US2828252A - Electrodeposition of bright zinc, copper, or nickel - Google Patents
Electrodeposition of bright zinc, copper, or nickel Download PDFInfo
- Publication number
- US2828252A US2828252A US425322A US42532254A US2828252A US 2828252 A US2828252 A US 2828252A US 425322 A US425322 A US 425322A US 42532254 A US42532254 A US 42532254A US 2828252 A US2828252 A US 2828252A
- Authority
- US
- United States
- Prior art keywords
- bath
- copper
- bright
- nickel
- baths
- 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
- 239000010949 copper Substances 0.000 title claims description 16
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims description 15
- 229910052802 copper Inorganic materials 0.000 title claims description 15
- 239000011701 zinc Substances 0.000 title claims description 9
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 title claims description 7
- 229910052725 zinc Inorganic materials 0.000 title claims description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title description 18
- 229910052759 nickel Inorganic materials 0.000 title description 9
- 238000004070 electrodeposition Methods 0.000 title description 2
- 239000007859 condensation product Substances 0.000 claims description 26
- 238000009713 electroplating Methods 0.000 claims description 22
- HGINCPLSRVDWNT-UHFFFAOYSA-N Acrolein Chemical compound C=CC=O HGINCPLSRVDWNT-UHFFFAOYSA-N 0.000 claims description 20
- 229910052751 metal Inorganic materials 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 20
- 239000004202 carbamide Substances 0.000 claims description 11
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000000047 product Substances 0.000 claims description 5
- 239000003792 electrolyte Substances 0.000 claims description 4
- 238000006467 substitution reaction Methods 0.000 claims description 3
- 238000007747 plating Methods 0.000 description 20
- 239000000203 mixture Substances 0.000 description 14
- 235000013877 carbamide Nutrition 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 229920001522 polyglycol ester Polymers 0.000 description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- 125000004432 carbon atom Chemical group C* 0.000 description 6
- 235000014113 dietary fatty acids Nutrition 0.000 description 6
- 229930195729 fatty acid Natural products 0.000 description 6
- 239000000194 fatty acid Substances 0.000 description 6
- 150000004665 fatty acids Chemical class 0.000 description 6
- 150000001299 aldehydes Chemical class 0.000 description 5
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 230000002378 acidificating effect Effects 0.000 description 4
- 150000002739 metals Chemical class 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- -1 urea aldehyde Chemical class 0.000 description 4
- 239000012991 xanthate Substances 0.000 description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 3
- 150000007513 acids Chemical class 0.000 description 3
- 125000002252 acyl group Chemical group 0.000 description 3
- 229910052783 alkali metal Inorganic materials 0.000 description 3
- 125000003342 alkenyl group Chemical group 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 125000003710 aryl alkyl group Chemical group 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920006395 saturated elastomer Polymers 0.000 description 3
- MNWBNISUBARLIT-UHFFFAOYSA-N sodium cyanide Chemical compound [Na+].N#[C-] MNWBNISUBARLIT-UHFFFAOYSA-N 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Chemical group 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910001369 Brass Inorganic materials 0.000 description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-N Guanidine Chemical compound NC(N)=N ZRALSGWEFCBTJO-UHFFFAOYSA-N 0.000 description 2
- 239000010951 brass Substances 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002659 electrodeposit Substances 0.000 description 2
- VKYKSIONXSXAKP-UHFFFAOYSA-N hexamethylenetetramine Chemical compound C1N(C2)CN3CN1CN2C3 VKYKSIONXSXAKP-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- NNFCIKHAZHQZJG-UHFFFAOYSA-N potassium cyanide Chemical compound [K+].N#[C-] NNFCIKHAZHQZJG-UHFFFAOYSA-N 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- XFXPMWWXUTWYJX-UHFFFAOYSA-N Cyanide Chemical compound N#[C-] XFXPMWWXUTWYJX-UHFFFAOYSA-N 0.000 description 1
