CN114438551A - Surface treatment method of titanium cathode roller - Google Patents
Surface treatment method of titanium cathode roller Download PDFInfo
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- CN114438551A CN114438551A CN202210090821.3A CN202210090821A CN114438551A CN 114438551 A CN114438551 A CN 114438551A CN 202210090821 A CN202210090821 A CN 202210090821A CN 114438551 A CN114438551 A CN 114438551A
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- titanium cathode
- polishing
- cathode roller
- roller
- titanium
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- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 title claims abstract description 163
- 239000010936 titanium Substances 0.000 title claims abstract description 163
- 229910052719 titanium Inorganic materials 0.000 title claims abstract description 163
- 238000000034 method Methods 0.000 title claims abstract description 48
- 238000004381 surface treatment Methods 0.000 title claims abstract description 27
- 238000005498 polishing Methods 0.000 claims abstract description 205
- 239000000126 substance Substances 0.000 claims abstract description 31
- 238000002360 preparation method Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims description 77
- 239000000463 material Substances 0.000 claims description 24
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 22
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 22
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 20
- 239000004094 surface-active agent Substances 0.000 claims description 20
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 19
- 239000003795 chemical substances by application Substances 0.000 claims description 19
- 238000005530 etching Methods 0.000 claims description 18
- 230000003647 oxidation Effects 0.000 claims description 14
- 238000007254 oxidation reaction Methods 0.000 claims description 14
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 229960005070 ascorbic acid Drugs 0.000 claims description 11
- 239000011668 ascorbic acid Substances 0.000 claims description 11
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 10
- 239000003082 abrasive agent Substances 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 10
- 235000010323 ascorbic acid Nutrition 0.000 claims description 10
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 9
- 239000003792 electrolyte Substances 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
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- 238000003756 stirring Methods 0.000 claims description 9
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 8
- 239000004310 lactic acid Substances 0.000 claims description 7
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 6
- GVGUFUZHNYFZLC-UHFFFAOYSA-N dodecyl benzenesulfonate;sodium Chemical compound [Na].CCCCCCCCCCCCOS(=O)(=O)C1=CC=CC=C1 GVGUFUZHNYFZLC-UHFFFAOYSA-N 0.000 claims description 6
- 235000014655 lactic acid Nutrition 0.000 claims description 6
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 6
- 238000007517 polishing process Methods 0.000 claims description 6
- 229940080264 sodium dodecylbenzenesulfonate Drugs 0.000 claims description 6
- 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 5
- 229910052581 Si3N4 Inorganic materials 0.000 claims description 5
- 238000001035 drying Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 4
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 claims description 4
- 229940106681 chloroacetic acid Drugs 0.000 claims description 4
- 239000007788 liquid Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- 239000011241 protective layer Substances 0.000 claims description 4
- 229960004889 salicylic acid Drugs 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 4
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- 229940075614 colloidal silicon dioxide Drugs 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 3
- 238000007654 immersion Methods 0.000 claims description 3
- 239000012535 impurity Substances 0.000 claims description 3
- 238000010907 mechanical stirring Methods 0.000 claims description 3
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 claims description 3
- 239000003381 stabilizer Substances 0.000 claims description 3
- 238000003860 storage Methods 0.000 claims description 3
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- AEDZKIACDBYJLQ-UHFFFAOYSA-N ethane-1,2-diol;hydrate Chemical compound O.OCCO AEDZKIACDBYJLQ-UHFFFAOYSA-N 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 abstract description 30
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 15
- 239000011889 copper foil Substances 0.000 abstract description 12
- 230000002035 prolonged effect Effects 0.000 abstract description 5
- 230000001737 promoting effect Effects 0.000 abstract description 4
- 230000003746 surface roughness Effects 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 11
- 230000000694 effects Effects 0.000 description 10
- 239000010410 layer Substances 0.000 description 9
- 229920000297 Rayon Polymers 0.000 description 8
- 229960000583 acetic acid Drugs 0.000 description 8
- 229910052681 coesite Inorganic materials 0.000 description 8
- 229910052906 cristobalite Inorganic materials 0.000 description 8
- 239000002964 rayon Substances 0.000 description 8
- 239000000377 silicon dioxide Substances 0.000 description 8
- 229910052682 stishovite Inorganic materials 0.000 description 8
- 229910052905 tridymite Inorganic materials 0.000 description 8
- 239000011888 foil Substances 0.000 description 7
- 229910052593 corundum Inorganic materials 0.000 description 6
- 229910001845 yogo sapphire Inorganic materials 0.000 description 6
- 239000012362 glacial acetic acid Substances 0.000 description 5
- ZGTMUACCHSMWAC-UHFFFAOYSA-L EDTA disodium salt (anhydrous) Chemical compound [Na+].[Na+].OC(=O)CN(CC([O-])=O)CCN(CC(O)=O)CC([O-])=O ZGTMUACCHSMWAC-UHFFFAOYSA-L 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 239000002002 slurry Substances 0.000 description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 3
- 238000007664 blowing Methods 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000012827 research and development Methods 0.000 description 2
- 238000012795 verification Methods 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004372 Polyvinyl alcohol Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000010191 image analysis Methods 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000013081 microcrystal Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 229920002451 polyvinyl alcohol Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000002344 surface layer Substances 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- -1 tetraethylammonium hydroxide-salicylic acid Chemical group 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D1/00—Electroforming
- C25D1/04—Wires; Strips; Foils
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
- C25D17/12—Shape or form
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
Abstract
The invention discloses a surface treatment method of a titanium cathode roller. Belongs to the technical field of electrolytic copper foil, and aims to solve the problems that the roughness Ra index judged in the surface treatment method of the titanium cathode roller in the prior art is single, the roughness of the roller surface of the titanium cathode roller cannot be reduced to the maximum extent, the uniformity of the roughness of the roller surface of the titanium cathode roller is improved, and the stable production time of the titanium cathode roller is prolonged. The method comprises the steps of preparation of polishing solution, pretreatment of the titanium cathode roller, chemical mechanical polishing and post-treatment of the chemical mechanical polishing titanium cathode roller. Compared with the traditional surface treatment process, the method has remarkable promoting effects of reducing the roughness of the roll surface of the titanium cathode roll, promoting the uniformity of the roughness of the roll surface of the titanium cathode roll and prolonging the stable production time of the titanium cathode roll, and has important economic significance in production. Therefore, the application of the invention has considerable economic value and excellent popularization prospect.
