CN109022932B - High-strength corrosion-resistant aluminum alloy cathode material for hydrometallurgy zinc electrodeposition and preparation method thereof - Google Patents
High-strength corrosion-resistant aluminum alloy cathode material for hydrometallurgy zinc electrodeposition and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-strength corrosion-resistant aluminum alloy cathode material for zinc electrowinning in hydrometallurgy and a preparation method thereof, belonging to the technical field of cathode materials. The aluminum alloy cathode material comprises, by mass, 0.05-0.15% of Si, 0.01-0.1% of Fe, 0.3-3% of Mn, 0.5-1.2% of Mg, 0.01-0.15% of Cr, 0-0.03% of Cu, 0.01-0.08% of Zn, 0.05-0.25% of Ti, 0.01-0.05% of B, 0.05-0.2% of Zr, 0.05-0.3% of Sb, 0.05-0.5% of RE (rare earth), not more than 0.05% of unavoidable impurities, and the balance of Al. The aluminum alloy cathode material is prepared by alloy proportioning, smelting, refining, deslagging, exhausting, filtering, ingot casting, surface milling, oil removal, homogenizing annealing, hot rolling, cold rolling, finishing and cutting to length. The aluminum alloy cathode material disclosed by the invention has the advantages of corrosion resistance, good electrochemical performance, high mechanical strength and excellent welding processability in an electrodeposited zinc system, and the corrosion resistance in fluorine-containing and chloride ion electrodeposited zinc melt is obviously superior to that of the traditional 1060 and 1070 type electrodeposited zinc-aluminum cathode plate.
Description
Technical Field
The invention relates to a high-strength corrosion-resistant aluminum alloy cathode material for zinc electrowinning in hydrometallurgy and a preparation method thereof, belonging to the technical field of cathode materials.
Background
In the hydrometallurgy zinc electrodeposition industry, the commonly used cathode material is mainly 1060 and 1070 series industrial pure aluminum, and the cathode material has the advantages of good conductivity, excellent processing and forming performance, high plasticity, good corrosion resistance in atmospheric environment and the like, so that the cathode material is widely applied. Along with the increasing shortage of high-quality zinc ore resources, the diversification of the zinc ore resources and the large recycling of secondary resources cause that the overproof fluorine and chloride ions in a hydrometallurgy electro-deposition zinc solution system are serious. In the electrolytic process, the aluminum negative plate works in severe environments such as acid mist corrosion for a long time, along with the improvement of the concentration of fluorine and chlorine ions in the electrolyte, the corrosion rate of the plate is rapidly accelerated, and pitting corrosion and pit corrosion occur on the surface of the plate to cause the surface of the plate to be uneven, so that the electrolytic efficiency, the zinc stripping performance of the plate, the zinc electrodeposition quality and the like are influenced, the service life of the plate is greatly shortened, and the production cost of smelting enterprises is greatly increased. On the other hand, the conventional 1060 and 1070 pure aluminum cathode has low strength, so that the cathode is easy to deform during zinc stripping and use, the use of the cathode is seriously affected, and even the phenomena of short circuit, scrapping and the like of the electrode are caused. Therefore, the service life of the aluminum cathode for zinc electrodeposition is prolonged, the strength and the corrosion resistance of the cathode material are improved, the production cost is effectively reduced, and the problem to be solved in the zinc hydrometallurgy industry is solved.
Patent CN201010139792.2 discloses a method for improving corrosion resistance of cathode aluminum plate for zinc electrolysis, which comprises rolling with rolling oil with special composition formula and treatment after rolling of aluminum plate. The rolling oil comprises base oil and additive, wherein the base oil is lubricating oil with distillation range of 225.7-243.3 ℃, the closed flash point is 95 ℃, the viscosity (40 ℃) is 1.9-2.0mm2/s, the additive is linear chain methyl alkanoate and dodecyl phosphate ester, and the base oil: the composition ratio of the methyl alkanoate to the dodecyl phosphate is 100:3:1-100:8:1, the aluminum plate is treated by sodium silicate solution with the concentration of 0.5-2% for 2-10 minutes at 70-90 ℃ after being rolled, and the service life of the aluminum plate is prolonged by more than three times. This patent is only through carrying out chemical treatment to the cathode surface, and the corrosion resistance of reinforcing aluminium cathode is after certain zinc cycle of shelling again, and the corrosion-resistant passive film in cathode surface is destroyed easily, needs to handle again, and its processing technology is also comparatively complicated when having increased manufacturing cost, and moreover, the intensity of aluminium cathode board is not improved.
Patent CN201510759943.7 provides an electrodeposited zinc cathode aluminum alloy and a preparation method thereof, and the electrodeposited zinc cathode aluminum alloy comprises cathode base metal aluminum and intermediate alloys of chromium, nickel and manganese. The preparation method comprises the steps of carrying out oil removal treatment on metal aluminum and intermediate alloy, then smelting the metal aluminum and the intermediate alloy by using a resistance furnace, when furnace burden is softened, uniformly scattering a layer of chloride salt as a covering agent on the surface of the metal, wherein the mass of the chloride salt is 0.5% of the total mass of the smelted alloy, stirring the furnace burden from bottom to top after the furnace burden is completely melted, then pressing hexachloroethane wrapped by aluminum foil as a refining agent, wherein the mass of the hexachloroethane is 0.3% of the total mass of the smelted alloy, pressing the hexachloroethane into a melt for refining, finally slagging off and casting to obtain an aluminum alloy blank, and carrying out hot rolling. Chromium, nickel and manganese are selected as alloy addition elements, the price of metal chromium/nickel is high, the addition content of the metal chromium/nickel is relatively high, the production cost of the cathode plate is increased invisibly, and meanwhile, the excessive addition of the alloy elements can possibly cause that the impurity ion content of an electrolyte system is too high due to the dissolution of the alloy elements after the cathode plate is corroded, so that the stability of the electrolyte system is influenced.
