copper layer and the aluminum-magnesium alloy wire are fully metallurgically bonded; then, hydroxylation treatment is performed, and a certain thickness of paint is coated on the surface of the copper-clad aluminum-magnesium alloy wire to form a physical embedding. The joint surface makes a stress buffer zone between the copper-clad aluminum-magnesium alloy wire and the coating, avoids crack initiation and expansion, and is conducive to improving the toughness of the aluminum-magnesium composite material.

The invention utilizes diethanolamine and boric acid to undergo esterification reaction to form a ring to form a nitrogen-containing borate group, and its amino cations generate electrostatic adsorption with negative ions on the surface of the copper-clad aluminum-magnesium alloy wire, thereby promoting the adsorption of the paint on the copper-clad aluminum-magnesium alloy wire Surface, forming an isolation protective layer, thereby improving the corrosion resistance of aluminum-magnesium composite materials; then, using the hydroxyl group of (3S,4E,6S)-4-ene-3,6-octanediol to react with phosphorus trichloride to form Phosphite, the phosphorus-hydrogen bond of phosphite reacts with the imine group of the nitrogen-containing borate group under the crosslinking action of formaldehyde, and the phosphorus atom connects with the metal empty orbital of the copper-clad aluminum-magnesium alloy wire through the lone electron pair Form a coordination bond, thereby forming multi-site adsorption with nitrogen-containing borate groups, making the coating strongly adsorbed on the surface of the aluminum-magnesium composite material, prolonging the life of the coating, and increasing the corrosion resistance of the aluminum-magnesium composite material; reuse (3S, The remaining unreacted hydroxyl groups of 4E,6S)-4-ene-3,6-octanediol react with the chlorine of epichlorohydrin to form epoxy resin; the double bonds of epoxy resin are then reacted with hydrogen-terminated phenyl silicone oil Hydrosilicon addition reaction, the introduction of organic silicon hydrophobic long chain, makes the epoxy resin oriented on the surface of the aluminum-magnesium composite material, forming a layer of hydrophobic network structure, which prevents the water vapor with corrosive substances from reaching the surface coating, and strengthens the aluminum alloy. Anticorrosion effect of magnesium composites.

Detailed ways

The technical solutions in the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention. Obviously, the described embodiments are only some of the embodiments of the present invention, not all of them. Based on the embodiments of the present invention, all other embodiments obtained by persons of ordinary skill in the art without making creative efforts belong to the protection scope of the present invention.

In order to illustrate more clearly that the method provided by the present invention is described in detail through the following examples, each index test method of the high toughness reinforced aluminum-magnesium composite material made in the following examples is as follows:

High strength and high toughness: Take the examples and comparative examples of the same length to measure the tensile strength and elongation with reference to JIS 2241 using a tensile testing machine.

Corrosion resistance: Take the examples and comparative examples of the same size with reference to IEC60811 and GB/T 19746, soak them in oxalic acid solution with an effective concentration of 45g/L, sodium hydroxide solution with an effective concentration of 40g/L, and 35g /L of neutral salt solution, soak for 7 days at 25°C, and calculate the change rate of tensile strength.

Example 1

(1) Mix high-purity aluminum ingots, pure magnesium ingots, and pure zinc ingots at a mass ratio of 42:1:0.04, melt at 720°C to obtain a melt, add carbon-containing metal powder 0.008 times the mass of the melt, and carbon-containing metal The mass ratio of chromium powder, carbon powder and iron powder in the powder is 7:3:1, vacuumize to 0.005Pa, power is 15kW electron beam irradiation after 5min, 400W ultrasonic 3min, repeat above-mentioned irradiation ultrasonic 2 times, obtain Al-Mg alloy melt;

(2) casting the aluminum-magnesium alloy melt at a casting temperature of 740°C and a casting speed of 23mm/min, and annealing at 450°C for 18 hours to obtain a round aluminum-magnesium alloy ingot with a diameter of 15mm;

(3) The aluminum-magnesium alloy round ingot was hot-extruded at 400°C and the extrusion speed was 0.8mm/s, cooled to room temperature in the air, and then cold-drawn in multiple passes at 1.5mm/min, each The diameter reduction of each pass of cold drawing is 0.05mm. After every 2 times of cold drawing, it is then hot-extruded under the same conditions to obtain fibers with a diameter of 5mm. In a heat treatment furnace at 950°C, keep warm for 5 minutes respectively, and cool to room temperature to obtain aluminum-magnesium alloy wires;