Description
Technical Field
The invention belongs to the technical field of electrolytic copper foil, and particularly relates to a surface treatment method of a titanium cathode roller.
Background
The electrolytic copper foil is an indispensable key material for lithium ion batteries and printed circuit boards, and plays a significant role in the fields of new energy and electronic circuits. In the production process of the electrolytic copper foil, copper ions in the electrolyte obtain electrons on the surface of the titanium cathode roller and are reduced into copper atoms, and the copper atoms are arranged according to a certain rule to form the electrolytic copper foil. In the process, the surface state of the titanium cathode roller can directly influence the nucleation and growth process of copper atoms, further influence the micro-crystal structure of the copper foil, and finally influence the surface density uniformity, tensile strength, elongation, warpage, appearance and other macroscopic properties of the copper foil. However, in the electrolytic foil-forming process, the surface of the titanium cathode roller is oxidized or hydrogenated to some extent due to the influence of the electrolyte, the current, and the electrochemical reaction. Particularly, along with the gradual extension of the electrolysis time, the oxide layer on the surface of the titanium cathode roller can be gradually and slowly accumulated, and the roller surface is oxidized in different degrees, so that the quality of the copper foil is influenced. Therefore, the titanium cathode roller needs to be polished off-line after a period of continuous electrolytic foil generation to remove the overgrown oxide layer on the surface.
At present, the surface oxide layer is removed by adopting a mechanical polishing mode in the offline polishing of the titanium cathode roller, and the roughness Ra value of the polished roller surface is generally used as a judgment standard of the offline polishing effect of the titanium cathode roller. The Ra value of the titanium cathode roller after mechanical polishing is generally between 0.1 and 0.3 μm.
The traditional mechanical polishing treatment can form polishing prints with different degrees on the roller surface, so that the roller surface has the phenomenon of non-uniformity in roughness. A layer of extremely thin oxide film can be generated on the surface of the titanium roller after mechanical polishing in the atmosphere, so that the titanium material is protected from being corroded. However, the oxide film layer formed by oxidation in a natural state has a non-uniform thickness, and further, the roughness and the conductivity of the roll surface vary to some extent.
Among the common polishing modes: the chemical polishing method removes surface substances through chemical reaction between the polishing solution and the material to be polished, and can obtain a polished surface with low roughness. The mechanical polishing method can remove the components on the surface layer of the material to be polished through mechanical acting force, and can realize the rapid polishing of the workpiece. The chemical mechanical polishing method combines the characteristics of chemical polishing and mechanical polishing, and effectively improves the polishing efficiency while obtaining a polished surface with lower roughness; in the chemical mechanical polishing process, the polishing solution and the components on the surface of the workpiece are subjected to chemical reaction to soften the surface substances of the workpiece; the polishing disk transfers the energy required to break the weakly bonded molecular chains to the polishing particles, removing the softened layer from the surface of the workpiece.
For the reasons of the process, mechanical polishing and grinding are combined with chemical mechanical polishing to process the roller surface in the prior art. However, the period of stable production of the titanium cathode roller still needs to be improved.
According to the existing research, the method comprises the following steps: the uniformity of the roughness of the titanium cathode roll surface can have a significant effect on the nucleation and growth of the electrolytic copper foil. The inventor also found through a large number of experiments that the roughness uniformity can be used as a quantitative index of the polishing effect of the titanium cathode roller. Roughness uniformity refers to the ratio between the range of roughness in the measurement area and the average value of roughness.
Wherein E isRFor roughness uniformity, Δ R is the range of roughness and R is the roughness average. General case E of the samplesRThe smaller the value, the better the roughness uniformity, the more convenient the nucleation and growth of the electrolytic copper foil, and the longer the stable production period of the titanium cathode roller.
Based on the new research and development direction and the lack of a processing method matched with the new research and development direction and the experimental result, the invention provides a surface processing technology of a titanium cathode roller.
Disclosure of Invention
The invention aims to provide a surface treatment method of a titanium cathode roller, which aims to solve the problems that the roughness Ra index judged in the surface treatment method of the titanium cathode roller in the prior art is single, the roughness of the roller surface of the titanium cathode roller cannot be reduced to the maximum extent, the uniformity of the roughness of the roller surface of the titanium cathode roller cannot be improved, and the stable production time of the titanium cathode roller cannot be prolonged.