Patent CN201510221461.6 provides a cathode aluminum plate for electrolytic zinc, the cathode aluminum plate requires that the aluminum purity is more than or equal to 99.7%, and the impurity content is: 0.10-0.13% of Fe; 0.06-0.09% of Si; the cathode aluminum plate is obtained by the following steps: smelting, online refining, casting and cold rolling; the online refining is carried out outside the furnace, the refiner is aluminum-titanium-boron wires, the using amount is 3.0-5.0 kg/t, and the online refining time is 10-20 s; the cold rolling cold working amount is 57-67%; the mass percentage of the antioxidant in the rolling oil used in the rolling is 0.5-1.0%. The cathode aluminum plate provided by the invention has the advantages that the corrosion resistance is obviously improved, the service life is prolonged to six to nine months, and the longest service life is more than one year. The corrosion resistance of the aluminum alloy cathode is improved only by controlling the contents of Fe and Si and the processing technology, but the strength of the polar plate is not effectively improved.
Patent CN201611141519.7 discloses an aluminum alloy cathode material for non-ferrous metal electro-deposition zinc and a preparation method thereof, wherein the cathode aluminum alloy material is an alloy material prepared by taking antirust aluminum as a cathode substrate and adding an aluminum-manganese intermediate alloy. The preparation method comprises the steps of smelting pretreated antirust aluminum and aluminum-manganese intermediate alloy in a resistance furnace until the intermediate alloy is softened, and uniformly scattering a layer of hexachloroethane refining agent and aluminum-titanium-boron wire alloy modifier on the surface of the metal; after the furnace burden is completely melted, stirring from bottom to top, and then pressing a refining agent and a modifier into the furnace burden for modification treatment and refining; and then spreading a layer of covering agent, slagging off and casting to prepare the aluminum alloy, and carrying out solid solution strengthening, aging treatment and hot rolling on the aluminum alloy. The prepared aluminum alloy cathode material has good corrosion resistance and high mechanical strength, can improve the zinc deposition rate, improve the hydrogen evolution condition and avoid the phenomena of bubbling and plate burning. The patent adopts 5xxx series antirust aluminum as a raw material, and adopts aluminum-manganese intermediate alloy for modification, although the raw material is simple, the subsequent heat treatment processing technology is more complex.
Although the performance of the aluminum cathode is improved in different aspects such as processing technology and alloy components, the corrosion resistance and strength of the aluminum alloy cathode material are effectively improved, the problems of complex technology, low pole plate strength, low production cost, easy plate burning and the like exist in the technical scheme in consideration of the characteristics of the electro-deposition zinc smelting industry, and further improvement is still needed.
Disclosure of Invention
The invention provides a high-strength corrosion-resistant aluminum alloy cathode material for hydrometallurgical zinc electrodeposition and a preparation method thereof, aiming at the defects of the prior art, the aluminum alloy cathode material has good corrosion resistance, high mechanical strength, difficult deformation of a plate surface, long service life of a polar plate and excellent zinc deposition performance in a fluorine-containing chloride ion zinc electrodeposition molten liquid system, and can effectively improve the production benefit of smelting enterprises.
The high-strength corrosion-resistant aluminum alloy cathode material for zinc electrowinning in hydrometallurgy comprises, by mass, 0.05-0.15% of Si, 0.01-0.1% of Fe, 0.3-3% of Mn, 0.5-1.2% of Mg, 0.01-0.15% of Cr, 0-0.03% of Cu, 0.01-0.08% of Zn, 0.05-0.25% of Ti, 0.01-0.05% of B, 0.05-0.2% of Zr, 0.05-0.3% of Sb0.05, 0.05-0.5% of RE, unavoidable impurities not higher than 0.05%, and the balance of Al;
the preparation method of the high-strength corrosion-resistant aluminum alloy cathode material for the hydrometallurgy zinc electrodeposition comprises the following specific steps:
(1) according to the composition components of the aluminum alloy cathode material, by mass percentage, 0.05-0.15% of Si, 0.01-0.1% of Fe, 0.3-3% of Mn, 0.5-1.2% of Mg, 0.01-0.15% of Cr, 0-0.03% of Cu, 0.01-0.08% of Zn, 0.05-0.25% of Ti, 0.01-0.05% of B, 0.05-0.2% of Zr, 0.05-0.3% of Sb, 0.05-0.5% of RE, not more than 0.05% of inevitable impurities, and the balance of Al, wherein pure aluminum ingots, intermediate alloys Al-Si, Al-Fe, Al-Mn, Al-Mg, Al-Cr, Al-Cu, Al-Zn, Al-Zr, Al-RE and Al-Sb are weighed;
(2) putting the pure aluminum ingot in the step (1) into a melting furnace, heating for melting, continuously heating to raise the temperature of the molten liquid to 690-720 ℃, sequentially adding Al-Si, Al-Fe, Al-Mn, Al-Mg, Al-Cr, Al-Cu, Al-Zn, Al-Zr, Al-RE and Al-Sb intermediate alloys in the step (1), continuously heating to raise the temperature to 725-785 ℃ after materials in the melting furnace are completely melted, smelting for 10-40 min under a stirring condition to obtain an alloy molten liquid, and blowing a refining agent into an 2/3-5/6 area below the surface of the alloy molten liquid by using argon for refining for 10-30 min; after slagging off, adding an alloy refiner Al-5% Ti-1% B into the alloy melt for grain refinement, uniformly covering the surface of the melt with a covering agent, standing for 10-30 min, introducing argon for degassing and refining for 20-40 min, slagging off, performing double filtration by an alumina ceramic filter, and then performing ingot casting at 680-720 ℃ to obtain an alloy ingot;
