CN1099185A - The oxide coated cathode of electron tube - Google Patents
The oxide coated cathode of electron tube Download PDFInfo
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- CN1099185A CN1099185A CN93121498A CN93121498A CN1099185A CN 1099185 A CN1099185 A CN 1099185A CN 93121498 A CN93121498 A CN 93121498A CN 93121498 A CN93121498 A CN 93121498A CN 1099185 A CN1099185 A CN 1099185A
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- Prior art keywords
- oxide
- emission material
- coated cathode
- oxide coated
- electron emission
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J1/00—Details of electrodes, of magnetic control means, of screens, or of the mounting or spacing thereof, common to two or more basic types of discharge tubes or lamps
- H01J1/02—Main electrodes
- H01J1/13—Solid thermionic cathodes
- H01J1/14—Solid thermionic cathodes characterised by the material
- H01J1/144—Solid thermionic cathodes characterised by the material with other metal oxides as an emissive material
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- Solid Thermionic Cathode (AREA)
- Discharge Lamp (AREA)
Abstract
Comprise metallic substrates, be formed on the electron emission material layer that contains Ba at least on the metallic substrates, and be used for heating the oxide coated cathode of the device of electron emission material layer, electron emission material layer further comprises at least a of lanthanum-oxides and terbium oxide, and formation acicular texture, or electronic emission material further comprises at least a in lanthanum-oxides and the terbium oxide, and metallic substrates is subjected to heat treatment under vacuum.This oxide coated cathode can life-saving, and the manufacture craft that might replace mutually with common process.
Description
The present invention relates to the oxide coated cathode of electron tube (as cathode ray tube or camera tube), more particularly, relate to novel oxide coated cathode with long-life electron tube.
Concerning the electron tube hot cathode of routine, a kind of " oxide coated cathode " arranged, it comprises that being formed on Ni is the alkaline earth carbide layer that forms on the metallic substrates of key component.This alkaline earth metal carbonate is converted into oxide in vacuum, thereby is called as oxide coated cathode.Oxide coated cathode works in lower temperature (700-800 ℃), because its work function is lower.Yet the life-span of oxide coated cathode is shorter.
Fig. 1 is a schematic diagram, has shown the structure of conventional oxide coated cathode.Conventional oxide coated cathode comprise plate-like metallic substrates 2, support metal substrate 2 cylindrical sleeve 3, be used for the heater 4 of heated cathode and be formed on the metallic substrates 2 and making the electron emission material layer 1 that main component is made with alkaline earth oxide.This conventional oxide coated cathode is to make by inserting sleeve 3 and form the electron emission material layer 1 that is mixed and made into by at least two kinds of alkaline earth oxides on the surface of metallic substrates 2 with an end of metallic substrates 2 sealing cylindrical sleeve 3, heater 4.
Support metal substrate 2 and wherein the sleeve 3 of having heaters 4 usually by making such as molybdenum (Mo), tantalum (Ta), tungsten (W) or stainless refractory metal.
The heater 4 that is arranged in sleeve 3 is by metallic substrates 2 heating electron emission material layers 1.It is to be made by the tungsten filament that is covered with aluminium etc.
Launch thermionic electron emission material layer 1 and be formed in alkaline-earth metal oxide layer on the metallic substrates 2.On metallic substrates 2, scribble the suspended matter of the carbon carbon salt of alkaline-earth metal (Ba, Sr, Ca etc.).After coating was in a vacuum by heater 4 heating, alkaline earth metal carbonate was converted into oxide.For example, brium carbonate resolves into barium monoxide:
BaCO
3→BaO+CO
2↑
Subsequently, alkaline earth oxide under 900 to 1000 ℃ high temperature by partial reduction, thereby make it to be activated, to have semi-conductive character.In this activation process, be included in electron emission material layer 1 in the metallic substrates 2, that form to alkaline earth oxide such as the reduction elements of Si or Mg and the interfacial diffusion between the metallic substrates 2, and react with alkaline earth oxide immediately.For example, barium monoxide is reduced element reduction, produces free barium:
BaO+Mg→MgO+Ba↑
4BaO+Si→Ba
2SiO
4+2Ba↑
The free barium that produces from BaO becomes the oxygen vacancies N-type semiconductor N.Therefore, under 700 to 800 ℃ working temperature, under normal condition, obtained 0.5 to 0.8A/cm
2Emission current.
