US2417461A - Electron tube and method of making same - Google Patents
Electron tube and method of making same Download PDFInfo
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- US2417461A US2417461A US613894A US61389445A US2417461A US 2417461 A US2417461 A US 2417461A US 613894 A US613894 A US 613894A US 61389445 A US61389445 A US 61389445A US 2417461 A US2417461 A US 2417461A
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- 238000004519 manufacturing process Methods 0.000 title description 10
- 238000000576 coating method Methods 0.000 description 36
- 239000011248 coating agent Substances 0.000 description 34
- 229910052751 metal Inorganic materials 0.000 description 27
- 239000002184 metal Substances 0.000 description 27
- 239000002245 particle Substances 0.000 description 26
- 150000002739 metals Chemical class 0.000 description 20
- 239000000203 mixture Substances 0.000 description 20
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 19
- 239000003870 refractory metal Substances 0.000 description 17
- 229910052715 tantalum Inorganic materials 0.000 description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 14
- 239000001301 oxygen Substances 0.000 description 14
- 229910052760 oxygen Inorganic materials 0.000 description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 13
- 238000010438 heat treatment Methods 0.000 description 13
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 13
- 239000011733 molybdenum Substances 0.000 description 12
- 230000009467 reduction Effects 0.000 description 12
- 229910052721 tungsten Inorganic materials 0.000 description 12
- 239000010937 tungsten Substances 0.000 description 12
- 229910052750 molybdenum Inorganic materials 0.000 description 10
- 239000010955 niobium Substances 0.000 description 10
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 10
- 238000005245 sintering Methods 0.000 description 9
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 9
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 8
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 8
- 229910052790 beryllium Inorganic materials 0.000 description 8
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 8
- 238000000034 method Methods 0.000 description 8
- 239000010936 titanium Substances 0.000 description 8
- 229910052726 zirconium Inorganic materials 0.000 description 8
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 7
- 239000011230 binding agent Substances 0.000 description 7
- 229910052804 chromium Inorganic materials 0.000 description 7
- 239000011651 chromium Substances 0.000 description 7
- 238000010304 firing Methods 0.000 description 7
- 229910052719 titanium Inorganic materials 0.000 description 7
- 229910052720 vanadium Inorganic materials 0.000 description 7
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 7
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 6
- PBCFLUZVCVVTBY-UHFFFAOYSA-N tantalum pentoxide Inorganic materials O=[Ta](=O)O[Ta](=O)=O PBCFLUZVCVVTBY-UHFFFAOYSA-N 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910001936 tantalum oxide Inorganic materials 0.000 description 4
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 3
- 229910052776 Thorium Inorganic materials 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
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- 239000004020 conductor Substances 0.000 description 2
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- 208000020442 loss of weight Diseases 0.000 description 2
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- 229910000476 molybdenum oxide Inorganic materials 0.000 description 2
- VVRQVWSVLMGPRN-UHFFFAOYSA-N oxotungsten Chemical class [W]=O VVRQVWSVLMGPRN-UHFFFAOYSA-N 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical class [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 230000036961 partial effect Effects 0.000 description 2
- 239000002344 surface layer Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- 229910001930 tungsten oxide Inorganic materials 0.000 description 2
- 229910001928 zirconium oxide Inorganic materials 0.000 description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 102100026933 Myelin-associated neurite-outgrowth inhibitor Human genes 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 241000234314 Zingiber Species 0.000 description 1
- 235000006886 Zingiber officinale Nutrition 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229940072049 amyl acetate Drugs 0.000 description 1
- PGMYKACGEOXYJE-UHFFFAOYSA-N anhydrous amyl acetate Natural products CCCCCOC(C)=O PGMYKACGEOXYJE-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- UOUJSJZBMCDAEU-UHFFFAOYSA-N chromium(3+);oxygen(2-) Chemical class [O-2].[O-2].[O-2].[Cr+3].[Cr+3] UOUJSJZBMCDAEU-UHFFFAOYSA-N 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
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- MNWFXJYAOYHMED-UHFFFAOYSA-M heptanoate Chemical compound CCCCCCC([O-])=O MNWFXJYAOYHMED-UHFFFAOYSA-M 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000006698 induction Effects 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
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- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002574 poison Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
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- 239000007787 solid Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- WTKKCYNZRWIVKL-UHFFFAOYSA-N tantalum Chemical compound [Ta+5] WTKKCYNZRWIVKL-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
Images
Classifications
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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
- H01J2893/002—Chemical composition and manufacture chemical
-
- 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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2927—Rod, strand, filament or fiber including structurally defined particulate matter
-
- 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
- Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
- Y10T428/2913—Rod, strand, filament or fiber
- Y10T428/2933—Coated or with bond, impregnation or core
- Y10T428/294—Coated or with bond, impregnation or core including metal or compound thereof [excluding glass, ceramic and asbestos]
- Y10T428/2958—Metal or metal compound in coating
Definitions
- a further object is to provide a method of making a coated electrode, which method simplifies the subsequent processing and evacuation of a tube incorporating the electrode.
