CN114086012A - Preparation method of low-copper low-titanium high-strength high-toughness high-corrosion-resistance zinc alloy plate and product - Google Patents
Preparation method of low-copper low-titanium high-strength high-toughness high-corrosion-resistance zinc alloy plate and product Download PDFInfo
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Abstract
The invention provides a preparation method of a low-copper low-titanium high-strength high-toughness high-corrosion-resistance zinc alloy plate and a product, wherein the method comprises the steps of preheating and drying alloy raw materials, putting the alloy raw materials into a melting furnace, heating to 460-650 ℃, and refining after the alloy raw materials are completely melted; cooling the refined zinc alloy melt to a casting temperature, and then preparing a zinc alloy casting blank by adopting a continuous casting machine; the continuous casting process parameters are the casting temperature of 450-; continuously rolling to obtain the zinc alloy plate with the thickness of 0.1-2.5 mm. The invention has low content of alloying elements, low cost, short rolling process flow, easy control and suitability for industrialized preparation, the prepared plate has mechanical and corrosion resistance and other performances which are obviously superior to the European EN988 standard, and the market competitiveness of the product is strong.
Description
Technical Field
The invention relates to the technical field of preparation and processing of zinc alloy and plates thereof, in particular to a preparation method and a product of a low-copper low-titanium high-strength high-toughness high-corrosion-resistance zinc alloy plate.
Background
The Zn-Cu-Ti alloy plate has good comprehensive properties, such as good processing property, forming property, welding property, corrosion resistance and embossing property, and durable color. The alloy has good creep resistance and can be compared favorably with brass. Due to the excellent performance of Zn-Cu-Ti alloy, the Zn-Cu-Ti alloy is widely used for building such as roofs of airports, exhibition halls, gymnasiums and the like in the seventies of the last century in foreign countries, especially in western developed countries. The performance and application of the material are also researched in China. The Zn-Cu-Ti alloy is reported to be used as a copper substitute material to trial manufacture water tank radiating fins, radiating pipes, automobile brake pipes, oil conveying pipes, medical high-speed dental drills and the like successfully. However, at present, the preparation and application of Zn-Cu-Ti alloy materials are still not mature in China. China imports Zn-Cu-Ti alloy plates in great amount from Europe, America and other countries with great cost. In the face of the domestic largest building industry in the world and huge actual market demands for Zn-Cu-Ti plates, a Zn-Cu-Ti alloy plate preparation technology is explored and optimized, so that the aim of jacking with production is achieved, the advantages of zinc resources in China are fully exerted, and the produced high-quality Zn-Cu-Ti alloy plates with the quality meeting or even exceeding the European EN988 standard have important social benefits and economic benefits.
In general, 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 is shortened in severe environments such as coastal environments, saline-alkali environments and the like, and because the construction and construction are difficult in severe environments, the service life of buildings in severe environments is expected to be prolonged; in addition, the Zn-Cu-Ti alloy sheet material on the market has low mechanical property, and although the sheet material is easy to bend and form, the sheet material has uneven wrinkles in the processing process, and meanwhile, the low mechanical property of the zinc sheet material easily causes the roof material to have the dangers of wind uncovering, water leakage and the like under extreme meteorological conditions such as storm and storm.
Disclosure of Invention
Therefore, the invention aims to solve the problems that the Zn-Cu-Ti alloy plate on the market at present has low mechanical property, and the corrosion resistance of the Zn-Cu-Ti alloy plate in the severe environments such as saline-alkaline and acidic environments is lower than expected. The invention provides a preparation method of a low-copper low-titanium high-strength high-toughness high-corrosion-resistance zinc alloy plate, which improves the corrosion resistance of a Zn-Cu-Ti alloy plate by reducing Cu and Ti, refines zinc alloy grains by adding Ce element into the Zn-Cu-Ti alloy, enhances the solid solution strengthening of Cu and Ti element, exerts the strengthening effect of ZnCe2 second phase, purifies melt by adding Nd element, and accelerates the formation of a fine passivation film on the surface; meanwhile, a newly developed continuous casting and rolling process suitable for processing the Zn-Cu-Ti alloy plate prepared in the industrialized mode is combined, wherein the hot rolling, warm rolling and cold rolling short-flow integrated continuous rolling process is adopted, the grains of the plate are further refined, and meanwhile, the granular second phase is remarkably crushed, so that the granular second phase is refined and homogenized; the design innovation of the component proportion is cooperated with the innovation and optimization of the continuous casting and rolling preparation process, so that the toughness and the corrosion resistance of the zinc alloy plate are synchronously improved.
