US3816079A - Method of producing grid electrodes for electronic discharge vessels - Google Patents

Method of producing grid electrodes for electronic discharge vessels Download PDF

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US3816079A
US3816079A US00314575A US31457572A US3816079A US 3816079 A US3816079 A US 3816079A US 00314575 A US00314575 A US 00314575A US 31457572 A US31457572 A US 31457572A US 3816079 A US3816079 A US 3816079A
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grid
electronic discharge
discharge vessels
grid electrodes
intermetallic compound
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US00314575A
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R Bachmann
C Buxbaum
B Zigerlig
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BBC Brown Boveri AG Switzerland
BBC Brown Boveri France SA
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BBC Brown Boveri France SA
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J19/00—Details of vacuum tubes of the types covered by group H01J21/00
    • H01J19/28—Non-electron-emitting electrodes; Screens
    • H01J19/30—Non-electron-emitting electrodes; Screens characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J2893/00—Discharge tubes and lamps
    • H01J2893/0001—Electrodes and electrode systems suitable for discharge tubes or lamps
    • H01J2893/0012—Constructional arrangements
    • H01J2893/0019—Chemical composition and manufacture
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/923—Physical dimension
    • Y10S428/924—Composite
    • Y10S428/926—Thickness of individual layer specified
    • 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
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S428/00—Stock material or miscellaneous articles
    • Y10S428/922—Static electricity metal bleed-off metallic stock
    • Y10S428/9335—Product by special process
    • Y10S428/934—Electrical process
    • 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
    • Y10T428/12014—All metal or with adjacent metals having metal particles
    • Y10T428/12028—Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12063—Nonparticulate metal component
    • Y10T428/12069—Plural nonparticulate metal components
    • 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
    • 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
    • Y10T428/12861—Group VIII or IB metal-base component
    • Y10T428/12875—Platinum group metal-base 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.]
    • Y10T428/12986—Adjacent functionally defined components

Definitions

  • ABSTRACT A grid electrode for an electronic discharge vessel wherein the wire which forms the grid is first covered with a layer of an intermetallic compound comprising a high-melting metal such as zirconium or titanium and a metal of Group VIII of the Periodic System, for example platinum.
  • the intermetallic compound is applied to the grid wire in powdered form and then sintered after which an outer layer of a noble metal, for example platinum is then applied electrolytically.
  • the present invention relates to a method of producing grid electrodes for electronic discharge vessels whereby an intermediate coating consisting of a highmelting intermetallic compound is applied to the wires forming the grid and the intermediate coating is then covered with a layer of a noble metal, and further to a grid electrode produced by the method.
  • the method is known whereby grid electrodes are coated with a noble metal of the Vlll group of the periodic system, preferably platinum, in order to reduce thermal emission.
  • a noble metal of the Vlll group of the periodic system preferably platinum
  • an intermediate coating should be provided between the basic metal and the outer coating.
  • Carbides, borides or silicides of high-melting metals have been proposed as suitable materials for the intermediate coating.
  • the principal object of the present invention is to create a grid electrode such that the thermal emission does not increase even at greatly increased loading, and which at the same time possesses a slight and reproducible secondary emission together with increased highvoltage strength.
  • the intermetallic compound for the intermediate coating comprises a highmelting metal, such as zirconium or titanium, and a metal of group Vlll of the periodic system.
  • the electrode produced by the method is characterized by the fact that the intermetallic compound comprises a high-melting metal and a noble metal of group Vlll of the periodic system.
  • the intermetallic compound is preferably applied to the electrode core as a powder and then sintered. By suitably choosing the grain size of the powder it is possible to determine exactly the surface roughness and hence to influence the secondary emission of the electrode as required.
  • the shaped grid of a conventional transmitting tube consisting of wires of molybdenum or tungsten, is annealed in hydrogen at l,000 to l,lO C to remove the oxides, etc.
  • the grid is then covered by cataphoresis with ZrPt the production of which in powder form has already been described, preferably to a coating thickness of 5 a.
  • the grid, together with the applied intermediate coating is then annealed in vacuo or a protective gas for minutes at l,500 l,600 C, whereupon the intermediate coating sinters, retaining 2 its roughness.
  • the grid with its sintered intermediate coating, is covered electrolytically with a layer of platinum 3 ,u thick and then degassed by annealing once more in vacuo at a temperature of l,500 1,600 C. Having been degassed, the grid is ready to be fitted.
  • Grids produced in this way exhibit great adhesion between the intermediate coating and the basic metal on the one hand, and the platinum coat on the other, resulting in increased high-voltage strength. This high adhesion also improves the mechanical properties of the grid, so that very fine grids, meshed grids, for example, can be produced.
  • the grain size of the ZrPt powder applied to the grid it is possible to vary the roughness of the grid surface, and consequently the secondary emission, in a reproducible manner.
  • Specific radiation values from 20 W/cm to 29 W/cm can be achieved at 1,525K, depending on the chosen roughness of the grid surface. This corresponds to between 65 and percent of the radiation of a black body.
  • a method of producing grid electrodes for electronic discharge vessels which comprises the steps of applying to the wires forming the grid an intermediate coating consisting of a high-melting intermetallic compound constituted by a high-melting metal and platinum, and then covering said intermediate coating with an 'outer layer of platinum.
  • a method as defined in claim 1 for producing grid electrodes for electronic discharge vessels wherein said intermetallic compound in powder form is applied to the wires forming said grid by electrophoresis until the thickness thereof is at least 5 t, preferably 5 to 10 ,u, and is then heated in an inert atmosphere or in vacuo to at least 1,500C, preferably l,500 to l,600C, to thereby sinter the same.
  • a method as defined in claim 1 for producing grid electrodes for electronic discharge vessels wherein said outer platinum layer is applied electrolytically to the intermediate coating and said grid is then annealed in vacuo at a temperature of at least l,00OC, preferably from l,500 to 1,600C.

