US3257294A - Acid metal electroplating process and baths - Google Patents
Acid metal electroplating process and baths Download PDFInfo
- Publication number
- US3257294A US3257294A US214490A US21449062A US3257294A US 3257294 A US3257294 A US 3257294A US 214490 A US214490 A US 214490A US 21449062 A US21449062 A US 21449062A US 3257294 A US3257294 A US 3257294A
- Authority
- US
- United States
- Prior art keywords
- bath
- concentration
- saturation concentration
- soluble
- electroplating
- 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
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/16—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms
- C07D295/20—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms acylated on ring nitrogen atoms by radicals derived from carbonic acid, or sulfur or nitrogen analogues thereof
- C07D295/21—Radicals derived from sulfur analogues of carbonic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/04—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
- C07D233/28—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
- C07D233/30—Oxygen or sulfur atoms
- C07D233/42—Sulfur atoms
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
-
- 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
-
- 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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
Definitions
- This invention relates to a method and bath for producing uniform electrodeposits of metals. It also relates to a method for maintaining uniformity of electroplating bath compositions. It has been found that by using difiicultly-soluble, electroplating-active organic additives which form a heterogeneous phase in acid metal electroplating baths it is possible to achieve a self-regulation of the brightening elfect and other bath properties which may be influenced by the addition of organic agents.
- electroplating-active additives such as brightening agents, leveling agents, grain-reducing agents, porosity-prevention agents, equalizing agents and wetting agents,'have been added to the electroplating baths in the form of aqueous solutions having a certain concentration.
- electroplating-active additives such as brightening agents, leveling agents, grain-reducing agents, porosity-prevention agents, equalizing agents and wetting agents.
- electroplating-active organic additives are used in accordance with the present invention which are difficultly soluble in the bath and form a heterogeneous phase.
- the electroplating bath is thereby continuously and in a-self-adjusting manner maintained near the saturation concentration of the additive component. If theconcentration of additives in the bath is reduced by normal consumption, the saturation concentration is again restored by the diificultly soluble substance lying on the bottom, so that further additions for the purpose of correcting the bath composition are not required during operation. Since the concentration of additives in the electrolyte remains constant, the bath does not require a continuous analytical surveillance. Consequently, in the baths compounded in accordance withthe present invention, the danger of an insutlicient orof an excessive electrolytes which are employed in each case.
- the difiicultly soluble additives of the heterogeneous bath phase may be liquid or solid and in the latter case ordinarily form a bottom deposit.
- the solid agents may also be employed in electroplating baths which are continuously or periodically cycled with the aid of a pump. Under these circumstances, for example, they may be introduced by means of solution filters into the cycling pump line.
- the substances employed as electroplating additives in accordance with the present invention are difficultly soluble organic compounds which are characterized by known groupings that bring about brightening, leveling, grain-improving or porosity-preventing effects.
- groups are, for example, nitrogen and/ or sulfur-containing groups, such as thiourea groups, dithiocarbamic acid groups, thioxanthogenic acid groups, trithiocarbonic acid groups, xanthogenic acid groups, thioimidazole or thiobenzimidazole groups, mercaptothiazole or mercaptobenzthiazole groups and other groups which contain a carbon atom attached only to hetero atoms, as well as azido groups, alkylene-diamine groups, polyamide groups and the like.
- These compounds may also contain watersolubilizing radicals, such as carboxyl groups and sulfonic acid groups, which form difficultly soluble metal salts with the heavy metal ions of the baths.
- the additives may contain the activating groups several times and in combination with each other, such as diificultly soluble compounds which contain simultaneously one or more thiourea groups and one or more dithiocarbamic acid groups.
- dificultly soluble compounds with known electroplating-active groups may be employed for the baths according to the present invention.
- suitable substituents such as aryl radicals.
- insoluble products with the above-mentioned active groups it is also possible to start from insoluble products with the above-mentioned active groups, and to render them soluble, for instance by an increase in the acid concentration of the bath electrolyte, or, in other instances, by addition of organic solvents, such as ethanol, isopropanol and the like.
- the saturation concentration of the difiicultly soluble agents amounts, as a rule, to at least twice the critical concentration of the agents.
