CA1089796A - Electroplating palladium - Google Patents
Electroplating palladiumInfo
- Publication number
- CA1089796A CA1089796A CA289,192A CA289192A CA1089796A CA 1089796 A CA1089796 A CA 1089796A CA 289192 A CA289192 A CA 289192A CA 1089796 A CA1089796 A CA 1089796A
- Authority
- CA
- Canada
- Prior art keywords
- palladium
- gpl
- bath
- substrate
- solution
- 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
Links
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 48
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 21
- 238000009713 electroplating Methods 0.000 title claims abstract description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims abstract description 15
- 239000000243 solution Substances 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 10
- RYCLIXPGLDDLTM-UHFFFAOYSA-J tetrapotassium;phosphonato phosphate Chemical compound [K+].[K+].[K+].[K+].[O-]P([O-])(=O)OP([O-])([O-])=O RYCLIXPGLDDLTM-UHFFFAOYSA-J 0.000 claims abstract description 9
- 239000007864 aqueous solution Substances 0.000 claims abstract description 5
- XPPKVPWEQAFLFU-UHFFFAOYSA-N diphosphoric acid Chemical compound OP(O)(=O)OP(O)(O)=O XPPKVPWEQAFLFU-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229940005657 pyrophosphoric acid Drugs 0.000 claims abstract description 5
- FFTOPVWHPZEWOI-UHFFFAOYSA-N diazanium dinitrite Chemical compound [NH4+].[NH4+].[O-]N=O.[O-]N=O FFTOPVWHPZEWOI-UHFFFAOYSA-N 0.000 claims abstract description 3
- 238000004070 electrodeposition Methods 0.000 claims abstract 2
- 238000007747 plating Methods 0.000 description 8
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 239000004332 silver Substances 0.000 description 2
- 229910001316 Ag alloy Inorganic materials 0.000 description 1
- 229910001369 Brass Inorganic materials 0.000 description 1
- 229910000906 Bronze Inorganic materials 0.000 description 1
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 229910000831 Steel Inorganic materials 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000010951 brass Substances 0.000 description 1
- 239000010974 bronze Substances 0.000 description 1
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 150000002940 palladium Chemical class 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010959 steel Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-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
- C25D3/50—Electroplating: Baths therefor from solutions of platinum group metals
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)
Abstract
Abstract 1. A method of electroplating palladium on a substrate comprises passing an electric current between an anode and the substrate in a bath comprising an aqueous solution of palladium diammonium dinitrite (Pd (NH3)2 (NO2)2) and tetrapotassium pyrophosphate. In a preferred method the electric current passes at a current density of 2 to 50 ASF (0.2 to 5.4 ASD) in a bath containing 4 to 18 gpl of palladium and 5 to 300 gpl of tetrapotassium pyrophosphate, the solution being at a pH of 8.5 to 11 and being maintained by the addition of pyrophosphoric acid or potassium hydroxide.
The baths for the electrodeposition of palladium also form part of the invention.
The baths for the electrodeposition of palladium also form part of the invention.
Description
Methods of electroplating palladium on a substrate are known and comprise passing an electric current between an anode and the substrate in a bath comprisinq an aqueous solution of a palladium salt.
In accordance with this invention the solution contains palladium diammonium dinitrite (Pd (NH3)2 (N02)2) and tetrapotassium pyrophosphate. It is preferred that the solution containX 4 to 18 gpl of palladium and 5 to 300 gpl of tetr~potassium pyrophosphate, ~ at a pH of 8.5 to 11, - 10 the pH being maintained by the addition of pyrophosphoric acid or potassium hydroxide to the solution, and the current pass~ at a density of 2 to 50 amperes per square foot (ASF) (0.2 to 5.4 amperes per square decimeter (ASD)).
The plating baths in question form a further feature of this invention.
Current densities higher than 50 AS~ (5.4 ASD) tend to result in burning of ths surface of the substrate. At current densities lower than 2 ASF the plating rate is low.
