US3349016A - Process for employing an auxiliary anode made of high purity nickel - Google Patents
Process for employing an auxiliary anode made of high purity nickel Download PDFInfo
- Publication number
- US3349016A US3349016A US425012A US42501265A US3349016A US 3349016 A US3349016 A US 3349016A US 425012 A US425012 A US 425012A US 42501265 A US42501265 A US 42501265A US 3349016 A US3349016 A US 3349016A
- Authority
- US
- United States
- Prior art keywords
- nickel
- auxiliary anode
- high purity
- current
- plating
- 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
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims description 122
- 229910052759 nickel Inorganic materials 0.000 title claims description 60
- 238000000034 method Methods 0.000 title description 9
- 238000007747 plating Methods 0.000 claims description 30
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 6
- 229910052717 sulfur Inorganic materials 0.000 claims description 6
- 239000011593 sulfur Substances 0.000 claims description 6
- 238000004070 electrodeposition Methods 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 7
- 238000005260 corrosion Methods 0.000 description 5
- 230000007797 corrosion Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 4
- 239000010802 sludge Substances 0.000 description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 3
- 229910052804 chromium Inorganic materials 0.000 description 3
- 239000011651 chromium Substances 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- 241000080590 Niso Species 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 239000010405 anode material Substances 0.000 description 1
- 239000011260 aqueous acid Substances 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- -1 electrolytic nickel Chemical compound 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 239000011133 lead Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910001453 nickel ion Inorganic materials 0.000 description 1
- KERTUBUCQCSNJU-UHFFFAOYSA-L nickel(2+);disulfamate Chemical compound [Ni+2].NS([O-])(=O)=O.NS([O-])(=O)=O KERTUBUCQCSNJU-UHFFFAOYSA-L 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- IIACRCGMVDHOTQ-UHFFFAOYSA-M sulfamate Chemical compound NS([O-])(=O)=O IIACRCGMVDHOTQ-UHFFFAOYSA-M 0.000 description 1
- FZUJWWOKDIGOKH-UHFFFAOYSA-N sulfuric acid hydrochloride Chemical compound Cl.OS(O)(=O)=O FZUJWWOKDIGOKH-UHFFFAOYSA-N 0.000 description 1
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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/18—Electroplating using modulated, pulsed or reversing current
-
- 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
Definitions
- Insoluble anodes are attended by disadvantages in the common or usual chloridecontaining nickel plating solutions in that chlorine is evolved from the surface of the insoluble anode during plating. Accordingly, it is advantageous in many situations to employ a high purity nickel, e.g., electrolytic nickel, as an auxiliary anode.
- a high purity nickel material is employed as the auxiliary anode in usual chloride-containing nickel plating baths, it dissolves therein.
- high purity nickel material such as electrolytic nickel containing not more than about 0.001% sulfur, tends to proceed unevenly and is attended by the generation of loose metallic nickel.
- the final plating step is a chromium plating operation and it is found that a nickel auxiliary anode of high purity may be employed satisfactorily in the chromium plating bath as Well as in the nickel plating bath.
- a nickel auxiliary anode of high purity may be employed satisfactorily in the chromium plating bath as Well as in the nickel plating bath.
- the fact that the auxiliary anode is mounted directly in the fixture with the work makes it impossible, as a practical matter, to employ anode bags about the auxiliary anode as is done in the case of anodes which remain fixed in their position in the nickel plating tank itself. Accordingly, a problem has remained in the art as to how high purity nickel auxiliary anodes could be employed in nickel plating operations without encountering the production of a metallic sludge.
- the present invention contemplates a process for electrodepositing nickel from a nickel plating bath containing at least about 3 grams per liter (g.p.l.) of chloride ion using an auxiliary anode made of high purity nickel wherein the current applied to the auxiliary anode comprises a direct plating current having an anode current density at the auxiliary anode of about 5 to about 75 amperes per square foot and having superimposed upon said direct current (DC) an alternating current (AC) in a ratio of alternating current to direct current of at least 4:1 and with the frequency of the al ternating current being not greater than 20 cycles per second.
- DC direct current
- AC alternating current
- the ratio of alternating current to direct current may be in a range of about 4 to 1 to about 6 to 1 and the frequency range employed for the alternating current may be about 5 cycles per second to about 20 cycles per sec ond, e.g., 5 cycles per second, 15 cycles per second or 20 cycles per second.
