CN113122885A - Application of aluminum alloy composite board - Google Patents
Application of aluminum alloy composite board Download PDFInfo
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- CN113122885A CN113122885A CN202110364485.2A CN202110364485A CN113122885A CN 113122885 A CN113122885 A CN 113122885A CN 202110364485 A CN202110364485 A CN 202110364485A CN 113122885 A CN113122885 A CN 113122885A
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- lead
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- 229910000838 Al alloy Inorganic materials 0.000 title claims abstract description 46
- 239000002131 composite material Substances 0.000 title claims abstract description 28
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims abstract description 39
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000011701 zinc Substances 0.000 claims abstract description 29
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 29
- 229910001512 metal fluoride Inorganic materials 0.000 claims abstract description 22
- 230000007704 transition Effects 0.000 claims abstract description 22
- 229910001316 Ag alloy Inorganic materials 0.000 claims abstract description 18
- LWUVWAREOOAHDW-UHFFFAOYSA-N lead silver Chemical compound [Ag].[Pb] LWUVWAREOOAHDW-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000000463 material Substances 0.000 claims abstract description 15
- 229910001199 N alloy Inorganic materials 0.000 claims abstract description 11
- QSPOIADTFASZLE-UHFFFAOYSA-N [N].[Cr].[Cu] Chemical compound [N].[Cr].[Cu] QSPOIADTFASZLE-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000011651 chromium Substances 0.000 claims description 37
- 229910052804 chromium Inorganic materials 0.000 claims description 28
- 239000002253 acid Substances 0.000 claims description 26
- 238000000227 grinding Methods 0.000 claims description 24
- ZTXONRUJVYXVTJ-UHFFFAOYSA-N chromium copper Chemical compound [Cr][Cu][Cr] ZTXONRUJVYXVTJ-UHFFFAOYSA-N 0.000 claims description 23
- 238000005266 casting Methods 0.000 claims description 19
- 238000000151 deposition Methods 0.000 claims description 19
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 16
- 238000010438 heat treatment Methods 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 15
- 238000002791 soaking Methods 0.000 claims description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 14
- 230000008021 deposition Effects 0.000 claims description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 8
- 238000001816 cooling Methods 0.000 claims description 8
- 150000002191 fatty alcohols Chemical class 0.000 claims description 8
- 230000008018 melting Effects 0.000 claims description 8
- 238000002844 melting Methods 0.000 claims description 8
- 239000002893 slag Substances 0.000 claims description 8
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 8
- 235000011152 sodium sulphate Nutrition 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000011261 inert gas Substances 0.000 claims description 7
- 238000005086 pumping Methods 0.000 claims description 7
- 239000012495 reaction gas Substances 0.000 claims description 7
- YOYLLRBMGQRFTN-SMCOLXIQSA-N norbuprenorphine Chemical compound C([C@@H](NCC1)[C@]23CC[C@]4([C@H](C3)C(C)(O)C(C)(C)C)OC)C3=CC=C(O)C5=C3[C@@]21[C@H]4O5 YOYLLRBMGQRFTN-SMCOLXIQSA-N 0.000 claims description 6
- 238000004140 cleaning Methods 0.000 claims description 3
- 239000010410 layer Substances 0.000 description 74
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 23
- 229910052782 aluminium Inorganic materials 0.000 description 23
- 238000003723 Smelting Methods 0.000 description 17
- 238000000034 method Methods 0.000 description 17
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 16
- 229910052802 copper Inorganic materials 0.000 description 16
- 239000010949 copper Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 8
- 238000005260 corrosion Methods 0.000 description 8
- 230000008569 process Effects 0.000 description 8
- 238000005096 rolling process Methods 0.000 description 8
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- 238000007747 plating Methods 0.000 description 6
- 238000004544 sputter deposition Methods 0.000 description 6
- 239000011159 matrix material Substances 0.000 description 5
- 230000035939 shock Effects 0.000 description 5
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Inorganic materials [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 5
- 235000013024 sodium fluoride Nutrition 0.000 description 5
- 239000011775 sodium fluoride Substances 0.000 description 5
- 239000013077 target material Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- GYWPBASZSBNAHN-UHFFFAOYSA-F [F-].[Al+3].[Na+].[Ti+4].[F-].[F-].[F-].[F-].[F-].[F-].[F-] Chemical group [F-].[Al+3].[Na+].[Ti+4].[F-].[F-].[F-].[F-].[F-].[F-].[F-] GYWPBASZSBNAHN-UHFFFAOYSA-F 0.000 description 4
- AZDRQVAHHNSJOQ-UHFFFAOYSA-N alumane Chemical group [AlH3] AZDRQVAHHNSJOQ-UHFFFAOYSA-N 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000004070 electrodeposition Methods 0.000 description 4