Below pH 8.5 the current efficiency tends to fall off and above pH 11 there is little increase in the plating rate.
We have found that a most satisfactory method involves plating at a current density of 20 ASF (2.1 ASD), the pH
being 8.7 to 9.5, the temperature of the bath being 125F
t57 C) and the solution containing 8 gpl of palladium.
The tetrapotassium pyrophosphate content of the solution can advantageously be 150 gpl; while this salt is conveniently added to the solution in the trih~drate form ' - : :
- :
., . ~ .
concentrations of the salt refer to the anhydrous form.
The current e~ficiency of plating methods in accordance with the invention is higher than has heretofore been obtainable for the electroplating of palladium. The efficiency is expressed as cathode efficiency and can be as high as 95% in accordance with the invention. The theoretical value for palladium deposition is calculated to be 33.1 milligrams per ampere-minute. If the current efficiency is 95%,palladium is being deposited at a rate of 31.4 milligrams per ampere-minute.
The anode used in the plating method may be in-soluble platinum, platinum-clad or tantalum bodies. An anode to cathode ratio of 1:1 as a minimum should be em-, ployed and the bath should be vigorously agitated, for example by mechanical means.
The substrate may be a base metal, such as copper and alloys thereof, such as brass and bronze, or nickel, silver, steel or alloys of nickel, silver, or iron e.g. stainless steel.
; The invention will now be described with reference to the following Examples.
; EXAMPLE 1 A solution was made up with the following composition and concentrations:
10 gpl Palladium (derived from Pd (~H3)2 (N02)2) ; 150 gpl Potassium Pyrophosphate.
~:- The solution was adjusted to pH 9 by the addition of pyrophosphoric acid or potassium hydroxide and heated to ':~
,.
,~
. . .
. , " 8864 130 F (54 . 5 C) .
The solution was then used as a bath to rack-plate palladium on copper samples, the current density being 20 ASF (2.1 ASD). During plating the bath was mechanically agitated. The cathode efficiency of the plating method was found to be approximately 94%.
; EXAMPLE 2 Example 1 was repeated at other current densities of 10, 30, 40 and 50 ASF (1.1, 3.2, 4.3 and 5.4 ASD) and the ; 10 cathode efficiency remained at approximately 94~ at densities of 10, 30 and 40 ASF (1.1, 3 . 2 and 4. 3 ASD). At 50 ASF
(5.4 ASD) the efficiency was 76%.
Example 3 was repeated at a temperature of 125 E
tS7C) with the solution at varying pH values, the pH having been adjusted by the addition of pyrophosphoric acid or potassium hydroxide. The cathode efficiencies were as follows:
pH Cathode Efficiency 8.0 89.3 ' 8.5 92.4 9.0 94.0 , 9.5 93.7 ` 10.0 94.3 ."
... .
.~ _ 4 _ . . ~
:
- . ,: - . - : .: :
,' ' ,' ' ~, " ' ~ ~ ' , ~. ',
In accordance with this invention the solution contains palladium diammonium dinitrite (Pd (NH3)2 (N02)2) and tetrapotassium pyrophosphate. It is preferred that the solution containX 4 to 18 gpl of palladium and 5 to 300 gpl of tetr~potassium pyrophosphate, ~ at a pH of 8.5 to 11, - 10 the pH being maintained by the addition of pyrophosphoric acid or potassium hydroxide to the solution, and the current pass~ at a density of 2 to 50 amperes per square foot (ASF) (0.2 to 5.4 amperes per square decimeter (ASD)).
The plating baths in question form a further feature of this invention.
Current densities higher than 50 AS~ (5.4 ASD) tend to result in burning of ths surface of the substrate. At current densities lower than 2 ASF the plating rate is low.
Below pH 8.5 the current efficiency tends to fall off and above pH 11 there is little increase in the plating rate.
We have found that a most satisfactory method involves plating at a current density of 20 ASF (2.1 ASD), the pH
being 8.7 to 9.5, the temperature of the bath being 125F
t57 C) and the solution containing 8 gpl of palladium.
