A corrosion-resistant zinc alloy material and preparation method thereof

Abstract

The present invention relates to the technical field of zinc alloy materials, and in particular to a corrosion-resistant zinc alloy material and a preparation method thereof. A corrosion-resistant zinc alloy material comprises the following components in percentage by mass: 8% to 11% aluminum, 0.25% to 0.45% copper, 0.1% to 0.3% nickel, 0.01% to 0.02% titanium, 0.01% to 0.03% cobalt, 0.01% to 0.03% lanthanum, 0.001% to 0.002% dysprosium, 0.003% to 0.005% manganese silicide, and the balance is zinc. The present application not only maintains the original good casting performance and mechanical strength of the zinc alloy through a specific ratio of alloy components and a sophisticated preparation process, but also significantly improves the corrosion resistance of the zinc alloy material, prolongs its service life, and broadens its application range.

Description

Technical Field

[0001] The invention relates to the technical field of zinc alloy materials, and in particular to a corrosion-resistant zinc alloy material and a preparation method thereof. Background Art

[0002] Zinc alloy material is an alloy material with zinc as the main component and aluminum, copper and other elements added. Due to its good casting performance, mechanical strength and relatively low cost, it is widely used in many fields such as automotive parts, building hardware, electronic and electrical products and daily necessities. However, zinc itself is a relatively active metal. It is easy to react with oxygen in the air to form zinc oxide in a humid environment, and then further converted into basic zinc carbonate, resulting in the formation of loose corrosion products on the surface, weakening the overall structure of the zinc alloy material. At the same time, in some cases, zinc alloy materials will undergo intergranular corrosion, especially in an environment containing chloride ions, where the corrosion rate is significantly accelerated. This corrosion resistance limits the use of zinc alloy materials in some application scenarios with high requirements for durability and reliability, such as aerospace, marine engineering and other fields. In order to extend the service life of zinc alloy materials, broaden their application scope and improve product quality, it is particularly urgent to improve their corrosion resistance. Therefore, it is necessary to further improve the corrosion resistance of zinc alloy materials, overcome the shortcomings of existing zinc alloy materials in corrosion resistance, thereby further broadening the application field of zinc alloy materials and meeting the needs of different industries for zinc alloy materials. Summary of the invention

[0003] In order to further improve the corrosion resistance of zinc alloy materials, the present application provides a zinc alloy material with good corrosion resistance. The present application not only maintains the original good casting performance and mechanical strength of the zinc alloy through a specific ratio of alloy components and a sophisticated preparation process, but also significantly improves the corrosion resistance of the zinc alloy material, prolongs its service life, and broadens its application range.

[0004] In the first aspect, the present application provides a corrosion-resistant zinc alloy material adopting the following technical solution:

[0005] A corrosion-resistant zinc alloy material comprises the following components in percentage by mass: 8% to 11% aluminum, 0.25% to 0.45% copper, 0.1% to 0.3% nickel, 0.01% to 0.02% titanium, 0.01% to 0.03% cobalt, 0.01% to 0.03% lanthanum, 0.001% to 0.002% dysprosium, 0.003% to 0.005% manganese silicide, and the balance is zinc.

[0006] In the above technical solution, the present application significantly improves the corrosion resistance of zinc alloy through the above formula design. Among them, aluminum forms a dense aluminum oxide protective film, which effectively prevents the external corrosive medium from contacting the base metal and refines the grains; copper enhances hardness and strength but not excessively to maintain ductility; nickel refines the grains and inhibits the formation of harmful phases, reducing local corrosion; titanium, as an effective grain refiner, improves strength and toughness and enhances corrosion resistance; cobalt promotes the formation of passivation film, especially in a chloride ion-containing environment to improve the stability of zinc alloy materials, enhance the stability of the passivation film, and prevent the film from cracking and peeling off; lanthanum and dysprosium, as rare earth elements, can increase the electrode potential and form a dense oxide layer on the surface. The two work synergistically to stabilize the passivation film, so that cobalt can more effectively promote the formation of the passivation film and maintain its integrity, reducing the generation of corrosion products; manganese silicide can remove oxygen from the melt during the smelting process, reduce oxide inclusions, and help lanthanum and dysprosium better play their role in purifying and refining grains, while also ensuring that cobalt can form a stable passivation film on the surface, because the local inhomogeneity that may be caused by oxide inclusions is reduced. The present application reduces the influence of corrosive media on zinc alloy materials through the synergistic effect of these elements, so that the zinc alloy materials exhibit good corrosion resistance in complex environments.

