US3922428A - Thermionic cathode comprising mixture of barium oxide, calcium oxide and samarium oxide - Google Patents

Thermionic cathode comprising mixture of barium oxide, calcium oxide and samarium oxide Download PDF

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US3922428A
US3922428A US22353972A US3922428A US 3922428 A US3922428 A US 3922428A US 22353972 A US22353972 A US 22353972A US 3922428 A US3922428 A US 3922428A
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oxide
barium
cathode
samarium
emission
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Leo J Cronin
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Spectra Mat Inc
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    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J1/00Details 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
    • H01J1/02Main electrodes
    • H01J1/13Solid thermionic cathodes
    • H01J1/14Solid thermionic cathodes characterised by the material
    • HELECTRICITY
    • H01BASIC ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J1/00Details 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
    • H01J1/02Main electrodes
    • H01J1/13Solid thermionic cathodes
    • H01J1/20Cathodes heated indirectly by an electric current; Cathodes heated by electron or ion bombardment
    • H01J1/28Dispenser-type cathodes, e.g. L-cathode
    • YGENERAL 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
    • Y10TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10TTECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00Stock material or miscellaneous articles
    • Y10T428/12All metal or with adjacent metals
    • Y10T428/12014All metal or with adjacent metals having metal particles
    • Y10T428/12028Composite; i.e., plural, adjacent, spatially distinct metal components [e.g., layers, etc.]
    • Y10T428/12042Porous component

Abstract

A cathode is disclosed utilizing an emission material of barium oxide, calcium oxide and samarium oxide.

Description

Unite States Meat Cronin Nov. 25, 1975 [54] THERMIONIC CATHODE COMPRISING 1,921,066 8/1933 Bedford 252/521 MIXTURE OF BARIUM OXIDE, CALCIUM 2,744,073 5/1956 Todd et a1. 1 1 252/521 2,813,807 11/1957 Levi 117/224 OXIDE AND SAMARIUM OXIDE 3,076,916 2/1963 K0ppius.... 1,17/224 [75] Inventor: Leo J. Cronin, Watsonville, Calif. 3, 8,08 H 964 K pp usnu 1 7/223 3,155,864 11/1964 Coppola... 117/224 Asslgneer Spectra-Mat, Watsonvflle, 3,719,856 3/1973 Koppius.... 313/346 R Calif. I

[22] Filed: 1972 Primary Examiner-Charles E. Van Horn 21 APPL 223 539 Assistant ExaminerMichael W. Ball Attorney, Agent, or FirmLimbach, Limbach & Sutton [52] US. Cl 428/312; 313/311; 313/346 R; 252/521; 428/472 [51] Int. Cl H01j l/l4;1-101j 12/06 [58] 'Field of Search 117/224, 223; 252/521; [57] ABSTRACT 313/346 311 A cathode is disclosed utilizing an emission material of barium oxide, calcium oxide and samarium oxide. [56] References Cited UNITED STATES PATENTS 8 Claims, 4 Drawing Figures 1,794,298 2/1931 Just 117/220 US. Patent Nov. 25, 1975 0 1500 5000 4500 0000 L|FE(HOURS) 050 900 950 BRIGHTNESS TEMPERATURE ("0) I000 2000 5000 LIFE (H0003) 0 0 00 0 n v 0 OOOOOOTO 0 0 0 0 4 2 0000 W. m 00 6 w98 FEGA THERMIONIC CATI-IODE COMPRISING MIXTURE OF BARIUM OXIDE, CALCIUM OXIDE AND SAMARIUM OXIDE The present invention is directed in general to cathodes and. more particularly, to thermionic dispenser cathodes.

Over the years various different cathode structures have been proposed with selected different materials to achieve high current densities, low evaporation and long life. Cathodes have been made in many forms. In one form, the emission material is sprayed or painted on the surface of a support member, typically nickel, tungsten or molybdenum. Ribbons, wires or screens have been added to the surface to aid in holding the emission material on the surface. Additionally, porous body structures have been utilized to slowly dispense the emission material through the pores to the emission surface. U.S. Pat. No. 2,543,728 to Lemmens et al. describes the use of a cavity to contain the emission material and a porous body portion providing communication between the cavity and the electron emission surface for migration of the emission material. U.S. Pat. No. 2,700,000 to Levi et a1. describes a cathode wherein the emission material is melted into the pores of the porous-sintered body.

