US3401097A - Electrodeposition of nickel - Google Patents
Electrodeposition of nickel Download PDFInfo
- Publication number
- US3401097A US3401097A US416911A US41691164A US3401097A US 3401097 A US3401097 A US 3401097A US 416911 A US416911 A US 416911A US 41691164 A US41691164 A US 41691164A US 3401097 A US3401097 A US 3401097A
- Authority
- US
- United States
- Prior art keywords
- nickel
- bath
- solution
- plating
- employed
- 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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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical group [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title description 36
- 229910052759 nickel Inorganic materials 0.000 title description 18
- 238000004070 electrodeposition Methods 0.000 title description 3
- 239000000243 solution Substances 0.000 description 16
- 238000007747 plating Methods 0.000 description 14
- 239000000654 additive Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- 125000004432 carbon atom Chemical group C* 0.000 description 9
- 150000002894 organic compounds Chemical class 0.000 description 9
- 230000000996 additive effect Effects 0.000 description 7
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 6
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 6
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 6
- 239000002585 base Substances 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000011260 aqueous acid Substances 0.000 description 4
- 125000003118 aryl group Chemical group 0.000 description 4
- 239000010953 base metal Substances 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 125000001301 ethoxy group Chemical group [H]C([H])([H])C([H])([H])O* 0.000 description 4
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 4
- NVBFHJWHLNUMCV-UHFFFAOYSA-N sulfamide Chemical compound NS(N)(=O)=O NVBFHJWHLNUMCV-UHFFFAOYSA-N 0.000 description 4
- 125000004417 unsaturated alkyl group Chemical group 0.000 description 4
- 229910000831 Steel Inorganic materials 0.000 description 3
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 3
- -1 chloroalkyl sulfonic acid Chemical compound 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000002659 electrodeposit Substances 0.000 description 3
- 238000000034 method Methods 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- 238000006467 substitution reaction Methods 0.000 description 3
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 241000080590 Niso Species 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 125000002877 alkyl aryl group Chemical group 0.000 description 2
- 125000003710 aryl alkyl group Chemical group 0.000 description 2
- 239000003637 basic solution Substances 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- 239000007795 chemical reaction product Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- UIIIBRHUICCMAI-UHFFFAOYSA-N prop-2-ene-1-sulfonic acid Chemical compound OS(=O)(=O)CC=C UIIIBRHUICCMAI-UHFFFAOYSA-N 0.000 description 2
- DEVUYWTZRXOMSI-UHFFFAOYSA-N (sulfamoylamino)benzene Chemical compound NS(=O)(=O)NC1=CC=CC=C1 DEVUYWTZRXOMSI-UHFFFAOYSA-N 0.000 description 1
- RXXCIBALSKQCAE-UHFFFAOYSA-N 3-methylbutoxymethylbenzene Chemical compound CC(C)CCOCC1=CC=CC=C1 RXXCIBALSKQCAE-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 1
- 239000003929 acidic solution Substances 0.000 description 1
- 150000001299 aldehydes Chemical class 0.000 description 1
- 235000019270 ammonium chloride Nutrition 0.000 description 1
- 238000005282 brightening Methods 0.000 description 1
- DLDJFQGPPSQZKI-UHFFFAOYSA-N but-2-yne-1,4-diol Chemical group OCC#CCO DLDJFQGPPSQZKI-UHFFFAOYSA-N 0.000 description 1
- 239000007859 condensation product Substances 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000001465 metallisation Methods 0.000 description 1
- 150000002816 nickel compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 229940124530 sulfonamide Drugs 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- 230000002195 synergetic effect Effects 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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
Definitions
- More brilliant and ductile nickel electrodeposits are obtained by incorporating into a conventional and known solution bath an additive having the formula in which the R radicals are selected from the group consisting of hydrogen, unsaturated alkyls with 2 to 6 carbon atoms, aryls, aralkyls, alkaryls, R-SO, radicals where R has 1 to 4 carbon atoms, ethoxy groups and halogenated aryls.
- the additive may be employed in very small quantities (as low as 0.05 gram/liter).
