CN114086218B - Energy-saving high-strength corrosion-resistant cathode aluminum alloy plate for zinc electrodeposition - Google Patents
Energy-saving high-strength corrosion-resistant cathode aluminum alloy plate for zinc electrodeposition Download PDFInfo
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- CN114086218B CN114086218B CN202111267587.9A CN202111267587A CN114086218B CN 114086218 B CN114086218 B CN 114086218B CN 202111267587 A CN202111267587 A CN 202111267587A CN 114086218 B CN114086218 B CN 114086218B
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 104
- 238000005260 corrosion Methods 0.000 title claims abstract description 54
- 230000007797 corrosion Effects 0.000 title claims abstract description 48
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 229910052725 zinc Inorganic materials 0.000 title claims abstract description 46
- 239000011701 zinc Substances 0.000 title claims abstract description 46
- 238000004070 electrodeposition Methods 0.000 title claims abstract description 33
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 88
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 88
- 239000002131 composite material Substances 0.000 claims abstract description 81
- 239000000843 powder Substances 0.000 claims abstract description 50
- 239000000126 substance Substances 0.000 claims abstract description 22
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910052751 metal Inorganic materials 0.000 claims abstract description 16
- 239000002184 metal Substances 0.000 claims abstract description 16
- 239000012535 impurity Substances 0.000 claims abstract description 15
- 229910045601 alloy Inorganic materials 0.000 claims description 47
- 239000000956 alloy Substances 0.000 claims description 47
- 238000005096 rolling process Methods 0.000 claims description 35
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 30
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000007670 refining Methods 0.000 claims description 22
- 238000007747 plating Methods 0.000 claims description 21
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 19
- 229910052802 copper Inorganic materials 0.000 claims description 19
- 239000010949 copper Substances 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 18
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 16
- 229910052709 silver Inorganic materials 0.000 claims description 16
- 239000004332 silver Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 238000003825 pressing Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 13
- 101710134784 Agnoprotein Proteins 0.000 claims description 12
- 238000005097 cold rolling Methods 0.000 claims description 12
- 238000005098 hot rolling Methods 0.000 claims description 12
- 238000002360 preparation method Methods 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 229910052708 sodium Inorganic materials 0.000 claims description 10
- 238000005238 degreasing Methods 0.000 claims description 9
- 238000010008 shearing Methods 0.000 claims description 9
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 8
- 239000004917 carbon fiber Substances 0.000 claims description 8
- 239000010936 titanium Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 7
- 238000003723 Smelting Methods 0.000 claims description 7
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical group C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 7
- 238000005266 casting Methods 0.000 claims description 6
- 238000009792 diffusion process Methods 0.000 claims description 6
- 238000001125 extrusion Methods 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910052748 manganese Inorganic materials 0.000 claims description 6
- 239000010731 rolling oil Substances 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 5
- 239000012300 argon atmosphere Substances 0.000 claims description 5
- 229910052791 calcium Inorganic materials 0.000 claims description 5
- 239000000839 emulsion Substances 0.000 claims description 5
- 239000011888 foil Substances 0.000 claims description 5
- 239000008103 glucose Substances 0.000 claims description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims description 5
- FEWJPZIEWOKRBE-LWMBPPNESA-N levotartaric acid Chemical compound OC(=O)[C@@H](O)[C@H](O)C(O)=O FEWJPZIEWOKRBE-LWMBPPNESA-N 0.000 claims description 5
- 238000007788 roughening Methods 0.000 claims description 5
- 239000002893 slag Substances 0.000 claims description 5
- 229910052726 zirconium Inorganic materials 0.000 claims description 5
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 4
- 230000003213 activating effect Effects 0.000 claims description 3
- 241000764238 Isis Species 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 9
- 238000007688 edging Methods 0.000 abstract description 5
- 238000003466 welding Methods 0.000 description 15
- 239000000203 mixture Substances 0.000 description 14
- 239000011572 manganese Substances 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 8
- 239000011575 calcium Substances 0.000 description 8
- 239000011734 sodium Substances 0.000 description 8
- 239000000460 chlorine Substances 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000004140 cleaning Methods 0.000 description 6
- 238000004880 explosion Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 239000011651 chromium Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 3
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 3
- 235000011114 ammonium hydroxide Nutrition 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000011737 fluorine Substances 0.000 description 3
- 229910052731 fluorine Inorganic materials 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052759 nickel Inorganic materials 0.000 description 3
- 229910052719 titanium Inorganic materials 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- 229910001094 6061 aluminium alloy Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 230000004913 activation Effects 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 239000000919 ceramic Substances 0.000 description 2
- -1 chlorine ions Chemical class 0.000 description 2
- 238000009854 hydrometallurgy Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 230000002035 prolonged effect Effects 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910000967 As alloy Inorganic materials 0.000 description 1
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910000914 Mn alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000004115 Sodium Silicate Substances 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000001174 ascending effect Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000010406 cathode material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005363 electrowinning Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000002161 passivation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 description 1
- 229910052911 sodium silicate Inorganic materials 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C7/00—Constructional parts, or assemblies thereof, of cells; Servicing or operating of cells
- C25C7/02—Electrodes; Connections thereof
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
- B21B3/003—Rolling non-ferrous metals immediately subsequent to continuous casting, i.e. in-line rolling
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B37/00—Control devices or methods specially adapted for metal-rolling mills or the work produced thereby
- B21B37/56—Elongation control
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B37/00—Control devices or methods specially adapted for metal-rolling mills or the work produced thereby
- B21B37/74—Temperature control, e.g. by cooling or heating the rolls or the product
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1005—Pretreatment of the non-metallic additives
- C22C1/101—Pretreatment of the non-metallic additives by coating
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1036—Alloys containing non-metals starting from a melt
- C22C1/1047—Alloys containing non-metals starting from a melt by mixing and casting liquid metal matrix composites
