US20220403538A1 - Sulfate based, ammonium free trivalent chromium decorative plating process - Google Patents
Sulfate based, ammonium free trivalent chromium decorative plating process Download PDFInfo
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- US20220403538A1 US20220403538A1 US17/755,503 US202017755503A US2022403538A1 US 20220403538 A1 US20220403538 A1 US 20220403538A1 US 202017755503 A US202017755503 A US 202017755503A US 2022403538 A1 US2022403538 A1 US 2022403538A1
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- ions
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- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 239000011651 chromium Substances 0.000 title claims abstract description 30
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 29
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 title claims abstract description 14
- 238000007747 plating Methods 0.000 title description 22
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 title 1
- 238000009713 electroplating Methods 0.000 claims abstract description 22
- 239000004327 boric acid Substances 0.000 claims abstract description 14
- 229910001430 chromium ion Inorganic materials 0.000 claims abstract description 14
- 150000003464 sulfur compounds Chemical class 0.000 claims abstract description 12
- 229910000599 Cr alloy Inorganic materials 0.000 claims abstract description 7
- 239000000788 chromium alloy Substances 0.000 claims abstract description 7
- 150000002500 ions Chemical class 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims description 20
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 18
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 17
- -1 ammonium ions Chemical class 0.000 claims description 16
- 239000011593 sulfur Substances 0.000 claims description 16
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 15
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 claims description 15
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims description 15
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 14
- 229910045601 alloy Inorganic materials 0.000 claims description 14
- 239000000956 alloy Substances 0.000 claims description 14
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 14
- 239000001630 malic acid Substances 0.000 claims description 14
- 235000011090 malic acid Nutrition 0.000 claims description 14
- 238000000151 deposition Methods 0.000 claims description 12
- 229920001515 polyalkylene glycol Polymers 0.000 claims description 12
- 229910001447 ferric ion Inorganic materials 0.000 claims description 11
- 229910001448 ferrous ion Inorganic materials 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 239000006174 pH buffer Substances 0.000 claims description 11
- 150000007524 organic acids Chemical class 0.000 claims description 10
- BWYYYTVSBPRQCN-UHFFFAOYSA-M sodium;ethenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C=C BWYYYTVSBPRQCN-UHFFFAOYSA-M 0.000 claims description 10
- 229910003455 mixed metal oxide Inorganic materials 0.000 claims description 9
- 229910052760 oxygen Inorganic materials 0.000 claims description 9
- 239000000758 substrate Substances 0.000 claims description 9
- 150000001450 anions Chemical class 0.000 claims description 7
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 239000008139 complexing agent Substances 0.000 claims description 6
- 230000008021 deposition Effects 0.000 claims description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 claims description 4
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 4
- WBZKQQHYRPRKNJ-UHFFFAOYSA-L disulfite Chemical compound [O-]S(=O)S([O-])(=O)=O WBZKQQHYRPRKNJ-UHFFFAOYSA-L 0.000 claims description 4
- GRWZHXKQBITJKP-UHFFFAOYSA-L dithionite(2-) Chemical compound [O-]S(=O)S([O-])=O GRWZHXKQBITJKP-UHFFFAOYSA-L 0.000 claims description 4
- 229910052741 iridium Inorganic materials 0.000 claims description 4
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 229910052715 tantalum Inorganic materials 0.000 claims description 4
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 claims description 4
- DHCDFWKWKRSZHF-UHFFFAOYSA-L thiosulfate(2-) Chemical compound [O-]S([S-])(=O)=O DHCDFWKWKRSZHF-UHFFFAOYSA-L 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 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
- 239000001301 oxygen Substances 0.000 claims description 3
- RTBFRGCFXZNCOE-UHFFFAOYSA-N 1-methylsulfonylpiperidin-4-one Chemical compound CS(=O)(=O)N1CCC(=O)CC1 RTBFRGCFXZNCOE-UHFFFAOYSA-N 0.000 claims description 2
- XNWFRZJHXBZDAG-UHFFFAOYSA-N 2-METHOXYETHANOL Chemical compound COCCO XNWFRZJHXBZDAG-UHFFFAOYSA-N 0.000 claims description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 2
- 239000001361 adipic acid Substances 0.000 claims description 2
- 235000011037 adipic acid Nutrition 0.000 claims description 2
- JFCQEDHGNNZCLN-UHFFFAOYSA-N anhydrous glutaric acid Natural products OC(=O)CCCC(O)=O JFCQEDHGNNZCLN-UHFFFAOYSA-N 0.000 claims description 2
- 229920001577 copolymer Polymers 0.000 claims description 2
- 150000001991 dicarboxylic acids Chemical class 0.000 claims description 2
- 229940117927 ethylene oxide Drugs 0.000 claims description 2
- 235000006408 oxalic acid Nutrition 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052707 ruthenium Inorganic materials 0.000 claims description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims description 2
- 125000005619 boric acid group Chemical group 0.000 claims 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 abstract description 13
- 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 abstract description 5
- 239000011734 sodium Substances 0.000 abstract description 5
- 229910052708 sodium Inorganic materials 0.000 abstract description 5
- 239000000654 additive Substances 0.000 abstract description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 18
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 150000003839 salts Chemical class 0.000 description 14
- 238000005260 corrosion Methods 0.000 description 13
