US2800439A - Bright metal plating - Google Patents
Bright metal plating Download PDFInfo
- Publication number
- US2800439A US2800439A US517652A US51765255A US2800439A US 2800439 A US2800439 A US 2800439A US 517652 A US517652 A US 517652A US 51765255 A US51765255 A US 51765255A US 2800439 A US2800439 A US 2800439A
- Authority
- US
- United States
- Prior art keywords
- bath
- metal
- gold
- electroplating
- bright
- Prior art date
- 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.)
- Expired - Lifetime
Links
- 229910052751 metal Inorganic materials 0.000 title claims description 29
- 239000002184 metal Substances 0.000 title claims description 29
- 238000007747 plating Methods 0.000 title description 30
- QGJOPFRUJISHPQ-UHFFFAOYSA-N Carbon disulfide Chemical compound S=C=S QGJOPFRUJISHPQ-UHFFFAOYSA-N 0.000 claims description 30
- 238000009713 electroplating Methods 0.000 claims description 28
- 239000007859 condensation product Substances 0.000 claims description 21
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 20
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 13
- 229910052709 silver Inorganic materials 0.000 claims description 12
- 239000004332 silver Substances 0.000 claims description 12
- 229910052783 alkali metal Inorganic materials 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- 229910001316 Ag alloy Inorganic materials 0.000 claims description 8
- PQTCMBYFWMFIGM-UHFFFAOYSA-N gold silver Chemical compound [Ag].[Au] PQTCMBYFWMFIGM-UHFFFAOYSA-N 0.000 claims description 8
- 239000012991 xanthate Substances 0.000 claims description 8
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 claims description 6
- 238000006467 substitution reaction Methods 0.000 claims description 6
- 150000001299 aldehydes Chemical class 0.000 claims description 5
- 239000002585 base Substances 0.000 claims description 5
- 150000003839 salts Chemical class 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 4
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 3
- 150000001340 alkali metals Chemical class 0.000 claims 1
- 239000010931 gold Substances 0.000 description 17
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 16
- 229910052737 gold Inorganic materials 0.000 description 15
- -1 fatty alcohol sulfonates Chemical class 0.000 description 9
- 238000005282 brightening Methods 0.000 description 8
- 239000003921 oil Substances 0.000 description 8
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 6
- 125000000129 anionic group Chemical group 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 229910052717 sulfur Inorganic materials 0.000 description 6
- 239000011593 sulfur Substances 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- RGCKGOZRHPZPFP-UHFFFAOYSA-N alizarin Chemical compound C1=CC=C2C(=O)C3=C(O)C(O)=CC=C3C(=O)C2=C1 RGCKGOZRHPZPFP-UHFFFAOYSA-N 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 239000004094 surface-active agent Substances 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 229920001522 polyglycol ester Polymers 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910045601 alloy Inorganic materials 0.000 description 3
- 239000000956 alloy Substances 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- SRDGTYWWLZMLTA-UHFFFAOYSA-N C(=O)C=C.C(=S)=S Chemical compound C(=O)C=C.C(=S)=S SRDGTYWWLZMLTA-UHFFFAOYSA-N 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 150000002148 esters Chemical class 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 102000009027 Albumins Human genes 0.000 description 1
- 108010088751 Albumins Proteins 0.000 description 1
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 150000008055 alkyl aryl sulfonates Chemical class 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 1
- QGJOPFRUJISHPQ-NJFSPNSNSA-N carbon disulfide-14c Chemical compound S=[14C]=S QGJOPFRUJISHPQ-NJFSPNSNSA-N 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 1
- 235000019797 dipotassium phosphate Nutrition 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- 229910000027 potassium carbonate Inorganic materials 0.000 description 1
- 235000015320 potassium carbonate Nutrition 0.000 description 1
- JCBJVAJGLKENNC-UHFFFAOYSA-M potassium ethyl xanthate Chemical compound [K+].CCOC([S-])=S JCBJVAJGLKENNC-UHFFFAOYSA-M 0.000 description 1
- 239000011541 reaction mixture Substances 0.000 description 1
- 150000003378 silver Chemical class 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 description 1
- 150000003464 sulfur compounds Chemical class 0.000 description 1
- 239000000725 suspension Substances 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
- C25D3/46—Electroplating: Baths therefor from solutions of silver
-
- 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
- C25D3/48—Electroplating: Baths therefor from solutions of gold
Definitions
- the presentinventio n relates to" an improved method and bath for bright electroplating metals and particularlyfor the bright plating of the noble metals, gold and silver and their alloys.
- The' brightening efiect obtained with such sulfur containing brighteners evidently depends upon sulfur being built into a certain extent in the silver being deposited and the optimum brightening efiect evidently depends upon having an exactly predetermined amount of sulfur taken up by the silver deposit.
- the problem, in producing bright electroplating baths for plating noble metals,'therefore, essentially lies in finding sulfur compounds whose controlled decomposition under the conditions of the electrolysis cause the optimum quantity of sulfur to be taken up by the deposited noble metal.