- the maximum content of the additive in the electrolyte is determined by the upper limit of the saturation concentration, and an excess concentration is thereby avoided with certainty.
- the critical concentrations amount to from one-half to one-eighth of the saturation concentration, so that even those baths which comprise only a saturation concentration of 50 or l2* /2% of additive still produce satisfactory metal electroplates.
- the hourly consumption of additives amounts to about 3 to 16% of the differential quantities between saturation concentration and critical concentration (concentration tolerance range), whereby a certain operation reserve against unforseen incidents is provided and local inadequate dosing is excluded.
- An advantageous embodiment of the process according to the present invention comprises placing the difficultly soluble agents into a solution filter which is inserted into the circulation pump line for a continuous bath filtration device.
- a contamination trap filter is inserted before the solution filter.
- the difficultly soluble additive may 'be admixed with kieselguhr, activated charcoal, special purpose fire clay and other porous masses, or in the case of liquid additive agents the porous materials may be saturated therewith. The permeability and incompressibility of the filter layer is thereby assured.
- the wettability of the solid difficultly soluble agent by the bath fluid may be improved by the addition. of wetting agents.
- suflicient to circulate the bath at the customary bath circulation rate of about one totwo bath volumes per hour, that is at the rate sufiicient to achieve an adequate continuous filtration.
- The'process according to the present invention may be applied in conjunction with acid electroplating baths for copper, zinc, nickel, lead, tin and cadmium.
- the baths may be modified with customary wetting agents, such as the known ethylene oxide addition products to high molecular organic compounds with exchangeable hydrogen atoms, alkyl sulfates and the like. These wetting agents are soluble, but they are effective over a broad range of concentrations and therefore do not require close surveillance.
- the difiicultly soluble additive is a brightening agent, whose leveling effect is insufficient, the leveling effect may be improved by simultaneously employing a leveling additive which is either in the form of a difiic-ultly soluble compound or also in soluble form.
- the content of leveling agentin the bath requires surveillance.
- the agent must from time to time be replenished in accordance with its consumption.
- particularly advantageous are diflicultly soluble additives which perform several functions, that is, which simultaneously produce full brightness, a leveling effect and also possess a temperature tolerance which is sufficient for practical requirements.
- Example I A bath having the following composition was used for acid copper electroplating: l
- solution fil ter contained, as the diflicultly soluble brightening agent, N,-N" di benzylthiocarbamyl-diethylene-triamine-N'-di- 4 thiocarbonyl-S-propane-w-copper sulfonate of the formula s orn-Nni-NH 1H2 3 H; s
- the bath produced bright, smooth, bud-free and pore-free copper electrodeposits in a current density range of 0.5 to 8 amps/dm. at a temperature tolerance of 17 to 30 C.
- the leveling effect of the bath was sufficient to meet the requirements of many practical uses, so that the concurrent employment of other additives was not necessary.
- the saturation concentration of the brightening agent lies in thevicinity of 10 mg./l., and the critical concentration amounts to about 50% of the saturation concentration and therefore lies at about 5 mg./l.
- the consumption of brightening agent per ampere hour amounted to 0.8 mg, so that satisfactory operation of the bath was assured for up to 6 ampere hours per liter, even upon failure of the solution filter.'
- Example 11 When an acid copper electroplating bath of the fol lowing composition 210 g./l. of copper sulfate, CuSO -5H O g./l. of sulfuric acid 8 g./l. of the addition product of 8 mols of ethylene oxide to 1 mol of a coconut fatty alcohol mixture C12 C18- was used and, analogous to Example 1, the solution filter was charged with pipera-zine-N,N bis-dithiocarbonyLS- propane-w-sodium sulfonate oft-he formula as the difiicultly soluble brightening agent, and the bath was recycled at a rate of one bath volume per hour, this bath produced bright, smooth, bud free and porefree copper electroplates within a current density range of 0.5 to 8 amps/dm.
- the leveling effect of the bath was adequate for many areas of application even without the addition of special leveling agents.
- the saturation concentration of the difficultly soluble additive lies around 40 mg./l. and the critical concentration is about 25% of the saturation concentration and therefore lies at about 10 mg./l.