- MGJKQDOBUOMPEZ-UHFFFAOYSA-N N,N'-dimethylurea Chemical compound CNC(=O)NC MGJKQDOBUOMPEZ-UHFFFAOYSA-N 0.000 description 1
- CHJJGSNFBQVOTG-UHFFFAOYSA-N N-methyl-guanidine Natural products CNC(N)=N CHJJGSNFBQVOTG-UHFFFAOYSA-N 0.000 description 1
- 229930040373 Paraformaldehyde Natural products 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical compound [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000007743 anodising Methods 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 1
- 239000004327 boric acid Substances 0.000 description 1
- KXZJHVJKXJLBKO-UHFFFAOYSA-N chembl1408157 Chemical compound N=1C2=CC=CC=C2C(C(=O)O)=CC=1C1=CC=C(O)C=C1 KXZJHVJKXJLBKO-UHFFFAOYSA-N 0.000 description 1
- 239000012295 chemical reaction liquid Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010924 continuous production Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- DOBRDRYODQBAMW-UHFFFAOYSA-N copper(i) cyanide Chemical compound [Cu+].N#[C-] DOBRDRYODQBAMW-UHFFFAOYSA-N 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- SWSQBOPZIKWTGO-UHFFFAOYSA-N dimethylaminoamidine Natural products CN(C)C(N)=N SWSQBOPZIKWTGO-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- ZOOODBUHSVUZEM-UHFFFAOYSA-N ethoxymethanedithioic acid Chemical compound CCOC(S)=S ZOOODBUHSVUZEM-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000004312 hexamethylene tetramine Substances 0.000 description 1
- 235000010299 hexamethylene tetramine Nutrition 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 229920002866 paraformaldehyde Polymers 0.000 description 1
- 229920000151 polyglycol Polymers 0.000 description 1
- 239000010695 polyglycol Substances 0.000 description 1
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- ZLUDZECJEZTVEX-UHFFFAOYSA-N prop-2-enal;urea Chemical compound C=CC=O.NC(N)=O ZLUDZECJEZTVEX-UHFFFAOYSA-N 0.000 description 1
- 239000001632 sodium acetate Substances 0.000 description 1
- 235000017281 sodium acetate Nutrition 0.000 description 1
- RZFBEFUNINJXRQ-UHFFFAOYSA-M sodium ethyl xanthate Chemical compound [Na+].CCOC([S-])=S RZFBEFUNINJXRQ-UHFFFAOYSA-M 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 description 1
- 150000003672 ureas Chemical class 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
Definitions
- the present invention relates to an improved electroplating bath for bright plating of metals, such as zinc, nickel and especially copper and copper alloys.
- urea reaction compounds found suitable for the preparation of the condensation products employed as brighteners according to the invention are of the following general formula R: N C R1 R: ⁇ NH2 in which R is oxygen, sulfur, or an imin group, and R and R are hydrogen, alkyl, alkenyl, aryl, aralkyl, or acyl groups of saturated or unsaturated acids.
- acrolein or an a substituted acrolein must be present in the aldehyde components of the urea or substituted urea aldehyde resins in order that the condensation products are active as brighteners.
- the acrolein or a substituted acroleins can be only a minor portion of the aldehyde component of the condensation product.
- the quantity of the condensation product added as a brightener to the electrolytic baths should be at least 0.5 g./l. and can otherwise vary within wide limits. In general smaller quantities are required in acidic baths than in alkaline baths .in which advantageously 3.5. to 35 g./l. of the condensation products are employed.
- condensation product added lies between 6 and 15, for examp1e, 10 g./l.
- other known brighteners such as, for example, potassium thiocyanate.
- the electroplating baths according to the invention can in addition to the urea condensation products, also contain water soluble polyglycol esters preferably those of fatty acids containing 4 to 15 carbon atoms.
- the polyglycol radical preferably is one produced from 5 to 25 moles of ethylene oxide.
- the polyglycol esters should be stable in alkalies up to 70 C. and at pH values up to about 13.
- the quantities of such polyglycol esters added can be between 2 and 20 g./l., preferably 5 and 10 g./l. of bath.