General oxide coated cathode works in the high temperature more than 750 ℃, so Ba, Sr or Ca are owing to high-vapor-pressure evaporates freely, and electron emission layer reduces when working.In addition, because the reduction of alkaline earth oxide, the boundary zone between electron emission material layer and metallic substrates has formed such as MgO and Ba
2SiO
4The oxide intermediate layer and as the barrier layer.So the barrier layer that forms has stoped reduction elements Mg or Si to diffuse into electron emission layer, thereby can not produce the free barium of q.s, and Ba, Sr or the Ca of evaporation are difficult to be replenished.In addition, electron emission current also is subjected to the high-resistance restriction in intermediate layer.Thereby shortening and other ill effects of cathode life caused in the intermediate layer.On the other hand, too much reduction elements is supplied with and is caused the over reduction of BaO, so can't obtain stable emission current.
As mentioned above, the shortcoming of traditional oxide coated cathode is that its working temperature in use uprises, and make emission effciency reduce to the about 75% of its initial characteristic, and its life-span has been shortened in the consumption of electronic emission material.
Recently picture tube develops to large-screen and high definition direction, so require picture tube that higher brightness and fineness are arranged.Therefore, the negative electrode of electron gun electronics emission and life-span of needing high current density will be grown.Yet the conventional general life-span of oxide coated cathode is shorter, so can't satisfy these requirements.
Known a kind of impregnated cathode has high current density and long-life, be make of complicated method and working temperature be 1100 ℃ or higher, this is than the high 300-400 of oxide coated cathode ℃.Therefore, people have carried out the effort that continues, are easy to make and life-span of oxide coated cathode that working temperature is low with prolongation.
In Japan Patent open (Japanese Patent Laid-Open Publication No.Sho 59-20941), lanthanum is by with LaNi
5And La
2O
3Form be dispersed in the metallic substrates, thereby the intensity that makes metallic substrates can be not weakened and reducing agent wherein can be not weakened and reducing agent wherein is not depleted.British patent (Britain Patent No.1592502) has been announced a kind of electronic emission material that is used for discharge lamp, wherein BeO and Y
2O
3Be added into Ba
2-xSr
xCaWO
6(wherein x from 0.0 to 0.5).
At United States Patent (USP) the 4th, in 797, No. 593, at least a rare-earth oxide of from the group of forming by the oxide of Y, La, Ce, Pr, Nd, Sm, Gd, Sc, Dy, Ho, Er and Tm, selecting, be added in the electronic emission material that contains Ba at least, to improve electron emission characteristic.
But above-mentioned negative electrode does not significantly improve the short life of oxide coated cathode.In addition, the manufacture craft of above-mentioned negative electrode is not can be with the exchange of general oxide coated cathode.Particularly need to change the activating process of negative electrode.For example, in above-mentioned United States Patent (USP) (No.4,797,593), with before alkaline earth oxide mixes, rare-earth oxide will be subjected to high-temperature heating treatment under reducing environment.
Consider the problems referred to above of conventional oxide coated cathode, an object of the present invention is to provide a kind of oxide coated cathode, wherein, in the longer time, keep stable electron emission characteristic by suppressing the excessive evaporation of Ba, thereby prolonged the life-span greatly, and manufacture craft can with the exchange of routine.
For realizing this purpose, according to one embodiment of present invention, provide a kind of oxide coated cathode, comprising:
Metallic substrates;
At least comprise the electron emission material layer that is formed on the Ba on the metallic substrates; And
Be used to heat the device of electron emission material layer,
It is characterized in that electron emission material layer further comprises at least a in lanthanum-oxides and the terbium oxide, and form needle-shaped crystal structure.