- 238000005265 energy consumption Methods 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- 239000004332 silver Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000005289 physical deposition Methods 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- BRRSNXCXLSVPFC-UHFFFAOYSA-N 2,3,4-Trihydroxybenzoic acid Chemical group OC(=O)C1=CC=C(O)C(O)=C1O BRRSNXCXLSVPFC-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- -1 aluminum fluoride titanium sodium oxide Chemical compound 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000005336 cracking Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- YADSGOSSYOOKMP-UHFFFAOYSA-N dioxolead Chemical compound O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 2
- 238000009713 electroplating Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005554 pickling Methods 0.000 description 2
- 235000013824 polyphenols Nutrition 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 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 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- WPPDFTBPZNZZRP-UHFFFAOYSA-N aluminum copper Chemical compound [Al].[Cu] WPPDFTBPZNZZRP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 230000005587 bubbling Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000567 combustion gas Substances 0.000 description 1
- 150000001879 copper Chemical class 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229910001610 cryolite Inorganic materials 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000000428 dust Substances 0.000 description 1
- 238000005485 electric heating Methods 0.000 description 1
- 238000003411 electrode reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000003574 free electron Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- JQJCSZOEVBFDKO-UHFFFAOYSA-N lead zinc Chemical compound [Zn].[Pb] JQJCSZOEVBFDKO-UHFFFAOYSA-N 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000005416 organic matter 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
- 239000011148 porous material Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000007670 refining Methods 0.000 description 1
- 239000000779 smoke Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
- 238000009858 zinc metallurgy Methods 0.000 description 1
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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
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/02—Pretreatment of the material to be coated
- C23C14/024—Deposition of sublayers, e.g. to promote adhesion of the coating
- C23C14/025—Metallic sublayers
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/0641—Nitrides
-
- 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
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
- C23C14/165—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon by cathodic sputtering
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Physical Vapour Deposition (AREA)
Abstract
The invention provides an application of an aluminum alloy composite plate for a zinc electrode, wherein the plate takes aluminum alloy as a base material, and a metal fluoride transition layer, a chromium metal layer, a chromium-copper-nitrogen alloy layer and a lead-silver alloy layer are respectively and sequentially arranged on the base material.
Description
Technical Field
The invention relates to the technical field of anode plate preparation, in particular to application of an aluminum alloy composite plate, and specifically relates to the field of electrode zinc.
Background
The modern zinc smelting method is divided into a fire method and a wet method, wherein the wet method is mainly used, the fire method zinc smelting comprises three main processes of roasting, reduction distillation and refining, and the three main processes mainly comprise closed blast furnace zinc smelting, open-pot zinc smelting, vertical-pot zinc smelting and electric heating zinc smelting. The flat tank zinc smelting and the vertical tank zinc smelting are both indirect heating, and have the reasons of high energy consumption, poor adaptability to raw materials and the like, the flat tank zinc smelting is almost eliminated, and the vertical tank zinc smelting is adopted by a small number of manufacturers such as a cucurbit island zinc factory and the like at present. The electrothermal zinc smelting method has the problems of small production capacity, high energy consumption and low direct yield of zinc although the direct heating method does not generate combustion gas, so the development prospect is not wide, and the electrothermal zinc smelting method is only suitable for places with low electric power. The closed blast furnace zinc smelting has the advantages of capacity of smelting lead and zinc simultaneously, direct heating by adopting fuel and high energy utilization rate, can treat various miscellaneous materials such as complex lead-zinc ore, steel plant smoke dust and the like, is the main existing pyrometallurgical zinc smelting equipment, and compared with pyrometallurgical zinc smelting, the hydrometallurgical zinc smelting is a mainstream of zinc metallurgy technology development due to good comprehensive utilization of resources, relatively low unit energy consumption and high environmental friendliness, and the yield of the hydrometallurgical zinc accounts for about 80 percent of the total zinc output in the world by the early 20 th century and 80 th year.
The anode for zinc electrodeposition at present generally must satisfy the following basic conditions: (1) good electric conductivity, (2) good electrocatalytic activity for electrode reaction; (3) the corrosion resistance is strong; (4) the mechanical strength and the processing performance are good; (5) long service life and low cost.
