CN112899739A - Corrosion-resistant zinc-nickel electroplating solution and preparation method thereof - Google Patents
Corrosion-resistant zinc-nickel electroplating solution and preparation method thereof Download PDFInfo
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- 238000009713 electroplating Methods 0.000 title claims abstract description 91
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 title claims abstract description 76
- 230000007797 corrosion Effects 0.000 title claims abstract description 69
- 238000005260 corrosion Methods 0.000 title claims abstract description 69
- 238000002360 preparation method Methods 0.000 title claims abstract description 58
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 140
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 109
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 109
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 70
- 239000004005 microsphere Substances 0.000 claims abstract description 49
- 239000003381 stabilizer Substances 0.000 claims abstract description 32
- 239000000243 solution Substances 0.000 claims description 156
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 91
- 238000003756 stirring Methods 0.000 claims description 72
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 62
- 239000001768 carboxy methyl cellulose Substances 0.000 claims description 59
- 229920001027 sodium carboxymethylcellulose Polymers 0.000 claims description 59
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 57
- 229920001661 Chitosan Polymers 0.000 claims description 55
- DPXJVFZANSGRMM-UHFFFAOYSA-N acetic acid;2,3,4,5,6-pentahydroxyhexanal;sodium Chemical compound [Na].CC(O)=O.OCC(O)C(O)C(O)C(O)C=O DPXJVFZANSGRMM-UHFFFAOYSA-N 0.000 claims description 55
- 235000019812 sodium carboxymethyl cellulose Nutrition 0.000 claims description 55
- 239000011550 stock solution Substances 0.000 claims description 54
- 239000008367 deionised water Substances 0.000 claims description 49
- 229910021641 deionized water Inorganic materials 0.000 claims description 49
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 44
- 229960000583 acetic acid Drugs 0.000 claims description 39
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 36
- 239000002131 composite material Substances 0.000 claims description 26
- 239000012362 glacial acetic acid Substances 0.000 claims description 26
- 229910052725 zinc Inorganic materials 0.000 claims description 26
- 239000011701 zinc Substances 0.000 claims description 26
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 25
- 239000008139 complexing agent Substances 0.000 claims description 24
- 239000011787 zinc oxide Substances 0.000 claims description 22
- 238000007873 sieving Methods 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 claims description 16
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- 239000004202 carbamide Substances 0.000 claims description 14
- 239000002270 dispersing agent Substances 0.000 claims description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 239000007864 aqueous solution Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 229920002873 Polyethylenimine Polymers 0.000 claims description 10
- 238000000227 grinding Methods 0.000 claims description 10
- 238000009849 vacuum degassing Methods 0.000 claims description 10
- 150000001875 compounds Chemical class 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 9
- 150000002815 nickel Chemical class 0.000 claims description 9
- 239000000080 wetting agent Substances 0.000 claims description 8
- LJCNRYVRMXRIQR-OLXYHTOASA-L potassium sodium L-tartrate Chemical compound [Na+].[K+].[O-]C(=O)[C@H](O)[C@@H](O)C([O-])=O LJCNRYVRMXRIQR-OLXYHTOASA-L 0.000 claims description 7
- 229940074439 potassium sodium tartrate Drugs 0.000 claims description 7
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 7
- 235000011006 sodium potassium tartrate Nutrition 0.000 claims description 7
- 239000001509 sodium citrate Substances 0.000 claims description 6
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 6
- 235000011083 sodium citrates Nutrition 0.000 claims description 6
- 239000003109 Disodium ethylene diamine tetraacetate Substances 0.000 claims description 5
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- 150000001412 amines Chemical class 0.000 claims description 5
- 235000019301 disodium ethylene diamine tetraacetate Nutrition 0.000 claims description 5
- CJXMVKYNVIGQBS-OWOJBTEDSA-N 4-hydroxycinnamaldehyde Chemical compound OC1=CC=C(\C=C\C=O)C=C1 CJXMVKYNVIGQBS-OWOJBTEDSA-N 0.000 claims description 4
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 4
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 4
- 229940078494 nickel acetate Drugs 0.000 claims description 4
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 4
- CJXMVKYNVIGQBS-UHFFFAOYSA-N p-hydroxycinnamaldehyde Natural products OC1=CC=C(C=CC=O)C=C1 CJXMVKYNVIGQBS-UHFFFAOYSA-N 0.000 claims description 4
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 4
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 4
- 235000012141 vanillin Nutrition 0.000 claims description 4
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 claims description 2
- SMQUZDBALVYZAC-UHFFFAOYSA-N salicylaldehyde Chemical compound OC1=CC=CC=C1C=O SMQUZDBALVYZAC-UHFFFAOYSA-N 0.000 claims description 2
- 229960001790 sodium citrate Drugs 0.000 claims description 2
- 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 claims 1
- 238000007747 plating Methods 0.000 abstract description 45
- 229910001453 nickel ion Inorganic materials 0.000 abstract description 10
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 abstract description 9
- 230000000694 effects Effects 0.000 abstract description 3
- 230000001502 supplementing effect Effects 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 44
- 229910052742 iron Inorganic materials 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 20
- 238000000576 coating method Methods 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 16
- 238000012360 testing method Methods 0.000 description 10
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 8
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 5
- PQLVXDKIJBQVDF-UHFFFAOYSA-N acetic acid;hydrate Chemical compound O.CC(O)=O PQLVXDKIJBQVDF-UHFFFAOYSA-N 0.000 description 5
- 239000003795 chemical substances by application Substances 0.000 description 5
- 238000009472 formulation Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 3
- 150000003839 salts Chemical class 0.000 description 3
- 239000007921 spray Substances 0.000 description 3
- UGZADUVQMDAIAO-UHFFFAOYSA-L zinc hydroxide Chemical compound [OH-].[OH-].[Zn+2] UGZADUVQMDAIAO-UHFFFAOYSA-L 0.000 description 3
- 229940007718 zinc hydroxide Drugs 0.000 description 3
- 229910021511 zinc hydroxide Inorganic materials 0.000 description 3
- BDOYKFSQFYNPKF-UHFFFAOYSA-N 2-[2-[bis(carboxymethyl)amino]ethyl-(carboxymethyl)amino]acetic acid;sodium Chemical compound [Na].[Na].OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O BDOYKFSQFYNPKF-UHFFFAOYSA-N 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000005282 brightening Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003094 microcapsule Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 230000007935 neutral effect Effects 0.000 description 2
- 241001163841 Albugo ipomoeae-panduratae Species 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 229960001484 edetic acid Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000003906 humectant Substances 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- YQUVCSBJEUQKSH-UHFFFAOYSA-N protochatechuic acid Natural products OC(=O)C1=CC=C(O)C(O)=C1 YQUVCSBJEUQKSH-UHFFFAOYSA-N 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000013589 supplement Substances 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- WKOLLVMJNQIZCI-UHFFFAOYSA-N vanillic acid Chemical compound COC1=CC(C(O)=O)=CC=C1O WKOLLVMJNQIZCI-UHFFFAOYSA-N 0.000 description 1
- TUUBOHWZSQXCSW-UHFFFAOYSA-N vanillic acid Natural products COC1=CC(O)=CC(C(O)=O)=C1 TUUBOHWZSQXCSW-UHFFFAOYSA-N 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/565—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of zinc
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention relates to the technical field of electroplating, in particular to a corrosion-resistant zinc-nickel electroplating solution and a preparation method thereof. The plating solution disclosed by the invention realizes the slow release effect of nickel sulfate in the plating solution by preparing the microencapsulated nickel sulfate microspheres as the nickel stabilizer, and the nickel content is always kept between 12 and 14 percent by supplementing the content of nickel ions in the plating solution, so that the electroplated zinc-nickel plating layer has better stability among batches, more compact plating layer and high corrosion resistance.