- abrightening agent consumption rate of 1.2 mg./ampere hour therefore, an operation reserve of 25 ampere hours per liter of the bath was assured.
- Example III In conjunction with an acid copper electroplating bath having the same composition as that in Example 2, N- stearyl-dithiocarbamylS-propane-w-sodium sulfonate of the formula which had been produced by known processes, was inampere hour amounted to about 1.5 mg, so that the bath could remain operative for 17 ampere hours per liter even after failure of the circulating apparatus.
- Example IV In conjunction with an acid copper electroplating bath composed of piperazine-N,N' bis-dithiocarbonyl-S-propionic acid sodium of the formula fix GET-CH2 S was charged as the difiicultly soluble brightening agent into a solution filter located downstream from a customary contamination trap filter. At a recycling rate of one bath volume per hour, the bath produced bright, smooth, bud-free and pore-free copper electroplates in a current density range of 0.5 to 8 arnps/dm. with a temperature tolerance of 17 to 30 C. At a saturation concentration of the difiicultly soluble additive of 30 mg./l., a critical concentration of about 12 mg./l. which amounts to 40% of the saturation concentration and a brightening agent consumption of 1.5 mg./ ampere hour, an operating reserve of 12 ampere hours per liter results for this bath.
- an acid copper electroplating bath composed of piperazine-N,N' bis-dithiocarbonyl-S
- Example V In conjunction with an acid copperplating bath having the same composition as the bath described in Example 4, thiazole-pyrazolone, which is known to be useful as a dye, was used as the solid brightening agent phase. At a recycling rate of one bath volume per hour, this bath produced uniform, clean, smooth, hard, but not brittle, pore-free and very fine-grain copper electroplates in a current density range of 0.5 to 8 amps/drn. with a temperature tolerance of 17 to 30 C. This bath was very highly suitable for galvano-plastic purposes. The saturation concentration of the difficulty soluble additive lies at about 96 mg./l., the critical concentration lies at about 12.5% of the saturation concentration and is therefore about 12 mg./l. At a consumption of 4 mg. of brightening agent per ampere hour, an operating reserve of 21 ampere hours per liter results for this bath.
- Example VI 6 Example VII In conjunction with an acid copper electroplating bath of the same composition as the bath described in Example IV, the solution filter located downstream from a customary contamination trap filter was charged with a mixture consisting of the solid, difiiculty soluble brightening agent used in Example I and the difiiculty soluble leveling agent 1-benzyl-thiocarbamyl-Z-mercaptoimidazoline of the formula At a recycling rate of one bath volume per hour, this bath produced uniformly bright copper electrodeposits with good leveling characteristics in a current density range of 0.5 to 8 amps/dm. with a temperature tolerance of 17 to 30 C. The saturation concentration of the ditficulty soluble leveling agent amounts to 6 mg./l. and
- the critical concentration lies at about 1.5 mg./l., which I corresponds to about 25% of the saturation concentration. From these values and based on a consumption of about 0.4 mg./l. per ampere hour, this bath has an operating reserve of 11 ampere hours per liter.
- this bath produced bright and pore-free copper electrodeposits with good leveling properties in a current density range of 1 to' 8 amps/drn. with a temperature tolerance of 17 to 30 C.
- a saturation concentration of the leveling agent of about 4 mg./l.
- a critical concentration of about 0.5 mg./l. corresponding to 12.5% of the saturation concentration
- a consumption of about 0.2 mg. per ampere hour an operating reserve of about 17 ampere hours per liter results for this bath.
- Example IX In conjunction with an-acid copper electroplating bath composed basically of 210 g./l. of copper sulfate, CuSO -5H O 60 g./l. of sulfuric acid 35 C.
- This bath is very highly suited for the production of phonograph record matrices and other galvano-plastic purposes.
- the saturation concentration of the additive lies at about 70 mg./l. and its critical concentration amounts to about 6% of the saturation concentration, and therefore lies at about 4 mg./l. Based on a consumption of about 2 mg. per ampere hour, an operating reserve of 32 ampere hours per liter results for this bath.