For realizing this purpose, oxide coated cathode according to another embodiment of the present invention also is provided, comprising:
Metallic substrates;
At least comprise the electron emission material layer that is formed on the Ba on the metallic substrates; And
Be used to heat the device of electron emission material layer,
It is characterized in that electron emission material layer further comprises at least a in lanthanum-oxides and the terbium oxide, and metallic substrates is subjected to heat treated under vacuum.
Be included in the lanthanum-oxides in the electron emission material layer or the content of terbium oxide,, be preferably in percentage by weight and be in 0.0001% to 5% the scope according to the total amount of electronic emission material.
In addition, in oxide coated cathode according to another embodiment of the present invention, metallic substrates is preferably in 10
-6Be subjected to the high-temperature process more than 900 ℃ in the vacuum more than the torr (torr).
By below in conjunction with accompanying drawing to the detailed description that most preferred embodiment of the present invention carried out, can have a better understanding to its above-mentioned purpose and other advantages.In the accompanying drawings:
Fig. 1 is a schematic sectional view, shows conventional oxide coated cathode;
Fig. 2 is an enlarged diagram, shows the electron emission material layer of oxide coated cathode according to an embodiment of the invention;
Fig. 3 is a curve chart, and the MIK that shows oxide coated cathode (a) and conventional oxide coated cathode (b) according to an embodiment of the invention is situation over time;
Fig. 4 is a curve chart, shows according to another embodiment of the present invention oxide coated cathode (9a) and the MIK of conventional oxide coated cathode (b) situation over time.
In oxide-coated cathode according to the present invention, electron emission material layer on the metallic substrates further comprises lanthanum-oxides and/or terbium oxide, and electron emission material layer forms needle-shaped crystal structure, or metallic substrates is subjected to high-temperature process under vacuum, thereby makes the stable and launch stability of electron emission characteristic can keeping the longer time than routine.
Be added to lanthanum-oxides and/or terbium oxide in the electronic emission material that comprises at least Ba, in electron emission material layer, forming stable BaO after the burin-in process, thereby making negative electrode that stable electron emission characteristic be arranged.
Except the stable electron emission characteristic that stable BaO causes, also considered the suitable supply of reducing metal, to prolong the life-span of oxide-coated cathode. This suitable supply of reducing metal can realize by following two kinds of methods. First kind is the needle-shaped crystal structure that forms electron emission material layer, and second is the heat treatment of metallic substrates. If electron emission material layer forms acicular crystal, the reducing metal is VELOCITY DIFFUSION suitably, thereby current density is remained on the bigger value in long-time, perhaps, under vacuum, be subjected to heat treatment if contain the metallic substrates of reducing metal, can prevent the excessive supply of reducing metal, thereby keep for a long time the stable state of the stable BaO of lanthanum-oxides and/or terbium oxide generation. In this way, can electron emission steady in a long-term, and prolonged life-span of oxide-coated cathode.
In the present invention, available such as (Ba, Sr, Ca) CO3Three heavy carbonate or such as (Ba, Sr) CO3Two heavy carbonate make electron emission material layer. For lanthanum-oxides or terbium oxide are added in the electronic emission material, can adopt any lanthanum compound or terbium compound and lanthanum-oxides and the terbium oxide itself that can convert through heating oxide to.
Contained lanthanum-oxides or the amount of terbium oxide according to the total amount of electronic emission material, are preferably in the scope that percentage by weight is 0.0001%-5% in the electronic emission material. The lanthanum-oxides or the terbium oxide that are lower than percentage by weight 0.0001% can't be realized stable BaO, and can not prolong. On the other hand, can make relatively poor initial transmissions characteristic degradation more than lanthanum-oxides or the terbium oxide of percentage by weight 5%, thereby reduce the effect of life-saving.