[0007] Preferably, the following components are included in mass percentage: 9.476% aluminum, 0.382% copper, 0.217% nickel, 0.018% titanium, 0.023% cobalt, 0.019% lanthanum, 0.001% dysprosium, 0.004% manganese silicide, and the balance is zinc.

[0008] Preferably, the particle size of the manganese silicide is 10-30 nm.

[0009] In a second aspect, the present application provides a method for preparing a corrosion-resistant zinc alloy material using the following technical solution:

[0010] A method for preparing a corrosion-resistant zinc alloy material comprises the following steps:

[0011] Step 1: preparing the ingredients of aluminum source, copper source, nickel source, titanium source, cobalt source, rare earth source, manganese silicide and pure zinc respectively according to mass percentage;

[0012] Step 2: Smelt aluminum source, copper source, nickel source, titanium source, cobalt source, lanthanum source, dysprosium source, manganese silicide and pure zinc, take samples from the furnace, conduct pre-furnace analysis, and proceed to the next process after passing the analysis;

[0013] Step 3: pouring the melt obtained in step 2 to obtain an ingot;

[0014] Step 4: After the ingot obtained in step 3 is kept warm for 2 to 3 hours, it is naturally cooled to obtain a corrosion-resistant zinc alloy material.

[0015] In the above technical scheme, the present application ensures the uniform distribution of each component in the alloy through a sophisticated preparation process, batching in step 1, smelting and furnace analysis in step 2, pouring in step 3 and heat preservation and natural cooling in step 4, which helps to improve the mechanical properties and corrosion resistance of the zinc alloy material. The preparation method of the present application is not only simple in process and easy to control, but also has good performance of the corrosion-resistant zinc alloy material prepared, and has broad application prospects.

[0016] Preferably, the aluminum source is a Zn-Al-Cu ternary master alloy; the copper source is electrolytic copper and a Zn-Al-Cu ternary master alloy; the nickel source is a Zn-Ni-Ti ternary master alloy; the titanium source is a Zn-Ni-Ti ternary master alloy; the cobalt source is a Co-Zn master alloy; the lanthanum source is a La-Zn master alloy; and the dysprosium source is pure dysprosium.

[0017] In the above technical solution, the present application can ensure the precise control and uniform distribution of alloy components by selecting specific master alloys as raw materials, avoiding the performance degradation caused by impure raw materials or improper proportions. At the same time, the introduction of these master alloys also helps to improve the fluidity during the smelting process, reduce casting defects, and further improve the overall performance of zinc alloy materials.

[0018] Preferably, the specific operation of step 2 is as follows: first, the gas furnace is heated to 450-500°C, pure zinc is added, and the temperature is gradually raised to 600-650°C until the pure zinc is completely melted, and then the temperature is gradually raised to 650-700°C, aluminum source and copper source are added until they are completely melted and stirred until they are evenly mixed, then the temperature is raised to 700-750°C, nickel source and titanium source are added until they are completely melted and stirred until they are evenly mixed, then the temperature is raised to 750-800°C, cobalt source, lanthanum source and dysprosium source are added until they are completely melted and stirred until they are evenly mixed, then the furnace temperature is maintained at 750-800°C, manganese silicide is added and stirred sufficiently, and finally samples are taken from the furnace for furnace front analysis, and the next process is carried out after passing the analysis.

[0019] In the above technical solution, the present application ensures uniform melting and mixing of each component in the melt by strictly controlling the melting temperature and addition order of step 2, thereby avoiding performance differences caused by uneven distribution of components. At the same time, by maintaining a certain furnace temperature and fully stirring, manganese silicide can be evenly dispersed in the melt, giving full play to its role in removing oxygen and refining grains.

[0020] Preferably, the pouring temperature of step 3 is 680-720°C.

[0021] In the above technical solution, by controlling the pouring temperature, it is possible to ensure the fluidity of the alloy while avoiding the coarsening of the structure and the degradation of the performance caused by excessively high temperature.

