CN110735066B - High-performance zinc alloy and preparation method thereof - Google Patents
High-performance zinc alloy and preparation method thereof Download PDFInfo
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- CN110735066B CN110735066B CN201911038451.3A CN201911038451A CN110735066B CN 110735066 B CN110735066 B CN 110735066B CN 201911038451 A CN201911038451 A CN 201911038451A CN 110735066 B CN110735066 B CN 110735066B
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C18/00—Alloys based on zinc
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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
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
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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
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
- C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
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- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22F—CHANGING THE PHYSICAL STRUCTURE OF NON-FERROUS METALS AND NON-FERROUS ALLOYS
- C22F1/00—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working
- C22F1/16—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon
- C22F1/165—Changing the physical structure of non-ferrous metals or alloys by heat treatment or by hot or cold working of other metals or alloys based thereon of zinc or cadmium or alloys based thereon
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
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- C22C26/00—Alloys containing diamond or cubic or wurtzitic boron nitride, fullerenes or carbon nanotubes
- C22C2026/002—Carbon nanotubes
Abstract
The invention relates to the technical field of zinc alloy, in particular to a high-performance zinc alloy and a preparation method thereof, wherein the high-performance zinc alloy comprises the following raw materials in percentage by weight: 0.1-2.0% of Cu, 0.5-1% of Mg, 1.0-1.5% of Mn, 0.4-0.8% of Zr, 0.05-1% of T, 0.1-1.0% of Sn, 0.1-1.0% of Ag, 1.0-3.0% of Gd, 0.1-1.0% of Al, 0.01-0.5% of Sr, 0.01-0.1% of Pb, 0.01-0.1% of graphene, 1.0-5.0% of modified carbon nano-tube and the balance of Zn and inevitable impurities. According to the invention, the prepared zinc alloy has excellent wear resistance, impact resistance, cutting processing capability, tensile strength, yield strength, elongation and overall hardness by adjusting the proportion of alloy elements, so that the service life of the die casting is prolonged, and the market competitiveness of enterprises is expanded.
Description
Technical Field
The invention relates to the technical field of zinc alloy, in particular to a high-performance zinc alloy and a preparation method thereof.
Background
The zinc alloy is an alloy formed by adding other metal elements and the like into zinc as a basic component, and the main added elements of the corresponding alloy comprise copper, manganese, magnesium, nickel, aluminum and the like.
The zinc alloy has low melting point, good fluidity and easy fusion welding, and is widely used for die-casting instruments, automobile parts, shells of various products and metal articles commonly used in life, wherein the metal articles commonly used in life comprise metal zippers, toys, lamps, ornaments and the like.
However, the existing die castings generally have the problems of low tensile strength, extremely poor shaping and easy fracture or crack initiation in subsequent processing and use, so that the service life of the product is shortened.
Disclosure of Invention
In order to overcome the defects and shortcomings in the prior art, the invention aims to provide the high-performance zinc alloy, and the prepared zinc alloy has excellent wear resistance, toughness, impact resistance, cutting processing capacity, casting performance, tensile strength, yield strength, elongation and overall hardness by adjusting alloy elements, optimizing a matched melt treatment process and other measures, so that the service life of a die casting is prolonged, and the market competitiveness of an enterprise is expanded; in addition, the addition of noble metal Cu is reduced, the production cost is reduced, the product competitiveness is improved, and the addition of the modified carbon nano tube can increase the binding force between the zinc alloy and the metal base material and the mechanical property of the zinc alloy.
The invention also aims to provide a preparation method of the high-performance zinc alloy, and the zinc alloy prepared by the method has excellent wear resistance, toughness, impact resistance, cutting processing capacity, casting performance, tensile strength, yield strength, elongation and overall hardness, thereby prolonging the service life of die castings and simultaneously expanding the market competitiveness of enterprises.
The purpose of the invention is realized by the following technical scheme: a high-performance zinc alloy comprises the following components in percentage by weight:
Cu 0.1-2.0%
Mg 0.5-1%
Mn 1.0-1.5%
Zr 0.4-0.8%
Ti 0.05-1%
Sn 0.1-1.0%
Ag 0.1-1.0%
Gd 1.0-3.0%
Al 0.1-1.0%
Sr 0.01-0.5%
Pb 0.01-0.1%
1.0 to 4.0 percent of graphene
1.0-5.0% of modified carbon nano tube
The balance of Zn and inevitable impurities.
The added Cu has certain solid solubility in the zinc alloy, the addition amount of the Cu needs to be strictly controlled to be 0.1-2.0%, if the addition amount is too high, a white strip-shaped epsilon phase is precipitated, if the addition amount is too low, the amount of the epsilon phase precipitated is small, the elongation of the alloy is increased under the condition of keeping smaller strength amplification, the hardness is basically kept unchanged, the comprehensive selection of 0.1-2.0% of the addition amount of the Cu is favorable for refining the matrix structure of the zinc-aluminum alloy, the density is improved, and the tendency of shrinkage cavity and shrinkage porosity is reduced; the addition of Mg can obviously improve the plasticity, corrosion resistance, solid solution hardenability, friction performance and the like of the alloy; the addition of Mn can obviously improve the toughness, strength, hardness and wear resistance of the zinc alloy; a small amount of Zr is added to play roles in degassing, purifying and refining crystal grains, so that the low-temperature performance of the zinc alloy is facilitated, and the stamping performance of the alloy is further improved; the mechanical property of the zinc alloy can be improved by adding Ti, but the conductivity is reduced, and Sn can be combined with Mg and Ti to form an intermediate alloy to improve the corrosion resistance of the zinc alloy; the addition of trace Ag and Pb can obviously improve the strength of the alloy, and the addition of Gd can purify, degas and improve the composition shape energy, the corrosion resistance and the welding performance of the alloy; in addition, the proportion of Pb, Mg, Sr and other components in the alloy is designed and adjusted, Zr and other elements are added, and the components are matched with each other, so that the microstructure of the zinc alloy is optimized, the heat-conducting property of the zinc alloy is improved, and the corrosion resistance and the mechanical property of the zinc alloy are improved.
