CN117187895A - Boric acid-free chloride electrogalvanizing method - Google Patents
Boric acid-free chloride electrogalvanizing method Download PDFInfo
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- CN117187895A CN117187895A CN202311046353.0A CN202311046353A CN117187895A CN 117187895 A CN117187895 A CN 117187895A CN 202311046353 A CN202311046353 A CN 202311046353A CN 117187895 A CN117187895 A CN 117187895A
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- electroplating
- chloride
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- zinc
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- 238000000034 method Methods 0.000 title claims abstract description 45
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 title claims abstract description 19
- 238000009713 electroplating Methods 0.000 claims abstract description 140
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims abstract description 110
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 110
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 claims abstract description 76
- 239000000758 substrate Substances 0.000 claims abstract description 65
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 239000001103 potassium chloride Substances 0.000 claims abstract description 55
- 235000011164 potassium chloride Nutrition 0.000 claims abstract description 55
- 239000011592 zinc chloride Substances 0.000 claims abstract description 55
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 55
- WXMKPNITSTVMEF-UHFFFAOYSA-M sodium benzoate Chemical compound [Na+].[O-]C(=O)C1=CC=CC=C1 WXMKPNITSTVMEF-UHFFFAOYSA-M 0.000 claims abstract description 45
- 239000004299 sodium benzoate Substances 0.000 claims abstract description 45
- 235000010234 sodium benzoate Nutrition 0.000 claims abstract description 45
- 239000004310 lactic acid Substances 0.000 claims abstract description 38
- 235000014655 lactic acid Nutrition 0.000 claims abstract description 38
- KPGXRSRHYNQIFN-UHFFFAOYSA-N 2-oxoglutaric acid Chemical compound OC(=O)CCC(=O)C(O)=O KPGXRSRHYNQIFN-UHFFFAOYSA-N 0.000 claims abstract description 34
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000004327 boric acid Substances 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 13
- 238000007747 plating Methods 0.000 claims description 82
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 43
- 229910052725 zinc Inorganic materials 0.000 claims description 43
- 239000011701 zinc Substances 0.000 claims description 43
- 238000003756 stirring Methods 0.000 claims description 28
- 239000008367 deionised water Substances 0.000 claims description 26
- 229910021641 deionized water Inorganic materials 0.000 claims description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 16
- 238000005554 pickling Methods 0.000 claims description 13
- 150000003839 salts Chemical class 0.000 claims description 12
- 238000005303 weighing Methods 0.000 claims description 9
- 229910052742 iron Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 4
- FAQYAMRNWDIXMY-UHFFFAOYSA-N trichloroborane Chemical compound ClB(Cl)Cl FAQYAMRNWDIXMY-UHFFFAOYSA-N 0.000 claims description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 239000011889 copper foil Substances 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 238000004506 ultrasonic cleaning Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000005260 corrosion Methods 0.000 abstract description 10
- 230000007613 environmental effect Effects 0.000 abstract description 7
- 239000000243 solution Substances 0.000 description 122
- 239000010410 layer Substances 0.000 description 53
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 18
- 238000000576 coating method Methods 0.000 description 17
- 229910052751 metal Inorganic materials 0.000 description 17
- 239000002184 metal Substances 0.000 description 17
- 239000011248 coating agent Substances 0.000 description 16
- 239000003795 chemical substances by application Substances 0.000 description 14
- 239000000654 additive Substances 0.000 description 12
- 238000005516 engineering process Methods 0.000 description 12
- 235000002639 sodium chloride Nutrition 0.000 description 12
- 235000019270 ammonium chloride Nutrition 0.000 description 9
- 238000005282 brightening Methods 0.000 description 9
- 230000007797 corrosion Effects 0.000 description 8
- 238000010438 heat treatment Methods 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 7
- 230000005496 eutectics Effects 0.000 description 7
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 7
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- 230000000996 additive effect Effects 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 239000002351 wastewater Substances 0.000 description 5
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 4
- 238000002425 crystallisation Methods 0.000 description 4
- 230000008025 crystallization Effects 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 239000006185 dispersion Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- RYZCLUQMCYZBJQ-UHFFFAOYSA-H lead(2+);dicarbonate;dihydroxide Chemical group [OH-].[OH-].[Pb+2].[Pb+2].[Pb+2].[O-]C([O-])=O.[O-]C([O-])=O RYZCLUQMCYZBJQ-UHFFFAOYSA-H 0.000 description 4
- 238000001556 precipitation Methods 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000008021 deposition Effects 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 231100000252 nontoxic Toxicity 0.000 description 3
- 230000003000 nontoxic effect Effects 0.000 description 3
- QDPYDWXGZVHLMJ-UHFFFAOYSA-K potassium;zinc;trichloride Chemical compound [Cl-].[Cl-].[Cl-].[K+].[Zn+2] QDPYDWXGZVHLMJ-UHFFFAOYSA-K 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- 239000004902 Softening Agent Substances 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 2
- 230000001070 adhesive effect Effects 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- -1 alkaline earth metal salt Chemical class 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000000872 buffer Substances 0.000 description 2
- 239000006172 buffering agent Substances 0.000 description 2
- 239000011247 coating layer Substances 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000006378 damage Effects 0.000 description 2
- 238000005238 degreasing Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000005246 galvanizing Methods 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000011787 zinc oxide Substances 0.000 description 2
- TUSDEZXZIZRFGC-UHFFFAOYSA-N 1-O-galloyl-3,6-(R)-HHDP-beta-D-glucose Natural products OC1C(O2)COC(=O)C3=CC(O)=C(O)C(O)=C3C3=C(O)C(O)=C(O)C=C3C(=O)OC1C(O)C2OC(=O)C1=CC(O)=C(O)C(O)=C1 TUSDEZXZIZRFGC-UHFFFAOYSA-N 0.000 description 1
- 239000001763 2-hydroxyethyl(trimethyl)azanium Substances 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 235000019743 Choline chloride Nutrition 0.000 description 1
- 239000001263 FEMA 3042 Substances 0.000 description 1
- 229910000677 High-carbon steel Inorganic materials 0.000 description 1