Barium oxide (BaO) has been the principal preferred emission material for many cathodes. However, barium oxide is extremely hygroscopic and in normal atmosphere readily converts to barium hydroxide. Consequently, many cathodes include barium oxide in a composition with another material whereby the barium oxide and/or free barium can be released for desired electron emission. Barium carbonate has frequently been used as one composition wherein the carbonate will convert to barium oxide at elevated temperatures.

In thermionic dispenser cathodes operating at higher temperatures and utilizing refractory metal bodies such as tungsten, molybdenum and the like as the poroussintered main body portion of the cathode, barium carbonate reacts with tungsten in a manner unproductive of free barium. Consequently, a number of alkaline earth metal compositions are suggested wherein barium oxide will be held in a stable form. Materials suggested in U.S. Pat. No. 2,700,118 to Hughes et al. are alkaline earth metal silicates, aluminates, thorates, berylliates, and borates. Of these materials, the barium aluminates were preferred and have been used most extensively.

Since it was known, as in Therminoic Emission from the BaO-CaO System by L. E. Grey, NATURE, Volume 165, pp. 773-774, May 13, 1950, that enhanced emission can be achieved by the substitution of calcium oxide for part of the barium oxide, barium calcium aluminate dispenser cathodes have been used. U.S. Pat. No. 3,076,916 to Koppius describes one such dispenser cathode having a porous-sintered tungsten body with an impregnate material formed of barium oxide, calcium oxide and aluminum oxide in the mole ratio of 4:1:1, respectively. U.S. Pat No. 3,201,639 describes a similar thermionic dispenser cathode wherein the impregnate material is barium oxide, calcium oxide and aluminum oxide in the mole ratio of 5:312, respectively.

U.S. Pat. 1,794,298 to Just describes a thermionic cathode using a mixture of an oxide of the alkaline earth group of metals with a very small addition of one of the oxides of the rare earth group of metals especially thorium oxide, praseodymium oxide and samarium oxide. The Just patent states that amount to which the rare earth oxide should be present for optimum results is determined to be approximately 0.1% of the amount of alkaline earth oxide or similar ingredient.

Broadly stated, the present invention is directed to a cathode having a metallic body and an emission material comprising a mixture of barium oxide, calcium oxide and samarium oxide and wherein the samarium oxide is present in more than trace amounts.

It has been found that cathodes having the preferred compositions of the present invention produce enhanced emission over cathodes similarly constructed but having the most popular prior art emission material made up of barium oxide, calcium oxide and aluminum oxide. The cathode of the present invention can produce the same emission as the most popular prior art cathode but up to about 50-75C cooler. This permits a lower heater wire temperature and faster tube warmup time to achieve emission and requires less heater power.

It has also been discovered that the cathode of the present invention produces up to 10 times less barium evaporation.

Additionally, the cathode of the present invention can be activated at a temperature approximately C lower than the activation temperature of the popular prior art cathodes.

Other objects and advantages of this invention will become apparent when reading the following description and referring to the accompanying drawing in which similar characters of reference represent corresponding parts in each of the several views.

In the drawings:

FIG. 1 is a side sectional view of a cathode inaccordance with one embodiment of the present invention.

FIG. 2 is a graph of emission in milliamps plotted versus life for a cathode in accordance with the present invention as contrasted with two cathodes in accordance with the prior art.

' FIG. 3 is a graph of current in milliamps plotted versus cathode temperature for two cathodes in accordance with the present invention as contrasted with two cathodes in accordance with the prior art.

FIG. 4 is a graph of temperature plotted versus life for a cathode in accordance with the present invention as contrasted with a cathode in accordance with the prior art.

Referring now to FIG. 1 there is shown one embodiment of the present invention. In this embodiment of the present invention the cathode 10 includes a porous metallic body 1 l, of a refractory material, such as tungsten, provided with an emission material 12 substantially uniformly dispersed throughout the pores of the body for migration through the pores to an emission surface 13. The emission material 12 can be placed in the pores by mixing, pressing and sintering material 12 with metal particles such as tungsten particles when the body is of tungsten. Alternately, the cathode 10 can be formed by first forming the porous sintered body 11 by pressing and sintering tungsten particles and then melting the emission material into the pores of the body. An example of such a cathode is described below.

The body 11 is supported for use in a vacuum tube by means of a support cylinder 14, such as molybdenum. A heater filament 15 such as a metal wire wound in a spiral is positioned within the cylinder 14 behind the body 11 for heating the body 11 and emission material 12 for thermionic emission of electrons from the emission surface 13 when the cathode is positioned within a vacuum envelope (not shown). Cathodes in accordance with this invention are suitable for use in most vacuum tubes or gas tubes. The cathode can be used as a cold cathode" wherein the heater 14 is utilized only to initiate emission or dispensed with entirely and emission derived in other ways such as by electron bombardment to produce secondary emission.

