CN118207437A - Zinc alloy cast ingot and preparation method thereof - Google Patents
Zinc alloy cast ingot and preparation method thereof Download PDFInfo
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- CN118207437A CN118207437A CN202410638084.5A CN202410638084A CN118207437A CN 118207437 A CN118207437 A CN 118207437A CN 202410638084 A CN202410638084 A CN 202410638084A CN 118207437 A CN118207437 A CN 118207437A
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- 229910001297 Zn alloy Inorganic materials 0.000 title claims abstract description 133
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 238000005266 casting Methods 0.000 claims abstract description 95
- 239000011701 zinc Substances 0.000 claims abstract description 73
- 238000007670 refining Methods 0.000 claims abstract description 71
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 69
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 63
- 238000007872 degassing Methods 0.000 claims abstract description 42
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 38
- 238000000034 method Methods 0.000 claims abstract description 35
- 238000001914 filtration Methods 0.000 claims abstract description 28
- 239000002994 raw material Substances 0.000 claims abstract description 26
- 238000007664 blowing Methods 0.000 claims abstract description 24
- 239000012535 impurity Substances 0.000 claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000004321 preservation Methods 0.000 claims abstract description 11
- 239000011261 inert gas Substances 0.000 claims description 34
- 239000000498 cooling water Substances 0.000 claims description 32
- 238000003723 Smelting Methods 0.000 claims description 18
- 238000004519 manufacturing process Methods 0.000 claims description 18
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 14
- 230000008569 process Effects 0.000 claims description 14
- 238000009826 distribution Methods 0.000 claims description 13
- 235000019270 ammonium chloride Nutrition 0.000 claims description 7
- 238000010128 melt processing Methods 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 6
- 239000000463 material Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- VHHHONWQHHHLTI-UHFFFAOYSA-N hexachloroethane Chemical compound ClC(Cl)(Cl)C(Cl)(Cl)Cl VHHHONWQHHHLTI-UHFFFAOYSA-N 0.000 claims description 3
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 239000011592 zinc chloride Substances 0.000 claims description 3
- 235000005074 zinc chloride Nutrition 0.000 claims description 3
- 239000000155 melt Substances 0.000 abstract description 28
- 230000007547 defect Effects 0.000 abstract description 11
- 239000002893 slag Substances 0.000 abstract description 11
- 230000001105 regulatory effect Effects 0.000 abstract description 6
- 238000009749 continuous casting Methods 0.000 abstract description 5
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 description 37
- 229910045601 alloy Inorganic materials 0.000 description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 33
- 239000007789 gas Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 238000001816 cooling Methods 0.000 description 14
- 229910052742 iron Inorganic materials 0.000 description 13
- 239000010949 copper Substances 0.000 description 12
- 229910052782 aluminium Inorganic materials 0.000 description 11
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 11
- 230000009286 beneficial effect Effects 0.000 description 11
- 238000012545 processing Methods 0.000 description 10
- WPPDFTBPZNZZRP-UHFFFAOYSA-N aluminum copper Chemical compound [Al].[Cu] WPPDFTBPZNZZRP-UHFFFAOYSA-N 0.000 description 9
- 230000004907 flux Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 9
- 239000002184 metal Substances 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 7
- 230000005484 gravity Effects 0.000 description 6
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000007599 discharging Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 238000010276 construction Methods 0.000 description 3
- 238000005336 cracking Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000010079 rubber tapping Methods 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- 229910002535 CuZn Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007667 floating Methods 0.000 description 1
- 238000005242 forging Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention provides a zinc alloy cast ingot and a preparation method thereof. The zinc alloy ingot comprises Cu, al, fe, zn with specific content and unavoidable impurities; the preparation method comprises the following steps: heating the raw materials, blowing a refining agent when the temperature of the obtained zinc melt reaches 530-580 ℃, and standing; feeding the obtained refined melt into a heat preservation furnace, blowing refining agent again, and standing; releasing when the temperature of the refined melt is more than or equal to 550 ℃, sequentially carrying out on-line degassing and on-line filtering, and then casting under specific casting technological parameters to obtain the zinc alloy cast ingot. The invention adopts a semi-continuous casting method, improves the purity of the melt by on-line degassing and filtering, and reduces the gas content and the slag content in the melt; the casting process parameters in the casting process are regulated, so that the zinc alloy cast ingot has uniform and fine structure, high density and no defects of air holes, looseness and the like.
Description
Technical Field
The invention relates to the technical field of zinc alloy materials, in particular to a zinc alloy cast ingot and a preparation method thereof.
Background
The metal zinc has good corrosion resistance, plasticity and toughness and casting performance, has stable mechanical properties under normal temperature conditions, and can be prepared into alloys meeting different performance requirements by alloying means with various metals such as aluminum, copper, titanium, magnesium and the like. Zinc alloy has been widely used in the fields of automobiles, buildings, home appliances, ships, light industry, machinery, batteries, etc. because of its excellent properties such as low melting point, good fluidity, easy forming, etc., and is being developed toward higher added values. The use of zinc alloy sheet materials as building curtain walls and roof panels has been reported abroad.
At present, the conventional method for preparing zinc alloy cast ingots in China mainly adopts a metal mold gravity casting method, namely, pre-prepared zinc alloy liquid is cast into a pre-prepared ingot mold, and alloy melt is cooled by a natural cooling or mold cooling method, but the two cooling modes can lead to uneven microstructure of the cast ingots due to uneven cooling strength of the side part and the center part. The microstructure is uneven, so that not only is coarse grains appear, but also a large number of phenomena such as loosening, shrinkage cavity and even cracking occur, and the yield of cast ingots is seriously affected. Moreover, the ingot prepared by the method is difficult to prepare a zinc alloy sheet by subsequent deformation processing. In addition, when preparing the zinc alloy ingot with larger specification, the cooling speed of the melt is very slow, and the production efficiency is greatly reduced.
Disclosure of Invention
The invention mainly aims to provide a zinc alloy cast ingot and a preparation method thereof, which are used for solving the problems that the zinc alloy cast ingot obtained by a metal mold gravity casting method in the prior art is macroscopically loose, has coarse pores and microstructure and is uneven.