- 229910001209 Low-carbon steel Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- IVPFCJFBIPBZJQ-CHUJMTOYSA-N OC[C@H]([C@@H]([C@H](CO)O)O)O.Cl Chemical compound OC[C@H]([C@@H]([C@H](CO)O)O)O.Cl IVPFCJFBIPBZJQ-CHUJMTOYSA-N 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Penta-digallate-beta-D-glucose Natural products OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 229920000805 Polyaspartic acid Polymers 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229960001231 choline Drugs 0.000 description 1
- OEYIOHPDSNJKLS-UHFFFAOYSA-N choline Chemical compound C[N+](C)(C)CCO OEYIOHPDSNJKLS-UHFFFAOYSA-N 0.000 description 1
- 229960003178 choline chloride Drugs 0.000 description 1
- SGMZJAMFUVOLNK-UHFFFAOYSA-M choline chloride Chemical compound [Cl-].C[N+](C)(C)CCO SGMZJAMFUVOLNK-UHFFFAOYSA-M 0.000 description 1
- 239000008139 complexing agent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002173 cutting fluid Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
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- 238000000227 grinding Methods 0.000 description 1
- 208000037824 growth disorder Diseases 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000005272 metallurgy Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- QELJHCBNGDEXLD-UHFFFAOYSA-N nickel zinc Chemical compound [Ni].[Zn] QELJHCBNGDEXLD-UHFFFAOYSA-N 0.000 description 1
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- LRBQNJMCXXYXIU-NRMVVENXSA-N tannic acid Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-NRMVVENXSA-N 0.000 description 1
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Landscapes
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The application relates to a boric acid-free chloride electrogalvanizing method, which comprises the steps of taking a pretreated substrate as a cathode and placing the substrate in an electroplate liquid to electroplate to obtain an electrogalvanizing layer, wherein the electroplate liquid comprises the following components: 70-150 g/L of zinc chloride, 200g/L of potassium chloride, 5-20 g/L of lactic acid, 3-8 g/L of sodium benzoate, 10-20 g/L of 2-oxoglutarate and the balance of water, wherein the pH of the electroplating solution is 5-6. The electrogalvanized layer prepared by adopting the electroplate liquid and a specific electroplating method matched with the electroplate liquid is compact and bright, has strong binding force with a base material, has better anti-corrosion performance, and meanwhile, the electrogalvanized process does not use boric acid, so that the environmental problem caused by using boric acid is avoided from the source, and the electrogalvanized layer has higher application value, economic value and environmental value.
Description
Technical Field
The application relates to a boric acid-free chloride electrogalvanizing method, and belongs to the technical field of electrogalvanizing.
Background
Electroplating is a common material surface treatment technology, in which the part to be plated is used as a cathode, a sacrificial anode or an inert electrode is used as an anode, and metal ions in the electrolyte are deposited on the surface of the plated part in the form of metal simple substances to form a layer of compact, uniform and bright metal film, namely an electroplated layer. The electroplated material can change the surface appearance to make the surface more attractive, improve the corrosion resistance, wear resistance, electrical property, magnetic property and the like of the material, and simultaneously can maintain the physicochemical property of the interior of the material. Therefore, electroplating is a surface processing technology and has extremely important significance for industrial production and scientific research.
Compared with other metals, zinc is a metal which is relatively cheap and easy to electroplate, and the electrogalvanizing technology is widely applied to the fields of metallurgy, machinery, aviation, materials and the like, and can effectively improve the corrosion resistance of steel. The method of electro-galvanizing is classified into sulfate type galvanization, zincate type galvanization, cyanide galvanization, chloride galvanization, and the like, according to the kind of plating solution. The galvanization technology which initially appears is a cyanide galvanization technology, the operation method is quite simple, complex treatment is not needed before galvanization, the requirements on plating solution and additives are not high in the galvanization process, but the technology has great pollution to the environment due to the extremely toxic cyanide, so that the cyanide galvanization technology gradually fades out of the view of people along with the continuous enhancement of environmental awareness. The sulfate galvanization technology has higher current efficiency and faster deposition rate of a plating layer, but the plating layer obtained by the technology is not bright enough, has weak crystallization capability, and has poor dispersion capability and deep plating capability.
The electrolyte for zincate electroplating mainly comprises zinc oxide, sodium hydroxide, a small amount of surfactant and brightening agent. The zincate galvanization electrolyte has simple components, and can obtain a qualified plating layer by using a proper additive, the technology is environment-friendly, and the quality of the obtained plating layer is good, for example, CN103014785B discloses an electroplating liquid which mainly comprises the following aqueous solutions: zinc, sodium hydroxide, sodium carbonate, a regulator, a cylinder opening agent, a main gloss agent and a positioning agent. By adding several additives into the electroplating solution, proper zinc ion concentration and current density are adjusted, so that the electroplating solution has perfect dispersion capability, and has better current efficiency, uniform plating capability and deep plating capability. CN101255581B discloses an alkaline chloride galvanization treating agent, which is characterized by comprising the following components in percentage by mass: 9.6 to 14.5 percent of sodium hydroxide, 5.0 to 7.0 percent of potassium chloride, 0.6 to 0.9 percent of zinc oxide, 0.35 to 0.45 percent of DPE-3 auxiliary agent, 0.35 to 0.45 percent of ZB-80 brightening agent and 76 to 84 percent of water, and the plating layer obtained by using the treating agent has the advantages of high bonding rate, bright and fine electroplated product, no brittleness, no peeling phenomenon at the baking temperature of 250 ℃, no color change, strong impurity resistance, little fogging and foaming phenomenon of the plating layer, low cost, energy saving and easy wastewater treatment, and can reach 150 to 200 hours in a salt spray test. However, zincate galvanization is carried out under alkaline conditions, the concentration of zinc ions in the plating solution is low, the deposition speed of the obtained plating layer is relatively slow, the current efficiency is low, the requirements on the plating solution and additives are relatively high, and the operation range is small.