- Figure l is a perspective view of a tube having a grid electrode embodying the improvements of my invention.
- Figure 2 is an enlarged cross-sectional View of one of the coated grid Wires.
- my tube comprises an envelope enclosing a thoriated-cathode and an improved non-emissive electrode.
- electrode comprises a core of suitable metal coated with finely divided particles including a refractory metal oxide sintered together to form a continuous sheath about the core; the particles preferably comprising at least tWo difierent refractory metals and oxygen combined as an oxide of at least one of the refractory metals.
- This coating is initially applied in any suitable mani .i.” may be applied to other base having prongs is cemented to the lower portions of the envelope.
- a plurality of electrodes including cathode 8, plate 9 and the improved grid I I are coaxially disposed within the envelope.
- Plate or anode 9 has a cap l2 connected by bracket I3 to a lead The latter I4 sealed to the top of the envelope.
- the plate may be of any suitable metal such as tantalum, and is preferably provided with a dark coating I5 to improve heat radiation.
- Cathode 8 is of the thoriated type, preferably a thoriated tungsten filament welded top and bottom to a pair of leads l7 sealed to stem 3. Flexible conductors l8 connect th'e cathode leads to a pair of base prongs.
- the thoriated cathode or filament is preferred because my improved grid exhibits special non-emissive properties in such a combination.
- thoriated cathode I mean a cathode containing thorium as the active emitter material, which thorium may be incorporated either as a pure metal or as a compound.
- grid H preferably comprises vertical Wire bars terminating at a base ring 2! supported by brackets 22 on a pair of rods 23 sealed to stem 3.
- One of these rods functions as a lead and is connected to a base prong by conductor 24.
- the shape of the grid and the character of its mounting means may be varied within Wide limits.
- My improved grid is initially fabricated by making the grid bars of suitable metal, which metal forms the core 25 ( Figure 2) upon which my non-emissive coating is applied.
- the core metal is preferably a refractory metal such as tantalum or molybdenum.
- An ordinary commerne a y prayi g. Sintering of the coating is cial grade of tantalum or molybdenum Wire may be used. Tantalum is preferred because its ductility lends itself to ready fabrication into a grid structure.
- the grid bars are Welded to base ring 2!. The fabricated grid is then cleaned, after which coating 26 is applied.
- the final coating 26 comprises finely divided particles including a refractory metal oxide sintered together to form a continuous sheath about core 25.
- refractory metal I mean a metal in the class having a relatively high melt ing point and low vapor pressure, the preferred metals in this class being tantalum, tungsten, molybdenum, columbium, titanium, chromium, zirconium, vanadium, and beryllium.
- the preferred final coating comprises at least two refractory metals and oxygen combined as an oxide of at least one of the metals.
- the tantalum pentoxide (TazOs) used is preferably formed-by burning 50 to 500 mesh tantalum powder in air until the whitish color characteristic of the pentoxide is produced.
- the tungsten trioxide (W03) employed is formed by burning in air tungsten powder, of a fineness similar to that of the tantalum powder, until the yellowish color characteristic of this oxide is produced. These finely dividedoxide powders are then thoroughly mixed; in the dry state.
- the preferred mixture comprises about 90% by weight of tantalum pentoxide and by weight of tungsten trioxide. These proportions may be varied within wide limits, depending upon the characteristics desired in the final grid.
- the base mixture is next fired in a reducing atmosphere, preferably hydrogen; Reduction may be accomplished by other means,- as by heating in an atmosphere of carbon monoxide, or by firing in vacuum.
- the time and temperature of firing may be varied, good results having been obtained'by heating to around 1000 C. for about 3 minutes in an excess of hydrogen.
