JPH0318287B2 - - Google Patents
Info
- Publication number
- JPH0318287B2 JPH0318287B2 JP6651783A JP6651783A JPH0318287B2 JP H0318287 B2 JPH0318287 B2 JP H0318287B2 JP 6651783 A JP6651783 A JP 6651783A JP 6651783 A JP6651783 A JP 6651783A JP H0318287 B2 JPH0318287 B2 JP H0318287B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- ultrafine metal
- metal powder
- nickel
- alkaline earth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 239000000843 powder Substances 0.000 claims description 20
- 239000002184 metal Substances 0.000 claims description 19
- 229910052751 metal Inorganic materials 0.000 claims description 19
- 238000004519 manufacturing process Methods 0.000 claims description 11
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims description 10
- 239000010953 base metal Substances 0.000 claims description 10
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 8
- 229910052788 barium Inorganic materials 0.000 claims description 8
- 238000000034 method Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 239000002245 particle Substances 0.000 claims description 5
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000011812 mixed powder Substances 0.000 claims description 2
- 238000000151 deposition Methods 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- 230000032683 aging Effects 0.000 description 3
- 239000011206 ternary composite Substances 0.000 description 3
- DKPFZGUDAPQIHT-UHFFFAOYSA-N Butyl acetate Natural products CCCCOC(C)=O DKPFZGUDAPQIHT-UHFFFAOYSA-N 0.000 description 2
- 239000000020 Nitrocellulose Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000007789 gas Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- FUZZWVXGSFPDMH-UHFFFAOYSA-N hexanoic acid Chemical compound CCCCCC(O)=O FUZZWVXGSFPDMH-UHFFFAOYSA-N 0.000 description 2
- 229920001220 nitrocellulos Polymers 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000005507 spraying Methods 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/02—Manufacture of electrodes or electrode systems
- H01J9/04—Manufacture of electrodes or electrode systems of thermionic cathodes
- H01J9/042—Manufacture, activation of the emissive part
Landscapes
- Engineering & Computer Science (AREA)
- Manufacturing & Machinery (AREA)
- Electrodes For Cathode-Ray Tubes (AREA)
- Solid Thermionic Cathode (AREA)
Description
【発明の詳細な説明】
この発明は、陰極線管などに使用される電子管
などの陰極体の製造方法に関するものである。DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for manufacturing a cathode body of an electron tube used in a cathode ray tube or the like.
最近、コンピユータ端末機のデイスプレー管と
して使用される高解像度陰極線管や投射形陰極線
管などは、電子ビームの直径を小さくして解像度
の向上を図つているため、高電流密度陰極体が盛
んに採用されている。 Recently, high-resolution cathode ray tubes and projection cathode ray tubes used as display tubes in computer terminals have been designed to improve resolution by reducing the diameter of the electron beam, so high current density cathode bodies have become popular. It has been adopted.
第１図は高電流密度陰極体の一例を示すもので
あり、Si、Mgなどの還元性元素を含みかつニツ
ケルを主成分とする基体金属１上に、（Ba、Sr、
Ca）CO3からなるアルカリ土類炭酸塩２と粒径
が0.3ミクロン以下のニツケル粉末、コバルト粉
末、または、ニツケル粉末とコバルト粉末との混
合粉末から成る金属超微粉３との混合体が被着さ
れている。従来では、このようなアルカリ土類炭
酸塩２と金属超微粉３との混合体として、たとえ
ば、アルカリ土類炭酸塩２に対して重量比で１〜
50％の金属超微粉３を添加混合し、この混合体に
ニトロセルロースおよび酢酸ブチルを加えて混合
することにより懸濁液またはペーストを作成し、
ついでスプレ法あるいは印刷法により基体金属１
上に被着形成する製造方法が採用される。 Figure 1 shows an example of a high current density cathode body, in which (Ba, Sr,
Ca) A mixture of alkaline earth carbonate 2 consisting of CO 3 and ultrafine metal powder 3 consisting of nickel powder, cobalt powder, or a mixed powder of nickel powder and cobalt powder with a particle size of 0.3 microns or less is deposited. has been done. Conventionally, a mixture of such alkaline earth carbonate 2 and ultrafine metal powder 3 has been prepared, for example, in a weight ratio of 1 to 1 to alkaline earth carbonate 2.
