US3677909A - Palladium-nickel alloy plating bath - Google Patents
Palladium-nickel alloy plating bath Download PDFInfo
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- US3677909A US3677909A US136588A US3677909DA US3677909A US 3677909 A US3677909 A US 3677909A US 136588 A US136588 A US 136588A US 3677909D A US3677909D A US 3677909DA US 3677909 A US3677909 A US 3677909A
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- United States
- Prior art keywords
- palladium
- nickel
- bath
- alloy plating
- nickel alloy
- Prior art date
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- Expired - Lifetime
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- 238000007747 plating Methods 0.000 title abstract description 15
- 229910000990 Ni alloy Inorganic materials 0.000 title abstract description 8
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical class [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 abstract description 64
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical class [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 abstract description 45
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 abstract description 15
- 238000013019 agitation Methods 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 229910021529 ammonia Inorganic materials 0.000 abstract description 4
- BSIDXUHWUKTRQL-UHFFFAOYSA-N nickel palladium Chemical compound [Ni].[Pd] BSIDXUHWUKTRQL-UHFFFAOYSA-N 0.000 abstract 1
- 229910052763 palladium Inorganic materials 0.000 description 30
- 229910052759 nickel Inorganic materials 0.000 description 20
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 7
- 235000011114 ammonium hydroxide Nutrition 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- -1 palladium ions Chemical class 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 229940124530 sulfonamide Drugs 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- CVHZOJJKTDOEJC-UHFFFAOYSA-N saccharin Chemical compound C1=CC=C2C(=O)NS(=O)(=O)C2=C1 CVHZOJJKTDOEJC-UHFFFAOYSA-N 0.000 description 5
- 229940081974 saccharin Drugs 0.000 description 5
- 235000019204 saccharin Nutrition 0.000 description 5
- 239000000901 saccharin and its Na,K and Ca salt Substances 0.000 description 5
- BFNBIHQBYMNNAN-UHFFFAOYSA-N ammonium sulfate Chemical compound N.N.OS(O)(=O)=O BFNBIHQBYMNNAN-UHFFFAOYSA-N 0.000 description 4
- 229910052921 ammonium sulfate Inorganic materials 0.000 description 4
- 235000011130 ammonium sulphate Nutrition 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 4
- LMYRWZFENFIFIT-UHFFFAOYSA-N toluene-4-sulfonamide Chemical compound CC1=CC=C(S(N)(=O)=O)C=C1 LMYRWZFENFIFIT-UHFFFAOYSA-N 0.000 description 4
- 229910001369 Brass Inorganic materials 0.000 description 3
- 229910001252 Pd alloy Inorganic materials 0.000 description 3
- 239000010951 brass Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 150000002815 nickel Chemical class 0.000 description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 description 3
- 239000013535 sea water Substances 0.000 description 3
- VEQPNABPJHWNSG-UHFFFAOYSA-N Nickel(2+) Chemical compound [Ni+2] VEQPNABPJHWNSG-UHFFFAOYSA-N 0.000 description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 150000003863 ammonium salts Chemical class 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 238000007654 immersion Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 2
- 229910001453 nickel ion Inorganic materials 0.000 description 2
- 150000002940 palladium Chemical class 0.000 description 2
- 239000006104 solid solution Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000080590 Niso Species 0.000 description 1
- WINXNKPZLFISPD-UHFFFAOYSA-M Saccharin sodium Chemical compound [Na+].C1=CC=C2C(=O)[N-]S(=O)(=O)C2=C1 WINXNKPZLFISPD-UHFFFAOYSA-M 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002939 deleterious effect Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- IDAGXRIGDWCIET-SDFKWCIISA-L disodium;(2s,3s,4s,5r)-2,3,4,5-tetrahydroxyhexanedioate Chemical compound [Na+].[Na+].[O-]C(=O)[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O IDAGXRIGDWCIET-SDFKWCIISA-L 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000002659 electrodeposit Substances 0.000 description 1
- 238000009713 electroplating Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- RFLFDJSIZCCYIP-UHFFFAOYSA-L palladium(2+);sulfate Chemical compound [Pd+2].[O-]S([O-])(=O)=O RFLFDJSIZCCYIP-UHFFFAOYSA-L 0.000 description 1
- 229910000364 palladium(II) sulfate Inorganic materials 0.000 description 1
- 239000011253 protective coating Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 159000000000 sodium salts Chemical class 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 150000003456 sulfonamides Chemical class 0.000 description 1
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/567—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of platinum group metals
Definitions
- a 'bath with a pH between 7 and 10 containing aqueous ammonia, palladium ions and nickel ions, and an aromatic sulfonamide yields an electrodeposited coating which is an alloy of palladium and nickel and which has a bright mirror finish.