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 preparation method of a low-copper low-titanium high-strength high-toughness high-corrosion-resistance zinc alloy plate comprises the following steps:
s1, preheating and drying the alloy raw material, putting the alloy raw material into a melting furnace, heating to 460-650 ℃, and refining after the alloy raw material is completely melted;
s2, cooling the refined zinc alloy melt to a casting temperature, and then preparing a zinc alloy casting blank by using a continuous casting machine; the continuous casting process parameters are the casting temperature of 450-;
s3, continuously rolling the casting blank obtained in the S2 to obtain the zinc alloy plate with the thickness of 0.1-2.5 mm.
The alloy raw materials are pure zinc, pure Cu or intermediate alloy containing Cu element, intermediate alloy containing Ti element, intermediate alloy containing Ce element and intermediate alloy containing Nd element.
The Cu-containing master alloy can be selected from one or more of Zn- (5-50) Cu, Ti- (10-50) Cu, Cu- (2-20) Ce, Cu- (2-20) Nd and Zn- (2-20) Cu- (2-20) Ti;
the intermediate alloy containing the Ti element can be selected from one or more of Zn- (1-15) Ti, Ti- (10-50) Cu, Ti- (2-20) Ce, Ti- (2-20) Nd and Zn- (2-20) Cu- (2-20) Ti;
the intermediate alloy containing Ce element can select one or more of Zn- (1-20) Ce, Ti- (2-20) Ce and Cu- (2-20) Ce;
the Nd-containing intermediate alloy can be one or more of Zn- (1-20) Nd, Ti- (2-20) Nd and Cu- (2-20) Nd.
And (5) putting the alloy raw material in the step S1 into a drying furnace or a holding furnace for preheating and drying.
The preheating and drying process in the S1 is characterized in that the preheating temperature is 100-300 ℃, and the preheating time is 2-20 min;
the refining process in the S1 comprises a rotary argon blowing method and N introduction2And Cl2Adding one of chlorine salts into the mixed gas, and refining for 3-20 min.
The continuous rolling in step S3 is:
firstly, continuously casting a casting blank which is just left from a casting machine and has the temperature of 220-360 ℃ is subjected to 1-3 times of hot rolling, and the reduction of each time is 20-50%; then spraying water to cool the hot-rolled plate to reduce the temperature to 100-200 ℃, and then carrying out 1-2 times of warm rolling, wherein the reduction of each time is 30-50%; then, spraying water to cool the plate, and then carrying out cold rolling for 1-3 times, wherein the reduction of each time is 10-30%; the total reduction of the sheet material is controlled to be 70-95%, and finally the zinc alloy sheet material with the thickness of 0.1-2.5mm is obtained.
The invention provides a copper low-titanium high-strength high-toughness high-corrosion-resistance zinc alloy plate which comprises the following components in mass: 0.03-0.2% of Cu, 0.03-0.2% of Ti, 0.20.8% of Ce, 0.020.1% of Nd, and the balance of Zn and inevitable impurities, wherein the total amount of the impurities is less than or equal to 0.25%.
The tensile strength of the copper-low-titanium high-strength high-toughness high-corrosion-resistance zinc alloy plate is 250-450MPa, the yield strength is 210-420MPa, the elongation is 40-110%, the corrosion rate is less than 0.08mm/a, and the corrosion medium is 3.5 wt.% of NaCl solution.
Compared with the prior art, the low-copper low-titanium high-strength high-toughness high-corrosion-resistance zinc alloy plate prepared by the invention has the following advantages:
(1) according to the invention, the Ce element is added into the Zn-Cu-Ti alloy, so that the zinc alloy crystal grains can be refined, the solid solubility of harmful impurity elements such as Si and Fe in a zinc alloy matrix can be reduced by adding the Ce element, the solid solubility of Cu and Ti elements in the matrix is improved, and the solid solution strengthening effect is enhanced. According to the invention, the Cu content and the Ti content of the alloy are reduced by reducing Cu and Ti, and the solid solubility of Cu and Ti elements in a matrix is increased, so that the content of the generated second phase TiZn15 phase is reduced, and the TiZn15 phase is easy to generate pitting corrosion, so that the reduction of the phase content is beneficial to improving the corrosion resistance of the alloy; meanwhile, the addition of Nd accelerates the uniform and stable formation of a fine passivation film on the surface of the zinc alloy. The Nd element is added to reduce the threshold of the chemical reaction between zinc and oxygen, accelerate the reaction between zinc and oxygen to generate zinc oxide, further react with water vapor in the environment to generate zinc hydroxide, and further react with carbon dioxide in the air to generate basic zinc carbonate. The basic zinc carbonate forms the main component of an alloy surface passivation film, and the surface passivation film enables a zinc alloy plate to have a high corrosion resistance effect. In addition, the addition of Nd can improve the purity of the zinc plate, reduce the impurity content and is beneficial to the improvement of the corrosion resistance and the mechanical property of the zinc plate.
