US2019546A - Oxide cathode and method of making same - Google Patents
Oxide cathode and method of making same Download PDFInfo
- Publication number
- US2019546A US2019546A US479922A US47992230A US2019546A US 2019546 A US2019546 A US 2019546A US 479922 A US479922 A US 479922A US 47992230 A US47992230 A US 47992230A US 2019546 A US2019546 A US 2019546A
- Authority
- US
- United States
- Prior art keywords
- cathode
- alkaline earth
- earth metal
- metal
- 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 - Lifetime
Links
- 238000004519 manufacturing process Methods 0.000 title description 3
- 229910052751 metal Inorganic materials 0.000 description 40
- 239000002184 metal Substances 0.000 description 40
- 229910052784 alkaline earth metal Inorganic materials 0.000 description 26
- 150000001342 alkaline earth metals Chemical class 0.000 description 24
- 238000000034 method Methods 0.000 description 20
- 229910000906 Bronze Inorganic materials 0.000 description 19
- 239000010974 bronze Substances 0.000 description 19
- KUNSUQLRTQLHQQ-UHFFFAOYSA-N copper tin Chemical compound [Cu].[Sn] KUNSUQLRTQLHQQ-UHFFFAOYSA-N 0.000 description 19
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 15
- 229910052721 tungsten Inorganic materials 0.000 description 15
- 239000010937 tungsten Substances 0.000 description 15
- 239000002253 acid Substances 0.000 description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 13
- 229910052750 molybdenum Inorganic materials 0.000 description 13
- 239000011733 molybdenum Substances 0.000 description 13
- 239000011248 coating agent Substances 0.000 description 12
- 238000000576 coating method Methods 0.000 description 12
- 150000007513 acids Chemical class 0.000 description 10
- 238000000354 decomposition reaction Methods 0.000 description 10
- 230000001376 precipitating effect Effects 0.000 description 10
- 239000012808 vapor phase Substances 0.000 description 10
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 150000002739 metals Chemical class 0.000 description 7
- 229910052788 barium Inorganic materials 0.000 description 6
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 4
- WMTSAHAFZXEJBV-UHFFFAOYSA-N [Ba].[W] Chemical compound [Ba].[W] WMTSAHAFZXEJBV-UHFFFAOYSA-N 0.000 description 3
- 150000001341 alkaline earth metal compounds Chemical class 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- -1 alkaline earth metal salt Chemical class 0.000 description 2
- RCMWGBKVFBTLCW-UHFFFAOYSA-N barium(2+);dioxido(dioxo)molybdenum Chemical compound [Ba+2].[O-][Mo]([O-])(=O)=O RCMWGBKVFBTLCW-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- WOVADLWDGDABII-UHFFFAOYSA-N [Ba].[Mo] Chemical compound [Ba].[Mo] WOVADLWDGDABII-UHFFFAOYSA-N 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/02—Manufacture of electrodes or electrode systems
- H01J9/04—Manufacture of electrodes or electrode systems of thermionic cathodes
- H01J9/042—Manufacture, activation of the emissive part
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
- H01J1/02—Main electrodes
- H01J1/13—Solid thermionic cathodes
- H01J1/14—Solid thermionic cathodes characterised by the material
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12535—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.] with additional, spatially distinct nonmetal component
- Y10T428/12611—Oxide-containing component
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T428/00—Stock material or miscellaneous articles
- Y10T428/12—All metal or with adjacent metals
- Y10T428/12493—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, joint, etc.]
- Y10T428/12771—Transition metal-base component
- Y10T428/12806—Refractory [Group IVB, VB, or VIB] metal-base component
- Y10T428/12826—Group VIB metal-base component
- Y10T428/12833—Alternative to or next to each other
Definitions
- My invention refers to a new kind of oxide cathodes, such as are used for instance in electrical discharge vessels, and to the method of producing same.
- oxide cathodes by which the metal body serving as core of the oxide cathode is provided with a coating of tungsten oxide or molybdenum oxide, these oxides being separated from suitable solutions of tungsten or molybdenum compounds by electrolytical decomposition and depositedon the metal body arranged in the solution and inserted in the electrolytical circuit as cathode.
- a cathode of this kind which is coated with one of these oxides is then mounted on the support and subjected in a well known manner in the discharge vessel to the action of alkaline earth metal vapors.