- the coating is essentially as corrosion and wear resistant as is palladium itself.
- an object of the present invention is to provide a bath from which a coating can be electrodeposited which is an alloy of palladium and nickel.
- Another object of the invention is to provide a bath from which an alloy of nickel and palladium can be deposited where the deposit has a bright mirror finish.
- the invention accordingly comprises a composition of matter possessing the characteristics, properties, and the relation of components which will be exemplified in the composition hereinafter described, and the scope of the invention will be indicated in the claims.
- palladium salts and nickel salts are soluble in aqueous ammonia to form ammine-complex salts wherein the metal atom is coordinated with NH Stable complex salts are formed regardless of the nature of the acidic radical used.
- a bath comprising amrnine-cornplex salts of palladium and nickel, that palladium and nickel codeposit in the form of a solid solution alloy.
- an aromatic sulfonamide would cause the deposit to have a bright mirror finish.
- Further examination revealed that the palladium content in the codeposited layer can be established at any point within the range of 30% and 90% by adjusting the composition of the bath or plating conditions and that the thus-plated surface obtained shows sufiicient brightness and corrosion-resistance.
- a monosalt such as palladium chloride, PdClg, or a complex salt such as diammine palladium chloride, Pd(Nl-I Cl can be used as sources of palladium.
- sources of nickel nickel sulfate, NiSO -7H O, nickel chloride, NiCl -6H O, etc. are used.
- an ammonium salt of inorganic acid or organic acid such as ammonium sulfate or ammonium citrate may be added.
- the electroconductivity of the bath is also improved and at the same time the pH is stabilized by the NH, -NH bufier system produced in the bath.
- the concentration of palladium and nickel in the bath is controlled in such a manner that the quantity of palladium present is 5 to 30 g./l., and nickel is present in the same quantity, i.e., 5 to 30 g./l.
- the ratio of palladium and nickel in the deposited layer depends on the concentration ratio of palladium and nickel in the bath. For instance, a combination of 20 g./l. of palladium and 10 g./l.
- the desired codeposited layer can be obtained if the concentration of palladium and nickel in the bath and the ratio thereof are controlled.
- aromatic sulfonamides examples include:
- Saccharin 2 The sodium salt of saccharin NNa (3 Para-toluenesulfonamide S O zNHz Example 1 Saccharin was used as follows:
- a bath containing 40 g. of diammine palladium (II) sulfate, Pd(NH SO 50 cc. of 28% aqueous ammonia, and 650 cc. of water was prepared. To this were added 50 g. of ammonium sulfate, 25 g. of nickel chloride and 1 g. of saccharin, and the bath was made up to 1000 cc. with water.
- a brass test piece was plated in this bath for 30 minutes at a pH of 8.4, temperature of 25 C. and current density of 1 a./dm. without agitation.
- the electrodeposit contained 80% of palladium and 20% of nickel and had a mirror surface. The deposit was unaffected by 24 hours ex posure to ammonia gas and by 6 days immersion in artificial seawater.
- Example 2 A bath containing 40 g. of diammine palladium chloride, Pd(NH Cl 50 cc. of 28% ammonia water and 700 cc. of water was prepared. Then were added 50 g. of ammonium sulfate, 50 g. of nickel sulfate, g. of sodium saccharate NNQHZHQO and water until the bath attained 1000 cc.
- a brass test piece was plated in the bath for 30 minutes at pH of 8.8, temperature of 30 C., and cathode current density of l a./dm. without agitation.
- a bath containing g. of diammine palladous chloride, 50 cc. of 28% aqueous ammonia and 700 cc. of water was prepared. To this were added 50 g. of ammonium sulfate, g. of nickel sulfate, 0.5 g. of para-toluenesulfonamide, and water to bring the final volume to 1000 cc.
- a brass test piece was plated in this bath for 30 minutes at a pH of 8.4, temperature of 30 C., and a cathode current density of l a./dm. without agitation.