(2) According to the preparation method of the low-copper low-titanium high-strength high-toughness high-corrosion-resistance zinc alloy plate, the corrosion resistance of the Zn-Cu-Ti alloy plate is synergistically improved by refining and homogenizing the second phase through continuous casting and continuous rolling, and the grains are further refined and the second phase is crushed, so that the toughness of the zinc alloy plate is greatly improved. Compared with the conventional method for preparing the zinc alloy plate by firstly continuously casting the zinc alloy casting blank, reheating the casting blank for multi-pass hot rolling, then cooling by water and then carrying out multi-pass cold rolling, the continuous casting and continuous rolling process is short and integrated, and continuous preparation is carried out in the process of cooling the zinc plate without reheating and heating, so that the method is high in efficiency, low in cost and more suitable for industrialization.
(3) Compared with the conventional rolling process, the rolling process can better refine the plate grains and obviously crush the granular second phases so as to refine and homogenize the granular second phases, which is beneficial to the improvement of the mechanical property and the corrosion resistance of the zinc alloy plate.
(4) The zinc alloy plate prepared by the invention has excellent toughness, corrosion resistance and surface quality through the design innovation of the chemical composition proportion of the zinc alloy and the process innovation of the rolling preparation of the zinc plate, and the market competitiveness of the product is strong. The alloy plate can be used for preparing a low-cost zinc alloy plate for a building roof, which has better corrosion resistance and higher toughness, so that the zinc alloy plate not only meets the European EN988 standard, but also has comprehensive performance superior to products such as European and American rhinestone zinc, French zinc, zinc Netherlands, Spanish zinc and the like.
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 shows the microstructure of Zn-0.05Cu-0.05Ti-0.2Ce-0.05Nd zinc alloy plate prepared in example 1 of the present invention.
FIG. 2 is a microstructure of a Zn-0.05Cu-0.05Ti zinc alloy plate prepared in comparative example 1 of the present invention.
FIG. 3 shows the second phase structure of Zn-0.05Cu-0.05Ti-0.2Ce-0.05Nd zinc alloy plate prepared in example 1 of the present invention.
FIG. 4 is a second phase structure of a Zn-0.05Cu-0.05Ti 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 preparation method of a high-strength high-toughness corrosion-resistant Zn-0.05Cu-0.05Ti-0.2Ce-0.05Nd alloy plate, which specifically comprises the following steps:
s1, weighing pure Zn, Zn-10Cu-10Ti, Zn-5Ce and Zn-3Nd intermediate alloys as raw materials required for preparing the Zn-0.05Cu-0.05Ti-0.2Ce-0.05Nd alloy plate as required, and then preserving heat in a drying furnace at 150 ℃ for 8min for preheating and drying;
putting the raw materials into a melting furnace, heating to 580 ℃, refining the melt by introducing a mixed gas method of nitrogen and chlorine (volume ratio is 10: 1) into the zinc alloy melt after the raw materials are completely melted, refining for 5min, degassing and slagging off.
S2, cooling the refined alloy melt to a casting temperature of 500 ℃ and pouring the alloy melt into a continuous casting machine, wherein the continuous casting speed is 8m/min, a Zn-0.05Cu-0.05Ti-0.2Ce-0.05Nd alloy casting blank with the width of 500mm and the thickness of 12mm is prepared, and the temperature of the casting blank leaving the continuous casting machine is tested to be about 320 ℃.
S3, immediately sending the casting blank into a rolling mill for continuous rolling, wherein the specific 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 to reduce the temperature to 150 ℃, and then carrying out 1-pass warm rolling with the pass reduction of 50%; then, spraying water to cool the plate, and then carrying out 2-pass cold rolling, wherein the reduction of each pass is 20%; the total reduction is 92%, and finally the Zn-0.05Cu-0.05Ti-0.2Ce-0.05Nd zinc alloy plate with the thickness of 0.96mm is prepared.
Example 2:
the embodiment provides a preparation method of a high-strength high-toughness corrosion-resistant Zn-0.15Cu-0.1Ti-0.6Ce-0.08Nd zinc alloy plate, which specifically comprises the following steps:
s1, weighing pure Zn, Zn-10Cu, Zn-5Ti, Zn-20Ce and Zn-5Nd intermediate alloys as raw materials required for preparing the Zn-0.15Cu-0.1Ti-0.6Ce-0.08Nd alloy plate as required, and then preserving heat in a drying furnace at 180 ℃ for 10min for preheating and drying;
putting the raw materials into a melting furnace, heating to 560 ℃, refining the zinc alloy melt by adopting a rotary argon blowing method after the raw materials are completely melted, wherein the refining time is 5min, degassing and slagging off.
S2, cooling the refined alloy melt to 480 ℃ and pouring the alloy melt into a continuous casting machine, wherein the casting speed is 10m/min, a Zn-0.15Cu-0.1Ti-0.6Ce-0.08Nd alloy casting blank with the width of 600mm and the thickness of 16mm is prepared, and the temperature of the casting blank leaving the continuous casting machine is tested to be about 300 ℃.