The tetrapotassium pyrophosphate content of the solution can advantageously be 150 gpl; while this salt is conveniently added to the solution in the trih~drate form ' - : :
- :
., . ~ .
concentrations of the salt refer to the anhydrous form.
The current e~ficiency of plating methods in accordance with the invention is higher than has heretofore been obtainable for the electroplating of palladium. The efficiency is expressed as cathode efficiency and can be as high as 95% in accordance with the invention. The theoretical value for palladium deposition is calculated to be 33.1 milligrams per ampere-minute. If the current efficiency is 95%,palladium is being deposited at a rate of 31.4 milligrams per ampere-minute.
The anode used in the plating method may be in-soluble platinum, platinum-clad or tantalum bodies. An anode to cathode ratio of 1:1 as a minimum should be em-, ployed and the bath should be vigorously agitated, for example by mechanical means.
The substrate may be a base metal, such as copper and alloys thereof, such as brass and bronze, or nickel, silver, steel or alloys of nickel, silver, or iron e.g. stainless steel.
; The invention will now be described with reference to the following Examples.
; EXAMPLE 1 A solution was made up with the following composition and concentrations:
10 gpl Palladium (derived from Pd (~H3)2 (N02)2) ; 150 gpl Potassium Pyrophosphate.
~:- The solution was adjusted to pH 9 by the addition of pyrophosphoric acid or potassium hydroxide and heated to ':~
,.
,~
. . .
. , " 8864 130 F (54 . 5 C) .
The solution was then used as a bath to rack-plate palladium on copper samples, the current density being 20 ASF (2.1 ASD). During plating the bath was mechanically agitated. The cathode efficiency of the plating method was found to be approximately 94%.
; EXAMPLE 2 Example 1 was repeated at other current densities of 10, 30, 40 and 50 ASF (1.1, 3.2, 4.3 and 5.4 ASD) and the ; 10 cathode efficiency remained at approximately 94~ at densities of 10, 30 and 40 ASF (1.1, 3 . 2 and 4. 3 ASD). At 50 ASF
(5.4 ASD) the efficiency was 76%.
Example 3 was repeated at a temperature of 125 E
tS7C) with the solution at varying pH values, the pH having been adjusted by the addition of pyrophosphoric acid or potassium hydroxide. The cathode efficiencies were as follows:
pH Cathode Efficiency 8.0 89.3 ' 8.5 92.4 9.0 94.0 , 9.5 93.7 ` 10.0 94.3 ."
... .
.~ _ 4 _ . . ~
:
- . ,: - . - : .: :
,' ' ,' ' ~, " ' ~ ~ ' , ~. ',
Claims (5)
1. A method of electroplating palladium on a substrate which comprises passing an electric current between an anode and the substrate in a bath comprising an aqueous solution of palladium diammonium dinitrite (Pd (NH3)2 (NO2)2) and tetrapotassium pyrophosphate.
2. A method of electroplating palladium on a substrate which comprises passing an electric current between an anode and the substrate at a current density of 2 to 50 ASF (O. 2 to 5. 4 ASD) in a bath comprising an aqueous solution of Pd (NH3)2 (NO2)2 in an amount to provide 4 to 18 gpl of palladium and 5 to 300 gpl of tetrapotassium pyrophosphate at a pH of 8. 5 to 11, the pH being maintained by the addition of pyrophosphoric acid or potassium hydroxide to the solution.
3. A method according to claim 1 or claim 2 in which the current density is 20 ASF (2.1 ASD), the pH 8.7 to 9.5 and the temperature of the bath 125°F (57°C).
4. A method according to claim 1 or claim 2 in which the solution contains 8 gpl of palladium.
5. A bath for the electrodeposition of palladium which comprises an aqueous solution of Pd (NH3)2 (NO2)2 in amount to provide 4 to 18 gpl of palladium and 5 to 300 gpl of tetrapotassium pyrophosphate at a pH of 8.5 to 11.