[0022] Preferably, the insulation temperature of step 4 is 350-400°C.

[0023] In the above technical solution, by keeping the temperature within this temperature range, the phase change in the ingot can be fully carried out, the structure can be further refined, and the performance of the alloy can be improved. At the same time, the natural cooling method also helps to reduce thermal stress and avoid the generation of defects such as cracks.

[0024] In summary, the present application includes at least one of the following beneficial technical effects:

[0025] Through the specific ratio of alloy components, the synergistic effect of the components reduces the impact of corrosive media on zinc alloy materials, so that zinc alloy materials can still maintain good corrosion resistance in complex environments, extend the service life of zinc alloy materials, and broaden their application range;

[0026] Through the sophisticated preparation process, the original good casting properties and mechanical strength of the zinc alloy material are maintained, which helps to improve the corrosion resistance of the zinc alloy material. DETAILED DESCRIPTION

[0027] In order to better illustrate the purpose, technical solutions and advantages of the present invention, the present invention will be further described below in conjunction with specific embodiments.

[0028] The contents of the components of the zinc alloy materials of Examples 1 to 3 are shown in Table 1.

[0029] Table 1:

[0030]

[0031] Embodiment 1: A method for preparing a corrosion-resistant zinc alloy material, comprising the following steps:

[0032] Step 1: Prepare the ingredients according to the mass percentages in Table 1, including aluminum source, copper source, nickel source, titanium source, cobalt source, rare earth source, manganese silicide and pure zinc.

[0033] Among them, the aluminum source is a Zn-Al-Cu ternary master alloy; the copper source is electrolytic copper and a Zn-Al-Cu ternary master alloy; the nickel source is a Zn-Ni-Ti ternary master alloy; the titanium source is a Zn-Ni-Ti ternary master alloy; the cobalt source is a Co-Zn master alloy; the lanthanum source is a La-Zn master alloy; and the dysprosium source is pure dysprosium.

[0034] Step 2: First, heat the gas furnace to 450°C, add pure zinc, and gradually heat it to 600°C until the pure zinc is completely melted, then gradually heat it to 650°C, add aluminum source and copper source until they are completely melted and stir until they are evenly mixed, then heat it to 700°C, add nickel source and titanium source until they are completely melted and stir until they are evenly mixed, then heat it to 750°C, add cobalt source, lanthanum source, and dysprosium source until they are completely melted and stir until they are evenly mixed, then maintain the furnace temperature at 750°C, add manganese silicide and stir thoroughly, finally take samples from the furnace for pre-furnace analysis, and proceed to the next process after the content of each component is within the qualified range and the impurity content is ≤0.01%.

[0035] Step 3: pouring the melt obtained in step 2 into a mold at 680° C. to obtain an ingot;

[0036] Step 4: The ingot obtained in step 3 is kept at 350° C. for 2.5 hours and then cooled naturally to obtain a corrosion-resistant zinc alloy material.

[0037] Embodiment 2: A method for preparing a corrosion-resistant zinc alloy material, comprising the following steps:

[0038] Step 1: Prepare the ingredients according to the mass percentages in Table 1, including aluminum source, copper source, nickel source, titanium source, cobalt source, rare earth source, manganese silicide and pure zinc.

[0039] Among them, the aluminum source is a Zn-Al-Cu ternary master alloy; the copper source is electrolytic copper and a Zn-Al-Cu ternary master alloy; the nickel source is a Zn-Ni-Ti ternary master alloy; the titanium source is a Zn-Ni-Ti ternary master alloy; the cobalt source is a Co-Zn master alloy; the lanthanum source is a La-Zn master alloy; and the dysprosium source is pure dysprosium.

[0040] Step 2: First, heat the gas furnace to 450°C, add pure zinc, and gradually heat it to 650°C until the pure zinc is completely melted, then gradually heat it to 680°C, add aluminum source and copper source until they are completely melted and stir until they are evenly mixed, then heat it to 720°C, add nickel source and titanium source until they are completely melted and stir until they are evenly mixed, then heat it to 780°C, add cobalt source, lanthanum source, and dysprosium source until they are completely melted and stir until they are evenly mixed, then maintain the furnace temperature at 780°C, add manganese silicide and stir thoroughly, finally take samples from the furnace for pre-furnace analysis, and proceed to the next process when the content of each component is within the qualified range and the impurity content is ≤0.01%.