- a nickel plating bath of the Watts type containing about 330 g.p.l. of nickel sulfate (NiSO .7H O), about 45 g.p.l. of nickel chloride (NiCl .6H O), and about 38 g.p.l. of boric acid, having a pH of about 4 and a temperature of about F. is established.
- Electrolytic nickel containing about 99.9% nickel and not more than about 0.001% sulfur is employed as an auxiliary anode in fixed relation to a recessed area in work to be plated. Bagged nicked anodes are also employed in the bath. About 10% of the total plating current is supplied to the auxiliary anode with the remainder being supplied to the bagged nickel anodes.
- the accompanying drawing depicts a schematic arrangement for carrying out the present invention, including an exemplary circuit for supplying AC superimposed on DC and including a schematic depiction of an auxiliary anode. assembly 1 connected to the current source.
- a workpiece having a recessed area is depicted at 11.
- This workpiece is mounted upon a rack 12 which also has afilxed thereon an auxiliary anode 13 which is mechanically fastened to, and electrically insulated from, rack 12;.
- the assembly is immersed in a plating tank 14. Additional fixed anodes, not shown in the drawing, may also be employed in the bath.
- the electrical circuit includes an AC source 15 which may be, for example, .an AC generator and amplifier, a commutator and battery, or any other convenient AC source, and a DC source :16 which may be, for example, a battery or a rectifier, etC., which may have the output thereof controlled by a variable resistance 17.
- Directcurrent may be measured by a DC ammeter 18 and the alternating current by an oscilloscope 19 which is advantageously connected in parallel with a fixed noninductive resistance 20.
- auxiliary anode By means of the auxiliary anode depicted in the drawing, nickel is plated in controlled amounts at and within recessed :areas, such as that depicted in section in the workpiece 11 at the same time nickel is being applied to other portions of the work by means of deposition from other anodes suspended in the tank 14.
- Superimposed alternating current need only be applied to the auxiliary anode in carrying out the invention and this procedure is advantageous from the standpoint of current economy.
- the process is operative when the superimposed alternating current is imposed uponall anodes in the plating bath.
- the plating bath may be a chloride-sulfate bath, such as the -Watts bath, an all-chloride bath, a sulfamate bath, etc.
- Such baths contain at least about 3 g.p.l. of chloride ions and, more advantageously, at least about g.p.l. of chloride ions.
- Satisfactory nickel plating bath compositions contain up to about 400 g.p.l., e.g., about 25 to about 330 g.p.l., of nickel sulfate (NiSO .7H O), about 3 to about 350 g.p.l., e.g., about 10 to about 300 g.p.l., of nickel chloride (NiCl .6H O), up to about 700 g.p.l. of nickel sulfamate, up to about 300 g.p.l. of nickel fiuoborate, and about 25 to about 40 g.p.l. of boric acid.
- NiSO .7H O nickel sulfate
- NiCl .6H O nickel chloride
- the nickel ion concentration in these baths is about 50 to about 150 g.p.l.; the baths are operated in the pH range of about 1.5 to about 5, at cathode current densities of upto about 300 or 400 amperes per square foot (a.s.f.), and at temperatures from room temperature up 4. to about F.
- Any of theusual proprietary chloridecontaining semibright and brightnickel plating baths and any of the usual proprietary chromiumplating baths may be employed.
- nickel material containing not more than about 0.001% sulfur, not more than about 0.03% carbon, not more than about 0.01% copper, not more than about 0.01% iron, not'more than about 0.1% cobalt, and the balance nickel, with the nickel content being at least about 99.85%.
- the process for electrodepositing nickel which comprises fastening an auxiliary anode made of high purity nickel containing not more than about 0.001% sulfur in fixed relation to a recessed area in .work to be plated, immersing said auxiliary anode and said work in a chloride-containing nickel plating bath, supplying to said auxiliary anode a plating current comprising a direct current and a superimposed ,laternating current having a frequency of about 5 cycles per second to 20 cycles per second and with the current ratio of alternating current to direct current being at least about 4 to 1.
