阅读说明：本技术 一种锌铝合金圆锭及其制备方法与应用、锌铝合金材料 (Zinc-aluminum alloy round ingot, preparation method and application thereof, and zinc-aluminum alloy material ) 是由 李新涛 刘明阳 周楠 于 2020-06-23 设计创作，主要内容包括：本发明公开了一种锌铝合金圆锭及其制备方法与应用、锌铝合金材料,属于合金技术领域。按质量百分数计,其化学成分包括小于0.05％且大于0的Ti和小于0.05％且大于0的B中的至少一种以及3.5-28.5％的Al、0.01-0.5％的Mg、0.5-3.5％的Cu、小于0.1％的Fe,余量为Zn。含上述含量的Ti和/或B,可有效细化圆锭的凝固组织,降低粗大晶粒的生成,减少气孔。采用垂直半连续铸造,能有效保证圆锭组织的均匀性,避免合金元素在圆锭的径向上发生重力偏析,并有利于防止粗大晶粒生成以及降低铸坯中出现气孔、夹渣等缺陷。该锌铝合金圆锭可用于制备锌铝合金材料,使其具有较佳的力学和耐腐蚀性能。(The invention discloses a zinc-aluminum alloy round ingot, a preparation method and application thereof, and a zinc-aluminum alloy material, and belongs to the technical field of alloys. The chemical composition comprises, by mass percent, at least one of Ti less than 0.05% and more than 0 and B less than 0.05% and more than 0, and 3.5-28.5% of Al, 0.01-0.5% of Mg, 0.5-3.5% of Cu, less than 0.1% of Fe, and the balance of Zn. The Ti and/or B with the content can effectively refine the solidification structure of the round ingot, reduce the generation of coarse grains and reduce pores. The vertical semi-continuous casting is adopted, so that the uniformity of the round ingot structure can be effectively ensured, the gravity segregation of alloy elements in the radial direction of the round ingot is avoided, and the generation of coarse grains is favorably prevented, and the defects of air holes, slag inclusion and the like in a casting blank are reduced. The zinc-aluminum alloy round ingot can be used for preparing a zinc-aluminum alloy material, so that the zinc-aluminum alloy round ingot has better mechanical and corrosion resistance properties.)

1. The zinc-aluminum alloy round ingot is characterized in that the chemical composition of the zinc-aluminum alloy round ingot comprises, by mass percent, less than 0.05% and more than 0% of Ti and less than 0.05% and more than 0% of B, 3.5-28.5% of Al, 0.01-0.5% of Mg, 0.5-3.5% of Cu, less than 0.1% of Fe, and the balance of Zn.

2. The round zinc-aluminum alloy ingot according to claim 1, wherein the chemical composition of the round zinc-aluminum alloy ingot comprises 11.5-28.5% of Al, 0.01-0.35% of Mg, 0.8-3.5% of Cu, less than 0.1% of Fe, less than or equal to 0.05% and greater than 0 of Ti, and less than or equal to 0.05% and greater than 0 of B, and the balance of Zn;

preferably, the diameter of the zinc-aluminum alloy round ingot is 80-320 mm.

3. The method for producing a zinc-aluminum alloy round ingot according to claim 1 or 2, comprising the steps of: and (3) carrying out vertical semi-continuous casting on the melt with the chemical composition.

4. The method of claim 3, wherein the conditions for vertical semi-continuous casting include: the casting speed is 80-200mm/min, the temperature of the melt in the casting process is 480-550 ℃, and the cooling water flow of each ingot is 1.5-4.5m³The temperature of cooling water is 10-35 ℃;

preferably, the vertical semi-continuous casting is carried out in a hot top crystallizer with a heat-retaining cap.

5. The method of claim 3, wherein the melt is prepared by essentially: and smelting the raw materials which are prepared according to the chemical components.

6. The method of manufacturing of claim 5, wherein smelting comprises: mixing the raw materials for 5-10min at the temperature of 500-580 ℃;

preferably, the mixing is carried out under stirring conditions;

preferably, the smelting is carried out in a resistance furnace.

