CN114457394B - Electrolyte and preparation method and application thereof - Google Patents
Electrolyte and preparation method and application thereof Download PDFInfo
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- CN114457394B CN114457394B CN202210052208.2A CN202210052208A CN114457394B CN 114457394 B CN114457394 B CN 114457394B CN 202210052208 A CN202210052208 A CN 202210052208A CN 114457394 B CN114457394 B CN 114457394B
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- 239000003792 electrolyte Substances 0.000 title claims abstract description 73
- 238000002360 preparation method Methods 0.000 title abstract description 7
- 239000011701 zinc Substances 0.000 claims abstract description 78
- 239000002608 ionic liquid Substances 0.000 claims abstract description 77
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims abstract description 70
- 229910052725 zinc Inorganic materials 0.000 claims abstract description 70
- 229910052751 metal Inorganic materials 0.000 claims abstract description 52
- 239000002184 metal Substances 0.000 claims abstract description 52
- LPXDNEQTGPFOPF-UHFFFAOYSA-N hydron;1h-imidazol-1-ium;phosphate Chemical compound C1=CNC=N1.OP(O)(O)=O LPXDNEQTGPFOPF-UHFFFAOYSA-N 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 43
- 150000001875 compounds Chemical class 0.000 claims abstract description 34
- 238000009713 electroplating Methods 0.000 claims abstract description 32
- 239000002904 solvent Substances 0.000 claims abstract description 14
- 150000002500 ions Chemical class 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 44
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 42
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- 239000003085 diluting agent Substances 0.000 claims description 25
- 239000011248 coating agent Substances 0.000 claims description 22
- 238000000576 coating method Methods 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 21
- 235000005074 zinc chloride Nutrition 0.000 claims description 21
- 239000011592 zinc chloride Substances 0.000 claims description 21
- -1 1-octyl-3-methylimidazole trioctyl phosphate Chemical compound 0.000 claims description 20
- 238000004140 cleaning Methods 0.000 claims description 16
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 claims description 14
- 238000010438 heat treatment Methods 0.000 claims description 12
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- LICFKPSOVGQYGX-UHFFFAOYSA-N P(=O)(OCC)(OCC)OCC.C(C)N1CN(C=C1)C Chemical compound P(=O)(OCC)(OCC)OCC.C(C)N1CN(C=C1)C LICFKPSOVGQYGX-UHFFFAOYSA-N 0.000 claims description 9
- 238000001816 cooling Methods 0.000 claims description 8
- 229960001763 zinc sulfate Drugs 0.000 claims description 8
- 229910000368 zinc sulfate Inorganic materials 0.000 claims description 8
- 229910019142 PO4 Inorganic materials 0.000 claims description 7
- 239000010452 phosphate Substances 0.000 claims description 7
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 5
- BPYFQLZSUUHXNV-UHFFFAOYSA-N P(=O)(OCCCC)(OCCCC)OCCCC.C(CCC)N1CN(C=C1)C Chemical compound P(=O)(OCCCC)(OCCCC)OCCCC.C(CCC)N1CN(C=C1)C BPYFQLZSUUHXNV-UHFFFAOYSA-N 0.000 claims description 3
- 239000001257 hydrogen Substances 0.000 abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000243 solution Substances 0.000 description 34
- 238000007747 plating Methods 0.000 description 21
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 11
- 238000003756 stirring Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 7
- 229910000831 Steel Inorganic materials 0.000 description 7
- 229910052802 copper Inorganic materials 0.000 description 7
- 239000010949 copper Substances 0.000 description 7
- 239000010959 steel Substances 0.000 description 7
- 230000001681 protective effect Effects 0.000 description 6
- 150000003752 zinc compounds Chemical class 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 5
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 238000004090 dissolution Methods 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000003912 environmental pollution Methods 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- GTLDTDOJJJZVBW-UHFFFAOYSA-N zinc cyanide Chemical compound [Zn+2].N#[C-].N#[C-] GTLDTDOJJJZVBW-UHFFFAOYSA-N 0.000 description 4
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 3
- 150000001450 anions Chemical class 0.000 description 3
