US4189358A
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Electrodeposition of ruthenium-iridium alloy
Assignee: Huntington Alloys Corp
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Filing: 1978-07-14
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Granted: 1980-02-19
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Expires: 1998-07-14
Abstract
Abstract Ruthenium-iridium electrodeposits are prepared from aqueous acid solution containing ruthenium, iridium, a fluoborate salt, fluoboric acid, and optionally sulfamic acid. The baths are especially useful for preparing insoluble anodes.
Inventors
- 👤 Anthony J. Scarpellino, Jr
- 👤 William G. Borner
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-11-05 19:08
CPC Classifications
C; C25; C25D; C25D3/00; C25D3/02; C25D3/56; C25D3/567; C25B; C25B11/00; C25B11/04; C25B11/051; C25B11/073; C25B11/091; C25B11/097; C25C; C25C7/00; C25C7/02
Claims Analysis
Total Claims: 47
Claim 1
Independent Claim
29 words
An aqueous electrolytic acid bath for electrodeposition of a ruthenium-iridium alloy, said bath comprising a soluble ruthenium compound, a soluble iridium compound, a soluble fluoborate salt, and fluoboric acid.
Claim 2
Dependent Claim
29 words
An aqueous electrolytic acid bath for electrodeposition of a ruthenium-iridium alloy, said bath comprising a soluble ruthenium compound, a soluble iridium compound, a soluble fluoborate salt, and fluoboric acid.
Claim 3
Dependent Claim
20 words
An aqueous electrolytic bath according to claim 1, wherein the fluoborate is a salt of an alkali metal or ammonium.
Claim 4
Dependent Claim
22 words
A method of electrodepositing a ruthenium-iridium alloy which comprises passing a substantially direct current through the aqueous acid bath of claim 1.
Claim 5
Dependent Claim
41 words
A method according to claim 3, wherein the current is passed through the bath at a cathode current density of about 5 to about 120 mA/cm 2 and at a temperature in the range of room temperature to about 95° C.
Claim 6
Dependent Claim
52 words
An aqueous electrolytic bath for electrodeposition of a ruthenium-iridium alloy, wherein the bath comprises about 1-12 g/l ruthenium, about 1-12 g/l iridium, about 10-200 g/l (equivalent to NaBF 4 ) fluoborate salt, about 1-100 g/l fluoboric acid and sulfamic acid in an amount of up to about 2 times the Ru-Ir concentration.
Claim 7
Dependent Claim
52 words
An aqueous electrolytic bath for electrodeposition of a ruthenium-iridium alloy, wherein the bath comprises about 1-12 g/l ruthenium, about 1-12 g/l iridium, about 10-200 g/l (equivalent to NaBF 4 ) fluoborate salt, about 1-100 g/l fluoboric acid and sulfamic acid in an amount of up to about 2 times the Ru-Ir concentration.
Claim 8
Dependent Claim
22 words
An aqueous electrolytic bath according to claim 5, wherein the Ru and Ir are present in concentrations of about 3-10 g/l, respectively.
Claim 9
Dependent Claim
25 words
An aqueous electrolytic bath according to claim 5, wherein the bath initially contains ruthenium and iridium in a ratio substantially of about 1:1, by weight.
Claim 10
Dependent Claim
19 words
An aqueous electrolytic bath according to claim 5, wherein the fluoborate salt concentration is at least about 25 g/l.
Claim 11
Dependent Claim
19 words
An aqueous electrolytic bath according to claim 5, wherein the fluoboric acid concentration is at least about 5 g/l.
Claim 12
Dependent Claim
18 words
An aqueous electrolytic bath according to claim 5, wherein the pH is between about 0.3 and about 1.5.
Claim 13
Dependent Claim
15 words
An aqueous electrolytic bath according to claim 5, wherein H 3 BO 3 is present.
Claim 14
Dependent Claim
21 words
An aqueous electrolytic bath according to claim 5, wherein the bath is prepared using RuNC as the source of soluble ruthenium.
Claim 15
Dependent Claim
32 words
An aqueous electrolytic bath according to claim 5, wherein the bath is prepared using the reaction product of diammonium hexahalo iridate IV refluxed in sulfamic acid as the source of soluble iridium.
Claim 16
Dependent Claim
38 words
An aqueous electrolytic acid bath for electrodeposition of a ruthenium-iridium alloy, said bath comprising a soluble ruthenium compound, a soluble iridium compound, a soluble fluoborate salt, and fluoboric acid, wherein the pH is between about 0.3 and 1.5.
Claim 17
Dependent Claim
38 words
An aqueous electrolytic acid bath for electrodeposition of a ruthenium-iridium alloy, said bath comprising a soluble ruthenium compound, a soluble iridium compound, a soluble fluoborate salt, and fluoboric acid, wherein the pH is between about 0.3 and 1.5.