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- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C1/00—Making non-ferrous alloys
- C22C1/10—Alloys containing non-metals
- C22C1/1094—Alloys containing non-metals comprising an after-treatment
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C21/00—Alloys based on aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
- C22C32/001—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides
- C22C32/0015—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ with only oxides with only single oxides as main non-metallic constituents
- C22C32/0036—Matrix based on Al, Mg, Be or alloys thereof
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/31—Coating with metals
- C23C18/42—Coating with noble metals
- C23C18/44—Coating with noble metals using reducing agents
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
- C25C1/16—Electrolytic production, recovery or refining of metals by electrolysis of solutions of zinc, cadmium or mercury
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/02—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors mainly consisting of metals or alloys
- H01B1/023—Alloys based on aluminium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B21—MECHANICAL METAL-WORKING WITHOUT ESSENTIALLY REMOVING MATERIAL; PUNCHING METAL
- B21B—ROLLING OF METAL
- B21B3/00—Rolling materials of special alloys so far as the composition of the alloy requires or permits special rolling methods or sequences ; Rolling of aluminium, copper, zinc or other non-ferrous metals
- B21B2003/001—Aluminium or its alloys
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- Chemical & Material Sciences (AREA)
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- Other Surface Treatments For Metallic Materials (AREA)
- Prevention Of Electric Corrosion (AREA)
Abstract
The invention relates to an energy-saving high-strength corrosion-resistant cathode aluminum alloy plate for zinc electrodeposition, belonging to the technical field of hydrometallurgical electrodeposition. The cathode aluminum alloy plate comprises a conductive cross beam, an aluminum alloy composite plate and insulating edging strips, wherein the aluminum alloy composite plate is welded at the bottom end of the conductive cross beam; based on the mass of 100% of substances in the aluminum alloy composite plate, the micro-nano silver coated aluminum oxide composite powder comprises 0.5-3.0% of Mn 0.6-3.0% of Ca 0.01-0.2% of Zr 0.03-0.5% of Mn 0.01-0.1% of Mn 0.06-0.5% of Ti 0.01-0.1% of B0.01-0.1% of La 0.01-0.2% of Ce 0.01-0.2% of Cr, unavoidable impurities less than 0.06% of Al and the balance of Al. The energy-saving high-strength corrosion-resistant cathode aluminum alloy plate has good conductivity and wear resistance, and compared with the traditional 1070 aluminum cathode plate, the tensile strength is improved by more than 2 times, the hardness is improved by 2.5 times, and the service life is 18-22 months in the process of extracting metal zinc.
Description
Technical Field
The invention relates to an energy-saving high-strength corrosion-resistant cathode aluminum alloy plate for zinc electrodeposition, belonging to the technical field of nonferrous metal smelting.
Background
In the production process of electrolytic zinc, a lead-silver alloy plate is usually used as an anode, an industrial 1070 pure aluminum plate is used as a cathode, and the 1070 industrial pure aluminum cathode has the advantages of low cost, easy forming and the like, but has the defects of low mechanical strength, poor corrosion resistance, difficult stripping of a cathode zinc plate, short service life and the like. The quality of the aluminum cathode plate has influence on the unit consumption of the zinc direct current precipitated, and the labor intensity of manual zinc stripping is related, and more importantly, the service life of the cathode plate is determined. High-quality aluminum plates with strict impurity content control can be used for 6-10 months, while low-quality aluminum plates with high impurity content can be used for 2-6 months only. Meanwhile, as the high-grade zinc concentrate resources are increasingly deficient and the zinc secondary resources are increasingly complex, the impurity content is increased, the concentration of impurity ions such as fluorine, chlorine and the like in the electrolyte shows an ascending trend, and the corrosion failure phenomenon of the aluminum cathode plate is more serious than before. Therefore, the aluminum cathode plate for zinc electrowinning is improved, a novel aluminum alloy cathode plate with high strength, corrosion resistance and long service life is developed, and the aluminum alloy cathode plate has very important practical significance for improving the economic benefit of zinc hydrometallurgy enterprises and promoting the development of hydrometallurgy industry.
However, in the prior art, a method for improving the corrosion resistance of an aluminum plate for zinc electrodeposition adopts rolling oil with special configuration, the aluminum material is rolled by a conventional two-roller irreversible intermittent rolling mill, and sodium silicate is immediately adopted for treatment after rolling, so that an oxide film with a flat surface and large and compact thickness is generated, and the corrosion resistance is improved; however, the corrosion resistance of the aluminum cathode is enhanced by only carrying out chemical treatment on the surface of the cathode, and after a certain zinc stripping period, the corrosion-resistant passivation film on the surface of the cathode is easily damaged, the treatment is needed again, the production cost is increased, the processing technology is complex, and moreover, the strength of the aluminum cathode plate is not improved. The preparation method of the long-life aluminum cathode plate comprises the step of growing Al in situ outside an aluminum beam, in an area above a liquid level line of an aluminum plate and at two side edges of the aluminum plate 2 O 3 The ceramic membrane can effectively prevent fluorine and chlorine ions in the electrolyte from corroding the aluminum cathode, and remarkably prolongs the service life of the ceramic membrane, but once a compact oxide film layer is damaged, the inner metal aluminum is corroded. An electrodeposited zinc cathode aluminum alloy and a preparation method thereof, wherein the electrodeposited zinc cathode aluminum alloy comprises cathode matrix metal aluminum and intermediate alloys of chromium, nickel and manganese; however, chromium, nickel and manganese are selected as alloy additive elements, the price of metal chromium/nickel is higher, the additive content of the metal chromium/nickel is relatively higher, the production cost of the cathode plate is increased intangibly, and meanwhile, the too high addition of the alloy elements is very likely to cause the too high impurity ion content of an electrolyte system caused by the dissolution of the alloy elements after the corrosion of the cathode plate, so that the stability of the electrolyte system is influenced. Cathode aluminum plate for electrolytic zinc, the purity of the cathode aluminum plate is more than or equal to 99.7%, and the impurity content is as follows: fe 0.10-0.13%; si 0.06-0.09%; however, the content of Fe and Si is controlled and the processing is performedThe process improves the corrosion resistance of the aluminum alloy cathode, but the strength of the polar plate is not effectively improved. The high-strength corrosion-resistant aluminum alloy cathode material for the hydrometallurgical electrodeposited zinc is prepared by alloy batching, smelting, refining, deslagging, exhausting, filtering, casting ingot, face milling, degreasing, homogenizing annealing, hot rolling, cold rolling, finishing and fixed-length shearing, but the number of selected elements is too large, the process steps are too large, and the component control is too complex.