- An alloy comprising 80% palladium and 20% nickel with a mirror finish was deposited. The deposit was unaffected by exposure to ammonia and seawater as described in the previous example.
- composition and internal stress of the deposited layer show no noticeable change by this bright plating. Satisfactory results can be obtained 'When the bath is operated at pH 7l0, temperature l5-40" C., cathode current density 0.5-1.5 amperes/dmP, using a palladium or a graphite anode. During plating, the concentration of palladium and nickel must be estimated by chemical analysis and always controlled properly. The metals are supplied by adding the appropriate salts directly to the bath. During the plating the ammonium salt gradually accumulates in the bath but it has no deleterious eflect. The pH is adjusted by adding ammonia water or dilute sulfuric acid.
- lowering of pH tends to make more noble the deposition potential of nickel and to increase the nickel content in the deposited layer. It sometimes occurs that the palladium content in the deposited layer does not fall within 30% and owing to improper composition of the bath or plating conditions. If the palladium content in the codeposited layer deviates substantially from the range of 30 to 90%, a solid solution of palladium and nickel is not formed completely, and when a thick plating is deposited, the surface loses its brightness and is fragile. Other plating conditions are the same as those in conventional methods. There are no restrictions as to the kind of the base metals.
- said aromatic sulfonamide is selected from the group consisting of saccharin, sodium saccharin, and para-toluenesulfonamide.
Abstract
A PALLADIUM-NICKEL ALLOY PLATING BATH IS FORMED OF A SOLUTION OF A PALLADIUM SALT AND A NICKEL SALT IN AMMONIA, AND A BRIGHTENER IN THE NATURE OF A SOLFONAMIDE IS ADDED TO THE BATH IN WHICH A METAL IS PLATED FOR APPROXIMATELY 30 MINUTES AT A PH BETWEEN 7 AND 10, TEMPERATURE BETWEEN 15*C. AND 40*C., AND A CATHODE CURRENT DENSITY OF 0.5 TO 1.5 A./DM.2 WITHOUT AGITATION.
Description
United States Patent O Int. Cl. czsb 5/32, 5/46 US. Cl. 204-43 3 Claims ABSTRACT OF THE DISCLOSURE -A palladium nickel alloy plating bath is formed of a solution of a palladium salt and a nickel salt in ammonia, and a brightener in the nature of a sulfonamide is added to the bath in which a metal is plated for approximately 30 minutes at a pH between 7 and 10, temperature between 15 C. and 40 C., and a cathode current density of 0.5 to 1.5 a./dm. without agitation.
CROSS-REFERENCE TO RELATED APPLICATION The present application is a continuation-in-part of the application bearing the serial number 695,576, now Pat. No. 3,580,820. The inventors are the same in both applications.
BACKGROUND OF THE INVENTION Methods of plating palladium were originally developed with the objective of eliminating some of the drawbacks of conventional light metal plating where the deposits consisted of silver or nickel. However, palladium coatings of a thickness great enough to give adequate corrosion resistance and wear resistance are expensive, so that it would be desirable to find a method of depositing a less expensive but sufliciently protective coating which in addition would have a mirror finish.
SUMMARY OF THE INVENTION According to the present invention, a 'bath with a pH between 7 and 10, containing aqueous ammonia, palladium ions and nickel ions, and an aromatic sulfonamide yields an electrodeposited coating which is an alloy of palladium and nickel and which has a bright mirror finish. The coating is essentially as corrosion and wear resistant as is palladium itself.
Accordingly, an object of the present invention is to provide a bath from which a coating can be electrodeposited which is an alloy of palladium and nickel.
Another object of the invention is to provide a bath from which an alloy of nickel and palladium can be deposited where the deposit has a bright mirror finish.
Still other objects and advantages of the invention will in part be obvious and will in part be apparent from the specification.
The invention accordingly comprises a composition of matter possessing the characteristics, properties, and the relation of components which will be exemplified in the composition hereinafter described, and the scope of the invention will be indicated in the claims.