Add and mix 50% ultrafine metal powder 3, add and mix nitrocellulose and butyl acetate to this mixture to create a suspension or paste,
Then, the base metal 1 is formed by spraying or printing.
A manufacturing method is adopted in which the material is deposited on top.
なお、５は陰極スリーブ４に収納されたヒータ
で、基体金属１を加熱するために設けられてい
る。 Note that 5 is a heater housed in the cathode sleeve 4, and is provided to heat the base metal 1.
上記アルカリ土類炭酸塩２は、真空排気工程に
おいて加熱されて、(1)式により、Ba、Ca、Srの
複合酸化物に変換される。このとき発生するCO2
は排気ポンプにより排出される。 The alkaline earth carbonate 2 is heated in the vacuum evacuation step and converted into a complex oxide of Ba, Ca, and Sr according to equation (1). CO 2 generated at this time
is exhausted by the exhaust pump.
（Ba、Sr、Ca）CO3→（Ba、Sr、Ca）Ｏ
＋CO2 ……(1)
排気工程完了後のエージング工程では、基体金
属１は900〜1100℃の高温に加熱され、（Ba、Sr、
Ca）Ｏから成る三元複合酸化物は、基体金属１
に含有されているSiやMgと反応してBaなどを遊
離生成する。この反応は(2)式のとうりである。 (Ba, Sr, Ca) CO 3 → (Ba, Sr, Ca) O + CO 2 ...(1) In the aging process after the completion of the exhaust process, the base metal 1 is heated to a high temperature of 900 to 1100°C, and (Ba ,Sr.
A ternary composite oxide consisting of Ca)O has a base metal of 1
Reacts with Si and Mg contained in the metal to liberate Ba and other substances. This reaction is as shown in equation (2).
BaO＋Mg→Ba＋MgO ……(2)
この反応により、たとえば、基体金属１上の
BaOの一部が還元されて遊離Baが生成し、酸素
欠乏型の半導体となり、700〜800℃の動作温度に
おいて電子放射が活発に行なわれるようになる。 BaO+Mg→Ba+MgO...(2) Through this reaction, for example,
Part of BaO is reduced to generate free Ba, which becomes an oxygen-deficient semiconductor that actively emits electrons at operating temperatures of 700-800°C.
一方、アルカリ土類炭酸塩２に添加した金属超
微粉３は、基体金属１と上記した三元複合酸化物
の表面までの電気的な導電性を向上させ、大電流
取出時に発生するジユール熱を抑制し、三元複合
酸化物の熱的破壊を防ぐ役目をもつている。 On the other hand, the ultrafine metal powder 3 added to the alkaline earth carbonate 2 improves the electrical conductivity between the base metal 1 and the surface of the above-mentioned ternary composite oxide, and reduces the Joule heat generated when drawing a large current. It has the role of suppressing the thermal breakdown of the ternary composite oxide.
また、前記金属超微粉３として0.3ミクロン以
下の粒径が選ばれている理由としては、平均粒径
が300〓（0.03ミクロン）の場合、その比表面積
が70〜10m2／ｇと極めて大きい値であるため、前
述のように基体金属１と複合三元酸化物のと導電
性の向上に寄与するとともに、複合三元酸化物中
へ分散性が極めて良いことが挙げられる。 In addition, the reason why a particle size of 0.3 microns or less is selected as the ultrafine metal powder 3 is that when the average particle size is 300〓 (0.03 microns), the specific surface area is extremely large at 70 to 10 m 2 /g. Therefore, as described above, it contributes to improving the electrical conductivity between the base metal 1 and the composite ternary oxide, and also has extremely good dispersibility in the composite ternary oxide.
ところで、上記した従来の製造方法においては
ガス中蒸発法と呼ばれる湿式雰囲気中で製造され
るため、その表面が緻密で安定な酸化膜で被われ
ている。したがつて、エージング工程や動作中
に、(3)式に示すように、酸化物が分解して酸素ガ
スを放出することになる。 By the way, in the above-described conventional manufacturing method, since manufacturing is performed in a wet atmosphere called evaporation in gas, the surface is covered with a dense and stable oxide film. Therefore, during the aging process or operation, the oxide decomposes and releases oxygen gas, as shown in equation (3).