- Example X In Conjunction with an acid copper-electroplating bath composed of 210 g./l. of copper sulfate, CuSO -5H O 120 g./l. of sulfuric acid and 8 g./l. of the addition product of 8 mols of ethylene oxide to 1 mol of coconut fatty alcohol mixture C C the difliculty soluble brightening agent N-phenyl-thiocarbamyl-piperazine N dithiocarbonyl S propane-wcopper sulfonate of the formula 4 was used. At a recycling rate of one bath volume per Example XI An acid Zinc electroplating bath composed of 240 g./l.
- this bath produced clean, pore-free and soft zinc electrodeposits in a current density range of L to 8 amps/dm. with a temperature tolerance of 17 to 30 C. and at a pH-value of the bath of 1.5 to 3.0.
- the saturation concentration of the difficultly soluble additive lies at about 18 mg./l., the critical concentration at about 7 mg./l., which therefore corresponds to about 39% of the saturation concentration.
- Example XII An acid nicket electroplating bath composed of was modified with 4-butyl-5,6-benzocumarin of the formula as the diflicultly soluble leveling agent lying at the bottom of the electroplating vessel.
- the leveling agent is self-regulating, whereas the dissolved brightening agent requires constant surveillance which, however, in view of its broad effective range, is without substantial importance.
- this bath produced pore-free, ductile nickel electrodeposits with uniform brightness and leveling properties in a current density range of 1 to 8 amps/ dm. with a temperature tolerance of 45 to 60 C.
- the saturation concentration of the difficultly soluble leveling agent lies at 55 C. in the neighborhood of about mg./l. and the critical concentration at the same temperature is about 50 mg./l. Based on a consumption of about 10 mg. per ampere hour, an operating reserve of 10 ampere hours perliter results for this bath.
- a self-regulating electroplating 'bath for the electrodeposition of metals capable of being electrodeposited from acid solution comprising (1) an acid solution of an inorganic salt of the metal to be electrodeposited, and
- a heterogeneous phase consisting solely of an auxiliary electroplate-improving organic addition agent which (a) is sparsely soluble in said acid electroplating bath, (b) has a saturation concentration of 0.5 to 500 mgm. per liter of electroplating bath liquid, and (c) has a critical concentration of about half of said saturation concentration, said addition agent being present in said bath in multiple quantities of said saturation concentration.
- the improved method of electrodepositing a metal capable of being electrodeposited from an acid electroplating bath in the presence of an auxiliary electroplateirnproving organic addition agent which comprises electrodepositing said metal from a self-regulating electroplating bath comprising (1) an acid solution of an inorganic salt of the metal to be electrodeposited, and i (2) a heterogeneous phase consisting solely of an auxiliary electroplate-improving organic addition agent which 9 (a) is sparsely soluble in said acid electroplating bath, (b) has a saturation concentration of 0.5 to 500 mgm. per liter of electroplating bath liquid, and (c) has a critical concentration of about half of said saturation concentration, said addition agent being present in said bath in multiple quantities of said saturation concentration.
- (b) has a saturation concentration of 0.5 to 500 mgm.