In order to achieve the above object, according to one aspect of the present invention, there is provided a method for producing a zinc alloy ingot, the zinc alloy ingot comprising, in mass percent: 0.05-0.3% of Cu, 0.05-4% of Al, 0.05-0.15% of Fe, and the balance of Zn and unavoidable impurities; the preparation method comprises the following steps: step S1, selecting materials: selecting raw materials according to the component proportion of the zinc alloy cast ingot; step S2, smelting: heating the raw materials in a smelting furnace at 520-620 ℃ to obtain zinc melt; step S3, in-furnace melt treatment: when the temperature of the zinc melt reaches 530-580 ℃, blowing a first refining agent into the zinc melt by using a first inert gas to perform first furnace refining, and performing first standing to obtain a first refined melt; feeding the first refined melt into a heat preservation furnace, blowing a second refining agent into the first refined melt by using a second inert gas to perform second furnace refining, and then performing second standing to obtain a second refined melt; step S4, online melt processing: releasing when the temperature of the second refined melt is more than or equal to 550 ℃, and sequentially carrying out online degassing and online filtering to obtain a zinc purified melt; step S5, casting: and (3) conveying the zinc purified melt into a crystallizer for casting, wherein the casting temperature is 450-550 ℃, the initial casting speed is 15-30 mm/min, the stable production casting speed is 35-50 mm/min, the flow rate of cooling water in the crystallizer is 40-65 m 3/h, and the temperature of the cooling water is less than or equal to 28 ℃, so that the zinc alloy cast ingot is obtained.
Further, the zinc alloy cast ingot comprises the following components in percentage by mass: 0.05-0.15% of Cu, 3-4% of Al, 0.05-0.1% of Fe, and the balance of Zn and unavoidable impurities.
Further, in step S2, the heating temperature is 530-580 ℃.
Further, in the step S3, when the temperature of the zinc melt reaches 530-560 ℃, blowing a first refining agent into the zinc melt by using a first inert gas; and/or the blowing time of the first inert gas is 10-25 min; and/or the first standing time is 15-30 min; and/or the first refined melt is fed into the holding furnace in a launder.
Further, in the step S3, the blowing time of the second inert gas is 10-20 min; and/or the second standing time is 15-20 min.
Further, the first refining agent and the second refining agent are each independently one or more of hexachloroethane, zinc chloride, and ammonium chloride; and/or the first refining agent accounts for 0.1-0.4% of the weight of the raw material, and/or the second refining agent accounts for 0.1-0.3% of the weight of the raw material.
Further, in the step S4, when the temperature of the second refined melt is 550-570 ℃, releasing; and/or performing online degassing with a third inert gas; and/or the on-line degassing device is selected from a single-rotor degassing machine, a double-rotor degassing machine or a three-rotor degassing machine; when the on-line degassing equipment is a double-rotor degassing machine, the rotating speed of the rotor is 400-600 rpm; and/or the on-line filtering equipment is a plate type filtering box and/or deep bed filtering; the plate type filter box is a two-stage plate type filter box.
Further, the first inert gas, the second inert gas and the third inert gas are respectively and independently selected from argon and/or nitrogen.
Further, in step S5, the manner of feeding the zinc-purified melt into the crystallizer is a distribution launder; and/or the casting temperature is 450-530 ℃; and/or the initial casting speed is 18-25 mm/min; and/or stably producing the casting speed of 37-48 mm/min.
Further, in the step S5, the flow rate of the cooling water is 43-61 m 3/h; and/or the temperature of the cooling water is 20-27 ℃.
According to another aspect of the invention, a zinc alloy ingot is provided, which is prepared by the preparation method.
Further, the average grain size of the zinc alloy cast ingot is less than 100 mu m, and the maximum grain size is less than 150 mu m.
Compared with the prior art, the invention mainly realizes the technical progress that:
1. Aiming at the prominent problems of large amount of loosening, shrinkage cavity, even crack defects, air holes and the like existing in the cast ingot caused by uneven microstructure in the existing zinc alloy cast ingot prepared by adopting metal mold gravity casting, the invention adopts a semi-continuous casting method to prepare the zinc alloy cast ingot, and controls the slag content in the melt by regulating and controlling the smelting and melt processing process steps and parameters, thereby improving the purity of the melt, and being beneficial to improving the metallurgical quality of the cast ingot.
2. Aiming at the problems of uneven microstructure, coarse grains and the like which are commonly existed in the existing preparation of zinc alloy cast ingots by adopting metal mold gravity casting, the invention ensures that the cooling strength of each part of the cast ingot tends to be uniform in the casting process by regulating and controlling the semi-continuous casting process parameters, thereby ensuring that the microstructure of the cast ingot is uniform and fine, the surface of the cast ingot is smooth and the inside is compact, and the defects of looseness, shrinkage cavity and the like are avoided, thus providing stable cast ingot conditions for manufacturing zinc alloy plates by subsequent processing.
In summary, by adopting the technical scheme of the invention, a zinc alloy ingot is prepared by adopting a semi-continuous casting method, and the smelting furnace and the heat preservation furnace are respectively subjected to melt refining, degassing and standing treatment, and the purity of the melt is improved by on-line degassing and filtering, so that the gas content and the slag content in the melt are reduced. In addition, the casting process parameters in the casting process are regulated, so that the structure of the zinc alloy cast ingot is uniform and fine. The cast ingot prepared by the preparation method disclosed by the invention has the advantages of uniform and fine structure, high density, no defects of air holes, looseness and the like, and the zinc alloy plate prepared by using the cast ingot can be used as a building curtain wall and a roof.
Drawings
The accompanying drawings, which are included to provide a further understanding of the application and are incorporated in and constitute a part of this specification, illustrate embodiments of the application and together with the description serve to explain the application. In the drawings:
FIG. 1 shows a zinc alloy ingot grain distribution diagram according to example 1 of the present invention;
FIG. 2 shows a microstructure view of a zinc alloy ingot according to example 1 of the present invention;
FIG. 3 shows a diagram of internal defects of a zinc alloy ingot according to comparative example 1 of the present invention; and
Fig. 4 shows a distribution diagram of a central grain of a zinc alloy ingot of comparative example 4 according to the present invention.