Lanthanum-oxides or terbium oxide, or the two, be comprised in such as co-precipitation three heavy carbonate (Ba, Sr, Ca) CO3In, as electronic emission material. Co-precipitation three heavy carbonate can be by handle such as Ba(NO3）
2、Sr（NO
3）
2Or Ca(NO3）
2Nitride be dissolved in the pure water, and Na2CO
3Or (NH4）
2CO
3Be added in the nitride solution with as the carbonate of Ba, Sr and Ca and co-precipitation as sediment. In this manufacturing process, the factors such as the solution temperature according to such as nitride concentration, pH value, precipitation the time or settling velocity, the carbonate crystal structure of gained is different. According to one embodiment of present invention, should control above-mentioned factor to form needle-shaped crystal structure. In three heavy carbonate electronic emission materials of the acicular crystal of co-precipitation, add lanthanide and/or terbium oxide, maybe can become by heating lanthanum compound or the terbium compound of oxide, to produce suspension. This suspension can with drip, spraying or sputter, be added on the metallic substrates, to provide oxide-coated cathode according to an embodiment of the invention.
In oxide-coated cathode according to another embodiment of the present invention, metallic substrates is preferably in 10-6Under the vacuum more than the torr (torr), be subjected to the heat treated more than 900 ℃. In addition, lanthanum-oxides and/or terbium oxide be comprised in as electronic emission material, such as co-precipitation (Ba, Sr, Ca) CO3The material of three heavy carbonate in.
Oxide-coated cathode of the present invention is inserted and secured in the electron gun, and heater is inserted and secured in the sleeve. After electron gun is enclosed in the cover of electron tube, in vacuum, make the carbonate decomposition of electron emission material layer become oxide by heater. Then, with traditional manufacture craft electron tube is carried out activation process.
To describe the present invention in detail by following Example, these examples are only represented and the present invention are described, and should not think that the present invention only limits to these concrete examples.
(example 1)
Carbonic acid ammonia is added into Ba(NO
3)
2, Sr(NO
3)
2And Ca(NO
3)
2Mixture solution in, wherein ratio Ba: Sr: Ca is 50: 40: 10, with the Ba, the Sr that form co-precipitation and the carbonate of Ca.At this moment, for forming co-precipitation three heavy carbonate of needle-shaped crystal structure, the tested control of reaction condition is as follows: the concentration of triple nitride is higher than 0.6M; With aqua ammonia pH is controlled at more than 8; And using (NH
4)
2CO
3When making sediment, the temperature of nitride solution is higher than 60 ℃, and sedimentary solution drips with the speed of per minute 30ml.In co-precipitation three heavy carbonate of needle-shaped crystal structure, add 1% La of the electronic emission material weight calculated with oxide
2O
3Then, nitrocellulose and organic solvent are stirred out, to make the suspension of electronic emission material.
The Ni metallic substrates that contains Si and Mg is cleaned.Then, as above the suspension of the electronic emission material of Zhi Zuoing is sprayed onto in the substrate, promptly obtains the oxide coated cathode according to one embodiment of the invention after the drying.
(example 2)
Repeat the step identical, just in three bicarbonate solutions of co-precipitation, add 5% Tb with the electronic emission material weight of oxide calculating with example 1
4O
7, to obtain oxide coated cathode according to an embodiment of the invention.
(example 3)
Repeat with example 1 in identical step, just in three bicarbonate solutions of co-precipitation, add 0.001% La with the electronic emission material weight of oxide calculating
2O
3, to obtain oxide coated cathode according to an embodiment of the invention.
(example 4)
Repeat with example 1 in identical step, just in three bicarbonate solutions of co-precipitation, add 0.001% Tb with the electronic emission material weight of oxide calculating
4O
7, to obtain oxide coated cathode according to an embodiment of the invention.
(example 5)
Repeat with example 1 in identical step, just in three bicarbonate solutions of co-precipitation, add 0.01% La with the electronic emission material weight of oxide calculating
2O
3With Tb
4O
7Mixture, to obtain oxide coated cathode according to an embodiment of the invention.
(example 6)
The Ni metallic substrates that contains Si and Mg is 10
-6In the vacuum more than the torr, be subjected to 1000 ℃ heat treated.