Claim 18
Dependent Claim
104 words
An aqueous electrolytic bath according to claim 14, wherein the bath comprises about 1-12 g/l ruthenium, about 1-12 g/l iridium, about 10-200 g/l (equivalent to NaBF 4 ) fluoborate salt, about 1-100 g/l fluoboric acid and sulfamic acid in an amount of up to about 2 times the ruthenium plus iridium concentration, and wherein the bath is prepared using a complex anion represented by the formula [Ru 2 N(H 2 O) 2 Y 8 ] 3- where Y is chlorine or bromine as the ruthenium component and the reaction product of a diammonium hexahalo iridate IV refluxed in sulfamic acid as the iridium component.
Claim 19
Dependent Claim
68 words
An aqueous electrolytic acid bath for electrodeposition of a ruthenium-iridium alloy, said bath comprising a soluble ruthenium compound providing about 1 to about 12 g/l ruthenium, a soluble iridium compound providing about 1 to about 12 g/l iridium, a soluble fluoborate salt providing an amount equivalent to about 10 to about 200 g/l sodium fluoborate, and fluoboric acid in an amount of about 1 to about 100 g/l.
Claim 20
Dependent Claim
68 words
An aqueous electrolytic acid bath for electrodeposition of a ruthenium-iridium alloy, said bath comprising a soluble ruthenium compound providing about 1 to about 12 g/l ruthenium, a soluble iridium compound providing about 1 to about 12 g/l iridium, a soluble fluoborate salt providing an amount equivalent to about 10 to about 200 g/l sodium fluoborate, and fluoboric acid in an amount of about 1 to about 100 g/l.
Claim 21
Dependent Claim
15 words
An aqueous electrolytic acid bath according to claim 16 wherein the bath contains sulfamic acid.
Claim 22
Dependent Claim
21 words
A method of depositing a ruthenium-iridium alloy which comprises passing a substantially direct current through an aqueous bath of claim 16.
Claim 23
Dependent Claim
42 words
A method according to claim 18, wherein the current is passed through the bath at a cathode current density of about 5 to about 120 mA/cm 2 and at a temperature in the range of about room temperature to about 95° C.
Claim 24
Independent Claim
58 words
A method of electrodepositing a ruthenium-iridium alloy which comprises passing a substantially direct current through the aqueous acid bath comprising about 1-12 g/l ruthenium, about 1-12 g/l iridium, about 10-200 g/l (equivalent to NaBF 4 ) fluoborate salt, about 1-100 g/l fluoboric acid and sulfamic acid in an amount of up to about 2 times the Ru-Ir concentration.
Claim 25
Independent Claim
58 words
A method of electrodepositing a ruthenium-iridium alloy which comprises passing a substantially direct current through the aqueous acid bath comprising about 1-12 g/l ruthenium, about 1-12 g/l iridium, about 10-200 g/l (equivalent to NaBF 4 ) fluoborate salt, about 1-100 g/l fluoboric acid and sulfamic acid in an amount of up to about 2 times the Ru-Ir concentration.
Claim 26
Independent Claim
91 words
A method of electrodepositing a ruthenium-iridium alloy which comprises passing a substantially direct current through the aqueous acid bath comprising about 1-12 g/l ruthenium, about 1-12 g/l iridium, about 10-200 g/l (equivalent to NaBF 4 ) fluoborate salt, about 1-100 g/l fluoboric acid and sulfamic acid in an amount of up to about 2 times the Ru-Ir concentration, wherein the bath is maintained at a temperature in the range of about room temperature to about 95° C. and the cathode current density of about 5 to about 120 mA/cm 2 .
Claim 27
Independent Claim
91 words
A method of electrodepositing a ruthenium-iridium alloy which comprises passing a substantially direct current through the aqueous acid bath comprising about 1-12 g/l ruthenium, about 1-12 g/l iridium, about 10-200 g/l (equivalent to NaBF 4 ) fluoborate salt, about 1-100 g/l fluoboric acid and sulfamic acid in an amount of up to about 2 times the Ru-Ir concentration, wherein the bath is maintained at a temperature in the range of about room temperature to about 95° C. and the cathode current density of about 5 to about 120 mA/cm 2 .
Claim 28
Dependent Claim
17 words
A method according to claim 21, wherein the pH is maintained at about 0.3 to about 1.5.
Claim 29
Dependent Claim
56 words
A method according to claim 21, wherein the bath is prepared using as the ruthenium and iridium components, respectively, a complex anion represented by the formula [Ru 2 N(H 2 O) 2 Y 8 ] 3- , wherein Y is chlorine or bromine, and the reaction product of diammonium hexachloro iridium IV refluxed in sulfamic acid.
Claim 30
Dependent Claim
84 words
In a process for electrowinning metals selected from the group consisting of nickel, copper, zinc, manganese, cobalt, cadmium, gallium, iridium, and alloys thereof, from an aqueous electrolyte, the improvement comprising using as the anode a composite electrode comprising a coating prepared from the bath comprising about 1-12 g/l ruthenium, about 1-12 g/l iridium, about 10-200 g/l (equivalent to NaBF 4 ) fluoborate salt, about 1-100 g/l fluoboric acid and sulfamic acid in an amount of up to 2 times the ruthenium plus iridium concentration.