Detailed Description
It should be noted that, without conflict, the embodiments of the present application and features of the embodiments may be combined with each other. The application will be described in detail below with reference to the drawings in connection with embodiments.
Term interpretation:
And (3) releasing: in industrial production, molten metal material is discharged from a melting apparatus for subsequent processing or manufacture.
As described in the background art of the invention, the problems of macroscopic porosity, coarse pores and microstructure and non-uniformity of zinc alloy cast ingots obtained by a metal mold gravity casting method exist in the prior art. In order to solve the above problems, in an exemplary embodiment of the present invention, there is provided a method for preparing a zinc alloy ingot, which comprises the following components in mass percent: 0.05-0.3% of Cu, 0.05-4% of Al, 0.05-0.15% of Fe, and the balance of Zn and unavoidable impurities; the preparation method comprises the following steps: step S1, selecting materials: selecting raw materials according to the component proportion of the zinc alloy cast ingot; step S2, smelting: heating the raw materials in a smelting furnace at 520-620 ℃ to obtain zinc melt; step S3, in-furnace melt treatment: when the temperature of the zinc melt reaches 530-580 ℃, blowing a first refining agent into the zinc melt by using a first inert gas to perform first furnace refining, and performing first standing to obtain a first refined melt; feeding the first refined melt into a heat preservation furnace, blowing a second refining agent into the first refined melt by using a second inert gas to perform second furnace refining, and then performing second standing to obtain a second refined melt; step S4, online melt processing: releasing when the temperature of the second refined melt is more than or equal to 550 ℃, and sequentially carrying out online degassing and online filtering to obtain a zinc purified melt; step S5, casting: and (3) conveying the zinc purified melt into a crystallizer for casting, wherein the casting temperature is 450-550 ℃, the initial casting speed is 15-30 mm/min, the stable production casting speed is 35-50 mm/min, the flow rate of cooling water in the crystallizer is 40-65 m 3/h, and the temperature of the cooling water is less than or equal to 28 ℃, so that the zinc alloy cast ingot is obtained.
In the zinc alloy cast ingot component, the Cu content is 0.05-0.3%, and the Cu in the range can form epsilon phase (CuZn 4) with zinc, so that the strength, the hardness and the fluidity of the zinc alloy are improved, the corrosion resistance and the processing performance of the zinc alloy are improved, the corrosion resistance of the zinc alloy cast ingot in a humid or corrosive environment is improved, the oxidation tendency of the alloy is reduced, the zinc alloy sheet obtained by the zinc alloy cast ingot is further applied to the field of buildings, and in addition, the addition of Cu is beneficial to improving the processing performance of the zinc alloy cast ingot. When the Cu content is less than 0.05%, the strength of the zinc alloy ingot is poor, the zinc alloy ingot is easy to deform or crack under stress, the corrosion resistance is low, the zinc alloy ingot is easy to be influenced by corrosion and oxidation, and the zinc alloy ingot is difficult to process by casting and other processes in the preparation process of the zinc alloy ingot. When the Cu content is more than 0.3%, on one hand, the cost of the zinc alloy cast ingot is increased, and on the other hand, the dimensional stability of the cast ingot and subsequent products is affected.
The addition of Al in a specific content range in the zinc alloy ingot casting component is also beneficial to improving the strength, hardness, corrosion resistance and processability of the zinc alloy. However, if the Al content is too high, the alloy structure is eutectoid (alpha+beta) phase and eutectoid beta phase, segregation transformation does not occur when the cooling rate is high, and the metastable alpha phase is easy to decompose, so that the dimensional stability of the zinc alloy product is affected.
The addition of Fe is not only beneficial to improving the hardness, strength and corrosion resistance of the zinc alloy cast ingot, but also can effectively reduce the melting point of the zinc alloy, so that the zinc alloy cast ingot is easier to process and mold. However, when the content of Fe is too large, coarse β -phase in the form of flakes or laths is formed at grain boundaries, and strength and formability of the alloy are lowered.
The components in the zinc alloy cast ingot are mutually cooperated, and the obtained zinc alloy has certain strength and good forming performance.
In the preparation process of the zinc alloy ingot, raw materials are heated to 520-620 ℃ in a smelting furnace, so that each element is fully melted, and a zinc melt is obtained. When the temperature of the zinc melt reaches 530-580 ℃, a first refining agent is blown into the zinc melt by using a first inert gas to perform first furnace refining, and the process can not only enable various raw materials to be fully melted and uniformly mixed to form uniform alloy liquid, but also effectively exhaust and remove impurities, remove hydrogen and impurities (such as aluminum oxide, zinc oxide and the like) in the zinc alloy, is favorable for reducing air holes and impurities in the zinc alloy cast ingot, and is further favorable for improving the purity, quality and mechanical property of the zinc alloy cast ingot.
Secondly, carrying out first standing on the melt, on one hand, effectively floating up and overflowing residual gas in the melt, thereby achieving the purpose of eliminating bubbles; on the other hand, zinc alloy grains can be gradually grown until the zinc alloy grains are in a uniform and stable state; in addition, the first standing process is also beneficial to releasing the stress in the alloy, so that the phenomena of deformation, cracking and the like of the zinc alloy cast ingot can be avoided.
And then, the first refined melt obtained after the first standing is sent into a heat preservation furnace, and the second furnace refining is carried out in the same mode, so that oxides, gases and impurities in the alloy can be further removed, the purity and uniformity of the alloy are improved, and the mechanical property and quality of the zinc alloy can be further improved. And then carrying out second standing on the melt to uniformly distribute the temperature of the alloy, thereby being beneficial to improving the uniformity and stability of the internal tissue structure of the alloy and further being beneficial to improving the mechanical property of the zinc alloy.