Disclosure of Invention
Aiming at the problems of corrosion resistance and energy conservation of the aluminum plate for zinc electrodeposition in the prior art, the invention provides an energy-saving high-strength corrosion-resistant cathode aluminum alloy plate for zinc electrodeposition, namely, an aluminum alloy is reinforced by conductive micro-nano silver coated aluminum oxide composite powder, so that the corrosion-resistant alpha-Al is prepared 2 O 3 The micro-nano particles are continuously appeared on the surface of the alloy to play a role in protecting to form the composite electrode aluminum plate, so that the composite electrode aluminum plate has the advantages of energy saving, high strength and corrosion resistance.
The energy-saving high-strength corrosion-resistant cathode aluminum alloy plate for zinc electrodeposition comprises a conductive cross beam 1, an aluminum alloy composite plate 2 and an insulating edging strip 3, wherein the aluminum alloy composite plate 2 is welded at the bottom end of the conductive cross beam 1, the insulating edging strip 3 is fixedly arranged at two sides of the aluminum alloy composite plate 2, and the conductive cross beam 1 comprises a conductive aluminum beam 11 and an aluminum-clad copper composite conductive head 12 arranged at the end head of the conductive cross beam 1;
the conductive aluminum beam 11 is 6 series aluminum alloy;
based on the mass of 100% of substances in the aluminum alloy composite plate, the micro-nano silver coated aluminum oxide composite powder comprises 0.5-3.0% of Mn 0.6-3.0% of Ca 0.01-0.2% of Zr 0.03-0.5% of Mn 0.01-0.1% of Mn 0.06-0.5% of Ti 0.01-0.1% of B0.01-0.1% of La 0.01-0.2% of Ce 0.01-0.2% of Cr, unavoidable impurities less than 0.06% of Al and the balance of Al.
The preparation method of the micro-nano silver-coated aluminum oxide composite powder comprises the following specific steps:
1) Placing the micro-nano alumina powder into a NaOH solution for ultrasonic degreasing, washing with deionized water, and then placing into an ammonium fluoride solution for ultrasonic roughening to obtain roughened micro-nano alumina powder;
2) Placing coarsened micro-nano alumina powder in AgNO 3 Ultrasonic activating in the solution to obtain activated micro-nano alumina powder;
3) Placing the activated micro-nano alumina powder into chemical plating solution, and performing chemical silver plating at the temperature of 20-40 ℃ for 30-60 min to obtain micro-nano silver coated alumina composite powder;
the mass concentration of the NaOH solution in the step 1) is 10-30%, and the concentration of the ammonium fluoride solution is 5-25 g/L; step 2) AgNO 3 The concentration of the solution is 1-5 g/L;
the plating solution for electroless silver plating in the step 3) contains 1-15 g/L AgNO 3 、10～30g/LNaOH、50～200ml/LNH 3 ·H 2 O, 10-30 g/L glucose, 4-10 g/L tartaric acid, 100-300 ml/L absolute ethyl alcohol and the balance H 2 O；
The particle size of the micro-nano silver coated alumina composite powder is 100-800 nm, and the alumina is alpha-Al 2 O 3 The alumina is spherical in shape.
The preparation method of the aluminum alloy composite plate comprises the following specific steps:
(1) Deoiling the metal aluminum and the aluminum intermediate alloy, and then placing the aluminum intermediate alloy into a vacuum for preheating for 1-2 h at the temperature of 100-300 ℃;
(2) Smelting preheated metal aluminum and aluminum intermediate alloy to obtain an alloy melt, adding a covering agent to the surface of the alloy melt, and preserving heat for 3-5 min at 680-700 ℃ to obtain aluminum liquid;
(3) In argon atmosphere, adding silver-coated aluminum oxide composite powder to the bottom surface of aluminum liquid, heating to 780-850 ℃ at constant speed under stirring, adding aluminum foil-coated refining agent, refining for 5-10 min, continuously stirring for 2-10 min after slag skimming, and casting at 700-760 ℃ to obtain an aluminum alloy blank;
(4) The aluminum alloy billet is sequentially subjected to hot rolling, cold rolling, finishing and fixed-length shearing to obtain the aluminum alloy composite plate.
The aluminum master alloy is Al-10wt.% Mn, al-1wt.% Ca, al-5wt.% Zr, al-1wt.% Sr, al-5wt.% Ti-0.5wt.% B, al-10wt.% Ce and Al-15wt.% La, and the impurity content of the master alloy is less than 0.05wt.%.
