CN115106492A - Method for preparing zinc alloy plate by boron microalloying-semi-solid continuous casting mode and product - Google Patents

Method for preparing zinc alloy plate by boron microalloying-semi-solid continuous casting mode and product Download PDF

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CN115106492A
CN115106492A CN202210446137.4A CN202210446137A CN115106492A CN 115106492 A CN115106492 A CN 115106492A CN 202210446137 A CN202210446137 A CN 202210446137A CN 115106492 A CN115106492 A CN 115106492A
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solid
zinc alloy
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李静媛
祁明凡
刘爱森
郝冰
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Center International Group Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc
    • C22C18/02—Alloys based on zinc with copper as the next major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22D—CASTING OF METALS; CASTING OF OTHER SUBSTANCES BY THE SAME PROCESSES OR DEVICES
    • B22D11/00—Continuous casting of metals, i.e. casting in indefinite lengths
    • B22D11/10—Supplying or treating molten metal
    • B22D11/11—Treating the molten metal
    • B22D11/112—Treating the molten metal by accelerated cooling
    • 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
    • C22C1/03—Making non-ferrous alloys by melting using master alloys
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22C—ALLOYS
    • C22C18/00—Alloys based on zinc

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Abstract

The invention provides a method for preparing a zinc alloy plate by boron microalloying-semisolid continuous casting and a product, wherein the method comprises the following steps: putting the alloy raw material for preparing Zn-Cu-Ti into a melting furnace, heating to 450-600 ℃, and completely melting; adding boron element into the melt in the form of intermediate alloy, and refining after the boron element is completely melted/dissolved; enabling the refined melt to flow through a cooling device, and cooling the melt to a semi-solid temperature range to obtain semi-solid slurry; the semi-solid slurry flowing out of the cooling device flows into a continuous casting machine, and a zinc alloy casting blank is obtained after rapid cooling; the obtained casting blank is continuously rolled to prepare the zinc alloy plate. The invention mainly relates to a method for preparing a zinc alloy plate by a boron microalloying-semi-solid continuous casting mode, which further refines and homogenizes epsilon-CuZn in the alloy plate in a Zn-Cu-Ti alloy 4 Phase and Zn 16 Ti phase, second phase epsilon-CuZn 4 Phase and Zn 16 The grain size of the Ti phase is less than 1 mu m, thereby improving the corrosion resistance of the zinc alloy plate.

Description

Method for preparing zinc alloy plate by boron microalloying-semi-solid continuous casting mode and product
Technical Field
The invention relates to the field of zinc alloy, in particular to a method for preparing a Zn-Cu-Ti alloy plate in a boron microalloying-semi-solid continuous casting mode.
Background
Zn-Cu-Ti alloy plate (Ti-Zn plate) is widely used in construction and decoration industry in developed countries in Europe and America from the seventies of the last century. Although the currently reported Zn-Cu-Ti alloy plate generally has a service life of more than 80 years in a common environment, the service life of the Zn-Cu-Ti alloy plate is shortened in severe environments such as coastal environments, saline-alkali environments and the like, and because the construction and the construction are difficult in the severe environments, the construction in the severe environments is generally expected to prolong the service life of the buildings in the severe environments; therefore, there is a need to develop a low-cost zinc alloy sheet for building roofs, which has better corrosion resistance than the current mainstream Zn-Cu-Ti alloy sheet, so that the zinc alloy sheet not only meets the European EN988 standard, but also has better corrosion resistance than products such as Rhine zinc, French zinc, Dutch zinc, Spain zinc and the like in Europe and America.
According to the research, the solid solubility of Cu in Zn is 2.7% at 425 ℃, and is only 0.2% at normal temperature; at 400 ℃, the solubility of Ti in Zn is only 0.02%, and at normal temperature is only 0.002%, therefore, the mass fraction of Cu and Ti elements which can be dissolved in solid solution in the Zn-Cu-Ti alloy is not high. In the Zn-Cu-Ti alloy, when the mass fraction of Zn is more than 78%, trace Cu and Ti are added, and only epsilon-CuZn is generated under the influence of factors such as solid solubility and the like 4 Intermediate compound and Zn 16 A Ti intermediate compound. Therefore, in the case of Zn-Cu-Ti alloys, the main phase compositions thereof are eta phase (solid solution of Zn), epsilon-CuZn 4 Phase and Zn 16 A Ti phase.