- 238000010668 complexation reaction Methods 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 238000006356 dehydrogenation reaction Methods 0.000 description 3
- 238000005868 electrolysis reaction Methods 0.000 description 3
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 3
- KAIPKTYOBMEXRR-UHFFFAOYSA-N 1-butyl-3-methyl-2h-imidazole Chemical compound CCCCN1CN(C)C=C1 KAIPKTYOBMEXRR-UHFFFAOYSA-N 0.000 description 2
- KTUWFYALZIAAGE-UHFFFAOYSA-N 1-methyl-3-octyl-2h-imidazole Chemical compound CCCCCCCCN1CN(C)C=C1 KTUWFYALZIAAGE-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 239000011253 protective coating Substances 0.000 description 2
- 238000004381 surface treatment Methods 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 231100000167 toxic agent Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 239000003440 toxic substance Substances 0.000 description 2
- STCOOQWBFONSKY-UHFFFAOYSA-N tributyl phosphate Chemical compound CCCCOP(=O)(OCCCC)OCCCC STCOOQWBFONSKY-UHFFFAOYSA-N 0.000 description 2
- YEVQZPWSVWZAOB-UHFFFAOYSA-N 2-(bromomethyl)-1-iodo-4-(trifluoromethyl)benzene Chemical compound FC(F)(F)C1=CC=C(I)C(CBr)=C1 YEVQZPWSVWZAOB-UHFFFAOYSA-N 0.000 description 1
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- JMMWKPVZQRWMSS-UHFFFAOYSA-N isopropanol acetate Natural products CC(C)OC(C)=O JMMWKPVZQRWMSS-UHFFFAOYSA-N 0.000 description 1
- 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 1
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910000601 superalloy Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 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
- C25D3/66—Electroplating: Baths therefor from melts
- C25D3/665—Electroplating: Baths therefor from melts from ionic liquids
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)
- Electroplating Methods And Accessories (AREA)
Abstract
The application discloses an electrolyte, a preparation method and application thereof, and relates to the technical field of metal surface electroplating. The electrolyte comprises a solute and a solvent; the solute comprises a zinc-containing compound, and the solventComprises imidazole phosphate ionic liquid; dissolving the zinc-containing compound in imidazole phosphate ionic liquid to obtain electrolyte for electrogalvanizing metal parts; wherein Zn in the zinc-containing compound 2+ The concentration of ions in the electrolyte is 6.4-64 g/L. The application aims to solve the technical problems of high pollution and hydrogen embrittlement threat existing in the electrogalvanizing process in the prior art.
Description
Technical Field
The application relates to the technical field of metal surface electroplating, in particular to an electrolyte and a preparation method and application thereof.
Background
The aviation parts use a large number of steel parts, corrosion easily occurs in the use process, and the galvanized layer is one of the most widely used protective coatings in the steel parts, and has excellent protective performance. The traditional electrogalvanizing process is an aqueous solution-based electrogalvanizing process, and common electrogalvanizing processes such as cyanide, zincate, potassium chloride and the like are adopted.
The most widely used electrogalvanizing process in the field of aviation surface treatment is the cyanide electrogalvanizing process. The cyanide zinc plating protective performance, the uniform plating capacity and the deep plating capacity of the plating solution are all superior to those of cyanide-free plating solution, and the cyanide zinc plating protective solution is suitable for plating parts with complex shapes and thicker plating layers. However, cyanide is a highly toxic substance, and has serious environmental pollution and high environmental treatment cost, so that many aviation manufacturing enterprises are developing cyanide-free electrogalvanizing processes at present. Most of aviation parts have higher strength and very strict requirements on the quality of the parts, and serious hydrogen embrittlement threats exist in both cyanide electrogalvanizing technology and non-cyanide electrogalvanizing technology under development, and long-time high-temperature baking is needed after the electrogalvanizing to remove hydrogen diffused into a steel matrix in the process of the electrogalvanizing. The dehydrogenation process not only increases costs, but also does not completely eliminate the hydrogen embrittlement threat.
