CN108866586B - Electroplating solution for electrodepositing ferrochromium alloy in trivalent chromium system and preparation method thereof - Google Patents
Electroplating solution for electrodepositing ferrochromium alloy in trivalent chromium system and preparation method thereof Download PDFInfo
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- 239000011651 chromium Substances 0.000 title claims abstract description 80
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 78
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 77
- 238000009713 electroplating Methods 0.000 title claims abstract description 59
- 229910000604 Ferrochrome Inorganic materials 0.000 title claims abstract description 30
- 229910045601 alloy Inorganic materials 0.000 title claims abstract description 27
- 239000000956 alloy Substances 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 46
- 239000008139 complexing agent Substances 0.000 claims abstract description 45
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000003381 stabilizer Substances 0.000 claims abstract description 16
- 239000002131 composite material Substances 0.000 claims abstract description 15
- 239000004094 surface-active agent Substances 0.000 claims abstract description 15
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 7
- 239000006172 buffering agent Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 4
- 238000007747 plating Methods 0.000 claims description 37
- 238000000034 method Methods 0.000 claims description 14
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 239000000872 buffer Substances 0.000 claims description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 6
- PVNIIMVLHYAWGP-UHFFFAOYSA-N Niacin Chemical compound OC(=O)C1=CC=CN=C1 PVNIIMVLHYAWGP-UHFFFAOYSA-N 0.000 claims description 6
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- JPJALAQPGMAKDF-UHFFFAOYSA-N selenium dioxide Chemical compound O=[Se]=O JPJALAQPGMAKDF-UHFFFAOYSA-N 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- GIPOFCXYHMWROH-UHFFFAOYSA-L 2-aminoacetate;iron(2+) Chemical compound [Fe+2].NCC([O-])=O.NCC([O-])=O GIPOFCXYHMWROH-UHFFFAOYSA-L 0.000 claims description 5
- 229920000056 polyoxyethylene ether Polymers 0.000 claims description 5
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- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- YHMYGUUIMTVXNW-UHFFFAOYSA-N 1,3-dihydrobenzimidazole-2-thione Chemical compound C1=CC=C2NC(S)=NC2=C1 YHMYGUUIMTVXNW-UHFFFAOYSA-N 0.000 claims description 3
- JHUFGBSGINLPOW-UHFFFAOYSA-N 3-chloro-4-(trifluoromethoxy)benzoyl cyanide Chemical compound FC(F)(F)OC1=CC=C(C(=O)C#N)C=C1Cl JHUFGBSGINLPOW-UHFFFAOYSA-N 0.000 claims description 3
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 claims description 3
- PDQAZBWRQCGBEV-UHFFFAOYSA-N Ethylenethiourea Chemical compound S=C1NCCN1 PDQAZBWRQCGBEV-UHFFFAOYSA-N 0.000 claims description 3
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 3
- 229920001732 Lignosulfonate Polymers 0.000 claims description 3
- MPDZSHFDLURJRA-UHFFFAOYSA-J O.[K+].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound O.[K+].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MPDZSHFDLURJRA-UHFFFAOYSA-J 0.000 claims description 3
- 229920000805 Polyaspartic acid Polymers 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 3
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-N Succinic acid Natural products OC(=O)CCC(O)=O KDYFGRWQOYBRFD-UHFFFAOYSA-N 0.000 claims description 3
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-L adipate(2-) Chemical compound [O-]C(=O)CCCCC([O-])=O WNLRTRBMVRJNCN-UHFFFAOYSA-L 0.000 claims description 3
- 239000001361 adipic acid Substances 0.000 claims description 3
- 235000011037 adipic acid Nutrition 0.000 claims description 3
- RSYUFYQTACJFML-DZGCQCFKSA-N afzelechin Chemical compound C1([C@H]2OC3=CC(O)=CC(O)=C3C[C@@H]2O)=CC=C(O)C=C1 RSYUFYQTACJFML-DZGCQCFKSA-N 0.000 claims description 3
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 claims description 3
- 229910052921 ammonium sulfate Inorganic materials 0.000 claims description 3
- 235000011130 ammonium sulphate Nutrition 0.000 claims description 3
- 235000010323 ascorbic acid Nutrition 0.000 claims description 3
- 229960005070 ascorbic acid Drugs 0.000 claims description 3
- 239000011668 ascorbic acid Substances 0.000 claims description 3
- 235000003704 aspartic acid Nutrition 0.000 claims description 3
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000004327 boric acid Substances 0.000 claims description 3
- KDYFGRWQOYBRFD-NUQCWPJISA-N butanedioic acid Chemical compound O[14C](=O)CC[14C](O)=O KDYFGRWQOYBRFD-NUQCWPJISA-N 0.000 claims description 3
- 235000021466 carotenoid Nutrition 0.000 claims description 3
- 150000001747 carotenoids Chemical class 0.000 claims description 3
- KVIYQADEXNCDCB-UHFFFAOYSA-H chromium(3+);trisulfate;hydrate Chemical compound O.[Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KVIYQADEXNCDCB-UHFFFAOYSA-H 0.000 claims description 3
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical group [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 235000001968 nicotinic acid Nutrition 0.000 claims description 3