7. The production method according to claim 5 or 6, further comprising degassing refining the melt after the melting.

8. The preparation method as claimed in claim 7, wherein the degassing refining is aeration refining at 580 ℃ for 5-15 min;

preferably, the gas used in the refining process comprises nitrogen or argon;

preferably, the purity of the gas is not less than 99.995%;

preferably, before the vertical semi-continuous casting, the method further comprises the step of standing the refined melt for 15-30min at the temperature of 500-580 ℃;

preferably, the method further comprises filtering the melt after standing, and then vertically and semi-continuously casting;

preferably, the means for filtering comprises an in-line filter means, further preferably a plate filter means having a ceramic filter plate;

preferably, the ceramic filter plate has a size of 30-40 ppi.

9. Use of a zinc-aluminium alloy round ingot according to claim 1 or 2 for the preparation of a zinc-aluminium alloy material;

preferably, the zinc-aluminum alloy material comprises a zinc-aluminum alloy wire, a zinc-aluminum alloy bar or a zinc-aluminum alloy wire.

10. A zinc-aluminum alloy material, characterized in that the zinc-aluminum alloy material is processed from a zinc-aluminum alloy round ingot as claimed in claim 1 or 2;

preferably, the zinc-aluminum alloy material comprises a zinc-aluminum alloy wire, a zinc-aluminum alloy bar or a zinc-aluminum alloy wire.

Technical Field

The invention relates to the technical field of alloys, in particular to a zinc-aluminum alloy round ingot, a preparation method and application thereof, and a zinc-aluminum alloy material.

Background

The zinc-aluminum alloy has good mechanical property and corrosion resistance, low melting point and good fluidity, is often processed into wires, wires or bars, is widely applied to the field of corrosion resistance, and is used for carrying out thermal spraying treatment on steel plates or products needing surface corrosion resistance treatment. Meanwhile, zinc and aluminum have the characteristics of good wear resistance, low friction coefficient, strong affinity to oil and the like, and can be used for manufacturing wear-resistant materials instead of copper alloys.

The zinc-aluminum alloy wire, wire and rod is produced through extrusion, drawing or post-extrusion drawing of cast round ingot. At present, the zinc-aluminum alloy round ingot has two main production modes: 1) and (5) casting by using an iron mold. After the zinc-aluminum alloy is melted in the furnace, the alloy liquid is cast into an iron mould one by adopting a manual casting method for cooling and forming. The method has low production efficiency, the produced round ingot has a plurality of defects such as slag inclusion, air holes and the like, the sawing and surface peeling quantity of the two ends of the round ingot are large, and the metal utilization rate is low. 2) And (4) horizontally continuously casting. The main defects of the production mode are that the production mode is influenced by gravity, the elements such as aluminum, copper and the like in the melt generate gravity segregation due to the density inconsistency with zinc, so that the upper part and the lower part of the blank have inconsistent components, the component segregation defect is serious, and the production of large-size round ingots is particularly obvious. Because the round ingot has the casting defects, the breakage rate is high in the subsequent deformation processing process, and the production efficiency is seriously influenced.

In view of this, the invention is particularly proposed.

Disclosure of Invention

One of the objects of the present invention is to provide a zinc-aluminum alloy ingot having a uniform structure and substantially no coarse grains, pores, slag inclusions, and the like.

The second purpose of the invention is to provide a preparation method of the zinc-aluminum alloy round ingot, which is simple, easy to operate, high in yield and high in production efficiency, and can effectively solve the gravity segregation problem of the existing round ingot.

The third object of the present invention includes providing an application of the above-mentioned zinc-aluminum alloy round ingot, such as can be used for preparing zinc-aluminum alloy materials.

The fourth object of the present invention is to provide a zinc-aluminum alloy material processed from the above-mentioned zinc-aluminum alloy round ingot.

The invention is realized by the following steps:

in a first aspect, the present application provides a zinc-aluminum alloy round ingot, whose chemical composition comprises, by mass, less than 0.05% and more than 0% of at least one of Ti and less than 0.05% and more than 0% of B, and 3.5 to 28.5% of Al, 0.01 to 0.5% of Mg, 0.5 to 3.5% of Cu, less than 0.1% of Fe, and the balance of Zn.