S3, immediately sending the casting blank into a rolling mill for continuous rolling, wherein the specific process comprises the following steps: firstly, carrying out 2-pass hot rolling on a continuous casting billet, wherein the reduction of each pass is 25%; then spraying water to cool the hot-rolled plate to reduce the temperature to 120 ℃, and carrying out 2-pass warm rolling with the pass reduction of 50%; then, spraying water to cool the plate, and then carrying out 3-pass cold rolling, wherein the pass reduction is 20%; the total pressure reduction of the zinc plate preparation is 93%, and finally the Zn-0.15Cu-0.1Ti-0.6Ce-0.08Nd zinc alloy plate with the thickness of 1.1mm is prepared.
Example 3:
the embodiment provides a preparation method of a high-strength high-toughness corrosion-resistant Zn-0.2Cu-0.2Ti-0.8Ce-0.1Nd zinc alloy plate, which specifically comprises the following steps:
s1, weighing pure Zn, Zn-10Cu, Zn-5Ti, Zn-20Ce and Zn-20Nd intermediate alloys as raw materials required for preparing the Zn-0.2Cu-0.2Ti-0.8Ce-0.1Nd alloy plate as required, and then preserving heat in a drying furnace at 300 ℃ for 2min for preheating and drying;
putting the raw materials into a melting furnace, heating to 650 ℃, refining the melt by a method of introducing a mixed gas of nitrogen and chlorine (volume ratio is 10: 1) into the zinc alloy melt after the raw materials are completely melted, refining for 10min, degassing and slagging off.
S2, cooling the refined alloy melt to a casting temperature of 550 ℃, pouring the alloy melt into a continuous casting machine, casting at a speed of 3m/min to prepare a Zn-0.2Cu-0.2Ti-0.8Ce-0.1Nd alloy casting blank with a width of 1000mm and a thickness of 10mm, and testing the temperature of the casting blank when the casting blank leaves the continuous casting machine to be about 360 ℃.
S3, immediately sending the casting blank into a rolling mill for continuous rolling, wherein the specific process comprises the following steps: firstly, carrying out 1-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 to reduce the temperature to 200 ℃, and then carrying out 1-pass warm rolling with the pass reduction of 50%; then, the plate is subjected to water spraying cooling, and then 1-pass cold rolling is carried out, wherein the pass reduction is 30%; the total reduction of the zinc plate preparation is 82.5 percent, and finally the Zn-0.2Cu-0.2Ti-0.8Ce-0.1Nd zinc alloy plate with the thickness of 1.75mm is prepared.
Example 4:
the embodiment provides a preparation method of a high-strength high-toughness corrosion-resistant Zn-0.03Cu-0.03Ti-0.2Ce-0.02Nd zinc alloy plate, which specifically comprises the following steps:
s1, weighing pure Zn, Zn-2Cu-2Ti, Zn-5Ce and Zn-1Nd intermediate alloys as raw materials required for preparing the Zn-0.03Cu-0.03Ti-0.2Ce-0.02Nd alloy plate as required, and then preserving heat in a drying furnace at 100 ℃ for 20min for preheating and drying;
putting the raw materials into a melting furnace, heating to 460 ℃, refining the zinc alloy melt by adopting a rotary argon blowing method after the raw materials are completely melted, wherein the refining time is 3min, and degassing and slagging off.
S2, cooling the refined alloy melt to a casting temperature of 450 ℃, pouring the alloy melt into a continuous casting machine, casting at a speed of 30m/min to prepare a Zn-0.03Cu-0.03Ti-0.2Ce-0.02Nd alloy casting blank with a width of 100mm and a thickness of 8mm, and testing the temperature of the casting blank when the casting blank leaves the continuous casting machine to be about 220 ℃.
S3, immediately sending the casting blank into a rolling mill for continuous rolling, wherein the specific process comprises the following steps: firstly, carrying out 2-pass hot rolling on a continuous casting billet, wherein the reduction of each pass is 20%; then spraying water to cool the hot-rolled plate to reduce the temperature to 100 ℃, and then carrying out 1-pass warm rolling with the pass reduction of 30%; then, the plate is subjected to water spraying cooling, and then 1-pass cold rolling is carried out, wherein the pass reduction is 30%; the total reduction of the zinc plate preparation is 70 percent, and finally the Zn-0.03Cu-0.03Ti-0.2Ce-0.02Nd zinc alloy plate with the thickness of 2.5mm is prepared.