- 229960003512 nicotinic acid Drugs 0.000 claims description 3
- 239000011664 nicotinic acid Substances 0.000 claims description 3
- 235000006408 oxalic acid Nutrition 0.000 claims description 3
- XNGIFLGASWRNHJ-UHFFFAOYSA-L phthalate(2-) Chemical compound [O-]C(=O)C1=CC=CC=C1C([O-])=O XNGIFLGASWRNHJ-UHFFFAOYSA-L 0.000 claims description 3
- 108010064470 polyaspartate Proteins 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 3
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 3
- 235000011151 potassium sulphates Nutrition 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 235000010352 sodium erythorbate Nutrition 0.000 claims description 3
- 239000004320 sodium erythorbate Substances 0.000 claims description 3
- 235000019333 sodium laurylsulphate Nutrition 0.000 claims description 3
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 3
- 235000011152 sodium sulphate Nutrition 0.000 claims description 3
- RBWSWDPRDBEWCR-RKJRWTFHSA-N sodium;(2r)-2-[(2r)-3,4-dihydroxy-5-oxo-2h-furan-2-yl]-2-hydroxyethanolate Chemical compound [Na+].[O-]C[C@@H](O)[C@H]1OC(=O)C(O)=C1O RBWSWDPRDBEWCR-RKJRWTFHSA-N 0.000 claims description 3
- KDYFGRWQOYBRFD-UHFFFAOYSA-L succinate(2-) Chemical compound [O-]C(=O)CCC([O-])=O KDYFGRWQOYBRFD-UHFFFAOYSA-L 0.000 claims description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 230000008021 deposition Effects 0.000 abstract description 4
- 229910001430 chromium ion Inorganic materials 0.000 abstract description 3
- 238000005282 brightening Methods 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 2
- 230000000536 complexating effect Effects 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 75
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 32
- 239000011248 coating agent Substances 0.000 description 24
- 238000000576 coating method Methods 0.000 description 24
- 229910052742 iron Inorganic materials 0.000 description 15
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 238000004070 electrodeposition Methods 0.000 description 5
- 230000008569 process Effects 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 229910017060 Fe Cr Inorganic materials 0.000 description 4
- 229910002544 Fe-Cr Inorganic materials 0.000 description 4
- UPHIPHFJVNKLMR-UHFFFAOYSA-N chromium iron Chemical compound [Cr].[Fe] UPHIPHFJVNKLMR-UHFFFAOYSA-N 0.000 description 4
- 230000007797 corrosion Effects 0.000 description 4
- 238000005260 corrosion Methods 0.000 description 4
- 238000000151 deposition Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 2
- GXDVEXJTVGRLNW-UHFFFAOYSA-N [Cr].[Cu] Chemical compound [Cr].[Cu] GXDVEXJTVGRLNW-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001844 chromium Chemical class 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
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- 230000009467 reduction Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910019589 Cr—Fe Inorganic materials 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910001069 Ti alloy Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 229910000808 amorphous metal alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000005238 degreasing Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N dioxoiridium Chemical compound O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910001448 ferrous ion Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 229910000457 iridium oxide Inorganic materials 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
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- 239000012266 salt solution Substances 0.000 description 1
- 230000035939 shock Effects 0.000 description 1
- 239000006076 specific stabilizer Substances 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 1
- FZUJWWOKDIGOKH-UHFFFAOYSA-N sulfuric acid hydrochloride Chemical compound Cl.OS(O)(=O)=O FZUJWWOKDIGOKH-UHFFFAOYSA-N 0.000 description 1
- 238000012876 topography Methods 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
The invention discloses an electroplating solution for electrodepositing a ferrochromium alloy in a trivalent chromium system and a preparation method thereof, wherein a solvent is water, the pH value is 2.7-4.5, and solutes comprise a trivalent chromium main salt, a trivalent chromium main complexing agent, a trivalent chromium auxiliary complexing agent, a ferrous main salt, a conductive salt, a buffering agent, a stabilizing agent, a surfactant and a composite brightening agent. The invention adopts a complex coordination mode to coordinate trivalent chromium, reduces the coordination capacity of water molecules to the trivalent chromium, and thus improves the deposition efficiency of the chromium on the surface of the cathode. The specific main complexing agent is micromolecular carboxylic acid and salt thereof, can replace water molecules to be complexed with trivalent chromium to promote the electroreduction of the trivalent chromium, and the main complexing agent and the specific auxiliary complexing agent are used for complexing trivalent chromium ions together to form a combined composite complex to further promote the electroreduction of the trivalent chromium.