The chloride galvanization comprises ammonium chloride galvanization and potassium chloride galvanization, the ammonium chloride galvanization has the advantages of high current efficiency, high deposition speed, fine and bright plating layer crystallization and less hydrogen permeation in the electroplating process, for example, CN105970254A discloses an acid perchloride system galvanization bright zinc-nickel alloy galvanization liquid and a galvanization process thereof, ammonium chloride, potassium chloride, a locating agent, a brightening agent and a complexing agent are added into the galvanization liquid, boric acid is not contained in the galvanization liquid, the ammonium chloride is used as a buffering agent of the galvanization liquid, the problem of precipitation of boric acid caused by low temperature is avoided, and the galvanization liquid is quite safe and stable. The electroplating solution only needs to be added with a small amount of additives, so that the electroplating wastewater is less discharged and the treatment is simple. CN113862742a discloses a metal galvanization process applied to an isolating switch, wherein a metal piece after pickling is placed into a plating tank, and a salt film is formed on the surface of the metal piece by adopting mixed electroplating of zinc chloride and ammonium chloride solution; cooling and shaping after galvanization, wherein the electroplating solution comprises the following raw materials in parts by weight: 50-55 parts of zinc chloride; 43-50 parts of ammonium chloride; 2-15 parts of alkaline earth metal salt; 2-5 parts of manganese chloride; 2-5 parts of nickel chloride, and the galvanized layer obtained by the process has better anti-corrosion capability, and meanwhile, the galvanized layer is tightly attached to a metal piece, so that the galvanized layer is not easy to fall off in use, and the service life of the isolating switch is prolonged. CN110318077a discloses a cyanide-free galvanization liquid, which comprises the following components: 35-50 g/L of zinc chloride, 260-320 g/L of ammonium chloride, 20-26 g/L of potassium chloride, 10-30 g/L of polyaspartic acid, 2-6 g/L of tannic acid, 0.8-2.4 g/L of sodium lignin sulfonate, 1-6 ml/L of brightening agent and 8-36 ml/L of softener, and the balance of deionized water. The plating layer prepared by the cyanide-free zinc plating solution has fine crystallization, good area coverage rate and long salt spray aging, and solves the problem that the traditional plating of the raw iron piece, the cast iron piece and the plating of the high-carbon steel cannot be directly performed with white spot. However, the ammonium chloride galvanization can generate pungent odor in the electroplating process, the dispersion capability of the obtained plating layer is poor, the plating solution has serious corrosion to equipment, and the wastewater treatment is troublesome.
The potassium chloride galvanization technology overcomes the defects, and the potassium chloride galvanization technology is easy to plate, has simple plating solution components, stable plating solution, fine and bright plating layer, high current density and low tank voltage, and has been widely applied in recent years. The typical formula of the potassium chloride zinc plating solution mainly comprises potassium chloride and zinc chloride, and additives such as boric acid, brightening agent and softening agent are added, wherein the zinc chloride is a main salt and is a donor of zinc ions. Zinc chloride is also a conductive salt, so that the conductivity of the plating solution can be increased, the concentration is high, the resistance is small, the tank voltage is lower, and the electric quantity can be saved; potassium chloride is a supporting electrolyte of the plating solution and mainly plays roles of conducting electricity and activating an anode; boric acid is a buffer with better performance, so that the pH value of the solution keeps certain stability; the brightening agent and the softening agent are important factors for determining the quality of the coating, and the use of the excellent additive can obtain the coating with fine crystallization and brightening. In a potassium chloride zinc plating system, boric acid is a key additive, but in a potassium chloride zinc plating system plating solution, various inorganic salts and organic matters exist, the generated salt effect can lead the solubility of boric acid to be lower than that in pure water, and in order to maintain higher solubility of boric acid, the higher temperature of the plating solution is required to be maintained. Since boric acid is sensitive to the temperature of plating solution when in use, when a cold workpiece enters a plating bath, crystal precipitation can be formed on the surface of the workpiece to roughen a plating layer; when the liquid temperature is low, fine crystals which are formed by separating out boric acid and suspending in the plating solution can cause coarse plating, and in addition, the boric acid can easily form white precipitate with zinc ions in the plating solution, thereby bringing adverse effects to production. And meanwhile, the recycling process of the boric acid is expensive, the removal of the boric acid and the boron in the electroplating wastewater is difficult, and the wastewater can be discharged to cause environmental damage, such as aquatic organism growth and growth disorder. With the rise of environmental awareness, various countries have also begun to develop standards related to boron release water by more stringent environmental regulations, such as the european chemical community, which has included boric acid as a candidate list of highly relevant substances. At present, most of treatment methods of boron-containing wastewater are a chemical precipitation method and a resin adsorption method, and the two methods can convert boron into solid to generate boron-containing solid waste, but have adverse effects on the environment.