In the electronic emission material that co-precipitation three heavy carbonate constitute, add 1% La of the electronic emission material weight calculated with oxide
2O
3Then, nitrocellulose and organic solution are stirred out, to make the suspension of electronic emission material.
Above-mentioned suspension is sprayed on the heat treated metallic substrates, obtains oxide coated cathode according to another embodiment of the present invention after the drying.
(example 7)
Repeat with example 6 in identical step, just in three bicarbonate solutions of co-precipitation, add 0.0001% La with the electronic emission material weight of oxide calculating
2O
3, to obtain oxide coated cathode according to another embodiment of the present invention.
(example 8)
Identical step in weight and the example 6 just adds 5% La of the electronic emission material weight calculated with oxide in three bicarbonate solutions of co-precipitation
2O
3, to obtain oxide coated cathode according to another embodiment of the present invention.
Fig. 2 is an enlarged diagram, shows the electron emission material layer of the oxide coated cathode of making by example 1.Fig. 2 illustrates, and the electronic emission material of making in example 1 has formed needle-shaped crystal structure.
For estimating the characteristic of oxide coated cathode of the present invention, the oxide coated cathode of as above making is inserted and is installed in the electron gun, and heater is inserted and is contained in the sleeve.After in the cover of electron gun being enclosed electron tube, in vacuum, utilize heater that the carbonate decomposition in the electron emission material layer is become oxide.After this, carry out activation processing with conventional electron tube manufacture craft, and measure its electron emission characteristic.
Initiating electron emission characteristics MIK(maximum cathode current) assessment, the latter is the maximum current that negative electrode is launched under constant running status.Life characteristic is assessed with the negative electrode electric current decrease behind the continuous operation certain hour under steady state that is contained in the electron tube.Be that it is assessed with the consistency of MIK in constant period.
Fig. 3 is a curve chart, shows the MIK situation over time of the oxide coated cathode (b) of the oxide coated cathode (a) made by example 1 and routine.As shown in Figure 3, the life-span of oxide coated cathode according to an embodiment of the invention than traditional prolongation 20%.The oxide coated cathode of making according to example 2 to 5 also demonstrated on their life-span same effect.
Fig. 4 is a curve chart, and the MIK that shows the oxide coated cathode (a) made by example 6 and conventional oxide coated cathode (b) is situation over time, as shown in Figure 4, the life-span of oxide coated cathode according to another embodiment of the present invention than the prolongation of routine 20%.The oxide coated cathodes of making according to example 7 and 8 also demonstrated on their life-span same effect.
As implied above, oxide coated cathode according to the present invention is characterised in that electron emission material layer contains lanthanum-oxides and/or terbium oxide and forms needle-shaped crystal structure, or it is characterized in that electronic emission material contains lanthanum-oxides and/or terbium oxide and metallic substrates and is subjected to heat treatment under vacuum, the effect of life-saving is arranged and the procedure that can replace mutually with conventional procedure is arranged.
Though it has been carried out concrete demonstration and description in conjunction with specific embodiments of the invention, it will be understood by those skilled in the art that, under the prerequisite that does not break away from the scope of the invention that limits as appended claims and spirit, can carry out multiple modification to wherein form and details.
Claims (5)
1, a kind of oxide coated cathode comprises:
Metallic substrates;
Be formed on the metallic substrates, comprise the electron emission material layer of Ba at least; And
Be used to heat the device of electron emission material layer,
It is characterized in that electron emission material layer further comprises at least a in lanthanum-oxides and the terbium oxide, and form needle-shaped crystal structure.
2, oxide coated cathode as claimed in claim 1, wherein at least a content in lanthanum-oxides and the terbium oxide is in the percentage by weight according to the total amount of electronic emission material is 0.0001% to 5% scope.
3, a kind of oxide coated cathode comprises:
Metallic substrates;
Be formed on the metallic substrates, comprise the electron emission material layer of Ba at least; And
Be used to heat the device of electron emission material layer,
It is characterized in that electron emission material layer further comprises at least a in lanthanum-oxides and the terbium thing, and metallic substrates is subjected to heat treatment under vacuum.