- the present invention relates to improvements in the production of electrodeposits, wherein the addition of certain agents to an aqueous acidic bath, in particular a nickel plating solution, will produce electrodeposits of superior brilliance, level, ductility and adhesion.
- the plating is conventionally expected to possess suflicient brightness'to be satisfactorily employable, ability to show all its surface imperfections filled in by the coating deposited thereon, and a good adhesion of the metal deposition upon the base metal especially while maintaining a desirably high degree of ductility. Furthermore, the plating should possess a satisfactory degree of throwing power and maintain a high receptivity to subsequent platings.
- a conventional plating bath for nickel generally consists of an aqueous acid solution of nickel sulfate or nickel chloride or a mixture of the two, a buffer compound such as boric acid or formic acid or nickel fluoborate, and sometimes other salts such as ammonium chloride, sodium sulfate, magnesium sulfate solutions, and the like.
- the bath is kept at temperatures of usually 75 to 160 F. depending on the particular composition of the bath and the current density employed in the plating process may range anywhere from 0.5 to 100 amperes per square foot.
- the following bath composition and operating conditions are typical of the art:
- the main object of the present invention to provide anadditi-ve to be employed in electrodeposition of nickel to obtain an extremely satisfactory deposit having all of the above-mentioned properties.
- the additive of this invention to be used in conjunction with conventional nickel plating bath solutions is an unsaturated organic compound having the general empirical formula:
- R R R and R are selected from the group consisting of hydrogen (to a maximum of three substitutions), unsaturated alkyls having at least 2 but not more than 6 carbon atoms, aryls, aralkyls, alkaryls, RfiSo radicals wherein R has from 1 to 4 carbon atoms, ethoxy groups and halogenated aryls.
- Example II To one liter of the basic solution of Example I was added 1 gram of diallyl sulfamide and the bath was em- 3 ployed to nickel plate a precleaned steel base at 140 F. a pH of 4.0 and at a current density of 40 amps/square foot. Substantially equal results were obtained as when using the additive of Example I.
- Example III To one liter of the basic solution of Example I were added 0.9 gram of monoallyl sulfamide, 2.0 grams of benzene sulfamide and, as a secondary brightener, 0.1 gram of Z-butyne-l, 4-diol and the bath was employed to nickel plate a precleaned steel base at 140 F., a pH of 4.2 and at a current density of 40 amps/ square foot. The results obtained were, when compared with those of Example I, well within the expectations and clearly superior to those of the prior art upon comparison with baths containing, for example, allyl sulfonic acid brighteners or conventional sulfamides.
- the conditions of the baths will vary within certain limits which are recognized as being suitable for the purpose by any person skilled in the art.
- the temperature of the bath may vary between 75 F. and 160 F.
- the pH of the solution may range from 1 to 6 depending on the basic bath constituents
- the current density during the electrodeposition may be of the order of 0.5 to 100 amperes per square foot.
- a bath for electrodepositing nickel comprising in an aqueous acid solution a material selected from the group consisting of nickel chloride, nickel sulfate, nickel fluoborate, and mixtures thereof, said solution having also dissolved therein an organic compound having the empirical formula wherein R R R and R are selected from the group consisting of hydrogen (to a maximum of three substitutions), unsaturated alkyls having from 2 to 6 carbon atoms, benzene rings, RSO radicals wherein R has from 1 to 4 carbon atoms, and ethoxy groups, said organic compound having a concentration in the aqueous acid solution ranging between about 0.05 gram per liter and saturation.
- a bath according to claim 1 wherein said organic compound is diallyl sulfamide.
- a bath according to claim 1 wherein said organic compound is employed in conjunction with other commonly known bath brighteners.
- a bath according to claim 6, wherein said other commonly known bath brightener is 2-butyne-1,4-diol.