For example, CN201911199298A discloses an aluminum/lead anode plate and a preparation method thereof, comprising the following steps: casting an alloy solution of lead-silver alloy by taking a substrate with a copper layer on the outer surface as a matrix to obtain an anode plate pre-product; sequentially carrying out heat treatment and rolling on the anode plate pre-product to obtain an aluminum/lead anode plate; the lead-silver alloy is an alloy using lead and silver as matrix elements. The copper layer forms intermetallic compounds between aluminum and lead, so that the bonding performance and the conductivity between the lead and the aluminum can be effectively improved, the resistance of the whole anode plate can be greatly reduced, and the electric energy consumption caused by overlarge resistance can be reduced. Meanwhile, the aluminum skeleton in the aluminum/lead anode plate obtained by the preparation method can be recycled after reaching the service life, a new composite material is manufactured again, and the recycling of resources is facilitated, but it should be clear that the patent has certain defects in theory, and mainly focuses on two points: (1) however, as the person skilled in the art knows, the copper layer is directly electroplated on the aluminum material, the difference of the thermal expansion coefficients of copper and aluminum is great, and under the condition of continuously high-temperature electrodeposition zinc, an obvious thermal stripping effect can occur, so that electrodeposition bulges are caused, and the service life is reduced; (2) the electrode potential of aluminum is very negative, and the patent adopts electroplating to plate copper, and during the electroplating process, the displacement reaction of aluminum and copper salt can firstly occur, and the formed copper metal seriously influences the bonding strength of a plating layer and an aluminum matrix.
In addition to the lead-silver alloy electrode plate, the prior art contains titanium-based DSA, wherein titanium is used as a matrix, and the surface of the anode is coated with an anode with an electrocatalytic active substance coating and stable shape; a noble metal-based DSA electrode; a stainless steel-based anode; aluminum-based anodes, graphite anodes, ceramic anodes, and the like.
Disclosure of Invention
The invention aims to provide the application of the aluminum alloy composite board, and the aluminum alloy composite board prepared by the preparation method provided by the invention has the advantages of good conductivity, strong interlayer bonding force and long service life.
The application of the aluminum alloy composite plate is used for a zinc electrode, the plate takes aluminum alloy as a base material, and a metal fluoride transition layer, a chromium metal layer, a chromium-copper-nitrogen alloy layer and a lead-silver alloy layer are respectively and sequentially arranged on the base material, wherein the preparation process of the chromium metal layer and the chromium-copper-nitrogen alloy layer is as follows:
(a) vacuum pumping was used to 5X 10-2After Pa, introducing inert gas argon, starting a pulse bias power supply, setting the voltage at 700V-800V, the duty ratio at 40% -50%, the frequency at 20KHz-30KHz and the time at 5-6min, and cleaning the aluminum alloy containing the metal fluoride transition layer;
(b) reducing the pulse bias amplitude to 400-500V, the duty ratio to 20-30 percent, the frequency to 10KHz-20KHz, adjusting the working air pressure to ensure that the vacuum reaches 0.6-1Pa, starting the chromium target to ensure that the arc current of the chromium target is 70-80A, the deposition time is 3-5min, and depositing a Cr layer;
(c) introducing 100sccm N2 as reaction gas, starting the chromium-copper target and continuing to start the chromium-copper target, wherein the pulse bias amplitude is 400-500V, the duty ratio is 20-30%, and the frequency is 10KHz-20KHz, so that the arc current of the chromium target is 70-80A, and the arc current of the chromium-copper target is 90-100A to deposit a CrCuN layer.
Further, the aluminum alloy is subjected to surface pretreatment: the pretreatment comprises the steps of mechanical grinding and acid washing, wherein the mechanical grinding is sequentially grinding by using 300#, 600#, 1000# abrasive paper, and the acid washing is 5g/L H2SO40.03 g/L HF, 0.5g/L fatty alcohol ether sodium sulfate, 35 deg.CoC, the time is 10 min.
Further, the thickness of the metal fluoride transition layer is 0.5-1 μm, the metal fluoride transition layer is obtained by soaking, the soaking solution contains 4-5g/L hexafluorotitanic acid, 2-3g/L NaF and 4-5g/L monobutyric acid, the pH of the soaking solution is =4 +/-0.2, the soaking time is 4-5min, and the metal fluoride transition layer is dried after soaking.
Further, the lead-silver alloy is obtained by casting: melting the lead block in a crucible furnace, adding silver powder, heating to 650-700 ℃, stirring for 10min, dragging out slag, casting, cooling in air and demoulding.
Further, the silver powder is added in an amount of 0.5 to 1wt.% based on the mass of the lead.