4, oxide coated cathode as claimed in claim 3, wherein at least a content in lanthanum-oxides and the terbium oxide is within 0.0001% to 5% the scope at the percentage by weight according to the total amount of electronic emission material.
5, oxide coated cathode as claimed in claim 3, wherein metallic substrates is 10
-6Be subjected to the heat treatment of temperature more than 900 ℃ under the vacuum more than the torr.
Applications Claiming Priority (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR16231/93 | 1993-08-20 | ||
| KR16231/1993 | 1993-08-20 | ||
| KR930016231 | 1993-08-20 | ||
| KR21670/93 | 1993-10-19 | ||
| KR1019930021670A KR950006911A (en) | 1993-08-20 | 1993-10-19 | Oxide cathode for electron tube |
| KR21670/1993 | 1993-10-19 | ||
| KR22124/1993 | 1993-10-23 | ||
| KR930022124 | 1993-10-23 | ||
| KR22124/93 | 1993-10-23 | ||
| KR1019930022490A KR100271484B1 (en) | 1993-10-23 | 1993-10-27 | Oxide cathode |
| KR22490/93 | 1993-10-27 | ||
| KR22490/1993 | 1993-10-27 |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1099185A true CN1099185A (en) | 1995-02-22 |
| CN1061462C CN1061462C (en) | 2001-01-31 |
Family
ID=27483006
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN93121498A Expired - Fee Related CN1061462C (en) | 1993-08-20 | 1993-12-29 | Oxide cathode for electron tube |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP0639848B1 (en) |
| JP (1) | JPH0765692A (en) |
| CN (1) | CN1061462C (en) |
| DE (1) | DE69313845T2 (en) |
| SG (1) | SG44617A1 (en) |
| TW (1) | TW259877B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100336154C (en) * | 2000-09-19 | 2007-09-05 | 皇家菲利浦电子有限公司 | Cathode ray tube comprising an oxide cathode |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100200661B1 (en) * | 1994-10-12 | 1999-06-15 | 손욱 | Cathode for electron tube |
| JP2007305438A (en) * | 2006-05-12 | 2007-11-22 | New Japan Radio Co Ltd | Oxide cathode and its manufacturing method, and method of manufacturing carbonate for oxide cathode used for it |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB182817A (en) * | 1921-07-11 | 1923-08-09 | Drahtlose Telegraphie Gmbh | Improvements in the cathodes of electric discharge tubes |
| US1794298A (en) * | 1926-09-21 | 1931-02-24 | Gen Electric | Thermionic cathode |
| CA1270890A (en) * | 1985-07-19 | 1990-06-26 | Keiji Watanabe | Cathode for electron tube |
-
1993
- 1993-12-13 EP EP19930310036 patent/EP0639848B1/en not_active Expired - Lifetime
- 1993-12-13 SG SG1996004185A patent/SG44617A1/en unknown
- 1993-12-13 DE DE1993613845 patent/DE69313845T2/en not_active Expired - Fee Related
- 1993-12-24 TW TW82110980A patent/TW259877B/zh active
- 1993-12-29 CN CN93121498A patent/CN1061462C/en not_active Expired - Fee Related
-
1994
- 1994-04-13 JP JP7484094A patent/JPH0765692A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100336154C (en) * | 2000-09-19 | 2007-09-05 | 皇家菲利浦电子有限公司 | Cathode ray tube comprising an oxide cathode |
Also Published As
| Publication number | Publication date |
|---|---|
| SG44617A1 (en) | 1997-12-19 |
| CN1061462C (en) | 2001-01-31 |
| DE69313845T2 (en) | 1998-04-02 |
| DE69313845D1 (en) | 1997-10-16 |
| EP0639848B1 (en) | 1997-09-10 |
| TW259877B (en) | 1995-10-11 |
| EP0639848A1 (en) | 1995-02-22 |
| JPH0765692A (en) | 1995-03-10 |
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