Abstract

A grid electrode for an electronic discharge vessel wherein the wire which forms the grid is first covered with a layer of an intermetallic compound comprising a high-melting metal such as zirconium or titanium and a metal of Group VIII of the Periodic System, for example platinum. The intermetallic compound is applied to the grid wire in powdered form and then sintered after which an outer layer of a noble metal, for example platinum is then applied electrolytically.

Description

mite States Patent [191 Bachmann et al.
Zigerlig, Nussbaumen, all of Switzerland Assignee:- BBC Brown Boveri & Company Limited, Baden, Switzerland Filed: Dec. 13, 1972 Appl. No.: 314,575
Foreign Application Priority Data Dec. 29, 1971 Switzerland 19037/71 US. Cl.- 29/182.3, 75/208 R, 117/22, 117/23, 117/217, 117/221, 117/231, 204/181 Int. Cl B22f 7/04.
Field of Search 75/208 R; 29/1823; 117/217,221,231,22,23;204/181 June 11, 1974 [5 6] References Cited UNITED STATES PATENTS 2,516,841 8/1950 Arditi et a1. 29/1823 X 2,520,760 8/1950 Gallet et a1. 75/208 R X 2,788,460 4/1957 De Santis et a1 213/355 X 2,826,541 3/1958 Barr et a1. 75/208 R X Primary ExaminerLe1and A. Sebastian Assistant Examiner-R. E. Schafer Attorney, Agent, or FirmPierce, Scheffler & Parker [5 7] ABSTRACT A grid electrode for an electronic discharge vessel wherein the wire which forms the grid is first covered with a layer of an intermetallic compound comprising a high-melting metal such as zirconium or titanium and a metal of Group VIII of the Periodic System, for example platinum. The intermetallic compound is applied to the grid wire in powdered form and then sintered after which an outer layer of a noble metal, for example platinum is then applied electrolytically.
10 Claims, No Drawings METHOD OF PRODUCING GRID ELECTRODES FUR ELECTRONIC DISCHARGE VESSELS The present invention relates to a method of producing grid electrodes for electronic discharge vessels whereby an intermediate coating consisting of a highmelting intermetallic compound is applied to the wires forming the grid and the intermediate coating is then covered with a layer of a noble metal, and further to a grid electrode produced by the method.
The method is known whereby grid electrodes are coated with a noble metal of the Vlll group of the periodic system, preferably platinum, in order to reduce thermal emission. To reduce diffusion of the platinum into the grid wire (basic metal) and increase the radiative capacity, it has been proposed that an intermediate coating should be provided between the basic metal and the outer coating. Carbides, borides or silicides of high-melting metals have been proposed as suitable materials for the intermediate coating.
These known methods have the disadvantage that the coating reacts more or less quickly with the basic metal or, in the case of several coating components, within itself, and the reaction products can be activated by the evaporation products of the Th-W cathode. All methods employing carbides as the intermediate coating have the added disadvantage that in time carbides form with the basic metal, and these carbides cause the grid to become brittle.
The principal object of the present invention is to create a grid electrode such that the thermal emission does not increase even at greatly increased loading, and which at the same time possesses a slight and reproducible secondary emission together with increased highvoltage strength.
This object is achieved in that the intermetallic compound for the intermediate coating comprises a highmelting metal, such as zirconium or titanium, and a metal of group Vlll of the periodic system.
The electrode produced by the method is characterized by the fact that the intermetallic compound comprises a high-melting metal and a noble metal of group Vlll of the periodic system. The intermetallic compound is preferably applied to the electrode core as a powder and then sintered. By suitably choosing the grain size of the powder it is possible to determine exactly the surface roughness and hence to influence the secondary emission of the electrode as required.