The preparation method of the aluminum alloy composite plate comprises the following processing steps:
(1) the surface of the aluminum alloy plate is pretreated to remove the oxide film on the surface.
The pretreatment comprises the steps of mechanical grinding and acid washing, wherein the mechanical grinding is implemented by sequentially grinding 300#, 600#, 1000# abrasive paper, and the acid washing is 5g/L H2SO40.03 g/L HF, 0.5g/L fatty alcohol ether sodium sulfate, 35 deg.CoC, the time is 10 min.
The mechanical polishing of the invention mainly aims to remove the oxidation on the surface of the aluminum alloy plate and simultaneously improve the flatness of the plate, and as known by the technical personnel in the field, an electrode is vertical to an electrolytic bath in the process of electrodeposition of zinc, the electrode can generate obvious deformation phenomenon in the use process, when an aluminum substrate is used, if the flatness of the aluminum substrate cannot be ensured, the service life of the electrode can be obviously influenced, and when the mechanical polishing is carried out, the aluminum can be preferentially carried out with heat treatment to remove internal stress, so as to maximally and obviously reduce the influence of subsequent thermal shock on the electrode.
And then carrying out acid pickling treatment on the aluminum material, wherein the acid pickling mainly aims to be carried out for two times: (1) further removing an oxide film on the surface of the aluminum material, and mechanically polishing the remaining scraps; (2) deoiling, degreasing and activating.
(2) Preparing a metal fluoride transition layer.
The thickness of the metal fluoride transition layer is 0.5-1 mu m, the main component of the metal fluoride is aluminum titanium sodium fluoride, the preparation process comprises the steps of soaking the aluminum alloy pretreated in the step (1) in a solution containing 4-5g/L hexafluorotitanic acid, 2-3g/L NaF and 4-5g/L monobutyric acid, wherein the pH value is =4 +/-0.2, and the time is 4-5min, and drying.
The invention aims to form a porous transition layer on the surface of a base material, wherein the passivation film is in a porous state, and the peeling phenomenon caused by different thermal expansion coefficients between a subsequent physical sputtering metal layer and an aluminum material can be obviously reduced.
The transition layer reacts in the solution as follows:
in the soaking process, the aluminum material can form a micro-battery locally, according to metal ions on the surface of the aluminum alloy based on the theory of double electric layers, polar water molecules attract aluminum atoms in metal lattices to enable the aluminum atoms to get rid of the coulomb attraction of free electrons, and the aluminum atoms enter the solution to form Al3+ under the action of the water molecules, and the following steps are carried out in a micro-anode region: al → Al3++3e-(ii) a F-is easily adsorbed on the surface of the aluminum alloy due to characteristic adsorption of F-ions, so that the F-concentration of the surface of the matrix is high, and the F-reacts with Al3 +: f-+Al3+=AlF6 3-Is combined with Na+Combine to form Na3AlF6In the cathode region, the following reactions occur: o is2+2H2O+3e-→4OH-Due to a local increase in OH, Ti4++4OH-→TiO2+2H2O； Al3++6OH-→Al2O3 .2H2O; as the plating solution contains monobutyric acid, the monobutyric acid has the following structural formula:
the organic matter containing polyphenol hydroxyl structure, the hydrolysate is trihydroxybenzoic acid and glucose, the trihydroxybenzoic acid has a poly-ortho-position phenolic hydroxyl structure, and the structure can be used as a polybase ligand to easily perform a complex reaction with metal ions, and finally the complex reaction in a soaking solution forms the following substances:
and then a porous aluminum fluoride titanium sodium oxide is formed in the subsequent drying process, wherein the pores are favorable for the adhesion of the subsequent physical deposition metal layer, and the porous structure is shown in figure 1.
(3) And physically sputtering a chromium metal layer and a chromium-copper-nitrogen alloy layer.
(a) Vacuum pumping was used to 5X 10-2And after Pa, introducing inert gas argon, starting a pulse bias power supply, setting the voltage at 700V-800V, the duty ratio at 40-50%, the frequency at 20KHz-30KHz and the time at 5-6mi, cleaning, and removing deposited particles with extremely weak surface bonding force in the transition layer, wherein the particles are clearly visible in the attached figure 1, and if the particles are not cleaned, the service life of the electrode plate is seriously influenced.
After the treatment of step (a), as shown in FIG. 2.
(b) Reducing the pulse bias amplitude to 400-500V, the duty ratio to 20-30 percent, the frequency to 10KHz-20KHz, adjusting the working air pressure to ensure that the vacuum reaches 0.6-1Pa, starting the chromium target to ensure that the arc current of the chromium target is 70-80A, the deposition time is 3-5min, and depositing a Cr layer.