In an alternative embodiment, the chemical composition of the zinc-aluminum alloy round ingot comprises 11.5-28.5% of Al, 0.01-0.35% of Mg, 0.8-3.5% of Cu, less than 0.1% of Fe, less than or equal to 0.05% and more than 0% of Ti, and less than or equal to 0.05% and more than 0% of B, and the balance of Zn.

In an alternative embodiment, the diameter of the zinc-aluminium alloy round ingot is 80-320 mm.

In a second aspect, the present application also provides a method for preparing the aforementioned zinc-aluminum alloy round ingot, comprising the following steps: the melt with the chemical composition is subjected to vertical semi-continuous casting.

In an alternative embodiment, the conditions for vertical semi-continuous casting include: the casting speed is 80-200mm/min, the temperature of the melt in the casting process is 480-550 ℃, and the cooling water flow of each ingot is 1.5-4.5m³The temperature of the cooling water is 10-35 ℃.

In an alternative embodiment, the vertical semi-continuous casting is performed in a hot top crystallizer with a heat retention cap.

In an alternative embodiment, the melt is prepared by essentially the following steps: smelting the raw materials which are prepared according to the chemical components.

In an alternative embodiment, smelting comprises: mixing the raw materials at the temperature of 500-580 ℃ for 5-10 min.

In an alternative embodiment, the mixing is performed under agitation.

In an alternative embodiment, the smelting is carried out in a resistance furnace.

In an optional embodiment, degassing and refining are further carried out on the smelted melt.

In an alternative embodiment, the degassing refining is aeration refining at 500-580 deg.C for 5-15 min.

In alternative embodiments, the gas used in the refining process comprises nitrogen or argon.

In an alternative embodiment, the purity of the gas is no less than 99.995%.

In an alternative embodiment, before the vertical semi-continuous casting, the method further comprises standing the refined melt for 15-30min at the temperature of 500-580 ℃.

In an alternative embodiment, the method further comprises filtering the melt after standing, and then vertically and semi-continuously casting.

In an alternative embodiment, the means for filtering comprises an in-line filter device, further preferably a plate filter device having a ceramic filter plate.

In an alternative embodiment, the ceramic filter plate has a size of 30-40 ppi.

In a third aspect, the application also provides the application of the zinc-aluminum alloy round ingot in preparing a zinc-aluminum alloy material.

In alternative embodiments, the zinc-aluminum alloy material comprises a zinc-aluminum alloy wire, a zinc-aluminum alloy rod, or a zinc-aluminum alloy wire.

In a fourth aspect, the present application also provides a zinc-aluminum alloy material processed from the zinc-aluminum alloy round ingot.

In alternative embodiments, the zinc-aluminum alloy material comprises a zinc-aluminum alloy wire, a zinc-aluminum alloy rod, or a zinc-aluminum alloy wire.

The beneficial effect of this application includes:

the chemical composition of the zinc-aluminum alloy contains at least one of Ti of less than or equal to 0.05 wt% and more than 0 and B of less than or equal to 0.05 wt% and more than 0, so that the solidification structure of the round ingot can be effectively refined, the generation of coarse grains can be reduced, and pores can be reduced. Through carrying out perpendicular semicontinuous casting to the fuse-element that has the chemical composition that this application provided, can effectively guarantee the homogeneity that the round ingot was organized, avoid the alloying element to take place gravity segregation in the footpath of round ingot, still be favorable to preventing the formation of thick crystalline grain and reduce defects such as gas pocket, inclusion sediment in the casting blank simultaneously, effectively solve current mode preparation zinc-aluminium alloy round ingot product defect many and big specification round ingot gravity segregation serious scheduling problem. The zinc-aluminum alloy round ingot can be used for preparing a zinc-aluminum alloy material, so that the zinc-aluminum alloy round ingot has better mechanical and corrosion resistance properties.

