CN110607462B - Preparation method of ZZnAl4Y zinc alloy with uniform microstructure and higher mechanical property - Google Patents

Preparation method of ZZnAl4Y zinc alloy with uniform microstructure and higher mechanical property Download PDF

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CN110607462B
CN110607462B CN201910976905.5A CN201910976905A CN110607462B CN 110607462 B CN110607462 B CN 110607462B CN 201910976905 A CN201910976905 A CN 201910976905A CN 110607462 B CN110607462 B CN 110607462B
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zinc alloy
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CN110607462A (en
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王建华
张凯
彭浩平
刘亚
苏旭平
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Changzhou University
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D27/00—Treating the metal in the mould while it is molten or ductile ; Pressure or vacuum casting
    • B22D27/04—Influencing the temperature of the metal, e.g. by heating or cooling the mould
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C1/00—Making non-ferrous alloys
    • C22C1/02—Making non-ferrous alloys by melting
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C22C18/04—Alloys based on zinc with aluminium as the next major constituent

Abstract

The invention discloses a method for improving the mechanical property of ZZnAl4Y zinc alloy by controlling the temperature of a metal mold, which comprises the step of casting molten zinc alloy liquid into a preheated metal mold with the sizes of phi 10 × 100 and phi 30 × 80 mm respectively. By controlling the metal mold temperature and prolonging the solidification time, the uniformity of the microstructure of the zinc alloy is improved, and the mechanical properties of the alloy, such as tensile strength, elongation, impact toughness and the like, can be improved, so that the industrial production cost can be reduced. The invention can prepare ZZnAl4Y zinc alloy with uniform microstructure and higher mechanical property, and is suitable for industrial production of the zinc alloy.

Description

Preparation method of ZZnAl4Y zinc alloy with uniform microstructure and higher mechanical property
Technical Field
The invention relates to a preparation technology of zinc alloy, in particular to a preparation method of ZZnAl4Y zinc alloy with uniform microstructure and higher mechanical property.
Background
The zinc alloy material has various excellent characteristics, such as good casting performance, can be used for producing precision parts with complex shapes and thin walls by die casting, has smooth casting surfaces, can be used for surface treatment such as electroplating, spraying, paint spraying and the like, and has the advantages of low casting energy consumption, low raw material cost and no environmental pollution in the production process. The Zn-Al alloy is widely applied to die-casting production in the fields of motorcycle carburetors, automobile parts, hardware products and the like due to good wear resistance, superplasticity and creep resistance. The low aluminum zinc alloy such as ZZnAl4Y die casting zinc alloy is widely applied to daily equipment superior to instruments and equipment due to the characteristics of low melting point, good casting performance and the like. The die-casting zinc alloy products are over 500, and can be widely applied to automobiles, tractors, daily building hardware, electromechanical equipment, instruments, stationery toys and the like. The die-casting zinc alloy is originated from the Zn-4Al-3Cu alloy developed and developed by New Jersey company in the beginning of 20 th century, and then a series of researches and researches on the performance improvement are carried out around the Zn-4Al-3Cu alloy. Through a series of subsequent improvements, a series of Aamak alloys are successfully developed.
To date, Zn-Al alloys have been developed to the point where the furnace fire is pure green, with ZZnAl4Y zinc alloy being widely used in industry. However, the domestic ZZnAl4Y zinc alloy has low quality, and the high-quality ZZnAl4Y zinc alloy is greatly imported. The main reason why the domestic ZZnAl4Y zinc alloy has lower quality is that: 1) the content of impurities in the alloy is too high; 2) the control precision of the alloy components is low; 3) the uniformity of the alloy structure is poor; 4) the mechanical property of the alloy is lower. Therefore, innovative technologies are needed to improve the quality of the zinc alloy, so as to improve the structural uniformity and mechanical properties of the zinc alloy.
