US4428770A
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Methods of manufacturing metal from a melt, determination of sulfur and carbon therein, sensors therefor and solid electrolyte compositions for said sensors
Assignee: University Patents Inc
•
Filing: 1982-02-23
•
Granted: 1984-01-31
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Expires: 2002-02-23
Abstract
Abstract Materials, methods and articles for the electrochemical determination of sulfur and carbon in fluids are provided. In accordance with a preferred embodiment, an electrolyte is furnished comprising a solid solution of an oxide of either zirconium, thorium or hafnium together with an oxide of an element of groups IIA or IIIB of the periodic table of the elements together with a sulfide or carbide of an element of groups IIA or IIIB of the periodic table. Processes employing such electrolytes together with articles incorporating them are also contemplated.
Inventors
- 👤 Wayne L. Worrell
- 👤 Qing-Guo Liu
Bibliographic Details
Application Number
—
Jurisdiction
US
Data Source
google_patents
Last Synchronized
2026-10-30 22:41
CPC Classifications
G; G01; G01N; G01N27/00; G01N27/26; G01N27/403; G01N27/406; G01N27/411; G01N27/4112; G01N27/4114
Claims Analysis
Total Claims: 81
Claim 1
Independent Claim
44 words
A solid solution of: from about 75 mole percent to about 98 mole percent of zirconium dioxide; from about 1 mole percent to about 20 mole percent of calcium oxide; and from about 1 mole percent to about 20 mole percent of calcium sulfide.
Claim 2
Dependent Claim
44 words
A solid solution of: from about 75 mole percent to about 98 mole percent of zirconium dioxide; from about 1 mole percent to about 20 mole percent of calcium oxide; and from about 1 mole percent to about 20 mole percent of calcium sulfide.
Claim 3
Dependent Claim
44 words
A solid solution of: from about 75 mole percent to about 98 mole percent of zirconium dioxide; from about 1 mole percent to about 20 mole percent of calcium oxide; and from about 1 mole percent to about 20 mole percent of calcium carbide.
Claim 4
Dependent Claim
44 words
A solid solution of: from about 75 mole percent to about 98 mole percent of zirconium dioxide; from about 1 mole percent to about 20 mole percent of calcium oxide; and from about 1 mole percent to about 20 mole percent of calcium carbide.
Claim 5
Dependent Claim
44 words
A solid solution of: from about 75 mole percent to about 98 mole percent of thorium dioxide; from about 1 mole percent to about 20 mole percent of calcium oxide; and from about 1 mole percent to about 20 mole percent of calcium sulfide.
Claim 6
Dependent Claim
44 words
A solid solution of: from about 75 mole percent to about 98 mole percent of thorium dioxide; from about 1 mole percent to about 20 mole percent of calcium oxide; and from about 1 mole percent to about 20 mole percent of calcium sulfide.
Claim 7
Dependent Claim
44 words
A solid solution of: from about 75 mole percent to about 98 mole percent of thorium dioxide; from about 1 mole percent to about 20 mole percent of calcium oxide; and from about 1 mole percent to about 20 mole percent of calcium carbide.
Claim 8
Dependent Claim
44 words
A solid solution of: from about 75 mole percent to about 98 mole percent of thorium dioxide; from about 1 mole percent to about 20 mole percent of calcium oxide; and from about 1 mole percent to about 20 mole percent of calcium carbide.
Claim 9
Dependent Claim
91 words
A solid solution of: from about 75 mole percent to about 98 mole percent of an oxide of a metal selected from the group consisting of zirconium, thorium, and hafnium; from about 1 mole percent to about 20 mole percent of an oxide of an element of either of groups IIA or IIIB of the periodic table of the elements; and from about 1 mole percent to about 20 mole percent of the sulfide of an element of either of groups IIA or IIIB of the periodic table of the elements.
Claim 10
Dependent Claim
91 words
A solid solution of: from about 75 mole percent to about 98 mole percent of an oxide of a metal selected from the group consisting of zirconium, thorium, and hafnium; from about 1 mole percent to about 20 mole percent of an oxide of an element of either of groups IIA or IIIB of the periodic table of the elements; and from about 1 mole percent to about 20 mole percent of the sulfide of an element of either of groups IIA or IIIB of the periodic table of the elements.