Drawings

In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the embodiments will be briefly described below, it should be understood that the following drawings only illustrate some embodiments of the present invention and therefore should not be considered as limiting the scope, and for those skilled in the art, other related drawings can be obtained according to the drawings without inventive efforts.

FIG. 1 is a diagram of a zinc-aluminum alloy round ingot finished product provided in example 1;

FIG. 2 is a structural diagram of a Zn-Al alloy of a round Zn-Al alloy ingot according to example 1;

FIG. 3 is a diagram of a finished zinc-aluminum alloy round ingot provided in example 2;

FIG. 4 is a structural diagram of a Zn-Al alloy of the round Zn-Al alloy ingot according to example 2.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below. The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially.

The zinc-aluminum alloy round ingot provided by the application, the preparation method and the application thereof, and the zinc-aluminum alloy material are specifically explained below.

The application provides a zinc-aluminum alloy round ingot, which comprises the following chemical components of at least one of Ti with the mass percent of less than 0.05 percent and more than 0, B with the mass percent of less than 0.05 percent and more than 0, Al with the mass percent of 3.5-28.5 percent, Mg with the mass percent of 0.01-0.5 percent, Cu with the mass percent of 0.5-3.5 percent, Fe with the mass percent of less than 0.1 percent, and Zn with the balance.

That is, the chemical composition of the zinc-aluminum alloy round ingot can include Al, Mg, Cu, Fe and Ti in the above ranges, and the balance of Zn; al, Mg, Cu, Fe and B in the above ranges may be included, and the balance Zn; al, Mg, Cu, Fe, Ti and B in the above ranges may be included, and Zn may be the rest. In other words, the chemical composition of the zinc-aluminum alloy round ingot can selectively contain at least one of Ti and B.

Alternatively, the Al content therein may be 3.5 wt%, 5 wt%, 8 wt%, 11.5 wt%, 12.5 wt%, 15 wt%, 20 wt%, 25 wt%, or 28.5 wt%, etc., and may also be other values within a range of 3.5 to 28.5 wt%. In the application, Al mainly influences the fluidity and mechanical properties of the zinc-aluminum alloy, the content of Al is controlled to be 3.5-28.5 wt%, the melt fluidity is reduced when the content of Al is less than 3.5 wt%, the tensile strength and the elongation are reduced when the content of Al is more than 28.5 wt%, and the zinc-aluminum alloy is easy to crack during casting.

The Mg content may be 0.01 wt%, 0.02 wt%, 0.1 wt%, 0.15 wt%, 0.2 wt%, 0.25 wt%, 0.3 wt%, 0.35 wt%, 0.5 wt%, or the like, or may be other values within a range of 0.01 to 0.5 wt%. In the application, Mg mainly influences the mechanical property and the wear resistance of the zinc-aluminum alloy, and the content of Mg is controlled to be 0.01-0.5 wt%, and the content of Mg is higher than 0.5 wt% to cause the reduction of elongation and increase the thermal cracking property of the alloy.

The Cu content may be 0.5 wt%, 0.8 wt%, 1.3 wt%, 2 wt%, 3.5 wt%, etc., or may be other values in the range of 0.5 to 3.5 wt%. In the application, Cu mainly influences the strength and high-temperature creep property of the zinc-aluminum alloy, the content of Cu is controlled to be 0.5-3.5 wt%, the strength and hardness are not obviously improved when the content of Cu is less than 0.5-wt%, eutectoid transformation is difficult to fully perform when the content of Cu is more than 3.5 wt%, and the size of a round ingot is unstable.

The Fe content may be less than 0.1 wt% or further less than 0.085 wt%. In the application, Fe mainly influences the corrosion resistance of the zinc-aluminum alloy round ingot, and the content of Fe is controlled to be less than 0.1 wt% and higher than 0.1 wt% to cause FeZn₇And the like, to accelerate intergranular corrosion.