EXAMPLE OF THE METHOD Stoichiometric quantities of zirconium and platinum are melted together in vacuo, yielding the intermetallic compound ZrPt The solidified specimens of this intermetallic compound are crushed in a mortar and then ground in a mill lined with a hard material such as tungsten carbide until the desired grain size preferably Bu, is attained.
The shaped grid of a conventional transmitting tube, consisting of wires of molybdenum or tungsten, is annealed in hydrogen at l,000 to l,lO C to remove the oxides, etc. The grid is then covered by cataphoresis with ZrPt the production of which in powder form has already been described, preferably to a coating thickness of 5 a. The grid, together with the applied intermediate coating, is then annealed in vacuo or a protective gas for minutes at l,500 l,600 C, whereupon the intermediate coating sinters, retaining 2 its roughness. After this the grid, with its sintered intermediate coating, is covered electrolytically with a layer of platinum 3 ,u thick and then degassed by annealing once more in vacuo at a temperature of l,500 1,600 C. Having been degassed, the grid is ready to be fitted.
Grids produced in this way exhibit great adhesion between the intermediate coating and the basic metal on the one hand, and the platinum coat on the other, resulting in increased high-voltage strength. This high adhesion also improves the mechanical properties of the grid, so that very fine grids, meshed grids, for example, can be produced.
By suitably selecting the grain size of the ZrPt powder applied to the grid it is possible to vary the roughness of the grid surface, and consequently the secondary emission, in a reproducible manner.
In addition, these grids yield higher measured radiation values and a higher thermal load capacity, thus allowing higher electrical loadings.
Specific radiation values from 20 W/cm to 29 W/cm can be achieved at 1,525K, depending on the chosen roughness of the grid surface. This corresponds to between 65 and percent of the radiation of a black body.
At the same temperature the specific primary emission is approx. l uAlcm This corresponds roughly to the operating conditions in electronic discharge vessels. This primary emission does not increase even after prolonged thermal overloading at 1,800 K.
We claim:
.1. A method of producing grid electrodes for electronic discharge vessels which comprises the steps of applying to the wires forming the grid an intermediate coating consisting of a high-melting intermetallic compound constituted by a high-melting metal and platinum, and then covering said intermediate coating with an 'outer layer of platinum.
2. A method as defined in claim 1 for producing grid electrodes for electronic discharge vessels wherein said high-melting metal is zirconium.
3. A method as defined in claim 2 for producing grid electrodes for electronic discharge vessels wherein said intermetallic compound is ZrPt 4. A method as defined in claim 1 for producing grid electrodes for electronic discharge vessels wherein said intermetallic compound is applied to the wires forming said grid in powder form and is then sintered.
5. A method as defined in claim 1 for producing grid electrodes for electronic discharge vessels wherein said intermetallic compound in powder form is applied to the wires forming said grid by electrophoresis until the thickness thereof is at least 5 t, preferably 5 to 10 ,u, and is then heated in an inert atmosphere or in vacuo to at least 1,500C, preferably l,500 to l,600C, to thereby sinter the same.
6. A method as defined in claim 5 for producing grid electrodes for electronic discharge vessels wherein the sintering time is approximately 20 minutes.
7. A method as defined in claim 1 for producing grid electrodes for electronic discharge vessels wherein said outer platinum layer is applied electrolytically to the intermediate coating and said grid is then annealed in vacuo at a temperature of at least l,00OC, preferably from l,500 to 1,600C.
4 comprising a base metal forming the grid wire, an intermediate layer of an intermetallic compound comprising a high-melting metal and platinum applied to said wire, and an outer layer of platinum applied to said intermediate layer.

Claims (9)