Claim 11
Dependent Claim
91 words
A solid solution of: from about 75 mole percent to about 98 mole percent of an oxide of a metal selected from the group consisting of zirconium, thorium, and hafnium; from about 1 mole percent to about 20 mole percent of an oxide of an element of either of groups IIA or IIIB of the periodic table of the elements; and from about 1 mole percent to about 20 mole percent of the carbide of an element of either of groups IIA or IIIB of the periodic table of the elements.
Claim 12
Dependent Claim
91 words
A solid solution of: from about 75 mole percent to about 98 mole percent of an oxide of a metal selected from the group consisting of zirconium, thorium, and hafnium; from about 1 mole percent to about 20 mole percent of an oxide of an element of either of groups IIA or IIIB of the periodic table of the elements; and from about 1 mole percent to about 20 mole percent of the carbide of an element of either of groups IIA or IIIB of the periodic table of the elements.
Claim 13
Dependent Claim
48 words
A solid solution of: the oxide of either zirconium, thorium, or hafnium; the oxide of an element of either of groups IIA or IIIB of the periodic table of the elements; and either the sulfide or the carbide of said element of either of groups IIA or IIIB.
Claim 14
Dependent Claim
48 words
A solid solution of: the oxide of either zirconium, thorium, or hafnium; the oxide of an element of either of groups IIA or IIIB of the periodic table of the elements; and either the sulfide or the carbide of said element of either of groups IIA or IIIB.
Claim 15
Dependent Claim
19 words
The solid solution of claim 7 containing the carbide of said element of either of Groups IIA or IIIB.
Claim 16
Independent Claim
45 words
A method of manufacturing a metal from a melt comprising: monitoring the amount of carbon in said melt by contacting said melt with the solid solution of claims 2, 4, 6, or 8; and modifying the composition of said melt in response to said monitoring.
Claim 17
Dependent Claim
19 words
The solid solution of claim 7 containing the sulfide of said element of either of Groups IIA or IIIB.
Claim 18
Independent Claim
45 words
A method of manufacturing a metal from a melt comprising: monitoring the amount of sulfur in said melt by contacting said melt with the solid solution of claims 1, 3, 5, or 10; and modifying the composition of said melt in response to said monitoring.
Claim 19
Independent Claim
26 words
A method of manufacturing melt from a melt comprising contacting said melt with the solid solution of claims 1, 2, 3, 4, 5, 6 or 7.
Claim 20
Dependent Claim
78 words
A process for the detection of sulfur in a fluid comprising: contacting said fluid with an electrolyte comprising a solid solution of: from about 75 mole percent to about 98 mole percent of zirconium dioxide; from about 1 mole percent to about 20 mole percent calcium oxide; from about 1 mole percent to about 20 mole percent calcium sulfide; providing a reference electrode in contact with said electrolyte; and detecting electrical potential between said electrolyte and said electrode.
Claim 21
Dependent Claim
78 words
A process for the detection of sulfur in a fluid comprising: contacting said fluid with an electrolyte comprising a solid solution of: from about 75 mole percent to about 98 mole percent of zirconium dioxide; from about 1 mole percent to about 20 mole percent calcium oxide; from about 1 mole percent to about 20 mole percent calcium sulfide; providing a reference electrode in contact with said electrolyte; and detecting electrical potential between said electrolyte and said electrode.
Claim 22
Dependent Claim
20 words
The process of claim 13 wherein said reference electrode comprises a solid solution of a metal and its metallic sulfide.
Claim 23
Dependent Claim
25 words
The process of claim 14 wherein said metal is an element of group VI B or VII B of the periodic table of the elements.
Claim 24
Dependent Claim
21 words
The process of claim 13 wherein said reference electrode comprises a solid solution of tungsten-tungsten sulfide, chromium-chromium sulfide or manganese-manganese sulfide.
Claim 25
Dependent Claim
42 words
The process of claim 13 wherein said electrolyte comprises: from about 85 mole percent to about 96 mole percent zirconium dioxide; from about 2 to about 10 mole percent calcium oxide; and from about 2 to about 10 mole percent calcium sulfide.
Claim 26
Dependent Claim
17 words
The process of claim 13, 14, 15, 16 or 17 wherein said fluid is a molten metal.
Claim 27
Dependent Claim
11 words
The process of claim 17 wherein said molten metal is steel.
Claim 28
Dependent Claim
16 words
The process of claim 13 wherein said fluid comprises at least about 1 ppm of oxygen.