Applications Claiming Priority (4)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US74248276A | 1976-11-17 | 1976-11-17 | |
| US742,482 | 1976-11-17 | ||
| US808,754 | 1977-06-22 | ||
| US05/808,754 US4092225A (en) | 1976-11-17 | 1977-06-22 | High efficiency palladium electroplating process, bath and composition therefor |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1089796A true CA1089796A (en) | 1980-11-18 |
Family
ID=27114016
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA289,192A Expired CA1089796A (en) | 1976-11-17 | 1977-10-20 | Electroplating palladium |
Country Status (8)
| Country | Link |
|---|---|
| JP (1) | JPS6035439B2 (en) |
| CA (1) | CA1089796A (en) |
| DE (1) | DE2751055A1 (en) |
| ES (1) | ES464140A1 (en) |
| FR (1) | FR2371530A1 (en) |
| GB (1) | GB1534452A (en) |
| IT (1) | IT1088629B (en) |
| NL (1) | NL183534C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4328286A (en) * | 1979-04-26 | 1982-05-04 | The International Nickel Co., Inc. | Electrodeposited palladium, method of preparation and electrical contact made thereby |
| 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 |
| JPH0750426B2 (en) * | 1986-06-09 | 1995-05-31 | 松下電器産業株式会社 | Transparent panel input device |
| ITFI20120098A1 (en) * | 2012-05-22 | 2013-11-23 | Bluclad Srl | GALVANIC BATH WITH BASE OF PALLADIUM AND PHOSPHORUS, ITS USE IN GALVANIC PROCESSES AND ALLOYS OBTAINED BY APPLYING THE GALVANIC PROCESS TO THOSE BATHROOMS. |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| BE371542A (en) * | 1929-07-02 | |||
| GB367588A (en) * | 1931-03-12 | 1932-02-25 | Alan Richard Powell | Improvements in or relating to the electrodeposition of the metals of the platinum group |
| US2984595A (en) * | 1956-06-21 | 1961-05-16 | Sel Rex Precious Metals Inc | Printed circuit manufacture |
| GB1035850A (en) * | 1964-06-12 | 1966-07-13 | Johnson Matthey Co Ltd | Improvements in and relating to the electrodeposition of palladium |
| GB1431548A (en) * | 1972-09-21 | 1976-04-07 | Engelhard Ind Ltd | Electrodeposition of plantinum |
| CH572989A5 (en) * | 1973-04-27 | 1976-02-27 | Oxy Metal Industries Corp |
-
1977
- 1977-10-20 CA CA289,192A patent/CA1089796A/en not_active Expired
- 1977-10-26 NL NL7711735A patent/NL183534C/en not_active IP Right Cessation
- 1977-10-27 GB GB4472077A patent/GB1534452A/en not_active Expired
- 1977-10-31 IT IT2919177A patent/IT1088629B/en active
- 1977-11-14 JP JP13579877A patent/JPS6035439B2/en not_active Expired
- 1977-11-15 ES ES464140A patent/ES464140A1/en not_active Expired
- 1977-11-15 DE DE19772751055 patent/DE2751055A1/en active Granted
- 1977-11-16 FR FR7734499A patent/FR2371530A1/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| IT1088629B (en) | 1985-06-10 |
| FR2371530B1 (en) | 1983-07-22 |
| JPS6035439B2 (en) | 1985-08-14 |
| GB1534452A (en) | 1978-12-06 |
| FR2371530A1 (en) | 1978-06-16 |
| DE2751055C2 (en) | 1987-06-11 |
| JPS5363226A (en) | 1978-06-06 |
| NL183534B (en) | 1988-06-16 |
| ES464140A1 (en) | 1978-09-01 |
| DE2751055A1 (en) | 1978-05-24 |
| NL183534C (en) | 1988-11-16 |
| NL7711735A (en) | 1978-05-19 |
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Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| MKEX | Expiry |