Example 5:
the embodiment provides a preparation method of a high-strength high-toughness corrosion-resistant Zn-0.2Cu-0.03Ti-0.8Ce-0.02Nd zinc alloy plate, which specifically comprises the following steps:
s1, weighing pure Zn, Zn-50Cu, Zn-15Ti, Zn-3Ce and Zn-1Nd intermediate alloys as raw materials required for preparing the Zn-0.2Cu-0.03Ti-0.8Ce-0.02Nd alloy plate as required, and then preserving heat in a drying furnace at 150 ℃ for 6min for preheating and drying;
putting the raw materials into a melting furnace, heating to 580 ℃, refining the melt by a method of introducing a mixed gas of nitrogen and chlorine (volume ratio of 20: 1) into the zinc alloy melt after the raw materials are completely melted, refining for 6min, degassing and slagging off.
S2, cooling the refined alloy melt to 480 ℃ and pouring the alloy melt into a continuous casting machine, wherein the casting speed is 3m/min, a Zn-0.2Cu-0.03Ti-0.8Ce-0.02Nd alloy casting blank with the width of 2000mm and the thickness of 20mm is prepared, and the temperature of the casting blank leaving the continuous casting machine is tested to be about 310 ℃.
S3, immediately sending the casting blank into a rolling mill for continuous rolling, wherein the specific 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 to reduce the temperature to 150 ℃, and carrying out warm rolling for 3 times, wherein the reduction of each time is 30%; then, the plate is subjected to water spraying cooling, and then 1-pass cold rolling is carried out, wherein the pass reduction is 30%; the total reduction of the zinc plate preparation is 94%, and finally the Zn-0.2Cu-0.03Ti-0.8Ce-0.02Nd zinc alloy plate with the thickness of 1.2mm is prepared.
Example 6:
the embodiment provides a preparation method of a high-strength high-toughness corrosion-resistant Zn-0.1Cu-0.05Ti-0.2Ce-0.1Nd zinc alloy plate, which specifically comprises the following steps:
s1, weighing pure Zn, Zn-5Cu, Zn-1Ti, Zn-5Ce and Zn-5Nd intermediate alloys as raw materials required for preparing the Zn-0.1Cu-0.05Ti-0.2Ce-0.1Nd alloy plate as required, and then preserving heat in a drying furnace at 180 ℃ for 5min for preheating and drying;
putting the raw materials into a melting furnace, heating to 520 ℃, refining the melt by a method of introducing a mixed gas of nitrogen and chlorine (volume ratio of 20: 1) into the zinc alloy melt after the raw materials are completely melted, refining for 4min, degassing and slagging off.
S2, cooling the refined alloy melt to the casting temperature of 460 ℃ and pouring the alloy melt into a continuous casting machine, wherein the casting speed is 28m/min, a Zn-0.1Cu-0.05Ti-0.2Ce-0.1Nd alloy casting blank with the width of 300mm and the thickness of 5mm is prepared, and the casting blank temperature is about 250 ℃ when the alloy casting blank leaves the continuous casting machine.
S3, immediately sending the casting blank into a rolling mill for continuous rolling, wherein the specific process comprises the following steps: firstly, carrying out 2-pass hot rolling on a continuous casting billet, wherein the reduction of each pass is 20%; then spraying water to cool the hot-rolled plate to reduce the temperature to 120 ℃, and carrying out 3 times of warm rolling with the reduction of 50% in each time; then, spraying water to cool the plate, and then carrying out 3-pass cold rolling, wherein the pass reduction is 10%; the total reduction of the zinc plate preparation is 95%, and finally the Zn-0.1Cu-0.05Ti-0.2Ce-0.1Nd zinc alloy plate with the thickness of 0.25mm is prepared.
Example 7:
the embodiment provides a preparation method of a high-strength high-toughness corrosion-resistant Zn-0.15Cu-0.15Ti-0.4Ce-0.05Nd zinc alloy plate, which specifically comprises the following steps:
s1, weighing pure Zn, Zn-5Cu-5Ti, Zn-5Ce and Zn-2Nd intermediate alloys as raw materials required for preparing the etched Zn-0.15Cu-0.15Ti-0.4Ce-0.05Nd alloy plate as required, and then preserving heat in a drying furnace at 200 ℃ for 6min for preheating and drying;
putting the raw materials into a melting furnace, heating to 500 ℃, refining the zinc alloy melt by adopting a mixture of chloride KCl and MgCl2 (the mass ratio of KCl to MgCl2 is 2: 1) after the raw materials are completely melted, refining for 8min, degassing and slagging off.
S2, cooling the refined melt to 480 ℃ and pouring the melt into a continuous casting machine, wherein the casting speed is 10m/min, preparing a Zn-0.15Cu-0.15Ti-0.4Ce-0.05 Nd-etched alloy casting blank with the width of 1000mm and the thickness of 10mm, and testing the temperature of the casting blank when the casting blank leaves the continuous casting machine to be about 260 ℃.
S3, immediately sending the casting blank into a rolling mill for continuous rolling, wherein the specific process comprises the following steps: firstly, carrying out 1-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 to reduce the temperature to 140 ℃, and carrying out warm rolling for 2 times, wherein the reduction of each time is 40%; then, spraying water to cool the plate, and then carrying out 3-pass cold rolling, wherein the pass reduction is 20%; the total reduction of the zinc plate preparation is 90%, and finally the Zn-0.15Cu-0.15Ti-0.4Ce-0.05 Nd-etched zinc alloy plate with the thickness of 1mm is prepared.