[0041] Step 3: pouring the melt obtained in step 2 into a mold at 700° C. to obtain an ingot;

[0042] Step 4: The ingot obtained in step 3 is kept at 380° C. for 2.5 hours and then cooled naturally to obtain a corrosion-resistant zinc alloy material.

[0043] Embodiment 3: A method for preparing a corrosion-resistant zinc alloy material, comprising the following steps:

[0044] Step 1: Prepare the ingredients according to the mass percentages in Table 1, including aluminum source, copper source, nickel source, titanium source, cobalt source, rare earth source, manganese silicide and pure zinc.

[0045] Among them, the aluminum source is a Zn-Al-Cu ternary master alloy; the copper source is electrolytic copper and a Zn-Al-Cu ternary master alloy; the nickel source is a Zn-Ni-Ti ternary master alloy; the titanium source is a Zn-Ni-Ti ternary master alloy; the cobalt source is a Co-Zn master alloy; the lanthanum source is a La-Zn master alloy; and the dysprosium source is pure dysprosium.

[0046] Step 2: First, heat the gas furnace to 500°C, add pure zinc, and gradually heat it to 650°C until the pure zinc is completely melted, then gradually heat it to 700°C, add aluminum source and copper source until they are completely melted and stir until they are evenly mixed, then heat it to 750°C, add nickel source and titanium source until they are completely melted and stir until they are evenly mixed, then heat it to 800°C, add cobalt source, lanthanum source, and dysprosium source until they are completely melted and stir until they are evenly mixed, then maintain the furnace temperature at 800°C, add manganese silicide and stir thoroughly, finally take samples from the furnace for pre-furnace analysis, and proceed to the next process after the content of each component is within the qualified range and the impurity content is ≤0.01%.

[0047] Step 3: pouring the melt obtained in step 2 into a mold at 720° C. to obtain an ingot;

[0048] Step 4: The ingot obtained in step 3 is kept at 400° C. for 2.5 hours and then cooled naturally to obtain a corrosion-resistant zinc alloy material.

[0049] The contents of the components of the zinc alloy materials of Comparative Examples 1 to 5 are shown in Table 2.

[0050] Table 2:

[0051]

[0052] Comparative Example 1: A zinc alloy material, which is different from Example 2 in that it does not contain a cobalt source. The specific dosage of each component is shown in Table 2.

[0053] Step 2 is as follows: first, heat the gas furnace to 450°C, add pure zinc, and gradually heat it to 650°C until the pure zinc is completely melted, then gradually heat it to 680°C, add aluminum source and copper source until they are completely melted and stir until they are evenly mixed, then heat it to 720°C, add nickel source and titanium source until they are completely melted and stir until they are evenly mixed, then heat it to 780°C, add lanthanum source and dysprosium source until they are completely melted and stir until they are evenly mixed, then maintain the furnace temperature at 780°C, add manganese silicide and stir thoroughly, finally take samples from the furnace, conduct pre-furnace analysis, and proceed to the next process after the content of each component is within the qualified range and the impurity content is ≤0.01%.

[0054] Comparative Example 2: A zinc alloy material, which is different from Example 2 in that it does not contain a lanthanum source. The specific amounts of each component are shown in Table 2.

[0055] Step 2 is as follows: first, heat the gas furnace to 450°C, add pure zinc, and gradually heat it to 650°C until the pure zinc is completely melted, then gradually heat it to 680°C, add aluminum source and copper source until they are completely melted and stir until they are evenly mixed, then heat it to 720°C, add nickel source and titanium source until they are completely melted and stir until they are evenly mixed, then heat it to 780°C, add cobalt source and dysprosium source until they are completely melted and stir until they are evenly mixed, then maintain the furnace temperature at 780°C, add manganese silicide and stir thoroughly, finally take samples from the furnace, conduct pre-furnace analysis, and proceed to the next process after the content of each component is within the qualified range and the impurity content is ≤0.01%.

[0056] Comparative Example 3: A zinc alloy material, which is different from Example 2 in that it does not contain a dysprosium source. The specific amounts of each component are shown in Table 2.