Description
Technical Field
The invention relates to the technical field of electroplating, in particular to a corrosion-resistant zinc-nickel electroplating solution and a preparation method thereof.
Background
Iron is widely applied to the fields of capital construction, aerospace, aviation and the like by virtue of the advantages of low cost, high yield and the like, but iron is also a material with the most serious corrosion all over the world. In general, in order to achieve corrosion resistance of iron products, electroplating methods such as cadmium plating, zinc plating, nickel plating, titanium plating, and the like are generally used in industry, and since the corrosion potential of these metals is relatively low, the corrosion rate is also low, and the application in industry is very wide, among which zinc plating is the most common.
Because the corrosion resistance of nickel element is better than that of zinc, and the flexibility of zinc makes the nickel element and the alloy combined highly, the zinc-nickel-plated layer becomes a corrosion-resistant layer with excellent electroplated iron. In the zinc-nickel electroplating process, a zinc solution is an amphoteric compound and can exist in an alkaline solution, and a nickel element cannot exist in an alkaline environment because the nickel element is an acidic metal, so the nickel element must be combined with a complexing agent firstly to be matched with the zinc solution for electroplating. In the electroplating process, when the current density is low, the zinc-nickel electroplated layer is codeposited, firstly, the nickel layer is deposited, and the zinc layer is deposited along with the gradual increase of the current density. Research shows that the nickel content in the zinc-nickel plating layer is between 12 and 14 percent, and the corrosion resistance of the coating is optimal. Because nickel element can prevent zinc hydroxide from being converted into zinc oxide during electroplating, the improvement of the nickel element is beneficial to improving the corrosion resistance of the zinc-nickel coating, the corrosion resistance is rapidly reduced when the content of the nickel element in the zinc-nickel coating is too low, but when the content of the nickel element is more than 14%, a large amount of zinc oxide is generated on a product on the zinc-nickel coating besides the zinc hydroxide, and the zinc oxide has a loose and non-dense structure, so the corrosion resistance is also reduced after the zinc oxide is generated. Therefore, the content of nickel element in the electroplating solution must be stabilized at a certain concentration level, i.e. not too high nor too low, otherwise, the corrosion resistance of the zinc-nickel plating layer is reduced sharply, the plating layer is loosened and peeled seriously, and the sample defect rate is increased.
Chinese patent CN 104805480A discloses an alkaline zinc-nickel electroplating solution, a preparation method and an electroplating method, wherein the alkaline zinc-nickel electroplating solution mainly comprises zinc ions, nickel ions, sodium hydroxide, an auxiliary brightening agent, a nickel complexing agent and deionized water, the prepared zinc-nickel electroplating solution has wide working current density range, can be applied to rack plating or barrel plating, has high electroplating efficiency and strong corrosion resistance, has no red rust for more than 1500 hours in a neutral salt spray test, has no white rust for more than 500 hours, and has long service life of an electroplated workpiece. However, since nickel ions in the formula cannot exist in a sodium hydroxide alkaline environment, the nickel ions must be complexed by a nickel complexing agent, and the nickel ions are continuously released in the solution through a complexing product, at this time, the content of the nickel ions in the electroplating solution cannot be kept relatively stable, so that the solution replenishing operation between batches is frequent, and the operation complexity is increased; in addition, the stability of the plated workpiece varies greatly from batch to batch, and the quality varies from batch to batch.
Disclosure of Invention
In order to overcome the technical problems in the prior art, the invention provides a corrosion-resistant zinc-nickel electroplating solution and a preparation method thereof.
The invention provides a corrosion-resistant zinc-nickel electroplating solution, which comprises the following components in parts by weight: 0.5-2 parts of zinc oxide, 0.2-1.5 parts of nickel salt, 5-30 parts of sodium hydroxide, 0.05-0.2 part of composite brightener, 2-8 parts of complexing agent, 0.5-5 parts of nickel stabilizer, 0.01-0.2 part of dispersing agent and 50-200 parts of deionized water; wherein the nickel stabilizer is a microencapsulated nickel sulfate microsphere.
Further, the electroplating solution comprises the following components in parts by weight: 0.6-1.5 parts of zinc oxide, 0.8-1.2 parts of nickel salt, 10-25 parts of sodium hydroxide, 0.1-0.15 part of composite brightener, 4-6 parts of complexing agent, 0.8-3 parts of nickel stabilizer, 0.05-0.1 part of dispersant and 100-150 parts of deionized water; wherein the nickel stabilizer is a microencapsulated nickel sulfate microsphere.
Preferably, the electroplating solution comprises the following components in parts by weight: 0.8 part of zinc oxide, 1 part of nickel salt, 20 parts of sodium hydroxide, 0.12 part of composite brightener, 5 parts of complexing agent, 1.5 parts of nickel stabilizer, 0.08 part of dispersing agent and 120 parts of deionized water; wherein the nickel stabilizer is a microencapsulated nickel sulfate microsphere.
Further, the nickel salt is one or more of nickel sulfate, nickel chloride, nickel acetate and nickel sulfamate.
Further, the microencapsulated nickel sulfate microspheres comprise the following components in parts by weight: 1-2 parts of chitosan, 2-5 parts of sodium carboxymethylcellulose, 0.2-2 parts of wetting agent, 0.01-0.1 part of N-N' -methylene bisacrylamide, 0.5-2 parts of anhydrous nickel sulfate, 0.2-0.5 part of glacial acetic acid and 100-200 parts of deionized water; the wetting agent is one or a combination of ethylene glycol or glycerol.
Preferably, the microencapsulated nickel sulfate microspheres comprise the following components in parts by weight: 1.2 parts of chitosan, 2.5 parts of sodium carboxymethylcellulose, 1.3 parts of wetting agent, 0.6 part of N-N' methylene bisacrylamide, 1 part of anhydrous nickel sulfate, 0.25 part of glacial acetic acid and 140 parts of deionized water; the humectant is glycerol.