The invention is particularly limited to refining when the temperature of the zinc melt reaches 530-580 ℃, the fluidity of the zinc alloy melt is suitable in the temperature range, the later-stage forming and processing are convenient, the growth speed of zinc alloy crystal grains is suitable, the crystal grains are uniform, in addition, the refining agent can react with harmful elements and slag in the melt in the temperature range, thereby being beneficial to obtaining a purified melt and effectively exhausting air. However, if the temperature is too high, the oxidation speed of the zinc alloy can be increased, so that an oxide layer is generated on the surface of the alloy, the appearance and performance of the alloy are affected, deformation or crack generation of the zinc alloy in the refining process is also caused, the forming and processing performance of a zinc alloy cast ingot are affected, in addition, impurities and partial elements in the alloy are quickly volatilized, the components of the zinc alloy are unstable, and the mechanical property of the cast ingot is affected. If the temperature is too low, alloy components (such as copper and the like) cannot be completely melted, the formation process of crystal grains is slow, the crystal grains are coarsened, partial impurities (such as aluminum oxide, zinc oxide and the like) and residual gases cannot be effectively removed, so that pores and cracks exist in the zinc alloy, and the mechanical property, purity, density and strength of the zinc alloy cast ingot are affected.
And properly regulating the temperature in the standing process, releasing when the temperature of the melt is more than or equal to 550 ℃, and sequentially carrying out online degassing and online filtering to obtain the zinc purified melt. The online degassing is carried out, so that the residual gas in the zinc alloy can be effectively removed, bubbles are avoided in the subsequent processing process, and the quality and mechanical properties of the zinc alloy cast ingot are improved. The impurities and solid particles in the alloy can be removed by online filtration, so that the purity of the alloy can be improved, the distribution of each component can be more uniform, and the mechanical property of the zinc alloy cast ingot can be improved. In consideration of that the tapping temperature not only directly affects the casting performance of the alloy, but also affects the hardness and strength of the alloy, the inventor obtains a specific tapping temperature range through multiple tests and combining the specific zinc alloy ingot casting components of the invention. If the releasing temperature is less than 550 ℃, the fluidity of the zinc alloy melt can be obviously reduced, the melt is excessively viscous in the casting process, even the casting failure can be caused, the defects of looseness, air holes and the like exist in the cast ingot, the tissue continuity of the cast ingot is damaged, and the mechanical property of the alloy is deteriorated.
And finally, conveying the zinc purified melt into a crystallizer for casting, wherein the casting temperature is 450-550 ℃, the initial casting speed is 15-30 mm/min, and the casting speed is 35-50 mm/min. Under the condition, the strength of the zinc alloy cast ingot solidified shell is moderate enough to support the core melt so as to smoothly complete the casting process. The flow of cooling water in the crystallizer is 40-65 m 3/h, the temperature of the cooling water is less than or equal to 28 ℃, under the condition, the cooling intensity of each part of the cast ingot tends to be uniform, the melt flows steadily, the obtained cast ingot has uniform and fine microstructure, the surface of the cast ingot is smooth, the inside is compact, the defects of looseness, shrinkage cavity and the like are avoided, the yield of the cast ingot can be effectively improved, stable cast ingot conditions are provided for the subsequent plate processing, and in addition, even if the cast ingot is used for preparing zinc alloy cast ingots with larger specifications, the cooling speed of the melt is relatively high, and the production efficiency can be remarkably improved.
In order to further improve the synergistic effect among the components, the strength and the hardness of the alloy cast ingot are more beneficial to improvement, and in a preferred embodiment, the zinc alloy cast ingot comprises the following components in percentage by mass: 0.05-0.15% of Cu, 3-4% of Al, 0.05-0.1% of Fe, and the balance of Zn and unavoidable impurities.
In a preferred embodiment, in step S1, the raw materials include zinc ingots, aluminum copper master alloys, aluminum ingots. The raw materials are wider in sources and easier to obtain.
In order to enable the components of the ingot to be more fully melted and further facilitate uniform grain growth, in a preferred embodiment, in step S2, the heating temperature is 530-580 ℃.
In a preferred embodiment, in step S3, when the temperature of the zinc melt reaches 530 to 560 ℃, the first refining agent is blown into the zinc melt by using the first inert gas. Under the above conditions, the fluidity of the zinc melt is more suitable and the crystal grains are more uniform. In order to enable the refining agent to react with harmful elements and slag in the melt more fully, so that the exhaust and slag removal are facilitated, in a preferred embodiment, the blowing time of the first inert gas is 10-25 min; and/or the first standing time is 15-30 min. In a preferred embodiment, the first refined melt is fed into the holding furnace in the form of launder introduction.
In order to further effectively remove oxides, impurities and gases in the alloy and enable the internal tissue structure of the alloy to be more uniform and stable, in a preferred embodiment, the blowing time of the second inert gas is 10-20 min; and/or the second standing time is 15-20 min.
In a preferred embodiment, the first refining agent and the second refining agent are each independently one or more of hexachloroethane, zinc chloride, and ammonium chloride; and/or the first refining agent accounts for 0.1-0.4% of the weight of the raw materials; and/or the second refining agent accounts for 0.1-0.3% of the total amount of the refining agents; preferably, the refining agent is in powder form. Under the above conditions, the refining agent can react more effectively with impurities in the alloy, and is more beneficial to forming volatile compounds (such as hydrogen chloride and the like), thereby being more convenient for removing the impurities.
In order to further make the grain size of the zinc alloy uniform and fine, thereby being more beneficial to improving the mechanical properties of the alloy, in a preferred embodiment, in step S4, the second refined melt is released when the temperature is 550-570 ℃. In a preferred embodiment, the on-line degassing is performed with a third inert gas; and/or the on-line degassing device is selected from a single-rotor degassing machine, a double-rotor degassing machine or a three-rotor degassing machine; when the on-line degassing equipment is a double-rotor degassing machine, the rotating speed of the rotor is 400-600 rpm; and/or the on-line filtering equipment is a plate type filtering box and/or deep bed filtering; the plate type filter box is a two-stage plate type filter box. Under the above conditions, bubbles and impurities in the alloy can be removed more effectively, and the production efficiency is higher.