Disclosure of Invention
The main purpose of the application is to provide an electrolyte, a preparation method and application thereof, and aims to solve the technical problem that the electrogalvanizing process in the prior art has hydrogen embrittlement threat.
To achieve the above object, the present application proposes an electrolyte comprising a solute and a solvent;
the solute comprises a zinc-containing compound, and the solvent comprises an imidazole phosphate ionic liquid;
dissolving the zinc-containing compound in imidazole phosphate ionic liquid to obtain electrolyte for electrogalvanizing metal parts;
wherein Zn in the zinc-containing compound 2+ The concentration of ions in the electrolyte is 6.4-64 g/L.
Optionally, the zinc-containing compound includes:
at least one of zinc chloride, zinc sulfate and zinc nitrate.
Optionally, the imidazole phosphate ionic liquid comprises:
at least one of triethyl 1-ethyl-3-methylimidazole phosphate, tributyl 1-butyl-3-methylimidazole phosphate and trioctyl 1-octyl-3-methylimidazole phosphate.
Optionally, the electrolyte further comprises:
a diluent.
Optionally, the concentration of the diluent in the electrolyte is 0-220 g/L.
Optionally, the diluent comprises:
at least one of ethanol, ethylene glycol, n-propanol, isopropanol, ethyl acetate and water.
Based on the same purpose, the application also provides a preparation method of the electrolyte, which comprises the following steps:
after dissolving the zinc-containing compound in the imidazole phosphate ionic liquid, obtaining an ionic liquid solution;
and cooling to 30-90 ℃, and adding a diluent into the ionic liquid solution to obtain the electrolyte.
Optionally, the step of obtaining an ionic liquid solution after dissolving the zinc-containing compound in the imidazole phosphate ionic liquid comprises:
and heating the imidazole phosphate ionic liquid to 80-120 ℃, and adding the zinc-containing compound to dissolve the zinc-containing compound to obtain an ionic liquid solution.
For the same purpose, the application also provides the application of the electrolyte, and the electrolyte is used for electrogalvanizing metal parts through the following steps:
taking a part to be plated with metal as a cathode of the electroplating bath, taking a pure zinc plate as an anode of the electroplating bath, and immersing the part to be plated with metal and the pure zinc plate in the electrolyte according to any one of claims 1-6 for electroplating treatment to obtain a plated metal part;
and cleaning the electroplated metal part with ethanol and water in sequence to obtain the metal part with the zinc coating.
Optionally, the plating treatment conditions include:
the current density is 20-50 mA/cm 2 The working temperature is 30-90 ℃.
The electrolyte comprises a solute and a solvent; the solute comprises a zinc-containing compound, and the solvent comprises an imidazole phosphate ionic liquid; and dissolving the zinc-containing compound in the imidazole phosphate ionic liquid to obtain the electrolyte for carrying out electrogalvanizing treatment on the metal parts. Compared with the water solvent in the existing electrolyte, the solvent of the electrolyte is the imidazole phosphate ionic liquid, and the imidazole phosphate ionic liquid mainly consists of dialkyl imidazole salt cations and dialkyl phosphate anions and completely consists of ions, so that the hydrogen evolution phenomenon can not occur, and the hydrogen embrittlement risk caused by water electrolysis in the electroplating process is eliminated; the electrolyte is cyanide-free electrolyte, so that the electrolyte does not contain toxic and harmful substances, is environment-friendly, and avoids the problem of environmental pollution. In addition, anions in the imidazole phosphate ionic liquid are dialkyl phosphate anions, can generate complexation with zinc ions, and can inhibit zinc branch growth in the electroplating process, so that the quality of a coating is improved.
Drawings
In order to more clearly illustrate the embodiments of the present application or the technical solutions in the prior art, the drawings that are required in the embodiments or the description of the prior art will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and that other drawings may be obtained from the structures shown in these drawings without inventive effort to a person of ordinary skill in the art.
FIG. 1 is a schematic flow chart of a method for preparing an electrolyte and electrogalvanizing according to the embodiment of the application;
FIG. 2 is a topographical view of a zinc coating obtained in accordance with an embodiment of the present application;
FIG. 3 is a topographical view of a zinc coating obtained in example two of the present application.