Claim 29
Dependent Claim
78 words
A process for the detection of sulfur in a fluid comprising: contacting said fluid with an electrolyte comprising a solid solution of: from about 75 mole percent to about 98 mole percent of thorium dioxide; from about 1 mole percent to about 20 mole percent calcium oxide; from about 1 mole percent to about 20 mole percent calcium sulfide; providing a reference electrode in contact with said electrode; and detecting electrical potential between said electrolyte and said electrode.
Claim 30
Dependent Claim
78 words
A process for the detection of sulfur in a fluid comprising: contacting said fluid with an electrolyte comprising a solid solution of: from about 75 mole percent to about 98 mole percent of thorium dioxide; from about 1 mole percent to about 20 mole percent calcium oxide; from about 1 mole percent to about 20 mole percent calcium sulfide; providing a reference electrode in contact with said electrode; and detecting electrical potential between said electrolyte and said electrode.
Claim 31
Dependent Claim
20 words
The process of claim 21 wherein said reference electrode comprises a solid solution of a metal and its metallic sulfide.
Claim 32
Dependent Claim
25 words
The process of claim 22 wherein said metal is an element of group VI B or VII B of the periodic table of the elements.
Claim 33
Dependent Claim
21 words
The process of claim 21 wherein said reference electrode comprises a solid solution of tungsten-tungsten sulfide, chromium-chromium sulfide or manganese-manganese sulfide.
Claim 34
Dependent Claim
42 words
The process of claim 21 wherein said electrolyte comprises: from about 85 mole percent to about 96 mole percent thorium dioxide; from about 2 to about 10 mole percent calcium oxide; and from about 2 to about 10 mole percent calcium sulfide.
Claim 35
Dependent Claim
17 words
The process of claim 21, 22, 23, 24 or 25 wherein said fluid is a molten metal.
Claim 36
Dependent Claim
11 words
The process of claim 26 wherein said molten metal is steel.
Claim 37
Dependent Claim
16 words
The process of claim 21 wherein said fluid comprises at least about 1 ppm of oxygen.
Claim 38
Dependent Claim
78 words
A process for the detection of carbon in a fluid comprising: contacting said fluid with an electrolyte comprising a solid solution of: from about 75 mole percent to about 98 mole percent of zirconium dioxide; from about 1 mole percent to about 20 mole percent calcium oxide; from about 1 mole percent to about 20 mole percent calcium carbide; providing a reference electrode in contact with said electrolyte; and detecting electrical potential between said electrolyte and said electrode.
Claim 39
Dependent Claim
78 words
A process for the detection of carbon in a fluid comprising: contacting said fluid with an electrolyte comprising a solid solution of: from about 75 mole percent to about 98 mole percent of zirconium dioxide; from about 1 mole percent to about 20 mole percent calcium oxide; from about 1 mole percent to about 20 mole percent calcium carbide; providing a reference electrode in contact with said electrolyte; and detecting electrical potential between said electrolyte and said electrode.
Claim 40
Dependent Claim
20 words
The process of claim 29 wherein said reference electrode comprises a solid solution of a metal and its metallic carbide.
Claim 41
Dependent Claim
25 words
The process of claim 30 wherein said metal is an element of group VI B or VII B of the periodic table of the elements.
Claim 42
Dependent Claim
21 words
The process of claim 29 wherein said reference electrode comprises a solid solution of tungsten-tungsten carbide, chromium-chromium carbide or manganese-manganese carbide.
Claim 43
Dependent Claim
42 words
The process of claim 29 wherein said electrolyte comprises: from about 85 mole percent to about 96 mole percent zirconium dioxide; from about 2 to about 10 mole percent calcium oxide; and from about 2 to about 10 mole percent calcium carbide.
Claim 44
Dependent Claim
17 words
The process of claim 29, 30, 31, 32 or 33 wherein said fluid is a molten metal.
Claim 45
Dependent Claim
11 words
The process of claim 34 wherein said molten metal is steel.
Claim 46
Dependent Claim
16 words
The process of claim 29 wherein said fluid comprises at least about 1 ppm of oxygen.
Claim 47
Dependent Claim
78 words
A process for the detection of carbon in a fluid comprising: contacting said fluid with an electrolyte comprising a solid solution of: from about 75 mole percent to about 98 mole percent of thorium dioxide; from about 1 mole percent to about 20 mole percent calcium oxide; from about 1 mole percent to about 20 mole percent calcium carbide; providing a reference electrode in contact with said electrolyte; and detecting electrical potential between said electrolyte and said electrode.
