Patent US4214971A successfully refreshed from Google Patents.
US4214971A
Expired / Lapsed
US
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Electrode coating process
Assignee: Dow Chemical Co
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Filing: 1978-08-14
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Granted: 1980-07-29
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Expires: 1998-08-14
Abstract
Abstract A method to produce an electrode by coating at least a portion of a valve metal substrate sequentially with first and second liquid solutions containing different proportions of dissolved ruthenium and valve metal values; the second solution having a greater valve metal to ruthenium weight ratio than the first solution. At least a portion of the substrate is contacted with a first liquid solution containing from about 0.25 to about 50 milligrams per milliliter ruthenium, and the valve metal in an amount of from about 0.06 to about 50 milligrams per milliliter, of the solution. The weight ratio of the valve metal to ruthenium in the first solution is from about 1:4 to about 2:1. The so-contacted surface is heated to oxidize the deposited ruthenium and valve metal values. Thereafter at least the oxidized surface is contacted with a second solution containing dissolved valve metal and ruthenium values in a weight ratio of from about 20:1 to about 2:1 and heated to oxidize the deposited metal values.
Inventors
- 👤 Henrik R. Heikel
- 👤 James J. Leddy
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-26 08:48
CPC Classifications
C; C25; C25B; C25B11/00; C25B11/04; C25B11/051; C25B11/073; C25B11/091; C25B11/093
Claims Analysis
Total Claims: 41
Claim 1
Independent Claim
273 words
A method to produce an electrode comprising sequentially: (a) contacting at least a portion of a valve metal substrate with a first solution containing, as a solute, ruthenium in an amount of from about 0.25 to about 50 milligrams per milliliter of the first solution and a valve metal in an amount of from about 0.06 to about 50 milligrams per milliliter of the first solution, the weight ratio of the valve metal to ruthenium being about 1:4 to about 2:1; at least one solvent suitable to dissolve the ruthenium and valve metal values; and a sufficient amount of an acid to maintain the solute in solution; (b) heating at least a portion of the contacted surface sufficiently to form a coating containing oxides of ruthenium and the valve metal on the substrate; (c) contacting at least a portion of the oxide coated surface with a second solution containing, as a solute, ruthenium in an amount of from about 0.25 to about 25 milligrams per milliliter of the second solution and a valve metal in an amount of from about 1 to about 100 milligrams per milliliter of the second solution, the weight ratio of the valve metal to ruthenium being from about 20:1 to about 2:1 and greater than the valve metal to ruthenium ratio of the first solution; at least one solvent suitable to dissolve the ruthenium and valve metal values; and a sufficient amount of an acid to maintain the solute in solution; (d) heating at least a portion of the contacted surface sufficiently to form a coating containing the oxides of ruthenium and the valve metal on the substrate.
Claim 2
Independent Claim
273 words
A method to produce an electrode comprising sequentially: (a) contacting at least a portion of a valve metal substrate with a first solution containing, as a solute, ruthenium in an amount of from about 0.25 to about 50 milligrams per milliliter of the first solution and a valve metal in an amount of from about 0.06 to about 50 milligrams per milliliter of the first solution, the weight ratio of the valve metal to ruthenium being about 1:4 to about 2:1; at least one solvent suitable to dissolve the ruthenium and valve metal values; and a sufficient amount of an acid to maintain the solute in solution; (b) heating at least a portion of the contacted surface sufficiently to form a coating containing oxides of ruthenium and the valve metal on the substrate; (c) contacting at least a portion of the oxide coated surface with a second solution containing, as a solute, ruthenium in an amount of from about 0.25 to about 25 milligrams per milliliter of the second solution and a valve metal in an amount of from about 1 to about 100 milligrams per milliliter of the second solution, the weight ratio of the valve metal to ruthenium being from about 20:1 to about 2:1 and greater than the valve metal to ruthenium ratio of the first solution; at least one solvent suitable to dissolve the ruthenium and valve metal values; and a sufficient amount of an acid to maintain the solute in solution; (d) heating at least a portion of the contacted surface sufficiently to form a coating containing the oxides of ruthenium and the valve metal on the substrate.
Claim 3
Dependent Claim
25 words
The method of claim 1 wherein the valve metal is selected from the group consisting of lead, molybdenum, niobium, tantalum, titanium, tungsten, vanadium and zirconium.
Claim 4
Dependent Claim
11 words
The method of claim 1 wherein the valve metal is titanium.
Claim 5
Dependent Claim
52 words
The method of claim 3 wherein the titanium present in the first solution is provided by a compound of titanium characterized as being thermally decomposable to an oxide of titanium in the presence of oxygen and soluble to the extent of at least about 0.06 milligram of titanium per milliliter of solution.
Claim 6
Dependent Claim
52 words
The method of claim 3 wherein the titanium present in the second solution is provided by a compound of titanium characterized as being thermally decomposable to an oxide of titanium in the presence of oxygen and soluble to the extent of at least about 1 milligram of titanium per milliliter of solution.