- (c) has a critical cocnentration of about half of said saturation concentration, in multiple quantities of said saturation concentration.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Automation & Control Theory (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Filtering Materials (AREA)
- Chemically Coating (AREA)
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DED36777A DE1224111B (de) | 1961-08-10 | 1961-08-10 | Saure galvanische Kupfer- und Nickelbaeder und Verfahren zum Abscheiden der UEberzuege |
DED0039520 | 1962-08-01 |
Publications (1)
Publication Number | Publication Date |
---|---|
US3257294A true US3257294A (en) | 1966-06-21 |
Family
ID=25971309
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US214490A Expired - Lifetime US3257294A (en) | 1961-08-10 | 1962-08-03 | Acid metal electroplating process and baths |
US298424A Expired - Lifetime US3245886A (en) | 1961-08-10 | 1963-07-29 | Electroplating process and self-regulating electroplating baths therefor |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US298424A Expired - Lifetime US3245886A (en) | 1961-08-10 | 1963-07-29 | Electroplating process and self-regulating electroplating baths therefor |
Country Status (6)
Country | Link |
---|---|
US (2) | US3257294A (fr) |
BE (1) | BE621297A (fr) |
CH (1) | CH429356A (fr) |
DE (2) | DE1224111B (fr) |
GB (2) | GB941823A (fr) |
NL (1) | NL281922A (fr) |
Cited By (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3518171A (en) * | 1969-07-24 | 1970-06-30 | Metalux Corp The | Purification of nickel electroplating solutions |
US4190514A (en) * | 1977-06-06 | 1980-02-26 | Tokuyama Soda Kabushiki Kaisha | Electrolytic cell |
US4244791A (en) * | 1979-04-19 | 1981-01-13 | Swiss Aluminium Ltd. | Acidic electrolyte containing SnII ions |
US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
US4614568A (en) * | 1983-06-14 | 1986-09-30 | Nihon Kogyo Kabushiki Kaisha | High-speed silver plating and baths therefor |
EP0219945A2 (fr) * | 1985-09-05 | 1987-04-29 | Solvay Interox Limited | Stabilisation de solutions acides de peroxyde d'hydrogène |
EP2128903A1 (fr) * | 2008-05-30 | 2009-12-02 | Atotech Deutschland Gmbh | Additif d'électrodéposition pour le dépôt d'un meéal ou d'un alliage binaire, ternaire, quaternaire ou pentanaire des éléments de groupe 11 (IB)-groupe 13 (lllA)-groupe 16 (VIA) |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH494824A (de) * | 1969-07-10 | 1970-08-15 | Fluehmann Werner | Verfahren zur elektrolytischen Abscheidung von Kupfer hoher Duktilität |
US3669853A (en) * | 1969-07-15 | 1972-06-13 | Chemetron Corp | Coumarin-carrier addition agent for nickel baths |
US4014761A (en) * | 1975-01-06 | 1977-03-29 | M & T Chemicals Inc. | Bright acid zinc plating |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1003092A (en) * | 1907-04-11 | 1911-09-12 | Ontario Nickel Company Ltd | Method of electrolyzing nickel-sulfate solutions. |
US1371414A (en) * | 1919-06-17 | 1921-03-15 | Thomas A Edison | Nickel-plating |
US2248092A (en) * | 1934-10-26 | 1941-07-08 | Sherka Chemical Co Inc | Method for treating electroplating baths |
US2449422A (en) * | 1944-04-15 | 1948-09-14 | Harshaw Chem Corp | Electrodeposition of nickel |
US2640021A (en) * | 1949-11-23 | 1953-05-26 | United Chromium Inc | Composition, bath, and process for chromium plating |
US2879211A (en) * | 1956-11-16 | 1959-03-24 | Hanson Van Winkle Munning Co | Electroplating duplex nickel coatings |
US2885399A (en) * | 1957-03-04 | 1959-05-05 | Univ Ohio State Res Found | Hydrazinium hexafluorophosphate salts |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE1071438B (de) * | 1959-12-17 | Deutsche Gold- und Silber-Scheideanstalt vormals Roessler, Frankfurt/M | Anode für galvanische Bäder und Verfahren zu ihrer Herstellung | |
AT172066B (de) * | 1950-03-27 | 1952-08-11 | H C Dr Wilhelm Dipl Pfanhauser | Verfahren zur Herstellung harter, glänzender Kupferniederschläge durch elektrolytische Abscheidung |