The capping agent was 30wt.% Na 2 CO 3 +25wt.％CaCl 2 +25wt.％Na 2 SiF 6 +20wt.% NaF, the addition of the covering agent being 0.2 to 0.5% of the total mass of the smelted alloy; the refining agent is 40wt.% ZnCl 2 +60wt.％NH 4 The adding amount of the Cl and the refining agent is 0.05-0.2% of the mass of the alloy solution.
The hot rolling temperature is 500-600 ℃, the rolling direction is the same direction, the rolling passes are 8-10 times, the pressing amount of each pass is 10-30%, and emulsion is sprayed in the rolling process; the cold rolling temperature is 20-40 ℃, the rolling direction is the same direction, the rolling passes are 2-4 times, the pressing amount of each pass is 2-10%, and the rolling oil is coated in the rolling process.
The section of the aluminum-clad copper composite conductive head is compounded into a special shape; an anti-corrosion layer is compositely arranged above the aluminum alloy plate liquid level line by a diffusion extrusion method, and the anti-corrosion layer is a carbon fiber film layer with the thickness of 0.5-2 mm.
The beneficial effects of the invention are as follows:
(1) The invention utilizes micro-nano alpha-Al 2 O 3 The aluminum alloy has the characteristics of small particle size, uniform distribution, good oxidation resistance, high hardness, good corrosion resistance and the like by adding micro-nano alpha-Al into the aluminum alloy 2 O 3 The material not only can improve the strength and the wear resistance of the existing aluminum alloy, but also does not need to improve the mechanical properties by heat treatment means such as quenching, aging and the like, thereby improving the production efficiency and saving the production cost;
(2) The invention adopts silver to coat micro-nano alpha-Al 2 O 3 The particle reinforced aluminum alloy has the advantages that the hardness is improved by more than 100%, the wear resistance is improved by 1-2 times, the wettability of particles and an aluminum matrix is improved, the interface resistance is reduced, and the conductivity of aluminum is improved;
(3) According to the invention, the calcium element and the manganese element are added into the aluminum alloy to form a synergistic effect, so that the conductivity and the mechanical strength of the aluminum alloy are improved, and the service life of the aluminum alloy is prolonged;
(4) The invention adopts hot rolling and cold rolling processes, and can obviously improve the compactness, mechanical strength and corrosion resistance of the alloy;
(5) The corrosion-resistant alpha-Al can be continuously generated in the use process of the aluminum cathode plate 2 O 3 The particles protect the cathode plate;
(6) The carbon fiber anticorrosive layer is a nonmetallic material, has low electrochemical activity, has excellent corrosion resistance in sulfuric acid solution containing fluorine and chlorine ions, and is coated above the liquid level line of the aluminum alloy plate, so that the service life of the cathode aluminum alloy plate is obviously prolonged.
Drawings
FIG. 1 is a schematic view of a structure of an energy-saving high-strength corrosion-resistant cathode aluminum alloy plate for zinc electrodeposition;
FIG. 2 is a cross-sectional view taken along line A-A of FIG. 1;
FIG. 3 is a cross-sectional view taken along line B-B of FIG. 1;
FIG. 4 is a cross-sectional view taken along line C-C of FIG. 1;
in the figure: the aluminum alloy composite wire comprises a 1-conductive cross beam, a 11-conductive aluminum beam, a 12-aluminum-clad copper composite conductive head, a 2-aluminum alloy composite plate, a 21-carbon fiber film layer and 3-edge clamping strips.
Detailed Description
The invention will be described in further detail with reference to specific embodiments, but the scope of the invention is not limited to the description.
The embodiment of the invention provides an energy-saving high-strength corrosion-resistant cathode aluminum alloy plate (see figures 1-4) for zinc electrodeposition, which comprises a conductive cross beam 1, an aluminum alloy composite plate 2 and an insulating edging strip 3, wherein the aluminum alloy composite plate 2 is welded at the bottom end of the conductive cross beam 1, the insulating edging strip 3 is fixedly arranged at two sides of the aluminum alloy composite plate 2, and the conductive cross beam 1 comprises a conductive aluminum beam 11 and an aluminum-clad copper composite conductive head 12 arranged at the end of the conductive cross beam 1;
the conductive aluminum beam 11 is 6 series aluminum alloy;
based on the mass of 100% of substances in the aluminum alloy composite plate, 0.5-3% of micro-nano silver coated aluminum oxide composite powder, 0.6-3.0% of Mn, 0.01-0.2% of Ca, 0.03-0.5% of Zr, 0.01-0.1% of S, 0.06-0.5% of Ti, 0.01-0.1% of B, 0.01-0.1% of La, 0.01-0.2% of Ce, less than 0.06% of unavoidable impurities and the balance of Al;
the section of the aluminum-clad copper composite conductive head is compounded into a special shape; an anti-corrosion layer is compositely arranged above the aluminum alloy plate liquid level line by a diffusion extrusion method, and the anti-corrosion layer is a carbon fiber film layer with the thickness of 0.5-2 mm.