(3) milling the alloy ingot obtained in the step (2), removing oil, performing homogenization annealing heat treatment for 1-8 hours at the temperature of 520-650 ℃, then sequentially performing hot rolling and medium-temperature rolling, then performing cold rolling, and performing finishing and fixed-length cutting to obtain the aluminum alloy cathode material;
the master alloy Al-Si is Al-10wt% Si, the master alloy Al-Fe is Al-20wt% Fe, the master alloy Al-Mn is Al-10wt% Mn, the master alloy Al-Mg is Al-l0wt% Mg, the master alloy Al-Cr is Al-5wt% Cr, the master alloy Al-Cu is Al-30wt% Cu, the master alloy Al-Zn is Al-30% Zn, the master alloy Al-Zr is Al-5wt% Zr, the master alloy Al-Sb is Al-5% Sb, the master alloy Al-RE is Al-10wt% RE, and RE is rare earth element;
furthermore, the rare earth element RE in the Al-10wt% RE alloy comprises 43-46.5 wt% of Ce, 26-29 wt% of La, 14-16.5 wt% of Nd, 6-9 wt% of Pr, 2-6 wt% (Sm + Er), less than or equal to 2wt% of other rare earth impurities and less than or equal to 1wt% of non-rare earth impurities;
in the step (2), the addition amount of an alloy refiner Al- (5 wt%) Ti- (1 wt%) B is 1-5% of the mass of an alloy melt, a refining agent is hexachloroethane, the addition amount of the refining agent is 0.3-1% of the mass of an alloy melt, and a covering agent is a mixture of 15wt% of expanded perlite, 25wt% of sodium chloride, 35wt% of potassium chloride and 25wt% of cryolite;
the hot rolling temperature in the step (3) is 450-540 ℃, and the rolling thickness is 4-10 cm;
the medium-temperature rolling temperature in the step (3) is 150-280 ℃, and the rolling thickness is 2-4 cm;
the cold rolling in the step (3) is room-temperature rolling, and the rolling thickness is 4-12 mm;
the surface roughness Ra of the alloy plate after finishing in the step (3) is not more than 0.5um, so that the surface has no phenomena of spots, oxidation, oil stain and the like;
preferably, the pure aluminum ingot is pure aluminum above grade 1A 95;
preferably, in the step (2), the alloy smelting temperature is 745-765 ℃;
preferably, the temperature of the homogenizing annealing heat treatment in the step (3) is 550-625 ℃, and the heat preservation time of the homogenizing annealing heat treatment is 2-6 hours;
the alloy refiner Al- (5 wt%) Ti- (1 wt%) B can not only refine the alloy, but also can be used as the addition of Ti and B microelements, thereby improving the strength and corrosion resistance of the aluminum alloy cathode material.
The invention has the beneficial effects that:
(1) the aluminum alloy cathode material has the characteristics of strong corrosion resistance, high mechanical strength and difficult deformation, the service life of the aluminum alloy cathode material in an electrodeposition zinc solution system containing fluorine and chloride ions is obviously prolonged, the performance of the cathode plate is stable, and the zinc precipitation efficiency is high.
(2) The invention optimizes the alloy components and proportion, is assisted by a matched processing technology, combines the interaction mechanism of metal alloying and multiple modified elements, and prepares the aluminum alloy cathode material with uniform and fine crystal grains, excellent corrosion resistance and mechanical property.
Drawings
FIG. 1 is a diagram of a gold phase of a conventional 1070 aluminum cathode material;
FIG. 2 is a gold phase diagram of the aluminum alloy cathode material of example 1;
FIG. 3 is a gold phase diagram of the aluminum alloy cathode material of example 2;
FIG. 4 is a gold phase diagram of the aluminum alloy cathode material of example 3;
FIG. 5 is a gold phase diagram of the aluminum alloy cathode material of example 4;
FIG. 6 is a gold phase diagram of the aluminum alloy cathode material of example 5.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: in this embodiment, the high-strength corrosion-resistant aluminum alloy cathode material for zinc hydrometallurgy electrodeposition comprises, by mass, 0.05% of Si, 0.02% of Fe, 1.8% of Mn, 0.5% of Mg, 0.02% of Cr, 0.01% of cu, 0.01% of Zn, 0.1% of Ti, 0.02% of B, 0.05% of Zr, 0.05% of Sb, 0.1% of RE, unavoidable impurities not higher than 0.05%, and the balance Al;
a preparation method of a high-strength corrosion-resistant aluminum alloy cathode material for zinc electrowinning in hydrometallurgy comprises the following specific steps:
(1) according to the composition components of the aluminum alloy cathode material, by mass percentage, Si is 0.05%, Fe is 0.02%, Mn1.8%, Mg is 0.5%, Cr is 0.02%, Cu is 0.01%, Zn is 0.01%, Ti is 0.1%, B is 0.02%, Zr is 0.05%, Sb is 0.05%, RE is 0.1%, inevitable impurities are not higher than 0.05%, and the balance is Al, and pure aluminum ingots, intermediate alloys Al-Si, Al-Fe, Al-Mn, Al-Mg, Al-Cr, Al-Cu, Al-Zn, Al-Zr, Al-RE and Al-Sb are weighed; wherein the master alloy Al-Si is Al-10wt% Si, the master alloy Al-Fe is Al-20wt% Fe, the master alloy Al-Mn is Al-10wt% Mn, the master alloy Al-Mg is Al-l0wt% Mg, the master alloy Al-Cr is Al-5wt% Cr, the master alloy Al-Cu is Al-30wt% Cu, the master alloy Al-Zn is Al-30% Zn, the master alloy Al-Zr is Al-5wt% Zr, the master alloy Al-Sb is Al-5% Sb, the master alloy Al-RE is Al-10wt% RE, RE is rare earth element; the composition of rare earth element RE in the Al-10wt% RE alloy is 43.5wt% Ce, 28wt% La, 16.5wt% Nd, 6.5wt% Pr, 3wt% (Sm + Er), 2wt% of other rare earth impurities and 0.5wt% of non-rare earth impurities;