However, the plating effect is mostly poor, and a rough plating layer with poor glossiness is easily produced. In addition, when the amount of acetic acid added is large, the smell is strong, and the working environment is bad. CN105256343B discloses a method for electrogalvanizing based on choline chloride-xylitol eutectic solvent, which comprises the steps of firstly stirring xylitol, choline chloride and distilled water at constant temperature to obtain a transparent eutectic solvent, then adding zinc chloride into the eutectic solvent, and stirring at constant temperature to obtain a zinc-containing eutectic solvent, wherein the zinc-containing eutectic solvent is used as an electroplating solution; the pure zinc plate is used as an anode, the low carbon steel is used as a cathode, and the plating solution is immersed into the plating solution to perform constant current plating. Although the zinc plating process is safe, nontoxic, environment-friendly and economical, and solves the environmental pollution problems of processes such as fluoborate zinc plating, halide zinc plating and the like, the preparation condition of the eutectic solvent used by the method is harsh, which is not beneficial to industrial mass production, and the eutectic solvent has poor stability in the electroplating process, so that the plating layer is rough.
Therefore, it is necessary to provide a new method for electroplating and depositing metal zinc without boric acid chloride to replace boric acid from the source, and solve the technical problems under the condition of ensuring that the original performance of the plating layer is maintained.
Disclosure of Invention
The application aims to provide a boric acid-free chloride electrogalvanizing method and a boric acid-free chloride electrogalvanizing solution for electrogalvanizing, compared with the currently used chloride electrogalvanizing solution, boric acid is not added into the electrogalvanizing solution, only simple zinc chloride main salt, potassium chloride, lactic acid, sodium benzoate and 2-oxoglutarate are adopted, the solvent is deionized water, the composition of the electrogalvanizing solution is simple, the cost is low, the solute in the electrogalvanizing solution has larger solubility in water, the electrogalvanizing solution system has low temperature sensitivity, the electrogalvanizing solution is stable, and the electrogalvanizing solution does not contain ammonium chloride and boric acid, and the electrogalvanizing system is nontoxic, and the treatment of the electrogalvanizing waste liquid is simple and environment-friendly.
In order to achieve the above purpose, the application adopts the following technical scheme:
a boric acid-free chloride electrogalvanizing method, comprising the steps of: 1) Pretreating a substrate; 2) Placing the pretreated substrate as a cathode in an electroplating solution for electroplating, wherein the electroplating solution comprises the following components: zinc chloride, potassium chloride, lactic acid, sodium benzoate, 2-oxoglutarate and water; 3) After the electroplating is finished, washing off the electroplating solution attached to the surface of the substrate by using clear water, putting the substrate into an oven, and drying at 80 ℃ for 4 hours to obtain the electrogalvanized layer.
Preferably, the base material is stainless steel, copper foil, or iron sheet.
Preferably, the substrate is pretreated before electroplating, and the pretreatment sequentially comprises: the substrate is placed in a 1M NaOH solution for ultrasonic cleaning for 5min to clean oil stains on the surface, and because a certain amount of oil stains, grinding cutting fluid and other dust dirt exist on the surface of the substrate inevitably in the production process, all subsequent procedures can not meet the requirements if oil stains and rust matters on the surface are not removed in advance before electroplating treatment, the rust rate of a workpiece can be increased, and the surface stains can also cause serious sand holes and burrs on a plating layer after galvanization, so that the quality of an electrogalvanizing layer is greatly influenced. After degreasing, the substrate is required to be cleaned, degreasing liquid adsorbed on the surface of the substrate is removed, the substrate is generally rinsed by deionized water, the substrate is rinsed by deionized water for 5min, and the cleaned substrate is dried and cooled for standby. And then the substrate is subjected to pickling and rust removal, rust spots or oxide films possibly existing on the surface of the substrate are removed when the main purpose of pickling and rust removal is to take care of preventing the substrate from being corroded or generating hydrogen embrittlement in the pickling process, and the concentration and time of pickling solution need to be strictly controlled. In the application, 0.5M dilute hydrochloric acid is adopted for the substrate pickling treatment solution, and a mixed solution composed of 5g/L thiourea is added into the dilute hydrochloric acid, so that the substrate is soaked in the pickling solution for 5min to remove the surface rust spots and the oxide films, and the applicant finds that the pickling solution can effectively remove the rust spots and the oxide films on the surface of the substrate without generating deeper corrosion on the substrate, and meanwhile, the hydrochloric acid in the solution after removing the surface stains can further activate the surface of the substrate, promote the adhesiveness of a metal layer in the subsequent electroplating and improve the stability of a coating. After pickling, the substrate is cleaned, rinsed with conventional deionized water, dried in a drying oven, and then taken out for later use.
Preferably, the plating solution includes: 70-150 g/L of zinc chloride, 200g/L of potassium chloride, 5-20 g/L of lactic acid, 3-8 g/L of sodium benzoate, 10-20 g/L of 2-oxoglutarate, and the balance of water, wherein the pH value is 5-6. The galvanizing of the electroplating solution comprises two stages, namely, firstly, the substrate is processed at the temperature of 10-20 ℃ and the cathode current density of 0.1-0.5A/dm 2 Electroplating for 0.5-2 min, and then at 20-50 deg.C, cathode current density is 1-5A/dm 2 Electroplating for 20-50 min. The preparation method of the electroplating solution comprises the following steps: firstly, weighing 70-150 g/L of zinc chloride as main salt and 200g/L of potassium chloride, sequentially dissolving the zinc chloride and the potassium chloride into deionized water, adding 5-20 g/L of lactic acid and 3-8 g/L of sodium benzoate into the deionized water under the stirring condition, continuously stirring until the zinc chloride and the potassium chloride are dissolved, adding 10-20 g/L of 2-oxoglutarate, and adjusting the pH of the electroplating solution to 5-6 by using 0.1M sodium hydroxide solution.