- 230000007797 corrosion Effects 0.000 description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 239000011696 chromium(III) sulphate Substances 0.000 description 10
- 235000015217 chromium(III) sulphate Nutrition 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 description 9
- 235000011152 sodium sulphate Nutrition 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 6
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 5
- 150000002894 organic compounds Chemical class 0.000 description 5
- 229920000573 polyethylene Polymers 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- JVBXVOWTABLYPX-UHFFFAOYSA-L sodium dithionite Chemical compound [Na+].[Na+].[O-]S(=O)S([O-])=O JVBXVOWTABLYPX-UHFFFAOYSA-L 0.000 description 5
- 229910002547 FeII Inorganic materials 0.000 description 4
- 229910002553 FeIII Inorganic materials 0.000 description 4
- 239000005864 Sulphur Substances 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000001636 atomic emission spectroscopy Methods 0.000 description 2
- 239000001110 calcium chloride Substances 0.000 description 2
- 229910001628 calcium chloride Inorganic materials 0.000 description 2
- 150000001845 chromium compounds Chemical class 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 239000007857 degradation product Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- JVTAAEKCZFNVCJ-UHFFFAOYSA-N lactic acid Chemical compound CC(O)C(O)=O JVTAAEKCZFNVCJ-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- YOSOSDBZAUWJJT-UHFFFAOYSA-L sodium dithionite monohydrate Chemical compound O.[Na+].[Na+].[O-]S(=O)S([O-])=O YOSOSDBZAUWJJT-UHFFFAOYSA-L 0.000 description 2
- 238000012935 Averaging Methods 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- KXDHJXZQYSOELW-UHFFFAOYSA-N Carbamic acid Chemical compound NC(O)=O KXDHJXZQYSOELW-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- ROTDIONFZZPYSU-UHFFFAOYSA-L [OH-].[Na+].C(=C)S(=O)(=O)[O-].[Na+] Chemical compound [OH-].[Na+].C(=C)S(=O)(=O)[O-].[Na+] ROTDIONFZZPYSU-UHFFFAOYSA-L 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000001464 adherent effect Effects 0.000 description 1
- 150000007933 aliphatic carboxylic acids Chemical class 0.000 description 1
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 1
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 1
- 235000011130 ammonium sulphate Nutrition 0.000 description 1
- 238000013475 authorization Methods 0.000 description 1
- 235000010338 boric acid Nutrition 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 230000003139 buffering effect Effects 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000001844 chromium Chemical class 0.000 description 1
- 229940117975 chromium trioxide Drugs 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 1
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000004310 lactic acid Substances 0.000 description 1
- 235000014655 lactic acid Nutrition 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 description 1
- 229910052939 potassium sulfate Inorganic materials 0.000 description 1
- 235000011151 potassium sulphates Nutrition 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229940085605 saccharin sodium Drugs 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000011975 tartaric acid Substances 0.000 description 1
- 235000002906 tartaric acid Nutrition 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/06—Electroplating: Baths therefor from solutions of chromium from solutions of trivalent chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D17/00—Constructional parts, or assemblies thereof, of cells for electrolytic coating
- C25D17/10—Electrodes, e.g. composition, counter electrode
-
- 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
- C25D3/04—Electroplating: Baths therefor from solutions of chromium
- C25D3/10—Electroplating: Baths therefor from solutions of chromium characterised by the organic bath constituents used
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D9/00—Electrolytic coating other than with metals
- C25D9/04—Electrolytic coating other than with metals with inorganic materials
- C25D9/08—Electrolytic coating other than with metals with inorganic materials by cathodic processes
Definitions
- the present invention refers to an electroplating bath for electroplating a chromium or chromium alloy layer, the bath comprising trivalent chromium ions, organic carboxylic acid, sulfate ions, sodium conductive ions, and additives in the form of inorganic sulfur compound and boric acid as well as a process using such an electroplating bath.
- Chrome deposits from trivalent chrome electrolytes are widely used in the industry due to their unique properties they allow substrates to work longer and under tougher conditions that they would normally survive in.
- Decorative chrome plating is designed to be aesthetically pleasing and durable. Thicknesses range from 0.05 to 0.5 ⁇ m, however they are usually between 0.13 and 0.25 ⁇ m. Decorative chrome plating is also very corrosion resistant and is often used on car parts, tools and kitchen utensils.
- hexavalent chrome deposits were featuring a blue-white appearance that is distinguishing from the trivalent chrome deposits. This colour is still very appreciated by customers that are used to hexavalent chrome products.
- JP2009035806 describes a trivalent chromium plating bath and a method for producing a chromium plating.
- This plating bath contains (1) complex solution of trivalent chromium obtained by maintaining under heating at least 1 type of component chosen from group which consists of aqueous solution aliphatic carboxylic acid and its salt, and aqueous solution containing trivalent chrome compound, (2) conductive salt (3) buffer for pH, and (4) at least 1 type of sulfur-containing compound chosen from the group having an SO2 group.
- the drawback of such a plating solution is the use of a sulfur-containing organic compound instead of inorganic one and they do not use iron in the plating bath.
- JP2010189673 describes novel trivalent chromium plating bath capable of forming a trivalent chromium plating film having better corrosion resistance as compared with the prior art.