(4) Put the copper strip and aluminum-magnesium alloy wire with a thickness of 0.4mm and a width of 30mm into deionized water, acetone, absolute ethanol and deionized water in sequence, and after 500W ultrasonic cleaning for 20min, blow dry with nitrogen, and then coat The cladding welding is carried out synchronously in the same direction on the welding machine, stretched to a diameter of 0.04mm, and the copper-clad aluminum-magnesium alloy wire is obtained;

(5) Mix boric acid, diethanolamine, and xylene in a mass ratio of 1:3:1, react at 160°C for 6h, vacuum -0.08MPa, distill at 75°C for 1h, wash with THF 4 times, vacuum -0.09MPa , Distill at 50°C for 30 minutes to obtain a nitrogen-containing borate compound;

(6) Mix carbon tetrachloride, (3S,4E,6S)-4-ene-3,6-octanediol, and phosphorus trichloride in a mass ratio of 10:1.5:1, stir at 60 rpm for 2 hours, and then use Wash with ethyl acetate, saturated aqueous solution of sodium bicarbonate, and deionized water three times, separate the organic phase, add anhydrous magnesium sulfate 0.5 times the mass of the organic phase, dry for 1 h, filter, vacuum -0.08MPa, and distill at 50°C for 3 h Get phosphite compounds;

(7) Mix the nitrogen-containing borate compound, hydrochloric acid with a mass fraction of 20%, and formaldehyde at a mass ratio of 1:0.1:0.5, heat up to 50°C, and add a phosphite compound that is 2.8 times the mass of the nitrogen-containing borate compound , after reacting for 2 hours, add toluene with 4 times the mass of the nitrogen-containing borate compound, stir at 60 rpm for 1.5 hours, vacuum -0.06MPa, and distill at 60°C for 4 hours to obtain intermediate A;

(8) Mix intermediate A, epichlorohydrin, and tetrabutylammonium bromide at a mass ratio of 1:10:0.07, heat up to 105°C, react for 5 hours, cool to room temperature, and add 0.2 times the mass of intermediate A The mass fraction is 40% sodium hydroxide solution. After reacting for 2 hours, add deionized water to wash until the pH of the solution is 7, let it stand and separate layers, take the organic phase, vacuum degree -0.07MPa, and distill at 60°C for 3.5 hours to obtain epoxy resin ;

(9) Mix the epoxy resin and the platinum catalyst at a mass ratio of 1:0.001, stir evenly, and then raise the temperature to 80°C under the protection of nitrogen, add hydrogen-terminated phenyl silicone oil 0.4 times the mass of the epoxy resin, and keep warm for the reaction After 3 hours, vacuum degree -0.07MPa, distillation at 70°C for 2 hours to obtain a modified epoxy resin; mix the modified epoxy resin and ethylenediamine at a mass ratio of 30:1 to obtain a coating;

(10) Immerse the copper-clad aluminum-magnesium alloy wire in the mixed solution A and the mixed solution B sequentially according to the material-to-liquid ratio of 1:20, the mass ratio of concentrated sulfuric acid and hydrogen peroxide in the mixed solution A is 14:1, and the ammonia water in the mixed solution B The mass ratio to hydrogen peroxide is 4.5:1. After 400W ultrasonic oscillation for 20 minutes, it is washed 6 times with deionized water, dried with nitrogen, coated with paint, and cured to obtain a high-toughness reinforced aluminum-magnesium composite material with a diameter of 0.1mm.

Example 2

(1) Mix high-purity aluminum ingots, pure magnesium ingots, and pure zinc ingots at a mass ratio of 42:1:0.05, melt at 740°C to obtain a melt, add carbon-containing metal powder 0.25 times the mass of the melt, and carbon-containing metal The mass ratio of chromium powder, carbon powder and iron powder in the powder is 7:3:1, vacuumize to 0.027Pa, power is 15kW electron beam irradiation after 6min, 450W ultrasonic 3min, repeat above-mentioned irradiation ultrasonic 3 times, obtain Al-Mg alloy melt;

(2) casting the aluminum-magnesium alloy melt at a casting temperature of 770°C and a casting speed of 28mm/min, and annealing at 475°C for 20 hours to obtain an aluminum-magnesium alloy round ingot with a diameter of 22mm;