Claim 48
Dependent Claim
78 words
A process for the detection of carbon in a fluid comprising: contacting said fluid with an electrolyte comprising a solid solution of: from about 75 mole percent to about 98 mole percent of thorium dioxide; from about 1 mole percent to about 20 mole percent calcium oxide; from about 1 mole percent to about 20 mole percent calcium carbide; providing a reference electrode in contact with said electrolyte; and detecting electrical potential between said electrolyte and said electrode.
Claim 49
Dependent Claim
20 words
The process of claim 37 wherein said reference electrode comprises a solid solution of a metal and its metallic carbide.
Claim 50
Dependent Claim
25 words
The process of claim 38 wherein said metal is an element of group VI B or VII B of the periodic table of the elements.
Claim 51
Dependent Claim
21 words
The process of claim 37 wherein said reference electrode comprises a solid solution of tungsten-tungsten carbide, chromium-chromium carbide or manganese-manganese carbide.
Claim 52
Dependent Claim
42 words
The process of claim 37 wherein said electrolyte comprises: from about 85 mole percent to about 96 mole percent thorium dioxide; from about 2 to about 10 mole percent calcium oxide; and from about 2 to about 10 mole percent calcium carbide.
Claim 53
Dependent Claim
17 words
The process of claim 37, 38, 39, 40 or 41 wherein said fluid is a molten metal.
Claim 54
Dependent Claim
11 words
The process of claim 42 wherein said molten metal is steel.
Claim 55
Dependent Claim
16 words
The process of claim 37 wherein said fluid comprises at least about 1 ppm of oxygen.
Claim 56
Dependent Claim
94 words
Apparatus for the measurement of sulfur in a fluid comprising: an electrolyte comprising: from about 75 to about 98 mole percent of an oxide of a metal selected from the group consisting of zirconium, thorium, and hafnium; from about 1 to about 20 mole percent of an oxide of an element of either of groups IIA or IIIB of the periodic table of the elements; and from about 1 to about 20 mole percent of the sulfide of an element of either of groups IIA or IIIB of the periodic table of the elements.
Claim 57
Dependent Claim
94 words
Apparatus for the measurement of sulfur in a fluid comprising: an electrolyte comprising: from about 75 to about 98 mole percent of an oxide of a metal selected from the group consisting of zirconium, thorium, and hafnium; from about 1 to about 20 mole percent of an oxide of an element of either of groups IIA or IIIB of the periodic table of the elements; and from about 1 to about 20 mole percent of the sulfide of an element of either of groups IIA or IIIB of the periodic table of the elements.
Claim 58
Dependent Claim
94 words
Apparatus for the measurement of carbon in a fluid comprising: an electrolyte comprising: from about 75 to about 98 mole percent of an oxide of a metal selected from the group consisting of zirconium, thorium, and hafnium; from about 1 to about 20 mole percent of an oxide of an element of either of groups IIA or IIIB of the periodic table of the elements; and from about 1 to about 20 mole percent of he carbide of an element of either of groups IIA or IIIB of the periodic table of the elements.
Claim 59
Dependent Claim
94 words
Apparatus for the measurement of carbon in a fluid comprising: an electrolyte comprising: from about 75 to about 98 mole percent of an oxide of a metal selected from the group consisting of zirconium, thorium, and hafnium; from about 1 to about 20 mole percent of an oxide of an element of either of groups IIA or IIIB of the periodic table of the elements; and from about 1 to about 20 mole percent of he carbide of an element of either of groups IIA or IIIB of the periodic table of the elements.
Claim 60
Independent Claim
48 words
An apparatus for the detection of sulfur in a fluid comprising: an electrolyte comprising a solid solution of zirconium, hafnium, or thorium oxide; an oxide of an element of either of groups IIA or IIIB of the periodic table of the elements; and the sulfide of said element.
Claim 61
Independent Claim
48 words
An apparatus for the detection of sulfur in a fluid comprising: an electrolyte comprising a solid solution of zirconium, hafnium, or thorium oxide; an oxide of an element of either of groups IIA or IIIB of the periodic table of the elements; and the sulfide of said element.
Claim 62
Dependent Claim
15 words
The apparatus of claim 47 further comprising a reference electrode in contact with said electrolyte.
Claim 63
Dependent Claim
27 words
The apparatus of claim 48 further comprising a first electrical contact connected to said reference electrode and a second electrical contact adapted for contact with said fluid.
Claim 64
Dependent Claim
22 words
The apparatus of claim 49 wherein said first and second electrical contacts are adapted for cooperation with an electric potential measuring means.