A preparation method of a high-performance zinc alloy is characterized by comprising the following steps:
1) according to the weight percentage, pure Zn, pure Gd, pure Pb, Mg-Ti-Sn intermediate alloy, Cu-Mn30 intermediate alloy, Mg-Sr intermediate alloy, Zn-Ag intermediate alloy, Al-Zn-Mg-Cu intermediate alloy and Mg-Mn-Zr intermediate alloy are used as raw materials for mixing; wherein the weight ratio of Mg in the Mg-Sr intermediate alloy, Mg in the Al-Zn-Mg-Cu intermediate alloy, Mg in the Mg-Ti-Sn intermediate alloy and Mg in the Mg-Mn-Zr intermediate alloy is 0.8-1.2:0.4-0.8:0.6-1.0: 0.1-0.5; the weight ratio of Mn in the Cu-Mn30 intermediate alloy to Mn in the Mg-Mn-Zr intermediate alloy is 0.8-1.2: 0.4-0.8; the weight ratio of Cu in the Cu-Mn30 master alloy to Cu in the Al-Zn-Mg-Cu master alloy is 0.6-1.0: 0.4-0.8;
2) adding a pure Zn ingot into refining equipment, heating to 400-plus-450 ℃ under a vacuum condition, melting to completely melt, adding a modified carbon nanotube, continuously melting for 20-40min under heat preservation to obtain molten slurry A, sequentially adding pure Gd, pure Pb, Mg-Sr intermediate alloy, Zn-Ag intermediate alloy, Al-Zn-Mg-Cu intermediate alloy and Mg-Mn-Zr intermediate alloy into the molten slurry A, heating to 500-plus-600 ℃ to melt for 15-20min, finally adding Mg-Ti-Sn intermediate alloy, Cu-Mn30 intermediate alloy and graphene, melting for 10-20min under heat preservation, fully stirring, slagging and degassing after the melting is finished to obtain a molten material B for later use;
3) cooling the melt B obtained in the step 2), removing the surface scum, and then pouring into a corresponding die to prepare as-cast zinc alloy for later use;
4) heating the as-cast zinc alloy obtained in the step 3) to 750-850 ℃ for hot rolling treatment, and then cooling the as-cast zinc alloy to 450-550 ℃ for solution treatment for 5-10h to obtain an ingot for later use;
5) heating the ingot obtained in the step 4) to 340 ℃ of temperature-changing at a constant speed, carrying out primary extrusion, wherein the extrusion deformation rate is 1.2-2.8m/min, the pressure ratio is 10-15, then continuously heating to 400 ℃ of temperature-changing at 380 ℃ for secondary extrusion, and cooling at room temperature after the extrusion is finished to finally obtain a high-performance zinc alloy finished product; the extrusion deformation rate of the second extrusion treatment is 1.5-2.0m/min, and the pressure ratio is 8-16.
The zinc alloy prepared by the method has excellent wear resistance, toughness, impact resistance, cutting processing capacity, casting performance, tensile strength, yield strength, elongation and overall hardness, the service life of the die casting is prolonged, and the market competitiveness of enterprises is expanded; in addition, the addition of noble metal Cu is reduced, the production cost is reduced, the product competitiveness is improved, and the addition of the modified carbon nano tube can increase the binding force between the zinc alloy and the metal base material and the mechanical property of the zinc alloy.
When the zinc alloy is prepared, the temperature of melting the pure Zn ingot in the step 2) needs to be controlled to be 400-450 ℃, if the temperature is too low, the Zn ingot is not easy to be completely melted, if the temperature is too high, the subsequent modified carbon nano tube is not easy to be added, in addition, the temperature of adding the Mg-Mn-Zr intermediate alloy into the melting slurry A needs to be controlled to be 500-600 ℃, if the temperature is too low, the melting of the intermediate alloy is not easy, and if the temperature is too high, the micro-crystallization grain homogenization is formed by recrystallization after the melting of the intermediate alloy; the zinc alloy of the invention takes Zn, Mg and Cu as main alloying elements, forms micron-sized Al-6Zn-2Mg-2Cu phase in the zinc alloy and can also delay the timeliness. The plasticity of the zinc alloy is improved through hot rolling and two times of extrusion treatment, the preparation for making organization and performance for cooling rolling processing is made, in the extrusion treatment process, the processing mode of low-temperature extrusion treatment is adopted, the growth of recrystallized grains of the alloy is inhibited, finally, the alloy is of a micro-nano double-peak structure consisting of micron-sized deformed grains and fine recrystallized grains, meanwhile, a large amount of nano-scale Al-6Zn-2Mg-2Cu phases are dynamically precipitated in the alloy, and the toughness of the zinc alloy is greatly improved, so that the high-toughness zinc alloy material with excellent room-temperature mechanical properties is developed in the alloy series.
Preferably, each part of the modified carbon nanotube consists of the following raw materials in parts by weight:
4-8 parts of modifier
15-20 parts of absolute ethyl alcohol
20-40 parts of carbon nano tube
5-10 parts of ethylene diamine tetraacetic acid
1-5 parts of N, N-diisopropylethylamine;
each part of the modifier is at least one of vinylpyridine-styrene-butadiene, styrene-isoprene-butadiene and N-hydroxysuccinimide; more preferably, the modifier is a mixture of pyridine-styrene-butadiene, styrene-isoprene-butadiene and N-hydroxysuccinimide in a weight ratio of 0.8-1.2:0.4-0.8: 0.6-1.0.
The modified carbon nano tube is prepared by the following method:
s1, adding the carbon nano tube and the ethylene diamine tetraacetic acid into absolute ethyl alcohol according to the parts by weight, heating to 40-60 ℃, and reacting for 20-30min to obtain a mixture A for later use;
s2, adding a modifier and N, N-diisopropylethylamine into the mixture A obtained in the step S1, heating to 60-80 ℃, and reacting for 15-30min to obtain a mixture B for later use;
s3, drying the mixture B obtained in the step S2, and then irradiating the mixture B by ultraviolet light for 30-60min to obtain the modified carbon nano tube; the ultraviolet light is monochromatic narrow-band light with the irradiation wavelength of 200-270nm, and the irradiation power is 15-40 mW.
The modified carbon nano tube mainly contained in the raw materials can obviously improve the tensile strength and hardness of the zinc alloy, and the adopted modifier and the ethylene diamine tetraacetic acid can well modify the surface of the carbon nano tube, so that the prepared modified carbon nano tube has more excellent mechanical property, and in addition, the structural stability, the adsorption strength, the stability and the practical application value of the carbon nano tube are improved. In the preparation process, the temperature of the carbon nano tube and the ethylene diamine tetraacetic acid added with the absolute ethyl alcohol in the step S1 is strictly controlled to be 40-60 ℃, if the temperature is too high, part of the absolute ethyl alcohol is volatilized, the absolute ethyl alcohol is not favorable for activating the surface of the carbon nano tube, and the ethylene diamine tetraacetic acid is not favorable for modifying the surface of the carbon nano tube; in step S3, the ultraviolet irradiation treatment time needs to be strictly controlled to be 30-60min, which is unfavorable for grafting the modifier with the carbon nanotubes if the irradiation time is too short, and wastes resources and increases the production cost if the irradiation time is too long.
The invention has the beneficial effects that: according to the invention, through a series of means such as adjustment of alloy elements, optimization of a matched melt treatment process and the like, the prepared zinc alloy has excellent wear resistance, toughness, impact resistance, cutting processing capacity, casting performance, tensile strength, yield strength, elongation and overall hardness, the service life of a die casting is prolonged, and the market competitiveness of an enterprise is expanded; in addition, the addition of noble metal Cu is reduced, the production cost is reduced, the product competitiveness is improved, and the addition of the modified carbon nano tube can increase the binding force between the zinc alloy and the metal base material and the mechanical property of the zinc alloy.