- the process of electrodepositing nickel onto a base metal which comprises preparing an aqueous acidic solution consisting of (a) a nickel compound selected from the group consisting of nickel chloride, nickel sulfate, mixtures of nickel chloride and sulfate, nickel chloride and fiuoborate, nickel sulfate and fiuoborate, and nickel chloride, sulfate, and fiuoborate, (b) an organic compound having the empirical general formula R Ra ⁇ N-SO2N/ R2 R4 wherein R R R R and R are selected from the group consisting of hydrogen (to a maximum of three substitutions), unsaturated alkyls having from 2 to 6 carbon atoms, benzene rings, R--SO radicals wherein R has from 1 to 4 carbon atoms, and ethoxy groups, said organic compound being present in a concentration of between 0.05 g./l. and saturation and electroplating the metal base at from to 160 F., at a pH of 1 to 6 and at a
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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)
Description
United States Patent ABSTRACT OF THE DISCLOSURE More brilliant and ductile nickel electrodeposits are obtained by incorporating into a conventional and known solution bath an additive having the formula in which the R radicals are selected from the group consisting of hydrogen, unsaturated alkyls with 2 to 6 carbon atoms, aryls, aralkyls, alkaryls, R-SO, radicals where R has 1 to 4 carbon atoms, ethoxy groups and halogenated aryls. The additive may be employed in very small quantities (as low as 0.05 gram/liter).
The present invention relates to improvements in the production of electrodeposits, wherein the addition of certain agents to an aqueous acidic bath, in particular a nickel plating solution, will produce electrodeposits of superior brilliance, level, ductility and adhesion.
It is known to modify nickel electroplating baths with brightening agents such as sulfonamides, sulfonimides, etc. The plating is conventionally expected to possess suflicient brightness'to be satisfactorily employable, ability to show all its surface imperfections filled in by the coating deposited thereon, and a good adhesion of the metal deposition upon the base metal especially while maintaining a desirably high degree of ductility. Furthermore, the plating should possess a satisfactory degree of throwing power and maintain a high receptivity to subsequent platings.
Various types of plating bath compositions are known for the bright plating of metals. Heretofore, the abovementioned properties'of the end product have been only partially improved by the introduction into the plating bath mixture of brighteners. A large number of organic or inorganic materials have been used'as brighteners but such brighteners are often only effective with certain metals other than nickel or have certain disadvantages which lead to difficulties when all of the abovementioned desired properties have to be enhanced'and/ or maintained to a satisfactory degree.
A conventional plating bath for nickel, for example, generally consists of an aqueous acid solution of nickel sulfate or nickel chloride or a mixture of the two, a buffer compound such as boric acid or formic acid or nickel fluoborate, and sometimes other salts such as ammonium chloride, sodium sulfate, magnesium sulfate solutions, and the like. The bath is kept at temperatures of usually 75 to 160 F. depending on the particular composition of the bath and the current density employed in the plating process may range anywhere from 0.5 to 100 amperes per square foot. The following bath composition and operating conditions :are typical of the art:
NiSO '7H O g./l 300 NiCl -6H O g./l 45 H3BO3 g./1 Temperature F 75 pH of solution 2-6 Current density "amps/ft" 10-75 3,401,097 Patented Sept. .10, 1968 To the above typical bath solution, and for that matter to all other similar composition described, for example, in US. Patent 2,523,191 to H. Brown, additives are added to improve the properties of the products, namely, the levelling power (or ability to fill in surface imperfections in the base metal) the brightness of the deposition, the adhesion of the coating, the ductility of the coated base metal, the throwin power of the deposited coating, the receptivity of the product to subsequent plating.
Additives such as allyl sulfonic acid, chloroalkyl sulfonic acid, reaction products of soluble acetylenic compounds having from 2 to 15 carbon atoms, condensation products of unsaturated aldehydes, and compounds con.- taining the group -SO N= are all known and described in the literature. They, admittedly, either alone or in combination with auxiliary additives improve some of the above-mentioned prerequisites of a product but not a satisfactorily suflicient number of them to render the product commercially excelling.
It is, therefore, the main object of the present invention to provide anadditi-ve to be employed in electrodeposition of nickel to obtain an extremely satisfactory deposit having all of the above-mentioned properties.
The additive of this invention to be used in conjunction with conventional nickel plating bath solutions, is an unsaturated organic compound having the general empirical formula:
wherein R R R and R are selected from the group consisting of hydrogen (to a maximum of three substitutions), unsaturated alkyls having at least 2 but not more than 6 carbon atoms, aryls, aralkyls, alkaryls, RfiSo radicals wherein R has from 1 to 4 carbon atoms, ethoxy groups and halogenated aryls.