Example 1: in the embodiment, the aluminum-clad copper composite conductive head is formed by explosion welding, and calculated by taking the mass of substances in an aluminum alloy composite plate as 100%, the micro-nano silver-clad aluminum oxide composite powder comprises 0.5%, mn0.6%, ca0.01%, zr0.03%, sr0.01%, ti0.06%, B0.01%, la0.01%, ce0.01%, unavoidable impurities less than 0.06% and the balance of Al;
the preparation method of the energy-saving high-strength corrosion-resistant cathode aluminum alloy plate for zinc electrodeposition comprises the following specific steps:
a. preparing a conductive cross beam: combining the heterogeneous conductive copper block and the aluminum block together, obtaining an aluminum-clad copper composite conductive head by adopting an explosion welding method, and welding the aluminum-clad copper composite conductive head and a 6061 aluminum alloy conductive aluminum beam together by friction stir welding to obtain a conductive cross beam;
b. preparing an aluminum alloy composite plate:
(1) Rolling and shearing metal pure aluminum (Al is more than or equal to 99.99%) and aluminum intermediate alloy blocks into small blocks, degreasing, cleaning by deionized water, and vacuum preheating for 1h at 100 ℃; wherein the aluminum master alloy is Al-10wt.% Mn, al-10wt.% Ca, al-5wt.% Zr, al-1wt.% Sr, al-5wt.% Ti-0.5wt.% B, al-10wt.% Ce and Al-15wt.% La;
(2) Adding preheated metal aluminum and aluminum intermediate alloy into an intermediate frequency furnace for smelting to obtain an alloy melt, adding a covering agent to the surface of the alloy melt, and preserving heat for 3min at 680 ℃ to obtain aluminum liquid; wherein the capping agent is 30wt.% Na 2 CO 3 +25wt.％CaCl 2 +25wt.％Na 2 SiF 6 +20wt.% NaF, the mass of the covering agent being 0.2% of the total amount of the smelted alloy;
(3) In argon atmosphere, blowing silver-coated aluminum oxide composite powder into the bottom surface of aluminum liquid through a titanium pipe, slowly increasing the frequency of an intermediate frequency furnace, uniformly heating to 780 ℃ under stirring, adding aluminum foil-coated refining agent, and pressing into alloy by a bell jarRefining for 5min below the solution, continuously stirring for 2min at the speed of 100rpm after slag skimming, and casting at the temperature of 700 ℃ to obtain an aluminum alloy blank; wherein the refining agent is 40wt.% ZnCl 2 +60wt.％NH 4 The adding amount of the Cl and the refining agent is 0.05% of the mass of the alloy solution;
the preparation method of the micro-nano silver coated alumina composite powder comprises the following specific steps:
1) Micro-nano alumina powder (spherical alpha-Al) 2 O 3 ) Placing the mixture into a NaOH solution with the concentration of 10wt.% for ultrasonic degreasing, washing the mixture by deionized water, placing the mixture into an ammonium fluoride solution with the concentration of 5g/L for ultrasonic roughening for 20min, and cleaning the mixture by hot water with the temperature of 50 ℃ to obtain roughened micro-nano alumina powder;
2) Placing coarsened micro-nano aluminum oxide powder into AgNO with concentration of 5g/L 3 Ultrasonic activating in the solution for 5min to obtain activated micro-nano alumina powder;
3) Placing the activated micro-nano aluminum oxide powder into chemical plating solution, performing chemical silver plating for 30min at the temperature of 20 ℃, washing with deionized water, filtering, and vacuum drying for 1h at the temperature of 60 ℃ to obtain micro-nano silver-coated aluminum oxide composite powder; the plating solution for chemical silver plating contains silver ammonia solution and reducing solution, and the composition of the plating solution is 1g/L AgNO 3 、10g/LNaOH、50ml/L NH 3 ·H 2 O, 10g/L glucose, 4g/L tartaric acid, 100ml/L absolute ethyl alcohol, the balance H 2 O；
(4) Sequentially carrying out hot rolling, cold rolling, finishing and fixed-length shearing on the aluminum alloy blank to obtain an aluminum alloy composite plate; the hot rolling temperature is 500 ℃, the rolling direction is the same direction, the rolling passes are 8 times, the pressing amount of each pass is 10%, and the great wall brand M1823 emulsion is sprayed in the rolling process; the cold rolling temperature is 20 ℃, the rolling direction is the same direction, the rolling passes are 2 times, the pressing amount of each pass is 2%, and the great wall brand M0721A rolling oil is coated in the rolling process;
c. carrying out argon protection welding on the conductive cross beam and the aluminum alloy composite plate by adopting a robot to realize metallurgical bonding of the conductive cross beam and the plate surface, coating a 0.5mm carbon fiber film layer above a liquid level line of the aluminum alloy composite plate by a diffusion extrusion method, and installing clamping strakes on two sides of the aluminum alloy composite plate to obtain the energy-saving high-strength corrosion-resistant cathode aluminum alloy plate for zinc electrodeposition;
the mechanical properties and the service lives of the energy-saving high-strength corrosion-resistant cathode aluminum alloy plate for zinc electrodeposition of this example are shown in Table 1, and the tensile strength of the energy-saving high-strength corrosion-resistant cathode aluminum alloy plate for zinc electrodeposition is improved by 1.42 times, and the hardness H is improved as compared with that of an industrial 1070 pure aluminum plate V 56N/mm 2 The service life of the polar plate is improved by 2 times, and the comprehensive performance is superior to that of an industrial 1070 pure aluminum plate.