- the quantity of such xanthate addition can forexample be 0.01 to 1.0 g./l., preferably, 0.05 to 0.2 g./l. of bath.
- electrolytic baths containing organic brighteners ordinarily are not suited or only poorly suited for electroplating with periodically reversing current it was unexpectedly found that periodically reversing current can be employed with success in baths according to the invention especially when thick platings are desired. For example, plating periods of about 25 seconds and deplating periods of about 5 seconds can be employed.
- Example 1 An aqueous potassium cyanide containing copper plating bath of the following composition was prepared:
- Example 2 An aqueous sodium cyanide containing zinc plating bath of the following composition was prepared:
- the pH value of such bath was about 3.
- Example 4 An aqueous acidic copper plating bath of the following composition was prepared:
- Example 5 An aqueous copper plating bath of the following composition was prepared:
- Example 6 An aqueous brass plating bath of the following com position was prepared:
- Example 7 An aqueous copper plating bath of the followingcornposition was prepared:
- NaCN V 34.0 Na CO 15 of the metal to be deposited which contains as a bright ener at least 0.5 gram per liter of a condensation product of an unsaturated aldehyde selected from the group consisting of acrolein and its alpha substitution products, and a urea of the general formula V R: 02R: R:
- R is selected from the group consisting of oxygen, sulfur and imin radicals and R, and R are each selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, aralkyl and acyl groups of saturated and unsaturated acids.
- a bright metal electroplating bath according to claim 1 in which the quantity of said condensation product is 3.5 to 35 grams per liter of bath.
- a bright metal electroplating bath according to claim 1 comprising in addition 2 to 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 5 to 10 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 0.01 to 1 gram per liter of bath of an alkali metal xanthate.
- a bright metal electroplating bath according to claim 1 comprising in addition 0.05 to 0.2 gram per liter of bath of an alkali metal xanthate.
- a bright metal plating bath according to claim 1' containing at least one other brightener in addition to the condensation product.
- a method for producing a bright metal electrodeposit of a metal selected from the group consisting of zinc, copper and nickel which comprises electroplating a material in an electroplating bath comprising an aqueous electrolyte of the metal to be deposited which contains as a brightener at least 0.5 gram per liter of a condensation product of an unsaturated aldehyde selected from the group consisting of acrolein and its alpha substitution products, and a urea of the general formula /R: Gilli Ra NH, wherein R is selected from the group consisting of oxygen, sulfur and imin radicals and R and R are each selected from the group consisting of hydrogen, alkyl, alkenyl, aryl, aralkyl and acyl groups of saturated and unsaturated acids.
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 (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE771683X | 1953-04-28 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US2828252A true US2828252A (en) | 1958-03-25 |
Family
ID=6679272
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US425322A Expired - Lifetime US2828252A (en) | 1953-04-28 | 1954-04-23 | Electrodeposition of bright zinc, copper, or nickel |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US2828252A (en)) |
| BE (1) | BE528448A (en)) |
| FR (1) | FR1099718A (en)) |
| GB (1) | GB771683A (en)) |
| NL (2) | NL90899C (en)) |
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3021266A (en) * | 1957-08-12 | 1962-02-13 | Barnet D Ostrow | Additive for copper plating bath |
| US3088887A (en) * | 1958-11-03 | 1963-05-07 | Diamond Alkali Co | Electropolishing of zinc-copper alloys |