Further, the microencapsulated nickel sulfate microspheres comprise the following preparation steps:
s1, preparation of a glacial acetic acid solution: adding water into glacial acetic acid in a formula amount to prepare an acetic acid aqueous solution with the mass fraction of 1-3 wt%;
s2, sieving: respectively grinding chitosan and sodium carboxymethylcellulose according to the formula ratio, and sieving to obtain powder of 50-100 meshes;
s3, preparing a chitosan stock solution: adding a wetting agent in a formula amount into chitosan in a formula amount, dropwise adding an acetic acid solution in S1 for dissolving, and stirring at a rotating speed of 1000-1500 r/min for 10-15 min to obtain a chitosan stock solution;
s4, preparing a sodium carboxymethyl cellulose stock solution: adding deionized water into sodium carboxymethylcellulose according to the formula amount, stirring, heating to 40-60 ℃, stopping heating after the solution is clarified, cooling, and standing for 12-24 hours to obtain sodium carboxymethylcellulose stock solution;
s5, preparation of a nickel sulfate solution: taking anhydrous nickel sulfate with the formula amount, and adding water for mixing to obtain the nickel sulfate;
s6, preparing the micro-encapsulated nickel sulfate microspheres: and (4) taking the chitosan stock solution in the step S3 and the sodium carboxymethyl cellulose stock solution in the step S4, stirring, vacuum degassing, dropwise adding N-N' methylene bisacrylamide in a formula amount, uniformly stirring, dropwise adding the nickel sulfate solution in the step S5, and dispersing and stirring at the rotating speed of 1500-2000 r/min for 15-30 min.
Preferably, the microencapsulated nickel sulfate microspheres comprise the following preparation steps:
s1, preparation of a glacial acetic acid solution: adding water into glacial acetic acid with the formula amount to prepare an acetic acid aqueous solution with the mass fraction of 2 wt%;
s2, sieving: respectively grinding chitosan and sodium carboxymethylcellulose according to the formula ratio, and sieving to obtain 60-mesh powder;
s3, preparing a chitosan stock solution: adding the chitosan with the formula amount into the wetting agent with the formula amount, dropwise adding the acetic acid aqueous solution as described in S1 for dissolving, and stirring at the rotating speed of 1200r/min for 12min to obtain a chitosan stock solution;
s4, preparing a sodium carboxymethyl cellulose stock solution: adding deionized water into sodium carboxymethylcellulose according to the formula amount, stirring, heating to 50 ℃, stopping heating after the solution is clarified, cooling, and standing for 15h to obtain sodium carboxymethylcellulose stock solution;
s5, preparation of a nickel sulfate solution: taking anhydrous nickel sulfate with the formula amount, and adding water for mixing to obtain the nickel sulfate;
s6, preparing the micro-encapsulated nickel sulfate microspheres: and (4) taking the chitosan stock solution in the step S3 and the sodium carboxymethyl cellulose stock solution in the step S4, stirring, vacuum degassing, dropwise adding N-N' methylene bisacrylamide in a formula amount, uniformly stirring, dropwise adding the nickel sulfate solution in the step S5, and dispersing and stirring at the rotating speed of 1800r/min for 25 min.
Further, the composite brightener is composed of two or more of urea, organic amine and organic aldehyde.
Further, the composite brightener is prepared from urea and organic amine according to the weight ratio of 5: 1 to 3 by mass.
Further, the composite brightener is prepared from urea and organic aldehyde according to the weight ratio of 3: 0.5-1 by mass.
Further, the organic amine is ethylenediamine and/or polyethyleneimine.
Preferably, the composite brightener is prepared from urea and polyethyleneimine according to the weight ratio of 5: 1.5 in mass ratio.
Further, the organic aldehyde is one or more of vanillin, 4-hydroxycinnamaldehyde and o-hydroxybenzaldehyde.
Preferably, the composite brightener is prepared from urea and 4-hydroxycinnamaldehyde in a weight ratio of 3: 0.8 in mass ratio.
Further, the complexing agent is one or more of disodium ethylene diamine tetraacetate, potassium sodium tartrate and sodium citrate.
Further, the complexing agent is prepared from potassium sodium tartrate, disodium ethylene diamine tetraacetate and sodium citrate according to the weight ratio of 1: 2: 0.1-0.5 by mass ratio.
Preferably, the complexing agent is prepared from potassium sodium tartrate, disodium ethylene diamine tetraacetate and sodium citrate according to the weight ratio of 1: 2: 0.3 in mass ratio.
Further, the dispersant is sodium lignosulfonate.
The second purpose of the invention is to provide a preparation method of the corrosion-resistant zinc-nickel electroplating solution, which comprises the following steps:
a1, preparation of zinc solution: taking sodium hydroxide with the formula amount, adding water for dissolving, adding zinc oxide with the formula amount, and stirring for dissolving;
a2, preparing a nickel solution: taking the complexing agent with the formula amount, adding water for dissolving, adding the nickel salt with the formula amount, and stirring for dissolving;
a3, preparation of corrosion-resistant zinc-nickel electroplating solution: and B, mixing the zinc solution obtained in the step A1 with the nickel solution obtained in the step A2, adding a compound brightener, a nickel stabilizer and a dispersant in a formula amount, and stirring at 40-60 ℃ to obtain the corrosion-resistant zinc-nickel electroplating solution.
Preferably, the preparation method comprises the following steps:
a1, preparation of zinc solution: taking sodium hydroxide with the formula amount, adding water for dissolving, adding zinc oxide with the formula amount, and stirring for dissolving;
a2, preparing a nickel solution: taking the complexing agent with the formula amount, adding water for dissolving, adding the nickel salt with the formula amount, and stirring for dissolving;
a3, preparation of corrosion-resistant zinc-nickel electroplating solution: and B, mixing the zinc solution obtained in the step A1 with the nickel solution obtained in the step A2, adding a compound brightener, a nickel stabilizer and a dispersant in a formula amount, and stirring at 50 ℃ to obtain the corrosion-resistant zinc-nickel electroplating solution.
Compared with the prior art, the corrosion-resistant zinc-nickel electroplating solution and the preparation method thereof provided by the invention have the following beneficial effects:
(1) according to the invention, the microencapsulated nickel sulfate microspheres are added as a stabilizer of the electroplating solution, and the nickel sulfate is wrapped in the chitosan-sodium carboxymethylcellulose three-dimensional network structure to form the microcapsule microspheres with a core-shell structure, so that the slow release effect of the nickel sulfate in the electroplating solution can be realized, and then the microcapsule microspheres are complexed with a complexing agent in the electroplating solution to continuously and slowly supplement the content of nickel ions in the electroplating solution, so that the content of nickel is always kept between 12% and 14%, and the electroplated coating has good stability and high corrosion resistance among batches.