PREFERRED EMBODIMENTS OF THE INVENTION Generally, palladium salts and nickel salts are soluble in aqueous ammonia to form ammine-complex salts wherein the metal atom is coordinated with NH Stable complex salts are formed regardless of the nature of the acidic radical used. In accordance with the invention, it has been found that when using a bath comprising amrnine-cornplex salts of palladium and nickel, that palladium and nickel codeposit in the form of a solid solution alloy. It was also found that the addition of an aromatic sulfonamide would cause the deposit to have a bright mirror finish. Further examination revealed that the palladium content in the codeposited layer can be established at any point within the range of 30% and 90% by adjusting the composition of the bath or plating conditions and that the thus-plated surface obtained shows sufiicient brightness and corrosion-resistance.
In preparing a bath for plating, a monosalt such as palladium chloride, PdClg, or a complex salt such as diammine palladium chloride, Pd(Nl-I Cl can be used as sources of palladium. As for sources of nickel, nickel sulfate, NiSO -7H O, nickel chloride, NiCl -6H O, etc. are used. When these salts are put in an aqueous solution of ammonia, the palladium and nickel salts are converted into ammine-complex salts. An ammonium salt of inorganic acid or organic acid such as ammonium sulfate or ammonium citrate may be added. These additions increase the solubility of palladium and nickel, by which stable dissolution at relatively low pH is achieved. The electroconductivity of the bath is also improved and at the same time the pH is stabilized by the NH, -NH bufier system produced in the bath. The concentration of palladium and nickel in the bath is controlled in such a manner that the quantity of palladium present is 5 to 30 g./l., and nickel is present in the same quantity, i.e., 5 to 30 g./l. The ratio of palladium and nickel in the deposited layer depends on the concentration ratio of palladium and nickel in the bath. For instance, a combination of 20 g./l. of palladium and 10 g./l. of nickel produces an alloy deposited layer comprising palladium in the amount of and an alloy deposited layer composed of 60% of palladium is obtained with a combination of 10 g./l. of palladium and 10 g./l. of nickel. Although it is not only the concentration ratio of palladium and nickel that affects the composition of the alloy deposited layer, nevertheless, other conditions such as pH of the bath, the temperature and cathode current density need cause no concern because it is easy to keep these conditions constant during the plating operation, and except for the pH of the bath, changes in the other conditions do not affect the product adversely. Therefore, the desired codeposited layer can be obtained if the concentration of palladium and nickel in the bath and the ratio thereof are controlled.
By adding aromatic sulfonarnides to the bath, a bright plating can be obtained. Discovery of these brighteners gives the bath great practical value.
Examples of aromatic sulfonamides that can be used are:
( 1 Saccharin (2) The sodium salt of saccharin NNa (3 Para-toluenesulfonamide S O zNHz Example 1 Saccharin was used as follows:
A bath containing 40 g. of diammine palladium (II) sulfate, Pd(NH SO 50 cc. of 28% aqueous ammonia, and 650 cc. of water was prepared. To this were added 50 g. of ammonium sulfate, 25 g. of nickel chloride and 1 g. of saccharin, and the bath was made up to 1000 cc. with water.
A brass test piece was plated in this bath for 30 minutes at a pH of 8.4, temperature of 25 C. and current density of 1 a./dm. without agitation. The electrodeposit contained 80% of palladium and 20% of nickel and had a mirror surface. The deposit was unaffected by 24 hours ex posure to ammonia gas and by 6 days immersion in artificial seawater.
Example 2 A bath containing 40 g. of diammine palladium chloride, Pd(NH Cl 50 cc. of 28% ammonia water and 700 cc. of water was prepared. Then were added 50 g. of ammonium sulfate, 50 g. of nickel sulfate, g. of sodium saccharate NNQHZHQO and water until the bath attained 1000 cc.
A brass test piece was plated in the bath for 30 minutes at pH of 8.8, temperature of 30 C., and cathode current density of l a./dm. without agitation.
An alloy comprising 85% palladium and nickel with a mirror surface was obtained from this bath. The deposit was unaifected after 24 hours exposure to ammonia gas and 6 days immersion in artificial seawater.
Example 3 Para-toluenesulfonamide was used as follows:
A bath containing g. of diammine palladous chloride, 50 cc. of 28% aqueous ammonia and 700 cc. of water was prepared. To this were added 50 g. of ammonium sulfate, g. of nickel sulfate, 0.5 g. of para-toluenesulfonamide, and water to bring the final volume to 1000 cc.