- the production of the coating on the metal body serving as the core of the cathode was effected with the aid of difierent kinds of solutions of tungstic or molybdic acids, for instance acidulated solutions of orthotungstates or orthomolybdates.
- oxide cathodes are produced by coating the metal body serving as the core of the cathode, before the alkaline earth metal vapor is precipitated thereon, with one or a plurality of compounds of metals of high melting point which do not form alloys with the alkaline earth metal, such compounds being for instance those compounds of tungsten or molybdenum, which already contain those alkaline earth metal oxides which shall be produced on the surface of the cathode.
- Compounds of this kind are for instance the so-called alkaline earth metal bronzes, for instance the barium tungsten bronze BaW3O9 described under this denomination for instance by Smithell on page 38 of Tungsten (London 1926).
- alkaline earth metal oxide is formed by the alkaline earth metal which is the" cause of the decomposition, the metal being oxidized by the oxygen in the bronze.
- the method according to which a coating or" 5 tungsten or molybdenum bronze is produced on a metal body is disclosed and claimed in a copending application of even date and no claim is made in the present application to this process.
- the process consists in placing the metal body 10 forming the core of the cathode in a solution of an alkaline earth metal salt of metaor polytungstic or molybdic acid or a mixture of such salts.
- the metal body placed in the solution is inserted as cathode in the electrolytic circuit and 15 exposed for a short time to the action of an electric current.
- electrolytic decomposition of the solution the alkaline earth metal bronze is deposited on the cathode body under the form of auniform firmly adhering layer.
- the adhesion 20 of the bronze layer to the core is such that the layer is not loosened when the cathode is subjected to mechanical treatment. Therefore the coating of the cathode body with the bronze layer can be efiected before fixing the cathode on its 25 support in the discharge tube.
- the decomposition of the alkaline earth metal bronzes by means of alkaline earth metal is effected within the discharge vessel, an alkaline earth metal being precipitated from the vapor phase on the cathode.
- the cathode is heatedto a temperature exceeding by some 100 degrees the normal temperature of operation of the discharge vessel (for instance 1500 C.) in order to make sure that the layer of alkaline earth metal oxide will firmly adhere to the cathode body.
- Example 1 A tungsten filament having a diameter of 0.1 mm. after having been purified by chemical methods and deprived of fat is caused to travel through a barium molybdate solution at the rate of about 35 cms. per minute, about 100 cms. of the filament being submerged in the solution.
- This filament is permanently connected With the negative pole of a source of current.
- the anode is formed by some suitable metal body, for instance a platinum body.
- a current of about 3 milliamp. is caused to flow through the solution.
- the filament leaving the solution which is coated with a blue layer of barium molybdenum bronze is rinsed with distilled water, dried in a current of hot air and placed on a reel.
- the filament thus prepared is mounted in a well known manner on the support of an electron tube and the cathode is then treated further preferably with metal vapor in a well known manner.
- the solution of barium molybdate mentioned above can be produced for instance by precipitating barium metamolybdate from 1 litre of a sodium meta-molybdate solution by means of a watery solution of about 40 grams crystallized barium chloride.
- the barium meta-molybdate is filtered, washed with cold water and then suspended in 800 com. distilled water, so much dilute hydrochloric acid being added to the suspension that the barium meta-molybdate is dissolved.
- the solution is filled up with water to a volume of 1 litre.
- Example 2 A molybdenum filament is first chemically purified and deprived of fat and. is then placed in a 10% barium meta-tungstate solution, heated to 80 0., the filament; being fully submerged in the solution and inserted in the electrolytic circuit as cathode, any metal body serving as anode.
- the filament may now be activated as cathode in a tube by the well known metal vapor method, the tube being evacuated, sealed and alkaline earth metal vapor produced therein.
- the cathode body or core may consist besides tungsten or molybdenum also of other metals having a correspondingly high melting point, such as for instance nickel.
- Cathodes produced according to this method have been found to be very eificient, their electron emission being particularly powerful and persisting.
- an oxide cathode comprising a metal core, a coating on the surface of said core, of an alkaline earth metal compound known under the name of bronze, of a metal of the group of metals constituted by tungsten and molybdenum and a layer of an alkaline earth metal oxide on said coating.
- an oxide cathode comprising a metal core a coating, on said core, of an alkaline earth metal tungsten bronze and a layer of an alkaline earth metal oxide on said coating.