In order to solve the problems, the technical scheme of the invention is as follows:
a surface treatment method of a titanium cathode roller comprises the following steps:
a, mechanically polishing and grinding a titanium cathode roller for pretreatment;
hoisting the titanium cathode roller needing surface treatment to a grinding machine by using a travelling crane, setting the rotating speed, cylinder pressure and transverse moving speed of a grinding wheel on a polishing disc, respectively starting rotating motors of the grinding wheel and the titanium cathode roller, and performing mechanical polishing pretreatment on the roller surface of the titanium cathode roller;
b, chemically and mechanically polishing the titanium cathode roller;
replacing the grinding wheels subjected to mechanical polishing with polishing disks symmetrically distributed on two sides of the horizontal diameter of the cathode roller, and setting the flow rate of a polishing solution nozzle and the rotating speed of the cathode roller to perform chemical mechanical polishing treatment on the titanium cathode roller;
step C, carrying out anodic oxidation treatment on the polished titanium cathode roller;
1. removing impurities remained on the roll surface of the titanium cathode roll after the chemical mechanical polishing treatment is finished by using deionized water;
2. drying the residual moisture on the surface of the titanium cathode roller by compressed air;
3. taking a metal titanium plate as a cathode, a polished titanium cathode roller as an anode and deionized water-glycol solution containing ammonium fluoride as electrolyte, and carrying out anodic oxidation treatment under a certain voltage to generate a thin and compact protective layer on the roller surface of the titanium cathode roller.
Further, the polishing solution in the step B consists of a nano grinding material, an etching agent, a pH regulator, a surfactant and deionized water; the preparation process comprises the following steps:
adding a proper amount of deionized water into a polishing solution preparation tank, adding a surfactant, an etching agent, a pH stabilizer and a nano grinding material under mechanical stirring, continuously stirring to fully and uniformly mix all components in the polishing solution, then conveying the polishing solution to a polishing solution storage tank with a stirring function, and continuously stirring for later use.
Further, electrolyte solutes used in the anodic oxidation treatment in step C-3 include, but are not limited to, ammonium fluoride and ammonium chloride, a solvent is deionized water-ethylene glycol, a voltage is between 35V and 50V, and a treatment time is between 3 minutes and 5 minutes.
Further, polishing the titanium cathode roller by using a polishing disc in the chemical mechanical polishing operation of the step B, wherein the polishing disc is symmetrically distributed on two sides of the titanium cathode roller, the polishing disc is directly contacted with the titanium cathode roller in the polishing process, and the polishing liquid is conveyed to a nozzle right above the highest point of the titanium cathode roller and above the contact point of the titanium cathode roller and the polishing disc through a conveying pump;
in the whole process, the polishing solution passing through the polishing disc finally collects into a low tank along the roll surface of the titanium cathode roll, the roll surface at the lower part of the titanium cathode roll is immersed in the polishing solution of the low tank, and the immersion height of the titanium cathode roll in the low tank is 1/6 which is larger than the diameter of the cathode roll;
in the process, the rotating linear speeds of the titanium cathode roller and the polishing disk are different, and the rotating linear speed of the polishing disk is greater than that of the titanium cathode roller.
Furthermore, the mesh number of the grinding wheel mechanically polished in the step A is 120-300 meshes.
Furthermore, the nano grinding material in the polishing solution is spherical, and the diameter of the nano grinding material is between 20 and 200 nm; the nano abrasive material is colloidal aluminum trioxide (Al)2O3) Colloidal silicon dioxide (SiO)2) Silicon nitride (Si)3N4) Or cerium oxide (CeO)2) One or more of the above; the mass concentration of the nano abrasive material in the polishing solution is between 1 and 4 weight percent.
Further, the etching agent in the polishing solution is two or more of lactic acid, chloroacetic acid, hydrogen peroxide, hydrofluoric acid, oxalic acid, citric acid and ethylene diamine tetraacetic acid-2 sodium (EDTA-2 Na); the mass concentration of the etching agent in the polishing solution is between 5 and 10 weight percent.
Further, the pH value of the polishing solution is between 3 and 5.
Further, the pH regulator in the polishing solution consists of inorganic-organic composite components;
wherein the inorganic pH regulator is at least two or more of acetic acid, hydrochloric acid, nitric acid, ammonia water and sodium hydroxide;
the organic pH regulator is two or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, salicylic acid and ascorbic acid;
the mass concentration of the pH regulator in the polishing solution is between 1 and 1.5 weight percent.
Further, the surfactant in the polishing solution is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, cetyl trimethyl ammonium bromide, polyvinylpyrrolidone and polyethylene glycol; the mass concentration of the surfactant in the polishing solution is between 0.01 and 0.1 weight percent.
The invention has the following beneficial effects:
(1) the invention introduces roughness uniformity E on the basis of roughness Ra of the polished roller surfaceRAs another quantitative index of the polishing and grinding effect of the titanium cathode roller, and in the grinding direction, in combination with the mechanical polishing and grinding pretreatment, the chemical mechanical polishing and the anodic oxidation treatment process, the mechanical polishing and grinding pretreatment is firstly carried out on the titanium cathode roller by using a grinding wheel to remove the oxidizing substances on the outermost layer of the roller surface; further polishing the pretreated titanium cathode roller by chemical mechanical polishing, so that the roughness of the roller surface is reduced and the uniformity of the roughness of the roller surface is improved; finally, a compact protective layer is generated on the roll surface of the polished titanium cathode roll by means of anodic oxidation treatment. The roughness uniformity of the roll surface can be improved while the roughness of the roll surface is reduced, and further through anodic oxidation treatment, the surface oxidation layer of the titanium cathode roll is more uniform and consistent, and the oxidation resistance is better. The roughness uniformity of the roll surface can be improved while the roughness of the roll surface is reduced, and the uniform protective oxide layer is rapidly generated on the surface of the titanium cathode roll, so that the stable production period of the titanium cathode roll can be effectively prolonged, the production utilization rate of equipment is improved, and the quality of electrolytic copper foil is improved.