In a preferred embodiment, the first inert gas, the second inert gas, the third inert gas are each independently selected from argon and/or nitrogen. The inert gas under the conditions can effectively prevent the zinc alloy from reacting with oxygen in the air, so that the generation of oxides can be effectively avoided, the quality and purity of the alloy are further improved, and the generation of waste materials can be effectively reduced.
In a preferred embodiment, in step S5, the zinc purge melt is fed into the crystallizer in the form of a distribution launder. In order to further ensure the strength of the solidified shell of the zinc alloy ingot during casting, which is sufficient to support the core melt, in a preferred embodiment the casting temperature is 450-530 ℃. In a preferred embodiment, the initial casting speed is 18-25 mm/min; and/or stably producing the casting speed of 37-48 mm/min. Under the conditions, the production speed is stable and rapid, the situation of melt leakage is not easy to occur, and the forging process is smoother.
In a preferred embodiment, in the step S5, the flow rate of the cooling water is 43-61 m 3/h; and/or the temperature of the cooling water is 20-27 ℃. Under the above conditions, the cooling intensity of each part of the cast ingot tends to be more uniform in the casting process, the microstructure of the cast ingot is more uniform and fine, the surface of the cast ingot is flat, and the inside of the cast ingot is more compact.
In yet another exemplary embodiment of the present invention, there is also provided a zinc alloy ingot prepared by the above-described preparation method. The microstructure of the cast ingot is uniform and fine, the surface of the cast ingot is flat, the inside of the cast ingot is compact, and the cast ingot has no defects of looseness, shrinkage cavity and the like.
In a preferred embodiment, the zinc alloy ingot has a grain average size of < 100 μm and a grain maximum size of < 150 μm.
The zinc alloy plate prepared from the zinc alloy cast ingot has excellent strength, hardness and corrosion resistance, has uniform and fine microstructure, has smooth surface and compact interior, has no defects of looseness, shrinkage cavity and the like, and can be used as a building curtain wall and a roof.
Typically, but not limited to, in the composition of the zinc alloy ingot, cu is 0.05%, 0.07%, 0.1%, 0.13%, 0.15%, 0.2%, 0.23%, 0.25%, 0.3% or any two thereof by mass percent, al is 0.05%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, 0.7%, 0.8%, 0.9%, 1%, 1.8%, 2%, 2.4%, 3%, 3.2%, 3.4%, 3.5%, 3.6%, 3.8%, 4% or any two thereof by mass percent, and Fe is 0.05%, 0.06%, 0.07%, 0.08%, 0.09%, 0.1%, 0.11%, 0.12%, 0.13%, 0.14%, 0.15% or any two thereof by mass percent.
Typically, but not limited to, in step S2, the heating temperature is 520 ℃, 530 ℃, 540 ℃, 545 ℃, 550 ℃, 553 ℃, 555 ℃, 560 ℃, 570 ℃, 580 ℃, 600 ℃, 620 ℃ or any two values thereof.
Typically, but not limited to, in step S3, when the first refining agent is blown into the zinc melt by the first inert gas, the temperature of the zinc melt is 530 ℃, 540 ℃, 545 ℃, 550 ℃, 553 ℃, 555 ℃, 560 ℃, 570 ℃, 580 ℃, or a range of values consisting of any two of the values thereof.
Typically, but not limited to, in step S4, the temperature of the second refined melt at the time of tapping is 550 ℃, 553 ℃, 555 ℃, 560 ℃, 570 ℃, or any two values thereof.
Typically, but not limited to, in step S5, the casting temperature is 450 ℃, 470 ℃, 490 ℃, 510 ℃, 530 ℃, 540 ℃, 550 ℃ or any two of them, the initial casting speed 15 mm/min、18 mm/min、19 mm/min、20 mm/min、21 mm/min、22 mm/min、23 mm/min、24 mm/min、25 mm/min、28 mm/min、30mm/min or any two of them is set to be a range of values for 35 mm/min、36 mm/min、37 mm/min、38 mm/min、39 mm/min、40 mm/min、41 mm/min、42 mm/min、43 mm/min、44 mm/min、45 mm/min、46 mm/min、47 mm/min、48 mm/min、49 mm/min、50mm/min or any two of them.
Typically, but not limited to, in step S5, the flow rate of the cooling water in the mold is 40 m3/h、43 m3/h、45 m3/h、47 m3/h、50 m3/h、55 m3/h、58 m3/h、60 m3/h、61 m3/h、62 m3/h、65m3/h or a range of any two values thereof, and the temperature of the cooling water is 20 ℃, 21 ℃, 22 ℃, 23 ℃,24 ℃, 25 ℃, 26 ℃, 27 ℃, 28 ℃ or a range of any two values thereof.
Typically, but not by way of limitation, zinc alloy ingots have average grain sizes ranging from 85 μm, 90 μm, 95 μm, 100 μm or any two thereof, and maximum grain sizes ranging from 126 μm, 130 μm, 135 μm, 140 μm, 145 μm, 150 μm or any two thereof.
The application is described in further detail below in connection with specific examples which are not to be construed as limiting the scope of the application as claimed.
Unless otherwise specified, "%" in the following examples and comparative examples means weight percent.
Example 1
S1, selecting raw materials: according to the component proportions of zinc alloy cast ingots (Al=3.5%, fe=0.08%, cu=0.07%, and the balance of Zn and unavoidable impurities), weighing pure zinc ingots, aluminum-copper intermediate alloys, industrial pure aluminum ingots and iron fluxes.
S2, smelting: adding pure zinc ingot, aluminum-copper intermediate alloy, industrial pure aluminum ingot and iron flux into a smelting furnace, and heating to 550 ℃ to obtain zinc melt.