(c) Introducing 100sccm N2 as reaction gas, starting the chromium-copper target and continuing to start the chromium-copper target, wherein the pulse bias amplitude is 400-500V, the duty ratio is 20-30%, and the frequency is 10KHz-20KHz, so that the arc current of the chromium target is 70-80A, and the arc current of the chromium-copper target is 90-100A to deposit a CrCuN layer.
The purity of the chromium target and the chromium-copper target is 99.99 percent, wherein the mass ratio of copper to chromium in the chromium-copper target is 8: 2.
The method comprises the steps of firstly forming a chromium layer on a porous structure of a transition layer, and then physically depositing chromium and copper; if physical deposition of CrCuN is directly carried out on the plating layer, the cracking phenomenon of the plating layer can occur, and if physical deposition of Cr is carried out before deposition of CrCuN is selected, the plating layer is smooth, probably because the Cr layer effectively relieves the stress between CrCuN and the porous aluminum fluoride titanium sodium oxide due to property difference, the cracking phenomenon of the metal layer is avoided, and the smooth metal layer is convenient to form.
(4) Casting a lead-silver alloy layer, wherein the step of casting the lead-silver alloy layer comprises the following steps: melting a lead block in a crucible furnace, adding silver powder, heating to 650-700 ℃, stirring for 10min, fishing out slag, casting, cooling in air and demoulding, wherein the adding amount of the silver powder is 0.5-1 wt% of the mass of the lead.
The lead-silver alloy anode is used for replacing a pure lead anode, wherein the addition of silver is not used for improving the conductivity, and the main reason is that the silver is a catalyst of an oxygen evolution reaction, and the silver is used as an alloy element in the lead-silver alloy, so that a lead dioxide film is compact, the corrosion resistance is improved, and the precipitation of oxygen is reduced.
(5) And carrying out heat treatment and rolling to obtain the aluminum alloy composite plate.
Further, the temperature of the heat treatment is 250-260-oC, the time is 120-150 s.
Further, the rolling reduction rate is 10-15%.
Furthermore, the aluminum alloy composite plate has the length of 900-1000mm, the width of 600-700mm and the thickness of 4-5 mm.
The beneficial technical effects are as follows: the aluminum alloy composite plate obtained by sequentially arranging the metal fluoride transition layer, the chromium metal layer, the chromium-copper-nitrogen alloy layer and the lead-silver alloy layer on the surface of the aluminum material has extremely high strength and corrosion resistance, and the bonding force of the composite plate is remarkably improved by layer arrangement, so that the loss of the plate caused by corrosion, deformation, stripping and other reasons when the plate is used as an anode is effectively avoided.
Drawings
FIG. 1 is an SEM image of the surface appearance of the aluminum material after the soaking treatment.
FIG. 2 is an SEM image of the surface topography of the invention after being cleaned in step 3 (a).
FIG. 3 is a cross-sectional view of the morphology of comparative example 2 of the present invention for depositing copper directly on aluminum.
FIG. 4 is a cross-sectional view of the thermal shock topography of comparative example 2 of the present invention with copper deposited directly on aluminum.
FIG. 5 is a cross-sectional view of the deposited chromium, copper and nitrogen profile of example 2.
FIG. 6 is a thermal shock topographic cross-sectional view of the topographic cross-sectional view after deposition of chromium, copper and nitrogen in example 2 of the present invention.
Detailed Description
The present invention will now be described in further detail with reference to specific examples, which are intended to be illustrative, but not limiting, of the invention.
Example 1
The application of the aluminum alloy composite plate comprises the following preparation steps:
(1) the surface of the aluminum alloy plate is pretreated to remove the oxide film on the surface.
The pretreatment comprises the steps of mechanical grinding and acid washing, wherein the mechanical grinding is sequentially grinding by using 300#, 600#, 1000# abrasive paper, and the acid washing is 5g/L H2SO40.03 g/L HF, 0.5g/L fatty alcohol ether sodium sulfate, 35 deg.CoC, the time is 10 min.
(2) Preparing a metal fluoride transition layer.
The thickness of the metal fluoride transition layer is 0.5-1 mu m, the main component of the metal fluoride is aluminum titanium sodium fluoride, and the preparation process comprises the steps of soaking the aluminum alloy pretreated in the step (1) in a solution containing 4g/L hexafluorotitanic acid, 2g/L NaF and 4g/L monobutyric acid, wherein the pH value is =4 +/-0.2, the time is 4min, and drying.