Claim 65
Dependent Claim
21 words
The apparatus of claim 48 wherein said reference electrode is isolated from physical contact with said fluid by a holder means.
Claim 66
Dependent Claim
20 words
The apparatus of claim 48 wherein said reference electrode comprises a solid solution of a metal and its metallic sulfide.
Claim 67
Dependent Claim
25 words
The apparatus of claim 52 wherein said metal is an element of group VI B or VII B of the periodic table of the elements.
Claim 68
Dependent Claim
21 words
The apparatus of claim 48 wherein said reference electrode comprises a solid solution of tungsten-tungsten sulfide; chromium-chromium sulfide or manganese-manganese sulfide.
Claim 69
Dependent Claim
62 words
The apparatus of claim 47 wherein: said zirconium, hafnium, or thorium oxide is present in an amount of from about 75 to about 98 mole percent; said oxide of an element is present in an amount of from about 1 to about 20 mole percent; and said sulfide is present in an amount of from about 1 to about 20 mole percent.
Claim 70
Dependent Claim
62 words
The apparatus of claim 47 wherein: said zirconium, hafnium, or thorium oxide is present in an amount of from about 85 to about 96 mole percent; said oxide of an element is present in an amount of from about 2 to about 10 mole percent; and said sulfide is present in an amount of from about 2 to about 10 mole percent.
Claim 71
Independent Claim
48 words
An apparatus for the detection of carbon in a fluid comprising: an electrolyte comprising a solid solution of zirconium, hafnium, or thorium oxide; an oxide of an element of either of groups IIA or IIIB of the periodic table of the elements; and the carbide of said element.
Claim 72
Independent Claim
48 words
An apparatus for the detection of carbon in a fluid comprising: an electrolyte comprising a solid solution of zirconium, hafnium, or thorium oxide; an oxide of an element of either of groups IIA or IIIB of the periodic table of the elements; and the carbide of said element.
Claim 73
Dependent Claim
15 words
The apparatus of claim 57 further comprising a reference electrode in contact with said electrolyte.
Claim 74
Dependent Claim
27 words
The apparatus of claim 58 further comprising a first electrical contact connected to said reference electrode and a second electrical contact adapted for contact with said fluid.
Claim 75
Dependent Claim
22 words
The apparatus of claim 59 wherein said first and second electrical contacts are adapted for cooperation with an electric potential measuring means.
Claim 76
Dependent Claim
21 words
The apparatus of claim 58 wherein said reference electrode is isolated from physical contact with said fluid by a holder means.
Claim 77
Dependent Claim
20 words
The apparatus of claim 58 wherein said reference electrode comprises a solid solution of a metal and its metallic carbide.
Claim 78
Dependent Claim
25 words
The apparatus of claim 62 wherein said metal is an element of group VI B or VII B of the periodic table of the elements.
Claim 79
Dependent Claim
21 words
The apparatus of claim 58 wherein said reference electrode comprises a solid solution of tungsten-tungsten carbide; chromium-chromium carbide or manganese-manganese carbide.
Claim 80
Dependent Claim
62 words
The apparatus of claim 57 wherein: said zirconium, hafnium, or thorium oxide is present in an amount of from about 75 to about 98 mole percent; said oxide of an element is present in an amount of from about 1 to about 20 mole percent; and said carbide is present in an amount of from about 1 to about 20 mole percent.
Claim 81
Dependent Claim
62 words
The apparatus of claim 57 wherein: said zirconium, hafnium, or thorium oxide is present in an amount of from about 85 to about 96 mole percent; said oxide of an element is present in an amount of from about 2 to about 10 mole percent; and said sulfide is present in an amount of from about 2 to about 10 mole percent.
References Cited (Backward Citations)
DE1523030A1
Cited
GB1211957A
Cited
USPTO Annuity & Maintenance Windows
| Annuity Stage | Window Opens | Payment Deadline | Surcharge Period Until | Estimated Fee | Status |
|---|---|---|---|---|---|
| 3.5 Years (Year 4) | 1987-01-30 | 1987-08-01 | 1988-01-31 | $2000.00 | Window Closed / Lapsed |
| 7.5 Years (Year 8) | 1991-01-30 | 1991-08-01 | 1992-01-31 | $3760.00 | Window Closed / Lapsed |
| 11.5 Years (Year 12) | 1995-01-30 | 1995-08-01 | 1996-01-31 | $7700.00 | Window Closed / Lapsed |