Example 2: in the embodiment, the aluminum-clad copper composite conductive head is formed by explosion welding, and calculated by taking the mass of substances in an aluminum alloy composite plate as 100%, 3% of micro-nano silver-clad aluminum oxide composite powder, 3.0% of Mn, 0.2% of Ca, 0.5% of Zr, 0.1% of S, 0.45% of Ti, 0.1% of B, 0.1% of La, 0.2% of Ce, less than 0.06% of unavoidable impurities and the balance of Al;
the preparation method of the energy-saving high-strength corrosion-resistant cathode aluminum alloy plate for zinc electrodeposition comprises the following specific steps:
a. preparing a conductive cross beam: combining the heterogeneous conductive copper block and the aluminum block together, obtaining an aluminum-clad copper composite conductive head by adopting an explosion welding method, and welding the aluminum-clad copper composite conductive head and a 6005 aluminum alloy conductive aluminum beam together by friction stir welding to obtain a conductive cross beam;
b. preparing an aluminum alloy composite plate:
(1) Rolling and shearing metal pure aluminum (Al is more than or equal to 99.99%) and aluminum intermediate alloy blocks into small blocks, degreasing, cleaning by deionized water, and vacuum preheating for 1.5h at 300 ℃; wherein the aluminum master alloy is Al-10wt.% Mn, al-10wt.% Ca, al-5wt.% Zr, al-1wt.% Sr, al-5wt.% Ti-0.5wt.% B, al-10wt.% Ce and Al-15wt.% La;
(2) Adding preheated metal aluminum and aluminum intermediate alloy into an intermediate frequency furnace for smelting to obtain an alloy melt, adding a covering agent to the surface of the alloy melt, and preserving heat for 5min at 700 ℃ to obtain aluminum liquid; wherein the capping agent is 30wt.% Na 2 CO 3 +25wt.％CaCl 2 +25wt.％Na 2 SiF 6 +20wt.% NaF, the mass of the covering agent being 0.5% of the total amount of the smelted alloy;
(3) Blowing the silver-coated aluminum oxide composite powder into the bottom surface of an aluminum liquid through a titanium tube in an argon atmosphere, slowly increasing the frequency of an intermediate frequency furnace, heating to 850 ℃ at a constant speed under the stirring condition, adding a refining agent wrapped by aluminum foil, pressing the refining agent into the lower part of an alloy solution by a bell jar for refining for 10min, continuously stirring at the speed of 500rpm for 10min after slag skimming, and casting at 760 ℃ to obtain an aluminum alloy blank; wherein the refining agent is 40wt.% ZnCl 2 +60wt.％NH 4 The adding amount of the Cl and the refining agent is 0.2% of the mass of the alloy solution;
the preparation method of the micro-nano silver coated alumina composite powder comprises the following specific steps:
1) Micro-nano alumina powder (spherical alpha-Al) 2 O 3 ) Placing the mixture into a NaOH solution with the concentration of 30wt.% for ultrasonic degreasing, washing the mixture by deionized water, placing the mixture into an ammonium fluoride solution with the concentration of 25g/L for ultrasonic roughening for 5min, and cleaning the mixture by hot water with the temperature of 70 ℃ to obtain roughened micro-nano alumina powder;
2) Placing coarsened micro-nano alumina powder into AgNO with concentration of 2g/L 3 Carrying out ultrasonic activation in the solution for 10min to obtain activated micro-nano alumina powder;
3) Placing the activated micro-nano aluminum oxide powder into chemical plating solution, performing chemical silver plating at 40 ℃ for 60min, washing with deionized water, filtering, and vacuum drying at 120 ℃ for 2h to obtain micro-nano silver-coated aluminum oxide composite powder; the plating solution for chemical silver plating contains silver ammonia solution and reducing solution, and the components are 8g/L AgNO 3 、30g/LNaOH、100ml/LNH 3 ·H 2 O, 20g/L glucose, 10g/L tartaric acid, 300ml/L absolute ethyl alcohol and the balance H 2 O；
(4) Sequentially carrying out hot rolling, cold rolling, finishing and fixed-length shearing on the aluminum alloy blank to obtain an aluminum alloy composite plate; the hot rolling temperature is 600 ℃, the rolling direction is the same direction, the rolling passes are 10 times, the pressing amount of each pass is 30%, and the great wall brand M1823 emulsion is sprayed in the rolling process; the cold rolling temperature is 40 ℃, the rolling direction is the same direction, the rolling passes are 4 times, the pressing amount of each pass is 10%, and the great wall brand M0721A rolling oil is coated in the rolling process;
c. carrying out argon protection welding on the conductive cross beam and the aluminum alloy composite plate by adopting a robot to realize metallurgical bonding of the conductive cross beam and the plate surface, coating a 5mm carbon fiber film layer above a liquid level line of the aluminum alloy composite plate by a diffusion extrusion method, and installing clamping strakes on two sides of the aluminum alloy composite plate to obtain the energy-saving high-strength corrosion-resistant cathode aluminum alloy plate for zinc electrodeposition;
the mechanical properties and the service lives of the energy-saving high-strength corrosion-resistant cathode aluminum alloy plate for zinc electrodeposition of this example are shown in Table 1, and the tensile strength of the energy-saving high-strength corrosion-resistant cathode aluminum alloy plate for zinc electrodeposition is improved by 1.81 times, and the hardness H is improved as compared with that of an industrial 1070 pure aluminum plate V 78N/mm 2 The service life of the polar plate is improved by 2.67 times, and the comprehensive performance is superior to that of an industrial 1070 pure aluminum plate.