Detailed Description
The present invention will be further described with reference to the following examples for facilitating understanding of those skilled in the art, and the description of the embodiments is not intended to limit the present invention.
Example 1
A high-performance zinc alloy comprises the following components in percentage by weight:
Cu 0.1%
Mg 0.5%
Mn 1.0%
Zr 0.4%
Ti 0.05%
Sn 0.1%
Ag 0.1%
Gd 1.0%
Al 0.1%
Sr 0.01%
Pb 0.01%
1.0 percent of graphene
1.0 percent of modified carbon nano tube
The balance of Zn and inevitable impurities.
Each part of the modified carbon nano tube is composed of the following raw materials in parts by weight:
4 portions of modifier
15 portions of absolute ethyl alcohol
20 parts of carbon nano tube
5 portions of ethylene diamine tetraacetic acid
1 part of O, N-diisopropylethylamine;
each part of the modifier is a mixture consisting of pyridine-styrene-butadiene, styrene-isoprene-butadiene and N-hydroxysuccinimide according to the weight ratio of 0.8-1.2:0.4-0.8: 0.6-1.0.
The modified carbon nano tube is prepared by the following method:
s1, adding the carbon nano tube and the ethylene diamine tetraacetic acid into absolute ethyl alcohol according to the parts by weight, heating to 40 ℃, and reacting for 20min to obtain a mixture A for later use;
s2, adding a modifier and N, N-diisopropylethylamine into the mixture A obtained in the step S1, heating to 60 ℃, and reacting for 15min to obtain a mixture B for later use;
s3, drying the mixture B obtained in the step S2, and irradiating the mixture B by ultraviolet light for 30min to obtain the modified carbon nano tube; the ultraviolet light is monochromatic narrow-band light with the irradiation wavelength of 200nm, and the irradiation power is 15 mW.
A preparation method of a high-performance zinc alloy is characterized by comprising the following steps:
1) according to the weight percentage, pure Zn, pure Gd, pure Pb, Mg-Ti-Sn intermediate alloy, Cu-Mn30 intermediate alloy, Mg-Sr intermediate alloy, Zn-Ag intermediate alloy, Al-Zn-Mg-Cu intermediate alloy and Mg-Mn-Zr intermediate alloy are used as raw materials for mixing; wherein the weight ratio of Mg in the Mg-Sr intermediate alloy, Mg in the Al-Zn-Mg-Cu intermediate alloy, Mg in the Mg-Ti-Sn intermediate alloy and Mg in the Mg-Mn-Zr intermediate alloy is 0.8:0.4:0.6: 0.1; the weight ratio of Mn in the Cu-Mn30 master alloy to Mn in the Mg-Mn-Zr master alloy is 0.8: 0.4; the weight ratio of Cu in the Cu-Mn30 master alloy to Cu in the Al-Zn-Mg-Cu master alloy is 0.6: 0.4;
2) adding a pure Zn ingot into refining equipment, heating to 400 ℃ under a vacuum condition, melting until the pure Zn ingot is completely melted, adding a modified carbon nano tube, continuously melting for 20min under heat preservation to obtain molten slurry A, sequentially adding pure Gd, pure Pb, Mg-Sr intermediate alloy, Zn-Ag intermediate alloy, Al-Zn-Mg-Cu intermediate alloy and Mg-Mn-Zr intermediate alloy into the molten slurry A, heating to 500 ℃ to melt for 15min, finally adding Mg-Ti-Sn intermediate alloy, Cu-Mn30 intermediate alloy and graphene, melting for 10min under heat preservation, fully stirring, slagging and degassing after the melting is finished to obtain a molten material B for later use;
3) cooling the melt B obtained in the step 2), removing the surface scum, and then pouring into a corresponding die to prepare as-cast zinc alloy for later use;
4) heating the as-cast zinc alloy obtained in the step 3) to 750 ℃ for hot rolling treatment, and then cooling the as-cast zinc alloy to 450 ℃ for solid solution treatment for 5h to obtain an ingot for later use;
5) heating the cast ingot obtained in the step 4) to 320 ℃ at a constant speed, performing first extrusion, wherein the extrusion deformation rate is 1.2m/min, the pressure ratio is 10, then continuously heating to 380 ℃ for second extrusion, and cooling at room temperature after the extrusion is finished to finally obtain a high-performance zinc alloy finished product; the second extrusion treatment was conducted at an extrusion deformation rate of 1.5m/min and a pressing ratio of 8.
Example 2
A high-performance zinc alloy comprises the following components in percentage by weight:
Cu 0.5%
Mg 0.6%
Mn 1.2%
Zr 0.5%
Ti 0.25%
Sn 0.25%
Ag 0.25%
Gd 1.5%
Al 0.25%
Sr 0.1%
Pb 0.25%
2.0 percent of graphene
2.0 percent of modified carbon nano tube
The balance of Zn and inevitable impurities.
Each part of the modified carbon nano tube is composed of the following raw materials in parts by weight:
5 portions of modifier
17 parts of absolute ethyl alcohol
Carbon nanotube 25 parts
6 portions of ethylene diamine tetraacetic acid
2 parts of P, N-diisopropylethylamine;
each part of the modifier is a mixture of pyridine-styrene-butadiene, styrene-isoprene-butadiene and N-hydroxysuccinimide according to the weight ratio of 0.9:0.4: 0.7.
The modified carbon nano tube is prepared by the following method:
s1, adding the carbon nano tube and the ethylene diamine tetraacetic acid into absolute ethyl alcohol according to the parts by weight, heating to 45 ℃, and reacting for 23min to obtain a mixture A for later use;
s2, adding a modifier and N, N-diisopropylethylamine into the mixture A obtained in the step S1, heating to 65 ℃, and reacting for 19min to obtain a mixture B for later use;
s3, drying the mixture B obtained in the step S2, and then irradiating the mixture B by ultraviolet light for 38min to obtain the modified carbon nano tube; the ultraviolet light is monochromatic narrow-band light with the irradiation wavelength of 215nm, and the irradiation power is 21 mW.