- a trivalent chromium plating bath comprising an aqueous solution containing a water-soluble trivalent chromium compound, a conductive salt, a pH buffer, a sulfur-containing compound and an aminocarboxylic acid.
- the drawback of such a plating bath is the lack of sodium and iron ions in the plating bath which will not get the desired color.
- WO2019117178 describes a trivalent chromium plating solution containing: a trivalent chromium compound; a complexing agent; potassium sulfate and ammonium sulfate as conductive salts; a pH buffer; and a sulfur-containing organic compound.
- the trivalent chromium plating solution is practical and has a high plating deposition rate.
- the drawback of such a plating solution is the use of a sulfur-containing organic compound instead of inorganic one and they do not use iron in the plating bath.
- EP2411567 describes a chromium electroplating solution comprising a chromium electroplating solution comprising: (1) a water soluble trivalent chromium salt; (2) at least one complexant for trivalent chromium ions; (3) a source of hydrogen ions sufficient to create a pH of from 2.8-4.2; (4) a pH buffering compound; and (5) a sulfur-containing organic compound.
- the chromium electroplating solution is usable in a method for producing an adherent metallic coating on a decorative article, such coating having enhanced resistance to corrosion in environments containing calcium chloride.
- the drawback of such a solution is the use of a sulfur-containing organic compound instead of inorganic one and the absence of iron ions in the solution.
- an electroplating bath for depositing a chromium or chromium alloy layer which comprises
- the sulfate based trivalent chromium ions bath allows to obtain a whiter colour of the plating opposed to chloride based bath that get a darker plating with a higher carbon percentage.
- the choice of the sodium is preferred to increase the whiteness of the plating.
- the use of ferric or ferrous ions also increase the corrosion resistance permitting to pass the PV1073 A test.
- the combination of ferric, sodium and sulfate ions permit to obtain a blue and white colour close to those from hexavalent chrome deposits.
- an inorganic sulfur such as an oxyacid anion containing sulfur having the valence lower than 6 is preferred.
- the degradation products of the organics sulfur compound cause chromability problems.
- the advantage of the use of oxyacid anions containing sulfur is that they will produce sulfate as a degradation product, so it will not affect the plating bath as it already contains sulfate ions.
- a further advantage of having an oxyacid anion containing sulfur with a valence lower than 6 in the bath is that the thicknesses of the deposits which are obtainable with the bath are higher than with baths which do not contain an oxyacid anion containing sulfur with a valence lower than 6.
- the at least one organic acid is selected from the group of dicarboxylic acids, preferably selected from the group consisting of malic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, and mixtures thereof.
- malic acid is selected from the group of dicarboxylic acids, preferably selected from the group consisting of malic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, and mixtures thereof.
- malic acid as organic acid.
- the concentration of the at least one organic acid is from 5 to 40 g/L, preferably from 10 to 30 g/L, more preferably from 15 to 25 g/L.
- the concentration of the at least one trivalent chromium ion is from 5 to 25 g/L, preferably from 8 to 20 g/L.
- the concentration of the sulfate ions from at least one source of sulfate ions is from 150 to 300 g/L, preferably from 180 to 280 g/L, more preferably from 200 to 250 g/L.
- the source of trivalent chromium ions is chromium(III) sulphate in acidic or basic form.
- the at least one inorganic sulfur compound is selected from the group of oxyacid anions comprising sulfur having a valence lower than 6, preferably selected from the group consisting of:
- the concentration of the at least one inorganic sulfur compound is from 5 to 500 mg/L, preferably from 10 to 200 mg/L.
- the electroplating bath can comprise at least one source of ferric or ferrous ions.
- concentration of the ferric or ferrous ions from at least one source of ferric or ferrous ions is preferably from 20 to 200 mg/L, more preferably from 30 to 150 mg/L, and even more preferably from 40 to 100 mg/L.
- the concentration of the at least one pH buffer is in a range from 50 to 120 g/L, preferably from 60 to 110 g/L, more preferably from 80 to 100 g/L.
- a pH buffer it is preferred to use at least one of the group boric acid, citric acid, succinic acid, lactic acid, tartaric acid, and mixtures thereof. Particular preferred is the use of boric acid as pH buffer.
- the pH of the bath is preferably in the range from 1 to 5, more preferably from 2 to 4, and even more preferably from 3.1 to 3.9.
- the concentration of the sodium vinyl sulfonate is preferably from 0.1 to 5 g/L, more preferably from 0.2 to 3 g/L.
- the bath is (substantially) free of at least one of chloride ions, ammonium ions, amino carboxylic acid ions and hexavalent chromium ions. In particular, it is preferred that some or all of these ions are absent.
- the concentration of sodium saccharin is from 0.1 to 10 g/L, and more preferably from 1 to 5 g/L.
- the at least one polyalkylene glycol has a molecular weight of lower than 2000 g/mol and is preferably selected from the group consisting of:
- the advantage of having at least one polyalkylene glycol, especially at least one polyalkylene glycol with a molecular weight of lower than 2000 g/mol, in the bath is that thicknesses of the deposits which are obtainable with the bath are higher than with baths that do not contain said polyalkylene glycol.