(2) putting the pure aluminum ingot in the step (1) into a melting furnace, heating for melting, continuously heating and raising the temperature to 700 ℃ of the melt, sequentially adding Al-Si, Al-Fe, Al-Mn, Al-Mg, Al-Cr, Al-Cu, Al-Zn, Al-Zr, Al-RE and Al-Sb intermediate alloys in the step (1), continuously heating and raising the temperature to 755 ℃ after materials in the melting furnace are completely melted, smelting for 30min under the stirring condition to obtain alloy melt, and blowing a refining agent (hexachloroethane serving as a refining agent) into 2/3 below the surface of the alloy melt by using argon gas for refining for 20 min; after slagging off, adding an alloy refiner Al-5% Ti-1% B into the alloy melt for grain refinement, uniformly covering the surface of the melt with a covering agent, standing for 20min, introducing argon for degassing and refining for 30min, slagging off, performing double filtration by an alumina ceramic filter, and then casting ingots at the temperature of 720 ℃ to obtain alloy ingots; wherein the addition of the refining agent (hexachloroethane) is 0.5 percent of the mass of the alloy melt, and the addition of the alloy refiner Al- (5 percent wt) Ti- (1 percent wt) B is 2 percent of the mass of the alloy melt;
(3) milling the alloy ingot in the step (2), removing oil, placing the alloy ingot at 550 ℃ for carrying out homogenization annealing heat treatment for 6 hours, then carrying out hot rolling and medium temperature rolling in sequence, then carrying out cold rolling, and carrying out finishing and fixed-length cutting to obtain the aluminum alloy cathode material; wherein the hot rolling temperature is 450 ℃, and the rolling thickness is 6 cm; the rolling temperature at the middle temperature is 200 ℃, and the rolling thickness is 2 cm; cold rolling is room temperature rolling, and the rolling thickness is 5 mm; the surface roughness Ra of the finished alloy plate is not more than 0.5um, so that the surface has no phenomena of spots, oxidation, oil stain and the like;
the conventional 1070 aluminum cathode material has a gold phase diagram as shown in fig. 1, and the aluminum alloy cathode material of the present embodiment has a gold phase diagram as shown in fig. 2, and as can be seen from fig. 2, the crystal grains of the present embodiment are uniform and fine, and the average grain size is 30-50 um; the material properties are shown in Table 1, and the Vickers hardness reaches 228N/mm2The zinc electrodeposition efficiency reaches 90.1 percent, the service life of the anode plate reaches 10-14 months, and the comprehensive performance of the anode plate is obviously superior to that of a common 1070 aluminum cathode plate.
Example 2: in this embodiment, the high-strength corrosion-resistant aluminum alloy cathode material for zinc hydrometallurgy electrodeposition comprises, by mass, 0.1% of Si, 0.01% of Fe, 2.4% of Mn, 0.8% of Mg, 0.01% of Cr, 0.02% of cu, 0.02% of Zn, 0.05% of Ti, 0.01% of B, 0.15% of Zr, 0.1% of Sb, 0.25% of RE, unavoidable impurities not higher than 0.05%, and the balance Al;
a preparation method of a high-strength corrosion-resistant aluminum alloy cathode material for zinc electrowinning in hydrometallurgy comprises the following specific steps:
(1) according to the composition components of the aluminum alloy cathode material, by mass percentage, Si is 0.1%, Fe is 0.01%, Mn2.4%, Mg is 0.8%, Cr is 0.01%, Cu is 0.02%, Zn is 0.02%, Ti is 0.05%, B is 0.01%, Zr is 0.15%, Sb is 0.1%, RE is 0.25%, inevitable impurities are not higher than 0.05%, and the balance is Al, and pure aluminum ingots, intermediate alloys Al-Si, Al-Fe, Al-Mn, Al-Mg, Al-Cr, Al-Cu, Al-Zn, Al-Zr, Al-RE and Al-Sb are weighed; wherein the master alloy Al-Si is Al-10wt% Si, the master alloy Al-Fe is Al-20wt% Fe, the master alloy Al-Mn is Al-10wt% Mn, the master alloy Al-Mg is Al-l0wt% Mg, the master alloy Al-Cr is Al-5wt% Cr, the master alloy Al-Cu is Al-30wt% Cu, the master alloy Al-Zn is Al-30% Zn, the master alloy Al-Zr is Al-5wt% Zr, the master alloy Al-Sb is Al-5% Sb, the master alloy Al-RE is Al-10wt% RE, RE is rare earth element; the composition of rare earth element RE in the Al-10wt% RE alloy is 46.5wt% Ce, 26wt% La, 15wt% Nd, 7.5wt% Pr, 2wt% (Sm + Er), 2wt% of other rare earth impurities and 1wt% of non-rare earth impurities;
(2) putting the pure aluminum ingot in the step (1) into a melting furnace, heating for melting, continuously heating to raise the temperature of the molten liquid to 710 ℃, sequentially adding Al-Si, Al-Fe, Al-Mn, Al-Mg, Al-Cr, Al-Cu, Al-Zn, Al-Zr, Al-RE and Al-Sb intermediate alloys in the step (1), continuously heating to 765 ℃ after materials in the melting furnace are completely melted, smelting for 40min under the stirring condition to obtain an alloy molten liquid, and blowing a refining agent (hexachloroethane is used as a refining agent) into 5/6 below the surface of the alloy molten liquid by argon for refining for 30 min; after slagging off, adding an alloy refiner Al-5% Ti-1% B into the alloy melt for grain refinement, uniformly covering the surface of the melt with a covering agent, standing for 15min, introducing argon for degassing and refining for 25min, slagging off, performing double filtration by an alumina ceramic filter, and then casting ingots at the temperature of 710 ℃ to obtain alloy ingots; wherein the addition of the refining agent (hexachloroethane) is 1 percent of the mass of the alloy melt, and the addition of the alloy refiner Al- (5 percent wt) Ti- (1 percent wt) B is 1 percent of the mass of the alloy melt;