The heater filament is placed in location within the cylinder 14 and potted in placed with an electrical insulating material 16 such as alumina ceramic.

The emission material 12 is a mixture of barium oxide, samarium oxide and another alkaline earth metal oxide, other than barium oxide, preferably calcium oxide. I prefer as an emission material one comprising barium oxide, calcium oxide and samarium oxide, Specific compositions of the emission material in accordance with the present invention are set forth in greater detail below and with reference to the method of formation of these materials.

However, the amount of samarium oxide must be greater than trace amounts. For a cathode in accordance with the present invention the mol percent of samarium oxide should not be less than about 12% and the samarium oxide should not be less than about by weight. The preferred range for the samarium is 16 to 20 mol percent or 34 to 43% by weight.

I have discovered that a cathode made generally in accordance with the present invention produces greater emission and has less barium evaporation than the conventional barium oxide, calcium oxide, and aluminum oxide cathode. Also, an identical cathode body impregnated with an emission material of barium oxide, calcium oxide and samarium oxide produces satisfactory emission at a lower temperature than the popular barium oxide, calcium oxide and aluminum oxide type cathodes.

' I have discovered that cathodes with emission materials formed of 4 moles of barium oxide, l mole of calcium oxide and 1 mole of samarium oxide as well as 5 moles of barium oxide, 3 moles of calcium oxide and 2 moles of samarium oxide produce greater emission and less barium evaporation than similar cathodes with emission materials of barium oxide, calcium oxide and aluminum oxide in these same mole ratios.

FIGS. 2 and 3 show graphs of emission versus life and emission versus operating temperature for cathodes in accordance with the present invention designated S as contrasted with the more popular barium oxide, calcium oxide and aluminum oxide cathodes designated type B. The subscript 1 (i.e., B-1 and S-l) refer to cathodes where the respective materials are in the mole ratio of 4:1:1, and the subscript 2 (i.e., B-2 and 8-2) refer to cathodes where the respective materials are in the mole ratio of 5:3:2.

FIG. 4 shows a graph of the apparent cathode temperature measured with an optical pyrometer through the glass of a test diode versus cathode life. A decrease in apparent temperature is a measure of the amount of barium evaporated from the cathode onto the glass bulb. FIG. 4 shows a lower evaporation rate for cathodes of the present invention contrasted with popular prior art cathodes. In FIG. 4 curves are shown only for B-1 and S-2; a B-2 cathode has 3 or 4 times the evaporation rate of a B-1 and the curve therefore would start higher at the left and decrease with a greater slope to the right; and 5-] has a slightly lower evaporation rate than 5-2.

4 While it is believed that the invention has been described thus far in sufficient detail to enable one skilled in the art to manufacture cathodes in accordance with the present invention, a detailed operative example ofa 5 cathode of the type illustrated in FIG. 1 will be given.

First of all, the body 11 is formed by pressing tungsten powder, approximately 5 microns average diameter, to form an ingot which is heated in hydrogen at about 2350C for approximately 20 minutes to form a porous-sintered body having a density in the range of 7884%. Next, the porous body is impregnated with a filler material such as a metal or plastic and the filled ingot machined to form individual buttons or bodies having the dimensions of the desired cathodes. In the case of metal, such as copper, the filler material can be melted into the pores, while in the case ofa plastic such as methyl methacrylate, the porous body can be impregnated with the liquid plastic which then sets up and hardens in the pores. After machining, the filler material is removed by heating to elevated temperature.

For the emobidment having an emission material of barium oxide, calcium oxide and samarium oxide in the mole ratio of 4:1:1, 4 moles barium carbonate, 1 mole calcium carbonate and 1 mole samarium oxide are heated to a temperature of about 1 100C in an air atmosphere. At this elevated temperature, the carbonates convert to the respective oxides and these oxides form compounds. The resultant material is allowed to cool.

For impregnating the emission material into the cathode body the cooled, hardened mass is pulverized to form a powder and heated in a hydrogen atmosphere to a temperature of about l550C. and brought to contact with the previously machined cathode body whereby the emission material will migrate into the pores of the body by capillary attraction. Excess emission material is removed from the emission surface.

The heater may be potted" (before impregnation) within the cylindrical support behind the cathode body by surrounding the heater with powdered alumina ceramic and heating the assembly to a temperature of about l900C. to sinter the alumina.