Research shows that for Zn-Cu-Ti alloy, the second phase epsilon-CuZn 4 Phase and Zn 16 Size and distribution of Ti phaseInfluences the mechanical property and bending property of the zinc alloy plate and also has important influence on the corrosion resistance of the zinc alloy plate. When CuZn 4 Phase and Zn 16 When the Ti phase particles are fine in size and are uniformly dispersed and distributed, and the microstructure is mostly isometric crystal, the plate has excellent bending property and mechanical property, and meanwhile, the corrosion resistance of the plate can be greatly improved. Therefore, for Zn-Cu-Ti alloy, a refining method of the second phase is developed, which has important significance for improving the corrosion resistance of the zinc alloy plate and prolonging the service life of the zinc alloy plate.
Disclosure of Invention
Accordingly, it is an object of the present invention to provide a method for manufacturing a zinc alloy sheet in a boron microalloying-semi-solid continuous casting manner, which further refines and homogenizes epsilon-CuZn in the alloy sheet in a Zn-Cu-Ti alloy 4 Phase and Zn 16 Ti phase such that epsilon-CuZn 4 Phase and Zn 16 The grain size of the second phase formed by the Ti phase is less than 1 mu m, thereby improving the corrosion resistance of the zinc alloy plate and breaking through the problems of low corrosion resistance, short service life and the like when the conventional Zn-Cu-Ti alloy plate is in service in severe environments such as saline-alkali acid environment and the like.
Further, the invention also provides the zinc alloy plate with low copper, low titanium, high strength, high toughness and high corrosion resistance prepared by the method.
In order to solve the technical problems, the invention adopts the following technical scheme:
a method for preparing a zinc alloy plate by a boron microalloying-semi-solid continuous casting mode comprises the following steps:
s1, putting the alloy raw material for preparing Zn-Cu-Ti into a melting furnace, heating to 450-600 ℃ to completely melt the alloy raw material;
s2, adding boron element into the melt in the form of intermediate alloy, and refining after the boron element is completely melted/dissolved;
s3, flowing the refined melt through a cooling device, and cooling the melt to a semi-solid temperature range to obtain semi-solid slurry, wherein the semi-solid temperature range is that the temperature is between the liquidus temperature and the solidus temperature of the alloy;
s4, enabling the semi-solid slurry flowing out of the cooling device to flow into a continuous casting machine, and rapidly cooling to obtain a zinc alloy casting blank;
and S5, continuously rolling the casting blank obtained in the S4 to prepare the zinc alloy plate.
The chemical components of the Zn-Cu-Ti alloy in the S1 are 0.05-2.0% of Cu, 0.02-0.2% of Ti and the balance of Zn and inevitable impurities, wherein the total amount of the impurities is less than or equal to 0.2%.
The boron-containing intermediate alloy in the S2 is one or a mixture of more of Zn- (1-10) B, Ti- (1-10) B, Cu- (1-20) B; the content of the boron element is 0.01-0.1% of the total mass of the alloy;
the refining can select a rotary argon blowing method and N is introduced 2 And Cl 2 Adding chlorine salt into the mixed gas, and refining for 2-15 min.
The cooling device for preparing the semi-solid slurry in the step S3 can select a single cooling inclined plate, a cooling tank, a mechanical stirring device, an electromagnetic stirring device, an ultrasonic stirring device or a composite device of two or more of the cooling inclined plate, the cooling tank, the mechanical stirring device, the electromagnetic stirring device and the ultrasonic stirring device; the cooling rate of the melt in the preparation process of the semi-solid slurry is 5-100 ℃/s, and the solid fraction of the semi-solid slurry is 1-50%.
The semi-solid continuous casting process parameters in the S4 are casting temperature of 400-425 ℃, casting speed of 5-40 m/min, and casting blanks with thickness of 4-30 mm, width of 100-2500 mm and temperature of 180-350 ℃ leaving the casting machine are prepared;
in S5, the casting blank which is continuously cast and just leaves the casting machine is subjected to hot rolling for 1-3 times, and the reduction of each time is 25-50%; then, spraying water to cool the plate, and then carrying out cold rolling for 1-4 times, wherein the reduction of each time is 5-30%; the total reduction of the sheet is controlled to be 80-98%, and finally the zinc alloy sheet with the thickness of 0.1-3 mm is prepared.
The alloy plate prepared by the method has fine and uniformly distributed particles in the second phase, and the particle size in the second phase is less than 1 mu m.