- the concentration of the at least one polyalkylene glycol is from 1 to 15 g/L, preferably from 5 to 10 g/L.
- a method for preparing an electroplated product by electroplating a substrate comprising the following steps:
- the cathode current density is in a range from 3 to 14 A/dm 2 , preferably from 5 to 10, and/or the anode current density is in a range from 4 to 12 A/dm 2 , preferably from 5 to 10 A/dm 2 .
- the anodes consist of a mixed metal oxide, preferably a mixed metal oxide selected from the group consisting of mixed metal oxides of at least two of platinum, ruthenium, iridium and tantalum, more preferably mixed metal oxides of iridium and tantalum.
- the deposition rate during step C) is from 0.01 to 0.5 ⁇ m/min, preferably from 0.02 to 0.3 ⁇ m/min, and more preferably from 0.03 to 0.2 ⁇ m/min.
- step C) is conducted at a temperature from 35 to 60° C., preferably from 40 to 58° C., more preferably from 45 to 55° C.
- the alloy obtainable from this method comprises or consists of carbon, sulphur, oxygen, chrome and, optionally, iron.
- the alloy has a colour measured by L, a, b values from 80 to 86, ⁇ 0.8 to 0, ⁇ 1.5 to 1.0.
- the L, a, b values are from 80 to 86, ⁇ 0.8 to 0, ⁇ 0.8 to 1.
- the L, a, b values are from 83 to 85, ⁇ 0.7 to ⁇ 0.4, ⁇ 0.5 to 0.2.
- the percentage of carbon in the alloy is preferably from 1 to 5 atomic % (at %), more preferably from 2 to 4 at %.
- the alloy preferably comprises from 0.5 to 4 at %, more preferably from 1 to 3 at % sulfur.
- the alloy preferably comprises from 1 to 5 at %, preferably from 2 to 4 at % of oxygen.
- the alloy preferably comprises from 0 to 12 at % of iron.
- the percentage of iron in the alloy is from 3 to 12 at %, preferably from 5 to 10 at %.
- the alloy preferably comprises from 74 to 94.5 at %, more preferably from 79 to 90 at %, chrome.
- the atomic % (at %) of the alloy can be determined by optical emission spectroscopy (OES).
- FIG. 1 shows the chromium coverage on a Hull cell panel with the three points (HCD, MCD, LCD) used for the examples.
- the panels were evaluated: the thickness of Chromium using the X-Ray method EN ISO 3497 in three points 1 cm from the left edge define as HCD (High Current Density), 5 cm from the left edge define as MCD (Medium Current Density), 7 cm from the left edge defined as LCD (Low Current Density).
- the colour at the point defined as MCD was measured by a Colorimeter KONICA MINOLTA CM2600 defining the colour as CIELAB (L, a, b).
- Chromium deposit coverage measuring the mm from the left edge to the maximum coverage of the deposit to the right.
- Chromium deposit was tested to the PV1073 A that is an automotive standard used to evaluate the corrosion performance of Chromium deposit to the Calcium Chloride.
- the results of the examples are shown in the table below.
- the table shows how each component has a different effect in terms of thicknesses, coverage, color and performance versus PV 1073 A corrosion test.
- n° 7 where the deposit was carried out from Hexavalent Chromium electrolyte shows a very bluish color due to a very negative values of a and b but it didn't pass the PV1073 A test.
- the present invention refers to the alloy carried out with the example n° 6 characterized in that the alloy composition contains 5-10 at % of Fe, 1-3 at % of S, 2-4 at % of C, 2-4 at % of O, remaining at % Cr (up to 100 at %) and reaching a comparable color to the reference example and a good deposition rate, with the features of claim 1 and the method for preparing an electroplated product by using the electroplating bath with the features of claim 10 .
- the bath did not contain Methyl Polyethylen Glycol (Mw 500).
- Mw 500 Methyl Polyethylen Glycol
- the disadvantage of omitting said compound in the bath is that the obtained thickness at HCD is much lower than with the bath according to the invention (bath n° 6).
- the oxyacid sulphur anion (anion of sodium dithionite) (alone) is not able to increase the compliance regarding the color, the coverage and the PV 1073A.
- the bath did not contain an oxyacid sulphur anion, i.e. did not contain sodium dithionite in the present case.
- the disadvantage of omitting said compound in the bath is that the thicknesses at HCD, MCD and LCD are much lower than with the bath according to the invention (bath n° 6). Color, coverage and PV 1073A are complying.
- n° 6b shows a similar results to the n° 6 but with the better colour performance.
- the b value reaches a very close value to the reference CrVI, wherein the efficiency is just a little bit, i.e. not significantly, reduced.
Abstract
Description
- The present invention refers to an electroplating bath for electroplating a chromium or chromium alloy layer, the bath comprising trivalent chromium ions, organic carboxylic acid, sulfate ions, sodium conductive ions, and additives in the form of inorganic sulfur compound and boric acid as well as a process using such an electroplating bath.
- Chrome deposits from trivalent chrome electrolytes are widely used in the industry due to their unique properties they allow substrates to work longer and under tougher conditions that they would normally survive in.
- During recent decades, deposition methods relying on trivalent chromium are more common for health- and environment purposes. Indeed Hexavalent chromium substances are under regulatory pressure due to their toxic nature. They were classified as CMR and the European Union decided to submit its use to specific authorization under REACH regulations.