S3, in-furnace melt treatment: when the temperature of the zinc melt reached 545 ℃, furnace refining was performed, a powdery ammonium chloride refining agent (mass is 0.2% of the total mass of the raw materials) was added to a refining tank, ar gas with a purity of more than 99% was blown into the zinc melt to perform primary furnace refining for 20min, and then, standing for 30min, to obtain a primary refined melt. And (3) introducing the molten iron into a heat preservation furnace through a launder, blowing a second refining agent into the first refined melt by using a second inert gas to perform secondary furnace refining, wherein the blowing time is 10min, and then standing for 15min to obtain a second refined melt.
S4, online melt processing: when the temperature of the second refined melt reaches 560 ℃, discharging, and sequentially carrying out online degassing and online filtering through an online double-rotor degassing machine and an online filtering box to obtain a zinc purified melt; wherein, the gas for degassing adopts Ar gas with purity more than 99 percent, the rotating speed of the rotor is 410 rpm, and the online filter box adopts 40-mesh and 60-mesh double-stage plate type filtration.
S5, casting: and (3) enabling the zinc purified melt to flow into a crystallizer through a distribution launder to start casting, wherein the casting temperature is 540 ℃, the initial casting speed is 28mm/min, the stable production casting speed is 47mm/min, the cooling water flow of the crystallizer is 62m 3/h, and the cooling water temperature is 27 ℃, so that the zinc alloy cast ingot is obtained. The zinc alloy cast ingot is used for preparing the zinc alloy plate, and is used in the field of construction.
The distribution diagram of zinc alloy cast ingot crystal grains is shown in fig. 1, and the microstructure diagram of zinc alloy cast ingot is shown in fig. 2.
Example 2
S1, selecting raw materials: weighing pure zinc ingot, aluminum copper master alloy, industrial pure aluminum ingot and iron flux according to the component proportion (Al=2.4%, fe=0.1%, cu=0.23%, and the balance of Zn and unavoidable impurities) of the zinc alloy ingot.
S2, smelting: adding pure zinc ingot, aluminum-copper intermediate alloy, industrial pure aluminum ingot and iron flux into a smelting furnace, and heating at 540 ℃ to obtain zinc melt.
S3, in-furnace melt treatment: when the temperature of the zinc melt reached 540 ℃, furnace refining was performed, a powdery ammonium chloride refining agent (mass is 0.4% of the total mass of the raw materials) was added to a refining tank, ar gas with a purity of more than 99% was blown into the zinc melt to perform first furnace refining for 15min, and then left to stand for 20min, to obtain a first refined melt. And (3) introducing the molten iron into a heat preservation furnace through a launder, blowing a second refining agent into the first refined melt by using a second inert gas to perform secondary furnace refining, wherein the blowing time is 20min, and then standing for 20min to obtain a second refined melt.
S4, online melt processing: when the temperature of the second refined melt reaches 555 ℃, discharging, and sequentially carrying out online degassing and online filtering through an online double-rotor degassing machine and an online filtering box to obtain a zinc purified melt; wherein, the gas for degassing adopts Ar gas with purity more than 99 percent, the rotating speed of the rotor is 560 rpm, and the online filter box adopts 40-mesh and 60-mesh double-stage plate type filtration.
S5, casting: and (3) enabling the zinc purified melt to flow into a crystallizer through a distribution launder to start casting, wherein the casting temperature is 460 ℃, the initial casting speed is 18mm/min, the stable production casting speed is 36 mm/min, the cooling water flow rate of the crystallizer is 43m 3/h, and the cooling water temperature is 20 ℃, so that the zinc alloy cast ingot is obtained. The zinc alloy cast ingot is used for preparing the zinc alloy plate, and is used in the field of construction.
Example 3
S1, selecting raw materials: weighing pure zinc ingot, aluminum copper master alloy, industrial pure aluminum ingot and iron flux according to the component proportion (Al=1.8%, fe=0.1%, cu=0.13%, and the balance of Zn and unavoidable impurities) of the zinc alloy ingot.
S2, smelting: adding pure zinc ingot, aluminum-copper intermediate alloy, industrial pure aluminum ingot and iron flux into a smelting furnace, heating to 560 ℃ to obtain zinc melt.
S3, in-furnace melt treatment: when the temperature of the zinc melt reached 530 ℃, furnace refining was performed, a powdery ammonium chloride refining agent (mass is 0.35% of the total mass of the raw materials) was added to a refining tank, ar gas with a purity of more than 99% was blown into the zinc melt to perform first furnace refining for 20min, and then, standing for 30min, to obtain a first refined melt. And (3) introducing the molten iron into a heat preservation furnace through a launder, blowing a second refining agent into the first refined melt by using a second inert gas to perform secondary furnace refining, wherein the blowing time is 10min, and then standing for 20min to obtain a second refined melt.
S4, online melt processing: when the temperature of the second refined melt reaches 553 ℃, discharging, and sequentially carrying out online degassing and online filtering through an online double-rotor degassing machine and an online filtering box to obtain a zinc purified melt; wherein, the gas for degassing adopts Ar gas with purity more than 99 percent, the rotating speed of the rotor is 470 rpm, and the online filter box adopts 40-mesh and 50-mesh double-stage plate type filtration.
S5, casting: and (3) enabling the zinc purified melt to flow into a crystallizer through a distribution launder to start casting, wherein the casting temperature is 510 ℃, the initial casting speed is 25 mm/min, the stable production casting speed is 50 mm/min, the cooling water flow rate of the crystallizer is 58m 3/h, and the cooling water temperature is 20 ℃, so that the zinc alloy cast ingot is obtained. The zinc alloy cast ingot is used for preparing the zinc alloy plate, and is used in the field of construction.
Examples 4 to 7
The only difference from example 1 is that:
The contents of the components of the zinc alloy cast ingot are different, and the specific contents of the components are shown in table 1.
Example 8
The only difference from example 1 is that:
The raw materials are different in types and comprise zinc ingots, electrolytic copper blocks, aluminum ingots and iron fluxes.
Example 9
The only difference from example 1 is that:
In step S2, the heating temperature was 530 ℃.
In step S3, when the temperature of the zinc melt reaches 530 ℃, a first furnace refining is performed.