(2) The invention is obtained in a large number of experiments and production verifications: roughness Sa can be reduced27%, the roughness Sq can be reduced by 42%, and the roughness uniformity ERCan improve 40 percent and prolong 33 percent of stable production time after polishing and grinding. Therefore, compared with the traditional surface treatment process, the method has remarkable promoting effects of reducing the roughness of the roll surface of the titanium cathode roll, promoting the uniformity of the roughness of the roll surface of the titanium cathode roll and prolonging the stable production time of the titanium cathode roll, and has important economic significance in production. Therefore, the application of the invention has considerable economic value and excellent popularization prospect.
Drawings
FIG. 1 is a schematic structural view of a chemical mechanical polishing apparatus for a titanium cathode roll;
FIG. 2 is a comparison graph of the analysis effect of the smooth-surface microscopic image of the electrolytic green foil produced by the titanium cathode roller treated by the method of the present invention and the conventional mechanical polishing method.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention more apparent, the technical solutions of the embodiments of the present invention will be described clearly and completely with reference to the accompanying drawings of the embodiments of the present invention, and it is obvious that the described embodiments are some, but not all embodiments of the present invention. All other embodiments, which can be obtained by a person skilled in the art without any inventive step based on the embodiments of the present invention, are within the scope of the present invention.
Thus, the following detailed description of the embodiments of the present invention, presented in the figures, is not intended to limit the scope of the invention, as claimed, but is merely representative of selected embodiments of the invention.
Detailed description of the preferred embodiments
A surface treatment method of a titanium cathode roller comprises the following steps:
a, mechanically polishing and grinding a titanium cathode roller for pretreatment;
hoisting the titanium cathode roller needing surface treatment to a grinding machine by using a travelling crane, selecting grinding wheels with the mesh number of 120-300 meshes, setting the rotating speed, the cylinder pressure and the transverse moving speed of the grinding wheels on a polishing and grinding disc, respectively starting rotating motors of the grinding wheels and the titanium cathode roller, and performing mechanical polishing and grinding pretreatment on the roller surface of the titanium cathode roller.
B, chemically and mechanically polishing the titanium cathode roller;
as shown in fig. 1, the mechanically polished grinding wheels were replaced with polishing disks symmetrically distributed on both sides of the horizontal diameter of the cathode roll. And setting the flow of the polishing solution nozzle and the rotating speed of the cathode roller, and then starting to perform chemical mechanical polishing treatment on the titanium cathode roller.
Specifically, the method comprises the following steps: the polishing discs are symmetrically distributed on two sides of the titanium cathode roller, the polishing discs are in direct contact with the titanium cathode roller in the polishing process, and polishing liquid is conveyed to a nozzle position right above the highest point of the titanium cathode roller and above the contact point of the titanium cathode roller and the polishing discs through a conveying pump.
In the whole process, the polishing solution passing through the polishing disc finally collects in the low tank along the roll surface of the titanium cathode roll, the roll surface at the lower part of the titanium cathode roll is immersed in the polishing solution in the low tank, and the immersion height of the titanium cathode roll in the low tank is 1/6 larger than the diameter of the cathode roll.
In the process, the rotating linear speeds of the titanium cathode roller and the polishing disk are different, and the rotating linear speed of the polishing disk is greater than that of the titanium cathode roller.
In the above steps, the polishing solution is composed of a nano abrasive material, an etching agent, a pH regulator, a surfactant and deionized water.
Wherein the nano grinding material is spherical, and the diameter of the nano grinding material is between 20 and 200 nm; the nano abrasive material is colloidal aluminum trioxide (Al)2O3) Colloidal silicon dioxide (SiO)2) Silicon nitride (Si)3N4) Or cerium oxide (CeO)2) One or more of the above; the mass concentration of the nano abrasive material in the polishing solution is between 1 and 4 weight percent.
The etching agent is composed of two or more of lactic acid, chloroacetic acid, hydrogen peroxide, hydrofluoric acid, oxalic acid, citric acid and EDTA-2Na with the mass concentration of 5 wt%.
The pH regulator consists of inorganic-organic composite components with the mass concentration of 1-1.5 wt%; wherein the inorganic regulator is at least two or more of acetic acid, hydrochloric acid, nitric acid, ammonia water and sodium hydroxide; the organic regulator is composed of two or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, salicylic acid and ascorbic acid.
The surfactant is composed of one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, cetyl trimethyl ammonium bromide, polyvinylpyrrolidone and polyvinyl alcohol with the mass concentration of 0.1 wt%.
In the preparation: firstly, adding a proper amount of deionized water into a polishing solution preparation tank, adding a surfactant, an etching agent, a pH stabilizer and a nano grinding material under mechanical stirring, continuously stirring to fully and uniformly mix all components in the polishing solution, then conveying the polishing solution to a polishing solution storage tank with a stirring function, and continuously stirring for later use.
The pH value of the finally prepared polishing solution is between 3 and 5.
In the polishing operation:
temperature of the polishing solution: 25 ℃; polishing solution nozzle pressure: 0.2-0.5 MPa; polishing time: 60-90 min; rotating speed of the titanium cathode roller: 2 m/min.
Step C, carrying out anodic oxidation treatment on the polished titanium cathode roller;
1. removing impurities remained on the roll surface of the titanium cathode roll after the chemical mechanical polishing treatment is finished by using deionized water;
2. drying the residual moisture on the surface of the titanium cathode roller by compressed air;
3. taking a metal titanium plate as a cathode, a polished titanium cathode roller as an anode and deionized water-glycol solution containing ammonium fluoride or ammonium chloride as electrolyte, carrying out anodic oxidation treatment for 3-5 minutes under the voltage of 35-50V, and generating a thin and compact protective layer on the roller surface of the titanium cathode roller.
