EP3067444A2 - Separation de revetements decoratifs en alliage palladium-fer sur des substances metalliques - Google Patents

Separation de revetements decoratifs en alliage palladium-fer sur des substances metalliques Download PDF

Info

Publication number: EP3067444A2
Authority: EP; European Patent Office
Prior art keywords: palladium; iron; objects; alloy; coating
Prior art date: 2015-03-09
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.): Granted

Application number

EP16156476.0A

Other languages

German (de)

English (en)

Other versions

EP3067444B1 (fr

EP3067444A3 (fr

Inventor

Claudia GARHÖFER-ONDREICSKA

Christian GARHÖFER

Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)

Ing W Garhofer GmbH

W Garhofer Ing GmbH

Original Assignee

Ing W Garhofer GmbH

W Garhofer Ing GmbH

Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)

2015-03-09

Filing date

2016-02-19

Publication date

2016-09-14

2016-02-19 Application filed by Ing W Garhofer GmbH, W Garhofer Ing GmbH filed Critical Ing W Garhofer GmbH

2016-09-14 Publication of EP3067444A2 publication Critical patent/EP3067444A2/fr

2016-12-07 Publication of EP3067444A3 publication Critical patent/EP3067444A3/fr

2019-03-27 Application granted granted Critical

2019-03-27 Publication of EP3067444B1 publication Critical patent/EP3067444B1/fr

Status Active legal-status Critical Current

2036-02-19 Anticipated expiration legal-status Critical

Links

KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 76
229910052763 palladium Inorganic materials 0.000 title claims abstract description 35
238000000576 coating method Methods 0.000 title claims abstract description 34
229910000640 Fe alloy Inorganic materials 0.000 title claims abstract description 17
239000007769 metal material Substances 0.000 title 1
238000000926 separation method Methods 0.000 title 1
XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 71
239000003792 electrolyte Substances 0.000 claims abstract description 45
238000005260 corrosion Methods 0.000 claims abstract description 18
230000007797 corrosion Effects 0.000 claims abstract description 18
229910052751 metal Inorganic materials 0.000 claims abstract description 18
239000002184 metal Substances 0.000 claims abstract description 18
QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims abstract description 12
230000008021 deposition Effects 0.000 claims abstract description 12
150000003839 salts Chemical class 0.000 claims abstract description 12
239000000080 wetting agent Substances 0.000 claims abstract description 12
229910002056 binary alloy Inorganic materials 0.000 claims abstract description 7
238000005275 alloying Methods 0.000 claims abstract description 6
229910021529 ammonia Inorganic materials 0.000 claims abstract description 6
239000003381 stabilizer Substances 0.000 claims abstract description 6
229910001252 Pd alloy Inorganic materials 0.000 claims abstract description 5
239000002280 amphoteric surfactant Substances 0.000 claims abstract description 5
239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
150000002739 metals Chemical class 0.000 claims abstract description 5
150000002736 metal compounds Chemical class 0.000 claims abstract description 4
PMVSDNDAUGGCCE-TYYBGVCCSA-L Ferrous fumarate Chemical compound [Fe+2].[O-]C(=O)\C=C\C([O-])=O PMVSDNDAUGGCCE-TYYBGVCCSA-L 0.000 claims abstract description 3
150000002941 palladium compounds Chemical class 0.000 claims abstract description 3
150000003868 ammonium compounds Chemical class 0.000 claims abstract 2
150000002505 iron Chemical class 0.000 claims abstract 2
150000002940 palladium Chemical class 0.000 claims abstract 2
229910052742 iron Inorganic materials 0.000 claims description 36
229910045601 alloy Inorganic materials 0.000 claims description 29
239000000956 alloy Substances 0.000 claims description 29
239000011248 coating agent Substances 0.000 claims description 22
239000010949 copper Substances 0.000 claims description 17
239000010948 rhodium Substances 0.000 claims description 15
229910052703 rhodium Inorganic materials 0.000 claims description 14
MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 14