Description
Technical Field
The invention belongs to the technical field of electroplating solution, and particularly relates to electroplating solution for electrodepositing ferrochrome alloy in a trivalent chromium system and a preparation method thereof.
Background
The ferrochrome alloy has higher mechanical strength and hardness, wherein the amorphous ferrochrome alloy also has excellent magnetic property, corrosion resistance and electrocatalytic activity.
The preparation method of the ferrochrome mainly comprises an electric furnace method, a shaft furnace method, a plasma method, a melting reduction method and an electrodeposition method. The preparation of the ferrochrome alloy by the electrodeposition method has the advantages of simple and convenient operation, low cost, controllable alloy components and thickness, capability of electroplating on the surface of a complex part and the like.
Mazhengqing and the like (Mazhengqing, Li literature, Tantangqiang, Xiaoyude, yuri jade, electrodeposition Fe-Cr alloy research [ J]Surface technology, 2001, 30 (1): 1-2, 9) researching the electrodeposition of Fe-Cr alloy in a dimethyl formamide (DMF) aqueous solution system of trivalent chromium salt, obtaining a bright alloy plating layer containing Cr 12-65% (mass fraction), and researching the influence of cathode current density, plating solution pH value and trivalent chromium salt concentration on plating layer components and the corrosion resistance of the alloy plating layer. But the plating solution does not containAdding a stabilizer, Fe2+Is easily oxidized into Fe3+The stability of the plating solution is reduced and the current density is only 3 to 6A/dm2The deposition effect is better within the range. Effect of current density on corrosion resistance of Fe-Cr alloy plating layer [ J]Electroplating and environmental protection, 2016, 36 (2): 12-14) preparing a 60-85% nanocrystalline Cr-Fe alloy coating on the brass matrix by changing the current density in the chloride-sulfate mixed system electrolyte, and researching the corrosion resistance of the ferrochrome coating. However, only a single complexing agent is used in the bath composition. Lvwei et al (Lvwei, Zhangyongxiang, Lineiqin. amorphous Fe-Cr alloy coating electrodeposition mechanism discussion [ J]The Fuqing school journal of Fujian university, 2008, (1): 13-17) the effect of glycine on the co-deposition of ferrochrome was studied in a simple trivalent chromium, ferrous main salt solution. The plating solution in the process also has the problems that the plating solution does not contain a stabilizer, and the main salt of the hydrated coordinated trivalent chromium is directly taken as a research object.
At present, the electroplating process for preparing the ferrochrome mostly adopts a single coordination agent, so that the difference of the deposition potentials of trivalent chromium and divalent iron complexes in the plating solution is easily larger, and the codeposition of the ferrochrome is not facilitated; most of the plating solution is lack of proper stabilizer, Fe2+Readily oxidized to Fe3+Affecting the stability of the plating solution; the ferrochrome alloy coating structure and the iron content are single, and the controllability of the ferrochrome content proportion and the coating crystal structure in the coating is lacked.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provides an electroplating solution for electrodepositing ferrochromium alloy in a trivalent chromium system.