A preparation method of a high-performance zinc alloy is characterized by comprising the following steps:
1) according to the weight percentage, pure Zn, pure Gd, pure Pb, Mg-Ti-Sn intermediate alloy, Cu-Mn30 intermediate alloy, Mg-Sr intermediate alloy, Zn-Ag intermediate alloy, Al-Zn-Mg-Cu intermediate alloy and Mg-Mn-Zr intermediate alloy are used as raw materials for mixing; wherein the weight ratio of Mg in the Mg-Sr intermediate alloy, Mg in the Al-Zn-Mg-Cu intermediate alloy, Mg in the Mg-Ti-Sn intermediate alloy and Mg in the Mg-Mn-Zr intermediate alloy is 0.9:0.5:0.7: 0.2; the weight ratio of Mn in the Cu-Mn30 master alloy to Mn in the Mg-Mn-Zr master alloy is 0.9: 0.5; the weight ratio of Cu in the Cu-Mn30 master alloy to Cu in the Al-Zn-Mg-Cu master alloy is 0.7: 0.5;
2) adding a pure Zn ingot into refining equipment, heating to 412 ℃ under a vacuum condition, melting until the pure Zn ingot is completely melted, adding a modified carbon nano tube, continuously melting for 25min under a heat preservation condition to obtain molten slurry A, sequentially adding pure Gd, pure Pb, Mg-Sr intermediate alloy, Zn-Ag intermediate alloy, Al-Zn-Mg-Cu intermediate alloy and Mg-Mn-Zr intermediate alloy into the molten slurry A, heating to 525 ℃ to melt for 17min, finally adding Mg-Ti-Sn intermediate alloy, Cu-Mn30 intermediate alloy and graphene, melting for 13min under a heat preservation condition, fully stirring, slagging and degassing after the melting is finished to obtain a molten material B for later use;
3) cooling the melt B obtained in the step 2), removing the surface scum, and then pouring into a corresponding die to prepare as-cast zinc alloy for later use;
4) heating the as-cast zinc alloy obtained in the step 3) to 775 ℃ for hot rolling treatment, and then cooling the as-cast zinc alloy to 475 ℃ for solution treatment for 6h to obtain an ingot for later use;
5) heating the cast ingot obtained in the step 4) to 325 ℃ at a constant speed, carrying out primary extrusion, wherein the extrusion deformation rate is 1.6m/min, the pressure ratio is 12, then continuously heating to 385 ℃ for secondary extrusion, and cooling at room temperature after the extrusion is finished to finally obtain a high-performance zinc alloy finished product; the second extrusion treatment was conducted at an extrusion deformation rate of 1.7m/min and a pressing ratio of 10.
Example 3
A high-performance zinc alloy comprises the following components in percentage by weight:
Cu 1.0%
Mg 0.75%
Mn 1.3%
Zr 0.6%
Ti 0.5%
Sn 0.5%
Ag 0.5%
Gd 2.0%
Al 0.5%
Sr 0.25%
Pb 0.5%
2.5 percent of graphene
3.0 percent of modified carbon nano tube
The balance of Zn and inevitable impurities.
Each part of the modified carbon nano tube is composed of the following raw materials in parts by weight:
6 portions of modifier
18 portions of absolute ethyl alcohol
30 parts of carbon nano tube
Ethylene diamine tetraacetic acid 8 parts
3 parts of Q, N-diisopropylethylamine;
each part of the modifier is a mixture of pyridine-styrene-butadiene, styrene-isoprene-butadiene and N-hydroxysuccinimide according to the weight ratio of 1.0:0.6: 0.8.
The modified carbon nano tube is prepared by the following method:
s1, adding the carbon nano tube and the ethylene diamine tetraacetic acid into absolute ethyl alcohol according to the parts by weight, heating to 50 ℃, and reacting for 25min to obtain a mixture A for later use;
s2, adding a modifier and N, N-diisopropylethylamine into the mixture A obtained in the step S1, heating to 70 ℃, and reacting for 23min to obtain a mixture B for later use;
s3, drying the mixture B obtained in the step S2, and then irradiating the mixture B by using ultraviolet light for 45min to obtain the modified carbon nano tube; the ultraviolet light is monochromatic narrow-band light with the irradiation wavelength of 235nm, and the irradiation power is 30 mW.
A preparation method of a high-performance zinc alloy is characterized by comprising the following steps:
1) according to the weight percentage, pure Zn, pure Gd, pure Pb, Mg-Ti-Sn intermediate alloy, Cu-Mn30 intermediate alloy, Mg-Sr intermediate alloy, Zn-Ag intermediate alloy, Al-Zn-Mg-Cu intermediate alloy and Mg-Mn-Zr intermediate alloy are used as raw materials for mixing; wherein the weight ratio of Mg in the Mg-Sr intermediate alloy, Mg in the Al-Zn-Mg-Cu intermediate alloy, Mg in the Mg-Ti-Sn intermediate alloy and Mg in the Mg-Mn-Zr intermediate alloy is 1.0:0.6:0.8: 0.3; the weight ratio of Mn in the Cu-Mn30 master alloy to Mn in the Mg-Mn-Zr master alloy is 1.0: 0.6; the weight ratio of Cu in the Cu-Mn30 master alloy to Cu in the Al-Zn-Mg-Cu master alloy is 0.8: 0.6;
2) adding a pure Zn ingot into refining equipment, heating to 425 ℃ under a vacuum condition, melting to completely melt, adding a modified carbon nanotube, continuously melting for 30min under a heat preservation condition to obtain molten slurry A, sequentially adding pure Gd, pure Pb, Mg-Sr intermediate alloy, Zn-Ag intermediate alloy, Al-Zn-Mg-Cu intermediate alloy and Mg-Mn-Zr intermediate alloy into the molten slurry A, heating to 550 ℃, melting for 18min, finally adding Mg-Ti-Sn intermediate alloy, Cu-Mn30 intermediate alloy and graphene, melting for 15min under a heat preservation condition, fully stirring, slagging and degassing after the melting is finished to obtain a molten material B for later use;
3) cooling the melt B obtained in the step 2), removing the surface scum, and then pouring into a corresponding die to prepare as-cast zinc alloy for later use;
4) heating the as-cast zinc alloy obtained in the step 3) to 800 ℃ for hot rolling treatment, and then cooling the as-cast zinc alloy to 500 ℃ for solid solution treatment for 8h to obtain an ingot for later use;
5) heating the cast ingot obtained in the step 4) to 330 ℃ at a constant speed, performing first extrusion, wherein the extrusion deformation rate is 2.0m/min, the pressure ratio is 13, then continuously heating to 390 ℃ for second extrusion, and cooling at room temperature after the extrusion is finished to finally obtain a high-performance zinc alloy finished product; the second extrusion treatment was conducted at an extrusion deformation rate of 1.8m/min and a pressing ratio of 12.
Example 4
A high-performance zinc alloy comprises the following components in percentage by weight:
Cu 1.5%
Mg 0.9%
Mn 1.4%
Zr 0.7%
Ti 0.75%
Sn 0.75%
Ag 0.75%
Gd 2.5%
Al 0.75%
Sr 0.3%
Pb 0.75%
3.0 percent of graphene
4.0 percent of modified carbon nano tube
The balance of Zn and inevitable impurities.
Each part of the modified carbon nano tube is composed of the following raw materials in parts by weight:
7 portions of modifier
19 parts of absolute ethyl alcohol
Carbon nanotube 35 parts
Ethylenediaminetetraacetic acid 9 parts
4 parts of R, N-diisopropylethylamine;
each part of the modifier is a mixture of pyridine-styrene-butadiene, styrene-isoprene-butadiene and N-hydroxysuccinimide according to the weight ratio of 1.1:0.7: 0.9.