(3) milling the alloy ingot in the step (2), removing oil, placing the alloy ingot at the temperature of 580 ℃ for homogenization annealing heat treatment for 4 hours, then sequentially carrying out hot rolling and medium-temperature rolling, then carrying out cold rolling, and carrying out finishing and fixed-length cutting to obtain the aluminum alloy cathode material; wherein the hot rolling temperature is 480 ℃, and the rolling thickness is 8 cm; the rolling temperature at the middle temperature is 250 ℃, and the rolling thickness is 3 cm; cold rolling is room temperature rolling, and the rolling thickness is 7 mm; the surface roughness Ra of the finished alloy plate is not more than 0.4um, so that the surface has no phenomena of spots, oxidation, oil stain and the like;
the gold phase diagram of the aluminum alloy cathode material of the embodiment is shown in fig. 3, the crystal grains are uniform and fine, and the average grain diameter is 50-100 um; the material properties are shown in Table 1, and the Vickers hardness reaches 247N/mm2The zinc electrodeposition efficiency reaches 92.4%, the service life reaches 12-15 months, and the comprehensive performance is obviously superior to that of a common 1070 aluminum cathode plate.
Example 3: in this embodiment, the high-strength corrosion-resistant aluminum alloy cathode material for hydrometallurgical zinc electrodeposition comprises, by mass, 0.15% of Si, 0.05% of Fe, 0.9% of Mn, 1.2% of Mg, 0.15% of Cr, 0.01% of cu, 0.04% of Zn, 0.2% of Ti, 0.04% of B, 0.1% of Zr, 0.2% of Sb, 0.3% of RE, unavoidable impurities not higher than 0.05%, and the balance Al;
a preparation method of a high-strength corrosion-resistant aluminum alloy cathode material for zinc electrowinning in hydrometallurgy comprises the following specific steps:
(1) according to the composition components of the aluminum alloy cathode material, by mass percentage, Si is 0.15%, Fe is 0.05%, Mn0.9%, Mg is 1.2%, Cr is 0.15%, Cu is 0.01%, Zn is 0.04%, Ti is 0.2%, B is 0.04%, Zr is 0.1%, Sb is 0.2%, RE is 0.3%, inevitable impurities are not higher than 0.05%, and the balance is Al, and pure aluminum ingots, intermediate alloys Al-Si, Al-Fe, Al-Mn, Al-Mg, Al-Cr, Al-Cu, Al-Zn, Al-Zr, Al-RE and Al-Sb are weighed; wherein the master alloy Al-Si is Al-10wt% Si, the master alloy Al-Fe is Al-20wt% Fe, the master alloy Al-Mn is Al-10wt% Mn, the master alloy Al-Mg is Al-l0wt% Mg, the master alloy Al-Cr is Al-5wt% Cr, the master alloy Al-Cu is Al-30wt% Cu, the master alloy Al-Zn is Al-30% Zn, the master alloy Al-Zr is Al-5wt% Zr, the master alloy Al-Sb is Al-5% Sb, the master alloy Al-RE is Al-10wt% RE, RE is rare earth element; the rare earth element RE in the Al-10wt% RE alloy comprises 45wt% of Ce, 29wt% of La, 14.5wt% of Nd, 7.5wt% of Pr, 2wt% (Sm + Er), 1.5wt% of other rare earth impurities and 0.5wt% of non-rare earth impurities;
(2) putting the pure aluminum ingot in the step (1) into a melting furnace, heating for melting, continuously heating and raising the temperature to 690 ℃, sequentially adding Al-Si, Al-Fe, Al-Mn, Al-Mg, Al-Cr, Al-Cu, Al-Zn, Al-Zr, Al-RE and Al-Sb intermediate alloys in the step (1), continuously heating and raising the temperature to 745 ℃ after materials in the melting furnace are completely melted, smelting for 35min under the stirring condition to obtain an alloy melt, and blowing a refining agent (hexachloroethane as a refining agent) into 3/4 below the surface of the alloy melt by using argon for refining for 25 min; after slagging off, adding an alloy refiner Al-5% Ti-1% B into the alloy melt for grain refinement, uniformly covering the surface of the melt with a covering agent, standing for 10min, introducing argon for degassing and refining for 40min, slagging off, performing double filtration by an alumina ceramic filter, and then casting ingots at the temperature of 700 ℃ to obtain alloy ingots; wherein the addition of the refining agent (hexachloroethane) is 0.4 percent of the mass of the alloy melt, and the addition of the alloy refiner Al- (5 percent wt) Ti- (1 percent wt) B is 4 percent of the mass of the alloy melt;
(3) milling the alloy ingot in the step (2), removing oil, placing the alloy ingot at the temperature of 600 ℃ for carrying out homogenization annealing heat treatment for 3 hours, then carrying out hot rolling and medium temperature rolling in sequence, then carrying out cold rolling, and carrying out finishing and fixed-length cutting to obtain the aluminum alloy cathode material; wherein the hot rolling temperature is 500 ℃, and the rolling thickness is 10 cm; the medium temperature rolling temperature is 280 ℃, and the rolling thickness is 4 cm; cold rolling is room temperature rolling, and the rolling thickness is 10 mm; the surface roughness Ra of the finished alloy plate is not more than 0.5um, so that the surface has no phenomena of spots, oxidation, oil stain and the like;
the gold phase diagram of the aluminum alloy cathode material of the embodiment is shown in FIG. 4, the crystal grains are uniform and fine, and the average grain diameter is 60-150 um; the material properties are shown in Table 1, and the Vickers hardness reaches 210N/mm2The zinc electrodeposition efficiency reaches 90.8%, the service life reaches 11-17 months, and the comprehensive performance is obviously superior to that of a common 1070 aluminum cathode plate.