Example 8:
the embodiment provides a preparation method of a high-strength high-toughness corrosion-resistant Zn-0.08Cu-0.16Ti-0.5Ce-0.05Nd zinc alloy plate, which specifically comprises the following steps:
s1, weighing pure Zn, Zn-5Cu-10Ti, Zn-5Ce and Zn-1Nd intermediate alloys as raw materials required for preparing the Zn-0.08Cu-0.16Ti-0.5Ce-0.05Nd alloy plate as required, and then preserving heat in a drying furnace at 130 ℃ for 7min for preheating and drying;
putting the raw materials into a melting furnace, heating to 520 ℃, refining the zinc alloy melt by adopting a mixture of chloride KCl and MgCl2 (the mass ratio of KCl to MgCl2 is 3: 1) after the raw materials are completely melted, refining for 6min, degassing and slagging off.
S2, cooling the refined alloy melt to a casting temperature of 460 ℃ and pouring the alloy melt into a continuous casting machine, wherein the casting speed is 28m/min, a Zn-0.08Cu-0.16Ti-0.5Ce-0.05Nd alloy casting blank with the width of 300mm and the thickness of 8mm is prepared, and the temperature of the casting blank leaving the continuous casting machine is tested to be about 220 ℃.
S3, immediately sending the casting blank into a rolling mill for continuous rolling, wherein the specific process comprises the following steps: firstly, carrying out 2-pass hot rolling on a continuous casting billet, wherein the first-pass reduction is 50%, and the second-pass reduction is 40%; then spraying water to cool the hot-rolled plate to reduce the temperature to 120 ℃, and carrying out 2 times of warm rolling, wherein the first time of reduction is 50%, and the second time of reduction is 30%; then, spraying water to cool the plate, and then carrying out 1-pass cold rolling, wherein the pass reduction is 10%; the total reduction of the zinc plate preparation is 91%, and finally the Zn-0.08Cu-0.16Ti-0.5Ce-0.05Nd zinc alloy plate with the thickness of 0.75mm is prepared.
Example 9:
the embodiment provides a preparation method of a high-strength high-toughness corrosion-resistant Zn-0.16Cu-0.08Ti-0.5Ce-0.03Nd zinc alloy plate, which specifically comprises the following steps:
s1, weighing pure Zn, Zn-20Cu-10Ti, Zn-6Ce and Zn-1Nd intermediate alloys as raw materials required for preparing the Zn-0.16Cu-0.08Ti-0.5Ce-0.03Nd alloy plate as required, and then preserving heat in a drying furnace at 180 ℃ for 4min for preheating and drying;
putting the raw materials into a melting furnace, heating to 550 ℃, refining the zinc alloy melt by adopting a mixture of chloride KCl and MgCl2 (the mass ratio of KCl to MgCl2 is 6: 1) after the raw materials are completely melted, refining for 7min, degassing and slagging off.
S2, cooling the refined alloy melt to 490 ℃ and pouring the alloy melt into a continuous casting machine, wherein the casting speed is 15m/min, a Zn-0.16Cu-0.08Ti-0.5Ce-0.03Nd alloy casting blank with the width of 750mm and the thickness of 10mm is prepared, and the temperature of the casting blank leaving the continuous casting machine is tested to be about 230 ℃.
S3, immediately sending the casting blank into a rolling mill for continuous rolling, wherein the specific process comprises the following steps: firstly, carrying out 2-pass hot rolling on a continuous casting billet, wherein the first-pass reduction is 40%, and the second-pass reduction is 50%; then spraying water to cool the hot-rolled plate to reduce the temperature to 150 ℃, and then carrying out 1-pass warm rolling with the pass reduction of 50%; then, water spraying cooling is carried out on the plate, and then 2-pass cold rolling is carried out, wherein the first-pass reduction is 20%, and the second-pass reduction is 30%; the total reduction of the zinc plate preparation is 92%, and finally the Zn-0.16Cu-0.08Ti-0.5Ce-0.03Nd zinc alloy plate with the thickness of 0.8mm is prepared.
Comparative example 1
The present comparative example provides a method for preparing a Zn-0.05Cu-0.05Ti alloy sheet, which is different from example 1 in that Ce and Nd elements are not introduced, and the others are the same as example 1.
Comparative example 2
The present comparative example provides a method for preparing a Zn-0.15Cu-0.1Ti alloy sheet, which is different from example 2 in that Ce and Nd elements are not introduced, and the others are the same as example 2.
Comparative example 3
The present comparative example provides a method for preparing a Zn-0.2Cu-0.2Ti alloy sheet, which is different from example 3 in that Ce and Nd elements are not introduced, and the others are the same as example 3.