The modified carbon nano tube is prepared by the following method:
s1, adding the carbon nano tube and the ethylene diamine tetraacetic acid into absolute ethyl alcohol according to the parts by weight, heating to 55 ℃, and reacting for 28min to obtain a mixture A for later use;
s2, adding a modifier and N, N-diisopropylethylamine into the mixture A obtained in the step S1, heating to 75 ℃, and reacting for 27min to obtain a mixture B for later use;
s3, drying the mixture B obtained in the step S2, and then carrying out ultraviolet irradiation treatment for 52min to obtain the modified carbon nano tube; the ultraviolet light is monochromatic narrow-band light with the irradiation wavelength of 250nm, and the irradiation power is 35 mW.
A preparation method of a high-performance zinc alloy is characterized by comprising the following steps:
1) according to the weight percentage, pure Zn, pure Gd, pure Pb, Mg-Ti-Sn intermediate alloy, Cu-Mn30 intermediate alloy, Mg-Sr intermediate alloy, Zn-Ag intermediate alloy, Al-Zn-Mg-Cu intermediate alloy and Mg-Mn-Zr intermediate alloy are used as raw materials for mixing; wherein the weight ratio of Mg in the Mg-Sr intermediate alloy, Mg in the Al-Zn-Mg-Cu intermediate alloy, Mg in the Mg-Ti-Sn intermediate alloy and Mg in the Mg-Mn-Zr intermediate alloy is 1.1:0.7:0.9: 0.4; the weight ratio of Mn in the Cu-Mn30 master alloy to Mn in the Mg-Mn-Zr master alloy is 1.1: 0.7; the weight ratio of Cu in the Cu-Mn30 master alloy to Cu in the Al-Zn-Mg-Cu master alloy is 0.9: 0.7;
2) adding a pure Zn ingot into refining equipment, heating to 437 ℃ under a vacuum condition, melting to completely melt, adding a modified carbon nanotube, continuously melting for 35min under a heat preservation condition to obtain molten slurry A, sequentially adding pure Gd, pure Pb, an Mg-Sr intermediate alloy, a Zn-Ag intermediate alloy, an Al-Zn-Mg-Cu intermediate alloy and an Mg-Mn-Zr intermediate alloy into the molten slurry A, heating to 575 ℃ to melt for 19min, finally adding the Mg-Ti-Sn intermediate alloy, the Cu-Mn30 intermediate alloy and graphene, melting for 18min under a heat preservation condition, fully stirring, slagging and degassing after the melting is finished to obtain a molten material B for later use;
3) cooling the melt B obtained in the step 2), removing the surface scum, and then pouring into a corresponding die to prepare as-cast zinc alloy for later use;
4) heating the as-cast zinc alloy obtained in the step 3) to 825 ℃ for hot rolling treatment, and then cooling the as-cast zinc alloy to 525 ℃ for solid solution treatment for 9h to obtain an ingot for later use;
5) heating the cast ingot obtained in the step 4) to 335 ℃ at a constant speed, performing first extrusion, wherein the extrusion deformation rate is 2.4m/min, the pressure ratio is 14, then continuously heating to 395 ℃ for second extrusion, and after the extrusion is finished, cooling at room temperature to finally obtain a high-performance zinc alloy finished product; the second extrusion treatment was conducted at an extrusion deformation rate of 1.9m/min and a pressing ratio of 14.
Example 5
A high-performance zinc alloy comprises the following components in percentage by weight:
Cu 2.0%
Mg 1%
Mn 1.5%
Zr 0.8%
Ti 1%
Sn 1.0%
Ag 1.0%
Gd 3.0%
Al 1.0%
Sr 0.5%
Pb 0.1%
4.0 percent of graphene
5.0 percent of modified carbon nano tube
The balance of Zn and inevitable impurities.
Each part of the modified carbon nano tube is composed of the following raw materials in parts by weight:
8 portions of modifier
20 portions of absolute ethyl alcohol
40 parts of carbon nano tube
10 portions of ethylene diamine tetraacetic acid
5 parts of S, N-diisopropylethylamine;
each part of the modifier is a mixture of pyridine-styrene-butadiene, styrene-isoprene-butadiene and N-hydroxysuccinimide according to the weight ratio of 1.2:0.8: 1.0.
The modified carbon nano tube is prepared by the following method:
s1, adding the carbon nano tube and the ethylene diamine tetraacetic acid into absolute ethyl alcohol according to the parts by weight, heating to 60 ℃, and reacting for 30min to obtain a mixture A for later use;
s2, adding a modifier and N, N-diisopropylethylamine into the mixture A obtained in the step S1, heating to 80 ℃, and reacting for 30min to obtain a mixture B for later use;
s3, drying the mixture B obtained in the step S2, and then irradiating the mixture B by ultraviolet light for 60min to obtain the modified carbon nano tube; the ultraviolet light is monochromatic narrow-band light with the irradiation wavelength of 270nm, and the irradiation power is 40 mW.
A preparation method of a high-performance zinc alloy is characterized by comprising the following steps:
1) according to the weight percentage, pure Zn, pure Gd, pure Pb, Mg-Ti-Sn intermediate alloy, Cu-Mn30 intermediate alloy, Mg-Sr intermediate alloy, Zn-Ag intermediate alloy, Al-Zn-Mg-Cu intermediate alloy and Mg-Mn-Zr intermediate alloy are used as raw materials for mixing; wherein the weight ratio of Mg in the Mg-Sr intermediate alloy, Mg in the Al-Zn-Mg-Cu intermediate alloy, Mg in the Mg-Ti-Sn intermediate alloy and Mg in the Mg-Mn-Zr intermediate alloy is 1.2:0.8:1.0: 0.5; the weight ratio of Mn in the Cu-Mn30 master alloy to Mn in the Mg-Mn-Zr master alloy is 1.2: 0.8; the weight ratio of Cu in the Cu-Mn30 master alloy to Cu in the Al-Zn-Mg-Cu master alloy is 1.0: 0.8;
2) adding a pure Zn ingot into refining equipment, heating to 450 ℃ under a vacuum condition, melting to completely melt, adding a modified carbon nanotube, continuously melting for 40min under heat preservation to obtain molten slurry A, sequentially adding pure Gd, pure Pb, Mg-Sr intermediate alloy, Zn-Ag intermediate alloy, Al-Zn-Mg-Cu intermediate alloy and Mg-Mn-Zr intermediate alloy into the molten slurry A, heating to 600 ℃ to melt for 20min, finally adding Mg-Ti-Sn intermediate alloy, Cu-Mn30 intermediate alloy and graphene, melting for 20min under heat preservation, fully stirring, slagging and degassing after the melting is finished to obtain a molten material B for later use;
3) cooling the melt B obtained in the step 2), removing the surface scum, and then pouring into a corresponding die to prepare as-cast zinc alloy for later use;
4) heating the as-cast zinc alloy obtained in the step 3) to 850 ℃ for hot rolling treatment, and then cooling the as-cast zinc alloy to 550 ℃ for solution treatment for 10h to obtain an ingot for later use;
5) heating the cast ingot obtained in the step 4) to 340 ℃ at a constant speed, carrying out first extrusion, wherein the extrusion deformation rate is 2.8m/min, the pressure ratio is 15, then continuously heating to 400 ℃ for second extrusion, and cooling at room temperature after the extrusion is finished to finally obtain a high-performance zinc alloy finished product; the second extrusion treatment was conducted at an extrusion deformation rate of 2.0m/min and a pressing ratio of 16.