Preferably, the plating solution includes: 80-100 g/L of zinc chloride, 200g/L of potassium chloride, 10-20 g/L of lactic acid, 5g/L of sodium benzoate, 15g/L of 2-oxoglutarate and the balance of water, wherein the pH value is 6. The preparation method of the electroplating solution comprises the following steps: firstly, 80-100 g/L of zinc chloride as main salt and 200g/L of potassium chloride as main salt are weighed and dissolved in deionized water, 10-20 g/L of lactic acid and 5g/L of sodium benzoate are added into the deionized water under the stirring condition, after the solution is continuously stirred until the solution is dissolved, 15g/L of 2-oxoglutarate is added, and 0.1M sodium hydroxide solution is used for regulating the pH value of the electroplating solution to 6.
The plating solution comprises two stages, wherein the substrate is first subjected to a cathodic current density of 0.3A/dm at 20 DEG C 2 Electroplating for 1min, heating the electroplating solution to 30deg.C, and adjusting cathode current density to 4A/dm 2 Electroplating for 30min.
The zinc chloride with the main salt of 70-150 g/L in the electroplating solution can be rapidly deposited under a larger current density compared with the conventional chloride electrogalvanizing system, namely the electroplating solution has a faster electroplating layer preparation speed, and 200g/L of potassium chloride can be usedSo as to ensure good conductivity of the plating solution and binding force between the galvanized layer and the base material, and simultaneously the applicant finds that the high-current rapid electrogalvanizing in an electroplating system can be maintained in the concentration range, and higher dispersion capability and deep plating capability can be ensured; lactic acid existing in the system can be taken as a buffering agent together with 2-oxoglutarate to maintain the stability of the pH of the system, and the lactic acid has stronger complexing ability to zinc ions, so that the content of free zinc ions in an electroplating system can be maintained relatively stable to a certain extent, the plating layer is more compact and uniform, and the corrosion resistance of the galvanized layer is improved. Sodium benzoate is used as additive and brightening agent to raise the brightness of coating. The lactic acid, sodium benzoate and 2-oxoglutarate have higher solubility in deionized water, the stability of the whole electroplating liquid system is higher, and various additives are seldom attached to the plating layer in the electroplating process, so that pinholes or burrs of the plating layer are avoided. The double buffer combination of lactic acid and 2-oxoglutarate better maintains the pH stability of the electroplating solution system, and experiments prove that the system can maintain the pH stability in the electroplating process of 1000 hours, and the electroplating solution does not have turbid precipitation. In the specific electroplating solution system of the application, in order to further improve the adhesiveness of the plating layer, the application adopts a two-step galvanization method, and the cathode current density is 0.1 to 0.5A/dm at 10 to 20 ℃ at first 2 Electroplating for 0.5-2 min, forming a zinc coating layer with small particles and even and compact arrangement on the surface of the substrate, wherein the zinc coating layer has strong surface acting force with the surface of the substrate, heating to 20-50 ℃ and setting cathode current density to 1-5A/dm 2 And electroplating for 20-50 min, and fast electroplating the zinc coating at a higher temperature and high current density, wherein the zinc coating can be fast deposited on the compact zinc coating, and the bonding force between the two zinc coatings and the substrate is stronger than that between the conventional zinc coating and the substrate, so that the adhesive force of the whole zinc coating on the substrate is obviously increased, and the stability of the coating is further improved.
As a preferable scheme, the anode of the electroplating reaction is a pure zinc plate, and the purity is 99.9%.
The present application further provides a plating solution for boric acid-free chloride electrogalvanizing a substrate surface, the plating solution comprising: zinc chloride, potassium chloride, lactic acid, sodium benzoate, 2-oxoglutarate and water, wherein the pH value of the electroplating solution is 5-6.
Preferably, the plating solution includes: 70-150 g/L of zinc chloride, 200g/L of potassium chloride, 5-20 g/L of lactic acid, 3-8 g/L of sodium benzoate, 10-20 g/L of 2-oxyglutaric acid and the balance of water.
Compared with the prior art, the technical scheme of the application has the following beneficial effects:
firstly, boric acid is not used in the electroplating solution system, the problem that the waste liquid containing boric acid is difficult to treat is solved, a large amount of industrial use is easy, and electroplating wastewater is convenient to treat; secondly, the electroplating solution has simple composition, common raw materials and lower cost, and besides, the solute and the additive are easy to dissolve in water, so that the electroplating solution is stable; lactic acid and 2-oxoglutarate are used as system additives, pH stability of the electroplating solution can be effectively maintained, precipitation phenomenon does not exist even if the electroplating solution is used for a long time, and the lactic acid has certain complexing capacity on zinc ions. In addition, the electroplating solution has low sensitivity to temperature, is nontoxic and environment-friendly, and does not corrode the reactor; the application does not use a large amount of brightening agent, softener and the like in the conventional chloride electrogalvanizing, and adopts a specific electroplating solution system and a specific electroplating process to obtain a galvanized layer which is fine and bright, has strong adhesive force and excellent corrosion resistance, reduces impurities in the galvanized layer and further improves the corrosion resistance of the galvanized layer. In conclusion, the electroplating solution system and the boric acid-free chloride electroplating process have higher use value, economic value and environmental value.