Claim 7
Dependent Claim
52 words
The method of claim 1 wherein the valve metal present in the first and second solutions is provided by a compound selected from at least one member of the group consisting of titanium tetrachloride, titanium tetrabromide, titanium tetrafluoride, tetra-isopropyltitanate, tetrakis(2-ethylhexyl)titanate, tetrastearyltitanate, tetrabutyl titanate, penta-ethyl-tantalate, vanadylacetylacetomate lead napthanate and hydrates of such compounds.
Claim 8
Dependent Claim
10 words
The method of claim 6 wherein the compound contains titanium.
Claim 9
Dependent Claim
11 words
The method of claim 7 wherein the compound is a titanate.
Claim 10
Dependent Claim
18 words
The method of claim 7 wherein the compound is tetra-isopropyltitanate, tetrakis(2-ethylhexyl)titanate, tetrastearyltitanate, tetrabutyltitanate and hydrates of such compounds.
Claim 11
Dependent Claim
52 words
The method of claim 1 wherein the ruthenium present in the first and second solutions is provided by a compound of ruthenium characterized as being thermally decomposable to an oxide of ruthenium in the presence of oxygen and soluble to the extent of at least about 0.25 milligram per milliliter of solution.
Claim 12
Dependent Claim
23 words
The method of claim 1 wherein steps (a) and (b) are repeated to apply at least two oxide layers with the first solution.
Claim 13
Dependent Claim
25 words
The methods of claims 1 or 11 wherein steps (c) and (d) are repeated to apply at least two oxide layers with the second solution.
Claim 14
Dependent Claim
43 words
The method of claim 12 wherein the first solution included ruthenium in an amount of from about 5 to about 25 milligrams per milliliter of solution and titanium in an amount of from about 5 to about 25 milligrams per milliliter of solution.
Claim 15
Dependent Claim
24 words
The method of claim 13 wherein the weight ratio of titanium to ruthenium in the first solution is from about 2:1 to about 1:2.
Claim 16
Dependent Claim
24 words
The method of claim 13 wherein the weight ratio of titanium to ruthenium in the first solution is from about 2:1 to about 1:1.
Claim 17
Dependent Claim
24 words
The method of claim 3 wherein the weight ratio of titanium to ruthenium in the first solution is from about 2:1 to about 1:2.
Claim 18
Dependent Claim
24 words
The method of claim 3 wherein the weight ratio of titanium to ruthenium in the first solution is from about 2:1 to about 1:1.
Claim 19
Dependent Claim
43 words
The method of claim 12 wherein the second solution includes ruthenium in an amount of from about 2 to about 10 milligrams per milliliter of solution and titanium in an amount of from about 20 to about 40 milligrams per milliliter of solution.
Claim 20
Dependent Claim
24 words
The method of claim 18 wherein the weight ratio of titanium to ruthenium in the second solution is from about 10:1 to about 2:1.
Claim 21
Dependent Claim
24 words
The method of claim 3 wherein the weight ratio of titanium to ruthenium in the second solution is from about 10:1 to about 2:1.
Claim 22
Dependent Claim
27 words
The method of claim 1 wherein the heating steps (b) and (d) are carried out within the temperature range of from about 300° to about 450° C.
Claim 23
Dependent Claim
27 words
The method of claim 3 wherein the heating steps (b) and (d) are carried out within the temperature range of from about 300° to about 450° C.
Claim 24
Dependent Claim
20 words
The method of claim 1 including the steps of drying the contacted substrate before the heating steps (b) and (d).
Claim 25
Dependent Claim
20 words
The method of claim 3 including the steps of drying the contacted substrate before the heating steps (b) and (d).
Claim 26
Independent Claim
368 words
A method to produce an electrode comprising sequentially: (a) contacting at least a portion of a titanium substrate with a first solution consisting essentially of dissolved ruthenium in an amount of from about 0.25 to about 50 milligrams per milliliter of the first solution, dissolved titanium in an amount of from about 0.06 to about 50 milligrams per milliliter of the first solution, at least one solvent suitable to dissolve the ruthenium and titanium values, and a sufficient amount of an acid to maintain the ruthenium and titanium in solution; the ruthenium and titanium being provided by compounds thermally decomposable to ruthenium and titanium oxides in the presence of oxygen and soluble to the extent of at least about 0.25 milligram ruthenium and 0.06 milligram titanium per milliliter of solution; the weight ratio of titanium to ruthenium in the first solution being about 1:4 to about 2:1; (b) drying at least a portion of the contacted substrate; (c) heating at least a portion of the contacted substrate sufficiently to form a coating containing oxides of ruthenium and titanium on the substrate; (d) contacting at least a portion of the oxide coating with a second solution consisting essentially of dissolved ruthenium in an amount of from about 0.25 to about 25 milligrams per milliliter of the second solution, dissolved titanium in an amount of from about 1 to about 100 milligrams per milliliter of the second solution, at least one solvent suitable to dissolve the ruthenium and titanium values, and a sufficient amount of an acid to maintain the ruthenium in solution; the ruthenium and titanium being provided by compounds thermally decomposable to ruthenium and titanium oxides in the presence of oxygen and soluble to the extent of at least about 0.25 milligram ruthenium and 1 milligram titanium per milliliter of the second solution; the weight ratio of titanium to ruthenium in the second solution being from about 20:1 to about 2:1 and greater than the titanium to ruthenium weight ratio of the first solution; (e) drying at least a portion of the contacted substrate; (f) heating at least a portion of the contacted substrate sufficiently to form a coating containing oxides of ruthenium and titanium on the substrate.