239000010931 gold Substances 0.000 claims description 12
RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 11
230000001464 adherent effect Effects 0.000 claims description 11
229910052802 copper Inorganic materials 0.000 claims description 11
238000000151 deposition Methods 0.000 claims description 11
PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 11
229910052737 gold Inorganic materials 0.000 claims description 11
BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 10
238000005299 abrasion Methods 0.000 claims description 9
KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims description 8
229910052707 ruthenium Inorganic materials 0.000 claims description 8
229910001369 Brass Inorganic materials 0.000 claims description 7
239000010951 brass Substances 0.000 claims description 7
239000010970 precious metal Substances 0.000 claims description 7
VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 6
229910002651 NO3 Inorganic materials 0.000 claims description 6
NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 6
QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 6
238000000034 method Methods 0.000 claims description 6
OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 6
CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 claims description 6
229940081974 saccharin Drugs 0.000 claims description 6
235000019204 saccharin Nutrition 0.000 claims description 6
239000000901 saccharin and its Na,K and Ca salt Substances 0.000 claims description 6
239000011135 tin Substances 0.000 claims description 6
239000000853 adhesive Substances 0.000 claims description 5
230000001070 adhesive effect Effects 0.000 claims description 5
229910052697 platinum Inorganic materials 0.000 claims description 5
KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 4
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 4
229910000831 Steel Inorganic materials 0.000 claims description 4
HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
-1 alkyl ether sulfonates Chemical class 0.000 claims description 4
125000003118 aryl group Chemical group 0.000 claims description 4
150000002191 fatty alcohols Chemical class 0.000 claims description 4
238000004519 manufacturing process Methods 0.000 claims description 4
229910052939 potassium sulfate Inorganic materials 0.000 claims description 4
235000011151 potassium sulphates Nutrition 0.000 claims description 4
239000010959 steel Substances 0.000 claims description 4
239000011701 zinc Substances 0.000 claims description 4
229910052725 zinc Inorganic materials 0.000 claims description 4
ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
229910000510 noble metal Inorganic materials 0.000 claims description 3
239000004033 plastic Substances 0.000 claims description 3
239000011734 sodium Substances 0.000 claims description 3
229910052718 tin Inorganic materials 0.000 claims description 3
FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 2
OFOBLEOULBTSOW-UHFFFAOYSA-L Malonate Chemical compound [O-]C(=O)CC([O-])=O OFOBLEOULBTSOW-UHFFFAOYSA-L 0.000 claims description 2
229910019142 PO4 Inorganic materials 0.000 claims description 2
229910001128 Sn alloy Inorganic materials 0.000 claims description 2
229910001297 Zn alloy Inorganic materials 0.000 claims description 2
PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
235000021317 phosphate Nutrition 0.000 claims description 2
229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
235000011152 sodium sulphate Nutrition 0.000 claims description 2
150000003871 sulfonates Chemical class 0.000 claims description 2
239000004094 surface-active agent Substances 0.000 claims description 2
229940095064 tartrate Drugs 0.000 claims description 2
238000005868 electrolysis reaction Methods 0.000 claims 2
239000000758 substrate Substances 0.000 claims 2
239000000654 additive Substances 0.000 abstract description 2
239000012670 alkaline solution Substances 0.000 abstract description 2
230000015572 biosynthetic process Effects 0.000 abstract 1
239000000047 product Substances 0.000 description 16
KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 15
QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 14
239000000463 material Substances 0.000 description 9
KWIUHFFTVRNATP-UHFFFAOYSA-N glycine betaine Chemical compound C[N+](C)(C)CC([O-])=O KWIUHFFTVRNATP-UHFFFAOYSA-N 0.000 description 8
XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
150000003863 ammonium salts Chemical class 0.000 description 5
239000008367 deionised water Substances 0.000 description 5
229910021641 deionized water Inorganic materials 0.000 description 5
239000000203 mixture Substances 0.000 description 5
239000000243 solution Substances 0.000 description 5
230000002378 acidificating effect Effects 0.000 description 4
QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 3
229960003237 betaine Drugs 0.000 description 3
XBDQKXXYIPTUBI-UHFFFAOYSA-N dimethylselenoniopropionate Natural products CCC(O)=O XBDQKXXYIPTUBI-UHFFFAOYSA-N 0.000 description 3
231100000206 health hazard Toxicity 0.000 description 3
238000010348 incorporation Methods 0.000 description 3
PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
238000012360 testing method Methods 0.000 description 3
229910000906 Bronze Inorganic materials 0.000 description 2
KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 2
PNTWXEIQXBRCPS-CLKGFSLHSA-N Pd-II Natural products C1=CC(=O)OC2=C3[C@H](OC(=O)C(/C)=C/C)[C@H](OC(=O)C(\C)=C\C)C(C)(C)OC3=CC=C21 PNTWXEIQXBRCPS-CLKGFSLHSA-N 0.000 description 2
RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
238000005238 degreasing Methods 0.000 description 2
229910052759 nickel Inorganic materials 0.000 description 2
230000003287 optical effect Effects 0.000 description 2
238000011160 research Methods 0.000 description 2
HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 2
239000010936 titanium Substances 0.000 description 2
229910052719 titanium Inorganic materials 0.000 description 2
238000004065 wastewater treatment Methods 0.000 description 2
229910000531 Co alloy Inorganic materials 0.000 description 1
229910001229 Pot metal Inorganic materials 0.000 description 1
229910000929 Ru alloy Inorganic materials 0.000 description 1
YPPQDPIIWDQYRY-UHFFFAOYSA-N [Ru].[Rh] Chemical compound [Ru].[Rh] YPPQDPIIWDQYRY-UHFFFAOYSA-N 0.000 description 1
150000001242 acetic acid derivatives Chemical class 0.000 description 1
239000002253 acid Substances 0.000 description 1
239000012298 atmosphere Substances 0.000 description 1
230000004888 barrier function Effects 0.000 description 1
239000010974 bronze Substances 0.000 description 1
238000012512 characterization method Methods 0.000 description 1
239000002738 chelating agent Substances 0.000 description 1
239000008139 complexing agent Substances 0.000 description 1
238000007796 conventional method Methods 0.000 description 1
KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
238000009792 diffusion process Methods 0.000 description 1
238000004870 electrical engineering Methods 0.000 description 1
239000008151 electrolyte solution Substances 0.000 description 1
239000007789 gas Substances 0.000 description 1
238000007654 immersion Methods 0.000 description 1
239000004615 ingredient Substances 0.000 description 1
150000007524 organic acids Chemical class 0.000 description 1
235000005985 organic acids Nutrition 0.000 description 1
XSKIUFGOTYHDLC-UHFFFAOYSA-N palladium rhodium Chemical compound [Rh].[Pd] XSKIUFGOTYHDLC-UHFFFAOYSA-N 0.000 description 1
OYJSZRRJQJAOFK-UHFFFAOYSA-N palladium ruthenium Chemical compound [Ru].[Pd] OYJSZRRJQJAOFK-UHFFFAOYSA-N 0.000 description 1
159000000001 potassium salts Chemical class 0.000 description 1
239000002244 precipitate Substances 0.000 description 1
235000019260 propionic acid Nutrition 0.000 description 1
IUVKMZGDUIUOCP-BTNSXGMBSA-N quinbolone Chemical compound O([C@H]1CC[C@H]2[C@H]3[C@@H]([C@]4(C=CC(=O)C=C4CC3)C)CC[C@@]21C)C1=CCCC1 IUVKMZGDUIUOCP-BTNSXGMBSA-N 0.000 description 1
229910052708 sodium Inorganic materials 0.000 description 1
229910052714 tellurium Inorganic materials 0.000 description 1
PORWMNRCUJJQNO-UHFFFAOYSA-N tellurium atom Chemical compound [Te] PORWMNRCUJJQNO-UHFFFAOYSA-N 0.000 description 1
229910052723 transition metal Inorganic materials 0.000 description 1