In the traditional casting process, the metal mold is usually adopted to cast and refine the alloy structure, thereby achieving the purpose of improving the mechanical property of the alloy. Generally speaking, it is generally recognized that the lower the temperature of the metal mold, the faster the cooling speed, the finer the microstructure of the alloy, and the higher the mechanical properties. The invention is completely different from the traditional cognition, obviously improves the uniformity of alloy structure by adopting the method of increasing the temperature of the metal mold, greatly improves the mechanical property of the zinc alloy, saves the subsequent heat treatment process and saves the production cost.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention provides a preparation method of ZZnAl4Y zinc alloy with uniform microstructure and higher mechanical property, so that the uniformity of the alloy microstructure is obviously improved, and the mechanical property of the alloy is obviously improved.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows: a method for preparing ZZnAl4Y zinc alloy with uniform microstructure and high mechanical property comprises the following steps: and casting the ZZnAl4Y zinc alloy liquid prepared by rapid smelting into a metal mold at 200-350 ℃, and then slowly cooling to room temperature along with the casting mold to prepare the ZZnAl4Y zinc alloy with uniform microstructure and high mechanical property.
Further, the rapid smelting method comprises the following steps: the ZZnAl4Y zinc alloy raw material is rapidly smelted at 680 +/-5 ℃, then cooled to 620 +/-5 ℃, degassed, deslagged and refined, and then kept warm and kept stand for 30 +/-3 minutes. The solidifying point of the ZZnAl4Y zinc alloy is about 390 ℃, the pouring temperature after smelting is about 620 ℃, the temperature of the metal mold in the embodiment is controlled to be about 200-350 ℃, the temperature difference is about 270-400 ℃, the cooling effect of the metal mold on the zinc alloy liquid is greatly weakened, and therefore the zinc alloy liquid is slowly cooled to the solidifying point of 390 ℃ from 620 ℃, so that the dendritic primary aluminum phase disappears and is further converted into the whole spherical primary aluminum phase. Meanwhile, the temperature difference in the casting section is obviously reduced, so that more uniform primary aluminum phase is obtained. In the case of non-equilibrium solidification, the faster the cooling rate, the lower the solidification point of the alloy, as compared with the equilibrium cooling conditions. In the examples, the cooling rate of the zinc alloy liquid was slow, so the freezing point depression of the alloy was small.
Further, the preheating temperature of the metal mold is 200 ℃, 250 ℃, 300 ℃ or 350 ℃.
In the common casting process of the zinc alloy, the metal mold is not preheated normally, the preheating temperature is lower or the cooling time is too short, when the zinc alloy liquid is poured into the metal mold, the outer layer of a common casting is fine isometric crystal, the middle part of the common casting is columnar crystal, the center of the common casting is thick isometric crystal, and the microstructure of the casting from the outer layer to the inner part is very uneven. The preheating temperature of the metal mold is below the liquidus of ZZnAl4Y zinc alloy and is 200-350 ℃, and the technical effects are as follows:
1. with the increase of the metal mold temperature, the initial solidification point of the zinc alloy liquid is increased due to the great reduction of the cooling speed, a relatively coarse spherical primary aluminum phase is obtained, and the dendritic crystal primary aluminum phase is eliminated. Meanwhile, the temperature gradient of the casting from the surface layer to the center is obviously reduced, so that the casting tends to be solidified simultaneously, and the structure uniformity of the casting from the center to the outer layer is obviously improved. Under the action of tensile stress, the alloy with good tissue uniformity can be deformed more uniformly without fracture, so that the comprehensive mechanical property of the alloy is obviously improved.
2. The invention has the outstanding effect that although the primary spherical aluminum phase in the alloy solidification structure is obviously coarse, higher mechanical property can be obtained due to good uniformity.
3. Because the temperature of the metal mold is higher, the casting can be slowly cooled in the casting mold, and the spherical primary aluminum phase becomes more round and smooth due to the sufficient atomic diffusion, which is equivalent to the homogenization annealing effect of the alloy, and the elongation of the alloy can be further improved.