Example 10
The only difference from example 1 is that:
In step S2, the heating temperature was 620 ℃.
In step S3, when the temperature of the zinc melt reached 580 ℃, a first furnace refining was performed.
Example 11
The only difference from example 1 is that:
In step S2, the heating temperature was 580 ℃.
In step S3, when the temperature of the zinc melt reached 560 ℃, a first furnace refining was performed.
Example 12
The only difference from example 1 is that:
In step S2, the heating temperature was 530 ℃.
In step S3, when the temperature of the zinc melt reaches 530 ℃, a first furnace refining is performed.
Example 13
The only difference from example 1 is that:
in step S4, when the temperature of the second refined melt is 550 ℃, the second refined melt is released.
In step S5, the casting temperature was 450 ℃.
Example 14
The only difference from example 1 is that:
in step S4, when the temperature of the second refined melt is 550 ℃, the second refined melt is released.
In step S5, the casting temperature was 550 ℃.
Example 15
The only difference from example 1 is that:
In step S4, when the temperature of the second refined melt is 570 ℃, releasing.
In step S5, the casting temperature was 530 ℃.
Example 16
The only difference from example 1 is that:
In step S4, when the temperature of the second refined melt is 570 ℃, releasing.
In step S5, the casting temperature was 450 ℃.
Example 17
The only difference from example 1 is that:
In step S5, the initial casting speed is 15 mm/min, and the stable production casting speed is 50 mm/min.
Example 18
The only difference from example 1 is that:
In step S5, the initial casting speed is 30 mm/min, and the stable production casting speed is 35 mm/min.
Example 19
The only difference from example 1 is that:
In step S5, the initial casting speed was 18 mm/min, and the stable production casting speed was 37mm/min.
Example 20
The only difference from example 1 is that:
in step S5, the initial casting speed was 25mm/min, and the stable production casting speed was 48 mm/min.
Example 21
The only difference from example 1 is that:
In step S5, the flow rate of cooling water in the crystallizer is 40m 3/h, and the temperature is 28 ℃.
Example 22
The only difference from example 1 is that:
In step S5, the flow rate of cooling water in the crystallizer is 65m 3/h, and the temperature is 28 ℃.
Example 23
The only difference from example 1 is that:
In step S5, the flow rate of cooling water in the crystallizer is 60m 3/h, and the temperature is 27 ℃.
Example 24
The only difference from example 1 is that:
In step S5, the flow rate of cooling water in the crystallizer is 43m 3/h, and the temperature is 20 ℃.
Comparative example 1
The only difference from example 1 is that:
the method for preparing the zinc alloy cast ingot by adopting a conventional metal mold gravity casting method comprises the following steps:
S1, selecting raw materials: according to the component proportions of zinc alloy cast ingots (Al=3.5%, fe=0.08%, cu=0.07%, and the balance of Zn and unavoidable impurities), weighing pure zinc ingots, aluminum-copper intermediate alloys, industrial pure aluminum ingots and iron fluxes.
S2, smelting: adding pure zinc ingot, aluminum-copper intermediate alloy, industrial pure aluminum ingot and iron flux into a smelting furnace, heating to 610 ℃ to obtain zinc melt.
S3, in-furnace melt treatment: when the temperature of the zinc melt reached 570 ℃, furnace refining was performed, a powdery ammonium chloride refining agent (mass is 0.2% of the total mass of the raw materials) was added to a refining tank, ar gas with a purity of 99% was blown into the zinc melt to perform first furnace refining for 20min, and then, standing for 30min, to obtain a first refined melt. And (3) introducing the molten iron into a heat preservation furnace through a launder, blowing a second refining agent into the first refined melt by using a second inert gas to perform secondary furnace refining, wherein the blowing time is 10min, and then standing for 15min to obtain a second refined melt.
S4, casting: and when the temperature of the second refined melt reaches 540 ℃, discharging, and naturally cooling after the melt is poured into the ingot mould to obtain the zinc alloy ingot.
The internal defect diagram of the zinc alloy cast ingot is shown in fig. 3. It is known that a large amount of slag inclusion and holes exist in the zinc alloy ingot tissue, and the tissue continuity is poor. Because the melt is not treated on line before casting, the purity of the melt is not high, and a certain drop exists when the melt is poured into an ingot mould in the casting process, so that the phenomena of gas coiling and slag formation of the melt exist in the casting process, meanwhile, the cooling speed of the melt in the ingot mould is affected by the flow of the melt, the distribution is uneven, the cooling of a central area is very slow, and holes are easily generated due to incomplete feeding in the solidification process. The slag inclusion and the holes greatly destroy the tissue continuity of the cast ingot, and are extremely easy to bring adverse effects such as slag inclusion and cracking in the remelting or subsequent processing process of the cast ingot. Moreover, the melt casting temperature is lower, the fluidity of the melt is poorer, and the feeding is insufficient.
Comparative example 2
The only difference from example 1 is that:
In step S5, the casting temperature was 580 ℃.
In the casting process of zinc alloy cast ingots, melt leakage occurs and casting fails. The casting temperature is mainly too high, and the strength of the cast ingot solidified shell is insufficient to support the core melt, so that zinc liquid is leaked.
Comparative example 3
The only difference from example 1 is that:
In the step S5, the flow rate of the cooling water is 35m 3/h, and the temperature of the cooling water is 29 ℃.
Melt leakage occurs during the casting process of zinc alloy ingots, and casting fails. Mainly, the cooling water quantity is insufficient, the water temperature is higher, the cooling strength is insufficient, the strength of the cast ingot solidified shell is insufficient for supporting the core melt, and therefore the zinc liquid is leaked.
Comparative example 4
The only difference from example 1 is that:
In the step S5, the flow rate of the cooling water is 38 m 3/h, and the temperature of the cooling water is 20 ℃.
The distribution diagram of the crystal grain at the center of the zinc alloy cast ingot is shown in fig. 4. It is known that the microstructure uniformity of zinc alloy ingots is poor.
Comparative example 5
The only difference from example 1 is that:
in step S2, the raw material is heated to a temperature of 500 ℃.