Comparative example 4
This comparative example provides a method for producing a Zn-0.03Cu-0.03Ti alloy sheet, which is different from example 4 in that Ce and Nd elements are not introduced, and the others are the same as example 4.
Comparative example 5
This comparative example provides a method for producing a Zn-0.2Cu-0.03Ti alloy sheet, which is different from example 5 in that Ce and Nd elements are not introduced, and the others are the same as example 5.
Comparative example 6
This comparative example provides a method for producing a Zn-0.1Cu-0.05Ti alloy sheet, which is different from example 6 in that Ce and Nd elements are not introduced, and the others are the same as example 6.
Comparative example 7
This comparative example provides a method for producing a Zn-0.15Cu-0.15Ti alloy sheet, which is different from example 7 in that Ce and Nd elements are not introduced, and the others are the same as example 7.
Comparative example 8
The comparative example provides a method for preparing a Zn-0.08Cu-0.16Ti alloy sheet, which is different from example 8 in that Ce and Nd elements are not introduced, and the others are the same as those in example 8.
Comparative example 9
The comparative example provides a method for preparing a Zn-0.16Cu-0.08Ti alloy sheet, which is different from example 9 in that Ce and Nd elements are not introduced, and the others are the same as those in example 9.
Comparative example 10
This comparative example provides a method for producing a Zn-0.05Cu-0.05Ti-0.2Ce-0.05Nd alloy sheet, which is the same as in example 1 except for the rolling process. The specific rolling process of the comparative example is that the steel is subjected to 2 times of hot rolling at the temperature of 320 ℃, and the reduction of each time is 50 percent; and then, carrying out water spray cooling on the plate, carrying out multi-pass cold rolling, wherein the reduction of each pass is 20%, and finally preparing the Zn-0.05Cu-0.05Ti-0.2Ce-0.05Nd zinc alloy plate with the thickness of 1 mm.
Comparative example 11
This comparative example provides a method for producing a Zn-0.15Cu-0.1Ti-0.6Ce-0.08Nd alloy sheet, which is the same as in example 2 except for the rolling process. The specific rolling process of the comparative example is that the steel is subjected to 2 times of hot rolling at the temperature of 300 ℃, and the reduction of each time is 25 percent; and then carrying out water spray cooling on the plate, carrying out multi-pass cold rolling, wherein the reduction of each pass is 20%, and finally preparing the Zn-0.15Cu-0.1Ti-0.6Ce-0.08Nd zinc alloy plate with the thickness of 1.1 mm.
Comparative example 12
This comparative example provides a method for producing a Zn-0.2Cu-0.2Ti-0.8Ce-0.1Nd alloy sheet, which is the same as in example 3 except for the rolling process. The specific rolling process of the comparative example is that the steel is subjected to 1-pass hot rolling at the temperature of 360 ℃, and the pass reduction is 50%; and then carrying out water spray cooling on the plate, carrying out multi-pass cold rolling, wherein the reduction of each pass is 30%, and finally preparing the Zn-0.2Cu-0.2Ti-0.8Ce-0.1Nd zinc alloy plate with the thickness of 1.75 mm.
Comparative example 13
This comparative example provides a method for producing a Zn-0.03Cu-0.03Ti-0.2Ce-0.02Nd alloy sheet, which is the same as in example 4 except for the rolling process. The specific rolling process of the comparative example is that the steel is subjected to 2-pass hot rolling at the temperature of 220 ℃, and the pass reduction is 20%; and then carrying out water spray cooling on the plate, carrying out multi-pass cold rolling, wherein the reduction of each pass is 30%, and finally preparing the Zn-0.03Cu-0.03Ti-0.2Ce-0.02Nd zinc alloy plate with the thickness of 2.5 mm.
Comparative example 14
This comparative example provides a method for producing a Zn-0.2Cu-0.03Ti-0.8Ce-0.02Nd alloy sheet, which is the same as in example 5 except for the rolling process. The specific rolling process of the comparative example is that the steel is subjected to 3 times of hot rolling at the temperature of 310 ℃, and the pass reduction is 50%; and then carrying out water spray cooling on the plate, carrying out multi-pass cold rolling, wherein the reduction of each pass is 30%, and finally preparing the Zn-0.2Cu-0.03Ti-0.8Ce-0.02Nd zinc alloy plate with the thickness of 1.2 mm.
The Zn-Cu-Ti-Ce-Nd alloy sheets prepared in examples 1 to 9 were compared with the zinc alloy sheets prepared in comparative examples 1 to 14 in terms of microstructure, mechanical properties, and corrosion resistance (corrosion medium of 3.5 wt.% NaCl solution), and the specific results are shown in table 1 and fig. 1 to 4.