(3) The aluminum-magnesium alloy round ingot was hot-extruded at 425°C and the extrusion speed was 0.8mm/s, cooled to room temperature in the air, and then cold-drawn in multiple passes at 1.7mm/min. The diameter reduction of each pass of cold drawing is 0.1mm. After every 3 times of cold drawing, it is then hot-extruded under the same conditions until a fiber with a diameter of 6.5mm is obtained. , 950 ℃ heat treatment furnace, heat preservation for 7 minutes respectively, and cool to room temperature to obtain aluminum-magnesium alloy wire;

(4) Put the copper strip and aluminum-magnesium alloy wire with a thickness of 0.45 mm and a width of 31 mm into deionized water, acetone, absolute ethanol and deionized water in sequence, and after 550W ultrasonic cleaning for 20 minutes, blow dry with nitrogen, and then coat The cladding welding is carried out synchronously in the same direction on the welding machine, stretched to a diameter of 3mm, and the copper-clad aluminum-magnesium alloy wire is obtained;

(5) Mix boric acid, diethanolamine, and xylene at a mass ratio of 1:3.5:1.12, react at 160°C for 8 hours, vacuum at -0.08MPa, distill at 75°C for 1.5h, wash with tetrahydrofuran for 5 times, and vacuum at -0.09 MPa, distillation at 50°C for 40 minutes to obtain nitrogen-containing borate compound;

(6) Mix carbon tetrachloride, (3S,4E,6S)-4-ene-3,6-octanediol, and phosphorus trichloride at a mass ratio of 11.5:1.85:1, stir at 70rpm for 2.5h, and then Wash 3 times with ethyl acetate, saturated aqueous solution of sodium bicarbonate, and deionized water, separate the organic phase, add anhydrous magnesium sulfate 0.65 times the mass of the organic phase, dry for 1 h, filter, vacuum -0.08 MPa, and distill at 50 °C 3.5h to get phosphite compound;

(7) Mix the nitrogen-containing borate compound, hydrochloric acid with a mass fraction of 20%, and formaldehyde at a mass ratio of 1:0.1:0.8, heat up to 50°C, and add a phosphite compound that is 4.3 times the mass of the nitrogen-containing borate compound , after reacting for 3 hours, add toluene 5 times the mass of the nitrogen-containing borate compound, stir at 70 rpm for 1.5 hours, vacuum -0.06MPa, and distill at 60°C for 4.5 hours to obtain intermediate A;

(8) Mix intermediate A, epichlorohydrin, and tetrabutylammonium bromide at a mass ratio of 1:13:0.07, heat up to 107°C, react for 6 hours, cool to room temperature, and add 0.25 times the mass of intermediate A The mass fraction is 40% sodium hydroxide solution. After reacting for 2.5 hours, add deionized water to wash until the pH of the solution is 7, let it stand and separate layers, take the organic phase, vacuum degree -0.07MPa, and distill at 60°C for 4 hours to obtain epoxy resin ;

(9) Mix epoxy resin and platinum catalyst at a mass ratio of 1:0.001, stir evenly, and under the protection of nitrogen, heat up to 80°C, add hydrogen-terminated phenyl silicone oil 0.75 times the mass of epoxy resin, and keep warm for reaction After 4 hours, vacuum degree -0.07MPa, distillation at 70°C for 2.25 hours to obtain modified epoxy resin; mix modified epoxy resin and ethylenediamine at a mass ratio of 30:1 to obtain a coating;

(10) Immerse the copper-clad aluminum-magnesium alloy wire in the mixed solution A and the mixed solution B sequentially according to the material-to-liquid ratio of 1:20, the mass ratio of concentrated sulfuric acid and hydrogen peroxide in the mixed solution A is 14:1, and the ammonia water in the mixed solution B The mass ratio to hydrogen peroxide is 4.5:1. After 500W ultrasonic oscillation for 20 minutes, it is washed 6 times with deionized water, dried with nitrogen, coated with paint, and cured to obtain a high-toughness reinforced aluminum-magnesium composite material with a diameter of 0.6mm.