Compared with the prior art, the alloy plate prepared by the invention has the following advantages:
the invention mainly uses boron micro-combinationThe gold is formed, namely trace boron element is introduced into the Zn-Cu-Ti alloy, and a fine boron-rich phase existing in the alloy melt in the form of crystalline solid is preferentially separated out in the solidification process of the zinc alloy melt to inhibit Zn 16 Upward floating of Ti phase and CuZn 4 Phase sinking not only improves component segregation, but also can be used as nucleation particles to refine matrix tissues; meanwhile, the introduction of boron leads to the increase of the supercooling of the melt component, causing CuZn 4 Phase and Zn 16 The Ti phase lamella spacing decreases. When no boron element is introduced into the Zn-Cu-Ti alloy, composition difference exists between free atom clusters in the melt, and the local Cu mass fraction of the melt is caused by concentration fluctuation caused by atomic thermal motion>2.7%, and coarse CuZn is directly precipitated from the melt 4 Phase (1); the introduction of trace boron element can improve the fluidity of the zinc alloy, which is beneficial to the homogenization of components and the preparation of the subsequent semi-solid slurry.
The invention prepares the zinc alloy casting blank by the semi-solid continuous casting method, abandons the blank preparation by the traditional liquid melt continuous casting method, namely in the process of preparing the semi-solid slurry by cooling the high-temperature melt, the slurry preparation with high cooling rate is utilized to shorten the formation and growth time of second-phase brittle particles, and the solidification characteristic in the semi-solid slurry preparation is utilized to improve the component field and the temperature field in the slurry, thereby refining and homogenizing the hard brittle phase CuZn 4 And Zn 16 Purpose of Ti.
The invention has little boron element introduction amount, and the preparation cost of the zinc alloy plate is basically equivalent to that of the conventional Zn-Cu-Ti alloy plate. The semi-solid continuous casting process adopted not only obviously refines the second phase, but also greatly reduces energy consumption and resource waste, is integrally connected with the subsequent rolling process, shortens the preparation time of the zinc alloy plate, improves the preparation efficiency, is a green and environment-friendly near-net forming process, and meets the realization of the double-carbon target.
According to the invention, the second phase of the Zn-Cu-Ti alloy plate is refined by cooperating with boron microalloying and semi-solid continuous casting, so that the mechanical property, the bending property and the surface quality of the zinc alloy plate are improved, the corrosion resistance of the plate is greatly improved, and the product has excellent market competitiveness.
The invention is mainly based on boron microalloying, i.e. inA trace amount of boron element is introduced into the Zn-Cu-Ti alloy, and a fine boron-rich phase existing in the alloy melt in the form of crystalline solid is preferentially precipitated in the solidification process of the alloy melt to inhibit Zn 16 Floating Ti phase and CuZn 4 Phase sinking not only improves component segregation, but also can be used as nucleation particles to refine matrix tissues; meanwhile, the introduction of boron leads to the increase of the supercooling of melt components, causing CuZn 4 Phase and Zn 16 The Ti phase lamella spacing decreases. And preparing a zinc alloy casting blank by semi-solid continuous casting, namely shortening the growth time of second-phase brittle particles by utilizing a large cooling rate in the preparation process of semi-solid slurry, and improving a component field and a temperature field in the slurry by utilizing the semi-solid solidification characteristic of the second-phase brittle particles so as to refine and homogenize the hard brittle phase CuZn 4 And Zn 16 Purpose of Ti, the second phase CuZn 4 And Zn 16 The particle size of Ti is < 1 μm. On the basis, the obtained semi-solid casting blank is rolled and formed to prepare the high corrosion resistant zinc alloy plate with the required thickness.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without creative efforts.
FIG. 1 is a second phase microstructure of a Zn-1Cu-0.06Ti zinc alloy sheet material prepared in example 1 of the present invention shown in FIG. 1.