It has been found that, besides obtaining over-all superior properties of the product (brighteness, levelling power, adhesion, ductility, throwing power, receptivity to plating), considerably minor amounts of the additive may be employed while maintaining a high degree of tolerance to metal contaminations of the solutions. Using the specific bath composition mentioned hereabove, quantities of the additive of the invention as low as 0.05 gram per liter of solution may be effectively employed. Generally, amounts of 1 gram per liter have been found to be ample.
The following are examples which illustrate the present invention.
EXAMPLE I One liter of an aqueous nickel plating bath of the following composition was prepared:
Grams NiSO -7H O 300 Boric acid 40 To this solution were added 0.9 gram of monoallyl sulfamide and the bath was employed to nickel plate a precleaned steel base at F. a pH of 4.2 and at a current density of 40 amperes per square foot. A nickel plate was obtained which showed an exceptionally gOOd levelling of the surface imperfections, was extremely bright, had excellent adhesion of the coating even when bent into a U-shaped form, showed very high throwing power and was found to be highly receptive to subsequent plating operations.
EXAMPLE II To one liter of the basic solution of Example I was added 1 gram of diallyl sulfamide and the bath was em- 3 ployed to nickel plate a precleaned steel base at 140 F. a pH of 4.0 and at a current density of 40 amps/square foot. Substantially equal results were obtained as when using the additive of Example I.
The various additives of the present invention need not be employed alone, but may be used in conjunction with other additives or brighteners. These auxiliary or secondary brighteners may be conventional or those of the present invention. Obviously, the results obtained may be, often, superior with respect to some of the properties. However, this is not always the case, that is, no synergistic or even additive effect are sometimes achieved. Results substantially equal to those of Example I were obtained in the following example.
EXAMPLE III To one liter of the basic solution of Example I were added 0.9 gram of monoallyl sulfamide, 2.0 grams of benzene sulfamide and, as a secondary brightener, 0.1 gram of Z-butyne-l, 4-diol and the bath was employed to nickel plate a precleaned steel base at 140 F., a pH of 4.2 and at a current density of 40 amps/ square foot. The results obtained were, when compared with those of Example I, well within the expectations and clearly superior to those of the prior art upon comparison with baths containing, for example, allyl sulfonic acid brighteners or conventional sulfamides.
The conditions of the baths will vary within certain limits which are recognized as being suitable for the purpose by any person skilled in the art. Thus, for example, the temperature of the bath may vary between 75 F. and 160 F., the pH of the solution may range from 1 to 6 depending on the basic bath constituents, and the current density during the electrodeposition may be of the order of 0.5 to 100 amperes per square foot.
Although the illustrative examples have been directed to the electroplating of nickel, it should be understood that the present inventive brightener is equally applicable to the electroplating of copper upon a metal base. The same process conditions and concentrations in the acidic bath are employed when copper is to be electrodeposited.
What is claimed is:
1. A bath for electrodepositing nickel comprising in an aqueous acid solution a material selected from the group consisting of nickel chloride, nickel sulfate, nickel fluoborate, and mixtures thereof, said solution having also dissolved therein an organic compound having the empirical formula wherein R R R and R are selected from the group consisting of hydrogen (to a maximum of three substitutions), unsaturated alkyls having from 2 to 6 carbon atoms, benzene rings, RSO radicals wherein R has from 1 to 4 carbon atoms, and ethoxy groups, said organic compound having a concentration in the aqueous acid solution ranging between about 0.05 gram per liter and saturation.
2. A bath according to claim 1 wherein said organic compound has a concentration in the aqueous acid solution ranging between about 0.05 gram per liter and 1.00 gram per liter.
3. A bath according to claim 1 wherein said organic compound is monoallyl sulfamide.
4. A bath according to claim 1 wherein said organic compound is diallyl sulfamide.
5. A bath according to claim 1 wherein two of the Rs selected from the group consisting of R R R and R are hydrogen and two others are benzene rings.
6. A bath according to claim 1 wherein said organic compound is employed in conjunction with other commonly known bath brighteners.