Example 3: in the embodiment, the aluminum-clad copper composite conductive head is formed by explosion welding, and calculated by taking the mass of substances in an aluminum alloy composite plate as 100%, 2% of micro-nano silver-clad aluminum oxide composite powder, 1.0% of Mn, 0.08% of Ca, 0.1% of Zr, 0.05% of S, 0.18% of Ti, 0.05% of B, 0.06% of La, 0.1% of Ce, less than 0.06% of unavoidable impurities and the balance of Al;
the preparation method of the energy-saving high-strength corrosion-resistant cathode aluminum alloy plate for zinc electrodeposition comprises the following specific steps:
a. preparing a conductive cross beam: combining the heterogeneous conductive copper block and the aluminum block together, obtaining an aluminum-clad copper composite conductive head by adopting an explosion welding method, and welding the aluminum-clad copper composite conductive head and a 6061 aluminum alloy conductive aluminum beam together by friction stir welding to obtain a conductive cross beam;
b. preparing an aluminum alloy composite plate:
(1) Rolling and shearing metal pure aluminum (Al is more than or equal to 99.99%) and aluminum intermediate alloy blocks into small blocks, degreasing, cleaning by deionized water, and vacuum preheating for 2h at 200 ℃; wherein the aluminum master alloy is Al-10wt.% Mn, al-10wt.% Ca, al-5wt.% Zr, al-1wt.% Sr, al-5wt.% Ti-0.5wt.% B, al-10wt.% Ce and Al-15wt.% La;
(2) Adding preheated metal aluminum and aluminum intermediate alloy into an intermediate frequency furnace for smelting to obtain an alloy melt, adding a covering agent to the surface of the alloy melt, and preserving the temperature at 700 ℃ for 4min to obtain aluminum liquid; wherein the capping agent is 30wt.% Na 2 CO 3 +25wt.％CaCl 2 +25wt.％Na 2 SiF 6 +20wt.% NaF, the mass of the covering agent being 0.3% of the total amount of the smelted alloy;
(3) Blowing the silver-coated aluminum oxide composite powder into the bottom surface of an aluminum liquid through a titanium tube in an argon atmosphere, slowly increasing the frequency of an intermediate frequency furnace, heating to 800 ℃ at a constant speed under the stirring condition, adding a refining agent wrapped by aluminum foil, pressing the refining agent into the lower part of an alloy solution by a bell jar for refining for 8min, continuously stirring at the speed of 300rpm for 8min after slag skimming, and casting at the temperature of 720 ℃ to obtain an aluminum alloy blank; wherein the refining agent is 40wt.% ZnCl 2 +60wt.％NH 4 The adding amount of the Cl and the refining agent is 0.13% of the mass of the alloy solution;
the preparation method of the micro-nano silver coated alumina composite powder comprises the following specific steps:
1) Micro-nano alumina powder (spherical alpha-Al) 2 O 3 ) Placing the mixture into a NaOH solution with the concentration of 20wt.% for ultrasonic degreasing, washing the mixture by deionized water, placing the mixture into an ammonium fluoride solution with the concentration of 15g/L for ultrasonic roughening for 12min, and cleaning the mixture by hot water with the temperature of 60 ℃ to obtain roughened micro-nano alumina powder;
2) Placing coarsened micro-nano aluminum oxide powder into AgNO with concentration of 5g/L 3 Performing ultrasonic activation in the solution for 8min to obtain activated micro-nano alumina powder;
3) Placing the activated micro-nano aluminum oxide powder into chemical plating solution, performing chemical silver plating at 30 ℃ for 50min, washing with deionized water, filtering, and vacuum drying at 100 ℃ for 2h to obtain micro-nano silver-coated aluminum oxide composite powder; the plating solution for chemical silver plating contains silver ammonia solution and reducing solution, and the composition is 12g/L AgNO 3 、20g/LNaOH、150ml/LNH 3 ·H 2 O, 25g/L glucose, 8g/L tartaric acid, 200ml/L absolute ethyl alcohol, the balance H 2 O；
(4) Sequentially carrying out hot rolling, cold rolling, finishing and fixed-length shearing on the aluminum alloy blank to obtain an aluminum alloy composite plate; the hot rolling temperature is 570 ℃, the rolling direction is the same direction, the rolling passes are 9 times, the pressing amount of each pass is 20%, and the great wall brand M1823 emulsion is sprayed in the rolling process; the cold rolling temperature is 30 ℃, the rolling direction is the same direction, the rolling passes are 3 times, the pressing amount of each pass is 5%, and the great wall brand M0721A rolling oil is coated in the rolling process;
c. carrying out argon protection welding on the conductive cross beam and the aluminum alloy composite plate by adopting a robot to realize metallurgical bonding of the conductive cross beam and the plate surface, coating a carbon fiber film layer with the thickness of 1.2mm above a liquid level line of the aluminum alloy composite plate by a diffusion extrusion method, and installing clamping strakes on two sides of the aluminum alloy composite plate to obtain the energy-saving high-strength corrosion-resistant cathode aluminum alloy plate for zinc electrodeposition;
the mechanical properties and the service lives of the energy-saving high-strength corrosion-resistant cathode aluminum alloy plate for zinc electrodeposition of this example are shown in Table 1,
TABLE 1 mechanical Properties and service Life of cathode aluminum alloy sheets of examples 1-3
Compared with an industrial 1070 pure aluminum plate, the tensile strength of the energy-saving high-strength corrosion-resistant cathode aluminum alloy plate for zinc electrodeposition is improved by 2.04 times, and the hardness is H V 103N/mm 2 The service life of the polar plate is improved by 3.67 times, and the comprehensive performance is superior to that of an industrial 1070 pure aluminum plate.
While the present invention has been described in detail with reference to the drawings, the present invention is not limited to the above embodiments, and various changes can be made without departing from the spirit of the present invention within the knowledge of those skilled in the art.