Example 4: in this embodiment, the high-strength corrosion-resistant aluminum alloy cathode material for hydrometallurgical zinc electrodeposition comprises, by mass, 0.08% of Si, 0.08% of fe, 0.3% of Mn, 1.2% of Mg, 0.1% of Cr, 0.03% of cu, 0.08% of Zn, 0.25% of Ti, 0.05% of B, 0.2% of Zr, 0.3% of Sb, 0.4% of RE, unavoidable impurities not higher than 0.05%, and the balance Al;
a preparation method of a high-strength corrosion-resistant aluminum alloy cathode material for zinc electrowinning in hydrometallurgy comprises the following specific steps:
(1) according to the composition components of the aluminum alloy cathode material, by mass, 0.08% of Si, 0.08% of FeI, 0.3% of MnI, 1.2% of Mg, 0.1% of Cr, 0.03% of Cu, 0.08% of Zn, 0.25% of Ti, 0.05% of B, 0.2% of Zr, 0.3% of Sb, 0.4% of RE, inevitable impurities of which are not higher than 0.05%, and the balance of Al, pure aluminum ingots, intermediate alloys Al-Si, Al-Fe, Al-Mn, Al-Mg, Al-Cr, Al-Cu, Al-Zn, Al-Zr, Al-RE and Al-Sb are weighed; wherein the master alloy Al-Si is Al-10wt% Si, the master alloy Al-Fe is Al-20wt% Fe, the master alloy Al-Mn is Al-10wt% Mn, the master alloy Al-Mg is Al-l0wt% Mg, the master alloy Al-Cr is Al-5wt% Cr, the master alloy Al-Cu is Al-30wt% Cu, the master alloy Al-Zn is Al-30% Zn, the master alloy Al-Zr is Al-5wt% Zr, the master alloy Al-Sb is Al-5% Sb, the master alloy Al-RE is Al-10wt% RE, RE is rare earth element; the rare earth element RE in the Al-10wt% RE alloy consists of 43wt% of Ce, 27wt% of La, 14wt% of Nd, 8wt% of Pr, 6wt% (Sm + Er), 1wt% of other rare earth impurities and 1wt% of non-rare earth impurities;
(2) putting the pure aluminum ingot in the step (1) into a melting furnace, heating for melting, continuously heating to raise the temperature of the molten liquid to 720 ℃, sequentially adding Al-Si, Al-Fe, Al-Mn, Al-Mg, Al-Cr, Al-Cu, Al-Zn, Al-Zr, Al-RE and Al-Sb intermediate alloys in the step (1), continuously heating to 785 ℃ after materials in the melting furnace are completely melted, smelting for 15min under the stirring condition to obtain an alloy molten liquid, and blowing a refining agent (hexachloroethane is used as a refining agent) into 3/4 below the alloy molten liquid level by using argon gas for refining for 15 min; after slagging off, adding an alloy refiner Al-5% Ti-1% B into the alloy melt for grain refinement, uniformly covering the surface of the melt with a covering agent, standing for 30min, introducing argon for degassing and refining for 20min, performing double filtration by an alumina ceramic filter, and then performing ingot casting at the temperature of 695 ℃ to obtain an alloy ingot; wherein the addition of the refining agent (hexachloroethane) is 0.8 percent of the mass of the alloy melt, and the addition of the alloy refiner Al- (5 percent wt) Ti- (1 percent wt) B is 5 percent of the mass of the alloy melt;
(3) milling the alloy ingot in the step (2), removing oil, placing the alloy ingot at 650 ℃ for carrying out homogenization annealing heat treatment for 1.5h, then sequentially carrying out hot rolling and medium-temperature rolling, then carrying out cold rolling, and carrying out finishing and fixed-length cutting to obtain the aluminum alloy cathode material; wherein the hot rolling temperature is 540 ℃, and the rolling thickness is 4 cm; the rolling temperature at the middle temperature is 150 ℃, and the rolling thickness is 2.5 cm; cold rolling is room temperature rolling, and the rolling thickness is 10 mm; the surface roughness Ra of the finished alloy plate is not more than 0.5um, so that the surface has no phenomena of spots, oxidation, oil stain and the like;
the gold phase diagram of the aluminum alloy cathode material of the embodiment is shown in FIG. 5, the crystal grains are uniform and fine, and the average grain diameter is about 80-150 um; the material properties are shown in Table 1, and the Vickers hardness reaches 207N/mm2The zinc electrodeposition efficiency reaches 89.6%, the service life reaches 9-12 months, and the comprehensive performance is obviously superior to that of a common 1070 aluminum cathode plate.