Comparative example 1
A high-performance zinc alloy comprises the following components in percentage by weight:
Cu 0.1%
Mg 5%
Mn 1.0%
Zr 0.4%
Ti 0.05%
Sn 0.1%
Ag 0.1%
Gd 1.0%
Al 0.1%
Sr 0.01%
Pb 0.01%
1.0 percent of graphene
1.0 percent of modified carbon nano tube
The balance of Zn and inevitable impurities.
Each part of the modified carbon nano tube is composed of the following raw materials in parts by weight:
4 portions of modifier
15 portions of absolute ethyl alcohol
20 parts of carbon nano tube
5 portions of ethylene diamine tetraacetic acid
1 part of T, N-diisopropylethylamine;
each part of the modifier is a mixture consisting of pyridine-styrene-butadiene, styrene-isoprene-butadiene and N-hydroxysuccinimide according to the weight ratio of 0.8-1.2:0.4-0.8: 0.6-1.0.
The modified carbon nano tube is prepared by the following method:
s1, adding the carbon nano tube and the ethylene diamine tetraacetic acid into absolute ethyl alcohol according to the parts by weight, heating to 40 ℃, and reacting for 20min to obtain a mixture A for later use;
s2, adding a modifier and N, N-diisopropylethylamine into the mixture A obtained in the step S1, heating to 60 ℃, and reacting for 15min to obtain a mixture B for later use;
s3, drying the mixture B obtained in the step S2, and irradiating the mixture B by ultraviolet light for 30min to obtain the modified carbon nano tube; the ultraviolet light is monochromatic narrow-band light with the irradiation wavelength of 200nm, and the irradiation power is 15 mW.
A preparation method of a high-performance zinc alloy is characterized by comprising the following steps:
1) according to the weight percentage, pure Zn, pure Gd, pure Pb, Mg-Ti-Sn intermediate alloy, Cu-Mn30 intermediate alloy, Mg-Sr intermediate alloy, Zn-Ag intermediate alloy, Al-Zn-Mg-Cu intermediate alloy and Mg-Mn-Zr intermediate alloy are used as raw materials for mixing; wherein the weight ratio of Mg in the Mg-Sr intermediate alloy, Mg in the Al-Zn-Mg-Cu intermediate alloy, Mg in the Mg-Ti-Sn intermediate alloy and Mg in the Mg-Mn-Zr intermediate alloy is 0.8:0.4:0.6: 0.1; the weight ratio of Mn in the Cu-Mn30 master alloy to Mn in the Mg-Mn-Zr master alloy is 0.8: 0.4; the weight ratio of Cu in the Cu-Mn30 master alloy to Cu in the Al-Zn-Mg-Cu master alloy is 0.6: 0.4;
2) adding a pure Zn ingot into refining equipment, heating to 400 ℃ under a vacuum condition, melting until the pure Zn ingot is completely melted, adding a modified carbon nano tube, continuously melting for 20min under heat preservation to obtain molten slurry A, sequentially adding pure Gd, pure Pb, Mg-Sr intermediate alloy, Zn-Ag intermediate alloy, Al-Zn-Mg-Cu intermediate alloy and Mg-Mn-Zr intermediate alloy into the molten slurry A, heating to 500 ℃ to melt for 15min, finally adding Mg-Ti-Sn intermediate alloy, Cu-Mn30 intermediate alloy and graphene, melting for 10min under heat preservation, fully stirring, slagging and degassing after the melting is finished to obtain a molten material B for later use;
3) cooling the melt B obtained in the step 2), removing the surface scum, and then pouring into a corresponding die to prepare as-cast zinc alloy for later use;
4) heating the as-cast zinc alloy obtained in the step 3) to 750 ℃ for hot rolling treatment, and then cooling the as-cast zinc alloy to 450 ℃ for solid solution treatment for 5h to obtain an ingot for later use;
5) heating the cast ingot obtained in the step 4) to 320 ℃ at a constant speed, performing first extrusion, wherein the extrusion deformation rate is 1.2m/min, the pressure ratio is 10, then continuously heating to 380 ℃ for second extrusion, and cooling at room temperature after the extrusion is finished to finally obtain a high-performance zinc alloy finished product; the second extrusion treatment was conducted at an extrusion deformation rate of 1.5m/min and a pressing ratio of 8.
Comparative example 2
A high-performance zinc alloy comprises the following components in percentage by weight:
Cu 1.0%
Mg 0.75%
Mn 1.3%
Zr 0.6%
Ti 0.5%
Sn 0.5%
Ag 0.5%
Gd 2.0%
Al 0.5%
Sr 0.25%
Pb 0.5%
2.5 percent of graphene
3.0 percent of modified carbon nano tube
The balance of Zn and inevitable impurities.
Each part of the modified carbon nano tube is composed of the following raw materials in parts by weight:
6 portions of modifier
18 portions of absolute ethyl alcohol
30 parts of carbon nano tube
Ethylene diamine tetraacetic acid 8 parts
3 parts of ethynyl triethoxysilane;
each part of the modifier is a mixture of pyridine-styrene-butadiene, styrene-isoprene-butadiene and N-hydroxysuccinimide according to the weight ratio of 1.0:0.6: 0.8.
The modified carbon nano tube is prepared by the following method:
s1, adding the carbon nano tube and the ethylene diamine tetraacetic acid into absolute ethyl alcohol according to the parts by weight, heating to 50 ℃, and reacting for 25min to obtain a mixture A for later use;
s2, adding a modifier and ethynyltriethoxysilane into the mixture A obtained in the step S1, heating to 70 ℃, and reacting for 23min to obtain a mixture B for later use;
s3, drying the mixture B obtained in the step S2, and then irradiating the mixture B by using ultraviolet light for 45min to obtain the modified carbon nano tube; the ultraviolet light is monochromatic narrow-band light with the irradiation wavelength of 235nm, and the irradiation power is 30 mW.