- Decorative chrome plating is designed to be aesthetically pleasing and durable. Thicknesses range from 0.05 to 0.5 μm, however they are usually between 0.13 and 0.25 μm. Decorative chrome plating is also very corrosion resistant and is often used on car parts, tools and kitchen utensils.
- But the hexavalent chrome deposits were featuring a blue-white appearance that is distinguishing from the trivalent chrome deposits. This colour is still very appreciated by customers that are used to hexavalent chrome products.
- JP2009035806 describes a trivalent chromium plating bath and a method for producing a chromium plating. This plating bath contains (1) complex solution of trivalent chromium obtained by maintaining under heating at least 1 type of component chosen from group which consists of aqueous solution aliphatic carboxylic acid and its salt, and aqueous solution containing trivalent chrome compound, (2) conductive salt (3) buffer for pH, and (4) at least 1 type of sulfur-containing compound chosen from the group having an SO2 group. The drawback of such a plating solution is the use of a sulfur-containing organic compound instead of inorganic one and they do not use iron in the plating bath.
- JP2010189673 describes novel trivalent chromium plating bath capable of forming a trivalent chromium plating film having better corrosion resistance as compared with the prior art. A trivalent chromium plating bath comprising an aqueous solution containing a water-soluble trivalent chromium compound, a conductive salt, a pH buffer, a sulfur-containing compound and an aminocarboxylic acid. The drawback of such a plating bath is the lack of sodium and iron ions in the plating bath which will not get the desired color.
- WO2019117178 describes a trivalent chromium plating solution containing: a trivalent chromium compound; a complexing agent; potassium sulfate and ammonium sulfate as conductive salts; a pH buffer; and a sulfur-containing organic compound. The trivalent chromium plating solution is practical and has a high plating deposition rate. The drawback of such a plating solution is the use of a sulfur-containing organic compound instead of inorganic one and they do not use iron in the plating bath.
- EP2411567 describes a chromium electroplating solution comprising a chromium electroplating solution comprising: (1) a water soluble trivalent chromium salt; (2) at least one complexant for trivalent chromium ions; (3) a source of hydrogen ions sufficient to create a pH of from 2.8-4.2; (4) a pH buffering compound; and (5) a sulfur-containing organic compound. The chromium electroplating solution is usable in a method for producing an adherent metallic coating on a decorative article, such coating having enhanced resistance to corrosion in environments containing calcium chloride. The drawback of such a solution is the use of a sulfur-containing organic compound instead of inorganic one and the absence of iron ions in the solution.
- None of those prior art documents has focused on obtaining L, a, b values close to those from hexavalent chrome deposits for trivalent chrome decorative application with a good corrosion resistance and high rate of deposition averaging 0.4 μm in 5 minutes.
- When starting from this prior art it was therefore the objective of the present invention to provide a chromium plated products obtained with a good rate of deposition with a good corrosion resistance (able to pass Volkswagen test PV1073 A) with L, a, b values (comprised from 80 to 85, −0.8 to 0, −0.5 to 1.0) values close to those from hexavalent chrome deposits.
- This problem is solved by the electroplating bath with the features of claim 1, the method for preparing an electroplated product by using the electroplating bath with the features of claim 10. The further dependent claims describe preferred embodiments.
- According to the present invention, an electroplating bath for depositing a chromium or chromium alloy layer is provided which comprises
-
- a) at least one source of trivalent chromium ions,
- b) at least one source of sulfate ions,
- c) at least one organic acid as a complexing agent,
- d) sodium saccharin,
- e) at least one polyalkylene glycol,
- f) sodium vinyl sulfonate,
- g) at least one inorganic sulfur compound,
- h) at least one pH buffer, and, optionally,
- i) at least one source of ferric or ferrous ions.
- It was surprisingly found that the sulfate based trivalent chromium ions bath allows to obtain a whiter colour of the plating opposed to chloride based bath that get a darker plating with a higher carbon percentage. With the conductive ion, the choice of the sodium is preferred to increase the whiteness of the plating. The use of ferric or ferrous ions also increase the corrosion resistance permitting to pass the PV1073 A test. The combination of ferric, sodium and sulfate ions permit to obtain a blue and white colour close to those from hexavalent chrome deposits.
- It was also found that the use of an inorganic sulfur such as an oxyacid anion containing sulfur having the valence lower than 6 is preferred. In fact, most of the time the degradation products of the organics sulfur compound cause chromability problems. The advantage of the use of oxyacid anions containing sulfur is that they will produce sulfate as a degradation product, so it will not affect the plating bath as it already contains sulfate ions. A further advantage of having an oxyacid anion containing sulfur with a valence lower than 6 in the bath is that the thicknesses of the deposits which are obtainable with the bath are higher than with baths which do not contain an oxyacid anion containing sulfur with a valence lower than 6.
- It is preferred that the at least one organic acid is selected from the group of dicarboxylic acids, preferably selected from the group consisting of malic acid, oxalic acid, succinic acid, glutaric acid, adipic acid, and mixtures thereof. In particular preferred is the use of malic acid as organic acid.