FIG. 2 is a second phase microstructure of a Zn-1Cu-0.06Ti zinc alloy sheet prepared in comparative example 1 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it should be understood that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1:
the embodiment provides a method for refining a second phase of a Zn-1Cu-0.06Ti alloy to improve the corrosion resistance of a plate, which specifically comprises the following steps:
s1, putting 1 ton of Zn-1Cu-0.06Ti alloy ingot into a melting furnace, heating to 550 ℃, and completely melting;
s2, adding 10kg of Zn-5B intermediate alloy into the melt, after the intermediate alloy is completely melted/dissolved, refining the melt by injecting mixed gas of nitrogen and chlorine (volume ratio is 8: 1) into the zinc alloy melt for 5min, degassing and slagging off;
s3, enabling the refined melt to flow through a cooling inclined plate through which cooling circulating water flows, and cooling the melt to a semi-solid temperature range to obtain semi-solid slurry;
s4, the temperature of the semi-solid slurry flowing out through the cooling inclined plate is about 416 ℃, the solid fraction is about 31%, the semi-solid slurry flows into a continuous casting machine, the continuous casting speed is 10m/min, and a zinc alloy casting blank with the width of 600mm and the thickness of 10mm is prepared after rapid cooling.
S5, continuously rolling the casting blank obtained in the S4 (the casting blank temperature is about 280 ℃ when the casting blank leaves a continuous casting machine), wherein the rolling process comprises the following steps: firstly, carrying out 2-pass hot rolling on a continuous casting billet, wherein the reduction of each pass is 50%; then spraying water to cool the hot-rolled plate, and then carrying out cold rolling for 3 times, wherein the reduction of each time is 20%; the total reduction was 87.2%, and finally a zinc alloy plate having a thickness of 1.28mm was prepared.
Example 2:
the embodiment provides a method for refining a second phase of a Zn-2Cu-0.02Ti alloy to improve the corrosion resistance of a plate, which specifically comprises the following steps:
s1, putting 1 ton of Zn-2Cu-0.02Ti alloy ingot into a melting furnace, heating to 450 ℃ and completely melting;
s2, adding 1kg of Zn-5B master alloy into the melt, and after the master alloy is completely melted/dissolved, adopting chloride KCl and MgCl 2 Mixture of (KCl) and MgCl 2 5: 1) to zinc complexRefining the gold melt for 10min, degassing and slagging off;
s3, enabling the refined melt to flow through a cooling inclined plate through which cooling circulating water flows, and cooling the melt to a semi-solid temperature range to obtain semi-solid slurry;
s4, the temperature of the semi-solid slurry flowing out through the cooling inclined plate is about 403 ℃, the solid fraction is about 50%, the semi-solid slurry flows into a continuous casting machine, the continuous casting speed is 15m/min, and a zinc alloy casting blank with the width of 300mm and the thickness of 10mm is prepared after rapid cooling.
S5, continuously rolling the casting blank obtained in the S4 (the temperature of the casting blank is about 230 ℃ when the casting blank leaves a continuous casting machine), wherein the rolling process comprises the following steps: firstly, carrying out 3-pass hot rolling on a continuous casting billet, wherein the reduction of each pass is 40%; then spraying water to cool the hot-rolled plate, and then carrying out cold rolling for 3 times, wherein the reduction of each time is 25%; the total reduction is 90.5%, and finally the zinc alloy plate with the thickness of 0.95mm is prepared.
Example 3:
the embodiment provides a method for refining a second phase of a Zn-0.05Cu-0.2Ti alloy to improve the corrosion resistance of a plate, which specifically comprises the following steps:
s1, putting 1 ton of Zn-0.05Cu-0.2Ti alloy ingot into a melting furnace, heating to 600 ℃ to completely melt the alloy ingot;
s2, adding 1kg of Cu-20B intermediate alloy into the melt, after the intermediate alloy is completely melted/dissolved, refining the melt by injecting mixed gas of nitrogen and chlorine (volume ratio is 5: 1) into the zinc alloy melt for min, and removing gas and slag;
s3, preparing semi-solid slurry from the refined melt by adopting a mechanical stirring device, and stirring at a speed of 600r/min to cool the melt to a semi-solid temperature range to obtain semi-solid slurry;
s4, the temperature of the semi-solid slurry prepared by the mechanical stirring process is about 421 ℃, the solid fraction is about 8%, the semi-solid slurry flows into a continuous casting machine, the continuous casting speed is 12m/min, and the zinc alloy casting blank with the width of 500mm and the thickness of 30mm is prepared after rapid cooling.
S5, continuously rolling the casting blank obtained in the S4 (the temperature of the casting blank is about 230 ℃ when the casting blank leaves a continuous casting machine), wherein the rolling process comprises the following steps: firstly, carrying out 3-pass hot rolling on a continuous casting billet, wherein the reduction of each pass is 50%; then spraying water to cool the hot-rolled plate, and then carrying out cold rolling for 4 times, wherein the reduction of each time is 30%; the total reduction is 97.1%, and finally the zinc alloy plate with the thickness of 0.88mm is prepared.