Example 3

(1) Mix high-purity aluminum ingots, pure magnesium ingots, and pure zinc ingots at a mass ratio of 62:1:0.06, melt at 760°C to obtain a melt, add carbon-containing metal powder 0.5 times the mass of the melt, and carbon-containing metal The mass ratio of chromium powder, carbon powder and iron powder in the powder is 7:3:1, vacuumize to 0.05Pa, power is 15kW electron beam irradiation after 8min, 500W ultrasonic 3min, repeat above-mentioned irradiation ultrasonic 3 times, obtain Al-Mg alloy melt;

(2) casting the aluminum-magnesium alloy melt at a casting temperature of 800°C and a casting speed of 33mm/min, and then annealing at 500°C for 22 hours to obtain an aluminum-magnesium alloy round ingot with a diameter of 30mm;

(3) The aluminum-magnesium alloy round ingot is hot-extruded at 450°C and the extrusion speed is 0.8mm/s, cooled to room temperature in the air, and then cold-drawn in multiple passes at 2mm/min. The diameter reduction of the second cold drawing is 0.15mm. After every 4th cold drawing, it is then hot-extruded under the same conditions until the fiber with a diameter of 8mm is obtained. ℃ heat treatment furnace, heat preservation for 10 minutes respectively, and cool to room temperature to obtain aluminum-magnesium alloy wire;

(4) Put the copper strip and aluminum-magnesium alloy wire with a thickness of 0.5mm and a width of 32mm into deionized water, acetone, absolute ethanol and deionized water in sequence, and after 600W ultrasonic cleaning for 20min, blow dry with nitrogen, and then coat The cladding welding is carried out synchronously in the same direction on the welding machine, stretched to a diameter of 6.0mm, and a copper-clad aluminum-magnesium alloy wire is obtained;

(5) Mix boric acid, diethanolamine, and xylene at a mass ratio of 1:4:1.25, react at 160°C for 10 hours, vacuum at -0.08MPa, distill at 75°C for 2h, wash with tetrahydrofuran for 6 times, and vacuum at -0.09MPa , Distill at 50°C for 50 minutes to obtain a nitrogen-containing borate compound;

(6) Mix carbon tetrachloride, (3S,4E,6S)-4-ene-3,6-octanediol, and phosphorus trichloride in a mass ratio of 13:2.2:1, stir at 80rpm for 3h, and then use Wash with ethyl acetate, saturated aqueous solution of sodium bicarbonate, and deionized water three times, separate the organic phase, add anhydrous magnesium sulfate 0.8 times the mass of the organic phase, dry for 1 h, filter, vacuum -0.08MPa, distill at 50°C for 4 h Get phosphite compounds;

(7) Mix the nitrogen-containing borate compound, hydrochloric acid with a mass fraction of 20%, and formaldehyde at a mass ratio of 1:0.1:1.1, heat up to 50°C, and add a phosphite compound that is 5.7 times the mass of the nitrogen-containing borate compound , after reacting for 4 hours, add toluene which is 6 times the mass of the nitrogen-containing borate compound, stir at 80 rpm for 1.5 hours, vacuum -0.06MPa, and distill at 60°C for 5 hours to obtain intermediate A;

(8) Mix intermediate A, epichlorohydrin, and tetrabutylammonium bromide at a mass ratio of 1:16:0.07, heat up to 110°C, react for 7 hours, cool to room temperature, and add 0.3 times the mass of intermediate A The mass fraction is 40% sodium hydroxide solution. After reacting for 3 hours, add deionized water to wash until the pH of the solution is 7, let it stand and separate layers, take the organic phase, vacuum degree -0.07MPa, and distill at 60°C for 4.5 hours to obtain epoxy resin ;

(9) Mix the epoxy resin and the platinum catalyst at a mass ratio of 1:0.001, stir evenly, and raise the temperature to 80°C under the protection of nitrogen, add hydrogen-terminated phenyl silicone oil 1.1 times the mass of the epoxy resin, and keep warm for reaction After 5 hours, vacuum degree -0.07MPa, 70°C distillation for 2.5 hours, to obtain modified epoxy resin; mix modified epoxy resin and ethylenediamine at a mass ratio of 30:1 to obtain a coating;

(10) Immerse the copper-clad aluminum-magnesium alloy wire in the mixed solution A and the mixed solution B sequentially according to the material-to-liquid ratio of 1:20, the mass ratio of concentrated sulfuric acid and hydrogen peroxide in the mixed solution A is 14:1, and the ammonia water in the mixed solution B The mass ratio to hydrogen peroxide is 4.5:1. After 600W ultrasonic oscillation for 20 minutes, it is washed 6 times with deionized water, dried with nitrogen, coated with paint, and cured to obtain a high-toughness reinforced aluminum-magnesium composite material with a diameter of 1.2mm.