TABLE 1
As can be seen from table 1 and fig. 1 to 4, the Zn-Cu-Ti-Ce-Nd alloy sheets prepared in examples 1 to 9 have not only significantly refined grains and second phases, more uniform distribution, but also higher corrosion resistance and mechanical properties, compared with the zinc alloy sheets prepared in comparative examples 1 to 14, and therefore the zinc alloy sheet prepared in the present invention has strong market competitiveness, a wide application range, and good application prospects.
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. And are neither required nor exhaustive of all embodiments. And obvious variations or modifications therefrom are within the scope of the invention.
Claims (9)
1. The preparation method of the low-copper low-titanium high-strength high-toughness high-corrosion-resistance zinc alloy plate is characterized by comprising the following steps of:
s1, preheating and drying the alloy raw material, putting the alloy raw material into a melting furnace, heating to 460-650 ℃, and refining after the alloy raw material is completely melted;
s2, cooling the refined zinc alloy melt to a casting temperature, and then preparing a zinc alloy casting blank by using a continuous casting machine; the continuous casting process parameters are the casting temperature of 450-;
s3, continuously rolling the casting blank obtained in the S2 to obtain the zinc alloy plate with the thickness of 0.1-2.5 mm.
2. The method for preparing the low-copper low-titanium high-strength high-toughness high-corrosion-resistance zinc alloy plate according to claim 1, wherein the alloy raw materials in the step S1 are pure zinc, pure Cu or an intermediate alloy containing Cu, an intermediate alloy containing Ti, an intermediate alloy containing Ce and an intermediate alloy containing Nd.
3. The method for preparing the low-copper low-titanium high-strength high-toughness high-corrosion-resistance zinc alloy plate according to claim 2,
the Cu-containing master alloy can be selected from one or more of Zn- (5-50) Cu, Ti- (10-50) Cu, Cu- (2-20) Ce, Cu- (2-20) Nd and Zn- (2-20) Cu- (2-20) Ti;
the intermediate alloy containing Ti element can select one or more of Zn- (1-15) Ti, Ti- (10-50) Cu, Ti- (2-20) Ce, Ti- (2-20) Nd and Zn- (2-20) Cu- (2-20) Ti;
the intermediate alloy containing Ce element can select one or more of Zn- (1-20) Ce, Ti- (2-20) Ce and Cu- (2-20) Ce;
the Nd-containing intermediate alloy can be one or more of Zn- (1-20) Nd, Ti- (2-20) Nd and Cu- (2-20) Nd.
4. The method for preparing the low-copper low-titanium high-strength high-toughness high-corrosion-resistance zinc alloy plate according to claim 2, wherein the alloy raw material in the step S1 is placed into a drying furnace or a holding furnace for preheating and drying.
5. The preparation method of the low-copper low-titanium high-strength high-toughness high-corrosion-resistance zinc alloy plate according to claim 4, wherein the preheating and drying process in S1 is carried out at a preheating temperature of 100-300 ℃ for 2-20 min.
6. The method for preparing the low-copper low-titanium high-strength high-toughness high-corrosion-resistance zinc alloy plate according to claim 1, wherein the refining process in the S1 is a rotary argon blowing method and N is introduced2And Cl2Adding one of chlorine salts into the mixed gas, and refining for 3-20 min.
7. The zinc alloy plate with low copper, low titanium, high strength, high toughness and high corrosion resistance and the preparation method thereof according to claim 1 are characterized in that: the continuous rolling in step S3 is:
firstly, continuously casting a casting blank which is just left from a casting machine and has the temperature of 220-360 ℃ is subjected to 1-3 times of hot rolling, and the reduction of each time is 20-50%; then spraying water to cool the hot-rolled plate to reduce the temperature to 100-200 ℃, and then carrying out 1-2 times of warm rolling, wherein the reduction of each time is 30-50%; then, spraying water to cool the plate, and then carrying out cold rolling for 1-3 times, wherein the reduction of each time is 10-30%; the total reduction of the sheet material is controlled to be 70-95%, and finally the zinc alloy sheet material with the thickness of 0.1-2.5mm is obtained.
8. A low-copper low-titanium high-strength high-toughness high-corrosion-resistance zinc alloy plate prepared by the method of any one of claims 1 to 7,
the zinc alloy plate comprises the following components in percentage by mass: 0.03-0.2% of Cu, 0.03-0.2% of Ti, 0.2-0.8% of Ce, 0.02-0.1% of Nd, and the balance of Zn and inevitable impurities.
9. The low-copper low-titanium high-strength high-toughness high-corrosion-resistance zinc alloy sheet material as claimed in claim 8,
the tensile strength of the copper-low-titanium high-strength high-toughness high-corrosion-resistance zinc alloy plate is 250-450MPa, the yield strength is 210-420MPa, the elongation is 40-110%, the corrosion rate is less than 0.08mm/a, and the corrosion medium is 3.5 wt.% of NaCl solution.
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