(3) And physically sputtering a chromium metal layer and a chromium-copper-nitrogen alloy layer.
(a) Vacuum pumping was used to 5X 10-2After Pa, introducing inert gas argon, starting a pulse bias power supply, setting the voltage at 700VV, the duty ratio at 40%, the frequency at 2KHz and the time at 5 min;
(b) reducing the pulse bias amplitude to 400V, the duty ratio to be 20 percent, the frequency to be 10KHz, adjusting the working air pressure to ensure that the vacuum reaches 0.6Pa, starting the chromium target to ensure that the arc current of the chromium target material is 70A, the deposition time is 3min, and depositing a Cr layer;
(c) introducing 100sccm N2 as a reaction gas, starting the chromium-copper target and continuing to start the chromium-copper target, wherein the pulse bias amplitude is 400V, the duty ratio is 20%, and the frequency is 10KHz, so that the arc current of the chromium target is 70A, and the arc current of the chromium-copper target is 90A to deposit a CrCuN layer;
(4) casting a lead-silver alloy layer;
melting the lead block in a crucible furnace, adding silver powder, heating to 650 ℃, stirring for 10min, dragging out slag, casting, cooling in air and demoulding.
(5) Heat treating and rolling to obtain composite aluminum alloy plate at 250 deg.coC, the time is 120-150 s.
Example 2
The application of the aluminum alloy composite plate comprises the following preparation steps:
(1) the surface of the aluminum alloy plate is pretreated to remove the oxide film on the surface.
The pretreatment comprises the steps of mechanical grinding and acid washing, wherein the mechanical grinding is sequentially grinding by using 300#, 600#, 1000# abrasive paper, and the acid washing is 5g/L H2SO40.03 g/L HF, 0.5g/L fatty alcohol ether sodium sulfate, 35 deg.CoC, the time is 10 min.
(2) Preparing a metal fluoride transition layer.
The thickness of the metal fluoride transition layer is 0.5-1 mu m, the main component of the metal fluoride is aluminum titanium sodium fluoride, the preparation process comprises the steps of soaking the aluminum alloy pretreated in the step (1) in a solution containing 4.5g/L hexafluorotitanic acid, 2.5g/L NaF, 4.5g/L monobutyric acid, pH =4 +/-0.2, and the time is 4.5min, and drying.
(3) And physically sputtering a chromium metal layer and a chromium-copper-nitrogen alloy layer.
(a) Vacuum pumping was used to 5X 10-2After Pa, introducing inert gas argon, starting a pulse bias power supply, setting the voltage at 750V, the duty ratio at 45%, the frequency at 25KHz, and the time at 5.5 min;
(b) reducing the pulse bias amplitude to 450V, controlling the duty ratio to be 25%, controlling the frequency to be 15KHz, adjusting the working air pressure to ensure that the vacuum reaches 0.8Pa, starting the chromium target to ensure that the arc current of the chromium target material is 75A, controlling the deposition time to be 4min, and depositing a Cr layer;
(c) introducing 100sccm N2 as a reaction gas, starting the chromium-copper target and continuing to start the chromium-copper target, wherein the pulse bias amplitude is 450V, the duty ratio is 25%, and the frequency is 15KHz, so that the arc current of the chromium target is 75A, and the arc current of the chromium-copper target is 95A to deposit a CrCuN layer;
(4) casting a lead-silver alloy layer;
melting the lead block in a crucible furnace, adding silver powder, heating to 675 ℃ and stirring for 10min, fishing out slag, casting, cooling in air and demoulding.
(5) Heat treating and rolling to obtain composite aluminum alloy plate at the temperature of 255 DEG CoC, the time is 135 s.
Example 3
The application of the aluminum alloy composite plate comprises the following preparation steps:
(1) the surface of the aluminum alloy plate is pretreated to remove the oxide film on the surface.
The pretreatment comprises the steps of mechanical grinding and acid washing, wherein the mechanical grinding is sequentially grinding by using 300#, 600#, 1000# abrasive paper, and the acid washing is 5g/L H2SO40.03 g/L HF, 0.5g/L fatty alcohol ether sodium sulfate, 35 deg.CoC, the time is 10 min.
(2) Preparing a metal fluoride transition layer.
The thickness of the metal fluoride transition layer is 0.5-1 mu m, the main component of the metal fluoride is aluminum titanium sodium fluoride, and the preparation process comprises the steps of soaking the aluminum alloy pretreated in the step (1) in a solution containing 5g/L hexafluorotitanic acid, 3g/L NaF and 5g/L monobutyric acid, wherein the pH value is =4 +/-0.2, the time is 5min, and drying.