The contents of Ti and B are respectively less than or equal to 0.05 wt%, the Ti and B in the application mainly influence the performance of the solidification structure of the zinc-aluminum alloy round ingot, and the solidification structure of the round ingot can be effectively refined by adding the Ti and/or B in the content range. It is worth mentioning that if the content of Ti or B exceeds 0.05 wt%, fine segregation and agglomeration are easily caused. The zinc-aluminum alloy round ingot contains less than 0.05 wt% of Ti and less than 0.05 wt% of B, and compared with the zinc-aluminum alloy round ingot containing less than 0.05 wt% of Ti or less than 0.05 wt% of B, the solidification structure in the zinc-aluminum alloy round ingot is finer, and meanwhile, coarse grains and air holes can be reduced to a certain extent.

In a further alternative embodiment, the chemical composition of the zinc-aluminum alloy round ingot may include 11.5 to 28.5% of Al, 0.01 to 0.35% of Mg, 0.8 to 3.5% of Cu, less than 0.1% and greater than 0 of Fe, less than or equal to 0.05% and greater than 0 of Ti, and less than or equal to 0.05% and greater than 0 of B, with the balance being Zn.

In some specific embodiments, the chemical composition of the zinc-aluminum alloy round ingot comprises 11.5-12.5 wt% of Al, 0.02-0.35 wt% of Mg, 0.8-1.3 wt% of Cu, less than 0.085 wt% of Fe, and less than or equal to 0.05 wt% of Ti, and the balance of Zn.

In other specific embodiments, the chemical composition of the zinc-aluminum alloy round ingot comprises 25-28.5 wt% of Al, 0.01-0.02 wt% of Mg, 2-3.5 wt% of Cu, less than 0.1 wt% of Fe, less than or equal to 0.05 wt% of Ti, and less than or equal to 0.05 wt% of B, with the balance being Zn.

In alternative embodiments, the zinc-aluminum alloy round ingot provided by the present application is mainly a large-scale zinc-aluminum alloy round ingot, and the diameter thereof may be, for example, 80-320mm, such as 80mm, 100mm, 150mm, 200mm, 250mm, 300mm, or 320 mm.

Raw materials for providing the chemical components comprise pure zinc ingots, pure aluminum ingots, pure magnesium ingots, aluminum-copper intermediate alloys, aluminum-titanium intermediate alloys, aluminum-boron intermediate alloys and aluminum-titanium-boron intermediate alloys.

In addition, the application also provides a preparation method of the zinc-aluminum alloy round ingot, which comprises the following steps: the melt with the chemical composition is subjected to vertical semi-continuous casting.

In an alternative embodiment, the conditions for vertical semi-continuous casting essentially comprise: the casting speed is 80-200mm/min, the temperature of the melt in the casting process is 480-550 ℃, and the cooling water flow of each ingot is 1.5-4.5m³The temperature of the cooling water is 10-35 ℃.

Wherein the casting speed can be 80mm/min, 100mm/min, 120mm/min, 150mm/min, 180mm/min or 200mm/min, etc. The casting speed mainly influences the structure and the surface quality of the zinc-aluminum alloy, the casting speed is controlled to be 80-200mm/min in the application, defects such as surface roughness and segregation tumor are easily caused when the casting speed is lower than 80mm/min, and melt leakage and casting failure are easily caused when the casting speed is higher than 200 mm/min.

The temperature of the melt in the casting process can be 480 ℃, 500 ℃, 520 ℃ or 550 ℃ and the like, and the temperature of the melt in the casting process can mainly influence the forming quality of the zinc-aluminum alloy, wherein the temperature of the melt is controlled to be 480 ℃ or 550 ℃, the temperature is lower than 480 ℃ and is easy to cause cold shut, the melt is easy to solidify in a crystallizer and the like, and the temperature is higher than 550 ℃ and is easy to cause melt leakage and casting failure.

The cooling water flow rate of each ingot can be 1.5m³/h、2m³/h、2.5m³/h、3m³/h、3.5m³/h、4m³H or 4.5m³H, etc. the cooling water flow mainly influences the casting forming and the structure refining degree of the zinc-aluminum alloy, and the cooling water flow is controlled to be 1.5-4.5m³H, less than 1.5m³The/h is easy to cause melt leakage and thick structure which is higher than 4.5m³The/h easily leads to crystallizer water return.