The completed cathode can be mounted and activiated in an electron discharge device by heating the cathode to 1100C. while exhausting the device. This activation temperature is at least 50100C. below the activation temperature required for the popular barium oxide, calcium oxide and aluminum oxide (513:2 mole ratio) cathodes.

While calcium oxide is preferred as the other alkaline earth metal to be utilized with barium oxide and samarium oxide, other alkaline earth metal oxides such as strontium oxide and magnesium oxide can be used.

The emission material can be applied to other surfaces such as by evaporation onto a metal surface from which emission is to be drawn.

Additionally the cathode can be made in the form of a directly heated cathode body as described in US. Pat. No. 3,514,66l to R. T. Reaves assigned to the assignee of this invention.

What is claimed is:

1. A cathode comprising:

a metallic body structure of a high melting point metal and an emission material supported by said body structure,

said emission material comprising a mixture of barium oxide, calcium oxide and samarium oxide with the amount of samarium oxide present in the mixture in excess of about 12 mol percent.

2. A dispenser cathode comprising:

a refractory metal body having an electron emission surface and a porous portion for migration of an emission material to said surface and emission material supported by and in contact with said body for migration through said porous portion to said surface.

said emission material comprising a mixture of barium oxide. samarium oxide and a second alkaline earth metal oxide other than barium oxide with the amount of samarium oxide present in the mixture in excess of about 12 mol percent.

3. The dispenser cathode in accordance with claim 2 wherein said second alkaline earth metal oxide is calcium oxide.

4. The dispenser cathode in accordance with claim 3 wherein said barium oxide, calcium oxide and samarium oxide are in the mole ratio of about 411:1, respectively.

5. The dispenser cathode in accordance with claim 3 wherein said barium oxide. calcium oxide and samarium oxide are in the mole ratio of about 513:2 respectively.

6. A dispenser cathode comprising:

a porous high-density tungsten body with interconnecting pores communicating with an electron emission surface and an emission material located within said pores for migration through said pores to said surface. said emission material comprising a mixture of barium oxide, samarium oxide and a second alkaline earth metal oxide other than barium oxide with the amount of samarium oxide present in the mixture in excess of about l2 mol percent.

7. The dispenser cathode in accordance with claim 6 wherein said second alkaline earth metal oxide is calcium oxide.

8. The dispenser cathode in accordance with claim 7 wherein said barium oxide. calcium oxide and samarium oxide are in the mole ratio of about 4:111, respectively.

Claims (8)

1. A CATHODE COMPRISING: A METALLIC BODY STRUCTURE OF A HIGH MELTING POINT METAL AND AN EMISSION SUPPORTED BY SAID BODY STRUCTURE, SAID EMISSION MATERIAL COMPRISING A MIXTURE OF BARIUM OXIDE, CALCIUM AND SAMARIUM OXIDE WITH THE AMOUNT OF SAMARIUM OXIDE PRESENT IN THE MIXTURE IN EXCESS OF ABOUT 12 MOL PERCENT.
2. A dispenser cathode comprising: a refractory metal body having an electron emission surface and a porous portion for migration of an emission material to said surface and emission material supported by and in contact with said body for migration through said porous portion to said surface, said emission material comprising a mixture of barium oxide, samarium oxide and a second alkaline earth metal oxide other than barium oxide with the amount of samarium oxide present in the mixture in excess of about 12 mol percent.
3. The dispenser cathode in accordance with claim 2 wherein said second alkaline earth metal oxide is calcium oxide.
4. The dispenser cathode in accordance with claim 3 wherein said barium oxide, calcium oxide and samarium oxide are in the mole ratio of about 4:1:1, respectively.
5. The dispenser cathode in accordance with claim 3 wherein said barium oxide, calcium oxide and samarium oxide are in the mole ratio of about 5:3:2 respectively.
6. A dispenser cathode comprising: a porous high-density tungsten body with interconnecting pores communicating With an electron emission surface and an emission material located within said pores for migration through said pores to said surface, said emission material comprising a mixture of barium oxide, samarium oxide and a second alkaline earth metal oxide other than barium oxide with the amount of samarium oxide present in the mixture in excess of about 12 mol percent.
7. The dispenser cathode in accordance with claim 6 wherein said second alkaline earth metal oxide is calcium oxide.
8. The dispenser cathode in accordance with claim 7 wherein said barium oxide, calcium oxide and samarium oxide are in the mole ratio of about 4:1:1, respectively.
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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4044276A (en) * 1976-04-09 1977-08-23 Gte Sylvania Incorporated High pressure mercury vapor discharge lamp having improved electrodes
US4136227A (en) * 1976-11-30 1979-01-23 Mitsubishi Denki Kabushiki Kaisha Electrode of discharge lamp
US4208208A (en) * 1977-11-18 1980-06-17 Hitachi, Ltd. Nickel alloy base metal plate for directly heated oxide cathodes
US4350920A (en) * 1979-07-17 1982-09-21 U.S. Philips Corporation Dispenser cathode
EP0063474A2 (en) * 1981-04-20 1982-10-27 David M. Corneille Thermionic cathode and process for preparing the same
US4518890A (en) * 1982-03-10 1985-05-21 Hitachi, Ltd. Impregnated cathode
EP0210805A3 (en) * 1985-07-19 1988-03-16 Mitsubishi Denki Kabushiki Kaisha Cathode for electron tube
US4864187A (en) * 1985-05-25 1989-09-05 Mitsubishi Denki Kabushiki Kaisha Cathode for electron tube and manufacturing method thereof
US4988869A (en) * 1989-08-21 1991-01-29 The Regents Of The University Of California Method and apparatus for electron-induced dissociation of molecular species