Detailed Description
In order to make the technical problems solved, the technical solutions adopted and the technical effects achieved by the present application more clear, the technical solutions of the embodiments of the present application will be described in further detail below, and it is obvious that the described embodiments are only some embodiments of the present application, but not all embodiments. All other embodiments, based on the embodiments of the application, which a person skilled in the art would obtain without making any inventive effort, are within the scope of the application.
It is noted that reference herein to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment may be included in at least one embodiment of the application. The appearances of such phrases in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. Those of skill in the art will explicitly and implicitly appreciate that the embodiments described herein may be combined with other embodiments.
The experimental methods in the following examples are conventional methods unless otherwise specified. Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
The substrates in the examples were pretreated as follows before use: removing oil, namely placing the substrate in a 1M NaOH solution for ultrasonic cleaning for 5min to clean oil stains on the surface; washing the deoiled base material with water for 5min; and (3) acid washing, namely soaking the washed base material in a mixed solution consisting of 0.5M dilute hydrochloric acid and 5g/L thiourea for 5min, washing with water, and drying in a drying oven for later use.
Example 1
Firstly, weighing zinc chloride, potassium chloride, sodium benzoate, 2-oxoglutarate and deionized water according to the proportion of 70g/L of zinc chloride, 200g/L of potassium chloride, 5g/L of lactic acid, 3g/L of sodium benzoate and 10g/L of 2-oxoglutarate, sequentially adding the zinc chloride and the potassium chloride into the deionized water, stirring until the zinc chloride and the potassium chloride are completely dissolved, sequentially adding 5g/L of lactic acid and 3g/L of sodium benzoate into the prepared solution under the stirring condition, continuously stirring until the lactic acid and the sodium benzoate are completely dissolved, slowly adding 10g/L of 2-oxoglutarate, uniformly mixing, and then adjusting the pH value of the electroplating solution to 5 by using 0.1M sodium hydroxide solution.
Adding the electroplating solution into an electroplating bath, taking 99.9% of pure zinc plates as anodes, and connecting the pretreated stainless steel as cathodes with a power supply for two timesConstant current electroplating. First, the current density was set at 0.1A/dm at 10 DEG C 2 Electroplating for 0.5min, heating the electroplating solution to 20deg.C, and setting current density to 1A/dm 2 Electroplating for 20min. After the electroplating is finished, the electroplating solution attached to the surface of the substrate is washed away by clean water, the substrate is placed into an oven, and the substrate is dried for 4 hours at 80 ℃ to obtain the metal piece with the electrogalvanized layer. The zinc coating obtained in the embodiment is a silver white zinc coating, has smooth and compact surface, no holes or burrs, and neat edges and no scorching phenomenon.
Example 2
Firstly, weighing zinc chloride, potassium chloride, sodium benzoate, 2-oxoglutarate and deionized water according to the proportion of 150g/L of zinc chloride, 200g/L of potassium chloride, 20g/L of lactic acid, 8g/L of sodium benzoate and 20g/L of 2-oxoglutarate, sequentially adding the zinc chloride and the potassium chloride into the deionized water, stirring until the zinc chloride and the potassium chloride are completely dissolved, sequentially adding 20g/L of lactic acid and 8g/L of sodium benzoate into the prepared solution under the stirring condition, continuously stirring until the lactic acid and the sodium benzoate are completely dissolved, slowly adding 20g/L of 2-oxoglutarate, uniformly mixing, and then adjusting the pH value of the electroplating solution to 6 by using 0.1M sodium hydroxide solution.
And (3) adding the electroplating solution into an electroplating bath, and carrying out constant current electroplating twice by taking 99.9% of pure zinc plates as anodes and taking the pretreated copper foil as a cathode to be connected with a power supply. First, the current density was set at 0.5A/dm at 20 DEG C 2 Electroplating for 2min, heating the electroplating solution to 50deg.C, and setting current density to 5A/dm 2 Electroplating for 50min. After the electroplating is finished, the electroplating solution attached to the surface of the substrate is washed away by clean water, the substrate is placed into an oven, and the substrate is dried for 4 hours at 80 ℃ to obtain the metal piece with the electrogalvanized layer. The zinc coating obtained in the embodiment is a silver white zinc coating, has smooth and compact surface, no holes or burrs, and neat edges and no scorching phenomenon.
Example 3
Firstly, weighing zinc chloride, potassium chloride, sodium benzoate, 2-oxoglutarate and deionized water according to the proportion of 80g/L of zinc chloride, 200g/L of potassium chloride, 10g/L of lactic acid, 5g/L of sodium benzoate and 15g/L of 2-oxoglutarate, sequentially adding the zinc chloride and the potassium chloride into the deionized water, stirring until the zinc chloride and the potassium chloride are completely dissolved, sequentially adding 10g/L of lactic acid and 5g/L of sodium benzoate into the prepared solution under the stirring condition, continuously stirring until the lactic acid and the sodium benzoate are completely dissolved, slowly adding 15g/L of 2-oxoglutarate, uniformly mixing, and then adjusting the pH value of the electroplating solution to 6 by using 0.1M sodium hydroxide solution.
And (3) adding the electroplating solution into an electroplating bath, and carrying out constant current electroplating twice by taking 99.9% of pure zinc plates as anodes and taking the pretreated iron sheets as cathodes to be connected with a power supply. First, the current density was set at 0.3A/dm at 20 DEG C 2 Electroplating for 1min, heating the electroplating solution to 30deg.C, and setting current density to 4A/dm 2 Electroplating for 30min. After the electroplating is finished, the electroplating solution attached to the surface of the substrate is washed away by clean water, the substrate is placed into an oven, and the substrate is dried for 4 hours at 80 ℃ to obtain the metal piece with the electrogalvanized layer. The zinc plating layer obtained in the embodiment is a silver white zinc plating layer, the surface is smooth and compact, holes and burrs are avoided, the edge is neat and has no scorching phenomenon, the electroplating solution is free from turbidity after long-time use, and the zinc plating layer is bright and compact.