- this heating treatment the mixture loses some weight and darkens materially in color, rangingfrom grey to black depending on the temperature and time of firing. From the practical standpoint it is immaterial if treatment is stopped after the powderhas turned grey or whetherit is allowed to darkenfurther. This fired mixture is still a powder, the particles retaining their finely divided granular form.
- the fired powder is then mixed with a suitable binder to cause adherence of the coating on the grid, a nitrocellulose binder being preferred, using amyl acetate as a, thinner.
- a suitable binder to cause adherence of the coating on the grid
- a nitrocellulose binder being preferred, using amyl acetate as a, thinner.
- Sufiicient amount of the liquid binder or vehicle is mixed with the powder to produce a fluid mixture having the proper consistency for spraying.
- An ordinary spray gun is preferably employed for applying the coating.
- On a grid made of .012! wire the coating applied is preferably about .002, thick.
- the binder functions to temporarily hold the particles on the grid. prior to further treatment.
- the coated grid is then prefired by heating in an oxygen-free atmosphere, preferably in vacu um, prior to mounting it in the envelope.
- I have preheated coated grids in an evacuated furnace to about 1700 C. (brightness temperature) for about minutes with good results, utilizing heat radiatedfrom an adjacent heating element.
- This preheating is important for sintering of the sintering operation also knits the particles sumciently to insure formation of a. continuous sheath about the core, and providesa hard sur face layer so that the grid may be safely handled during assembly into the tube Without danger of dislodging the coating.
- Sintering the particles to effect bonding has the further advantage of making it unnecessary to have any foreign binder material in the final coating. In my process the temporary binder is volatilized during the firing operation.
- An oil diffusion pump is preferred, capable of reducing the pressure to a low value.
- the electrodes are heated in situ by suitable means preferably-by electron
- This method energizing the filament and applying positive potentials to the plate and grid Heating of the plate and grid is caused by the kinetic energy dissipated when the fast moving electrons are suddenly stopped, the temperature depending upon the potentials applied.
- Other systems of heating the electrodes in the tube such as the high frequency induction method, may be emcoating particles together .and to the core, it being understood that up to this point the particles are merely held by the temporary binder.
- the step of preheating thegrid in vacuum prior to mounting it in the envelope has several advantages. Itnot only accomplishes the desired sintering of the particles, but it also functions to outgas the coating. Considerable I gas is trapped between the particles when the coating is applied, and some gas is occluded in the solid particles. Unless this gas is removed from the coat priorto evacuating the tube it cancause much damage. For one thing, gas liberated during the exhaust of the tube can poison the filament. Also, excessive gassing of the coated electrode produces undesirable ionization in the envelope, and prolongs the time required to exhaust the tube. In my process of firing the electrode in vacuum the coating is thoroughly outgassed 7 first described is preferred however, because the results are better and more consistent.
- the change in color and loss of Weight points to at least a partial reduction of at least one of the oxides.
- the final mixture includes the threeelements; tantalum and tungsten and oxygen, the oxygen being combined as an oxide of. at least one of these metals.
- Combination of two or more refractory metal oxides other than those of tantalum and tungsten may be used in the basic mixture for the coating.
- some of the combinations I have used with especially good results include: molybdenum and columbium oxides; tungsten and columbium oxides; molybdenum and tungsten oxides; molybdenum and tantalum oxides; tantalum and columbium oxides; tungsten and chromium oxides; tantalum and titanium oxides; titanium and Zirconium oxides; tantalum and zirconium oxides; and zirconium and beryllium oxides.
- an electrode surfacing layer is produced which inhibits primary emission.
- the presence of two refractory metals with the combined oxygen gives the coating electrical con-- ducting properties, which is desirable, particularly on grids, as will be readily understood.
- Another feature of an electrode coating formed by my process is that the step of prefiring the coated grid to sinter the particle may be controlled to give either a rough or smooth surface, thereby controlling the secondary emitting properties of the grid. Thus, if more secondary electrons are desired from a particular grid, a smoother coating is produced. If little or no secondary emission is desired, a rough coating is provided. The smoothness of the surface depends upon the degree of sintering, which is determined by the temperature of firing.
- the sintering operation is carried only far enough to fuse adjacent surfaces of the particles, leaving the coating with a clinker-like appearance.
- the sintering temperature is raised to a point where the particles of the coating more completely fuse or fiow together.