(3) And physically sputtering a chromium metal layer and a chromium-copper-nitrogen alloy layer.
(a) Vacuum pumping was used to 5X 10-2After Pa, introducing inert gas argon, starting a pulse bias power supply, setting the voltage at 800V, the duty ratio at 50%, the frequency at 30KHz and the time at 6 min;
(b) reducing the pulse bias amplitude to 500V, the duty ratio to be 30 percent, the frequency to be 20KHz, adjusting the working air pressure to ensure that the vacuum reaches 1Pa, starting the chromium target to ensure that the arc current of the chromium target material is 80A, the deposition time is 5min, and depositing a Cr layer;
(c) introducing 100sccm N2 as a reaction gas, starting the chromium-copper target and continuing to start the chromium-copper target, wherein the pulse bias amplitude is 500V, the duty ratio is 30%, and the frequency is 20KHz, so that the arc current of the chromium target is 80A, and the arc current of the chromium-copper target is 100A to deposit a CrCuN layer;
(4) casting a lead-silver alloy layer;
melting the lead block in a crucible furnace, adding silver powder, heating to 700 ℃, stirring for 10min, dragging slag, casting, cooling in air and demoulding.
(5) Heat treating and rolling to obtain composite aluminum alloy plate at the temperature of 260 deg.coC, the time is 150 s.
Comparative example 1
The application of the aluminum alloy composite plate comprises the following preparation steps:
(1) the surface of the aluminum alloy plate is pretreated to remove the oxide film on the surface.
The pretreatment comprises the steps of mechanical grinding and acid washing, wherein the mechanical grinding is sequentially grinding by using 300#, 600#, 1000# abrasive paper, and the acid washing is 5g/L H2SO40.03 g/L HF, 0.5g/L fatty alcohol ether sodium sulfate, 35 deg.CoC, the time is 10 min.
(2) And physically sputtering a chromium metal layer and a chromium-copper-nitrogen alloy layer.
(a) Vacuum pumping was used to 5X 10-2After Pa, introducing inert gas argon, starting a pulse bias power supply, setting the voltage at 750V, the duty ratio at 45%, the frequency at 25KHz, and the time at 5.5 min;
(b) reducing the pulse bias amplitude to 450V, controlling the duty ratio to be 25%, controlling the frequency to be 15KHz, adjusting the working air pressure to ensure that the vacuum reaches 0.8Pa, starting the chromium target to ensure that the arc current of the chromium target material is 75A, controlling the deposition time to be 4min, and depositing a Cr layer;
(c) introducing 100sccm N2 as a reaction gas, starting the chromium-copper target and continuing to start the chromium-copper target, wherein the pulse bias amplitude is 450V, the duty ratio is 25%, and the frequency is 15KHz, so that the arc current of the chromium target is 75A, and the arc current of the chromium-copper target is 95A to deposit a CrCuN layer;
(3) casting a lead-silver alloy layer;
melting the lead block in a crucible furnace, adding silver powder, heating to 675 ℃ and stirring for 10min, fishing out slag, casting, cooling in air and demoulding.
(4) Heat treating and rolling to obtain composite aluminum alloy plate at the temperature of 255 DEG CoC, the time is 135 s.
Comparative example 2
The application of the aluminum alloy composite plate comprises the following preparation steps:
(1) the surface of the aluminum alloy plate is pretreated to remove the oxide film on the surface.
The pretreatment comprises the steps of mechanical grinding and acid washing, wherein the mechanical grinding is sequentially grinding by using 300#, 600#, 1000# abrasive paper, and the acid washing is 5g/L H2SO40.03 g/L HF, 0.5g/L fatty alcohol ether sodium sulfate, 35 deg.CoC, the time is 10 min.
(2) Copper is physically sputtered.
The pulse bias amplitude is 450V, the duty ratio is 25%, the frequency is 15KHz, the working air pressure is adjusted to enable the vacuum to reach 0.8Pa, the copper target is started, the arc current of the chromium target material is 75A, the deposition time is 4min, and a copper layer is deposited;
(3) casting a lead-silver alloy layer;
melting the lead block in a crucible furnace, adding silver powder, heating to 675 ℃ and stirring for 10min, fishing out slag, casting, cooling in air and demoulding.
(4) Heat treating and rolling to obtain composite aluminum alloy plate at the temperature of 255 DEG CoC, the time is 135 s.
The electrode plates of example 2, comparative example 1, comparative example 2 were tested.