The realization, functional characteristics and advantages of the present application will be further described with reference to the embodiments, referring to the attached drawings.
Detailed Description
The following description of the embodiments of the present application will be made clearly and fully with reference to the accompanying drawings, in which it is evident that the embodiments described are only some, but not all, of the embodiments of the present application. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments herein without making any inventive effort, are intended to be within the scope of the present application.
The aviation parts use a large number of steel parts, corrosion easily occurs in the use process, and the galvanized layer is one of the most widely used protective coatings in the steel parts, and has excellent protective performance. The traditional electrogalvanizing process is an aqueous solution-based electrogalvanizing process, and common electrogalvanizing processes such as cyanide, zincate, potassium chloride and the like are adopted.
The most widely used electrogalvanizing process in the field of aviation surface treatment is the cyanide electrogalvanizing process. The cyanide zinc plating protective performance, the uniform plating capacity and the deep plating capacity of the plating solution are all superior to those of cyanide-free plating solution, and the cyanide zinc plating protective solution is suitable for plating parts with complex shapes and thicker plating layers. However, cyanide is a highly toxic substance, and has serious environmental pollution and high environmental treatment cost, so that many aviation manufacturing enterprises are developing cyanide-free electrogalvanizing processes at present. Most of aviation parts have higher strength and very strict requirements on the quality of the parts, and serious hydrogen embrittlement threats exist in both cyanide electrogalvanizing technology and non-cyanide electrogalvanizing technology under development, and long-time high-temperature baking is needed after the electrogalvanizing to remove hydrogen diffused into a steel matrix in the process of the electrogalvanizing. The dehydrogenation process not only increases costs, but also does not completely eliminate the hydrogen embrittlement threat.
In view of the technical problems of the prior electrogalvanizing method, the application provides an electrolyte, which comprises a solute and a solvent;
the solute comprises a zinc-containing compound, and the solvent comprises an imidazole phosphate ionic liquid;
dissolving the zinc-containing compound in imidazole phosphate ionic liquid to obtain electrolyte for electrogalvanizing metal parts;
wherein Zn in the zinc-containing compound 2+ The concentration of ions in the electrolyte is 6.4-64 g/L.
The electrolyte adopts ionic liquid to replace solvent water in traditional electrolyte, and the ionic liquid does not contain water, so that the electrolytic reaction of water can not occur, and hydrogen is not evolved to cause hydrogen embrittlement threat. In addition, the electrolyte does not contain toxic and harmful substances such as cyanide and the like, and environmental pollution is avoided.
As an embodiment of the present application, the zinc-containing compound includes:
at least one of zinc chloride, zinc sulfate and zinc nitrate.
Although the solubility of zinc chloride, zinc sulfate or zinc nitrate is different, the concentration of the zinc chloride, the zinc sulfate or the zinc nitrate in the electrolyte can be Zn 2+ The ions are calculated, i.e. Zn in the zinc-containing compound 2+ The concentration of ions in the electrolyte is 6.4-64 g/L; of course, in some embodiments, the amount of zinc compound added may be adjusted to ensure the electroplating effect, such as Zn in zinc chloride when the zinc compound is zinc chloride 2+ The concentration of ions in the electrolyte is 64g/L; such asWhen the zinc-containing compound is zinc sulfate, zn in the zinc sulfate 2+ The concentration of ions in the electrolyte is 6.4g/L; such as Zn in the zinc-containing compound when the zinc-containing compound is zinc nitrate 2+ The concentration of ions in the electrolyte was 32g/L.
As an embodiment of the present application, the imidazole phosphate ionic liquid includes:
at least one of triethyl 1-ethyl-3-methylimidazole phosphate, tributyl 1-butyl-3-methylimidazole phosphate and trioctyl 1-octyl-3-methylimidazole phosphate.