- an electrode coated with a mixture of 50% tantalum pentoxide and 50% titanium dioxide, and fired to 1850 C. in vacuum produces a smooth enamel-like surface having fairly good secondary emitting properties. This sintering at higher temperatures to get a smooth surface does not adversely affect that property of the coating which inhibits primary emission.
- My improved electrode exhibits remarkable non-emissive properties, particularly in combination with a thoriated cathode.
- Primary emission is of a low order and does not increase upon contamination of the electrode with thorium from the cathode.
- a non-emissive electrode having a coating comprising finely divided particles sintered together, said particles including two refractory metals and oxygen combined as an oxide of :at.
- At least one of said metals formed by reduction-0f a mixture of oxides of said metals said metals being selected from the group consisting of tantalum, tungsten, molybdenum, columbium, vanadium, chromium, titanium, zirconium and beryllium,
- An electron tube comprising a thoriated cathode and a cooperating electrode having a coating comprising finely divided particles sintered together, said particles including two refractory metals and oxygen combined as an oxide of at least one of said metals, formed by reduction of a mixture of oxides of said metals said metals being selected from the group consisting of tantalum, tungsten, molybdenum, columbium, vanadium, chromium, titanium, zirconium and beryllium.
- the method of making an electrode for an electron tube which comprises coating the electrode with a mixture of finely divided oxides of two refractory metals selected from the group consisting of tantalum, tungsten, molybdenum, columbium, vanadium, chromium, titanium, zirconium and beryllium, and then heating the coated electrode in vacuum at a temperature sufiicient to effect reduction of the mixture and to form particles comprising the metals and oxygen combined as an oxide of at least one of said metals, said reduction being efiected prior to placing the electrode in the tube.
- two refractory metals selected from the group consisting of tantalum, tungsten, molybdenum, columbium, vanadium, chromium, titanium, zirconium and beryllium
- the method of making an electrode for an electron tube which comprises coating the electrode with a mixture of finely divided oxides of two refractory metals selected from the group consisting of tantalum, tungsten, molybdenum, columbium, vanadium, chromium, titanium, zirconium and beryllium, and then heating the coated electrode in an atmosphere from which free oxygen is excluded at a temperature sufficient to efiect reduction of the mixture and to form particles comprising the metals and oxygen combined as an oxide of at least one of said metals, said reduction being effected prior to placing the electrode in the tube.
- two refractory metals selected from the group consisting of tantalum, tungsten, molybdenum, columbium, vanadium, chromium, titanium, zirconium and beryllium
- the method of making an electrode for an electron tube which comprises mixing together finely divided oxides of two refractory metals selected from the group consisting of tantalum, tungsten, molybdenum, columbium, vanadium, chromium, titanium, zirconium and beryllium, heating the mixed oxides in a reducing atmosphere at a temperature sufiicient to effect reduction of said oxides and to form particles comprising the metals and oxygen combined as an oxide of at least one of said metals, and then coating the electrode with the mixture.
- two refractory metals selected from the group consisting of tantalum, tungsten, molybdenum, columbium, vanadium, chromium, titanium, zirconium and beryllium
Description
March 18, 1947. BECKER 2,417,461
ELECTRON TUBE AND METHOD OF MAKING SAME Filed Aug. 51, 1945 Na -e 1195/ r/ IN VEN TOR. George A. Becker ATTORNEY Patented Mar. 18, 1947 UNITED STATES v ginger ATENT OFFICE ELECTRUN TUBE METHOD OF MAKING SAME Application August 31, 1945, Serial No. 613,894
7 Claims. 1
This is a continuation-impart of my copending applications, Serial Nos. 467,455, filed November 30, 1942; 501,721; 501,722; 501,723; and 501,724, filed September 8,1943.
My invention relates to electron tubes and more particularly to improvements in non-emissive electrodes having a surface layer including a refractory metal oxide of the type disclosed in the application of William W. Eitel and Jack A. McCullough, Serial No. 527 ,294,
Itv is among the objects of my invention to provide an improved method of forming a nonemissive coating on a'nelectrode.
Another object is to provide an electrode of the character described having a coating comprising particles sintered together to form a continuous sheath about a core.
A further object is to provide a method of making a coated electrode, which method simplifies the subsequent processing and evacuation of a tube incorporating the electrode.