Another object of the present invention is to provide a method for producing the plating solution.
The technical scheme of the invention is as follows:
an electroplating solution for electrodepositing a ferrochromium alloy in a trivalent chromium system is prepared by using water as a solvent, setting the pH value to be 2.7-4.5, and using solutes comprising a trivalent chromium main salt, a trivalent chromium main complexing agent, a trivalent chromium auxiliary complexing agent, a ferrous main salt, a conductive salt, a buffering agent, a stabilizing agent, a surfactant and a composite brightener(ii) a Wherein, Cr3+And Fe2+The molar ratio of the iron content to the iron content is 4.5-27: 1, and the iron content in the corresponding coating is 9.3-45.4 wt%; the molar ratio of the total complexing agent to the trivalent chromium main salt is 0.9-2.2: 1, and the total complexing agent consists of a trivalent chromium main complexing agent and a trivalent chromium auxiliary complexing agent;
the trivalent chromium main salt is chromium sulfate, chromium sulfate hydrate (Cr)2(SO4)3·6H2O), chromium potassium sulfate or chromium potassium sulfate hydrate (KCr (SO)4)2·12H2O) with a content of 10 to 80g/L in the plating solution and a content of 2.1 to 8.4g/L in the plating solution;
the trivalent chromium main complexing agent comprises at least one of adipic acid, adipate, succinic acid, succinate, oxalic acid and oxalate, and the content of the trivalent chromium main complexing agent in the electroplating solution is 2-18.4 g/L;
the content of the trivalent chromium auxiliary complexing agent in the electroplating solution is 1-9.2 g/L;
the ferrous main salt comprises ferrous glycinate ((NH)2CH2COO)2Fe) in an amount of 0.31 to 8.24g/L in the plating liquid;
the conductive salt can improve the conductive capability of the plating solution and reduce the power consumption, and the content of the conductive salt in the plating solution is 70-100 g/L;
the buffer can stabilize the pH value of the electroplating solution and maintain the stability of the electroplating solution, and the content of the buffer in the electroplating solution is 70-120 g/L;
the stabilizer is used for preventing Fe2+Is oxidized into Fe3+The stability of the plating solution is improved, the stress of the plating layer is reduced, and the content of the plating solution in the plating solution is 1-8 g/L;
the content of the surfactant in the electroplating solution is 5-120 mg/L;
the content of the composite brightener in the electroplating solution is 45-550 mg/L.
In a preferred embodiment of the present invention, the trivalent chromium co-complexing agent includes at least one of glycine, aspartic acid, polyaspartic acid, and nicotinic acid.
In a preferred embodiment of the present invention, the conductive salt includes at least one of potassium sulfate, sodium sulfate, and ammonium sulfate.
In a preferred embodiment of the present invention, the buffer comprises at least one of acetic acid, acetate, boric acid, borate, phthalic acid and phthalate.
In a preferred embodiment of the present invention, the stabilizer comprises at least one of carotenoid, ascorbic acid, sodium erythorbate, hydrazine hydrate and selenium dioxide.
In a preferred embodiment of the present invention, the surfactant comprises at least one of sodium lauryl sulfate, lignosulfonate, polyoxyethylene ether, polyethylene glycol and isomeric polyoxyethylene lauryl ether.
In a preferred embodiment of the invention, the composite brightener is composed of a first component and a second component, wherein the first component is bis-benzenesulfonylimide, and the second component is at least one of sodium allylsulfonate, thiourea, ethylene thiourea, 2-mercaptobenzimidazole and sodium phenyl-polydithio-propane sulfonate.
The preparation method of the electroplating solution comprises the following steps:
(1) adding trivalent chromium main salt, trivalent chromium main complexing agent and trivalent chromium auxiliary complexing agent into water, stirring for dissolving, and keeping the temperature at 60-65 ℃ for 1.8-2.5 hours to obtain a first solution;
(2) adding ferrous main salt and a stabilizing agent into the first solution, and stirring and dissolving to obtain a second solution;
(3) adding conductive salt and a buffer agent into the second solution, stirring and dissolving to obtain a third solution;
(4) adding a surfactant and a composite brightener into the third solution, and adding water to a required volume to obtain a fourth solution;
(5) and adjusting the pH value of the fourth solution to 2.7-4.5 by using sulfuric acid or sodium hydroxide to obtain the electroplating solution.