The imidazole phosphate ionic liquid consists of dialkyl imidazole salt cations and dialkyl phosphate anions, and is an ionic liquid insensitive to oxygen and moisture. Therefore, the electrolyte prepared by taking the imidazole phosphate ionic liquid as a solvent is used for electrogalvanizing the metal parts, and can be exposed in the air; the method avoids the phenomenon that like other ionic liquids which are sensitive to oxygen and water, the method can only be operated in a glove box and is not suitable for industrial application. In addition, anions in the imidazole phosphate ionic liquid are dialkyl phosphate anions, can generate complexation with zinc ions, and can inhibit zinc branch growth in the electroplating process, so that the quality of a coating is improved.
When the imidazole phosphate ionic liquid is a combination of two or three of 1-ethyl-3-methylimidazole triethyl phosphate, 1-butyl-3-methylimidazole tributyl phosphate and 1-octyl-3-methylimidazole trioctyl phosphate, the mixture can be mixed in any ratio.
As an embodiment of the present application, the electrolyte further includes:
a diluent.
As described above, the imidazole phosphate ionic liquid in the electrolyte can be 1-ethyl-3-methylimidazole triethyl phosphate, 1-butyl-3-methylimidazole tributyl phosphate, 1-octyl-3-methylimidazole trioctyl phosphate, or a combination of two or three of the above. While the viscosity of ionic liquid solutions composed of different components is different. When the viscosity of the ionic liquid solution is higher, a diluent is added into the ionic liquid solution to dilute the ionic liquid solution.
Optionally, the concentration of the diluent in the electrolyte is 0-220 g/L; in certain embodiments of the present application, when the concentration of the diluent in the electrolyte is 0g/L, it is stated that in these embodiments, the ionic liquid solution has sufficiently low viscosity, good fluidity, and a high mass transfer rate of each ion in the ionic liquid solution; however, it is not to be said that the more the mass of the diluent in the electrolyte is, for example, when the diluent is water, the more the diluent is used in the range described herein, and because the water and the cations in the ionic liquid described herein are in a complex state, the water is not prone to hydrogen evolution; however, if the amount is too large, even if the water and cations in the ionic liquid are in a complex state, the risk of hydrogen evolution exists; if the amount of the diluent is too high, the current efficiency is low, that is, the ratio of the amount of the substance actually deposited or dissolved on the electrode to the precipitation or dissolution amount calculated by theory is low at the time of electrolysis, which is not preferable.
The foregoing water and glycol are merely illustrative of the amounts of diluents described herein, including but not limited to water and glycol, which may also be ethanol, n-propanol, isopropanol or ethyl acetate; the amount is likewise adjusted according to the viscosity of the ionic liquid solution obtained.
Based on the same inventive concept, the embodiment of the application also provides a preparation method of the electrolyte, which comprises the following steps:
after dissolving the zinc-containing compound in the imidazole phosphate ionic liquid, obtaining an ionic liquid solution;
and cooling to 30-90 ℃, and adding the diluent into the ionic liquid solution to obtain the electrolyte.
In some embodiments of the present application, the step of obtaining an ionic liquid solution after dissolving the zinc-containing compound in the imidazole phosphate ionic liquid comprises:
and heating the imidazole phosphate ionic liquid to 80-120 ℃, and adding the zinc-containing compound to dissolve the zinc-containing compound to obtain an ionic liquid solution.
The method comprises the steps of heating the imidazole phosphate ionic liquid to 80-120 ℃, adding the zinc compound, and taking the dissolution rate of the zinc compound in the imidazole phosphate ionic liquid into consideration, so as to improve the dissolution rate of the zinc compound in the imidazole phosphate ionic liquid, wherein in the preferred scheme, the zinc compound is added for dissolution after the imidazole phosphate ionic liquid is heated to 80-120 ℃. However, if the temperature of the imidazole phosphate ionic liquid is increased to more than 120 ℃, the ionic liquid is easily decomposed, and the rate of the imidazole phosphate ionic liquid is not obviously increased due to excessive energy consumption, so that the imidazole phosphate ionic liquid is not recommended.
In some embodiments of the present application, the ionic liquid solution is cooled to 30-90 ℃, and then the diluent is added into the ionic liquid solution, because the alcohols such as ethanol and glycol are volatile substances, if the system temperature is too high, the diluent will volatilize.