- It is preferred that the concentration of the at least one organic acid is from 5 to 40 g/L, preferably from 10 to 30 g/L, more preferably from 15 to 25 g/L.
- In a preferred embodiment, the concentration of the at least one trivalent chromium ion is from 5 to 25 g/L, preferably from 8 to 20 g/L.
- In a preferred embodiment, the concentration of the sulfate ions from at least one source of sulfate ions is from 150 to 300 g/L, preferably from 180 to 280 g/L, more preferably from 200 to 250 g/L.
- In a preferred embodiment, the source of trivalent chromium ions is chromium(III) sulphate in acidic or basic form.
- It is preferred that the at least one inorganic sulfur compound is selected from the group of oxyacid anions comprising sulfur having a valence lower than 6, preferably selected from the group consisting of:
-
- disulfite or metabisulfite,
- dithionite or hydrosulfite,
- thiosulfate,
- tetrathionate,
- sulphite and
- mixtures thereof.
- In a preferred embodiment, the concentration of the at least one inorganic sulfur compound is from 5 to 500 mg/L, preferably from 10 to 200 mg/L.
- The electroplating bath can comprise at least one source of ferric or ferrous ions. The concentration of the ferric or ferrous ions from at least one source of ferric or ferrous ions is preferably from 20 to 200 mg/L, more preferably from 30 to 150 mg/L, and even more preferably from 40 to 100 mg/L.
- It is preferred that the concentration of the at least one pH buffer is in a range from 50 to 120 g/L, preferably from 60 to 110 g/L, more preferably from 80 to 100 g/L.
- As a pH buffer, it is preferred to use at least one of the group boric acid, citric acid, succinic acid, lactic acid, tartaric acid, and mixtures thereof. Particular preferred is the use of boric acid as pH buffer. The pH of the bath is preferably in the range from 1 to 5, more preferably from 2 to 4, and even more preferably from 3.1 to 3.9.
- The concentration of the sodium vinyl sulfonate is preferably from 0.1 to 5 g/L, more preferably from 0.2 to 3 g/L.
- It is preferred that the bath is (substantially) free of at least one of chloride ions, ammonium ions, amino carboxylic acid ions and hexavalent chromium ions. In particular, it is preferred that some or all of these ions are absent.
- According to a preferred embodiment, the concentration of sodium saccharin is from 0.1 to 10 g/L, and more preferably from 1 to 5 g/L.
- In a specific embodiment, the at least one polyalkylene glycol has a molecular weight of lower than 2000 g/mol and is preferably selected from the group consisting of:
-
- polyethylene glycol monomethyl ether,
- ethyleneoxide/propyleneoxyde copolymer,
- polyethylene glycol and
- mixtures thereof.
- The advantage of having at least one polyalkylene glycol, especially at least one polyalkylene glycol with a molecular weight of lower than 2000 g/mol, in the bath is that thicknesses of the deposits which are obtainable with the bath are higher than with baths that do not contain said polyalkylene glycol.
- In a preferred embodiment, the concentration of the at least one polyalkylene glycol is from 1 to 15 g/L, preferably from 5 to 10 g/L.
- A preferred embodiment of the electroplating bath for depositing a chromium or chromium alloy layer comprises:
-
- a) 5 to 25 g/L of trivalent chromium ions from at least one source of chromium ions,
- b) 150 to 300 g/L of sulfate ions from at least one source of sulfate ions,
- c) 5 to 40 g/L of at least one organic acid as a complexing agent,
- d) 0.1 to 10 g/L of sodium saccharin,
- e) 1 to 15 g/L of at least one polyalkylene glycol,
- f) 0.1 to 5 g/L of sodium vinyl sulfonate,
- g) 5 to 500 mg/L of at least one inorganic sulfur compound,
- h) 50 to 120 g/L of at least one pH buffer, and, optionally,
- i) 20 to 200 mg/L of ferric or ferrous ions from at least one source of ferric or ferrous ions.
- According to the present invention, a method for preparing an electroplated product by electroplating a substrate is also provided comprising the following steps:
-
- A) providing an electroplating bath comprising:
- a) at least one source of trivalent chromium ions,
- b) at least one source of sulfate ions,
- c) at least one organic acid as a complexing agent,
- d) sodium saccharin,
- e) at least one polyalkylene glycol,
- f) sodium vinyl sulfonate,
- g) at least one inorganic sulfur compound,
- h) at least one pH buffer, and, optionally,
- i) at least one source of ferric or ferrous ions;
- A) providing an electroplating bath comprising:
- B) immersing a substrate into the electroplating bath and
- C) applying an electrical current between an anode and the substrate as a cathode for depositing the chromium or chromium alloy layer on the substrate.
- In a preferred embodiment, the cathode current density is in a range from 3 to 14 A/dm2, preferably from 5 to 10, and/or the anode current density is in a range from 4 to 12 A/dm2, preferably from 5 to 10 A/dm2.
- It is preferred that the anodes consist of a mixed metal oxide, preferably a mixed metal oxide selected from the group consisting of mixed metal oxides of at least two of platinum, ruthenium, iridium and tantalum, more preferably mixed metal oxides of iridium and tantalum.
- In a preferred embodiment, the deposition rate during step C) is from 0.01 to 0.5 μm/min, preferably from 0.02 to 0.3 μm/min, and more preferably from 0.03 to 0.2 μm/min.