Drawings
The invention is further illustrated with reference to the following figures and examples:
FIG. 1 is a photograph of the microstructure at the center of the cross section of a specimen of a zinc alloy ZZnAl4Y of a comparative example.
FIG. 2 is a photograph of the microstructure of a test specimen 1/2R of a zinc alloy of ZZnAl4Y in a comparative example.
FIG. 3 is a photograph of the microstructure at the surface of a test piece of a zinc alloy of ZZnAl4Y of a comparative example.
FIG. 4 is a photograph of the microstructure at the center of the cross section of a specimen of the zinc alloy of example 1ZZnAl 4Y.
FIG. 5 is a photograph of the microstructure of a test specimen 1/2R of the zinc alloy of EXAMPLE 1ZZnAl 4Y.
FIG. 6 is a photograph of the microstructure at the surface of a sample of the zinc alloy of example 1ZZnAl 4Y.
FIG. 7 is a photograph of the microstructure at the center of the cross section of a specimen of zinc alloy ZZnAl4Y of example 2.
FIG. 8 is a photograph of the microstructure of a zinc alloy specimen 1/2R of EXAMPLE 2ZZnAl 4Y.
FIG. 9 is a photograph of the microstructure at the surface of a sample of zinc alloy of example 2ZZnAl 4Y.
FIG. 10 is a photograph of the microstructure at the center of the cross section of a specimen of zinc alloy ZZnAl4Y of example 3.
FIG. 11 is a photograph of the microstructure of a zinc alloy specimen 1/2R of EXAMPLE 3ZZnAl 4Y.
FIG. 12 is a photograph of the microstructure at the surface of a test piece of the zinc alloy of example 3ZZnAl 4Y.
FIG. 13 is a photograph of the microstructure at the center of the cross section of a specimen of zinc alloy ZZnAl4Y of example 4.
FIG. 14 is a photograph of the microstructure of a zinc alloy specimen 1/2R of example 4ZZnAl 4Y.
FIG. 15 is a photograph of the microstructure at the surface of a zinc alloy specimen of example 4ZZnAl 4Y.
Detailed Description
The invention is described in more detail below with reference to the following examples:
the cross-sections of the ZZnAl4Y zinc alloy specimen 1/2R were taken as microstructural photographs of the cross-sections of the ZZnAl4Y zinc alloy specimen in the following examples and comparative examples, wherein the ZZnAl4Y zinc alloy specimen was a cylinder, R was the radius of the cross-section of the cylinder, and the cross-section at 1/2R was the cross-section at 1/2R from the end of the cylinder (i.e., the cross-section was taken perpendicular to the axis of the cylinder).
Comparative example:
step 1, zinc alloy raw material proportioning: the raw materials adopted are industrial pure zinc (99.9%) and industrial pure aluminum (99.9%). The mass ratio of each component is calculated, and the components are weighed by adopting a Mettler XS105 electronic balance, and the weight percentage of the components is as follows: 95.9 percent of industrial pure zinc and 4.1 percent of industrial pure aluminum.
Step 2, smelting zinc alloy
The prepared zinc alloy raw material and the covering agent are put into a high-temperature-resistant corundum crucible, and the crucible is put into a furnace when the temperature in the furnace reaches 680 ℃. And after the sample is completely melted, fully stirring the melt by using a high-temperature-resistant quartz rod to prevent component segregation. Stopping supplying power, reducing the temperature of the metal liquid to 620 ℃, refining the alloy liquid by hexachloroethane, and then keeping the temperature and standing for 30 minutes.
Step 3, tapping and casting
And pouring the zinc alloy liquid into metal molds with the sizes of inner cavities of phi 10 x 100 (tensile and impact test samples) and phi 30 x 80 (metallographic analysis samples) at the non-preheating temperature respectively to obtain the required alloy samples.
The tensile test sample adopts a standard test sample (GB-T228-.