Example 1
Hoisting the titanium cathode roller with the oxidized surface to a grinding machine by using a travelling crane, and sequentially carrying out the following treatment:
a, mechanically polishing and grinding a titanium cathode roller for pretreatment;
grinding wheel granularity: 120 meshes;
the rotating speed of the grinding wheel is as follows: 20 m/min;
the transverse moving speed of the grinding wheel is as follows: 50 mm/min
Cathode roll rotation speed: 2 m/min;
polishing and grinding time: 30 min;
b, chemically and mechanically polishing the titanium cathode roller;
the polishing disc is made of: a short-staple Micro Met rayon;
the polishing solution consists of a grinding material, an etching agent, a pH regulator and a surfactant, and comprises the following specific components:
colloidal SiO2: diameter 50 nm, concentration 4 wt%; colloidal Al2O3: diameter of 200 nm, concentration of 1 wt%;
H2O2concentration: 5 wt%; concentration of lactic acid: 5 wt%;
acetic acid concentration: 1 wt%; the concentration of ammonia water is 1 wt%;
concentration of tetramethylammonium hydroxide: 1.5 wt%; ascorbic acid concentration: 1.5 wt%;
polyvinylpyrrolidone concentration: 0.1 wt%;
temperature of the polishing solution: 25 ℃;
polishing solution nozzle pressure: 0.4 MPa;
the rotating speed of the polishing disc is as follows: 25 m/min;
chemical mechanical polishing time: 60 min;
rotating speed of the titanium cathode roller: 2 m/min;
step C, carrying out anodic oxidation treatment on the polished titanium cathode roller;
the electrolyte comprises the following specific components:
NH4f concentration: 0.3 wt%;
deionized water content: 10 vol%;
content of ethylene glycol: 90 vol%;
temperature of the electrolyte: 25 ℃;
voltage: 50V;
treatment time: 5 min;
as a result: roll surface roughness S of titanium cathode roll treated by this examplea=0.207 μm，Sq=0.281 μm， ER=8.1%, and the continuous stable production time is 60 days.
Example 2
This example differs from example 1 in that the compounding ratio of the abrasive material in step B was changed.
B, chemically and mechanically polishing the titanium cathode roller;
the polishing disc is made of: a short-staple Micro Met rayon;
the polishing solution consists of a grinding material, an etching agent, a pH regulator and a surfactant, and comprises the following specific components:
colloidal SiO2: diameter 20 nm, concentration 3 wt%; colloidal Al2O3: diameter of 200 nm, concentration of 2 wt%;
H2O2concentration: 5 wt%; the concentration of chloroacetic acid: 10 wt%;
hydrochloric acid concentration: 1 wt%; the concentration of ammonia water is 1 wt%;
concentration of tetramethylammonium hydroxide: 1.5 wt%; ascorbic acid concentration: 1.5 wt%;
polyvinylpyrrolidone concentration: 0.1 wt%;
temperature of polishing liquid: 25 ℃;
polishing solution nozzle pressure: 0.2 MPa;
the rotating speed of the polishing disc is as follows: 25 m/min;
chemical mechanical polishing time: 90 min;
titanium cathode roller rotation speed: 2 m/min;
as a result: roll surface roughness S of titanium cathode roll treated by this examplea=0.243 μm，Sq=0.324 μm，ER=8.5%, and the continuous stable production time is 55 days.
Example 3
This example differs from example 1 in that the size of one of the abrasive materials in step B is changed.
B, chemically and mechanically polishing the titanium cathode roller;
the polishing disc is made of: a short-staple Micro Met rayon;
the polishing solution consists of a grinding material, an etching agent, a pH regulator and a surfactant, and comprises the following specific components:
colloidal SiO2: diameter 100 nm, concentration 4 wt%; colloidal Al2O3Diameter of 200 nm, concentration of 1 wt%;
H2O2concentration: 5 wt%; concentration of hydrofluoric acid: 5 wt%;
concentration of nitric acid: 1 wt%; the concentration of ammonia water is 1 wt%;
concentration of tetramethylammonium hydroxide: 1.5 wt%; ascorbic acid concentration: 1.5 wt%;
polyvinylpyrrolidone concentration: 0.1 wt%;
temperature of the polishing solution: 25 ℃;
polishing solution nozzle pressure: 0.4 MPa;
the rotating speed of the polishing disc is as follows: 25 m/min;
chemical mechanical polishing time: 60 min;
rotating speed of the titanium cathode roller: 2 m/min;
as a result: roll surface roughness S of titanium cathode roll treated by this examplea=0.282 μm，Sq=0.356 μm，ER=9.2%, and the continuous stable production time was 54 days.
Example 4
The difference between this example and example 1 is that the ratio of the grinding material in step B is changed, and colloidal Al is added2O3Replaced by nano CeO with the same size2And (3) particles.
B, chemically and mechanically polishing the titanium cathode roller;
the polishing disc is made of: a short-staple Micro Met rayon;
the polishing solution consists of a grinding material, an etching agent, a pH regulator and a surfactant, and comprises the following specific components:
colloidal SiO2: diameter 50 nm, concentration 4 wt%; nano CeO2: diameter of 200 nm, concentration of 1 wt%;
H2O2concentration: 5 wt%; concentration of oxalic acid: 5 wt%;
glacial acetic acid concentration: 1 wt%; the concentration of sodium hydroxide is 1 wt%;
concentration of tetramethylammonium hydroxide: 1.5 wt%; ascorbic acid concentration: 1.5 wt%;
cetyl trimethyl ammonium bromide concentration: 0.1 wt%;
temperature of the polishing solution: 25 ℃;
polishing solution nozzle pressure: 0.4 MPa;
the rotating speed of the polishing disc is as follows: 25 m/min;
chemical mechanical polishing time: 60 min;
rotating speed of the titanium cathode roller: 2 m/min;
as a result: roll surface roughness S of titanium cathode roll treated by this examplea=0.225 μm，Sq=0.303 μm，ER=8.7%, and the continuous stable production time is 58 days.