A brass test piece was plated in this bath for 30 minutes at a pH of 8.4, temperature of 30 C., and a cathode current density of l a./dm. without agitation. An alloy comprising 80% palladium and 20% nickel with a mirror finish was deposited. The deposit was unaffected by exposure to ammonia and seawater as described in the previous example.
Composition and internal stress of the deposited layer show no noticeable change by this bright plating. Satisfactory results can be obtained 'When the bath is operated at pH 7l0, temperature l5-40" C., cathode current density 0.5-1.5 amperes/dmP, using a palladium or a graphite anode. During plating, the concentration of palladium and nickel must be estimated by chemical analysis and always controlled properly. The metals are supplied by adding the appropriate salts directly to the bath. During the plating the ammonium salt gradually accumulates in the bath but it has no deleterious eflect. The pH is adjusted by adding ammonia water or dilute sulfuric acid. Generally, lowering of pH tends to make more noble the deposition potential of nickel and to increase the nickel content in the deposited layer. It sometimes occurs that the palladium content in the deposited layer does not fall within 30% and owing to improper composition of the bath or plating conditions. If the palladium content in the codeposited layer deviates substantially from the range of 30 to 90%, a solid solution of palladium and nickel is not formed completely, and when a thick plating is deposited, the surface loses its brightness and is fragile. Other plating conditions are the same as those in conventional methods. There are no restrictions as to the kind of the base metals.
It will thus be seen that the objects set forth above, among those made apparent from the preceding description, are efficiently attained, and since certain changes may be made in the above compositions without departing from the spirit and scope of the invention, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.
It is also to be understood that the following claims are intended to cover all of the generic and specific features of the invention herein described, and all statements of the scope of the invention which, as a matter of language, might be said to fall therebetween.
What is claimed is:
1. A palladium-nickel alloy aqueous electroplating bath having a pH between 7 and 10, comprising aqueous ammonia containing 5 to 30 g./l. of palladium ions, 5 to 30 g. of nickel ions, and an aromatic sulfonamide in an amount eifective for obtaining a bright electrodeposited layer of a palladium-nickel alloy therefrom.
2. Bath as defined in claim 1, wherein said aromatic sulfonamide is selected from the group consisting of saccharin, sodium saccharin, and para-toluenesulfonamide.
3. Bath as defined in claim 1, wherein the quantity of said brightener added lies between 0.5 and 5 g./l.
References Cited UNITED STATES PATENTS 1,981,715 11/1934 Atkinson 20443 2,452,308 10/ 1948 Lambros 204-47 FOREIGN PATENTS 958,685 5/ 1964 Great Britain 204-47 1,017,950 1/ 1966 Great Britain 204-47 GERALD L. KAPLAN, Primary Examiner
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP186867A JPS4733176B1 (en) | 1967-01-11 | 1967-01-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| US3677909A true US3677909A (en) | 1972-07-18 |
Family
ID=11513510
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US695576A Expired - Lifetime US3580820A (en) | 1967-01-11 | 1968-01-04 | Palladium-nickel alloy plating bath |
| US136588A Expired - Lifetime US3677909A (en) | 1967-01-11 | 1971-04-22 | Palladium-nickel alloy plating bath |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| US695576A Expired - Lifetime US3580820A (en) | 1967-01-11 | 1968-01-04 | Palladium-nickel alloy plating bath |
Country Status (3)
| Country | Link |
|---|---|