Claim 31
Dependent Claim
84 words
In a process for electrowinning metals selected from the group consisting of nickel, copper, zinc, manganese, cobalt, cadmium, gallium, iridium, and alloys thereof, from an aqueous electrolyte, the improvement comprising using as the anode a composite electrode comprising a coating prepared from the bath comprising about 1-12 g/l ruthenium, about 1-12 g/l iridium, about 10-200 g/l (equivalent to NaBF 4 ) fluoborate salt, about 1-100 g/l fluoboric acid and sulfamic acid in an amount of up to 2 times the ruthenium plus iridium concentration.
Claim 32
Dependent Claim
11 words
The process of claim 24, wherein the metal electrowon is nickel.
Claim 33
Dependent Claim
11 words
The process of claim 24, wherein the metal electrowon is nickel-cobalt.
Claim 34
Dependent Claim
83 words
A composite electrode comprising an electrically conductive substrate and a coating, said coating comprising a ruthenium-iridium alloy electrolytically deposited from a bath comprising, in solution: ruthenium in the amount of about 1 to about 12 grams per liter, iridium in the amount of about 1 to about 12 grams per liter, a fluoborate salt an amount equivalent to about 10 to about 200 grams per liter sodium fluoborate, and fluoboric acid in the amount of about 1 to about 100 grams per liter.
Claim 35
Dependent Claim
83 words
A composite electrode comprising an electrically conductive substrate and a coating, said coating comprising a ruthenium-iridium alloy electrolytically deposited from a bath comprising, in solution: ruthenium in the amount of about 1 to about 12 grams per liter, iridium in the amount of about 1 to about 12 grams per liter, a fluoborate salt an amount equivalent to about 10 to about 200 grams per liter sodium fluoborate, and fluoboric acid in the amount of about 1 to about 100 grams per liter.
Claim 36
Dependent Claim
15 words
A composite according to claim 27, wherein the electrically conductive substrate comprises a valve metal.
Claim 37
Dependent Claim
38 words
A composite electrode according to claim 28, wherein the valve metal is coated with a barrier layer selected from the group consisting of platinum group metals and gold, and the ruthenium-iridium alloy is deposited on the barrier layer.
Claim 38
Dependent Claim
22 words
A composite electrode according to claim 29, wherein the barrier layer is selected from the group consisting of palladium, iridium and gold.
Claim 39
Dependent Claim
21 words
A composite electrode according to claim 28, wherein the ruthenium-iridium alloy deposit has a thickness of at least about 0.1 μm.
Claim 40
Dependent Claim
20 words
A composite electrode according to claim 28, wherein the ruthenium-iridium alloy deposit is at least partially oxidized at the surface.
Claim 41
Dependent Claim
112 words
A composite electrode comprising an electrically conductive substrate and a coating, said coating comprising a ruthenium-iridium alloy electrolytically deposited at a cathode current density of about 5 to about 120 mA/cm 2 and at a temperature in the range of about room temperature to about 95° C. from a bath comprising, in solution: ruthenium in the amount of about 1 to about 12 grams per liter, iridium in the amount of about 1 to about 12 grams per liter, a fluoborate salt in an amount equivalent to about 10 to about 200 grams per liter sodium fluoborate, and fluoboric acid in the amount of about 1 to about 100 grams per liter.
Claim 42
Dependent Claim
112 words
A composite electrode comprising an electrically conductive substrate and a coating, said coating comprising a ruthenium-iridium alloy electrolytically deposited at a cathode current density of about 5 to about 120 mA/cm 2 and at a temperature in the range of about room temperature to about 95° C. from a bath comprising, in solution: ruthenium in the amount of about 1 to about 12 grams per liter, iridium in the amount of about 1 to about 12 grams per liter, a fluoborate salt in an amount equivalent to about 10 to about 200 grams per liter sodium fluoborate, and fluoboric acid in the amount of about 1 to about 100 grams per liter.
Claim 43
Dependent Claim
15 words
A composite according to claim 33, wherein the electrically conductive substrate comprises a valve metal.
Claim 44
Dependent Claim
38 words
A composite electrode according to claim 34, wherein the valve metal is coated with a barrier layer selected from the group consisting of platinum group metals and gold, and the ruthenium-iridium alloy is deposited on the barrier layer.
Claim 45
Dependent Claim
22 words
A composite electrode according to claim 35, wherein the barrier layer is selected from the group consisting of palladium, iridium and gold.
Claim 46
Dependent Claim
21 words
A composite electrode according to claim 33, wherein the ruthenium-iridium alloy deposit has a thickness of at least about 0.1 μm.
Claim 47
Dependent Claim
20 words
A composite electrode according to claim 33, wherein the ruthenium-iridium alloy deposit is at least partially oxidized at the surface.
References Cited (Backward Citations)
US3616445A
Cited
US3846273A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1983-02-18 | 1983-08-20 | 1984-02-19 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1987-02-18 | 1987-08-20 | 1988-02-19 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1991-02-18 | 1991-08-20 | 1992-02-19 | $7700.00 | Window Closed / Lapsed |