The electroplating technological parameters of the electroplating solution for electrodepositing the ferrochromium by using the trivalent chromium system are preferably as follows: the use temperature of the electroplating solution is 40 toThe optimal cathode current density range is 1.0-25.0A/dm at 65 DEG C2The electroplating time is 1-120 min, and the stirring mode of the electroplating solution is mechanical stirring.
When the electroplating solution for electrodepositing the ferrochromium alloy by using the trivalent chromium system is used for electroplating, DSA (coating iridium oxide and the like on the surface of the titanium alloy) material is used as an anode. The DSA anode is beneficial to the precipitation of oxygen at the anode, prevents trivalent chromium from being oxidized into hexavalent chromium, and improves the stability of electroplating solution.
The invention has the beneficial effects that:
1. the invention adopts a complex coordination mode to coordinate trivalent chromium, reduces the coordination capacity of water molecules to the trivalent chromium, and thus improves the deposition efficiency of the chromium on the surface of the cathode.
2. The specific main complexing agent is micromolecular carboxylic acid and salt thereof, can replace water molecules to be complexed with trivalent chromium to promote the electroreduction of the trivalent chromium, and the main complexing agent and the specific auxiliary complexing agent are used for complexing trivalent chromium ions together to form a combined composite complex to further promote the electroreduction of the trivalent chromium.
3. The invention selects ferrous glycinate as ferrous main salt, and ferrous glycinate can form a hexa-coordination complex when dissolved in water, so that the reduction potential of trivalent chromium and ferrous ions is similar, the codeposition of ferrochromium is promoted, and the codeposition efficiency is improved.
4. The electroplating solution of the invention is added with a specific stabilizer to prevent Fe2+Is oxidized into Fe3+The stability of the plating solution is improved, and the tensile stress of the ferrochrome plating layer is also reduced.
5. The specific brightener and the surfactant are added into the electroplating solution, so that the quality of the ferrochrome alloy coating is remarkably improved, and the characteristics of fine grains, bright and flat appearance, less pores and the like are shown; wherein the ferrochrome electroplating process is accompanied by a large amount of hydrogen evolution. The surface active agent has surface activity, can be used as a carrier of a brightening agent, can improve the brightness of a coating and the brightness current density range, reduce the pores of the coating, improve the binding force between the coating and a substrate, and can refine the particles of the coating, remarkably improve the performance of the coating and improve the brightness of the coating.
6. According to the invention, by regulating the proportion of chromium and iron metal salts in the plating solution, the ferrochrome alloy can be plated to replace solid solution crystalline alloy (the iron content is more than or equal to 9.3 wt% and less than 13.8 wt%), crystalline and amorphous mixed alloy (the iron content is 13.8-24.1 wt%) and amorphous alloy (the iron content is more than 24.1 wt% and less than or equal to 45.4 wt%), so that the structure of the ferrochrome alloy is controllable.
Drawings
FIG. 1 is an SEM topography of the coating of example 1 of the present invention.
FIG. 2 is an XRD pattern of different iron contents of the ferrochrome coating of the present invention.
Detailed Description
The technical solution of the present invention will be further illustrated and described below with reference to the accompanying drawings by means of specific embodiments.
Examples 1 to 3
The plating solution of this example was prepared as follows:
(1) adding trivalent chromium main salt, trivalent chromium main complexing agent and trivalent chromium auxiliary complexing agent into water, stirring for dissolving, and keeping the temperature at 60-65 ℃ for 1.8-2.5 hours to obtain a first solution;
(2) adding ferrous main salt and a stabilizing agent into the first solution, and stirring and dissolving to obtain a second solution;
(3) adding conductive salt and a buffer agent into the second solution, stirring and dissolving to obtain a third solution;
(4) adding a surfactant and a composite brightener into the third solution, and adding water to a required volume to obtain a fourth solution;
(5) and adjusting the pH value of the fourth solution to 2.7-4.5 by using sulfuric acid or sodium hydroxide to obtain the electroplating solution.
The copper sheet is used as a substrate material, and the process flow of the prepared electroplating solution is as follows: ultrasonic degreasing (50-70 ℃ for 3-5 min) → water washing → acid washing activation (sulfuric acid 30mL/L, 20-40 s) → water washing → deionized water washing → electroplating ferrochrome → water washing.