7. A bath according to claim 6, wherein said other commonly known bath brightener is 2-butyne-1,4-diol.
8. The process of electrodepositing nickel onto a base metal Which comprises preparing an aqueous acidic solution consisting of (a) a nickel compound selected from the group consisting of nickel chloride, nickel sulfate, mixtures of nickel chloride and sulfate, nickel chloride and fiuoborate, nickel sulfate and fiuoborate, and nickel chloride, sulfate, and fiuoborate, (b) an organic compound having the empirical general formula R Ra \N-SO2N/ R2 R4 wherein R R R and R are selected from the group consisting of hydrogen (to a maximum of three substitutions), unsaturated alkyls having from 2 to 6 carbon atoms, benzene rings, R--SO radicals wherein R has from 1 to 4 carbon atoms, and ethoxy groups, said organic compound being present in a concentration of between 0.05 g./l. and saturation and electroplating the metal base at from to 160 F., at a pH of 1 to 6 and at a current density of 0.5 to amperes per square foot in said solution.
References Cited UNITED STATES PATENTS 2,191,813 2/1940 Brown 204-49 3,152,975 10/1964 Kardos et al. 204-49 JOHN H. MACK, Primary Examiner.
G. KAPLAN, Assistant Examiner.
Priority Applications (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US416911A US3401097A (en) | 1964-12-08 | 1964-12-08 | Electrodeposition of nickel |
| GB44038/65A GB1069970A (en) | 1964-12-08 | 1965-10-18 | Improvements in or relating to electro-plating processes |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US416911A US3401097A (en) | 1964-12-08 | 1964-12-08 | Electrodeposition of nickel |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3401097A true US3401097A (en) | 1968-09-10 |
Family
ID=23651811
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US416911A Expired - Lifetime US3401097A (en) | 1964-12-08 | 1964-12-08 | Electrodeposition of nickel |
Country Status (2)
| Country | Link |
|---|---|
| US (1) | US3401097A (en) |
| GB (1) | GB1069970A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3518170A (en) * | 1965-07-26 | 1970-06-30 | Ibm | Electrodeposition of iron group metals |
| US4071353A (en) * | 1972-09-05 | 1978-01-31 | Stauffer Chemical Company | Sulfonamide herbicide antidote compositions and methods of use |
| US4243418A (en) * | 1976-06-25 | 1981-01-06 | Ciba-Geigy Corporation | Compositions for fireproofing polyester fiber materials with substituted sulphurylamides |
| US20110219971A1 (en) * | 2008-09-30 | 2011-09-15 | Daetwyler Swisstec Ag | Doctor blade |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2191813A (en) * | 1939-12-01 | 1940-02-27 | Udylite Corp | Electrodeposition of nickel from an acid bath |
| US3152975A (en) * | 1961-02-07 | 1964-10-13 | Hanson Van Winkle Munning Co | Electrodeposition of nickel |
-
1964
- 1964-12-08 US US416911A patent/US3401097A/en not_active Expired - Lifetime
-
1965
- 1965-10-18 GB GB44038/65A patent/GB1069970A/en not_active Expired
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US2191813A (en) * | 1939-12-01 | 1940-02-27 | Udylite Corp | Electrodeposition of nickel from an acid bath |
| US3152975A (en) * | 1961-02-07 | 1964-10-13 | Hanson Van Winkle Munning Co | Electrodeposition of nickel |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3518170A (en) * | 1965-07-26 | 1970-06-30 | Ibm | Electrodeposition of iron group metals |
| US4071353A (en) * | 1972-09-05 | 1978-01-31 | Stauffer Chemical Company | Sulfonamide herbicide antidote compositions and methods of use |
| US4243418A (en) * | 1976-06-25 | 1981-01-06 | Ciba-Geigy Corporation | Compositions for fireproofing polyester fiber materials with substituted sulphurylamides |
| US20110219971A1 (en) * | 2008-09-30 | 2011-09-15 | Daetwyler Swisstec Ag | Doctor blade |
| US9044927B2 (en) * | 2008-09-30 | 2015-06-02 | Daetwyler SwissTech AG | Doctor blade |
Also Published As
| Publication number | Publication date |
|---|---|
| GB1069970A (en) | 1967-05-24 |
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