| US3101305A (en) * | 1957-03-16 | 1963-08-20 | Riedel & Co | Acid copper plating bath |
| US3116225A (en) * | 1960-07-30 | 1963-12-31 | Dehydag Gmbh | Nickel electroplating baths |
| US3168453A (en) * | 1961-06-28 | 1965-02-02 | Debe Anthony | Zinc cyanide plating bath |
| US3227638A (en) * | 1961-06-16 | 1966-01-04 | Robert H Burnson | Alkali cyanide bath and process for electroplating therewith |
| US3309293A (en) * | 1964-11-16 | 1967-03-14 | Elechem Corp | Copper cyanide electroplating bath |
| US3770599A (en) * | 1971-05-24 | 1973-11-06 | Oxy Metal Finishing Corp | Acid zinc plating baths |
| US3923613A (en) * | 1972-02-22 | 1975-12-02 | Kampschulte & Cie Dr W | Acidic galvanic copper bath |
| US4218292A (en) * | 1979-03-22 | 1980-08-19 | Mcgean Chemical Company, Inc. | Bright zinc electroplating 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 |
| US9234291B2 (en) | 2010-09-09 | 2016-01-12 | Globalfoundries Inc. | Zinc thin films plating chemistry and methods |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2101581A (en) * | 1936-05-02 | 1937-12-07 | Udylite Company | Process for obtaining bright zinc coating |
| US2146439A (en) * | 1934-11-12 | 1939-02-07 | Du Pont | Zinc plating |
| US2451341A (en) * | 1945-08-10 | 1948-10-12 | Westinghouse Electric Corp | Electroplating |
| US2457152A (en) * | 1943-07-07 | 1948-12-28 | Du Pont | Electrodepositing composition and bath |
| US2677654A (en) * | 1951-05-10 | 1954-05-04 | Poor & Co | Copper electroplating and compositions therefor |
-
0
- NL NLAANVRAGE8900197,A patent/NL187117B/xx unknown
- NL NL90899D patent/NL90899C/xx active
- BE BE528448D patent/BE528448A/xx unknown
-
1954
- 1954-04-23 US US425322A patent/US2828252A/en not_active Expired - Lifetime
- 1954-04-27 GB GB12165/54A patent/GB771683A/en not_active Expired
- 1954-04-27 FR FR1099718D patent/FR1099718A/fr not_active Expired
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2146439A (en) * | 1934-11-12 | 1939-02-07 | Du Pont | Zinc plating |
| US2101581A (en) * | 1936-05-02 | 1937-12-07 | Udylite Company | Process for obtaining bright zinc coating |
| US2457152A (en) * | 1943-07-07 | 1948-12-28 | Du Pont | Electrodepositing composition and bath |
| US2451341A (en) * | 1945-08-10 | 1948-10-12 | Westinghouse Electric Corp | Electroplating |
| US2677654A (en) * | 1951-05-10 | 1954-05-04 | Poor & Co | Copper electroplating and compositions therefor |
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3101305A (en) * | 1957-03-16 | 1963-08-20 | Riedel & Co | Acid copper plating bath |
| US3021266A (en) * | 1957-08-12 | 1962-02-13 | Barnet D Ostrow | Additive for copper plating bath |
| US3088887A (en) * | 1958-11-03 | 1963-05-07 | Diamond Alkali Co | Electropolishing of zinc-copper alloys |
| US3116225A (en) * | 1960-07-30 | 1963-12-31 | Dehydag Gmbh | Nickel electroplating baths |
| US3227638A (en) * | 1961-06-16 | 1966-01-04 | Robert H Burnson | Alkali cyanide bath and process for electroplating therewith |
| US3168453A (en) * | 1961-06-28 | 1965-02-02 | Debe Anthony | Zinc cyanide plating bath |
| US3309293A (en) * | 1964-11-16 | 1967-03-14 | Elechem Corp | Copper cyanide electroplating bath |
| US3770599A (en) * | 1971-05-24 | 1973-11-06 | Oxy Metal Finishing Corp | Acid zinc plating baths |
| US3923613A (en) * | 1972-02-22 | 1975-12-02 | Kampschulte & Cie Dr W | Acidic galvanic copper bath |
| US4218292A (en) * | 1979-03-22 | 1980-08-19 | Mcgean Chemical Company, Inc. | Bright zinc electroplating 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 |
| US9234291B2 (en) | 2010-09-09 | 2016-01-12 | Globalfoundries Inc. | Zinc thin films plating chemistry and methods |
Also Published As
| Publication number | Publication date |
|---|---|
| NL90899C (en)) | |
| FR1099718A (fr) | 1955-09-08 |
| GB771683A (en) | 1957-04-03 |
| NL187117B (nl) | |
| BE528448A (en)) |
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