(2) When the plating solution is dissolved in the electroplating solution, the microencapsulated nickel sulfate microspheres continuously release nickel sulfate, and the chitosan-sodium carboxymethylcellulose three-dimensional network structure of the shell structure is also continuously dissolved in the plating solution, so that the dispersibility of the plating solution is improved, an electroplated zinc coating is more compact, and the corrosion resistance is greatly improved.
Detailed Description
The present invention is further illustrated by the following description of specific embodiments, which are not intended to limit the invention, and various modifications and improvements can be made by those skilled in the art based on the basic idea of the invention, but within the scope of the invention, without departing from the basic idea of the invention. In the present invention, the method for preparing the texture-making agent is not particularly limited, and the method for operating the texture-making agent known to those skilled in the art may be used. The invention has no special brand restriction on the substances in the formulation of the texturing agent. The reagents used are those not indicated by the manufacturer, and are all conventional products commercially available.
Example 1
The corrosion-resistant zinc-nickel electroplating solution of example 1, comprising the following components in parts by weight: 0.5 part of zinc oxide, 0.2 part of nickel chloride, 5 parts of sodium hydroxide, 0.05 part of composite brightener, 2 parts of potassium sodium tartrate, 0.5 part of nickel stabilizer, 0.01 part of sodium lignosulfonate and 50 parts of deionized water; the composite brightener is prepared from urea and ethylenediamine by the following steps of: 1, wherein the nickel stabilizer is a microencapsulated nickel sulfate microsphere. The microencapsulated nickel sulfate microspheres comprise the following components in parts by weight: 1 part of chitosan, 2 parts of sodium carboxymethylcellulose, 0.2 part of ethylene glycol, 0.01 part of N-N' methylene bisacrylamide, 0.5 part of anhydrous nickel sulfate, 0.2 part of glacial acetic acid and 100 parts of deionized water;
preparing microencapsulated nickel sulfate microspheres:
s1, preparation of a glacial acetic acid solution: adding 20 parts of water into glacial acetic acid with the formula amount to prepare an acetic acid aqueous solution with the mass fraction of 1 wt%;
s2, sieving: respectively grinding chitosan and sodium carboxymethylcellulose according to the formula ratio, and sieving to obtain 50-mesh powder;
s3, preparing a chitosan stock solution: adding the formula amount of chitosan into the formula amount of glycol, dropwise adding the acetic acid aqueous solution described in S1 for dissolving, and stirring at the rotation speed of 1000r/min for 15min to obtain chitosan stock solution;
s4, preparing a sodium carboxymethyl cellulose stock solution: taking sodium carboxymethylcellulose with a formula amount, adding 60 parts of deionized water, stirring, heating to 40 ℃, stopping heating after a solution is clarified, cooling, and standing for 12 hours to obtain a sodium carboxymethylcellulose stock solution;
s5, preparation of a nickel sulfate solution: taking anhydrous nickel sulfate with the formula amount, and adding 20 parts of deionized water for mixing to obtain the nickel sulfate;
s6, preparing the micro-encapsulated nickel sulfate microspheres: and (4) taking the chitosan stock solution in the step S3 and the sodium carboxymethyl cellulose stock solution in the step S4, stirring, vacuum degassing, dropwise adding N-N' methylene bisacrylamide in a formula amount, uniformly stirring, dropwise adding the nickel sulfate solution in the step S5, and dispersing and stirring at the rotating speed of 1500r/min for 30 min.
Preparing corrosion-resistant zinc-nickel electroplating solution:
a1, preparation of zinc solution: taking sodium hydroxide with the formula amount, adding 30 parts of deionized water for dissolving, then adding zinc oxide with the formula amount, and stirring for dissolving;
a2, preparing a nickel solution: taking the complexing agent with the formula amount, adding 20 parts of deionized water for dissolving, adding the nickel chloride with the formula amount, and stirring for dissolving;
a3, preparation of corrosion-resistant zinc-nickel electroplating solution: and B, mixing the zinc solution obtained in the step A1 with the nickel solution obtained in the step A2, adding a compound brightener, a nickel stabilizer and a dispersant in a formula amount, and stirring at 40 ℃ to obtain the corrosion-resistant zinc-nickel electroplating solution.
Example 2
The corrosion-resistant zinc-nickel electroplating solution of example 2, comprising the following components in parts by weight: 2 parts of zinc oxide, 1.5 parts of nickel acetate, 30 parts of sodium hydroxide, 0.2 part of composite brightening agent, 8 parts of ethylene diamine tetraacetic acid, 5 parts of nickel stabilizer, 0.2 part of sodium lignosulfonate and 200 parts of deionized water; the composite brightener is prepared from urea and polyethyleneimine according to the weight ratio of 5: 3 in a mass ratio; wherein the nickel stabilizer is a microencapsulated nickel sulfate microsphere. The microencapsulated nickel sulfate microspheres comprise the following components in parts by weight: 2 parts of chitosan, 5 parts of sodium carboxymethylcellulose, 2 parts of glycerol, 0.1 part of N-N' methylene bisacrylamide, 2 parts of anhydrous nickel sulfate, 0.5 part of glacial acetic acid and 200 parts of deionized water;
preparing microencapsulated nickel sulfate microspheres:
s1, preparation of a glacial acetic acid solution: adding 17 parts of deionized water into glacial acetic acid with the formula amount to prepare an acetic acid aqueous solution with the mass fraction of 3 wt%;
s2, sieving: respectively grinding chitosan and sodium carboxymethylcellulose according to the formula ratio, and sieving to obtain 60-mesh powder;
s3, preparing a chitosan stock solution: adding formula amount of chitosan into formula amount of glycerol, adding dropwise acetic acid water solution as described in S1 for dissolving, and stirring at rotation speed of 1500r/min for 10min to obtain chitosan stock solution;
s4, preparing a sodium carboxymethyl cellulose stock solution: taking sodium carboxymethylcellulose according to the formula amount, adding 83 parts of deionized water, stirring, heating to 60 ℃, stopping heating after the solution is clarified, cooling, and standing for 24 hours to obtain sodium carboxymethylcellulose stock solution;
s5, preparation of a nickel sulfate solution: taking anhydrous nickel sulfate according to the formula amount, adding 100 parts of deionized water, and mixing to obtain the nickel sulfate;
s6, preparing the micro-encapsulated nickel sulfate microspheres: and (4) taking the chitosan stock solution in the step S3 and the sodium carboxymethyl cellulose stock solution in the step S4, stirring, vacuum degassing, dropwise adding N-N' methylene bisacrylamide in a formula amount, uniformly stirring, dropwise adding the nickel sulfate solution in the step S5, and dispersing and stirring at the rotating speed of 2000r/min for 15 min.