Example 4:
the embodiment provides a method for refining a second phase of a Zn-0.1Cu-0.1Ti alloy to improve the corrosion resistance of a plate, which specifically comprises the following steps:
s1, putting 1 ton of Zn-0.1Cu-0.01Ti alloy ingot into a melting furnace, heating to 600 ℃ to completely melt the alloy ingot;
s2, adding 1kg of Ti-10B intermediate alloy into the melt, refining the zinc alloy melt by adopting a rotary argon blowing method (with the air flow of 1L/min) after the intermediate alloy is completely melted/dissolved, refining for 2min, degassing and slagging off;
s3, preparing the semi-solid slurry from the refined melt by adopting a composite process of electromagnetic stirring and mechanical stirring, wherein the mechanical stirring speed is 500r/min, the electromagnetic stirring current is 50A, and the frequency is 50Hz, and cooling the melt to a semi-solid temperature range to obtain the semi-solid slurry;
s4, the temperature of the semi-solid slurry prepared by the composite process is about 424 ℃, the solid fraction is about 1%, the semi-solid slurry flows into a continuous casting machine, the continuous casting speed is 20m/min, and the zinc alloy casting blank with the width of 800mm and the thickness of 4mm is prepared after rapid cooling.
S5, continuously rolling the casting blank obtained in the S4 (the temperature of the casting blank is about 280 ℃ when the casting blank leaves a continuous casting machine), wherein the rolling process comprises the following steps: firstly, carrying out 1-pass hot rolling on a continuous casting billet, wherein the pass reduction is 50%; then spraying water to cool the hot-rolled plate, and then carrying out cold rolling for 3 times, wherein the reduction of each time is 30%; the total reduction is 82.5%, and finally the zinc alloy plate with the thickness of 0.7mm is prepared.
Example 5:
the embodiment provides a method for refining a second phase of a Zn-0.2Cu-0.1Ti alloy to improve the corrosion resistance of a plate, which specifically comprises the following steps:
s1, putting 1 ton of Zn-0.2Cu-0.1Ti alloy ingot into a melting furnace, and heating to 480 ℃ to completely melt the alloy ingot;
s2, adding 5kg of Zn-10B master alloy into the melt, refining the zinc alloy melt by adopting a rotary argon blowing method (with the ventilation volume of 1L/min) after the zinc alloy melt is completely melted/dissolved, refining for 15min, degassing and slagging off;
s3, enabling the refined melt to flow through a cooling inclined plate through which cooling circulating water flows, and cooling the melt to a semi-solid temperature range to obtain semi-solid slurry;
s4, the temperature of the semi-solid slurry prepared by the composite process is about 418 ℃, the solid fraction is about 15%, the semi-solid slurry flows into a continuous casting machine, the continuous casting speed is 30m/min, and a zinc alloy casting blank with the width of 100mm and the thickness of 6mm is prepared after the semi-solid slurry is rapidly cooled.
S5, continuously rolling the casting blank obtained in the S4 (the temperature of the casting blank is about 260 ℃ when the casting blank leaves a continuous casting machine), wherein the rolling process comprises the following steps: firstly, carrying out 3-pass hot rolling on a continuous casting billet, wherein the reduction of the first two passes is 50%, and the reduction of the third pass is 25%; then spraying water to cool the hot-rolled plate, and then carrying out 1-pass cold rolling, wherein the pass reduction is 5%; the total reduction is 82.5%, and finally the zinc alloy plate with the thickness of 1.05mm is prepared.
Comparative example 1
The present comparative example provides a method for manufacturing a Zn-1Cu-0.06Ti alloy sheet, which is different from example 1 in that boron is not introduced and a semi-solid continuous casting process is not used for forming a billet, and the others are the same as example 1.
Comparative example 2
This comparative example provides a Zn-1Cu-0.06Ti alloy sheet preparation method, which is different from example 1 in that boron element is not introduced, and the others are the same as example 1.
Comparative example 3
The comparative example provides a method for preparing a Zn-1Cu-0.06Ti alloy sheet, which is different from example 1 in that a semi-solid continuous casting process is not employed for forming a billet, and the others are the same as those in example 1.