Example 5
This example is different from example 1 in that one of the abrasive materials in step B and the composition of the etchant in the polishing slurry are changed, and colloidal Al is added2O3Replacement by colloidal Si3N4Lactic acid was replaced with EDTA-2Na at the same concentration.
B, chemically and mechanically polishing the titanium cathode roller;
the polishing disc is made of: a short-staple Micro Met rayon;
the polishing solution consists of a grinding material, an etching agent, a pH regulator and a surfactant, and comprises the following specific components:
colloidal SiO2: diameter 50 nm, concentration 4 wt%; colloidal Si3N4: diameter of 200 nm, concentration of 1 wt%;
H2O2concentration: 5 wt%; EDTA-2Na concentration: 10 wt%;
glacial acetic acid concentration: 1 wt%; the concentration of ammonia water is 1 wt%;
concentration of tetramethylammonium hydroxide: 1.5 wt%; ascorbic acid concentration: 1.5 wt%;
concentration of sodium lauryl sulfate: 0.1wt%
Temperature of the polishing solution: 25 ℃;
polishing solution nozzle pressure: 0.4 MPa;
the rotating speed of the polishing disc is as follows: 25 m/min;
chemical mechanical polishing time: 60 min;
titanium cathode roller rotation speed: 2 m/min;
as a result: roll surface roughness S of titanium cathode roll treated by this examplea=0.314 μm，Sq=0.401 μm， ER=9.5%, and the continuous stable production time is 50 days.
Example 6
This example differs from example 1 in that the organic components of the pH adjuster in the step B slurry were changed: tetramethylammonium hydroxide 1.5wt% -ascorbic acid 1.5wt% was replaced with tetraethylammonium hydroxide-salicylic acid at the same concentration.
B, chemically and mechanically polishing the titanium cathode roller;
the polishing disc is made of: a short-staple Micro Met rayon;
the polishing solution consists of a grinding material, an etching agent, a pH regulator and a surfactant, and comprises the following specific components:
colloidal SiO2: diameter 50 nm, concentration 4 wt%; colloidal Al2O3: diameter of 200 nm, concentration of 1 wt%;
H2O2concentration: 5 wt%; the concentration of citric acid: 5 wt%;
glacial acetic acid concentration: 1 wt%; the concentration of ammonia water is 1 wt%;
tetraethylammonium hydroxide concentration: 1.5 wt%; the concentration of salicylic acid is: 1.5 wt%;
polyvinylpyrrolidone concentration: 0.1 wt%;
temperature of the polishing solution: 25 ℃;
polishing solution nozzle pressure: 0.5 MPa;
the rotating speed of the polishing disc is as follows: 25 m/min;
chemical mechanical polishing time: 60 min;
rotating speed of the titanium cathode roller: 2 m/min;
as a result: roll surface roughness S of titanium cathode roll treated by this examplea=0.271 μm，Sq=0.358 μm，ER=9.1%, and the production time was 54 days.
Example 7
This example differs from example 1 in that the surfactant composition in the polishing slurry of step B was changed and polyvinylpyrrolidone (PVP) was replaced with sodium dodecylbenzene sulfonate (SDBS) at the same concentration.
B, chemically and mechanically polishing the titanium cathode roller;
the polishing disc is made of: a short-staple Micro Met rayon;
the polishing solution consists of a grinding material, an etching agent, a pH regulator and a surfactant, and comprises the following specific components:
colloidal SiO2: diameter 50 nm, concentration 5 wt%; colloidal Al2O3: diameter of 200 nm, concentration of 1 wt%;
H2O2concentration: 5 wt%; concentration of lactic acid: 5 wt%;
glacial acetic acid concentration: 1 wt%; the concentration of ammonia water is 1 wt%;
concentration of tetramethylammonium hydroxide: 1.5 wt%; ascorbic acid concentration: 1.5 wt%;
sodium dodecylbenzenesulfonate concentration: 0.1 wt%;
temperature of the polishing solution: 25 ℃;
polishing solution nozzle pressure: 0.4 MPa;
the rotating speed of the polishing disc is as follows: 25 m/min;
chemical mechanical polishing time: 60 min;
rotating speed of the titanium cathode roller: 2 m/min;
as a result: roll surface roughness S of titanium cathode roll treated by this examplea=0.257 μm，Sq=0.339 μm，ER=8.9%, and the continuous stable production time is 56 days.
Example 8
This example is different from example 1 in that the chemical mechanical polishing time in step B was changed.
B, chemically and mechanically polishing the titanium cathode roller;
the polishing disc is made of: a short-staple Micro Met rayon;
the polishing solution consists of a grinding material, an etching agent, a pH regulator and a surfactant, and comprises the following specific components:
colloidal SiO2: diameter 50 nm, concentration 5 wt%; colloidal Al2O3: diameter of 200 nm, concentration of 1 wt%;
H2O2concentration: 5 wt%; concentration of lactic acid: 5 wt%;
glacial acetic acid concentration: 1 wt%; the concentration of ammonia water is 1 wt%;
concentration of tetramethylammonium hydroxide: 1.5 wt%; ascorbic acid concentration: 1.5 wt%;
concentration of polyethylene glycol: 0.1 wt%;
temperature of the polishing solution: 25 ℃;
polishing solution nozzle pressure: 0.4 MPa;
the rotating speed of the polishing disc is as follows: 25 m/min;
chemical mechanical polishing time: 60 min;
rotating speed of the titanium cathode roller: 2 m/min;
as a result: roll surface roughness S of titanium cathode roll treated by this examplea=0.406 μm，Sq=0.482 μm，ER=10.3%, and the production time can be continuously stabilized to 50 days.