The invention possesses other objects and features of advantage, some of Which, with the foregoing, will be set forth in the following description of my invention. It is to be understood that I do not limit myself to this disclosure of my invention as I may adopt variant embodiments thereof within the scope of the claims.
Referring to the drawing:
Figure l is a perspective view of a tube having a grid electrode embodying the improvements of my invention; and
Figure 2 is an enlarged cross-sectional View of one of the coated grid Wires.
In terms of broad inclusion, my tube comprises an envelope enclosing a thoriated-cathode and an improved non-emissive electrode. electrode comprises a core of suitable metal coated with finely divided particles including a refractory metal oxide sintered together to form a continuous sheath about the core; the particles preferably comprising at least tWo difierent refractory metals and oxygen combined as an oxide of at least one of the refractory metals. This coating is initially applied in any suitable mani .i." may be applied to other base having prongs is cemented to the lower portions of the envelope.
A plurality of electrodes including cathode 8, plate 9 and the improved grid I I are coaxially disposed within the envelope. Plate or anode 9 has a cap l2 connected by bracket I3 to a lead The latter I4 sealed to the top of the envelope. The plate may be of any suitable metal such as tantalum, and is preferably provided with a dark coating I5 to improve heat radiation. I
From the structural standpoint, grid H preferably comprises vertical Wire bars terminating at a base ring 2! supported by brackets 22 on a pair of rods 23 sealed to stem 3. One of these rods functions as a lead and is connected to a base prong by conductor 24. The shape of the grid and the character of its mounting means may be varied within Wide limits.
My improved grid is initially fabricated by making the grid bars of suitable metal, which metal forms the core 25 (Figure 2) upon which my non-emissive coating is applied. The core metal is preferably a refractory metal such as tantalum or molybdenum. An ordinary commerne a y prayi g. Sintering of the coating is cial grade of tantalum or molybdenum Wire may be used. Tantalum is preferred because its ductility lends itself to ready fabrication into a grid structure. After being formed on a suitable mandrel the grid bars are Welded to base ring 2!. The fabricated grid is then cleaned, after which coating 26 is applied.
Both tantalum and molybdenum have been used in the past for making grids. As is well known, such grids are subject to considerable thermionic emission, even at relatively low temperatures, and are receptive to contamination from a thoriated cathode. My improved coating 25, hereinafter described, overcomes this difilculty and renders the grid permanently nonemissive from the standpoint of primary emission at operating temperatures normally contended with. Not only is primary (thermionic) emission largely eliminated, but also secondary emission is brought under control.
The final coating 26 comprises finely divided particles including a refractory metal oxide sintered together to form a continuous sheath about core 25. By the term refractory metal I mean a metal in the class having a relatively high melt ing point and low vapor pressure, the preferred metals in this class being tantalum, tungsten, molybdenum, columbium, titanium, chromium, zirconium, vanadium, and beryllium.
The preferred final coating comprises at least two refractory metals and oxygen combined as an oxide of at least one of the metals. I have had good results from a coating prepared from abase mixture of tantalumpentoxide and tungsten trioxide. The tantalum pentoxide (TazOs) used is preferably formed-by burning 50 to 500 mesh tantalum powder in air until the whitish color characteristic of the pentoxide is produced. The tungsten trioxide (W03) employed is formed by burning in air tungsten powder, of a fineness similar to that of the tantalum powder, until the yellowish color characteristic of this oxide is produced. These finely dividedoxide powders are then thoroughly mixed; in the dry state. 'The preferred mixture comprises about 90% by weight of tantalum pentoxide and by weight of tungsten trioxide. These proportions may be varied within wide limits, depending upon the characteristics desired in the final grid.
In my. preferred process the base mixture is next fired in a reducing atmosphere, preferably hydrogen; Reduction may be accomplished by other means,- as by heating in an atmosphere of carbon monoxide, or by firing in vacuum. The time and temperature of firing may be varied, good results having been obtained'by heating to around 1000 C. for about 3 minutes in an excess of hydrogen. During this heating treatment the mixture loses some weight and darkens materially in color, rangingfrom grey to black depending on the temperature and time of firing. From the practical standpoint it is immaterial if treatment is stopped after the powderhas turned grey or whetherit is allowed to darkenfurther. This fired mixture is still a powder, the particles retaining their finely divided granular form.