Based on the same inventive concept, embodiments of the present application also provide for the use of an electrolyte as described above for electrogalvanizing a metal part by:
taking a part to be plated with metal as a cathode of the electroplating bath, taking a pure zinc plate as an anode of the electroplating bath, immersing the part to be plated with metal and the pure zinc plate in the electrolyte for electroplating treatment, and obtaining the electroplated metal part;
and cleaning the electroplated metal part with ethanol and water in sequence to obtain the metal part with the zinc coating.
The metal part with zinc coating obtained by the electrogalvanizing step overcomes the hydrogen embrittlement threat caused by the traditional electroplating method, and does not need to carry out the subsequent dehydrogenation step; the cleaning treatment is sequentially performed through ethanol and water, so that the electrolyte remained on the surface of the electroplated metal part is in a hydrophobic state, and if the electrolyte is directly washed by water in the traditional method, the cleaning is incomplete, and the application of the electrolyte in the subsequent processing of the surface part of the aircraft is affected; therefore, the method uses ethanol to clean the electrolyte remained on the surface of the electroplated metal part, and uses water to clean the residual ethanol, so that the metal part with the zinc coating obtained after cleaning can be directly applied to the processing of subsequent aviation parts, and corrosion of the metal part in the use process is avoided.
To ensure that the obtained electrogalvanized layer is more dense and complete, while avoiding obtaining some flocculent electrogalvanized layer, the electroplating rate is ensured, in some embodiments of the present application, the conditions of the electroplating process include: the current density is 20-50 mA/cm 2 The working temperature is 30-90 ℃. In some embodiments of the present application, the current density may be 20mA/cm 2 May also be 40mA/cm 2 Can also be 60mA/cm 2 。
It can be seen that the electrogalvanizing method optimizes the composition of the electrolyte and correspondingly optimizes the electroplating conditions and the subsequent cleaning steps, so that the finally obtained metal part with the electrogalvanizing layer has no hydrogen embrittlement threat and is environment-friendly. Meanwhile, the ionic liquid in the electrolyte is imidazole phosphate ionic liquid which is insensitive to oxygen and water, so that the ionic liquid can be directly operated in the air without being operated in a glove box, and compared with the existing electroplating process, the ionic liquid is more suitable for industrial production.
As shown in fig. 1, the present application should include the following steps during actual operation:
s1, dissolving the zinc-containing compound in imidazole phosphate ionic liquid to obtain an ionic liquid solution;
s2, cooling to 30-90 ℃, and adding a diluent into the ionic liquid solution to obtain an electrolyte;
s3, taking the part to be plated as a cathode of the electroplating bath and a pure zinc plate as an anode of the electroplating bath, and immersing the part to be plated and the pure zinc plate in the electrolyte for electroplating treatment to obtain an electroplated metal part;
and S4, cleaning the electroplated metal part by using ethanol and water in sequence to obtain the metal part with the zinc coating.
The electrolytic solution and the electrogalvanizing method described in the present application will be described in detail with reference to the following embodiments, and the following examples are examples of industrial red copper, but it is not meant that the present application can only perform electrogalvanizing treatment on industrial red copper, and the present application can also perform electrogalvanizing treatment on metal parts such as other copper and copper alloy products, various steel products, titanium and titanium alloy products, superalloy products, and the like.
Example 1
Heating the 1-ethyl-3-methylimidazole triethyl phosphate to 90 ℃, adding zinc chloride powder a small amount of times, stopping heating, and stirring to dissolve zinc chloride to obtain transparent pale yellow liquid, namely 1-ethyl-3-methylimidazole triethyl phosphate solution with zinc chloride content of 0.5 mol/L;
cooling to 60 ℃, adding ethylene glycol which is taken as a diluent according to 20% of the mass of the 1-ethyl-3-methylimidazole triethyl phosphate solution with zinc chloride content of 0.5mol/L, and stirring and mixing to obtain electrolyte;
the industrial red copper is used as a cathode, a pure zinc sheet is used as an anode to be connected with a power supply, and the current density is set to be 50mA/cm 2 Electroplating to obtain electroplated metal parts;
and cleaning the electroplated metal part with ethanol and water in sequence, and drying the electroplated metal part with compressed air after cleaning to obtain the metal part with the zinc coating.