The microstructure of the zinc alloy is shown in FIGS. 1 to 3, and the microstructure is mostly non-equiaxed crystals such as dendrites and quincunx crystals, and the size difference of primary aluminum phase crystal grains from the center of the cross section to the surface structure is large. The tensile strength of the alloy is 245MPa, and the elongation is 2.5%; the impact work of the alloy was 23J.
Example 1:
step 1, zinc alloy raw material batching: the raw materials adopted are industrial pure zinc (99.9%) and industrial pure aluminum (99.9%). The mass ratio of each component is calculated, and the components are weighed by adopting a Mettler XS105 electronic balance, and the weight percentage of the components is as follows: 95.9 percent of industrial pure zinc and 4.1 percent of industrial pure aluminum
Step 2, preheating the metal mold
The molds with internal cavity sizes phi 10 x 100 (tensile and impact test samples) and phi 30 x 80 (metallographic samples) were preheated to 200 ℃ for use as casting molds.
Step 3, smelting zinc alloy
And (3) putting the zinc alloy raw material and the covering agent prepared in the step (1) into a high-temperature-resistant corundum crucible, and putting the high-temperature-resistant corundum crucible into a smelting furnace when the temperature in the smelting furnace reaches 680 ℃. And after the sample is completely melted into molten metal, fully stirring the molten metal by using a high-temperature-resistant quartz rod to prevent component segregation. Stopping supplying power, reducing the temperature of the metal liquid to 620 ℃ to prepare zinc alloy liquid, refining the zinc alloy liquid by adopting hexachloroethane, and then keeping the temperature and standing for 30 minutes.
Step 4, tapping and casting
Pouring the zinc alloy liquid refined in the step 3 into the casting molds with different sizes in the step 2, and naturally cooling the casting molds to room temperature under the room temperature condition to obtain ZZnAl4Y zinc alloy samples.
In the step 4, ZZnAl4Y zinc alloy samples prepared in two casting molds with the inner cavity size of phi 10 x 100 are respectively used as tensile and impact test samples, the tensile test sample adopts a standard test sample (GB-T228-.
The ZZnAl4Y zinc alloy sample prepared in the casting mold with the cavity size of phi 30 x 80 is used as a metallographic analysis sample, the microstructure of the metallographic analysis sample is shown in figures 4-6, primary aluminum phase crystal grains in the central structure from the surface of the cross section gradually change from quincunx-shaped anisometric crystals to spherical isometric crystals, and the size of the primary aluminum phase crystal grains in the central structure from the surface is different. The microstructure of the ZZnAl4Y zinc alloy prepared in this example is superior to that of the comparative example. The tensile strength of the ZZnAl4Y zinc alloy prepared in the embodiment is 269MPa, the elongation is 3.2%, the impact energy is 25J, and the mechanical property of the ZZnAl4Y zinc alloy prepared in the embodiment is greatly improved compared with that of the zinc alloy prepared in the embodiment.
Example 2:
step 1, zinc alloy raw material proportioning: the raw materials adopted are industrial pure zinc (99.9%) and industrial pure aluminum (99.9%). The mass ratio of each component is calculated, and the components are weighed by adopting a Mettler XS105 electronic balance, and the weight percentage of the components is as follows: 95.9 percent of industrial pure zinc and 4.1 percent of industrial pure aluminum.
Step 2, preheating the metal mold
The molds with internal cavity sizes phi 10 x 100 (tensile and impact test samples) and phi 30 x 80 (metallographic samples) were preheated to 250 ℃ for use as molds.
Step 3, smelting zinc alloy
And (3) putting the zinc alloy raw material and the covering agent prepared in the step (1) into a high-temperature-resistant corundum crucible, and putting the crucible into a smelting furnace when the temperature in the smelting furnace reaches 680 ℃. And after the sample is completely melted into molten metal, fully stirring the molten metal by using a high-temperature-resistant quartz rod to prevent component segregation. Stopping supplying power, reducing the temperature of the metal liquid to 620 ℃ to prepare zinc alloy liquid, refining the zinc alloy liquid by adopting hexachloroethane, and then keeping the temperature and standing for 30 minutes.