The fired powderis then mixed with a suitable binder to cause adherence of the coating on the grid, a nitrocellulose binder being preferred, using amyl acetate as a, thinner. Sufiicient amount of the liquid binder or vehicle is mixed with the powder to produce a fluid mixture having the proper consistency for spraying. An ordinary spray gun is preferably employed for applying the coating. On a grid made of .012! wire the coating applied is preferably about .002, thick. The binder functions to temporarily hold the particles on the grid. prior to further treatment.
, The coated grid is then prefired by heating in an oxygen-free atmosphere, preferably in vacu um, prior to mounting it in the envelope. I have preheated coated grids in an evacuated furnace to about 1700 C. (brightness temperature) for about minutes with good results, utilizing heat radiatedfrom an adjacent heating element. This preheatingis important for sintering of the sintering operation also knits the particles sumciently to insure formation of a. continuous sheath about the core, and providesa hard sur face layer so that the grid may be safely handled during assembly into the tube Without danger of dislodging the coating. Sintering the particles to effect bonding has the further advantage of making it unnecessary to have any foreign binder material in the final coating. In my process the temporary binder is volatilized during the firing operation.
H bombardment from the filament.
of exhausting tubes is well known; comprising. connecting the electrodes in a suitable circuit,
A. An oil diffusion pump is preferred, capable of reducing the pressure to a low value.
During exhaust the electrodes are heated in situ by suitable means preferably-by electron This method energizing the filament and applying positive potentials to the plate and grid Heating of the plate and grid is caused by the kinetic energy dissipated when the fast moving electrons are suddenly stopped, the temperature depending upon the potentials applied. Other systems of heating the electrodes in the tube, such as the high frequency induction method, may be emcoating particles together .and to the core, it being understood that up to this point the particles are merely held by the temporary binder. The
ployed. After exhaust, the envelope is sealed oil the pump and base 6 is applied.
The step of preheating thegrid in vacuum prior to mounting it in the envelope has several advantages. Itnot only accomplishes the desired sintering of the particles, but it also functions to outgas the coating. Considerable I gas is trapped between the particles when the coating is applied, and some gas is occluded in the solid particles. Unless this gas is removed from the coat priorto evacuating the tube it cancause much damage. For one thing, gas liberated during the exhaust of the tube can poison the filament. Also, excessive gassing of the coated electrode produces undesirable ionization in the envelope, and prolongs the time required to exhaust the tube. In my process of firing the electrode in vacuum the coating is thoroughly outgassed 7 first described is preferred however, because the results are better and more consistent.
Just what happens to the mixture of oxides during the firing step is not fullyunderfstood.
The change in color and loss of Weight points to at least a partial reduction of at least one of the oxides. The fact that the oxides are in intimate admixture during reduction appears to be im-' portant. In thecase of the preferred mixture of tantalum and tungsten oxides there is probably at least a partial reduction of the tungsten trioxide and also possibly of the tantalum pentoxide to the lower order of oxides of these metals.
From the loss of weight however, it is evident that considerable oxygen is retained so that the final mixture includes the threeelements; tantalum and tungsten and oxygen, the oxygen being combined as an oxide of. at least one of these metals.
Combination of two or more refractory metal oxides other than those of tantalum and tungsten may be used in the basic mixture for the coating. For example, some of the combinations I have used with especially good results include: molybdenum and columbium oxides; tungsten and columbium oxides; molybdenum and tungsten oxides; molybdenum and tantalum oxides; tantalum and columbium oxides; tungsten and chromium oxides; tantalum and titanium oxides; titanium and Zirconium oxides; tantalum and zirconium oxides; and zirconium and beryllium oxides.
In any case, an electrode surfacing layer is produced which inhibits primary emission. The presence of two refractory metals with the combined oxygen gives the coating electrical con-- ducting properties, which is desirable, particularly on grids, as will be readily understood. Another feature of an electrode coating formed by my process is that the step of prefiring the coated grid to sinter the particle may be controlled to give either a rough or smooth surface, thereby controlling the secondary emitting properties of the grid. Thus, if more secondary electrons are desired from a particular grid, a smoother coating is produced. If little or no secondary emission is desired, a rough coating is provided. The smoothness of the surface depends upon the degree of sintering, which is determined by the temperature of firing. For a rough surface the sintering operation is carried only far enough to fuse adjacent surfaces of the particles, leaving the coating with a clinker-like appearance. For a smooth surface the sintering temperature is raised to a point where the particles of the coating more completely fuse or fiow together. For example, an electrode coated with a mixture of 50% tantalum pentoxide and 50% titanium dioxide, and fired to 1850 C. in vacuum, produces a smooth enamel-like surface having fairly good secondary emitting properties. This sintering at higher temperatures to get a smooth surface does not adversely affect that property of the coating which inhibits primary emission.