Example 5: in this embodiment, the high-strength corrosion-resistant aluminum alloy cathode material for hydrometallurgical zinc electrodeposition comprises, by mass, 0.12% of Si, 0.1% of Fe, 3% of Mn, 1% of Mg, 0.05% of Cr, 0.06% of Zn, 0.15% of Ti, 0.03% of B, 0.05% of Zr, 0.05% of Sb, 0.5% of RE, not more than 0.05% of unavoidable impurities, and the balance Al;
a preparation method of a high-strength corrosion-resistant aluminum alloy cathode material for zinc electrowinning in hydrometallurgy comprises the following specific steps:
(1) according to the composition components of the aluminum alloy cathode material, by mass, 0.12% of Si, 0.1% of Fe, 3% of Mn, 1% of Mg, 0.05% of Cr, 0.06% of Zn, 0.15% of Ti, 0.03% of B, 0.05% of Zr, 0.05% of Sb, 0.5% of RE, not more than 0.05% of unavoidable impurities, and the balance of Al; weighing pure aluminum ingots, intermediate alloys Al-Si, Al-Fe, Al-Mn, Al-Mg, Al-Cr, Al-Zn, Al-Zr, Al-RE and Al-Sb; wherein the master alloy Al-Si is Al-10wt% Si, the master alloy Al-Fe is Al-20wt% Fe, the master alloy Al-Mn is Al-10wt% Mn, the master alloy Al-Mg is Al-l0wt% Mg, the master alloy Al-Cr is Al-5wt% Cr, the master alloy Al-Zn is Al-30% Zn, the master alloy Al-Zr is Al-5wt% Zr, the master alloy Al-Sb is Al-5% Sb, the master alloy Al-RE is Al-10wt% RE, RE is rare earth element; the rare earth element RE in the Al-10wt% RE alloy comprises 44wt% Ce, 26.5wt% La, 15.5wt% Nd, 9wt% Pr, 4wt% (Sm + Er), 0.5wt% of other rare earth impurities and 0.5wt% of non-rare earth impurities;
(2) putting the pure aluminum ingot in the step (1) into a melting furnace, heating for melting, continuously heating to raise the temperature of the melt to 710 ℃, sequentially adding Al-Si, Al-Fe, Al-Mn, Al-Mg, Al-Cr, Al-Zn, Al-Zr, Al-RE and Al-Sb intermediate alloys in the step (1), continuously heating to 725 ℃ after materials in the melting furnace are completely melted, smelting for 25min under the stirring condition to obtain an alloy melt, and blowing a refining agent (hexachloroethane is used as the refining agent) into 2/3 below the surface of the alloy melt by using argon gas for refining for 20 min; after slagging off, adding an alloy refiner Al-5% Ti-1% B into the alloy melt for grain refinement, uniformly covering the surface of the melt with a covering agent, standing for 20min, introducing argon for degassing and refining for 25min, slagging off, performing double filtration by an alumina ceramic filter, and then casting ingots at 715 ℃ to obtain alloy ingots; wherein the addition of the refining agent (hexachloroethane) is 0.3 percent of the mass of the alloy melt, and the addition of the alloy refiner Al- (5 percent wt) Ti- (1 percent wt) B is 3 percent of the mass of the alloy melt;
(3) milling the alloy ingot in the step (2), removing oil, performing homogenization annealing heat treatment for 8 hours at the temperature of 520 ℃, then performing hot rolling and medium-temperature rolling in sequence, performing cold rolling, and performing finishing and fixed-length cutting to obtain the aluminum alloy cathode material; wherein the hot rolling temperature is 520 ℃, and the rolling thickness is 9 cm; the medium temperature rolling temperature is 260 ℃, and the rolling thickness is 3 cm; cold rolling is room temperature rolling, and the rolling thickness is 12 mm; the surface roughness Ra of the finished alloy plate is not more than 0.5um, so that the surface has no phenomena of spots, oxidation, oil stain and the like;
the gold phase diagram of the aluminum alloy cathode material of the embodiment is shown in FIG. 6, the crystal grains are uniform and fine, and the average grain diameter is 70-120 um; the material properties are shown in table 1 below,
TABLE 1
| Categories | Hardness (HV) N/mm2 | Efficiency of Zinc analysis (%) | Service life of polar plate (moon) |
| 1070 aluminium cathode plate | 154 | 87.6% | 6~8 |
| Example 1 | 228 | 90.1% | 10~14 |
| Example 2 | 247 | 92.4% | 12~15 |
| Example 3 | 210 | 90.8% | 11~17 |
| Example 4 | 207 | 89.6% | 9~12 |
| Example 5 | 239 | 91.5% | 12.5~16 |
Vickers hardness up to 239N/mm2The zinc electrodeposition efficiency reaches 91.5 percent, the service life reaches 12.5-16 months, and the comprehensive performance is obviously superior to that of a common 1070 aluminum cathode plate.
Claims (9)
1. The high-strength corrosion-resistant aluminum alloy cathode material for zinc electrowinning in hydrometallurgy is characterized by comprising, by mass, 0.05-0.15% of Si, 0.01-0.1% of Fe, 0.3-3% of Mn, 0.5-1.2% of Mg, 0.01-0.15% of Cr, 0.01-0.03% of Cu, 0.01-0.08% of Zn, 0.05-0.25% of Ti, 0.01-0.05% of B, 0.05-0.2% of Zr, 0.05-0.3% of Sb, 0.05-0.5% of RE, unavoidable impurities not higher than 0.05%, and the balance Al.