| US (2) | US3580820A (en) |
| JP (1) | JPS4733176B1 (en) |
| GB (1) | GB1143178A (en) |
Cited By (16)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| USB435844I5 (en) * | 1974-01-23 | 1975-01-28 | ||
| US3933602A (en) * | 1973-04-27 | 1976-01-20 | Oxy Metal Industries Corporation | Palladium electroplating bath, process, and preparation |
| DE2649738A1 (en) * | 1975-10-29 | 1977-05-12 | Mitsubishi Electric Corp | SEMI-CONDUCTOR DEVICE WITH A SCHOTTKY BARRIER |
| DE2654476A1 (en) * | 1975-12-03 | 1977-06-23 | Mitsubishi Electric Corp | METHOD OF MANUFACTURING AN ELECTRODE IN A SEMICONDUCTOR DEVICE |
| DE2747955A1 (en) * | 1976-11-11 | 1978-05-18 | Ibm | PROCESS FOR ELECTROLYTIC COATING OF METALLIC OBJECTS WITH A PALLADIUM-NICKEL ALLOY |
| US4297177A (en) * | 1980-09-19 | 1981-10-27 | American Chemical & Refining Company Incorporated | Method and composition for electrodepositing palladium/nickel alloys |
| DE3108508A1 (en) * | 1981-03-06 | 1982-09-16 | Langbein-Pfanhauser Werke Ag, 4040 Neuss | BATH FOR GALVANIC DEPOSITION OF A PALLADIUM / NICKEL ALLOY |
| FR2512845A1 (en) * | 1981-09-11 | 1983-03-18 | Langbein Pfanhauser Werke Ag | PROCESS FOR INCREASING THE CORROSION RESISTANCE OF A PALLADIUM-NICKEL ALLOY REMOVED BY ELECTROLYSIS |
| US4392921A (en) * | 1980-12-17 | 1983-07-12 | Occidental Chemical Corporation | Composition and process for electroplating white palladium |
| US4487665A (en) * | 1980-12-17 | 1984-12-11 | Omi International Corporation | Electroplating bath and process for white palladium |
| US4699697A (en) * | 1984-05-24 | 1987-10-13 | Electroplating Engineers Of Japan, Limited | High-purity palladium-nickel alloy plating solution and process |
| US4741818A (en) * | 1985-12-12 | 1988-05-03 | Learonal, Inc. | Alkaline baths and methods for electrodeposition of palladium and palladium alloys |
| US4778574A (en) * | 1987-09-14 | 1988-10-18 | American Chemical & Refining Company, Inc. | Amine-containing bath for electroplating palladium |
| US5415685A (en) * | 1993-08-16 | 1995-05-16 | Enthone-Omi Inc. | Electroplating bath and process for white palladium |
| US20090038950A1 (en) * | 2007-07-20 | 2009-02-12 | Rohm And Haas Electronic Materials Llc | High speed method for plating palladium and palladium alloys |
| US20110147225A1 (en) * | 2007-07-20 | 2011-06-23 | Rohm And Haas Electronic Materials Llc | High speed method for plating palladium and palladium alloys |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4098656A (en) * | 1976-03-11 | 1978-07-04 | Oxy Metal Industries Corporation | Bright palladium electroplating baths |
| JPS5615656A (en) * | 1979-07-18 | 1981-02-14 | Nissan Shoji Kk | Preservation of formed rice |
| JPS5760090A (en) * | 1980-09-29 | 1982-04-10 | Nisshin Kasei Kk | Supplying method for palladium to palladium-nickel alloy plating solution |
| DE3108467C2 (en) * | 1981-03-06 | 1983-05-26 | Langbein-Pfanhauser Werke Ag, 4040 Neuss | Use of an acetyleneamine and / or an amino alcohol in a bath for the electrodeposition of a palladium / nickel alloy |
| DE3108466C2 (en) * | 1981-03-06 | 1983-05-26 | Langbein-Pfanhauser Werke Ag, 4040 Neuss | Use of an acetylene alcohol in a bath for the electrodeposition of a palladium / nickel alloy |
| GB2113477B (en) * | 1981-12-31 | 1985-04-17 | Hara J B O | Method of producing printed circuits |
| FR2539145B1 (en) * | 1983-01-07 | 1986-08-29 | Omi Int Corp | PROCESS FOR FORMING AT HIGH SPEED, BY ELECTROLYSIS, A PALLADIUM COATING LAYER ON A SUBSTRATE AND A BATH FOR THE IMPLEMENTATION OF THIS PROCESS |
| JPS6051992U (en) * | 1983-09-19 | 1985-04-12 | 株式会社 ダイケイ | Skewered rice processed food |
| GB2168381B (en) * | 1984-12-12 | 1988-03-09 | Stc Plc | Gold plated electrical contacts |
| JPS63110227A (en) * | 1986-10-27 | 1988-05-14 | Sanyo Electric Co Ltd | Styrene resin molded article |