A preparation method of a high-performance zinc alloy is characterized by comprising the following steps:
1) according to the weight percentage, pure Zn, pure Gd, pure Pb, Mg-Ti-Sn intermediate alloy, Cu-Mn30 intermediate alloy, Mg-Sr intermediate alloy, Zn-Ag intermediate alloy, Al-Zn-Mg-Cu intermediate alloy and Mg-Mn-Zr intermediate alloy are used as raw materials for mixing; wherein the weight ratio of Mg in the Mg-Sr intermediate alloy, Mg in the Al-Zn-Mg-Cu intermediate alloy, Mg in the Mg-Ti-Sn intermediate alloy and Mg in the Mg-Mn-Zr intermediate alloy is 1.0:0.6:0.8: 0.3; the weight ratio of Mn in the Cu-Mn30 master alloy to Mn in the Mg-Mn-Zr master alloy is 1.0: 0.6; the weight ratio of Cu in the Cu-Mn30 master alloy to Cu in the Al-Zn-Mg-Cu master alloy is 0.8: 0.6;
2) adding a pure Zn ingot into refining equipment, heating to 425 ℃ under a vacuum condition, melting to completely melt, adding a modified carbon nanotube, continuously melting for 30min under a heat preservation condition to obtain molten slurry A, sequentially adding pure Gd, pure Pb, Mg-Sr intermediate alloy, Zn-Ag intermediate alloy, Al-Zn-Mg-Cu intermediate alloy and Mg-Mn-Zr intermediate alloy into the molten slurry A, heating to 550 ℃, melting for 18min, finally adding Mg-Ti-Sn intermediate alloy, Cu-Mn30 intermediate alloy and graphene, melting for 15min under a heat preservation condition, fully stirring, slagging and degassing after the melting is finished to obtain a molten material B for later use;
3) cooling the melt B obtained in the step 2), removing the surface scum, and then pouring into a corresponding die to prepare as-cast zinc alloy for later use;
4) heating the as-cast zinc alloy obtained in the step 3) to 800 ℃ for hot rolling treatment, and then cooling the as-cast zinc alloy to 500 ℃ for solid solution treatment for 8h to obtain an ingot for later use;
5) heating the cast ingot obtained in the step 4) to 330 ℃ at a constant speed, performing first extrusion, wherein the extrusion deformation rate is 2.0m/min, the pressure ratio is 13, then continuously heating to 390 ℃ for second extrusion, and cooling at room temperature after the extrusion is finished to finally obtain a high-performance zinc alloy finished product; the second extrusion treatment was conducted at an extrusion deformation rate of 1.8m/min and a pressing ratio of 12.
Comparative example 3
A high-performance zinc alloy comprises the following components in percentage by weight:
Cu 2.0%
Mg 1%
Mn 1.5%
Zr 0.8%
Ti 1%
Sn 1.0%
Ag 1.0%
Gd 3.0%
Al 1.0%
Sr 0.5%
Pb 0.1%
4.0 percent of graphene
5.0 percent of modified carbon nano tube
The balance of Zn and inevitable impurities.
Each part of the modified carbon nano tube is composed of the following raw materials in parts by weight:
8 portions of modifier
20 portions of absolute ethyl alcohol
40 parts of carbon nano tube
10 portions of ethylene diamine tetraacetic acid
5 parts of U, N-diisopropylethylamine;
each part of the modifier is a mixture of pyridine-styrene-butadiene, styrene-isoprene-butadiene and N-hydroxysuccinimide according to the weight ratio of 1.2:0.8: 1.0.
The modified carbon nano tube is prepared by the following method:
s1, adding the carbon nano tube and the ethylene diamine tetraacetic acid into absolute ethyl alcohol according to the parts by weight, heating to 60 ℃, and reacting for 30min to obtain a mixture A for later use;
s2, adding a modifier and N, N-diisopropylethylamine into the mixture A obtained in the step S1, heating to 80 ℃, and reacting for 30min to obtain a mixture B for later use;
s3, drying the mixture B obtained in the step S2, and then irradiating the mixture B by ultraviolet light for 60min to obtain the modified carbon nano tube; the ultraviolet light is monochromatic narrow-band light with the irradiation wavelength of 270nm, and the irradiation power is 40 mW.
A preparation method of a high-performance zinc alloy is characterized by comprising the following steps:
1) according to the weight percentage, pure Zn, pure Gd, pure Pb, Mg-Ti-Sn intermediate alloy, Cu-Mn30 intermediate alloy, Mg-Sr intermediate alloy, Zn-Ag intermediate alloy, Al-Zn-Mg-Cu intermediate alloy and Mg-Mn-Zr intermediate alloy are used as raw materials for mixing; wherein the weight ratio of Mg in the Mg-Sr intermediate alloy, Mg in the Al-Zn-Mg-Cu intermediate alloy, Mg in the Mg-Ti-Sn intermediate alloy and Mg in the Mg-Mn-Zr intermediate alloy is 1.2:0.8:1.0: 0.5; the weight ratio of Mn in the Cu-Mn30 master alloy to Mn in the Mg-Mn-Zr master alloy is 1.2: 0.8; the weight ratio of Cu in the Cu-Mn30 master alloy to Cu in the Al-Zn-Mg-Cu master alloy is 1.0: 0.8;
2) adding a pure Zn ingot into refining equipment, heating to 450 ℃ under a vacuum condition, melting to completely melt, adding a modified carbon nanotube, continuously melting for 40min under heat preservation to obtain molten slurry A, sequentially adding pure Gd, pure Pb, Mg-Sr intermediate alloy, Zn-Ag intermediate alloy, Al-Zn-Mg-Cu intermediate alloy and Mg-Mn-Zr intermediate alloy into the molten slurry A, heating to 600 ℃ to melt for 20min, finally adding Mg-Ti-Sn intermediate alloy, Cu-Mn30 intermediate alloy and graphene, melting for 20min under heat preservation, fully stirring, slagging and degassing after the melting is finished to obtain a molten material B for later use;
3) cooling the melt B obtained in the step 2), removing the surface scum, and then pouring into a corresponding die to prepare as-cast zinc alloy for later use;
4) cooling the as-cast zinc alloy to 550 ℃ and carrying out solution treatment for 10h to obtain an ingot for later use;
5) heating the cast ingot obtained in the step 4) to 340 ℃ at a constant speed, carrying out first extrusion, wherein the extrusion deformation rate is 2.8m/min, the pressure ratio is 15, then continuously heating to 400 ℃ for second extrusion, and cooling at room temperature after the extrusion is finished to finally obtain a high-performance zinc alloy finished product; the second extrusion treatment was conducted at an extrusion deformation rate of 2.0m/min and a pressing ratio of 16.
The zinc alloys obtained in examples 1 to 5 and comparative examples 1 to 3 were subjected to mechanical property tests (yield strength, tensile strength and elongation). The test method comprises the following steps: the mechanical property test is carried out according to the national standard GB6397-86 metal tensile test sample, the test equipment is (SHIMADZU) AG-I250 kN precision universal tester tensile machine, the tensile speed is 1mm/min, and the test results are shown in the following table 1.
TABLE 1
| Item | Yield strength (MPa) | Tensile strength (MPa) | Elongation (%) |
| Example 1 | 223 | 281 | 16.0 |
| Example 2 | 226 | 2834 | 16.1 |
| Example 3 | 225 | 285 | 16.0 |
| Example 4 | 224 | 284 | 16.0 |
| Example 5 | 225 | 284 | 15.7 |
| Comparative example 1 | 183 | 251 | 10.3 |
| Comparative example 2 | 188 | 253 | 9.6 |
| Comparative example 3 | 211 | 258 | 11.8 |
From the above results, it can be seen that the zinc alloys prepared in the embodiments 1 to 5 of the present invention have excellent mechanical properties, significantly improved yield strength, tensile strength and elongation, and good environmental protection.