- It is preferred that step C) is conducted at a temperature from 35 to 60° C., preferably from 40 to 58° C., more preferably from 45 to 55° C.
- According to the present invention, the alloy obtainable from this method comprises or consists of carbon, sulphur, oxygen, chrome and, optionally, iron. The alloy has a colour measured by L, a, b values from 80 to 86, −0.8 to 0, −1.5 to 1.0. In a preferred embodiment, the L, a, b values are from 80 to 86, −0.8 to 0, −0.8 to 1. In a more preferred embodiment, the L, a, b values are from 83 to 85, −0.7 to −0.4, −0.5 to 0.2.
- The percentage of carbon in the alloy is preferably from 1 to 5 atomic % (at %), more preferably from 2 to 4 at %. The alloy preferably comprises from 0.5 to 4 at %, more preferably from 1 to 3 at % sulfur. The alloy preferably comprises from 1 to 5 at %, preferably from 2 to 4 at % of oxygen. The alloy preferably comprises from 0 to 12 at % of iron. Optionally, the percentage of iron in the alloy is from 3 to 12 at %, preferably from 5 to 10 at %. The alloy preferably comprises from 74 to 94.5 at %, more preferably from 79 to 90 at %, chrome. The atomic % (at %) of the alloy can be determined by optical emission spectroscopy (OES).
- With reference to the following FIGURES and examples, the subject-matter according to the present invention is intended to be explained in more detail without wishing to restrict said subject-matter to the specific embodiments shown here.
-
FIG. 1 shows the chromium coverage on a Hull cell panel with the three points (HCD, MCD, LCD) used for the examples. - All the examples were carried out in Hull cell (250 mL) using a brass panels nickel plated applying 5A for 5 min at 55° C. using a MMO anodes (Titanium mesh cover by mix metal oxide Ir/Ta).
- The panels were evaluated: the thickness of Chromium using the X-Ray method EN ISO 3497 in three points 1 cm from the left edge define as HCD (High Current Density), 5 cm from the left edge define as MCD (Medium Current Density), 7 cm from the left edge defined as LCD (Low Current Density). The colour at the point defined as MCD was measured by a Colorimeter KONICA MINOLTA CM2600 defining the colour as CIELAB (L, a, b).
- The same panels were evaluated the Chromium deposit coverage measuring the mm from the left edge to the maximum coverage of the deposit to the right. Moreover the Chromium deposit was tested to the PV1073 A that is an automotive standard used to evaluate the corrosion performance of Chromium deposit to the Calcium Chloride.
-
g/L Components No1 115 Basic Chromium Sulphate 230 Sodium Sulphate 90 Boric Acid 25 Malic Acid 3 Sodium Saccharin Sodium Hydroxide to have pH 3.5 No2 115 Basic Chromium Sulphate 230 Sodium Sulphate 90 Boric Acid 25 Malic Acid 3 Sodium Saccharin 5 Methyl Polyethylen Glycol Mw 500 Sodium Hydroxide to have pH 3.5 No3 115 Basic Chromium Sulphate 230 Sodium Sulphate 90 Boric Acid 25 Malic Acid 3 Sodium Saccharin 1 Sodium Vinyl sulfonate Sodium Hydroxide to have pH 3.5 No4 115 Basic Chromium Sulphate 230 Sodium Sulphate 90 Boric Acid 25 Malic Acid 3 Sodium Saccharin 0.200 Sodium Dithionite Sodium Hydroxide to have pH 3.5 No5 115 Basic Chromium Sulphate 230 Sodium Sulphate 90 Boric Acid 25 Malic Acid 3 Sodium Saccharin 0.050 FeII or FeIII Sodium Hydroxide to have pH 3.5 No 5 b 115 Basic Chromium Sulphate 230 Sodium Sulphate 90 Boric Acid 25 Malic Acid 3 Sodium Saccharine 1 Sodium Vinyl sulfonate 0.200 Sodium Dithionite 0.050 FeII or FeIII Sodium Hydroxide to have pH 3.5 No5c 115 Basic Chromium Sulphate 230 Sodium Sulphate 90 Boric Acid 25 Malic Acid 3 Sodium Saccharine 5 Methyl Polyethylen Glycol Mw 500 1 Sodium Vinyl sulfonate 0.200 Sodium Dithionite 0.050 FeII or FeIII Sodium Hydroxide to have pH 3.5 No6 115 Basic Chromium Sulphate 230 Sodium Sulphate 90 Boric Acid 25 Malic Acid 3 Sodium Saccharin 5 Methyl Polyethylen Glycol Mw 500 1 Sodium Vinyl sulfonate 0.200 Sodium Dithionite 0.050 FeII or FeIII Sodium Hydroxide to have pH 3.5 No6b 55 Basic Chromium Sulphate 230 Sodium Sulphate 90 Boric Acid 25 Malic Acid 3 Sodium Saccharin 5 Methyl Polyethylen Glycol Mw 500 1 Sodium Vinyl sulfonate 0.200 Sodium Dithionite Sodium Hydroxide to have pH 3.5 No7 Reference test 250 Chromium Trioxide 1 Sulfuric Acid 1 Magnesium Hexafluorosilicate - The results of the examples are shown in the table below. The table shows how each component has a different effect in terms of thicknesses, coverage, color and performance versus PV 1073 A corrosion test.