The zinc coating obtained in the embodiment is a silver white zinc coating, the surface is smooth and compact, and the appearance of the coating is shown in figure 2.
Example 2
Heating the 1-ethyl-3-methylimidazole triethyl phosphate to 90 ℃, adding zinc chloride powder a small amount of times, stopping heating, and stirring to dissolve zinc chloride to obtain transparent pale yellow liquid, namely 1-ethyl-3-methylimidazole triethyl phosphate solution with zinc chloride content of 0.5 mol/L;
cooling to 60 ℃, adding water which is 5% of the mass of the 1-ethyl-3-methylimidazole triethyl phosphate solution with zinc chloride content of 0.5mol/L as a diluent, and stirring and mixing to obtain electrolyte;
the industrial red copper is used as a cathode, a pure zinc sheet is used as an anode to be connected with a power supply, and the current density is set to be 20mA/cm 2 Electroplating to obtain electroplated metal parts;
and cleaning the electroplated metal part with ethanol and water in sequence, and drying the electroplated metal part with compressed air after cleaning to obtain the metal part with the zinc coating.
The zinc plating layer obtained in the embodiment is silvery white with slight blue, the appearance of the plating layer is shown in fig. 3, the electroplating current efficiency is 97%, and no gas is generated at the anode in the electroplating process.
Example 3
Heating the tributyl 1-butyl-3-methylimidazole phosphate to 120 ℃, adding zinc sulfate powder a small amount of times, stopping heating, and stirring to dissolve zinc chloride to obtain a transparent light brown yellow liquid, namely ZnCl/1-butyl-3-methylimidazole tributyl phosphate solution with zinc chloride content of 0.5 mol/L;
cooling to 30 ℃, adding ethylene glycol which is taken as a diluent according to 40% of the mass of the ZnCl/1-butyl-3-methylimidazole tributyl phosphate solution with the zinc chloride content of 0.5mol/L, and stirring and mixing to obtain electrolyte;
the industrial red copper is used as a cathode, a pure zinc sheet is used as an anode to be connected with a power supply, and the current density is set to be 20mA/cm 2 Electroplating to obtain electroplated metal parts;
and cleaning the electroplated metal part with ethanol and water in sequence, and drying the electroplated metal part with compressed air after cleaning to obtain the metal part with the zinc coating.
The zinc coating obtained in the embodiment is a grey zinc coating, and the surface is smooth and compact.
Example 4
Heating the trioctyl 1-octyl-3-methylimidazole phosphate to 80 ℃, adding zinc nitrate powder a small amount of times, stopping heating, and stirring to dissolve zinc chloride to obtain a transparent brown yellow liquid, namely ZnCl/1-octyl-3-methylimidazole phosphate trioctyl solution with zinc chloride content of 0.5 mol/L;
cooling to 90 ℃, adding ethylene glycol which is 20% of the mass of the solution of ZnCl/1-octyl-3-methylimidazole trioctyl phosphate with zinc chloride content of 0.5mol/L as a diluent, and stirring and mixing to obtain electrolyte;
the industrial red copper is used as a cathode, a pure zinc sheet is used as an anode to be connected with a power supply, and the current density is set to be 50mA/cm 2 Electroplating to obtain electroplated metal parts;
and cleaning the electroplated metal part with ethanol and water in sequence, and drying the electroplated metal part with compressed air after cleaning to obtain the metal part with the zinc coating.
The zinc coating obtained in the embodiment is a grey zinc coating, and the surface is smooth and compact.