Compared with the embodiment 1, in the comparative example 1, the Mn element is added to 5% when the zinc alloy is prepared, and the zinc alloy prepared by using the raw materials is subjected to various physical property tests, and the analysis shows that the tensile yield strength, the tensile strength and the elongation of the zinc alloy are relatively reduced; the invention shows that when the zinc alloy is prepared, the dosage of the Mn element is controlled to be 0.5 percent, so that various mechanical properties of the prepared zinc alloy can be optimized, and the prepared zinc alloy has excellent yield strength, tensile strength, elongation, impact resistance and stable size and is suitable for large-scale production.
Compared with the embodiment 3, in the comparative example 2, the carbon nano tube is modified by adopting the ethynyltriethoxysilane when the modified carbon nano tube is used for preparing the zinc alloy, and various physical property tests are carried out on the zinc alloy prepared by using the raw materials, and the analysis shows that the tensile yield strength, the tensile strength and the elongation of the zinc alloy are obviously reduced; the invention shows that the modified carbon nano tube is added when the zinc alloy is prepared, so that various mechanical properties of the prepared zinc alloy can be optimized, and the prepared zinc alloy has excellent yield strength, tensile strength, elongation, impact resistance and stable size and is suitable for large-scale production.
In comparison with example 5, in comparative example 3, the hot rolling treatment of heating the as-cast zinc alloy obtained in step 3) to 850 ℃ was not performed in step 4) of preparing the zinc alloy, and physical property tests were performed on the zinc alloy prepared using the above raw materials, and it was found that the tensile yield strength, tensile strength and elongation of the zinc alloy were relatively decreased; the invention shows that when the zinc alloy is prepared, the cast zinc alloy obtained in the step 3) is heated to 850 ℃ for hot rolling treatment, so that various mechanical properties of the prepared zinc alloy can be optimized, and the prepared zinc alloy has excellent yield strength, tensile strength, elongation, impact resistance and stable size and is suitable for large-scale production.
The above-described embodiments are preferred implementations of the present invention, and the present invention may be implemented in other ways without departing from the spirit of the present invention.
Claims (8)
1. A high-performance zinc alloy is characterized in that: comprises the following components in percentage by weight:
Cu 0.1-2.0%
Mg 0.5-1%
Mn 1.0-1.5%
Zr 0.4-0.8%
Ti 0.05-1%
Sn 0.1-1.0%
Ag 0.1-1.0%
Gd 1.0-3.0%
Al 0.1-1.0%
Sr 0.01-0.5%
Pb 0.01-0.1%
1.0 to 4.0 percent of graphene
1.0-5.0% of modified carbon nano tube
The balance of Zn and inevitable impurities;
the high-performance zinc alloy is prepared by the following method:
1) according to the weight percentage, pure Zn, pure Gd, pure Pb, Mg-Ti-Sn intermediate alloy, Cu-Mn30 intermediate alloy, Mg-Sr intermediate alloy, Zn-Ag intermediate alloy, Al-Zn-Mg-Cu intermediate alloy and Mg-Mn-Zr intermediate alloy are used as raw materials for mixing;
2) adding a pure Zn ingot into refining equipment, heating and melting under a vacuum condition until the pure Zn ingot is completely melted, adding a modified carbon nano tube, continuously preserving heat and melting to obtain molten slurry A, sequentially adding pure Gd, pure Pb, Mg-Sr intermediate alloy, Zn-Ag intermediate alloy, Al-Zn-Mg-Cu intermediate alloy and Mg-Mn-Zr intermediate alloy into the molten slurry A, heating and melting, finally adding Mg-Ti-Sn intermediate alloy, Cu-Mn30 intermediate alloy and graphene into the molten slurry A, preserving heat and melting, fully stirring, slagging and degassing after the melting is finished to obtain a molten material B for later use;
3) cooling the melt B obtained in the step 2), removing the surface scum, and then pouring into a corresponding die to prepare as-cast zinc alloy for later use;
4) carrying out hot rolling treatment on the as-cast zinc alloy obtained in the step 3), and then carrying out solid solution treatment on the as-cast zinc alloy to obtain an ingot for later use;
5) and (3) heating the cast ingot obtained in the step 4) at a constant speed to perform first extrusion, then continuously heating to perform second extrusion, and cooling at room temperature after the extrusion is finished to finally obtain a high-performance zinc alloy finished product.
2. The high performance zinc alloy of claim 1, wherein: the modified carbon nanotube is prepared from the following raw materials in parts by weight:
4-8 parts of modifier
15-20 parts of absolute ethyl alcohol
20-40 parts of carbon nano tube
5-10 parts of ethylene diamine tetraacetic acid
1-5 parts of N, N-diisopropylethylamine.
3. A high performance zinc alloy according to claim 2, wherein: each part of the modifier is at least one of vinylpyridine-styrene-butadiene, styrene-isoprene-butadiene and N-hydroxysuccinimide.
4. A high performance zinc alloy according to any one of claims 2 to 3, wherein: the modified carbon nano tube is prepared by the following method:
s1, adding the carbon nano tube and the ethylene diamine tetraacetic acid into absolute ethyl alcohol according to the parts by weight, heating to 40-60 ℃, and reacting for 20-30min to obtain a mixture A for later use;
s2, adding a modifier and N, N-diisopropylethylamine into the mixture A obtained in the step S1, heating to 60-80 ℃, and reacting for 15-30min to obtain a mixture B for later use;
s3, drying the mixture B obtained in the step S2, and then irradiating the mixture B by ultraviolet light for 30-60min to obtain the modified carbon nano tube; the ultraviolet light is monochromatic narrow-band light with the irradiation wavelength of 200-270nm, and the irradiation power is 15-40 mW.
5. The high performance zinc alloy of claim 1, wherein: in the step 2), after adding pure Zn ingot, the temperature is 400-450 ℃ when heating and melting, and the time for adding the modified carbon nano tube and keeping the temperature for melting is 20-40 min.
6. The high performance zinc alloy of claim 1, wherein: in the step 2), pure Gd, pure Pb, Mg-Sr intermediate alloy, Zn-Ag intermediate alloy and Mg-Mn-Zr intermediate alloy are added, the temperature is increased to 600 ℃ for smelting, the smelting time is 15-20min, and the smelting is continued for 10-20min after the graphene is added.
7. The high performance zinc alloy of claim 1, wherein: the temperature for the first extrusion treatment in the step 5) is 320-340 ℃, the extrusion deformation rate is 1.2-2.8m/min, and the pressure ratio is 10-15.
8. The high performance zinc alloy of claim 1, wherein: the temperature for the second extrusion treatment in the step 5) is 380-400 ℃, the extrusion deformation rate is 1.5-2.0m/min, and the pressure ratio is 8-16.
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