- condensation products have the advantage that they are soluble in alkaline plating baths and practically do not decompose in such a way as to contaminate the baths even after long use of the baths containing them. It was unexpectedly found that the brightening elfect of such condensation products is not only substantially better than those of carbon disulfide and xanthate but also that they are suited for gold plating baths as well as'for silver plating baths. The latter is most surprising as none of the previously employed brighteners could be effectively employed in plating both metals. V
- the condensation product which is used. as a brightener in electroplating baths according to the invention canbe produced as follows: 1600 grams of carhon disulfide aremixed with a solution of 850 grams of NaOH in 4 liters o f water and then adding 1200 grams of acrolein lwith stirring while maintaining the temperaice,
- xanthate instead of starting with carbon disulfide, it is also posisible to start with xanthate which is more easy to handle.
- 1 kilogram of potassium ethyl xanthate can be suspended in500 cc. of water and 400 cc. of acrolein are added to the suspension with strong stirring.
- the condensation product can be precipitated with water or a 0.5% aqueous acetic acid solution. In the first instance a pH of 10.11 is obtained and in the latter instance a pH of 67 is obtained.
- the condensation product is carefullydried at aslow a temperature as possible.
- Optimum brightening effects can be achieved with baths according to the invention which also contain an anionic surface active agent.
- Sulfonated oils such as, Turkeyred oil
- the anionic surface active agents can beused'in quantities of 0.2 to 4.0 grams per liter and preferably 0.5 to 2.0 grams perliter of bath liquid.
- the brightener according to the invention is not only effective in producing bright silver platings but also bright gold and bright goldsilver alloy platings. It was found however that it is advantageous in the case of gold and gold-silver alloy electroplating baths to use baths containing a high content of free cyanide.
- the gold to cyanide ratio preferably should be between about 1:20 to 1:60.
- Conductive salts such as carbonates or phosphates can also be incorporated in the gold plating baths. 0 7 h
- the brightening elfect of the baths according to the invention is independent of the thickness of the plating produced in wide ranges, so that generally platings of any desired thickness between several ,u.
- the plating bath is free of dirt.
- a weak brown colored film forms on the anode when the bath stands with the current cut off, and such film upon switching. on of the current again can lead to an abnormalincrease in potential, This phenomena is .often.accompanied with the formation of a light haze on thecathode. .
- This haze however can easily be removed without difficulty by polishing.
- the formation of the film on the anode and haze on the cathode however can easily be avoided by adding a small amount of fresh brightener to the baths at the beginning of the passage of current. The increase in potential and haze formation on the cathode are thereby avoided with certainty.
- the brightening effect according to the invention can also be promoted by moderate movement of the plating bath.
- a simple quiet movement of the cathode suffices.
- turbulent currents are in any event to be avoided in the plating baths.
- Example 1 An aqueous bath for bright plating of silver of the following composition was prepared:
- Example 2 An aqueous bath for bright plating gold of the following composition was prepared:
- Example 3 An aqueous bath for bright plating a gold and silver alloy containing 73 to 76% of the following composition was prepared:
- the baths according to the invention furthermore have the advantage that the platings obtained are relatively harder than those obtainable with previously known electroplating baths.
- the platings obtained with the bath of Example 2 had a hardness of -130 kg./mm.
- the hardness of the plating obtained with the bath according to Example 1 was also 110-130 kg./mm. and the hardness of the plating with the bath according to Example 3 was even higher, namely, l40-160 kg./mm.
- a bright metal electroplating bath for electroplating a metal from the group consisting of gold, silver and gold-silver alloys comprising an aqueous cyanide solution of a salt of the selected metal and containing as a brightener a condensation product of carbon disulfide and an unsaturated aldehyde selected from the group consisting of acrolein and its alpha substitution products products in an amount sufiicient to impart brightness to the electro-deposited metal.
- a bright metal electroplating bath for electroplating a metal from the group consisting of gold, silver and goldsilver alloys comprising an aqueous cyanide solution of a salt of-the selected metal and containing as a brightener a condensation product obtained by condensing an alkali metal xanthate with an unsaturated aldehyde selected from the group consisting of acrolein and its alpha substitution products in an amount suflicient to impart brightmess to the electro-deposited metal.
- a bright metal electroplating bath according to claim 1 in which the quantity of said condensation product is 0.4 to 1.0 gram of the condensation product per liter of bath.
- a bright metal electroplating bath according to claim 1 comprising in addition 0.1 to 2.0 grams per liter of bath of a water soluble polyglycol ester of a fatty acid containing 4 to 15 carbon atoms.
- a bright metal electroplating bath according to claim 1 comprising in addition 0.2 to 0.8 gram per liter of bath of a water soluble polyglycol ester of a fatty acid containing 4 to 15 carbon atoms.