[0057] Step 2 is as follows: first, heat the gas furnace to 450°C, add pure zinc, and gradually heat it to 650°C until the pure zinc is completely melted, then gradually heat it to 680°C, add aluminum source and copper source until they are completely melted and stir until they are evenly mixed, then heat it to 720°C, add nickel source and titanium source until they are completely melted and stir until they are evenly mixed, then heat it to 780°C, add cobalt source and lanthanum source until they are completely melted and stir until they are evenly mixed, then maintain the furnace temperature at 780°C, add manganese silicide and stir thoroughly, finally take samples from the furnace, conduct pre-furnace analysis, and proceed to the next process after the content of each component is within the qualified range and the impurity content is ≤0.01%.

[0058] Comparative Example 4: A zinc alloy material, which is different from Example 2 in that it does not contain a lanthanum source or a dysprosium source. The specific amounts of each component are shown in Table 2.

[0059] Step 2 is as follows: first, heat the gas furnace to 450°C, add pure zinc, and gradually heat it to 650°C until the pure zinc is completely melted, then gradually heat it to 680°C, add aluminum source and copper source until they are completely melted and stir until they are evenly mixed, then heat it to 720°C, add nickel source and titanium source until they are completely melted and stir until they are evenly mixed, then heat it to 780°C, add cobalt source until it is completely melted and stir until it is evenly mixed, then maintain the furnace temperature at 780°C, add manganese silicide and stir thoroughly, finally take samples from the furnace, conduct pre-furnace analysis, and proceed to the next process after the content of each component is within the qualified range and the impurity content is ≤0.01%.

[0060] Comparative Example 5: A zinc alloy material, which is different from Example 2 in that it does not contain manganese silicide. The specific dosage of each component is shown in Table 2.

[0061] Step 2 is as follows: first heat the gas furnace to 450°C, add pure zinc, and gradually heat it to 650°C until the pure zinc is completely melted, then gradually heat it to 680°C, add aluminum source and copper source until they are completely melted and stir until they are evenly mixed, then heat it to 720°C, add nickel source and titanium source until they are completely melted and stir until they are evenly mixed, then heat it to 780°C, add cobalt source, lanthanum source, and dysprosium source until they are completely melted and stir until they are evenly mixed, finally take samples from the furnace and conduct pre-furnace analysis, and proceed to the next process after the content of each component is within the qualified range and the impurity content is ≤0.01%.

[0062] Performance testing of zinc alloy materials:

[0063] Test samples: zinc alloy materials of the above embodiments and comparative examples.

[0064] Detection method: The weight loss method was used to detect the corrosion rate of samples in seawater, 30# engine oil, tap water, water vapor, and 2% NaOH. The detection temperature was 25°C and the time was 1000h.

[0065] Refer to GB / T228.1-2010 to test the elongation (%) of the sample.

[0066] Corrosion resistance rate (g / m 2 ·h)=(w0-w1) / [(s0-s1) / 2*t]

[0067] Wherein, w0: sample mass before test (g), w1: sample mass after test (g), s0: sample surface area before test (m 2 ), s1: surface area of ​​sample after test (m 2 ), t: corrosion time (h).

[0068] In the above test, three groups of parallel tests were performed on each sample, and the test results were averaged. The test results are shown in Table 3.

[0069] Table 3:

[0070]

[0071] As shown in Table 3, the zinc alloy materials of Examples 1 to 3 have low corrosion rates in seawater, 30# engine oil, tap water, water vapor, and 2% NaOH, and high elongations, which indicates that the zinc alloy materials of Examples 1 to 3 have good corrosion resistance and mechanical properties. In particular, the zinc alloy material of Example 2 has low corrosion resistance and high elongation in various corrosive environments, showing good corrosion resistance and mechanical properties.