I have also used coatings made from single oxides instead of using the mixed oxides. Grids made in this way tend to contaminate more readily, have a higher resistance surface, and therefore coatings made of mixed oxides are preferred.
My improved electrode exhibits remarkable non-emissive properties, particularly in combination with a thoriated cathode. Primary emission is of a low order and does not increase upon contamination of the electrode with thorium from the cathode.
While I have described my improvements in connection with a grid, it is understood that other electrodes may be so treated to suppress emission. For example, a plate coated in accordance with my invention makes an excellent anode for a rectifier tube where elimination of reverse current is highly desirable.
I claim:
1. A non-emissive electrode having a coating comprising finely divided particles sintered together, said particles including two refractory metals and oxygen combined as an oxide of :at.
least one of said metals, formed by reduction-0f a mixture of oxides of said metals said metals being selected from the group consisting of tantalum, tungsten, molybdenum, columbium, vanadium, chromium, titanium, zirconium and beryllium,
2. An electron tube comprising a thoriated cathode and a cooperating electrode having a coating comprising finely divided particles sintered together, said particles including two refractory metals and oxygen combined as an oxide of at least one of said metals, formed by reduction of a mixture of oxides of said metals said metals being selected from the group consisting of tantalum, tungsten, molybdenum, columbium, vanadium, chromium, titanium, zirconium and beryllium.
3. The method of making an electrode for an electron tube, which comprises coating the electrode with a mixture of finely divided oxides of two refractory metals selected from the group consisting of tantalum, tungsten, molybdenum, columbium, vanadium, chromium, titanium, zirconium and beryllium, and then heating the coated electrode in vacuum at a temperature sufiicient to effect reduction of the mixture and to form particles comprising the metals and oxygen combined as an oxide of at least one of said metals, said reduction being efiected prior to placing the electrode in the tube.
4. The method of making an electrode for an electron tube, which comprises coating the electrode with a mixture of finely divided oxides of two refractory metals selected from the group consisting of tantalum, tungsten, molybdenum, columbium, vanadium, chromium, titanium, zirconium and beryllium, and then heating the coated electrode in an atmosphere from which free oxygen is excluded at a temperature sufficient to efiect reduction of the mixture and to form particles comprising the metals and oxygen combined as an oxide of at least one of said metals, said reduction being effected prior to placing the electrode in the tube.
5. The method of making an electrode for an electron tube, which comprises mixing together finely divided oxides of two refractory metals selected from the group consisting of tantalum, tungsten, molybdenum, columbium, vanadium, chromium, titanium, zirconium and beryllium, heating the mixed oxides in a reducing atmosphere at a temperature sufiicient to effect reduction of said oxides and to form particles comprising the metals and oxygen combined as an oxide of at least one of said metals, and then coating the electrode with the mixture.
6. The method of making an electrode for an electron tube, which comprises mixing together finely divided oxides of two refractory metals selected from the group consisting of tantalum,
tungsten, molybdenum, columbium, vanadium,
chromium, titanium, zirconium and beryllium,
heating the mixed oxides in a reducing atmosphere at a temperature sufficient to effect reduction of said oxides and to form particles comprising the metals and oxygen combined as an oxide of at least one of said metals, then coating the electrode with the mixture, and then heating the coated electrode in vacuum prior to mounting it in the tube.
'7. In the manufacture of an electron tube wherein an electrode is coated with finely divided particles of primary emission inhibiting material comprising two refractory metals and oxygen'combined as an oxide of atleast one of said metals, formed by reduction of a mixture of oxides of said metals, the step of heating the. coated electrode to a temperature sufiicient to completely fuse and sinter said particles together 5 2,213,558
Number into asmooth-surface coating prior to mounting 2,343 045 it in the tube, to enhance secondary emission from said electrode.