Step 4, tapping and casting
Pouring the refined zinc alloy liquid in the step 3 into the preheated metal mold in the step 2, and slowly cooling to room temperature along with the casting mold to obtain a ZZnAl4Y zinc alloy sample.
In the step 4, ZZnAl4Y zinc alloy samples prepared in two casting molds with the inner cavity size of phi 10 x 100 are respectively used as tensile and impact test samples, the tensile test sample adopts a standard test sample (GB-T228-.
The ZZnAl4Y zinc alloy sample prepared in the casting mold with the cavity size of phi 30 x 80 is used as a metallographic analysis sample, the microstructure of the sample is shown in figures 7-9, the primary aluminum phase crystal grains in the central structure from the surface of the cross section gradually change from quincunx-shaped anisometric crystals to spherical isometric crystals, and the size of the primary aluminum phase crystal grains in the central structure from the surface is still greatly different, but the uniformity of the microstructure of the ZZnAl4Y zinc alloy prepared in the embodiment from the surface to the center is better than that of the microstructure of the embodiment 1. The tensile strength of the alloy is 273 MPa. The elongation was 3.3%. The impact energy of the ZZnAl4Y zinc alloy prepared in the embodiment is 25J, and the mechanical property of the ZZnAl4Y zinc alloy prepared in the embodiment is slightly improved compared with that of the embodiment 1.
Example 3:
step 1, zinc alloy raw material proportioning: the raw materials adopted are industrial pure zinc (99.9%) and industrial pure aluminum (99.9%). The mass ratio of each component is calculated, and the components are weighed by adopting a Mettler XS105 electronic balance, and the weight percentage of the components is as follows: 95.9 percent of industrial pure zinc and 4.1 percent of industrial pure aluminum.
Step 2, preheating the metal mold
The molds with internal cavity sizes phi 10 x 100 (tensile and impact test samples) and phi 30 x 80 (metallographic samples) were preheated to 300 ℃ for use as molds.
Step 3, smelting zinc alloy
And (3) putting the zinc alloy raw material and the covering agent prepared in the step (1) into a high-temperature-resistant corundum crucible, and putting the crucible into a smelting furnace when the temperature in the smelting furnace reaches 680 ℃. And after the sample is completely melted into molten metal, fully stirring the molten metal by using a high-temperature-resistant quartz rod to prevent component segregation. Stopping supplying power, reducing the temperature of the metal liquid to 620 ℃ to prepare zinc alloy liquid, refining the zinc alloy liquid by adopting hexachloroethane, and then keeping the temperature and standing for 30 minutes.
Step 4, tapping and casting
Pouring the refined zinc alloy liquid in the step 3 into preheated metal molds with two sizes in the step 2, and slowly cooling the metal molds to room temperature along with the casting molds to obtain ZZnAl4Y zinc alloy samples.
In the step 4, ZZnAl4Y zinc alloy samples prepared in two casting molds with the inner cavity size of phi 10 x 100 are respectively used as tensile and impact test samples, the tensile test sample adopts a standard test sample (GB-T228-.
The ZZnAl4Y zinc alloy sample prepared in the casting mold with the cavity size of phi 30 x 80 is used as a metallographic analysis sample, the microstructure of the cast alloy is shown as figures 10-12, most of primary aluminum phase grains from the surface of the cross section to the central structure are uniform spherical isometric crystals, and the difference degree of the grain sizes of the primary aluminum phase grains from the surface to the central structure is obviously reduced. The microstructure of the ZZnAl4Y zinc alloy prepared in this example is significantly better from the surface to the center than that of example 2. The tensile strength of the ZZnAl4Y zinc alloy prepared in this example was 293 MPa. The elongation is 3.7 percent, the impact energy is 27J, and the mechanical property of the ZZnAl4Y zinc alloy prepared by the embodiment is obviously improved compared with that of the embodiment 2.