Classifications

- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/567—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of platinum group metals
- 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
- C25D3/20—Electroplating: Baths therefor from solutions of iron
- 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
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
- 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
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- 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
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
- C25D5/611—Smooth layers
- 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
- C25D7/00—Electroplating characterised by the article coated
- C25D7/005—Jewels; Clockworks; Coins
- 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
- C25D5/34—Pretreatment of metallic surfaces to be electroplated

Definitions

the present invention is directed to an electrolytic bath composition for depositing white, high-gloss, crack-free, abrasion and corrosion-resistant palladium-iron alloys from alkaline aqueous baths, objects and articles coated with these alloys, and a process for producing the coated objects Items.
the electrolytes are out JP, 2001-192885 A, are also based on ammonium salts and contain additional brighteners and possibly different alloying metals such as iron or tellurium.
JP, 2001-181887 A describes palladium-iron alloy baths which are also based on ammonium salts and additionally contain EDTA.
strong chelating agents are generally undesirable in electrolytes since they introduce difficulties in wastewater treatment.
JP, 10-046384 A describes palladium alloy baths for the electronics industry. Iron as alloying metal is mentioned, the electrolytes are based on ammonium salts. The examples, however, relate only to palladium-cobalt alloys. Alloys of palladium-iron, palladium-nickel, palladium-rhodium and palladium-ruthenium should be produced in the same way.
DE2657925 describes ammonia-free, semi-glossy to bright palladium and palladium alloy baths for electrical engineering, but iron is not mentioned as alloying metal.
the object of the present invention to develop baths from which high gloss, binary palladium-iron alloys can be deposited without any addition of other metals and.
the alloy baths during operation should not present an odor nuisance or health hazard through the release of irritating gases or vapors, and moreover contain no strong complexing agents such as EDTA or NTA, which would cause problems in wastewater treatment.
the production is to be cheapened by the use of such alloy baths, and resources of the expensive palladium are spared.
Such alloys are therefore particularly well suited for any metallic white decorative coating, e.g. of costume jewelery, but also for industrial applications, especially in the electronics industry.
the baths contain 0.5-15 g / l of palladium, 0.2-2 g / l of iron, conductive salts, brighteners and wetting agents. It is possible to deposit layer thicknesses> 5 ⁇ high-gloss, crack-free. The corrosion resistance is comparable to pure palladium, the abrasion resistance is better than pure palladium.
the invention relates to a novel electrolyte bath for the cathodic deposition of binary alloys and / or layer sequences to form white, corrosion-resistant, crack-free and high-gloss coatings on at least on their surface metallic or electrically conductive or conductive coated objects, which bath as electrolyte at least one complex Palladium compound and at least one iron salt, and characterized in that it - for the deposition of a PdFe alloy containing 5-15 wt .-% Fe - as aqueous, alkaline solution is present and in addition to containing as metal compounds, as a further essential component at least one wetting agent from the group of amphoteric surfactants and additionally at least one of the additives contained in galvanic palladium in the usual manner brightener and conductive salts, pH stabilizers and stress reducer.
the pH of the new alloy bath should be maintained in the range of 7.5 - 9, since at lower pH values (approximately between 7 and 7.5) the incorporation rates of iron decrease. At higher pH values (approximately between 9 and 10), burns occur in the high current density range.