Comparative example 1

The difference between Comparative Example 1 and Example 2 lies in the difference in step (1), change step (1) to: mix high-purity aluminum ingots and pure magnesium ingots at a mass ratio of 42:1, and melt at 740°C to obtain a melt , add carbon-containing metal powder of 0.25 times the mass of the melt, the mass ratio of chromium powder, carbon powder, and iron powder in the carbon-containing metal powder is 7:3:1, vacuumize to 0.027Pa, and irradiate with an electron beam with a power of 15kW After 6 minutes, 450W ultrasonic for 3 minutes, repeat the above-mentioned irradiation and ultrasonic for 3 times, to obtain aluminum-magnesium alloy melt. All the other steps are the same as in Example 2.

Comparative example 2

The difference between comparative example 2 and embodiment 2 lies in the difference of step (1), and step (1) is changed into: high-purity aluminum ingot, pure magnesium ingot, pure zinc ingot are mixed by mass ratio 42:1:0.05, at 740 Melt at ℃ to get aluminum-magnesium alloy melt. All the other steps are the same as in Example 2.

Comparative example 3

The difference between Comparative Example 3 and Example 2 lies in the difference in step (3), and step (3) is changed to: drawing an aluminum-magnesium alloy round ingot at 500° C. to obtain an aluminum-magnesium alloy wire with a diameter of 6.5 mm. All the other steps are the same as in Example 2.

Comparative example 4

The difference between comparative example 4 and embodiment 2 is that there is no step (5), (7), and step (8) is changed into: phosphorous acid ester compound, epichlorohydrin, tetrabutylammonium bromide are by mass ratio 1: Mix 13:0.07, heat up to 107°C, react for 6 hours, cool to room temperature, add 40% sodium hydroxide solution with a mass fraction of 0.25 times the mass of the phosphite compound, react for 2.5 hours, add deionized water to wash to the pH of the solution It is 7, standing for stratification, taking the organic phase, vacuum degree -0.07MPa, distillation at 60°C for 4h, to obtain epoxy resin. All the other steps are the same as in Example 2.

Comparative example 5

The difference between Comparative Example 5 and Example 2 is that there is no step (6), and step (7) is changed to: mix nitrogen-containing borate compound, hydrochloric acid and formaldehyde with a mass fraction of 20% in a mass ratio of 1:0.1:0.8, Raise the temperature to 50°C, add (3S,4E,6S)-4-ene-3,6-octanediol with 4.3 times the mass of the nitrogen-containing borate compound, and after 3 hours of reaction, add 5 times the mass of the nitrogen-containing borate compound After stirring at 70rpm for 1.5h, distilled at 60°C for 4.5h at a vacuum degree of -0.06MPa to obtain intermediate A. All the other steps are the same as in Example 2.

Comparative example 6

The difference between Comparative Example 6 and Example 2 is that there is no step (9), and step (8) is changed to: mix intermediate A, epichlorohydrin, and tetrabutylammonium bromide in a mass ratio of 1:13:0.07, and heat up to 107°C, react for 6 hours, cool to room temperature, add 40% sodium hydroxide solution with a mass fraction of 0.25 times the mass of intermediate A, react for 2.5 hours, add deionized water to wash until the pH of the solution is 7, let stand and separate , take the organic phase, vacuum -0.07MPa, 60 ℃ distillation for 4h, to obtain epoxy resin; mix epoxy resin and ethylenediamine at a mass ratio of 30:1 to prepare a coating. All the other steps are the same as in Example 2.

Effect example

Table 1 below shows the performance analysis results of the high-toughness reinforced aluminum-magnesium composite materials of Examples 1 to 3 and Comparative Examples 1 to 6 of the present invention.

Table 1

From the comparison of the tensile strength and elongation experiments of the examples and comparative examples, it can be found that the present invention realizes high-strength, high-toughness aluminum-magnesium composite materials by regulating and controlling the content of aluminum, magnesium and other tough chemical components, and utilizes electron beam irradiation - Ultrasonic treatment, carbon powder and surrounding metal elements synthesize carbides in situ, and evenly disperse in the melt, which is beneficial to refine the grains, eliminate dendrites in the structure, and improve the strength and toughness of the aluminum-magnesium composite material; then through Repeated hot extrusion-cold drawing process further refines and uniforms the crystal grains, and strengthens the strength and toughness of the aluminum-magnesium composite material; it can be found that the present invention utilizes Diethanolamine and boric acid are generated to form a nitrogen-containing borate compound, and (3S,4E,6S)-4-ene-3,6-octanediol is used to react with phosphorus trichloride to form a phosphite compound. Under the action, the two combine to form multi-site adsorption, forming a dense protective layer, and then further react with epichlorohydrin and hydrogen-terminated phenyl silicone oil. After the coating is cured, a layer of hydrophobic network structure is formed on the surface to prevent the retardation zone. The water vapor with corrosive substances contacts the surface coating, which strengthens the anti-corrosion effect of the aluminum-magnesium composite material.