Comparative example 1
Firstly, weighing zinc chloride, potassium chloride, sodium benzoate, 2-oxoglutarate and deionized water according to the proportion of 80g/L of zinc chloride, 200g/L of potassium chloride, 5g/L of sodium benzoate and 15g/L of 2-oxoglutarate, sequentially adding the zinc chloride and the potassium chloride into the deionized water, stirring until the zinc chloride and the potassium chloride are completely dissolved, adding 5g/L of sodium benzoate into the prepared solution under the stirring condition, continuously stirring until the sodium benzoate is completely dissolved, slowly adding 15g/L of 2-oxoglutarate after the sodium benzoate is continuously stirred until the sodium benzoate is completely dissolved, and regulating the pH of the electroplating solution to 6 by using a 0.1M sodium hydroxide solution after the uniform mixing.
And (3) adding the electroplating solution into an electroplating bath, and carrying out constant current electroplating twice by taking 99.9% of pure zinc plates as anodes and taking the pretreated iron sheets as cathodes to be connected with a power supply. First, the current density was set at 0.3A/dm at 20 DEG C 2 Electroplating for 1min, heating the electroplating solution to 30deg.C, and setting current density to 4A/dm 2 Electroplating for 30min. After the electroplating is finished, the electroplating solution attached to the surface of the substrate is washed away by clean water, the substrate is placed into an oven, and the substrate is dried for 4 hours at 80 ℃ to obtain the metal piece with the electrogalvanized layer. The zinc coating obtained in this example is a grey zinc coating with a rough surfaceA few holes are formed, and part of the non-galvanized area is arranged at the edge.
Comparative example 2
Firstly, weighing zinc chloride, potassium chloride, lactic acid, sodium benzoate and deionized water according to the proportion of 80g/L of zinc chloride, 200g/L of potassium chloride, 10g/L of lactic acid and 5g/L of sodium benzoate, sequentially adding the zinc chloride and the potassium chloride into the deionized water, stirring until the zinc chloride and the potassium chloride are completely dissolved, sequentially adding 10g/L of lactic acid and 5g/L of sodium benzoate into the prepared solution under the stirring condition, continuously stirring until the mixture is uniform, and then adjusting the pH of the electroplating solution to 6 by using 0.1M sodium hydroxide solution.
And (3) adding the electroplating solution into an electroplating bath, and carrying out constant current electroplating twice by taking 99.9% of pure zinc plates as anodes and taking the pretreated iron sheets as cathodes to be connected with a power supply. First, the current density was set at 0.3A/dm at 20 DEG C 2 Electroplating for 1min, heating the electroplating solution to 30deg.C, and setting current density to 4A/dm 2 Electroplating for 30min. After the electroplating is finished, the electroplating solution attached to the surface of the substrate is washed away by clean water, the substrate is placed into an oven, and the substrate is dried for 4 hours at 80 ℃ to obtain the metal piece with the electrogalvanized layer. The zinc plating layer obtained in the embodiment is gray zinc plating layer, has rough surface, more holes and more unplated areas at the edge, and has obvious pH change after the electroplating solution is used for a period of time, and the electroplating solution is turbid.
Comparative example 3
Firstly, weighing zinc chloride, potassium chloride, sodium benzoate, 2-oxoglutarate and deionized water according to the proportion of 80g/L of zinc chloride, 200g/L of potassium chloride, 3g/L of lactic acid, 5g/L of sodium benzoate and 8g/L of 2-oxoglutarate, sequentially adding the zinc chloride and the potassium chloride into the deionized water, stirring until the zinc chloride and the potassium chloride are completely dissolved, sequentially adding 3g/L of lactic acid and 5g/L of sodium benzoate into the prepared solution under the stirring condition, continuously stirring until the lactic acid and the sodium benzoate are completely dissolved, slowly adding 8g/L of 2-oxoglutarate, uniformly mixing, and then adjusting the pH value of the electroplating solution to 6 by using 0.1M sodium hydroxide solution.
And (3) adding the electroplating solution into an electroplating bath, and carrying out constant current electroplating twice by taking 99.9% of pure zinc plates as anodes and taking the pretreated iron sheets as cathodes to be connected with a power supply. First, the current density was set at 0.3A/dm at 20 DEG C 2 Electroplating for 1min, heating the electroplating solution to 30deg.C, and setting current density to 4A/dm 2 Electroplating for 30min. After the electroplating is finished, the electroplating solution attached to the surface of the substrate is washed away by clean water, the substrate is placed into an oven, and the substrate is dried for 4 hours at 80 ℃ to obtain the metal piece with the electrogalvanized layer. The zinc plating layer obtained in the embodiment has silvery white zinc plating layer in the middle, gray edges, smooth and compact surfaces, scattered holes and rough edge parts.
Comparative example 4
Firstly, weighing zinc chloride, potassium chloride, sodium benzoate, 2-oxoglutarate and deionized water according to the proportion of 80g/L of zinc chloride, 200g/L of potassium chloride, 10g/L of lactic acid, 5g/L of sodium benzoate and 15g/L of 2-oxoglutarate, sequentially adding the zinc chloride and the potassium chloride into the deionized water, stirring until the zinc chloride and the potassium chloride are completely dissolved, sequentially adding 10g/L of lactic acid and 5g/L of sodium benzoate into the prepared solution under the stirring condition, continuously stirring until the lactic acid and the sodium benzoate are completely dissolved, slowly adding 15g/L of 2-oxoglutarate, uniformly mixing, and then adjusting the pH value of the electroplating solution to 6 by using 0.1M sodium hydroxide solution.