- In particular the reference example n° 7 where the deposit was carried out from Hexavalent Chromium electrolyte shows a very bluish color due to a very negative values of a and b but it didn't pass the PV1073 A test.
- The present invention refers to the alloy carried out with the example n° 6 characterized in that the alloy composition contains 5-10 at % of Fe, 1-3 at % of S, 2-4 at % of C, 2-4 at % of O, remaining at % Cr (up to 100 at %) and reaching a comparable color to the reference example and a good deposition rate, with the features of claim 1 and the method for preparing an electroplated product by using the electroplating bath with the features of claim 10.
- In the example n° 5 b, the bath did not contain Methyl Polyethylen Glycol (Mw 500). The disadvantage of omitting said compound in the bath is that the obtained thickness at HCD is much lower than with the bath according to the invention (bath n° 6). Besides, in the absence of said compound, the oxyacid sulphur anion (anion of sodium dithionite) (alone) is not able to increase the compliance regarding the color, the coverage and the PV 1073A.
- In the example n° 5 c, the bath did not contain an oxyacid sulphur anion, i.e. did not contain sodium dithionite in the present case. The disadvantage of omitting said compound in the bath is that the thicknesses at HCD, MCD and LCD are much lower than with the bath according to the invention (bath n° 6). Color, coverage and PV 1073A are complying.
- The example n° 6b shows a similar results to the n° 6 but with the better colour performance. In particular the b value reaches a very close value to the reference CrVI, wherein the efficiency is just a little bit, i.e. not significantly, reduced.
- Table Showing the Results:
-
Thickness Color in MCD Alloy Composition by Example HCD MCD LCD L a b Coverage PV1073 A XPS profile (at %)* 1 0,12 0,1 0,05 82,8 −0,2 0,92 85/100 Corrosion 2 0,25 0,11 0,05 82,8 −0,21 0,90 86/100 Corrosion 3 0,11 0,1 0,04 83,2 −0,5 −0,1 86/100 Corrosion 4 0,18 0,4 0,18 83 −0,3 0,8 80/100 Corrosion 2-4% C 2-4% O; 1-3% S; remaining % Cr 5 0,11 0,1 0,04 82 −0,1 1,05 98/100 Unchanged 5b 0,12 0,4 0,02 83 −0,5 −0,1 95/100 Unchanged 5-10% Fe; 2-4% 2-4% O; 1-3% S 5c 0,25 0,18 0,05 83 −0,5 0,3 98/100 Unchanged 5-10% Fe; 2-4% 2-4% O; 1-3% S 6 0,35 0,4 0,02 83,5 −0,5 −0,1 95/100 Unchanged 5-10% Fe; 2-4% 2-4% O; 1-3% S 6b 0,25 0,25 0,15 84,5 −0,5 −1,0 90/100 Unchanged 2-4% C 1-4% O; 1-3% S 7 0,92 0,2 0,07 85,2 −1,1 −1,2 75/100 Corrosion 96-98% Cr; 2-4% O *Regarding the alloy composition, if not indicated otherwise, remaining % are represented by Cr.
Claims (16)
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EP20154909.4 | 2020-01-31 | ||
PCT/EP2020/080584 WO2021084103A1 (en) | 2019-10-31 | 2020-10-30 | Sulfate based, ammonium free trivalent chromium decorative plating process |
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EP0079771A1 (en) * | 1981-11-18 | 1983-05-25 | International Business Machines Corporation | Electrodeposition of chromium and its alloys |
US4448649A (en) * | 1981-11-18 | 1984-05-15 | International Business Machines Corporation | Trivalent chromium electroplating baths |
KR20050052214A (en) * | 2003-11-29 | 2005-06-02 | 테크앤라이프 주식회사 | Chrom galvanizing solution and manufacturing process of it |
KR100858711B1 (en) * | 2007-03-30 | 2008-09-17 | 한국기계연구원 | Trivalent chromium galvanizing solution |
CN105671599A (en) * | 2016-04-11 | 2016-06-15 | 济南德锡科技有限公司 | Sulfate trivalent chromium electroplating solution and preparation method thereof |
CN106086949A (en) * | 2016-08-26 | 2016-11-09 | 武汉迪赛环保新材料股份有限公司 | A kind of trivalent chromium plating solution and electro-plating method |
US20210172081A1 (en) * | 2017-12-13 | 2021-06-10 | Jcu Corporation | Trivalent chromium plating solution and method for chromium-plating using same |
US20210317589A1 (en) * | 2018-07-03 | 2021-10-14 | Jcu Corporation | Trivalent chromium plating solution and chromium plating method using same |
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MX2022004290A (en) | 2022-05-10 |
EP4051829A1 (en) | 2022-09-07 |
KR20220119012A (en) | 2022-08-26 |
JP7342253B2 (en) | 2023-09-11 |
WO2021084103A1 (en) | 2021-05-06 |
CA3155524A1 (en) | 2021-05-06 |
CN114729463A (en) | 2022-07-08 |
CA3155524C (en) | 2024-02-27 |
JP2022551461A (en) | 2022-12-09 |
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