In the process of electrodepositing the ferrochromium alloy in the trivalent chromium system in the embodiments 1-3, the composition and the amount of the raw materials of the electroplating solution, the experimental parameters and some experimental results are shown in the following table 1.
TABLE 1 preparation of 1L of the ferrochrome electroplating solution
Evaluation of Performance
When the electroplating solution is used for electroplating, the appearance of the plating layer is observed by adopting a visual method, and the plating layer is stainless steel color within the allowable range of process conditions;
through a thermal shock experiment, namely heating the copper chromium plating iron piece to 200 ℃ in an oven, preserving heat for 2 hours, and quenching the copper chromium plating iron piece in cold water, wherein the coating does not bubble, which shows that the coating has good binding force with a matrix;
the coating was observed to have a dense cell structure using a Scanning Electron Microscope (SEM) (see fig. 1). The coating structure is found to have a corresponding relation with the content of the iron in the coating through X-ray diffraction (XRD) analysis, and as shown in figure 2, the coating structure is changed into a replacement solid solution crystalline state → crystalline state and amorphous state mixed state → amorphous state along with the increase of the content of the iron. The plating layer with corresponding structural characteristics can be obtained by simply regulating and controlling the proportion of the metal salt in the plating solution.
It is obvious to those skilled in the art that the technical solution of the present invention can still obtain the same or similar technical effects as the above embodiments when changed within the following scope, and still fall into the protection scope of the present invention:
an electroplating solution for electrodepositing a ferrochromium alloy in a trivalent chromium system is characterized in that: the solvent is water, the pH value is 2.7-4.5, and the solute comprises trivalent chromium main salt, trivalent chromium main complexing agent, trivalent chromium auxiliary complexing agent, ferrous main salt, conductive salt, buffering agent, stabilizer, surfactant and composite brightener; wherein, Cr3+And Fe2+The molar ratio of the iron content to the iron content is 4.5-27: 1, and the iron content in the corresponding coating is 9.3-45.4 wt%; the molar ratio of the total complexing agent to the trivalent chromium main salt is 0.9-2.2: 1, and the total complexing agent isThe agent consists of a trivalent chromium main complexing agent and a trivalent chromium auxiliary complexing agent;
the trivalent chromium main salt is chromium sulfate, chromium sulfate hydrate, chromium potassium sulfate or chromium potassium sulfate hydrate, the content of the trivalent chromium main salt in the electroplating solution is 10-80 g/L, and the content of the trivalent chromium in the electroplating solution is 2.1-8.4 g/L;
the trivalent chromium main complexing agent comprises at least one of adipic acid, adipate, succinic acid, succinate, oxalic acid and oxalate, and the content of the trivalent chromium main complexing agent in the electroplating solution is 2-18.4 g/L;
the content of the trivalent chromium auxiliary complexing agent in the electroplating solution is 1-9.2 g/L;
the ferrous main salt comprises ferrous glycinate, and the content of the ferrous main salt in the electroplating solution is 0.31-8.24 g/L;
the content of the conductive salt in the electroplating solution is 70-100 g/L;
the content of the buffer in the electroplating solution is 70-120 g/L;
the stabilizer is used for preventing Fe2+Is oxidized into Fe3+The content of the metal oxide in the electroplating solution is 1-8 g/L;
the content of the surfactant in the electroplating solution is 5-120 mg/L;
the content of the composite brightener in the electroplating solution is 45-550 mg/L.
The trivalent chromium auxiliary complexing agent comprises at least one of glycine, aspartic acid, polyaspartic acid and nicotinic acid. The conductive salt includes at least one of potassium sulfate, sodium sulfate, and ammonium sulfate. The buffering agent includes at least one of acetic acid, acetate, boric acid, borate, phthalic acid, and phthalate. The stabilizer comprises at least one of carotenoid, ascorbic acid, sodium erythorbate, hydrazine hydrate and selenium dioxide. The surfactant comprises at least one of sodium lauryl sulfate, lignosulfonate, polyoxyethylene ether, polyethylene glycol and isomeric dodecyl alcohol polyoxyethylene ether. The composite brightener is composed of a first component and a second component, wherein the first component is bis-benzenesulfonylimine, and the second component is at least one of sodium allylsulfonate, thiourea, ethylene thiourea, 2-mercaptobenzimidazole and phenyl poly-sodium dithiopropane sulfonate.