Preparing corrosion-resistant zinc-nickel electroplating solution:
a1, preparation of zinc solution: taking sodium hydroxide with the formula amount, adding 150 parts of deionized water for dissolving, adding zinc oxide with the formula amount, and stirring for dissolving;
a2, preparing a nickel solution: taking a complexing agent with a formula amount, adding 50 parts of deionized water for dissolving, adding nickel acetate with a formula amount, and stirring for dissolving;
a3, preparation of corrosion-resistant zinc-nickel electroplating solution: and B, mixing the zinc solution obtained in the step A1 with the nickel solution obtained in the step A2, adding a compound brightener, a nickel stabilizer and a dispersant in a formula amount, and stirring at 60 ℃ to obtain the corrosion-resistant zinc-nickel electroplating solution.
Example 3
The corrosion-resistant zinc-nickel electroplating solution of example 3, comprising the following components in parts by weight: 0.6 part of zinc oxide, 0.8 part of nickel sulfate, 10 parts of sodium hydroxide, 0.1 part of composite brightener, 4 parts of disodium ethylene diamine tetraacetate, 0.8 part of nickel stabilizer, 0.05 part of sodium lignosulfonate and 100 parts of deionized water; the brightener is prepared from urea and 4-hydroxycinnamaldehyde according to the weight ratio of 3: 0.8 mass ratio; wherein the nickel stabilizer is a microencapsulated nickel sulfate microsphere. The microencapsulated nickel sulfate microspheres comprise the following components in parts by weight: 1.2 parts of chitosan, 2.5 parts of sodium carboxymethylcellulose, 1.3 parts of glycerol, 0.6 part of N-N' methylene bisacrylamide, 1 part of anhydrous nickel sulfate, 0.25 part of glacial acetic acid and 140 parts of deionized water;
preparing microencapsulated nickel sulfate microspheres:
s1, preparation of a glacial acetic acid solution: adding 12.5 parts of deionized water into glacial acetic acid with the formula amount to prepare an acetic acid aqueous solution with the mass fraction of 2 wt%;
s2, sieving: respectively grinding chitosan and sodium carboxymethylcellulose according to the formula amount, and sieving to obtain 100-mesh powder;
s3, preparing a chitosan stock solution: adding formula amount of chitosan into formula amount of glycerol, adding dropwise acetic acid water solution as described in S1 for dissolving, and stirring at 1200r/min for 12min to obtain chitosan stock solution;
s4, preparing a sodium carboxymethyl cellulose stock solution: taking sodium carboxymethylcellulose according to the formula amount, adding 87.5 parts of deionized water, stirring, heating to 50 ℃, stopping heating after the solution is clarified, cooling, and standing for 15 hours to obtain sodium carboxymethylcellulose stock solution;
s5, preparation of a nickel sulfate solution: taking anhydrous nickel sulfate according to the formula amount, adding 40 parts of deionized water, and mixing to obtain the nickel sulfate;
s6, preparing the micro-encapsulated nickel sulfate microspheres: and (4) taking the chitosan stock solution in the step S3 and the sodium carboxymethyl cellulose stock solution in the step S4, stirring, vacuum degassing, dropwise adding N-N' methylene bisacrylamide in a formula amount, uniformly stirring, dropwise adding the nickel sulfate solution in the step S5, and dispersing and stirring at the rotating speed of 1800r/min for 25 min.
Preparing corrosion-resistant zinc-nickel electroplating solution:
a1, preparation of zinc solution: taking sodium hydroxide with the formula amount, adding 80 parts of deionized water for dissolving, adding zinc oxide with the formula amount, and stirring for dissolving;
a2, preparing a nickel solution: taking the complexing agent with the formula amount, adding 20 parts of deionized water for dissolving, adding the nickel sulfate with the formula amount, and stirring for dissolving;
a3, preparation of corrosion-resistant zinc-nickel electroplating solution: and B, mixing the zinc solution obtained in the step A1 with the nickel solution obtained in the step A2, adding a compound brightener, a nickel stabilizer and a dispersant in a formula amount, and stirring at 50 ℃ to obtain the corrosion-resistant zinc-nickel electroplating solution.
Example 4
The corrosion-resistant zinc-nickel electroplating solution of example 4, comprising the following components in parts by weight: 0.6 part of zinc oxide, 1.2 parts of nickel sulfate, 25 parts of sodium hydroxide, 0.15 part of composite brightener, 6 parts of complexing agent, 3 parts of nickel stabilizer, 0.1 part of sodium lignosulfonate and 150 parts of deionized water; the brightener is prepared from urea and vanillin according to the weight ratio of 3: 0.8 mass ratio; the complexing agent is prepared from potassium sodium tartrate, ethylene diamine tetraacetic acid disodium and sodium citrate according to the weight ratio of 1: 2: 0.3 in mass ratio. Wherein the nickel stabilizer is a microencapsulated nickel sulfate microsphere. The microencapsulated nickel sulfate microspheres comprise the following components in parts by weight: 1.2 parts of chitosan, 2.5 parts of sodium carboxymethylcellulose, 1.3 parts of glycerol, 0.6 part of N-N' methylene bisacrylamide, 1 part of anhydrous nickel sulfate, 0.25 part of glacial acetic acid and 140 parts of deionized water;
preparing microencapsulated nickel sulfate microspheres:
s1, preparation of a glacial acetic acid solution: adding 12.5 parts of deionized water into glacial acetic acid with the formula amount to prepare an acetic acid aqueous solution with the mass fraction of 2 wt%;
s2, sieving: respectively grinding chitosan and sodium carboxymethylcellulose according to the formula amount, and sieving to obtain 100-mesh powder;
s3, preparing a chitosan stock solution: adding formula amount of chitosan into formula amount of glycerol, adding dropwise acetic acid water solution as described in S1 for dissolving, and stirring at 1200r/min for 12min to obtain chitosan stock solution;
s4, preparing a sodium carboxymethyl cellulose stock solution: taking sodium carboxymethylcellulose according to the formula amount, adding 87.5 parts of deionized water, stirring, heating to 50 ℃, stopping heating after the solution is clarified, cooling, and standing for 15 hours to obtain sodium carboxymethylcellulose stock solution;
s5, preparation of a nickel sulfate solution: taking anhydrous nickel sulfate according to the formula amount, adding 40 parts of deionized water, and mixing to obtain the nickel sulfate;
s6, preparing the micro-encapsulated nickel sulfate microspheres: and (4) taking the chitosan stock solution in the step S3 and the sodium carboxymethyl cellulose stock solution in the step S4, stirring, vacuum degassing, dropwise adding N-N' methylene bisacrylamide in a formula amount, uniformly stirring, dropwise adding the nickel sulfate solution in the step S5, and dispersing and stirring at the rotating speed of 1800r/min for 25 min.