Comparative example 1
The titanium cathode roller is mechanically polished by using a conventional grinding wheel, and the specific polishing process is as follows:
(1) rough grinding
Grinding wheel granularity: 120 meshes;
the rotating speed of the grinding wheel is as follows: 20 m/min;
the transverse moving speed of the grinding wheel is as follows: 50 mm/min;
cathode roll rotation speed: 2 m/min;
polishing and grinding time: 30 min;
(2) finish grinding
Grinding wheel granularity: 300 meshes;
the rotating speed of the grinding wheel is as follows: 20 m/min;
the transverse moving speed of the grinding wheel is as follows: 25 mm/min;
cathode roll rotation speed: 2 m/min;
polishing and grinding time: 120 min;
(3) washing and drying
And (4) cleaning the roll surface of the titanium cathode roll by using deionized water after the mechanical polishing treatment is finished, and then removing residual moisture on the roll surface by blowing and showering compressed air.
As a result: roll surface roughness S of titanium cathode roll treated by this examplea=0.324 μm，Sq=0.541 μm, ER=13.5%, and the continuous stable production time is 45 days.
Comparative example 2
The titanium cathode roller is mechanically polished by using a conventional grinding wheel, and the specific polishing process is as follows:
(1) coarse grinding
Grinding wheel granularity: 120 meshes;
the rotating speed of the grinding wheel is as follows: 20 m/min;
the transverse moving speed of the grinding wheel is as follows: 25 mm/min;
cathode roll rotation speed: 2 m/min;
polishing and grinding time: 60 min;
(2) finish grinding
Grinding wheel granularity: 300 meshes;
the rotating speed of the grinding wheel is as follows: 20 m/min;
the transverse moving speed of the grinding wheel is as follows: 50 mm/min;
cathode roll rotation speed: 2 m/min;
polishing and grinding time: 90 min;
(3) washing and drying
And (4) cleaning the roll surface of the titanium cathode roll by using deionized water after the mechanical polishing treatment is finished, and then removing residual moisture on the roll surface by blowing and showering compressed air.
As a result: roll surface roughness S of titanium cathode roll treated by this examplea=0.283 μm，Sq=0.484 μm, ER=12.7%, and the production time was 40 days.
From the observations made in examples 1 to 8 and comparative examples 1 to 2, it is evident that:
1. introduction of ERThe rationality of (2).
As can be seen by comparing example 8 with the comparative example, even in the case where the chemical mechanical polishing time was only 30min, S wasa=0.406 μm, the data is significantly worse than the comparative example; s. theq=0.482 μm, data comparable to comparative example 2; but ER=10.3%, clearly lower than 2 comparative examples, which brings about the direct difference effect in production: the titanium cathode roller in example 8 can be continuously and stably produced for 50 days; while the titanium cathode rolls of comparative example 1 and comparative example 2, respectively, could be continuously stabilized for a production time of 50 days.
As can be seen, the roughness uniformity ERThe method is feasible as another quantitative index of the polishing and grinding effect of the titanium cathode roller, and no matter production data or production period, the method shows that once the roughness uniformity of the roller surface is improved and the control of reducing the roughness of the roller surface is carried out simultaneously, the polishing and grinding effect of the titanium cathode roller can be achievedUnexpected technical effect.
2. The method of the invention shows a significant reduction in Sa and Sq over conventional polishing times.
Taking example 1 and comparative example 1 as examples, the Sa is reduced by 16.4%, the Sq is reduced by 18%, and the E is reducedRThe reduction is 40%. The lower surface roughness and higher roughness uniformity are not only advantageous for reducing the consumption of leveling agent, but also can suppress the point discharge and improve the uniformity of the copper foil.
3. The continuous stable production time is obviously prolonged.
Taking example 1 and comparative example 1 as examples, the continuous stable production time is prolonged by 1/3, and the production utilization rate of the titanium cathode roller is obviously improved.
For visual verification, the smooth surface of the first roll of raw electrolytic foil after surface treatment is subjected to microscopic image analysis. Because the smooth surface appearance of the electrolytic green foil and the roller surface state of the titanium cathode roller are in a mirror image relationship, the effect of surface treatment can be compared by analyzing the smooth surface of the first roll of electrolytic green foil after surface treatment.
FIG. 2 (a) is a micrograph of the shiny side of an electrolytically-formed foil after treatment in accordance with the method of the invention;
FIG. 2 (b) shows a micrograph of the shiny side of an electrodeposited foil after a conventional mechanical polishing treatment.
From this figure it is clearly observed that the surface roughness and uniformity of the titanium cathode roller after the treatment of the invention is significantly better than that of the conventional mechanical polishing treatment.
Claims (10)
1. A surface treatment method of a titanium cathode roller is characterized in that: the method comprises the following steps:
a, mechanically polishing and grinding a titanium cathode roller for pretreatment;
hoisting the titanium cathode roller needing surface treatment to a grinding machine by using a travelling crane, setting the rotating speed, cylinder pressure and transverse moving speed of a grinding wheel on a polishing disc, respectively starting rotating motors of the grinding wheel and the titanium cathode roller, and performing mechanical polishing pretreatment on the roller surface of the titanium cathode roller;
b, chemically and mechanically polishing the titanium cathode roller;
replacing the grinding wheels subjected to mechanical polishing with polishing disks symmetrically distributed on two sides of the horizontal diameter of the cathode roller, and setting the flow rate of a polishing solution nozzle and the rotating speed of the cathode roller to perform chemical mechanical polishing treatment on the titanium cathode roller;
step C, carrying out anodic oxidation treatment on the polished titanium cathode roller;
1. removing impurities remained on the roll surface of the titanium cathode roll after the chemical mechanical polishing treatment is finished by using deionized water;
2. drying the residual moisture on the surface of the titanium cathode roller by compressed air;
3. taking a metal titanium plate as a cathode, a polished titanium cathode roller as an anode and deionized water-glycol solution containing ammonium fluoride as electrolyte, and carrying out anodic oxidation treatment under a certain voltage to generate a thin and compact protective layer on the roller surface of the titanium cathode roller.