| US5976344A (en) * | 1996-05-10 | 1999-11-02 | Lucent Technologies Inc. | Composition for electroplating palladium alloys and electroplating process using that composition |
| JP6663335B2 (en) * | 2016-10-07 | 2020-03-11 | 松田産業株式会社 | Palladium-nickel alloy coating and method for producing the same |
-
1967
- 1967-01-11 JP JP186867A patent/JPS4733176B1/ja active Pending
-
1968
- 1968-01-04 US US695576A patent/US3580820A/en not_active Expired - Lifetime
- 1968-01-10 GB GB1474/68A patent/GB1143178A/en not_active Expired
-
1971
- 1971-04-22 US US136588A patent/US3677909A/en not_active Expired - Lifetime
Cited By (21)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3933602A (en) * | 1973-04-27 | 1976-01-20 | Oxy Metal Industries Corporation | Palladium electroplating bath, process, and preparation |
| US3925170A (en) * | 1974-01-23 | 1975-12-09 | American Chem & Refining Co | Method and composition for producing bright palladium electrodepositions |
| USB435844I5 (en) * | 1974-01-23 | 1975-01-28 | ||
| DE2649738A1 (en) * | 1975-10-29 | 1977-05-12 | Mitsubishi Electric Corp | SEMI-CONDUCTOR DEVICE WITH A SCHOTTKY BARRIER |
| DE2654476A1 (en) * | 1975-12-03 | 1977-06-23 | Mitsubishi Electric Corp | METHOD OF MANUFACTURING AN ELECTRODE IN A SEMICONDUCTOR DEVICE |
| US4224115A (en) * | 1975-12-03 | 1980-09-23 | Mitsubishi Denki Kabushiki Kaisha | Process for forming electrode on semiconductor device |
| DE2747955A1 (en) * | 1976-11-11 | 1978-05-18 | Ibm | PROCESS FOR ELECTROLYTIC COATING OF METALLIC OBJECTS WITH A PALLADIUM-NICKEL ALLOY |
| FR2370802A1 (en) * | 1976-11-11 | 1978-06-09 | Ibm | NICKEL-PALLADIUM METALLIZATION BATH FOR ELECTROLYTIC DEPOSIT AND METALLIZATION PROCESS USING SUCH A BATH |
| US4100039A (en) * | 1976-11-11 | 1978-07-11 | International Business Machines Corporation | Method for plating palladium-nickel alloy |
| US4297177A (en) * | 1980-09-19 | 1981-10-27 | American Chemical & Refining Company Incorporated | Method and composition for electrodepositing palladium/nickel alloys |
| US4392921A (en) * | 1980-12-17 | 1983-07-12 | Occidental Chemical Corporation | Composition and process for electroplating white palladium |
| US4487665A (en) * | 1980-12-17 | 1984-12-11 | Omi International Corporation | Electroplating bath and process for white palladium |
| DE3108508A1 (en) * | 1981-03-06 | 1982-09-16 | Langbein-Pfanhauser Werke Ag, 4040 Neuss | BATH FOR GALVANIC DEPOSITION OF A PALLADIUM / NICKEL ALLOY |
| FR2512845A1 (en) * | 1981-09-11 | 1983-03-18 | Langbein Pfanhauser Werke Ag | PROCESS FOR INCREASING THE CORROSION RESISTANCE OF A PALLADIUM-NICKEL ALLOY REMOVED BY ELECTROLYSIS |
| US4699697A (en) * | 1984-05-24 | 1987-10-13 | Electroplating Engineers Of Japan, Limited | High-purity palladium-nickel alloy plating solution and process |
| US4741818A (en) * | 1985-12-12 | 1988-05-03 | Learonal, Inc. | Alkaline baths and methods for electrodeposition of palladium and palladium alloys |
| US4778574A (en) * | 1987-09-14 | 1988-10-18 | American Chemical & Refining Company, Inc. | Amine-containing bath for electroplating palladium |
| US5415685A (en) * | 1993-08-16 | 1995-05-16 | Enthone-Omi Inc. | Electroplating bath and process for white palladium |
| US20090038950A1 (en) * | 2007-07-20 | 2009-02-12 | Rohm And Haas Electronic Materials Llc | High speed method for plating palladium and palladium alloys |
| US20110147225A1 (en) * | 2007-07-20 | 2011-06-23 | Rohm And Haas Electronic Materials Llc | High speed method for plating palladium and palladium alloys |
| US9435046B2 (en) | 2007-07-20 | 2016-09-06 | Rohm And Haas Electronics Llc | High speed method for plating palladium and palladium alloys |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS4733176B1 (en) | 1972-08-23 |
| US3580820A (en) | 1971-05-25 |
| GB1143178A (en) | 1969-02-19 |
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