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1794298A (en) * 1926-09-21 1931-02-24 Gen Electric Thermionic cathode
US1921066A (en) * 1928-11-16 1933-08-08 Western Electric Co Cathode for electron discharge devices and method of making the same
US2744073A (en) * 1952-11-22 1956-05-01 Battelle Development Corp Thermionic emitter materials
US2813807A (en) * 1954-07-19 1957-11-19 Philips Corp Method of making a dispenser cathode
US3076916A (en) * 1959-01-21 1963-02-05 Semicon Associates Inc Impregnated tungsten cathode structures and methods for fabricating same
US3118080A (en) * 1959-12-10 1964-01-14 Semicon Associates Inc Tungsten dispenser cathodes and impregnants therefor
US3155864A (en) * 1960-03-21 1964-11-03 Gen Electric Dispenser cathode
US3719856A (en) * 1971-05-19 1973-03-06 O Koppius Impregnants for dispenser cathodes

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US1794298A (en) * 1926-09-21 1931-02-24 Gen Electric Thermionic cathode
US1921066A (en) * 1928-11-16 1933-08-08 Western Electric Co Cathode for electron discharge devices and method of making the same
US2744073A (en) * 1952-11-22 1956-05-01 Battelle Development Corp Thermionic emitter materials
US2813807A (en) * 1954-07-19 1957-11-19 Philips Corp Method of making a dispenser cathode
US3076916A (en) * 1959-01-21 1963-02-05 Semicon Associates Inc Impregnated tungsten cathode structures and methods for fabricating same
US3118080A (en) * 1959-12-10 1964-01-14 Semicon Associates Inc Tungsten dispenser cathodes and impregnants therefor
US3155864A (en) * 1960-03-21 1964-11-03 Gen Electric Dispenser cathode
US3719856A (en) * 1971-05-19 1973-03-06 O Koppius Impregnants for dispenser cathodes

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4044276A (en) * 1976-04-09 1977-08-23 Gte Sylvania Incorporated High pressure mercury vapor discharge lamp having improved electrodes
US4136227A (en) * 1976-11-30 1979-01-23 Mitsubishi Denki Kabushiki Kaisha Electrode of discharge lamp
US4208208A (en) * 1977-11-18 1980-06-17 Hitachi, Ltd. Nickel alloy base metal plate for directly heated oxide cathodes
US4350920A (en) * 1979-07-17 1982-09-21 U.S. Philips Corporation Dispenser cathode
EP0063474A2 (en) * 1981-04-20 1982-10-27 David M. Corneille Thermionic cathode and process for preparing the same
EP0063474A3 (en) * 1981-04-20 1983-01-12 David M. Corneille Thermionic cathode and process for preparing the same
US4518890A (en) * 1982-03-10 1985-05-21 Hitachi, Ltd. Impregnated cathode
US4864187A (en) * 1985-05-25 1989-09-05 Mitsubishi Denki Kabushiki Kaisha Cathode for electron tube and manufacturing method thereof
EP0210805A3 (en) * 1985-07-19 1988-03-16 Mitsubishi Denki Kabushiki Kaisha Cathode for electron tube
US4797593A (en) * 1985-07-19 1989-01-10 Mitsubishi Denki Kabushiki Kaisha Cathode for electron tube
US4988869A (en) * 1989-08-21 1991-01-29 The Regents Of The University Of California Method and apparatus for electron-induced dissociation of molecular species

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