Comparative example 4
This comparative example provides a method for manufacturing a Zn-2Cu-0.02Ti alloy plate, which is different from example 1 in that no boron element is introduced and a semi-solid continuous casting process is not used for forming a billet, but is otherwise the same as example 1.
Comparative example 5
This comparative example provides a Zn-2Cu-0.02Ti alloy sheet preparation method, which is different from example 1 in that boron element is not introduced, and the others are the same as example 1.
Comparative example 6
The present comparative example provides a method for manufacturing a Zn-2Cu-0.02Ti alloy sheet, which is different from example 1 in that a semi-solid continuous casting process is not used for forming a billet, and the others are the same as example 1.
Comparative example 7
This comparative example provides a method for manufacturing a Zn-0.05Cu-0.2Ti alloy plate, which is different from example 1 in that boron is not introduced and a semi-solid continuous casting process is not used for forming a billet, but is otherwise the same as example 1.
Comparative example 8
This comparative example provides a Zn-0.05Cu-0.2Ti alloy sheet preparation method, which is different from example 1 in that boron element is not introduced, and the others are the same as example 1.
Comparative example 9
The present comparative example provides a method for manufacturing a Zn-0.05Cu-0.2Ti alloy plate, which is different from example 1 in that a semi-solid continuous casting process is not used for forming a billet, and the others are the same as example 1.
Comparative example 10
The present comparative example provides a method for manufacturing a Zn-0.1Cu-0.1Ti alloy plate, which is different from example 1 in that boron is not introduced and a semi-solid continuous casting process is not used for preparing a billet, and the others are the same as example 1.
Comparative example 11
This comparative example provides a Zn-0.1Cu-0.1Ti alloy sheet preparation method, which is different from example 1 in that boron element is not introduced, and the others are the same as example 1.
Comparative example 12
The present comparative example provides a method for manufacturing a Zn-0.1Cu-0.1Ti alloy sheet, which is different from example 1 in that a semi-solid continuous casting process is not employed for forming a billet, and the others are the same as example 1.
Comparative example 13
The present comparative example provides a method for manufacturing a Zn-0.2Cu-0.1Ti alloy plate, which is different from example 1 in that boron is not introduced and a semi-solid continuous casting process is not used for preparing a billet, and the others are the same as example 1.
Comparative example 14
This comparative example provides a Zn-0.2Cu-0.1Ti alloy sheet preparation method, which is different from example 1 in that boron element is not introduced, and the others are the same as example 1.
Comparative example 15
The present comparative example provides a method for manufacturing a Zn-0.2Cu-0.1Ti alloy plate, which is different from example 1 in that a semi-solid continuous casting process is not employed for forming a billet, and the others are the same as example 1.
The Zn-Cu-Ti alloy sheets prepared in examples 1 to 5 above and the zinc alloy sheets prepared in comparative examples 1 to 15 were compared in terms of the size of the second phase and the corrosion resistance (corrosion medium of 3.5 wt.% NaCl solution), and the results are shown in table 1, fig. 1 and fig. 2.
TABLE 1
Figure BDA0003616949370000111
As can be seen from Table 1 and FIGS. 1-2, the Zn-Cu-Ti alloy sheets prepared in examples 1-5 have not only significantly refined second phases, more uniform distribution and more excellent corrosion resistance compared with the zinc alloy sheets prepared in comparative examples 1-15, so that the zinc alloy sheets prepared in the invention have wide application prospects and strong product competitiveness.
The method for refining the second phase of the Zn-Cu-Ti alloy to improve the corrosion resistance of the plate provided by the embodiment of the application patent is described in detail above. The above description of the embodiments is only intended to help understand the method of the present application and its core ideas.
It should be understood that the above examples are only for clarity of illustration and are not intended to limit the embodiments. Other variations and modifications will be apparent to persons skilled in the art in light of the above description. This need not be, nor should it be exhaustive of all embodiments. And obvious variations or modifications derived therefrom are intended to be within the scope of the invention.

Claims (7)

1. A method for preparing a zinc alloy plate by a boron microalloying-semisolid continuous casting mode is characterized by comprising the following steps:
s1, putting the alloy raw material for preparing Zn-Cu-Ti into a melting furnace, heating to 450-600 ℃ to completely melt the alloy raw material;
s2, adding boron element into the melt in the form of intermediate alloy, and refining after the boron element is completely melted/dissolved;
s3, enabling the refined melt to flow through a cooling device, and cooling the melt to a semi-solid temperature range to obtain semi-solid slurry;
s4, enabling the semi-solid slurry flowing out of the cooling device to flow into a continuous casting machine, and rapidly cooling to obtain a zinc alloy casting blank;
and S5, continuously rolling the casting blank obtained in the S4 to prepare the zinc alloy plate.