Comparative example 6
The only difference from example 1 is that:
In step S3, the refining temperature was 515 ℃.
Comparative example 7
The only difference from example 1 is that:
in step S4, the second refined melt is released when the temperature is 534 ℃.
Comparative example 8
The only difference from example 1 is that:
In step S4, no on-line degassing and on-line filtering are performed.
Comparative example 9
The only difference from example 1 is that:
the temperature of the cooling water was 33 ℃.
The composition content of the zinc alloy ingots of examples 1 to 7 is shown in table 1, and the structure and grain size results of the zinc alloy ingots of the above examples and comparative examples are shown in table 2.
The testing method comprises the following steps:
Structural member air hole distribution: the photographs were taken under a metallographic microscope and observed.
Grain size: the grain size analysis was performed with reference to the standard GB/T6394-2017 method for detecting average grain size of metals.
TABLE 1
TABLE 2
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Compared with the comparative example, the zinc alloy ingot casting is prepared by limiting the components of the zinc alloy ingot casting in a specific range and adopting a semi-continuous casting method, the melt refining, degassing and standing treatment are respectively carried out in a smelting furnace and a heat preservation furnace, the purity of the melt is improved by on-line degassing and filtering, and the gas content and the slag content in the melt are reduced. In addition, the casting process parameters in the casting process are regulated, so that the structure of the zinc alloy cast ingot is uniform and fine. The cast ingot obtained by the preparation method disclosed by the invention has the advantages of uniform and fine structure, high density, no defects of air holes, looseness and the like, and the zinc alloy plate obtained by using the zinc alloy cast ingot has excellent mechanical properties and can be used as a building curtain wall and a roof. In addition, it can be seen that when all the technological parameters are within the preferred range of the invention, the structure of the zinc alloy cast ingot is more uniform and finer, and the compactness is higher.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (12)
1. The preparation method of the zinc alloy cast ingot is characterized in that the zinc alloy cast ingot comprises the following components in percentage by mass: 0.05-0.3% of Cu, 0.05-4% of Al, 0.05-0.15% of Fe, and the balance of Zn and unavoidable impurities; the preparation method comprises the following steps:
step S1, selecting materials: selecting raw materials according to the component proportion of the zinc alloy cast ingot;
Step S2, smelting: heating the raw materials in a smelting furnace at 520-620 ℃ to obtain zinc melt;
Step S3, in-furnace melt treatment: when the temperature of the zinc melt reaches 530-580 ℃, blowing a first refining agent into the zinc melt by using a first inert gas to perform first furnace refining, and performing first standing to obtain a first refined melt; feeding the first refined melt into a heat preservation furnace, blowing a second refining agent into the first refined melt by using a second inert gas to perform second furnace refining, and then performing second standing to obtain a second refined melt;
step S4, online melt processing: releasing when the temperature of the second refined melt is more than or equal to 550 ℃, and sequentially carrying out online degassing and online filtering to obtain a zinc purified melt;
Step S5, casting: and (3) conveying the zinc purified melt into a crystallizer for casting, wherein the casting temperature is 450-550 ℃, the initial casting speed is 15-30 mm/min, the stable production casting speed is 35-50 mm/min, the flow of cooling water in the crystallizer is 40-65 m 3/h, and the temperature of the cooling water is less than or equal to 28 ℃, so that the zinc alloy cast ingot is obtained.
2. The method according to claim 1, wherein,
The zinc alloy cast ingot comprises the following components in percentage by mass: 0.05-0.15% of Cu, 3-4% of Al, 0.05-0.1% of Fe, and the balance of Zn and unavoidable impurities.
3. The method according to claim 1 or 2, wherein in the step S2,
The heating temperature is 530-580 ℃.
4. The method according to claim 1 or 2, wherein in the step S3,
When the temperature of the zinc melt reaches 530-560 ℃, blowing the first refining agent into the zinc melt by using the first inert gas; and/or
The blowing time of the first inert gas is 10-25 min; and/or
The first standing time is 15-30 min; and/or
The first refined melt is fed into the holding furnace in a launder-in mode.
5. The method according to claim 1 or 2, wherein in the step S3,
The blowing time of the second inert gas is 10-20 min; and/or
And the second standing time is 15-20 min.
6. The process according to claim 1 or 2, wherein,
The first refining agent and the second refining agent are each independently one or more of hexachloroethane, zinc chloride and ammonium chloride; and/or the first refining agent accounts for 0.1-0.4% of the weight of the raw materials, and/or the second refining agent accounts for 0.1-0.3% of the weight of the raw materials.
7. The method according to claim 1 or 2, wherein in the step S4,
Releasing when the temperature of the second refined melt is 550-570 ℃; and/or
Carrying out on-line degassing by adopting a third inert gas; and/or
The on-line degassing equipment is selected from a single-rotor degassing machine, a double-rotor degassing machine or a three-rotor degassing machine; when the on-line degassing equipment is the double-rotor degassing machine, the rotating speed of the rotor is 400-600 rpm; and/or
The on-line filtering equipment is a plate type filtering box and/or deep bed filtering equipment; the plate type filter box is a two-stage plate type filter box.
8. The method according to claim 7, wherein,
The first inert gas, the second inert gas and the third inert gas are respectively and independently selected from argon and/or nitrogen.
9. The method according to claim 1 or 2, wherein in the step S5,
The way of feeding the zinc purified melt into the crystallizer is a distribution launder; and/or
The casting temperature is 450-530 ℃; and/or
The initial casting speed is 18-25 mm/min; and/or
And the casting speed of stable production is 37-48 mm/min.
10. The method according to claim 1 or 2, wherein in the step S5,
The flow rate of the cooling water is 43-61 m 3/h; and/or
The temperature of the cooling water is 20-27 ℃.
11. A zinc alloy ingot prepared by the preparation method of any one of claims 1 to 10.
12. The zinc alloy ingot according to claim 11, characterized in that the zinc alloy ingot has a grain average size of < 100 μm and a grain maximum size of < 150 μm.
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