- a bright metal electroplating bath according to claim 1 comprising in addition 0.2 to 0.4 gram per liter of bath of an anionic surface active agent.
- a bright metal electroplating bath according to claim 1 comprising in addition 0.5 to 2.0 grams per liter of bath of Turkey-red oil.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DED18105A DE958795C (de) | 1954-06-26 | 1954-06-26 | Bad fuer das galvanische Abscheiden glaenzender UEberzuege von Silber, Gold und Legierungen dieser Metalle |
| DED21150A DE1008079B (de) | 1954-06-26 | 1955-08-25 | Bad fuer das galvanische Abscheiden glaenzender UEberzuege von Silber, Gold und Legierungen dieser Metalle |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2800439A true US2800439A (en) | 1957-07-23 |
Family
ID=25970699
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US517652A Expired - Lifetime US2800439A (en) | 1954-06-26 | 1955-06-23 | Bright metal plating |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US2800439A (enrdf_load_stackoverflow) |
| CH (1) | CH338073A (enrdf_load_stackoverflow) |
| DE (2) | DE958795C (enrdf_load_stackoverflow) |
| FR (1) | FR1126363A (enrdf_load_stackoverflow) |
| GB (1) | GB807095A (enrdf_load_stackoverflow) |
| NL (2) | NL106458C (enrdf_load_stackoverflow) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2978390A (en) * | 1957-07-22 | 1961-04-04 | Bell Telephone Labor Inc | Gold plating solutions |
| US3020217A (en) * | 1956-10-19 | 1962-02-06 | Sel Rex Precious Metals Inc | Mirror bright gold alloy electroplating |
| US3446716A (en) * | 1966-01-05 | 1969-05-27 | Max Schlotter Dr Ing | Electrodeposition of bright silver |
| US3475292A (en) * | 1966-02-10 | 1969-10-28 | Technic | Gold plating bath and process |
| US4121982A (en) * | 1978-02-03 | 1978-10-24 | American Chemical & Refining Company Incorporated | Gold alloy plating bath and method |
| FR2825721A1 (fr) * | 2001-06-12 | 2002-12-13 | Engelhard Clal Sas | Melange utilisable comme brillanteur dans un bain de depot electrolytique d'argent, d'or ou d'un de leurs alliages |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE1232351B (de) | 1961-02-04 | 1967-01-12 | Degussa | Verfahren zur Herstellung von schwefelhaltigen Kondensationsprodukten |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2666738A (en) * | 1950-09-15 | 1954-01-19 | Hanson Van Winkle Munning Co | Bright silver plating |
-
0
- NL NL197948D patent/NL197948A/xx unknown
-
1954
- 1954-06-26 DE DED18105A patent/DE958795C/de not_active Expired
-
1955
- 1955-05-27 CH CH338073D patent/CH338073A/de unknown
- 1955-06-10 NL NL197948A patent/NL106458C/xx active
- 1955-06-22 FR FR1126363D patent/FR1126363A/fr not_active Expired
- 1955-06-23 US US517652A patent/US2800439A/en not_active Expired - Lifetime
- 1955-06-27 GB GB18534/55A patent/GB807095A/en not_active Expired
- 1955-08-25 DE DED21150A patent/DE1008079B/de active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2666738A (en) * | 1950-09-15 | 1954-01-19 | Hanson Van Winkle Munning Co | Bright silver plating |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3020217A (en) * | 1956-10-19 | 1962-02-06 | Sel Rex Precious Metals Inc | Mirror bright gold alloy electroplating |
| US2978390A (en) * | 1957-07-22 | 1961-04-04 | Bell Telephone Labor Inc | Gold plating solutions |
| US3446716A (en) * | 1966-01-05 | 1969-05-27 | Max Schlotter Dr Ing | Electrodeposition of bright silver |
| US3475292A (en) * | 1966-02-10 | 1969-10-28 | Technic | Gold plating bath and process |
| US4121982A (en) * | 1978-02-03 | 1978-10-24 | American Chemical & Refining Company Incorporated | Gold alloy plating bath and method |
| FR2825721A1 (fr) * | 2001-06-12 | 2002-12-13 | Engelhard Clal Sas | Melange utilisable comme brillanteur dans un bain de depot electrolytique d'argent, d'or ou d'un de leurs alliages |
| WO2002101119A1 (fr) * | 2001-06-12 | 2002-12-19 | Metalor Technologies France S.A.S. | Melange utilisable comme brillanteur dans un bain de depot electrolytique d'argent, d'or ou d'un de leurs alliages |
Also Published As
| Publication number | Publication date |
|---|---|
| DE958795C (de) | 1957-02-21 |
| FR1126363A (fr) | 1956-11-21 |
| CH338073A (de) | 1959-04-30 |
| NL106458C (enrdf_load_stackoverflow) | 1963-06-17 |
| GB807095A (en) | 1959-01-07 |
| DE1008079B (de) | 1957-05-09 |
| NL197948A (enrdf_load_stackoverflow) |
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