the pH is advantageously adjusted by means of sodium or potassium hydroxide.
the iron content of the deposited alloy at 5-15 wt .-% Fe, since at incorporation rates> 15 wt .- Fe Fe the layers are cracked, and at incorporation rates ⁇ 5% by weight, the deposition receives a milky appearance.
palladium in divalent form e.g. as palladium chloride, sulfate, nitrate, and iron
the ferric salt e.g. be present as sulfate, chloride, nitrate or citrate in the electrolyte bath.
an electrolyte bath is advantageously provided for the deposition of a coating, which is characterized in that it has a content of palladium of 0.5 to 15 g / l, preferably from 2 to 8 g / l, and particularly preferably from 4 to 6 g / l, and iron of 0.2 to 2 g / l, preferably from 0.5 to 1.5 g / l.
the wetting agents essential to the extraordinary properties of the novel alloy coatings in particular from the group of amphoteric surfactants, e.g. Betaine and sulfobetaines are advantageously added to the electrolyte in amounts of 0.5-2 g / l.
the new electrolyte bath As for other components of the new electrolyte bath than the essential metal compounds and wetting agents, it has proven to be advantageous if it contains brighteners. Such brighteners for palladium baths are known and come for example from the group of substituted aromatic N-heterocycles. It has also proved to be advantageous if the electrolyte contains stress reducers such as saccharin or organic sulfonates.
conductive salts and pH stabilizers such as sodium or potassium sulfate, nitrate, chloride, citrate, tartrate or malonate, and possibly further surface-active or wetting agents, for example alkyl ether sulfonates, alkyl ether phosphates or fatty alcohol alkoxylates.
All conductive salts or pH stabilizers used in the invention are sodium or potassium salts.
ammonia or ammonium salts When using ammonia or ammonium salts at elevated temperatures of about 50 ° C, ammonia is constantly expelled. As a result, the pH of the bath constantly adjusted and continuous work is much more difficult. In addition, there is a constant odor nuisance and health hazard for the operator of the electrolyte.
no organic acids or salts are used which, when the bath is heated at elevated temperature, release vapors which can lead to an odor nuisance and / or health hazard to the operators of the electrolyte, e.g. Propionic acid / propionates, acetic acid / acetates.
Another very important object of the invention are objects or articles, in particular jewelery or decorative articles, and further electro-technical or electronic components and components of a preferably physiologically acceptable metal, in particular brass, zinc, tin, iron or steel, or from alloys thereof or else from a conductive plastic with a coating of a binary alloy of palladium and iron deposited from an abovementioned electrolyte bath, in which the iron content is from 5 to 12% by weight, to which in particular reference is made to claim 7 becomes.
a preferably physiologically acceptable metal in particular brass, zinc, tin, iron or steel, or from alloys thereof or else from a conductive plastic with a coating of a binary alloy of palladium and iron deposited from an abovementioned electrolyte bath, in which the iron content is from 5 to 12% by weight, to which in particular reference is made to claim 7 becomes.
the total thickness of the binary palladium-iron coating to be achieved in the context of the invention is 0.1 to 5 ⁇ m, in particular about 0.5 to 3 ⁇ m, depending on the field of use.
the intermediate layer of adhesive gold has a thickness of 0.05 to 0.3 microns.
the new objects or articles will have a final layer of one with rhodium and ruthenium, preferably in the weight% ratio of (70 to 90) to (30 to 10), especially about 80 to 20 , formed alloy.
the working temperature of the electrolyte baths according to the invention is between 35 and 75 ° C.
the current density can be set to between 0.01 and 10 amps / dm 2 , depending on the type of coating system.
insoluble anodes those made of a material selected from the group consisting of platinized titanium and iridium-transition metal mixed oxide or combinations of these materials are preferably used. Particular preference is given to using platinized titanium anodes.