(1) And (3) thickness testing: preparing an electrode plate with the thickness of 5mm in advance, cutting the electrode plate into 9 pieces after the electrode plate is used as an anode for 3 months in the electrode zinc process, respectively naming the 9 pieces as A-I, and testing the thickness of the central position of each cut electrode plate.
As in the above table, where example 2 has an average thickness of 4.73mm with a standard deviation of 0.122; comparative example 1 had an average thickness of 4.79mm with a standard deviation of 0.44; comparative example 2 had an average thickness of 6.02 mm; the corrosion rate of the example 2 is the minimum, the standard deviation of the corrosion is the minimum, namely the corrosion is uniform, the stability is the best, the average thickness of the comparative example 1 is similar to the example 2, but the average deviation is extremely large, even the thickness is more than 5mm, which indicates that the electrode plate is obviously bubbled or separated from the layer in the using process, and the bubbling of the comparative example 2 is serious, and the corrosion loss is higher.
Thermal shock experiments were performed before lead casting and post-treatment for both example 2 and comparative example 2, i.e. example 2 is an aluminum-transition layer-chromium copper layer and comparative example 2 is an aluminum-copper layer: and (3) placing the test piece into an oven at 200-300 ℃, heating for 30 minutes, taking out, immediately immersing into water at room temperature, taking out, and drying in the air.
As shown in fig. 3 and 4, in the case of comparative example 2 in which copper was physically sputtered directly on aluminum, a significant plating peeling phenomenon occurred.
As shown in fig. 5 and 6, the thermal shock test was performed on example 2, and no peeling phenomenon was observed.
Although the present invention has been described above by way of examples of preferred embodiments, the present invention is not limited to the specific embodiments, and can be modified as appropriate within the scope of the present invention.
Claims (5)
1. The application of the aluminum alloy composite plate is characterized in that the plate is used for a zinc electrode, the plate takes aluminum alloy as a base material, and a metal fluoride transition layer, a chromium metal layer, a chromium-copper-nitrogen alloy layer and a lead-silver alloy layer are respectively and sequentially arranged on the base material, wherein the preparation processes of the chromium metal layer and the chromium-copper-nitrogen alloy layer are as follows:
(a) vacuum pumping was used to 5X 10-2After Pa, introducing inert gas argon, starting a pulse bias power supply, setting the voltage at 700V-800V, the duty ratio at 40% -50%, the frequency at 20KHz-30KHz and the time at 5-6min, and cleaning the aluminum alloy containing the metal fluoride transition layer;
(b) reducing the pulse bias amplitude to 400-500V, the duty ratio to 20-30 percent, the frequency to 10KHz-20KHz, adjusting the working air pressure to ensure that the vacuum reaches 0.6-1Pa, starting the chromium target to ensure that the arc current of the chromium target is 70-80A, the deposition time is 3-5min, and depositing a Cr layer;
(c) introducing 100sccm N2 as reaction gas, starting the chromium-copper target and continuing to start the chromium-copper target, wherein the pulse bias amplitude is 400-500V, the duty ratio is 20-30%, and the frequency is 10KHz-20KHz, so that the arc current of the chromium target is 70-80A, and the arc current of the chromium-copper target is 90-100A to deposit a CrCuN layer.
2. The use of an aluminum alloy composite sheet according to claim 1, wherein the aluminum alloy is subjected to surface pretreatment: the pretreatment comprises the steps of mechanical grinding and acid washing, wherein the mechanical grinding is sequentially grinding by using 300#, 600#, 1000# abrasive paper, and the acid washing is 5g/L H2SO40.03 g/L HF, 0.5g/L fatty alcohol ether sodium sulfate, 35 deg.CoC, the time is 10 min.
3. The use of an aluminum alloy composite sheet according to claims 1-2, wherein the transition layer of metal fluoride has a thickness of 0.5-1 μm and is obtained by soaking in a solution containing 4-5g/L hexafluorotitanic acid, 2-3g/L NaF, and 4-5g/L monobutyric acid, the solution having a pH =4 ± 0.2 for a soaking time of 4-5min, and drying after soaking.
4. Use of an aluminium alloy composite sheet according to claims 1-3, wherein said lead-silver alloy is obtained by casting: melting the lead block in a crucible furnace, adding silver powder, heating to 650-700 ℃, stirring for 10min, dragging out slag, casting, cooling in air and demoulding.
5. Use of an aluminium alloy composite sheet according to claim 4, wherein the silver powder is added in an amount of 0.5-1wt.% based on the mass of lead.
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