Example 4:
step 1, zinc alloy raw material proportioning: the raw materials adopted are industrial pure zinc (99.9%) and industrial pure aluminum (99.9%). The mass ratio of each component is calculated, and the components are weighed by adopting a Mettler XS105 electronic balance, and the weight percentage of the components is as follows: 95.9 percent of industrial pure zinc and 4.1 percent of industrial pure aluminum.
Step 2, preheating the metal mold
The molds with internal cavity sizes phi 10 x 100 (tensile and impact test samples) and phi 30 x 80 (metallographic samples) were preheated to 350 ℃ for use as molds.
Step 3, smelting zinc alloy
And (3) putting the zinc alloy raw material and the covering agent prepared in the step (1) into a high-temperature-resistant corundum crucible, and putting the crucible into a smelting furnace when the temperature in the smelting furnace reaches 680 ℃. And after the sample is completely melted into molten metal, fully stirring the molten metal by using a high-temperature-resistant quartz rod to prevent component segregation. Stopping supplying power, reducing the temperature of the metal liquid to 620 ℃ to prepare zinc alloy liquid, refining the alloy liquid by adopting hexachloroethane, and then keeping the temperature and standing for 30 minutes.
Step 4, tapping and casting
And (3) pouring the refined zinc alloy liquid in the step (3) into the preheated metal molds with two sizes in the step (2), and slowly cooling the metal molds to room temperature along with the casting molds to obtain ZZnAl4Y zinc alloy samples.
In the step 4, ZZnAl4Y zinc alloy samples prepared in two casting molds with the inner cavity size of phi 10 x 100 are respectively used as tensile and impact test samples, the tensile test sample adopts a standard test sample (GB-T228-.
The microstructure of the ZZnAl4Y zinc alloy sample prepared in the casting mold with the cavity size of phi 30 x 80 is shown in figures 13-15, the microstructure is mostly spherical equiaxed crystal, the size difference of primary aluminum phase crystal grains in the structure from the center of the cross section to the surface is reduced, but the size is obviously larger than that of the sample in the embodiment 3. The ZZnAl4Y zinc alloy prepared by the embodiment has the tensile strength of 288MPa, the elongation of 3.6 percent and the impact energy of 26J. The mechanical properties of the ZZnAl4Y zinc alloy prepared by the embodiment are reduced compared with the embodiment 3.
The tensile test results of examples 1 to 4 and comparative example are shown in Table 1 and the impact test results are shown in Table 2.
TABLE 1ZZnAl4Y Zinc alloy tensile test data
Figure BDA0002233939280000101
TABLE 2ZZnAl4Y Zinc alloy impact test data
Figure BDA0002233939280000102
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and their concepts should be equivalent or changed within the technical scope of the present invention.

Claims (2)

1. A method for preparing ZZnAl4Y zinc alloy with uniform microstructure and higher mechanical property is characterized in that: the method comprises the steps of casting a ZZnAl4Y zinc alloy liquid prepared by rapid smelting into a metal mold with the preheating temperature of 200-350 ℃, and then cooling to the room temperature along with a casting mold to prepare the ZZnAl4Y zinc alloy;
the preheating temperature of the metal mold is below a ZZnAl4Y zinc alloy liquidus line, and the casting temperature of the ZZnAl4Y zinc alloy liquid is 620 ℃;
the rapid smelting method comprises the following steps: the ZZnAl4Y zinc alloy raw material is rapidly smelted at 680 +/-5 ℃, then cooled to 620 +/-5 ℃, degassed, deslagged and refined, and then kept warm and kept stand for 30 +/-3 minutes.
2. A method of making ZZnAl4Y zinc alloy of uniform microstructure and higher mechanical properties as defined in claim 1, wherein: the preheating temperature of the metal mold is 200 ℃, 250 ℃, 300 ℃ or 350 ℃.
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