Preparing corrosion-resistant zinc-nickel electroplating solution:
a1, preparation of zinc solution: taking sodium hydroxide with the formula amount, adding 80 parts of deionized water for dissolving, adding zinc oxide with the formula amount, and stirring for dissolving;
a2, preparing a nickel solution: taking the complexing agent with the formula amount, adding 20 parts of deionized water for dissolving, adding the nickel sulfate with the formula amount, and stirring for dissolving;
a3, preparation of corrosion-resistant zinc-nickel electroplating solution: and B, mixing the zinc solution obtained in the step A1 with the nickel solution obtained in the step A2, adding a compound brightener, a nickel stabilizer and a dispersant in a formula amount, and stirring at 50 ℃ to obtain the corrosion-resistant zinc-nickel electroplating solution.
Example 5
The corrosion-resistant zinc-nickel electroplating solution of example 5, comprising the following components in parts by weight: 0.8 part of zinc oxide, 1 part of nickel sulfate, 20 parts of sodium hydroxide, 0.12 part of composite brightener, 5 parts of complexing agent, 1.5 parts of nickel stabilizer, 0.08 part of sodium lignosulfonate and 120 parts of deionized water; the composite brightener is prepared from urea and polyethyleneimine according to the weight ratio of 5: 1.5 in mass ratio; the complexing agent is prepared from potassium sodium tartrate, ethylene diamine tetraacetic acid disodium and sodium citrate according to the weight ratio of 1: 2: 0.3 in mass ratio. Wherein the nickel stabilizer is a microencapsulated nickel sulfate microsphere. The microencapsulated nickel sulfate microspheres comprise the following components in parts by weight: 1.2 parts of chitosan, 2.5 parts of sodium carboxymethylcellulose, 1.3 parts of glycerol, 0.6 part of N-N' methylene bisacrylamide, 1 part of anhydrous nickel sulfate, 0.25 part of glacial acetic acid and 140 parts of deionized water;
preparing microencapsulated nickel sulfate microspheres:
s1, preparation of a glacial acetic acid solution: adding 12.5 parts of deionized water into glacial acetic acid with the formula amount to prepare an acetic acid aqueous solution with the mass fraction of 2 wt%;
s2, sieving: respectively grinding chitosan and sodium carboxymethylcellulose according to the formula amount, and sieving to obtain 100-mesh powder;
s3, preparing a chitosan stock solution: adding formula amount of chitosan into formula amount of glycerol, adding dropwise acetic acid water solution as described in S1 for dissolving, and stirring at 1200r/min for 12min to obtain chitosan stock solution;
s4, preparing a sodium carboxymethyl cellulose stock solution: taking sodium carboxymethylcellulose according to the formula amount, adding 87.5 parts of deionized water, stirring, heating to 50 ℃, stopping heating after the solution is clarified, cooling, and standing for 15 hours to obtain sodium carboxymethylcellulose stock solution;
s5, preparation of a nickel sulfate solution: taking anhydrous nickel sulfate according to the formula amount, adding 40 parts of deionized water, and mixing to obtain the nickel sulfate;
s6, preparing the micro-encapsulated nickel sulfate microspheres: and (4) taking the chitosan stock solution in the step S3 and the sodium carboxymethyl cellulose stock solution in the step S4, stirring, vacuum degassing, dropwise adding N-N' methylene bisacrylamide in a formula amount, uniformly stirring, dropwise adding the nickel sulfate solution in the step S5, and dispersing and stirring at the rotating speed of 1800r/min for 25 min.
Preparing corrosion-resistant zinc-nickel electroplating solution:
a1, preparation of zinc solution: taking sodium hydroxide with the formula amount, adding 90 parts of deionized water for dissolving, adding zinc oxide with the formula amount, and stirring for dissolving;
a2, preparing a nickel solution: taking the complexing agent with the formula amount, adding 30 parts of deionized water for dissolving, adding the nickel sulfate with the formula amount, and stirring for dissolving;
a3, preparation of corrosion-resistant zinc-nickel electroplating solution: and B, mixing the zinc solution obtained in the step A1 with the nickel solution obtained in the step A2, adding a compound brightener, a nickel stabilizer and a dispersant in a formula amount, and stirring at 50 ℃ to obtain the corrosion-resistant zinc-nickel electroplating solution.
Comparative example 1
Comparative example 1 no nickel stabilizer was added and the formulation and composition of the other plating solutions and the preparation of the corrosion resistant zinc-nickel plating solution were identical to those of example 5.
Comparative example 2
The microencapsulated nickel sulfate microspheres of comparative example 2 were prepared by embedding nickel sulfate with chitosan alone, and the other formulation and components of the plating solution and the preparation of the corrosion-resistant zinc-nickel plating solution were all the same as those in example 5.
Wherein, the preparation of the micro-encapsulated nickel sulfate microspheres is as follows:
s1, preparation of a glacial acetic acid solution: adding 12.5 parts of deionized water into glacial acetic acid with the formula amount to prepare an acetic acid aqueous solution with the mass fraction of 2 wt%;
s2, sieving: grinding chitosan according to the formula amount, and sieving to obtain powder of 100 meshes;
s3, preparing a chitosan stock solution: adding formula amount of chitosan into formula amount of glycerol, adding dropwise acetic acid water solution as described in S1 for dissolving, and stirring at 1200r/min for 12min to obtain chitosan stock solution;
s4, preparation of a nickel sulfate solution: adding 127.5 parts of deionized water into anhydrous nickel sulfate according to the formula amount, and mixing to obtain the nickel sulfate powder;
s5, preparing the micro-encapsulated nickel sulfate microspheres: and (4) taking the chitosan stock solution in the step S3, stirring, vacuum degassing, dropwise adding N-N' methylene bisacrylamide in a formula amount, uniformly stirring, dropwise adding the nickel sulfate solution in the step S4, and dispersing and stirring at the rotating speed of 1800r/min for 25 min.
Comparative example 3
The microencapsulated nickel sulfate microspheres of comparative example 3 were prepared by embedding nickel sulfate with sodium carboxymethylcellulose alone, and the other formulation and components of the plating solution and the preparation of the corrosion-resistant zinc-nickel plating solution were all the same as those in example 5.