  1. 2. A method as defined in claim 1 for producing grid electrodes for electronic discharge vessels wherein said high-melting metal is zirconium.
  2. 3. A method as defined in claim 2 for producing grid electrodes for electronic discharge vessels wherein said intermetallic compound is ZrPt3.
  3. 4. A method as defined in claim 1 for producing grid electrodes for electronic discharge vessels wherein said intermetallic compound is applied to the wires forming said grid in powder form and is then sintered.
  4. 5. A method as defined in claim 1 for producing grid electrodes for electronic discharge vessels wherein said intermetallic compound in powder form is applied to the wires forming said grid by electrophoresis until the thickness thereof is at least 5 Mu , preferably 5 to 10 Mu , and is then heated in an inert atmosphere or in vacuo to at least 1,500*C, preferably 1,500* to 1,600*C, to thereby sinter the same.
  5. 6. A method as defined in claim 5 for producing grid electrodes for electronic discharge vessels wherein the sintering time is approximately 20 minutes.
  6. 7. A method as defined in claim 1 for producing grid electrodes for electronic discharge vessels wherein said outer platinum layer is applied electrolytically to the intermediate coating and said grid is then annealed in vacuo at a temperature of at least 1,000*C, preferably from 1,500* to 1,600*C.
  7. 8. A method as defined in claim 7 for producing grid electrodes for electronic discharge vessels wherein the thickness of the applied platinum is at least 3 Mu .
  8. 9. A method as defined in claim 1 for producing grid electrodes for electronic discharge vessels wherein said high-melting metal is titanium.
  9. 10. A grid electrode for electronic discharge vessels comprising a base metal forming the grid wire, an intermediate layer of an intermetallic compound comprising a high-melting metal and platinum applied to said wire, and an outer layer of platinum applied to said intermediate layer.
US00314575A 1971-12-29 1972-12-13 Method of producing grid electrodes for electronic discharge vessels Expired - Lifetime US3816079A (en)

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CH1903771A CH539945A (en) 1971-12-29 1971-12-29 Process for the production of grid electrodes for electrical discharge vessels

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JP (1) JPS5812694B2 (en)
CH (1) CH539945A (en)
DE (1) DE2202827C3 (en)
FR (1) FR2166052B1 (en)
GB (1) GB1362351A (en)
IT (1) IT972899B (en)
NL (1) NL176320C (en)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4137370A (en) * 1977-08-16 1979-01-30 The United States Of America As Represented By The Secretary Of The Air Force Titanium and titanium alloys ion plated with noble metals and their alloys
WO1982001510A1 (en) * 1980-10-27 1982-05-13 Owens Corning Fiberglass Corp Articles for contacting molten glass

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE2919028A1 (en) * 1979-04-20 1980-10-30 Bbc Brown Boveri & Cie ELECTRIC DISCHARGE VESSEL
GB2117795A (en) * 1982-04-06 1983-10-19 Standard Telephones Cables Ltd Fabricating capacitors; forming ceramic films
RU2604836C1 (en) * 2015-06-30 2016-12-10 Федеральное государственное бюджетное образовательное учреждение высшего профессионального образования "Рязанский государственный радиотехнический университет" Method and device for determining anti-emission materials thermal characteristics

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2516841A (en) * 1946-01-16 1950-08-01 Standard Telephones Cables Ltd Grid for electron discharge devices
US2520760A (en) * 1946-03-05 1950-08-29 Csf Method of producing cathodes for electronic tubes
US2788460A (en) * 1951-05-23 1957-04-09 Itt Electrodes for electron discharge devices and methods of making same
US2826541A (en) * 1954-06-15 1958-03-11 Vitro Corp Of America Method of making ceramic-clad metal structures

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1111301B (en) * 1958-11-28 1961-07-20 Tesla Np Grid for electron tubes with a grid wire, the surface of which has a coating made of a noble metal alloy
US3164740A (en) * 1960-04-29 1965-01-05 Rca Corp Electron tube grids and method of making the same
DE1614398B2 (en) * 1967-01-04 1971-10-21 Siemens AG, 1000 Berlin u 8000 München LATTICE WIRE FOR ELECTRON TUBES
NL6809010A (en) * 1967-07-21 1969-01-23

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2516841A (en) * 1946-01-16 1950-08-01 Standard Telephones Cables Ltd Grid for electron discharge devices
US2520760A (en) * 1946-03-05 1950-08-29 Csf Method of producing cathodes for electronic tubes
US2788460A (en) * 1951-05-23 1957-04-09 Itt Electrodes for electron discharge devices and methods of making same
US2826541A (en) * 1954-06-15 1958-03-11 Vitro Corp Of America Method of making ceramic-clad metal structures

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4137370A (en) * 1977-08-16 1979-01-30 The United States Of America As Represented By The Secretary Of The Air Force Titanium and titanium alloys ion plated with noble metals and their alloys
WO1982001510A1 (en) * 1980-10-27 1982-05-13 Owens Corning Fiberglass Corp Articles for contacting molten glass

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GB1362351A (en) 1974-08-07
NL7217592A (en) 1973-07-03
DE2202827C3 (en) 1984-05-30
DE2202827B2 (en) 1979-11-08
FR2166052A1 (en) 1973-08-10
FR2166052B1 (en) 1976-08-27
NL176320B (en) 1984-10-16
NL176320C (en) 1985-03-18
JPS5812694B2 (en) 1983-03-09
IT972899B (en) 1974-05-31
CH539945A (en) 1973-07-31
DE2202827A1 (en) 1973-07-05
JPS4874968A (en) 1973-10-09

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