And (3) adding the electroplating solution into an electroplating bath, and carrying out constant current electroplating by taking 99.9% of pure zinc plates as anodes and taking the pretreated iron sheets as cathodes to be connected with a power supply. At 30℃and a current density of 4A/dm 2 Electroplating for 30min. After the electroplating is finished, the electroplating solution attached to the surface of the substrate is washed away by clean water, the substrate is placed into an oven, and the substrate is dried for 4 hours at 80 ℃ to obtain the metal piece with the electrogalvanized layer. The zinc plating layer obtained in the embodiment is a silver white zinc plating layer, the surface is smooth and compact, holes and burrs are avoided, scattered unplated points appear on the edge, and cracks appear on the plating layer in part of the edge area.
Through the comparison of the above examples and comparative examples, the electrogalvanized layer prepared by adopting the specific electroplating solution and the electroplating process matched with the specific electroplating solution effectively solves the problem of harm of boric acid in conventional chloride galvanization, and the prepared electrogalvanized layer has strong binding force with the surface of a substrate, smooth and bright surface, qualified appearance and strong overall corrosion resistance.
While a boric acid-free chloride electrogalvanizing method has been described in detail, the foregoing is a further detailed description of the application in connection with specific preferred embodiments, and it is not intended that the application be limited to such description. For those skilled in the art, the architecture of the application can be flexible and changeable without departing from the concept of the application, and serial products can be derived. But a few simple derivatives or substitutions should be construed as falling within the scope of the application as defined by the appended claims.
Claims (9)
1. A boric acid-free chloride electrogalvanizing method, characterized by comprising the steps of: 1) Pretreating a substrate; 2) Placing the pretreated substrate as a cathode in an electroplating solution for electroplating, wherein the electroplating solution comprises the following components: zinc chloride, potassium chloride, lactic acid, sodium benzoate, 2-oxoglutarate and water; 3) After the electroplating is finished, washing the base material and the electroplating liquid on the surface of the plating layer by using clear water, putting the base material into an oven, and drying at 80 ℃ for 4 hours to obtain the electrogalvanized layer.
2. The boric acid chloride free electrogalvanizing method of claim 1, wherein the substrate is stainless steel, copper foil, iron sheet.
3. A boric acid chloride free electrogalvanizing method according to claim 1, characterized in that the pretreatment of the substrate comprises: removing oil, and placing the substrate in a 1M NaOH solution for ultrasonic cleaning for 5min; washing the substrate with water for 5min; and (3) pickling, namely soaking the substrate after water washing in a pickling solution for 5min, wherein the pickling solution is prepared by mixing 5g/L thiourea with 0.5M dilute hydrochloric acid, washing the substrate with water after pickling, and drying.
4. A boric acid chloride free electrogalvanizing method according to claim 1, characterized in that the plating solution comprises: 70-150 g/L of zinc chloride, 200g/L of potassium chloride, 5-20 g/L of lactic acid, 3-8 g/L of sodium benzoate, 10-20 g/L of 2-oxoglutarate, and the balance of water, wherein the pH value is 5-6.
5. The method of zinc chloride plating without boric acid according to claim 1, wherein the process of zinc plating with the plating solution comprises two stages, wherein the substrate is first subjected to a cathode current density of 0.1 to 0.5A/dm at 10 to 20 °c 2 Electroplating for 0.5-2 min, and then at 20-50 deg.C, cathode current density is 1-5A/dm 2 Electroplating for 20-50 min.
6. The method of claim 1, wherein the anode of the electroplating reaction is a pure zinc sheet with a purity of 99.9%.
7. The boric acid chloride-free electrogalvanizing method of claim 4, wherein the plating solution is prepared by the following steps: weighing 70-150 g/L of zinc chloride as main salt and 200g/L of potassium chloride according to a proportion, sequentially dissolving the zinc chloride and the potassium chloride into deionized water, sequentially adding 5-20 g/L of lactic acid and 3-8 g/L of sodium benzoate into the deionized water under stirring, continuously stirring until the zinc chloride and the potassium chloride are dissolved, then adding 10-20 g/L of 2-oxoglutarate, and adjusting the pH of the electroplating solution to 5-6 by using 0.1M sodium hydroxide solution.
8. A plating solution for use in the boric acid chloride-free electrogalvanizing method of claim 1, characterized in that the plating solution is used for surface electrogalvanizing a substrate, said plating solution comprising: zinc chloride, potassium chloride, lactic acid, sodium benzoate, 2-oxoglutarate and water, wherein the pH value of the electroplating solution is 5-6.
9. The plating solution of claim 8, wherein said plating solution comprises: 70-150 g/L of zinc chloride, 200g/L of potassium chloride, 5-20 g/L of lactic acid, 3-8 g/L of sodium benzoate, 10-20 g/L of 2-oxyglutaric acid and the balance of water.
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| CN117552059A (en) * | 2024-01-11 | 2024-02-13 | 深圳市协成达科技有限公司 | Zinc-plating electroplating solution and preparation method and application thereof |
| CN117552059B (en) * | 2024-01-11 | 2024-03-15 | 深圳市协成达科技有限公司 | Zinc-plating electroplating solution and preparation method and application thereof |
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