The temperature of the cooling water can be 10 ℃, 15 ℃, 20 ℃, 25 ℃, 30 ℃ or 35 ℃, the temperature of the cooling water mainly influences the cooling effect of the zinc-aluminum alloy, and the temperature of the cooling water is controlled to be 10-35 ℃ in the application, and is higher than 35 ℃ to easily cause poor cooling effect.

In an alternative embodiment, the vertical semi-continuous casting is carried out in a hot top crystallizer with a heat-retaining cap. The melt may be introduced into the hot top crystallizer through a launder or a conduit, as referred to above.

On the bearing, the uniformity of the round ingot structure can be effectively ensured by adopting a vertical semi-continuous casting technology, and the gravity segregation of alloy elements in the radial direction of the round ingot is avoided; the casting blank is strongly cooled in the crystallizer, and the surface of the casting blank is directly covered by cooling water after the casting blank is discharged from the crystallizer, so that the generation of coarse grains is prevented; gas and slag in the melt are convenient to float upwards in the crystallizer in the casting process, and the defects of air holes, slag inclusion and the like in the casting blank can be reduced. In addition, the vertical semi-continuous casting technology also solves the problem of low material utilization rate in the conventional iron mold casting, the length of the prepared cast ingot can reach 6 meters, the removal amount of the head and the tail of the cast ingot is 0.2-0.3 meter, and the material utilization rate can reach 91.7% -95%.

In an alternative embodiment, the melt in the present application can be prepared essentially by: smelting the raw materials which are prepared according to the chemical components.

Smelting may be carried out in an electric resistance furnace, and the smelting process may include: mixing the raw materials at the temperature of 500-580 ℃ for 5-10 min. In the smelting process, the temperature is not suitable to be too high or too low, alloy elements such as Zn, Mg and the like are easy to volatilize when the temperature is too high, the melting efficiency is too low when the temperature is too low, and similarly, the time is not suitable to be too long or too short, the elements are easy to be insufficiently mixed when the temperature is too low, and the elements are easy to volatilize and oxidize seriously when the temperature is too long. Preferably, the mixing is carried out under stirring.

During smelting, the prepared pure zinc ingot, pure aluminum ingot and aluminum-copper intermediate alloy can be placed into a resistance furnace to be smelted, and the pure magnesium ingot and the aluminum-titanium intermediate alloy (or the aluminum-boron intermediate alloy or the aluminum-titanium-boron intermediate alloy) are added when the temperature reaches 500-550 ℃ for continuous smelting.

Further, in an optional embodiment, degassing refining is carried out on the smelted melt.

In an alternative embodiment, the degassing refining may be conducted for 5-15min at 500-580 deg.C. The gas used in the refining process includes nitrogen or argon, and the purity of the above gas is preferably not less than 99.995%.

In an optional embodiment, before the vertical semi-continuous casting, the method further comprises the step of standing the refined melt for 15-30min at the temperature of 500-580 ℃ so as to facilitate the floating of gas and inclusion.

Further, in an alternative embodiment, the method further comprises filtering the melt after standing, and then vertically and semi-continuously casting.

Wherein the means for filtering comprises an in-line filter device, preferably a plate filter device, which may for example be a plate filter device with ceramic filter plates. By reference, the ceramic filter plate may be sized to be 30-40ppi to effectively filter inclusions in the melt.

The yield of the zinc-aluminum alloy round ingot prepared by the method provided by the application is 92-94%, and the yield can be effectively improved compared with the prior art.

In addition, the application also provides the application of the zinc-aluminum alloy round ingot in preparing a zinc-aluminum alloy material and the zinc-aluminum alloy material obtained by corresponding processing.

In alternative embodiments, the zinc-aluminum alloy material may include zinc-aluminum alloy wire, zinc-aluminum alloy rod, or zinc-aluminum alloy wire. The zinc-aluminum alloy material can be formed by performing deformation processing such as extrusion, drawing or drawing after extrusion on a zinc-aluminum alloy round ingot. The obtained zinc-aluminum alloy material has better mechanical and corrosion resistance properties.

The features and properties of the present invention are described in further detail below with reference to examples.