NL202744A (fr) * | 1953-09-19 | |||
US2799634A (en) * | 1954-02-26 | 1957-07-16 | Westinghouse Electric Corp | Combined addition agents for acid copper plating |
BE550706A (fr) * | 1956-01-27 | |||
DE1152863B (de) * | 1957-03-16 | 1963-08-14 | Riedel & Co | Saure Baeder zur Herstellung von einebnenden Kupferueberzuegen |
-
0
- BE BE621297D patent/BE621297A/xx unknown
- NL NL281922D patent/NL281922A/xx unknown
-
1961
- 1961-08-10 DE DED36777A patent/DE1224111B/de active Pending
-
1962
- 1962-03-24 CH CH355962A patent/CH429356A/de unknown
- 1962-07-12 GB GB26837/62A patent/GB941823A/en not_active Expired
- 1962-08-01 DE DE19621421977 patent/DE1421977B2/de active Pending
- 1962-08-03 US US214490A patent/US3257294A/en not_active Expired - Lifetime
-
1963
- 1963-07-29 US US298424A patent/US3245886A/en not_active Expired - Lifetime
- 1963-07-31 GB GB30313/63A patent/GB1055243A/en not_active Expired
Patent Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US1003092A (en) * | 1907-04-11 | 1911-09-12 | Ontario Nickel Company Ltd | Method of electrolyzing nickel-sulfate solutions. |
US1371414A (en) * | 1919-06-17 | 1921-03-15 | Thomas A Edison | Nickel-plating |
US2248092A (en) * | 1934-10-26 | 1941-07-08 | Sherka Chemical Co Inc | Method for treating electroplating baths |
US2449422A (en) * | 1944-04-15 | 1948-09-14 | Harshaw Chem Corp | Electrodeposition of nickel |
US2640021A (en) * | 1949-11-23 | 1953-05-26 | United Chromium Inc | Composition, bath, and process for chromium plating |
US2879211A (en) * | 1956-11-16 | 1959-03-24 | Hanson Van Winkle Munning Co | Electroplating duplex nickel coatings |
US2885399A (en) * | 1957-03-04 | 1959-05-05 | Univ Ohio State Res Found | Hydrazinium hexafluorophosphate salts |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3518171A (en) * | 1969-07-24 | 1970-06-30 | Metalux Corp The | Purification of nickel electroplating solutions |
US4190514A (en) * | 1977-06-06 | 1980-02-26 | Tokuyama Soda Kabushiki Kaisha | Electrolytic cell |
US4244791A (en) * | 1979-04-19 | 1981-01-13 | Swiss Aluminium Ltd. | Acidic electrolyte containing SnII ions |
US4376685A (en) * | 1981-06-24 | 1983-03-15 | M&T Chemicals Inc. | Acid copper electroplating baths containing brightening and leveling additives |
US4614568A (en) * | 1983-06-14 | 1986-09-30 | Nihon Kogyo Kabushiki Kaisha | High-speed silver plating and baths therefor |
EP0219945A2 (fr) * | 1985-09-05 | 1987-04-29 | Solvay Interox Limited | Stabilisation de solutions acides de peroxyde d'hydrogène |
EP0219945A3 (fr) * | 1985-09-05 | 1988-11-30 | Solvay Interox Limited | Stabilisation de solutions acides de peroxyde d'hydrogène |
EP2128903A1 (fr) * | 2008-05-30 | 2009-12-02 | Atotech Deutschland Gmbh | Additif d'électrodéposition pour le dépôt d'un meéal ou d'un alliage binaire, ternaire, quaternaire ou pentanaire des éléments de groupe 11 (IB)-groupe 13 (lllA)-groupe 16 (VIA) |
WO2009144036A1 (fr) * | 2008-05-30 | 2009-12-03 | Atotech Deutschland Gmbh | Additif de dépôt électrolytique pour le dépôt d’un alliage de métal binaire, ternaire, quaternaire ou pentanaire d'éléments du groupe 11 (ib) -groupe 13 (iiia) - groupe 16 (via) |
US20110094583A1 (en) * | 2008-05-30 | 2011-04-28 | Atotech Deutschland Gmbh | Electroplating additive for the deposition of metal, a binary, ternary, quaternary or pentanary alloy of elements of group 11 (ib)-group 13 (iiia)-group 16 (via) |
US8828278B2 (en) * | 2008-05-30 | 2014-09-09 | Atotech Deutschland Gmbh | Electroplating additive for the deposition of metal, a binary, ternary, quaternary or pentanary alloy of elements of group 11 (IB)—group 13 (IIIA)—Group 16 (VIA) |
Also Published As
Publication number | Publication date |
---|---|
GB1055243A (en) | 1967-01-18 |
DE1224111B (de) | 1966-09-01 |
NL281922A (fr) | |
CH429356A (de) | 1967-01-31 |
DE1421977A1 (de) | 1968-11-07 |
BE621297A (fr) | |
GB941823A (en) | 1963-11-13 |
DE1421977B2 (de) | 1970-02-19 |
US3245886A (en) | 1966-04-12 |
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