2. The method for preparing the zinc alloy sheet material in the boron microalloying-semi-solid continuous casting mode according to claim 1, wherein the method comprises the following steps:
the chemical components of the Zn-Cu-Ti alloy in the S1 are 0.05-2.0% of Cu, 0.02-0.2% of Ti and the balance of Zn and inevitable impurities, wherein the total amount of the impurities is less than or equal to 0.2%.
3. The method for preparing the zinc alloy sheet material in the boron microalloying-semi-solid continuous casting mode according to claim 1, wherein the method comprises the following steps:
the boron-containing intermediate alloy in the S2 is one or a mixture of more of Zn- (1-10) B, Ti- (1-10) B, Cu- (1-20) B; the content of the boron element is 0.01-0.1% of the total mass of the alloy;
said refining being selectively rotatableBlowing argon gas, introducing N 2 And Cl 2 Adding chlorine salt into the mixed gas, and refining for 2-15 min.
4. The method for preparing the zinc alloy sheet material in the boron microalloying-semi-solid continuous casting mode according to claim 1, wherein the method comprises the following steps:
the cooling device for preparing the semi-solid slurry in the step S3 can select a single cooling inclined plate, a cooling tank, a mechanical stirring device, an electromagnetic stirring device, an ultrasonic stirring device or a composite device of two or more of the cooling inclined plate, the cooling tank, the mechanical stirring device, the electromagnetic stirring device and the ultrasonic stirring device; the cooling rate of the melt in the preparation process of the semi-solid slurry is 5-100 ℃/s, and the solid fraction of the semi-solid slurry is 1-50%.
5. The method for preparing the zinc alloy sheet material in the boron microalloying-semi-solid continuous casting mode according to claim 1, wherein the method comprises the following steps:
and in the S4, the semi-solid continuous casting process parameters are casting temperature of 400-425 ℃, the casting speed is 5-40 m/min, and the casting blank with thickness of 4-30 mm, width of 100-2500 mm and temperature of 180-350 ℃ when leaving the casting machine is prepared.
6. The method for preparing the zinc alloy sheet material in the boron microalloying-semi-solid continuous casting mode according to claim 1, wherein the method comprises the following steps:
in S5, the casting blank which is continuously cast and just leaves the casting machine is subjected to hot rolling for 1-3 times, and the reduction of each time is 25-50%; then, spraying water to cool the plate, and then carrying out cold rolling for 1-4 times, wherein the reduction of each time is 5-30%; the total reduction of the sheet is controlled to be 80-98%, and finally the zinc alloy sheet with the thickness of 0.1-3 mm is prepared.
7. An alloy sheet produced by the method of any one of claims 1 to 6, wherein the particles in the second phase of the alloy sheet are fine and uniformly distributed, and wherein the size of the particles in the second phase is < 1 μm.
CN202210446137.4A 2022-04-26 2022-04-26 Method for preparing zinc alloy plate by boron microalloying-semi-solid continuous casting mode and product Pending CN115106492A (en)

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CN105018765A (en) * 2015-07-09 2015-11-04 上海交通大学 Titanium-zinc alloy and fabrication method of titanium-zinc alloy plate
CN113122740A (en) * 2021-04-07 2021-07-16 森特士兴集团股份有限公司 Method for preparing Zn-Cu-Ti alloy ingot, alloy ingot and alloy plate
CN113512667A (en) * 2021-06-22 2021-10-19 北京科技大学 Zn-Cu-Ti-Mo alloy and plate with high corrosion resistance, high toughness and excellent processability and preparation method thereof
CN113699398A (en) * 2021-08-24 2021-11-26 湘潭大学 Short-process preparation method of high-strength high-toughness corrosion-resistant deformation ZnCuTi plate

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US4051887A (en) * 1975-03-13 1977-10-04 Rheinisches Zinkwalzwerk Gmbh & Co. Kg Process for producing sheets and strip of zinc-copper-titanium alloy
CN101660070A (en) * 2008-08-27 2010-03-03 徐凯 Zinc copper titanium complex alloy functional and structural material and preparation method thereof
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