It will be apparent to those skilled in the art that the invention is not limited to the details of the above-described exemplary embodiments, but that the invention can be embodied in other specific forms without departing from the spirit or essential characteristics of the invention. Accordingly, the embodiments should be regarded in all points of view as exemplary and not restrictive, the scope of the invention being defined by the appended claims rather than the foregoing description, and it is therefore intended that the scope of the invention be defined by the appended claims rather than by the foregoing description. All changes within the meaning and range of equivalents of the elements are embraced in the present invention. Any sign in a claim should not be construed as limiting the claim concerned.

Claims (10)

1. A high-toughness reinforced aluminum-magnesium composite material is characterized in that, the high-toughness reinforced aluminum-magnesium composite material is smelted by high-purity aluminum ingots, pure magnesium ingots, and pure zinc ingots, and then added carbon-containing metal powder, which is processed by electron beam After irradiation and ultrasonic treatment, the aluminum-magnesium alloy melt is obtained, and after being melted and cast into an aluminum-magnesium alloy round ingot, the aluminum-magnesium alloy wire is obtained through multiple hot extrusion-cold drawing and heat treatments, and then combined with the copper strip Copper-clad aluminum-magnesium alloy wire is obtained by cladding welding, which is processed by hydroxylation and coated with paint. 2. A kind of high toughness reinforced aluminum-magnesium composite material according to claim 1, is characterized in that, described coating comprises modified epoxy resin, curing agent and makes; Described modified epoxy resin is made of diethanolamine, boric acid , (3S,4E,6S)-4-ene-3,6-octanediol, phosphorus trichloride, epichlorohydrin, hydrogen-terminated phenyl silicone oil. 3. A method for preparing a high-toughness reinforced aluminum-magnesium composite material, characterized in that it comprises the following preparation steps: (1) Put the copper strip and aluminum-magnesium alloy wire with a thickness of 0.4-0.5mm and a width of 30-32mm into deionized water, acetone, absolute ethanol and deionized water in sequence, and after 500-600W ultrasonic cleaning for 20min, nitrogen gas Blow dry, carry out cladding welding simultaneously in the same direction on a cladding welding machine, stretch to a diameter of 0.04mm-6.0mm, and obtain copper-clad aluminum-magnesium alloy wire; (2) Mix nitrogen-containing borate compound, hydrochloric acid with a mass fraction of 20%, and formaldehyde at a mass ratio of 1:0.1:0.5 to 1:0.1:1.1, heat up to 50°C, and add nitrogen-containing borate compound with a mass of 2.8 ~5.7 times the phosphite compound, after reacting for 2~4 hours, add toluene with 4~6 times the mass of the nitrogen-containing borate compound, stir at 60~80rpm for 1.5h, vacuum -0.06MPa, distill at 60°C for 4~5h Get intermediate A; (3) Mix intermediate A, epichlorohydrin, and tetrabutylammonium bromide in a mass ratio of 1:10:0.07～1:16:0.07, heat up to 105～110°C, react for 5～7 hours, and cool to At room temperature, add a 40% sodium hydroxide solution with a mass fraction of 0.2 to 0.3 times the mass of intermediate A. After reacting for 2 to 3 hours, add deionized water to wash until the pH of the solution is 7, leave to separate and separate, take the organic phase, and vacuum Distill at -0.07MPa and 60°C for 3.5 to 4.5 hours to obtain epoxy resin; (4) Mix the epoxy resin and the platinum catalyst at a mass ratio of 1:0.001, stir evenly, and then raise the temperature to 80°C under the protection of nitrogen, and add 0.4 to 1.1 times the mass of the epoxy resin with a hydrogen-terminated phenyl silicone oil, After heat preservation reaction for 3-5 hours, vacuum degree -0.07MPa, distillation at 70°C for 2.0-2.5 hours to obtain modified epoxy resin; mix modified epoxy resin with ethylenediamine at a mass ratio of 30:1 to obtain a coating; (5) Immerse the copper-clad aluminum-magnesium alloy