This palladium-iron alloy can be either final or final layer, or further coated by methods known per se. Further z. B. intermediate or final coatings may, as mentioned above, gold-containing or other noble metal-containing layers, such as those of rhodium, platinum, ruthenium or their alloys.
the base material is first copper-plated, then coated with palladium and finally receives the desired finish by coating with gold, rhodium or other precious metals or their alloys.
a thickness of the palladium layer of about 0.5-5 microns is recommended. Usually a layer thickness of about 1 ⁇ m is considered sufficient.
rhodium-ruthenium alloy instead of a rhodium final layer. If, for example, an alloy in the ratio by weight of rhodium to ruthenium of 80:20 is deposited as the final layer, in addition to the savings in the intermediate layers mentioned above, 20% of the very expensive rhodium would be saved.
the invention further relates to a per se conventional method for cathodic deposition of the binary alloys according to the invention with an Fe content of 5-15% by weight on at least on their surface metallic or electrically conductive or conductive coated objects or articles using the electrolyte according to the invention according to claim 15.
the invention further relates to the use of the electrolyte bath according to the invention for the cathodic deposition of binary alloys on at least on their surface metallic or electrically conductive or conductive coated objects or articles according to claim 16.
the jewelry blank is rinsed in deionized water, dekapiert in 5% sulfuric acid solution for 30 s and in an acidic copper bath with 50 g / l Cu and 60 g / l sulfuric acid ("IWG Cu 550", product of the company. Ing. Garhöfer GesmbH), 20 ⁇ m copper are deposited in a shiny, shiny finish at 4 A / dm 2 and 25 ° C. The blank is rinsed again.
the corrosion resistance of the palladium-iron alloy in comparison with a coating of a pure palladium electrolyte (Gapal TS, product of Garhöfer GesmbH), produced on the same base material in the SO 2 test is equally good.
a brass disc in the palladium-iron electrolyte of example 1 and a brass disc in a pure palladium electrolyte (Gapal TS, product of Garhöfer GesmbH) were coated with 2 .mu.m. Ansch manend both discs were abraded. The pure palladium was rubbed much earlier than the palladium-iron alloy.
a jewelery blank made of die-cast zinc is electrolytically degreased in a weakly alkaline cyanide-free cleaner (degreasing 1018, product of the company Ing. W. Garhöfer GesmbH) at 25 ° C. for 30 seconds at 10 A / dm 2 .
a weakly alkaline cyanide-free cleaner degreasing 1018, product of the company Ing. W. Garhöfer GesmbH
the jewelry blank is rinsed in deionized water and in an alkaline cyanide Vorkupferbad with 22 g / l Cu and 34 g / l KCN ("Cuproga", product of the company Ing. W. Garhöfer GesmbH) were 5 microns of copper at 1 A / dm 2 and 50 ° C deposited.
the pre-coppered jewelry blank is then dekapiert in 5% sulfuric acid solution for 30 s and in an acidic copper bath with 50 g / l Cu and 60 g / l sulfuric acid ("IWG Cu 550", product of the company Ing. W. Garhöfer GesmbH) 15 ⁇ m copper leveling and high gloss deposited at 4 A / dm 2 and 25 ° C.
the thus coppered part is rinsed and pre-immersed in a 10% KCN solution.

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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)

EP16156476.0A 2015-03-09 2016-02-19 Deposition de revetements decoratifs en alliage palladium-fer sur des substances metalliques Active EP3067444B1 (fr)

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ATA50188/2015A AT516876B1 (de)	2015-03-09	2015-03-09	Abscheidung von dekorativen Palladium-Eisen-Legierungsbeschichtungen auf metallischen Substanzen

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number	Priority date	Publication date	Assignee	Title
US10612149B1 (en)	2019-09-05	2020-04-07	Chow Sang Sang Jewellery Company Limited	Platinum electrodeposition bath and uses thereof
EP3733930A1 (fr) *	2019-05-03	2020-11-04	IWG Ing. W. Garhöfer Gesellschaft m. b. H.	Système de revêtement destiné à l'application par dépôt galvanique sur un lingot
AT523922A4 (de) *	2020-09-08	2022-01-15	Iwg Ing W Garhoefer Ges M B H	Elektrolytbad für Palladium-Ruthenium-Beschichtungen

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