Wherein, the preparation of the micro-encapsulated nickel sulfate microspheres is as follows:
s1, sieving: grinding and sieving sodium carboxymethylcellulose according to the formula amount to obtain 100-mesh powder;
s2, preparing a sodium carboxymethyl cellulose stock solution: taking sodium carboxymethylcellulose with a formula amount, adding 100 parts of deionized water, stirring, heating to 50 ℃, stopping heating after a solution is clarified, cooling, and standing for 15 hours to obtain sodium carboxymethylcellulose stock solution;
s3, preparation of a nickel sulfate solution: taking anhydrous nickel sulfate according to the formula amount, adding 40 parts of deionized water, and mixing to obtain the nickel sulfate;
s4, preparing the micro-encapsulated nickel sulfate microspheres: and (4) taking the sodium carboxymethylcellulose stock solution obtained in the step S2, stirring, vacuum degassing, dropwise adding N-N' methylene bisacrylamide in a formula amount, uniformly stirring, dropwise adding the nickel sulfate solution obtained in the step S3, and dispersing and stirring at the rotating speed of 1800r/min for 25 min.
Comparative example 4
The composite brightener of comparative example 4 is prepared by adding 0.12 part of polyethyleneimine as a single-component brightener without adding urea, and the other proportions and components of the plating solution, the proportion and preparation method of the microencapsulated nickel sulfate microspheres, and the preparation of the corrosion-resistant zinc-nickel plating solution are the same as those of example 5.
Comparative example 5
The brightener of comparative example 5 does not use the composite brightener of the present invention, and the composite brightener is prepared by compounding vanillic acid and polyethyleneimine, and adding 0.12 part of the composite brightener, wherein the composite brightener is prepared by mixing vanillin and polyethyleneimine in a proportion of 5: the composition of 1.5 by mass, the other proportions and components of the plating solution, the proportion and preparation method of the microencapsulated nickel sulfate microspheres and the preparation of the corrosion-resistant zinc-nickel plating solution are all the same as those in example 5.
Comparative example 6
The composite brightener of comparative example 6 is prepared by adding 0.5 part of polyethyleneimine as a single-component brightener without adding urea, and the other proportions and components of the plating solution, the proportion and preparation method of the microencapsulated nickel sulfate microspheres, and the preparation of the corrosion-resistant zinc-nickel plating solution are the same as those in example 5.
Test example 1 measurement results of changes in the content of zinc and nickel in different batches of plating layers
Using a low-carbon steel sheet as an anode and an iron sheet as a cathode, respectively preparing 3 low-carbon steel sheets and 3 iron sheets with the size of 30mm multiplied by 50mm multiplied by 1mm, and dividing the low-carbon steel sheets and the iron sheets into 3 groups after oil removal and rust removal. Putting a first group of low-carbon steel and iron sheets into the electroplating solutions of examples 1-5 and comparative examples 1-6, introducing a direct-current power supply to carry out electroplating, putting a second group into the electroplating solutions to carry out electroplating after the first group is electroplated, and then putting a third group into the electroplating solutions to carry out electroplating, wherein the current density is 2A/square decimeter, the electroplating temperature is 30 ℃, and the electroplating time of each group is 20 min; after the experiment, the nickel content in the zinc-nickel coating in each group of iron sheets was analyzed by EDS, expressed in wt%.
TABLE 1 measurement results of the variation of Zn and Ni contents in different batches of electroplated coatings
From the test results in table 1, the iron sheets plated with the plating solutions of examples 1 to 5 had nickel contents in the zinc-nickel plating layers of 12.6 to 13.8 wt%, and after three times of plating, the nickel contents were still maintained at a stable level, and the nickel stabilizer was continuously released in the plating solution, thereby ensuring the stability of the nickel ion concentration in the plating solution. Comparative example 1 because no nickel stabilizer was added, the nickel content of the iron sheet was greatly reduced after multiple electroplating, and the phenomenon of fine and loose plating layer structure and pinhole appearance was observed by naked eyes.
Test example 2 plating layer Performance test of plating solution of the present invention
And (3) neutral salt spray test: after the low-carbon steel sheet is used as an anode and the iron sheet is used as a cathode, the size of the low-carbon steel sheet is 30mm multiplied by 50mm multiplied by 1mm, after oil and rust removal, the low-carbon steel and the iron sheet are placed into the electroplating solution of the examples 1-5 and the comparative examples 1-6, a direct-current power supply is introduced, electroplating is carried out, the current density is 2A/square decimeter, the electroplating temperature is 30 ℃, the electroplating time is 20min, after the electroplating is finished, the electroplated zinc-nickel coating iron sheet is placed into a salt spray box, the corrosion resistance test is carried out on the zinc-nickel coating iron sheet according to American standard ASTM B117, and the time (h) for red rust of the zinc-nickel coating iron sheet is recorded.
And (3) testing the binding force of the zinc-nickel coating: the iron sheet with the thickness of 150mm multiplied by 25mm multiplied by 1mm is respectively placed into the electroplating solution of the embodiment 1-5 and the comparative example 1-6 for electroplating, the current density is 2A/square decimeter, the electroplating temperature is 30 ℃, the electroplating time is 20min, after the electroplating is finished, a 180-degree bending test is carried out according to the national standard GB 232-containing 2010, whether visible cracks appear on the zinc-nickel electroplating iron sheet is observed by naked eyes, if not, the zinc-nickel electroplating iron sheet is qualified, and if so, the zinc-nickel electroplating iron sheet is unqualified.
TABLE 2 plating Performance results for plating solutions of the present invention
From the test results in Table 2, the iron sheets plated in examples 1 to 5 all showed red rust development in the zinc-nickel plating layer of 1460h or more, and the best example was found in example 5, in which the zinc-nickel plating layer showed red rust development of 1680 h. Compared with the prior art, the method has the advantages that no nickel stabilizer is added in the comparative example 1, the time of red rust appearing on the zinc-nickel electroplated layer is greatly short, and only 1250 hours exist; the microencapsulated nickel sulfate microspheres of comparative examples 2 and 3 are not embedded by using a chitosan-sodium carboxymethylcellulose composite coating material, and only by using single chitosan or sodium carboxymethylcellulose, the time for red rust of a zinc-nickel electroplated layer is slightly reduced, which is probably because the slow release effect of the microencapsulated nickel sulfate microspheres is inferior to that of the chitosan-sodium carboxymethylcellulose composite coating material, so that the content of nickel ions in an electroplating solution is too high, the corrosion resistance of a prepared coating is reduced, and when the content of nickel ions is too high, a large amount of zinc oxide is generated on a zinc-nickel coating besides zinc hydroxide, so that the coating is loose; the brighteners of comparative examples 4 to 6, in which no urea was added, were inferior in corrosion resistance to those of example 5, in which the corrosion resistance was inferior when the amount of polyethyleneimine was increased; bending test is carried out, cracks appear on the zinc-nickel electroplated iron sheet through visual observation, wherein the cracks of the plating layer prepared by the electroplating solution of the comparative example 6 are more serious, because when the content of organic components in the brightener is increased to cause interference to the electroplating solution, and when the brightener is accumulated to a certain degree, the brightness of the plating layer is deteriorated, and the problems of pinholes, fogging, darkening, large brittleness, high porosity and the like are caused.