wire in the mixed solution A and the mixed solution B in turn according to the material-to-liquid ratio of 1:20. After 400-600W ultrasonic vibration for 20 minutes, wash it with deionized water for 6 times, dry it with nitrogen, and apply Coating, curing to obtain a high toughness reinforced aluminum-magnesium composite material with a diameter of 0.1-1.2 mm. 4. The preparation method of a kind of high toughness reinforced aluminum-magnesium composite material according to claim 3, characterized in that, the preparation method of the aluminum-magnesium alloy wire described in step (1) is: casting an aluminum-magnesium alloy round ingot at 400 Hot extrusion at ~450°C and extrusion speed of 0.8mm/s, cooling to room temperature in the air, and then multi-pass cold drawing at 1.5-2.0mm/min, the diameter reduction of each cold drawing The weight is 0.05-0.15mm, after every 2-4 times of cold drawing, and then hot-extruded under the same conditions, until the fiber with a diameter of 5-8mm is obtained, it is placed in 450°C, 550°C, 750°C, 950°C in sequence In the heat treatment furnace, keep warm for 5 to 10 minutes, and cool to room temperature. 5. The preparation method of a kind of high toughness reinforced aluminum-magnesium composite material according to claim 4, characterized in that, the preparation method of the aluminum-magnesium alloy round ingot is: high-purity aluminum ingot, pure magnesium ingot, pure Melt the zinc ingot at 720-760°C to obtain the melt, add carbon-containing metal powder with a mass of 0.008-0.5 times the melt, vacuumize to 0.005-0.05Pa, and irradiate the electron beam with a power of 15kW for 5-8min. 500W ultrasonic for 3 minutes, repeat the above-mentioned irradiated ultrasonic for 2 to 3 times to obtain aluminum-magnesium alloy melt; cast the aluminum-magnesium alloy melt at a casting temperature of 740-800°C and a casting speed of 23-33mm/min, and then cast it at a casting temperature of 450-800 Annealing at 500°C for 18-22 hours to obtain an aluminum-magnesium alloy round ingot with a diameter of 15-30 mm. 6. A kind of preparation method of high toughness reinforced aluminum-magnesium composite material according to claim 5, is characterized in that, the mass ratio of described high-purity aluminum ingot, pure magnesium ingot, pure zinc ingot is 42:1:0.04～ 62:1:0.06; the mass ratio of chromium powder, carbon powder and iron powder in the carbon-containing metal powder is 7:3:1. 7. the preparation method of a kind of high toughness reinforced aluminum-magnesium composite material according to claim 3, is characterized in that, the preparation method of nitrogen-containing borate compound described in step (2) is: boric acid, diethanolamine, two Toluene is mixed according to the mass ratio of 1:3:1.0～1:4:1.25. After reacting at 160℃ for 6～10h, the vacuum degree is -0.08MPa, and the distillation is at 75℃ for 1～2h. After washing with THF for 4～6 times, the vacuum degree is -0.08MPa. Distill at 0.09MPa, 50°C for 30-50min. 8. the preparation method of a kind of high toughness reinforced aluminum-magnesium composite material according to claim 3, is characterized in that, the preparation method of the phosphite compound described in step (2) is: carbon tetrachloride, (3S, 4E,6S)-4-ene-3,6-octanediol and phosphorus trichloride were mixed according to the mass ratio of 10:1.5:1～13:2.2:1, stirred at 60～80rpm for 2～3h, and then washed with ethyl acetate Wash three times with ester, saturated aqueous solution of sodium bicarbonate and deionized water, separate the organic phase, add anhydrous magnesium sulfate 0.5 to 0.8 times the mass of the organic phase, dry for 1 hour, filter, vacuum -0.08MPa, and distill at 50°C for 3 ~4h. 9. A method for preparing a high-toughness reinforced aluminum-magnesium composite material according to claim 3, wherein the mass ratio of concentrated sulfuric acid and hydrogen peroxide in the mixed solution A in step (5) is 14:1. 10. A method for preparing a high-toughness reinforced aluminum-magnesium composite material according to claim 3, wherein the mass ratio of ammonia water and hydrogen peroxide in the mixed liquid B in step (5) is 4.5:1.