2. The preparation method of the high-strength corrosion-resistant aluminum alloy cathode material for the hydrometallurgy zinc electrodeposition as recited in claim 1, is characterized by comprising the following specific steps:
(1) according to the composition components of the aluminum alloy cathode material, by mass, 0.05-0.15% of Si, 0.01-0.1% of Fe, 0.3-3% of Mn, 0.5-1.2% of Mg, 0.01-0.15% of Cr, 0.01-0.03% of Cu, 0.01-0.08% of Zn, 0.05-0.25% of Ti, 0.01-0.05% of B, 0.05-0.2% of Zr, 0.05-0.3% of Sb, 0.05-0.5% of RE, not more than 0.05% of inevitable impurities, and the balance of Al, pure aluminum ingots, intermediate alloys Al-Si, Al-Fe, Al-Mn, Al-Mg, Al-Cr, Al-Cu, Al-Zn, Al-Zr, Al-RE and Al-Sb are weighed;
(2) putting the pure aluminum ingot in the step (1) into a melting furnace, heating for melting, continuously heating to raise the temperature of the molten liquid to 690-720 ℃, sequentially adding Al-Si, Al-Fe, Al-Mn, Al-Mg, Al-Cr, Al-Cu, Al-Zn, Al-Zr, Al-RE and Al-Sb intermediate alloys in the step (1), continuously heating to raise the temperature to 725-785 ℃ after materials in the melting furnace are completely melted, smelting for 10-40 min under a stirring condition to obtain an alloy molten liquid, and blowing a refining agent into an 2/3-5/6 area below the surface of the alloy molten liquid by using argon for refining for 10-30 min; after slagging off, adding an alloy refiner Al-5wt% Ti-1 wt% B into the alloy melt for grain refinement, uniformly covering the surface of the melt with a covering agent, standing for 10-30 min, introducing argon for degassing and refining for 20-40 min, slagging off, performing double filtration by an alumina ceramic filter, and then performing ingot casting at 680-720 ℃ to obtain an alloy ingot;
(3) and (3) milling the alloy ingot in the step (2), removing oil, performing homogenization annealing heat treatment for 1-8 hours at the temperature of 520-650 ℃, then sequentially performing hot rolling and medium-temperature rolling, then performing cold rolling, and performing finishing and fixed-length cutting to obtain the aluminum alloy cathode material.
3. The preparation method of the high-strength corrosion-resistant aluminum alloy cathode material for the hydrometallurgical zinc electrodeposition according to claim 2, characterized in that: the intermediate alloy Al-Si is Al-10wt% Si, the intermediate alloy Al-Fe is Al-20wt% Fe, the intermediate alloy Al-Mn is Al-10wt% Mn, the intermediate alloy Al-Mg is Al-l0wt% Mg, the intermediate alloy Al-Cr is Al-5wt% Cr, the intermediate alloy Al-Cu is Al-30wt% Cu, the intermediate alloy Al-Zn is Al-30% Zn, the intermediate alloy Al-Zr is Al-5wt% Zr, the intermediate alloy Al-Sb is Al-5% Sb, the intermediate alloy Al-RE is Al-10wt% RE, RE is rare earth element, and the impurity content of the intermediate alloy is not higher than 0.1 wt%.
4. The preparation method of the high-strength corrosion-resistant aluminum alloy cathode material for the hydrometallurgical zinc electrodeposition according to claim 3, characterized in that: the rare earth element RE in the Al-10wt% RE alloy comprises 43-46.5 wt% of Ce, 26-29 wt% of La, 14-16.5 wt% of Nd, 6-9 wt% of Pr, 2-6 wt% (Sm + Er), less than or equal to 2wt% of other rare earth impurities and less than or equal to 1wt% of non-rare earth impurities.
5. The preparation method of the high-strength corrosion-resistant aluminum alloy cathode material for the hydrometallurgical zinc electrodeposition according to claim 2, characterized in that: in the step (2), the addition amount of an alloy refiner Al-5wt% Ti-1 wt% B is 1-5% of the mass of the alloy melt, the refining agent is hexachloroethane, the addition amount of the refining agent is 0.3-1% of the mass of the alloy melt, and the covering agent is a mixture of 15wt% expanded perlite, 25wt% sodium chloride, 35wt% potassium chloride and 25wt% cryolite.
6. The preparation method of the high-strength corrosion-resistant aluminum alloy cathode material for the hydrometallurgical zinc electrodeposition according to claim 2, characterized in that: the hot rolling temperature in the step (3) is 450-540 ℃, and the rolling thickness is 4-10 cm.
7. The preparation method of the high-strength corrosion-resistant aluminum alloy cathode material for the hydrometallurgical zinc electrodeposition according to claim 2, characterized in that: and (4) rolling at the medium temperature of 150-280 ℃ in the step (3) to obtain the rolled thickness of 2-4 cm.
8. The preparation method of the high-strength corrosion-resistant aluminum alloy cathode material for the hydrometallurgical zinc electrodeposition according to claim 2, characterized in that: and (4) cold rolling in the step (3) is room-temperature rolling, and the rolling thickness is 4-12 mm.
9. The preparation method of the high-strength corrosion-resistant aluminum alloy cathode material for the hydrometallurgical zinc electrodeposition according to claim 2, characterized in that: and (4) the surface roughness Ra of the alloy plate after finishing in the step (3) is not more than 0.5 um.
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