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)
- Electroplating Methods And Accessories (AREA)
Priority Applications (9)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US425012A US3349016A (en) | 1965-01-12 | 1965-01-12 | Process for employing an auxiliary anode made of high purity nickel |
| GB884/66A GB1059899A (en) | 1965-01-12 | 1966-01-07 | Electrodeposition of nickel |
| CH30566A CH439907A (fr) | 1965-01-12 | 1966-01-11 | Procédé de dépôt électrolytique du nickel |
| AT20366A AT264241B (de) | 1965-01-12 | 1966-01-11 | Verfahren zur elektrolytischen Abscheidung von Nickel |
| FR45536A FR1463437A (fr) | 1965-01-12 | 1966-01-11 | Procédé perfectionné de nickelage par galvanoplastie |
| ES0321622A ES321622A1 (es) | 1965-01-12 | 1966-01-11 | Un procedimiento para deposicion electrolitica de niquel. |
| NL6600324A NL6600324A (es) | 1965-01-12 | 1966-01-11 | |
| LU50239A LU50239A1 (es) | 1965-01-12 | 1966-01-12 | |
| BE675013D BE675013A (es) | 1965-01-12 | 1966-01-12 |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US425012A US3349016A (en) | 1965-01-12 | 1965-01-12 | Process for employing an auxiliary anode made of high purity nickel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3349016A true US3349016A (en) | 1967-10-24 |
Family
ID=23684775
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US425012A Expired - Lifetime US3349016A (en) | 1965-01-12 | 1965-01-12 | Process for employing an auxiliary anode made of high purity nickel |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US3349016A (es) |
| AT (1) | AT264241B (es) |
| BE (1) | BE675013A (es) |
| CH (1) | CH439907A (es) |
| ES (1) | ES321622A1 (es) |
| GB (1) | GB1059899A (es) |
| LU (1) | LU50239A1 (es) |
| NL (1) | NL6600324A (es) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3450605A (en) * | 1966-10-25 | 1969-06-17 | United Aircraft Corp | Minimization of anode passivation in electroplating processes |
| US20090242409A1 (en) * | 2008-03-31 | 2009-10-01 | Nec Electronics Corporation | Plating method, semiconductor device manufacturing method and plate processing system |
| US20140061035A1 (en) * | 2007-10-05 | 2014-03-06 | Create New Technology S.R.L. | System and method of plating metal alloys by using galvanic technology |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2274056A (en) * | 1940-05-29 | 1942-02-24 | Int Nickel Co | Extruded anode |
| US2470775A (en) * | 1947-07-09 | 1949-05-24 | Westinghouse Electric Corp | Electroplating nickel and cobalt with periodic reverse current |
| US2706170A (en) * | 1951-11-15 | 1955-04-12 | Sperry Corp | Electroforming low stress nickel |
| US2951978A (en) * | 1957-05-29 | 1960-09-06 | Thor P Ulvestad | Reverse pulse generator |
-
1965
- 1965-01-12 US US425012A patent/US3349016A/en not_active Expired - Lifetime
-
1966
- 1966-01-07 GB GB884/66A patent/GB1059899A/en not_active Expired
- 1966-01-11 NL NL6600324A patent/NL6600324A/xx unknown
- 1966-01-11 ES ES0321622A patent/ES321622A1/es not_active Expired
- 1966-01-11 AT AT20366A patent/AT264241B/de active
- 1966-01-11 CH CH30566A patent/CH439907A/fr unknown
- 1966-01-12 BE BE675013D patent/BE675013A/xx unknown
- 1966-01-12 LU LU50239A patent/LU50239A1/xx unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2274056A (en) * | 1940-05-29 | 1942-02-24 | Int Nickel Co | Extruded anode |
| US2470775A (en) * | 1947-07-09 | 1949-05-24 | Westinghouse Electric Corp | Electroplating nickel and cobalt with periodic reverse current |
| US2706170A (en) * | 1951-11-15 | 1955-04-12 | Sperry Corp | Electroforming low stress nickel |
| US2951978A (en) * | 1957-05-29 | 1960-09-06 | Thor P Ulvestad | Reverse pulse generator |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3450605A (en) * | 1966-10-25 | 1969-06-17 | United Aircraft Corp | Minimization of anode passivation in electroplating processes |
| US20140061035A1 (en) * | 2007-10-05 | 2014-03-06 | Create New Technology S.R.L. | System and method of plating metal alloys by using galvanic technology |
| US20090242409A1 (en) * | 2008-03-31 | 2009-10-01 | Nec Electronics Corporation | Plating method, semiconductor device manufacturing method and plate processing system |
Also Published As
| Publication number | Publication date |
|---|---|
| AT264241B (de) | 1968-08-26 |
| GB1059899A (en) | 1967-02-22 |
| CH439907A (fr) | 1967-07-15 |
| NL6600324A (es) | 1966-07-13 |
| BE675013A (es) | 1966-07-12 |
| ES321622A1 (es) | 1966-07-01 |
| LU50239A1 (es) | 1966-03-24 |
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