As can be seen by combining the drawings, the surface of the zinc plating layer obtained by the electrolyte and the electrogalvanizing method is smooth and compact, and the ionic liquid in the electrolyte is the imidazole phosphate ionic liquid which is insensitive to oxygen and water, so the zinc plating layer can be directly operated in the air without being operated in a glove box, and is more suitable for industrial production compared with the existing electrogalvanizing technology; meanwhile, the electrolyte adopts imidazole phosphate ionic liquid as a solvent instead of water in the existing electroplating process, so that the hydrogen embrittlement threat caused by hydrogen evolution after water electrolysis is avoided; in addition, anions in the imidazole phosphate ionic liquid are dialkyl phosphate anions, can generate complexation with zinc ions, and can inhibit zinc branch growth in the electroplating process, so that the quality of a coating is improved.
The foregoing description is only of the optional embodiments of the present application, and is not intended to limit the scope of the patent application, and all equivalent structural changes made by the specification and drawings of the present application or direct/indirect application in other related technical fields are included in the scope of the patent protection of the present application.
Claims (6)
1. An electrolyte, characterized in that the electrolyte consists of a solute, a solvent and a diluent;
the solute is a zinc-containing compound, and the solvent is an imidazole phosphate ionic liquid;
the diluent is at least one of ethanol, ethylene glycol, n-propanol, isopropanol, ethyl acetate and water;
the imidazole phosphate ionic liquid is at least one of 1-ethyl-3-methylimidazole triethyl phosphate, 1-butyl-3-methylimidazole tributyl phosphate and 1-octyl-3-methylimidazole trioctyl phosphate;
the imidazole phosphate ionic liquid consists of dialkyl imidazole salt cations and dialkyl phosphate anions;
dissolving the zinc-containing compound in imidazole phosphate ionic liquid to obtain electrolyte for electrogalvanizing metal parts;
wherein Zn in the zinc-containing compound 2+ The concentration of ions in the electrolyte is 6.4-64 g/L;
the concentration of the diluent in the electrolyte is 0-220 g/L.
2. The electrolyte of claim 1, wherein the zinc-containing compound comprises:
at least one of zinc chloride, zinc sulfate and zinc nitrate.
3. A method for preparing an electrolyte according to any one of claims 1-2, comprising the steps of:
after dissolving the zinc-containing compound in the imidazole phosphate ionic liquid, obtaining an ionic liquid solution;
and cooling to 30-90 ℃, and adding the diluent into the ionic liquid solution to obtain the electrolyte.
4. The method of claim 3, wherein the step of obtaining an ionic liquid solution after dissolving the zinc-containing compound in the imidazole phosphate ionic liquid comprises:
and heating the imidazole phosphate ionic liquid to 80-120 ℃, and adding the zinc-containing compound to dissolve the zinc-containing compound to obtain an ionic liquid solution.
5. Use of the electrolyte according to any one of claims 1-2 for electrogalvanizing metal parts by:
taking a part to be plated with metal as a cathode of the electroplating bath, taking a pure zinc plate as an anode of the electroplating bath, immersing the part to be plated with metal and the pure zinc plate in the electrolyte according to any one of claims 1-3 for electroplating treatment, and obtaining an electroplated metal part;
and cleaning the electroplated metal part with ethanol and water in sequence to obtain the metal part with the zinc coating.
6. The use of the electrolyte according to claim 5, wherein the conditions of the electroplating process comprise:
the current density is 20-50 mA/cm 2 The working temperature is 30-90 ℃.
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| CN105463535A (en) * | 2015-12-23 | 2016-04-06 | 苏州市金星工艺镀饰有限公司 | Electroplating method of cyanide-free copper-zinc electroplating solution containing ionic liquid |
| CN105483778A (en) * | 2015-12-23 | 2016-04-13 | 苏州市金星工艺镀饰有限公司 | Cyanide-free copper zinc electroplating solution containing ionic liquid |
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| CN105463535A (en) * | 2015-12-23 | 2016-04-06 | 苏州市金星工艺镀饰有限公司 | Electroplating method of cyanide-free copper-zinc electroplating solution containing ionic liquid |
| CN105483778A (en) * | 2015-12-23 | 2016-04-13 | 苏州市金星工艺镀饰有限公司 | Cyanide-free copper zinc electroplating solution containing ionic liquid |
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