[0072] Further, comparative example 1 does not contain a cobalt source, and the corrosion resistance and mechanical properties have a certain degree of decline, indicating that the addition of cobalt elements has a positive effect on improving the corrosion resistance and mechanical properties of zinc alloy materials. Comparative example 2 does not contain a lanthanum source, and the corrosion resistance and mechanical properties are also reduced, indicating that the lanthanum element also contributes to improving the performance of zinc alloy materials. Comparative example 3 does not contain a dysprosium source, and the performance change is similar to that of comparative example 2, but the degree of influence is slightly smaller. Comparative example 4 does not contain both a lanthanum source and a dysprosium source, and the corrosion resistance and mechanical properties decrease more significantly, indicating that the lanthanum element and the dysprosium element act together to improve the performance of the zinc alloy material. Comparative example 5 does not contain manganese silicide, and the corrosion resistance and mechanical properties also decrease to a certain extent, indicating that manganese silicide plays a key role in improving the corrosion resistance and mechanical properties of zinc alloy materials. It can be seen that the present application significantly improves the corrosion resistance of zinc alloy materials through a specific ratio of alloy components and a sophisticated preparation process.

[0073] This specific embodiment is merely an explanation of the present application and is not a limitation of the present application. After reading this specification, those skilled in the art may make modifications to the present embodiment without any creative contribution as needed, but such modifications are protected by the patent law as long as they are within the scope of the claims of the present application.

Claims

1. A corrosion-resistant zinc alloy material, characterized in that: The composition comprises the following components in percentage by mass: 8% to 11% aluminum, 0.25% to 0.45% copper, 0.1% to 0.3% nickel, 0.01% to 0.02% titanium, 0.01% to 0.03% cobalt, 0.01% to 0.03% lanthanum, 0.001% to 0.002% dysprosium, 0.003% to 0.005% manganese silicide, and the balance is zinc; The particle size of the manganese silicide is 10-30 nm; The aluminum source is a Zn-Al-Cu ternary master alloy; the copper source is electrolytic copper and a Zn-Al-Cu ternary master alloy; the nickel source is a Zn-Ni-Ti ternary master alloy; the titanium source is a Zn-Ni-Ti ternary master alloy; the cobalt source is a Co-Zn master alloy; the lanthanum source is a La-Zn master alloy; and the dysprosium source is pure dysprosium.

2. The corrosion-resistant zinc alloy material according to claim 1, characterized in that: The composition includes the following components in mass percentage: 9.476% aluminum, 0.382% copper, 0.217% nickel, 0.018% titanium, 0.023% cobalt, 0.019% lanthanum, 0.001% dysprosium, 0.004% manganese silicide, and the balance is zinc.

3. A method for preparing the corrosion-resistant zinc alloy material according to any one of claims 1 to 2, characterized in that: The method comprises the following steps: Step 1: respectively preparing aluminum source, copper source, nickel source, titanium source, cobalt source, rare earth source, manganese silicide and pure zinc according to mass percentage; Step 2: smelting the aluminum source, copper source, nickel source, titanium source, cobalt source, lanthanum source, dysprosium source, manganese silicide and pure zinc, taking samples from the furnace, conducting pre-furnace analysis, and proceeding to the next process after passing the analysis; Step 3: pouring the melt obtained in step 2 to obtain an ingot; Step 4: keeping the ingot obtained in step 3 warm for 2 to 3 hours, cooling it naturally, and obtaining a corrosion-resistant zinc alloy material.

4. The method for preparing a corrosion-resistant zinc alloy material according to claim 3, characterized in that: The specific operation of step 2 is as follows: first, the gas furnace is heated to 450-500°C, pure zinc is added, and the temperature is gradually raised to 600-650°C until the pure zinc is completely melted, and then the temperature is gradually raised to 650-700°C, aluminum source and copper source are added until they are completely melted and stirred until they are evenly mixed, then the temperature is raised to 700-750°C, nickel source and titanium source are added until they are completely melted and stirred until they are evenly mixed, then the temperature is raised to 750-800°C, cobalt source, lanthanum source and dysprosium source are added until they are completely melted and stirred until they are evenly mixed, then the furnace temperature is maintained at 750-800°C, manganese silicide is added and stirred sufficiently, and finally samples are taken from the furnace for furnace front analysis, and the next process is carried out after passing the analysis.

5. The method for preparing a corrosion-resistant zinc alloy material according to claim 3, characterized in that: The pouring temperature of step 3 is 680~720℃.

6. The method for preparing a corrosion-resistant zinc alloy material according to claim 3, characterized in that: The insulation temperature of step 4 is 350~400℃.

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