The foregoing illustrates and describes the principles, general features, and advantages of the present invention. It will be understood by those skilled in the art that the present invention is not limited to the embodiments described above, which are described in the specification and illustrated only to illustrate the principle of the present invention, but that various changes and modifications may be made therein without departing from the spirit and scope of the present invention, which fall within the scope of the invention as claimed. The scope of the invention is defined by the appended claims and equivalents thereof.
Claims (10)
1. The corrosion-resistant zinc-nickel electroplating solution is characterized in that: the electroplating solution comprises the following components in parts by weight: 0.5-2 parts of zinc oxide, 0.2-1.5 parts of nickel salt, 5-30 parts of sodium hydroxide, 0.05-0.2 part of composite brightener, 2-8 parts of complexing agent, 0.5-5 parts of nickel stabilizer, 0.01-0.2 part of dispersing agent and 50-200 parts of deionized water; wherein the nickel stabilizer is a microencapsulated nickel sulfate microsphere.
2. The corrosion-resistant zinc-nickel electroplating bath as claimed in claim 1, wherein: the nickel salt is one or more of nickel sulfate, nickel chloride, nickel acetate and nickel sulfamate.
3. The corrosion-resistant zinc-nickel electroplating bath as claimed in claim 1, wherein: the microencapsulated nickel sulfate microspheres comprise the following components in parts by weight: 1-2 parts of chitosan, 2-5 parts of sodium carboxymethylcellulose, 0.2-2 parts of wetting agent, 0.01-0.1 part of N-N' -methylene bisacrylamide, 0.5-2 parts of anhydrous nickel sulfate, 0.2-0.5 part of glacial acetic acid and 100-200 parts of deionized water; the wetting agent is one or a combination of ethylene glycol or glycerol.
4. The corrosion-resistant zinc-nickel electroplating bath as claimed in claim 3, wherein: the microencapsulated nickel sulfate microspheres comprise the following preparation steps:
s1, preparation of a glacial acetic acid solution: adding water into glacial acetic acid in a formula amount to prepare an acetic acid aqueous solution with the mass fraction of 1-3 wt%;
s2, sieving: respectively grinding chitosan and sodium carboxymethylcellulose according to the formula ratio, and sieving to obtain powder of 50-100 meshes;
s3, preparing a chitosan stock solution: adding a wetting agent in a formula amount into chitosan in a formula amount, dropwise adding an acetic acid solution in S1 for dissolving, and stirring at a rotating speed of 1000-1500 r/min for 10-15 min to obtain a chitosan stock solution;
s4, preparing a sodium carboxymethyl cellulose stock solution: adding deionized water into sodium carboxymethylcellulose according to the formula amount, stirring, heating to 40-60 ℃, stopping heating after the solution is clarified, cooling, and standing for 12-24 hours to obtain sodium carboxymethylcellulose stock solution;
s5, preparation of a nickel sulfate solution: taking anhydrous nickel sulfate with the formula amount, and adding water for mixing to obtain the nickel sulfate;
s6, preparing the micro-encapsulated nickel sulfate microspheres: and (4) taking the chitosan stock solution in the step S3 and the sodium carboxymethyl cellulose stock solution in the step S4, stirring, vacuum degassing, dropwise adding N-N' methylene bisacrylamide in a formula amount, uniformly stirring, dropwise adding the nickel sulfate solution in the step S5, and dispersing and stirring at the rotating speed of 1500-2000 r/min for 15-30 min.
5. The corrosion-resistant zinc-nickel electroplating bath as claimed in claim 1, wherein: the composite brightener is composed of two or more of urea, organic amine and organic aldehyde.
6. The corrosion-resistant zinc-nickel electroplating bath as claimed in claim 5, wherein: the organic amine is ethylenediamine and/or polyethyleneimine.
7. The corrosion-resistant zinc-nickel electroplating bath as claimed in claim 5, wherein: the organic aldehyde is one or more of vanillin, 4-hydroxycinnamaldehyde and o-hydroxybenzaldehyde.
8. The corrosion-resistant zinc-nickel electroplating bath as claimed in claim 1, wherein: the complexing agent is one or more of disodium ethylene diamine tetraacetate, potassium sodium tartrate and sodium citrate.
9. The corrosion-resistant zinc-nickel electroplating bath as claimed in claim 1, wherein: the dispersant is sodium lignosulfonate.
10. A method for preparing the corrosion-resistant zinc-nickel electroplating solution according to any one of claims 1 to 9, comprising: the method comprises the following steps:
a1, preparation of zinc solution: taking sodium hydroxide with the formula amount, adding water for dissolving, adding zinc oxide with the formula amount, and stirring for dissolving;
a2, preparing a nickel solution: taking the complexing agent with the formula amount, adding water for dissolving, adding the nickel salt with the formula amount, and stirring for dissolving;
a3, preparation of corrosion-resistant zinc-nickel electroplating solution: and B, mixing the zinc solution obtained in the step A1 with the nickel solution obtained in the step A2, adding a compound brightener, a nickel stabilizer and a dispersant in a formula amount, and stirring at 40-60 ℃ to obtain the corrosion-resistant zinc-nickel electroplating solution.
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| CN107376859A (en) * | 2017-08-14 | 2017-11-24 | 东华理工大学 | A kind of glutaraldehyde cross-linking chitosan/nickel hydroxide microballoon compound adsorbent preparation method |
| CN109092326A (en) * | 2018-07-02 | 2018-12-28 | 曲阜师范大学 | A kind of nucleocapsid shape nickel tungstate micro-ball load palladium catalyst and its preparation method and application |
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2021
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| US4610937A (en) * | 1983-11-28 | 1986-09-09 | Nisshin Steel Company | Product of and process for preparing Zn-Ni-alloy-electroplated steel sheets excellent in corrosion resistance |
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| CN104120465A (en) * | 2013-04-28 | 2014-10-29 | 国家电网公司 | Alkaline zinc-nickel alloy electroplating solution as well as preparation method and application thereof |
| CN104805480A (en) * | 2015-05-21 | 2015-07-29 | 广东达志环保科技股份有限公司 | Alkaline zinc-nickel electroplating liquid, preparation method and electroplating method |
| CN107376859A (en) * | 2017-08-14 | 2017-11-24 | 东华理工大学 | A kind of glutaraldehyde cross-linking chitosan/nickel hydroxide microballoon compound adsorbent preparation method |
| CN109092326A (en) * | 2018-07-02 | 2018-12-28 | 曲阜师范大学 | A kind of nucleocapsid shape nickel tungstate micro-ball load palladium catalyst and its preparation method and application |
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