The above description is only a preferred embodiment of the present invention, and therefore should not be taken as limiting the scope of the invention, which is defined by the appended claims.
Claims (5)
1. The electroplating solution for electrodepositing the ferrochromium alloy in the trivalent chromium system is characterized in that a solvent is water, the pH is =2.7 ~ 4.5.5, and a solute consists of trivalent chromium main salt, trivalent chromium main complexing agent, trivalent chromium auxiliary complexing agent, ferrous main salt, conductive salt, buffering agent, stabilizing agent, surfactant and composite brightener3+And Fe2+The molar ratio of the total complexing agent to the trivalent chromium main salt is 0.9 ~.2: 1, and the total complexing agent consists of a trivalent chromium main complexing agent and a trivalent chromium auxiliary complexing agent;
the trivalent chromium main salt is chromium sulfate, chromium sulfate hydrate, chromium potassium sulfate or chromium potassium sulfate hydrate, the content of the trivalent chromium main salt in the electroplating solution is 10 ~ 80g/L, and the content of the trivalent chromium in the electroplating solution is 2.1 ~ 8.4.4 g/L;
the trivalent chromium main complexing agent comprises at least one of adipic acid, adipate, succinic acid, succinate, oxalic acid and oxalate, and the content of the trivalent chromium main complexing agent in the electroplating solution is 2 ~ 18.4.4 g/L;
the trivalent chromium auxiliary complexing agent comprises at least one of glycine, aspartic acid, polyaspartic acid and nicotinic acid, and the content of the trivalent chromium auxiliary complexing agent in the electroplating solution is 1 ~ 9.2.2 g/L;
the ferrous main salt comprises ferrous glycinate, and the content of the ferrous main salt in the electroplating solution is 0.31 ~ 8.24.24 g/L;
the conductive salt comprises at least one of potassium sulfate, sodium sulfate and ammonium sulfate, and the content of the conductive salt in the electroplating solution is 70 ~ 100 g/L;
the content of the buffer in the plating solution was 70 ~ 120 g/L;
the stabilizer is used for preventing Fe2+Is oxidized into Fe3+The content thereof in the plating solution was 1 ~ 8 g/L;
the content of the surfactant in the electroplating solution is 5 ~ 120 mg/L;
the content of the composite brightener in the electroplating solution is 45 ~ 550mg/L, and the composite brightener is composed of a first component and a second component, wherein the first component is bis-benzenesulfonylimine, and the second component is at least one of sodium allylsulfonate, thiourea, ethylene thiourea, 2-mercaptobenzimidazole and sodium phenyl-polydithio-propane sulfonate.
2. The plating solution as set forth in claim 1, wherein: the buffering agent includes at least one of acetic acid, acetate, boric acid, borate, phthalic acid, and phthalate.
3. The plating solution as set forth in claim 1, wherein: the stabilizer comprises at least one of carotenoid, ascorbic acid, sodium erythorbate, hydrazine hydrate and selenium dioxide.
4. The plating solution as set forth in claim 1, wherein: the surfactant comprises at least one of sodium lauryl sulfate, lignosulfonate, polyoxyethylene ether, polyethylene glycol and isomeric dodecyl alcohol polyoxyethylene ether.
5. The method for preparing an electroplating solution as set forth in any one of claims 1 to 4, wherein: the method comprises the following steps:
(1) adding trivalent chromium main salt, trivalent chromium main complexing agent and trivalent chromium auxiliary complexing agent into water, stirring for dissolving, and keeping the temperature at 60 ~ 65 ℃ for 1.8 ~ 2.5.5 h to obtain a first solution;
(2) adding ferrous main salt and a stabilizing agent into the first solution, and stirring and dissolving to obtain a second solution;
(3) adding conductive salt and a buffer agent into the second solution, stirring and dissolving to obtain a third solution;
(4) adding a surfactant and a composite brightener into the third solution, and adding water to a required volume to obtain a fourth solution;
(5) and adjusting the pH value of the fourth solution to 2.7 ~ 4.5.5 by using sulfuric acid or sodium hydroxide to obtain the electroplating solution.
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