Claims (10)
1. Energy-conserving high strength corrosion resistance negative pole aluminium alloy plate for zinc electrodeposition, its characterized in that: the aluminum alloy composite plate is welded at the bottom end of the conductive beam, the insulating edge strips are fixedly arranged at two sides of the aluminum alloy composite plate, and the conductive beam comprises a conductive aluminum beam and an aluminum-clad copper composite conductive head arranged at the end head of the conductive beam;
the conductive aluminum beam is 6 series aluminum alloy;
based on the mass of 100% of substances in the aluminum alloy composite plate, the micro-nano silver coated aluminum oxide composite powder comprises 0.5-3.0% of Mn 0.6-3.0% of Ca 0.01-0.2% of Zr 0.03-0.5% of Mn 0.01-0.1% of Mn 0.06-0.5% of Ti 0.01-0.1% of B0.01-0.1% of La 0.01-0.2% of Ce 0.01-0.2% of Cr, unavoidable impurities less than 0.06% of Al and the balance of Al.
2. The energy-saving high-strength corrosion-resistant cathode aluminum alloy sheet for zinc electrodeposition according to claim 1, wherein: the preparation method of the micro-nano silver coated alumina composite powder comprises the following specific steps:
1) Placing the micro-nano alumina powder into a NaOH solution for ultrasonic degreasing, washing with deionized water, and then placing into an ammonium fluoride solution for ultrasonic roughening to obtain roughened micro-nano alumina powder;
2) Placing coarsened micro-nano alumina powder in AgNO 3 Ultrasonic activating in the solution to obtain activated micro-nano alumina powder;
3) And (3) placing the activated micro-nano aluminum oxide powder into chemical plating solution, and performing chemical silver plating at the temperature of 20-40 ℃ for 30-60 min to obtain the micro-nano silver coated aluminum oxide composite powder.
3. The energy-saving high-strength corrosion-resistant cathode aluminum alloy sheet for zinc electrodeposition according to claim 2, wherein: step 1), the mass concentration of NaOH solution is 10-30%, and the concentration of ammonium fluoride solution is 5-25 g/L; step 2) AgNO 3 The concentration of the solution is 1-5 g/L.
4. An energy-saving high-strength corrosion-resistant cathode aluminum alloy sheet for zinc electrodeposition according to claim 2 or 3, wherein: the plating solution of the step 3) of chemical silver plating contains 1-15 g/L AgNO 3 、10～30g/L NaOH、50～200ml/L NH 3 ·H 2 O, 10-30 g/L glucose, 4-10 g/L tartaric acid, 100-300 ml/L absolute ethyl alcohol and the balance H 2 O。
5. The energy-saving high-strength corrosion-resistant cathode aluminum alloy sheet for zinc electrodeposition according to claim 2, wherein: the grain diameter of the micro-nano silver coated alumina composite powder is 100-800 nm, and the alumina is alpha-Al 2 O 3 The alumina is spherical in shape.
6. The energy-saving high-strength corrosion-resistant cathode aluminum alloy sheet for zinc electrodeposition according to claim 2, wherein: the preparation method of the aluminum alloy composite plate comprises the following specific steps:
(1) Deoiling the metal aluminum and the aluminum intermediate alloy, and then placing the aluminum intermediate alloy into a vacuum for preheating for 1-2 h at the temperature of 100-300 ℃;
(2) Smelting preheated metal aluminum and aluminum intermediate alloy to obtain an alloy melt, adding a covering agent to the surface of the alloy melt, and preserving heat for 3-5 min at 680-700 ℃ to obtain aluminum liquid;
(3) In argon atmosphere, adding silver-coated aluminum oxide composite powder to the bottom surface of aluminum liquid, heating to 700-850 ℃ at constant speed under stirring, adding aluminum foil-coated refining agent, refining for 5-10 min, continuously stirring for 2-10 min after slag skimming, and casting at 700-760 ℃ to obtain an aluminum alloy blank;
(4) The aluminum alloy billet is sequentially subjected to hot rolling, cold rolling, finishing and fixed-length shearing to obtain the aluminum alloy composite plate.
7. The energy-saving high-strength corrosion-resistant cathode aluminum alloy sheet for zinc electrodeposition according to claim 6, wherein: the aluminum master alloy is Al-10wt.% Mn, al-10wt.% Ca, al-5wt.% Zr, al-1wt.% Sr, al-5wt.% Ti-0.5wt.% B, al-10wt.% Ce and Al-15wt.% La, and the impurity content of the master alloy is less than 0.05wt.%.
8. The energy-saving high-strength corrosion-resistant cathode aluminum alloy sheet for zinc electrodeposition according to claim 6, which isIs characterized in that: the covering agent is 30wt.% Na 2 CO 3 +25wt.％CaCl 2 +25wt.％Na 2 SiF 6 +20wt.% NaF, the addition of the covering agent being 0.2 to 0.5% of the total mass of the smelted alloy; the refining agent is 40wt.% ZnCl 2 +60wt.％NH 4 The adding amount of the Cl and the refining agent is 0.05-0.2% of the mass of the alloy solution.
9. The energy-saving high-strength corrosion-resistant cathode aluminum alloy sheet for zinc electrodeposition according to claim 6, wherein: the hot rolling temperature is 500-600 ℃, the rolling direction is the same direction, the rolling passes are 8-10 times, the pressing amount of each pass is 10-30%, and emulsion is sprayed in the rolling process; the cold rolling temperature is 20-40 ℃, the rolling direction is the same direction, the rolling passes are 2-4 times, the pressing amount of each pass is 2-10%, and the rolling oil is coated in the rolling process.
10. The energy-saving high-strength corrosion-resistant cathode aluminum alloy sheet for zinc electrodeposition according to claim 1, wherein: the section of the aluminum-clad copper composite conductive head is compounded into a special shape; an anti-corrosion layer is compositely arranged above the aluminum alloy plate liquid level line by a diffusion extrusion method, and the anti-corrosion layer is a carbon fiber film layer with the thickness of 0.5-2 mm.
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