' GEORGE A. BECKER. Number REFERENCES CITED The following references are of record in the file of this patent:
German July 21, 1932
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US613894A US2417461A (en) | 1945-08-31 | 1945-08-31 | Electron tube and method of making same |
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US613894A US2417461A (en) | 1945-08-31 | 1945-08-31 | Electron tube and method of making same |
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Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2513255A (en) * | 1948-03-03 | 1950-06-27 | Electrons Inc | Grid control metal envelope gas tube |
US2527513A (en) * | 1947-08-19 | 1950-10-31 | Int Standard Electric Corp | Nonemissive electrode for use in electron discharge devices |
US2527514A (en) * | 1947-08-19 | 1950-10-31 | Int Standard Electric Corp | Nonemissive electrode for use in electron discharge devices |
US2552535A (en) * | 1949-01-24 | 1951-05-15 | Int Standard Electric Corp | Electron discharge device electrode |
US2814574A (en) * | 1954-07-06 | 1957-11-26 | Raytheon Mfg Co | Black coatings for metal parts and methods for forming such coatings |
US2846609A (en) * | 1954-02-08 | 1958-08-05 | Philips Corp | Non-emissive electrode for electron discharge device |
US3069292A (en) * | 1958-07-16 | 1962-12-18 | Du Pont | Composition comprising particles of refractory oxide, coated with an oxide of a transition metal |
US3235655A (en) * | 1962-12-31 | 1966-02-15 | Gen Motors Corp | Resistor composition and devices embodying same |
US3402078A (en) * | 1968-09-17 | Gen Electric | Solid stabilized zirconia or thoria having a layer of tantalum pentoxide and titanium oxide thereon | |
US3485744A (en) * | 1966-11-21 | 1969-12-23 | Westinghouse Electric Corp | Zirconium electrode for electro-chemical machining |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE555324C (en) * | 1930-02-20 | 1932-07-21 | U S S R Elektrotechnische Vere | Process for the production of rough electrode surfaces |
US1981620A (en) * | 1932-03-26 | 1934-11-20 | Cutler Hammer Inc | Electrode for electron discharge devices |
US2213558A (en) * | 1938-02-22 | 1940-09-03 | Rca Corp | Emission suppression means |
US2348045A (en) * | 1942-01-01 | 1944-05-02 | Bell Telephone Labor Inc | Electron discharge device and method of manufacture |
-
1945
- 1945-08-31 US US613894A patent/US2417461A/en not_active Expired - Lifetime
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE555324C (en) * | 1930-02-20 | 1932-07-21 | U S S R Elektrotechnische Vere | Process for the production of rough electrode surfaces |
US1981620A (en) * | 1932-03-26 | 1934-11-20 | Cutler Hammer Inc | Electrode for electron discharge devices |
US2213558A (en) * | 1938-02-22 | 1940-09-03 | Rca Corp | Emission suppression means |
US2348045A (en) * | 1942-01-01 | 1944-05-02 | Bell Telephone Labor Inc | Electron discharge device and method of manufacture |
Cited By (10)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3402078A (en) * | 1968-09-17 | Gen Electric | Solid stabilized zirconia or thoria having a layer of tantalum pentoxide and titanium oxide thereon | |
US2527513A (en) * | 1947-08-19 | 1950-10-31 | Int Standard Electric Corp | Nonemissive electrode for use in electron discharge devices |
US2527514A (en) * | 1947-08-19 | 1950-10-31 | Int Standard Electric Corp | Nonemissive electrode for use in electron discharge devices |
US2513255A (en) * | 1948-03-03 | 1950-06-27 | Electrons Inc | Grid control metal envelope gas tube |
US2552535A (en) * | 1949-01-24 | 1951-05-15 | Int Standard Electric Corp | Electron discharge device electrode |
US2846609A (en) * | 1954-02-08 | 1958-08-05 | Philips Corp | Non-emissive electrode for electron discharge device |
US2814574A (en) * | 1954-07-06 | 1957-11-26 | Raytheon Mfg Co | Black coatings for metal parts and methods for forming such coatings |
US3069292A (en) * | 1958-07-16 | 1962-12-18 | Du Pont | Composition comprising particles of refractory oxide, coated with an oxide of a transition metal |
US3235655A (en) * | 1962-12-31 | 1966-02-15 | Gen Motors Corp | Resistor composition and devices embodying same |
US3485744A (en) * | 1966-11-21 | 1969-12-23 | Westinghouse Electric Corp | Zirconium electrode for electro-chemical machining |
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