Claim 27
Independent Claim
368 words
A method to produce an electrode comprising sequentially: (a) contacting at least a portion of a titanium substrate with a first solution consisting essentially of dissolved ruthenium in an amount of from about 0.25 to about 50 milligrams per milliliter of the first solution, dissolved titanium in an amount of from about 0.06 to about 50 milligrams per milliliter of the first solution, at least one solvent suitable to dissolve the ruthenium and titanium values, and a sufficient amount of an acid to maintain the ruthenium and titanium in solution; the ruthenium and titanium being provided by compounds thermally decomposable to ruthenium and titanium oxides in the presence of oxygen and soluble to the extent of at least about 0.25 milligram ruthenium and 0.06 milligram titanium per milliliter of solution; the weight ratio of titanium to ruthenium in the first solution being about 1:4 to about 2:1; (b) drying at least a portion of the contacted substrate; (c) heating at least a portion of the contacted substrate sufficiently to form a coating containing oxides of ruthenium and titanium on the substrate; (d) contacting at least a portion of the oxide coating with a second solution consisting essentially of dissolved ruthenium in an amount of from about 0.25 to about 25 milligrams per milliliter of the second solution, dissolved titanium in an amount of from about 1 to about 100 milligrams per milliliter of the second solution, at least one solvent suitable to dissolve the ruthenium and titanium values, and a sufficient amount of an acid to maintain the ruthenium in solution; the ruthenium and titanium being provided by compounds thermally decomposable to ruthenium and titanium oxides in the presence of oxygen and soluble to the extent of at least about 0.25 milligram ruthenium and 1 milligram titanium per milliliter of the second solution; the weight ratio of titanium to ruthenium in the second solution being from about 20:1 to about 2:1 and greater than the titanium to ruthenium weight ratio of the first solution; (e) drying at least a portion of the contacted substrate; (f) heating at least a portion of the contacted substrate sufficiently to form a coating containing oxides of ruthenium and titanium on the substrate.
Claim 28
Dependent Claim
33 words
The method of claim 25 wherein the titanium compound in the first and second solutions is selected from at least one member of the group consisting of titanium-isopropyl-titanate, tetrakis(2-ethylhexyl)titanate, tetrastearyl-titanate and tetrabutyl titanate.
Claim 29
Dependent Claim
24 words
The method of claim 25 wherein steps (a), (b) and (c) are repeated to apply at least two oxide layers with the first solution.
Claim 30
Dependent Claim
26 words
The methods of claims 25 or 27 wherein steps (d), (e) and (f) are repeated to apply at least two oxide layers with the second solution.
Claim 31
Dependent Claim
43 words
The method of claim 28 wherein the first solution includes ruthenium in an amount of from about 5 to about 25 milligrams per milliliter of solution and titanium in an amount of from about 5 to about 25 milligrams per milliliter of solution.
Claim 32
Dependent Claim
24 words
The method of claim 29 wherein the weight ratio of titanium to ruthenium in the first solution is from about 2:1 to about 1:2.
Claim 33
Dependent Claim
24 words
The method of claim 28 wherein the weight ratio of titanium to ruthenium in the first solution is from about 2:1 to about 1:1.
Claim 34
Dependent Claim
43 words
The method of claim 28 wherein the second solution includes ruthenium in an amount of from about 2 to about 10 milligrams per milliliter of solution and titanium in an amount of from about 20 to about 40 milligrams per milliliter of solution.
Claim 35
Dependent Claim
24 words
The method of claim 26 wherein the weight ratio of titanium to ruthenium in the second solution is from about 10:1 to about 2:1.
Claim 36
Dependent Claim
43 words
The method of claim 29 wherein the second solution includes ruthenium in an amount of from about 2 to about 10 milligrams per milliliter of solution and titanium in an amount of from about 20 to about 40 milligrams per milliliter of solution.
Claim 37
Dependent Claim
11 words
An electrode produced by the methods of claims 1 or 25.
Claim 38
Dependent Claim
9 words
An electrode produced by the method of claim 12.
Claim 39
Dependent Claim
11 words
An electrode produced by the method of claims 11 or 27.
Claim 40
Dependent Claim
9 words
An electrode produced by the method of claim 28.
Claim 41
Dependent Claim
9 words
An electrode produced by the method of claim 34.
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USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1983-07-29 | 1984-01-28 | 1984-07-29 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1987-07-29 | 1988-01-28 | 1988-07-29 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1991-07-29 | 1992-01-28 | 1992-07-29 | $7700.00 | Window Closed / Lapsed |