- an oxide cathode comprising a metal core, a coating, on said core, of an alkaline earth metal molybdenum bronze and a layer of an alkaline earth metal oxide on said coating.
- the method of producing an oxide cathode comprising producing on a metal body serving as cathode core a layer of an alkaline earth metal compound, known under the name of bronze, of a metal of the group of metals constituted by tungsten and molybdenum and thereafter precipitating on this layer an alkaline earth metal from the Vapor phase.
- the method of producing an oxide cathode comprising producing on a metal body serving as cathode core a layer of an alkaline earth metal tungsten bronze and molybdenum bronze and thereafter precipitating on this layer an alkaline earth metal from the vapor phase.
- the method of producing an oxide cathode 5 comprising placing a metal body in a solution of barium meta-tungstate BaWeOrs-kQI-IzO, connecting said body as cathode in an electrolytic j circuit, causing the electrolytic current to act on the solution to deposit barium tungsten bronze on 10 the metal body, and thereafter precipitating on this layer an alkaline earth metal from the vapor phase.
- the method of producing an oxide cathode comprising placing a metal body in a solution of barium metatungstate BaW4013+9H20, connecting said body as cathode in an electrolytic circuit, causing the electrolytic current to act on the solution to deposit on the metal body a layer of barium tungsten bronze and thereafter precipitating on this layer an alkaline earth metal from the vapor phase.
- the method of producing an oxide cathode comprising placing a metal body forming the core of the cathode in a solution of an alkaline earth metal salt of an acid of the group of acids constituted by metaand polytungstic and molybdic acids, connecting said body as cathode in an electrolytic circuit, causing the electrolytic circuit to act on the solution to deposit on the metal body 40 by electrolytic decomposition a layer of a compound, known under the name of bronze, of a metal of the group of metals constituted by tungsten and molybdenum and thereafter precipitating on this layer an alkaline earth metal from the vapor phase.
- the method of producing an oxide cathode comprising placing a metal body in a solution of a salt of an acid of the group of acids constituted by metaand polytungstic and molybdic acids, connecting said body as cathode in an electrolytic circuit, causing the electrolytic circuit to act on the solution to deposit on the metal body by electrolytic decomposition an alkaline earth metal compound of one of these acids, and thereafter precipitating on this deposit an alkaline earth metal from the vapor phase.
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Solid Thermionic Cathode (AREA)
- Lasers (AREA)
- Electroluminescent Light Sources (AREA)
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
HU356715X | 1929-12-23 |
Publications (1)
Publication Number | Publication Date |
---|---|
US2019546A true US2019546A (en) | 1935-11-05 |
Family
ID=10978920
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US479922A Expired - Lifetime US2019546A (en) | 1929-12-23 | 1930-09-05 | Oxide cathode and method of making same |
Country Status (5)
Country | Link |
---|---|
US (1) | US2019546A (en, 2012) |
BE (1) | BE370724A (en, 2012) |
FR (1) | FR696590A (en, 2012) |
GB (1) | GB356715A (en, 2012) |
NL (1) | NL34392C (en, 2012) |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2417133A (en) * | 1940-11-23 | 1947-03-11 | Du Pont | Electrodepositing and heat-treating molybdenum-oxygen deposits |
US2512141A (en) * | 1945-06-14 | 1950-06-20 | Westinghouse Electric Corp | Coating articles with molybdenum |
-
0
- NL NL34392D patent/NL34392C/xx active
- BE BE370724D patent/BE370724A/xx unknown
-
1930
- 1930-06-03 FR FR696590D patent/FR696590A/fr not_active Expired
- 1930-06-06 GB GB17582/30A patent/GB356715A/en not_active Expired
- 1930-09-05 US US479922A patent/US2019546A/en not_active Expired - Lifetime
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2417133A (en) * | 1940-11-23 | 1947-03-11 | Du Pont | Electrodepositing and heat-treating molybdenum-oxygen deposits |
US2512141A (en) * | 1945-06-14 | 1950-06-20 | Westinghouse Electric Corp | Coating articles with molybdenum |
Also Published As
Publication number | Publication date |
---|---|
BE370724A (en, 2012) | |
GB356715A (en) | 1931-09-07 |
FR696590A (fr) | 1931-01-05 |
NL34392C (en, 2012) |
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