2. The surface treatment method of a titanium cathode roller according to claim 1, characterized in that: the polishing solution in the step B consists of a nano grinding material, an etching agent, a pH regulator, a surfactant and deionized water; the preparation process comprises the following steps:
adding a proper amount of deionized water into a polishing solution preparation tank, adding a surfactant, an etching agent, a pH stabilizer and a nano grinding material under mechanical stirring, continuously stirring to fully and uniformly mix all components in the polishing solution, then conveying the polishing solution to a polishing solution storage tank with a stirring function, and continuously stirring for later use.
3. The surface treatment method of a titanium cathode roller according to claim 2, characterized in that: electrolyte solutes used in the anodic oxidation treatment in the step C-3 include but are not limited to ammonium fluoride and ammonium chloride, a solvent is deionized water-ethylene glycol, the voltage is between 35V and 50V, and the treatment time is between 3 minutes and 5 minutes.
4. The surface treatment method of a titanium cathode roll according to claim 2 or 3, characterized in that: b, polishing the titanium cathode roller by using a polishing disc in the chemical mechanical polishing operation, wherein the polishing disc is symmetrically distributed on two sides of the titanium cathode roller, the polishing disc is directly contacted with the titanium cathode roller in the polishing process, and polishing liquid is conveyed to a nozzle right above the highest point of the titanium cathode roller and above the contact point of the titanium cathode roller and the polishing disc through a conveying pump;
in the whole process, the polishing solution passing through the polishing disc finally collects into a low tank along the roll surface of the titanium cathode roll, the roll surface at the lower part of the titanium cathode roll is immersed in the polishing solution of the low tank, and the immersion height of the titanium cathode roll in the low tank is 1/6 which is larger than the diameter of the cathode roll;
in the process, the rotating linear speeds of the titanium cathode roller and the polishing disk are different, and the rotating linear speed of the polishing disk is greater than that of the titanium cathode roller.
5. The surface treatment method of a titanium cathode roller according to claim 4, characterized in that: the mesh number of the grinding wheel mechanically polished in the step A is 120-300 meshes.
6. The surface treatment method of a titanium cathode roller according to claim 2, characterized in that: the nano grinding material in the polishing solution is spherical, and the diameter of the nano grinding material is between 20 and 200 nm; the nano abrasive material is colloidal aluminum trioxide (Al)2O3) Colloidal silicon dioxide (SiO)2) Silicon nitride (Si)3N4) Or cerium oxide (CeO)2) One or more of the above; the mass concentration of the nano abrasive material in the polishing solution is between 1 and 4 weight percent.
7. The surface treatment method of a titanium cathode roller according to claim 2, characterized in that: the etchant in the polishing solution is two or more of lactic acid, chloroacetic acid, hydrogen peroxide, hydrofluoric acid, oxalic acid, citric acid and ethylene diamine tetraacetic acid-2 sodium (EDTA-2 Na); the mass concentration of the etching agent in the polishing solution is between 5 and 10 weight percent.
8. The surface treatment method of a titanium cathode roller according to claim 2, characterized in that: the pH value of the polishing solution is between 3 and 5.
9. The surface treatment method of a titanium cathode roller according to claim 8, characterized in that: the pH regulator in the polishing solution consists of inorganic-organic composite components;
wherein the inorganic pH regulator is at least two or more of acetic acid, hydrochloric acid, nitric acid, ammonia water and sodium hydroxide;
the organic pH regulator is two or more of tetramethylammonium hydroxide, tetraethylammonium hydroxide, salicylic acid and ascorbic acid;
the mass concentration of the pH regulator in the polishing solution is between 1 and 1.5 weight percent.
10. The surface treatment method of a titanium cathode roller according to claim 2, characterized in that: the surfactant in the polishing solution is one or more of sodium dodecyl benzene sulfonate, sodium dodecyl sulfate, hexadecyl trimethyl ammonium bromide, polyvinylpyrrolidone and polyethylene glycol; the mass concentration of the surfactant in the polishing solution is between 0.01 and 0.1 weight percent.
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| CN115287726A (en) * | 2022-08-25 | 2022-11-04 | 广东腐蚀科学与技术创新研究院 | Preparation device and method of titanium roller oxide film, copper foil and preparation method of copper foil |
| CN115369455A (en) * | 2022-08-25 | 2022-11-22 | 广东腐蚀科学与技术创新研究院 | Copper foil and production equipment and production method thereof |
| CN115449302A (en) * | 2022-09-20 | 2022-12-09 | 江西鑫铂瑞科技有限公司 | Use method of novel polishing solution for electrolytic copper foil cathode titanium roller |
| CN116240479A (en) * | 2023-02-14 | 2023-06-09 | 九江德福科技股份有限公司 | Treatment method for surface reconstruction of titanium roller for electrolytic copper foil |
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| CN113478358A (en) * | 2021-06-25 | 2021-10-08 | 铜陵市华创新材料有限公司 | Cathode roll polishing process for reducing defects of 4.5 mu m copper foil |
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| CN115287726A (en) * | 2022-08-25 | 2022-11-04 | 广东腐蚀科学与技术创新研究院 | Preparation device and method of titanium roller oxide film, copper foil and preparation method of copper foil |
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