2NiO→2Ni＋O2 ……(3)
この酸素ガスは(2)式で生成した遊離バリウムと
素早く反応し、(4)式に示すように、BaOとなつ
て電子放出能力を損つてしまう。 2NiO→2Ni+O 2 ...(3) This oxygen gas quickly reacts with the free barium generated in equation (2), and as shown in equation (4), becomes BaO, impairing the electron emission ability.
2Ba＋O2→2BaO ……(4)
以上のように、湿式雰囲気中で製造される超微
粉の金属粉を使用する従来の製造方法による場合
は、その表面の酸化層の影響で十分な電子放出能
力が得られないという欠点があつた。 2Ba＋O 2 →2BaO ...(4) As mentioned above, when using the conventional manufacturing method using ultrafine metal powder produced in a wet atmosphere, sufficient electron emission ability is achieved due to the influence of the oxide layer on the surface. The disadvantage was that it was not possible to obtain
この発明は、上記のような従来のものの欠点を
除去するためになされたもので、金属超微粉の表
面の酸化物の影響をなくして、高い電子放出能力
を発揮する電子管などの陰極体を製造することが
できる電子管などの陰極体の製造方法を提供する
ことを目的としている。以下、この発明の一実施
例について説明する。平均粒径で300〓のニツケ
ル粉末を水素雰囲気中で、450〜850℃の温度で５
分間熱処理する第１工程と、その熱処理後のニツ
ケル粉末をアルカリ土類炭酸塩に10％の重量比で
混合する第２工程と、この混合体にニトロセルロ
ース溶液や酢酸ブチルを混入して懸濁液またはペ
ーストを作成する第３工程と、この懸濁液または
ペーストをスプレ法あるいは印刷法により基体金
属１上に塗布して被着形成する第４工程とを経
て、所定の電子管用陰極体を製造する。なお、塗
布厚みは基体金属１の直径が２mmの場合、60〜
100μが好適である。 This invention was made in order to eliminate the drawbacks of the conventional products as described above, and eliminates the influence of oxides on the surface of ultrafine metal powder to produce cathode bodies such as electron tubes that exhibit high electron emission ability. The purpose of the present invention is to provide a method for manufacturing cathode bodies such as electron tubes, which can be used to produce cathode bodies such as electron tubes. An embodiment of the present invention will be described below. Nickel powder with an average particle size of 300 mm was heated in a hydrogen atmosphere at a temperature of 450 to 850 degrees Celsius.
The first step is heat treatment for minutes, the second step is to mix the heat-treated nickel powder with alkaline earth carbonate at a weight ratio of 10%, and the mixture is mixed with nitrocellulose solution or butyl acetate and suspended. A predetermined cathode body for an electron tube is produced through a third step of creating a liquid or paste, and a fourth step of applying this suspension or paste onto the base metal 1 by a spraying method or printing method to form an adhesion. Manufacture. In addition, the coating thickness is 60 to 60 mm when the diameter of the base metal 1 is 2 mm.
100μ is suitable.
以上の方法によつて製造された電子管用陰極体
は、第１図のものと同様な構成を有する。 The cathode body for an electron tube manufactured by the above method has a structure similar to that shown in FIG.
第２図は、上記第１工程における金属超微粉の
水素雰囲気中での処理温度（H2処理温度）と電
子放出能力（エミツシヨン）との関係を示したも
のである。この図より、450℃以下の温度では、
電子放出能力が極端に劣化することがわかる。こ
れは、金属超微粉の表面の酸化物層が十分に還元
されていないため、エージング中または動作中に
熱分解を起こして酸素ガスを発生し、この酸素ガ
スと遊離バリウムとが結合して酸化バリウムに変
化するためである。 FIG. 2 shows the relationship between the treatment temperature (H 2 treatment temperature) of the ultrafine metal powder in a hydrogen atmosphere and the electron emission ability (emission) in the first step. From this figure, at temperatures below 450℃,
It can be seen that the electron emission ability deteriorates extremely. This is because the oxide layer on the surface of the ultrafine metal powder is not sufficiently reduced, causing thermal decomposition during aging or operation to generate oxygen gas, and this oxygen gas and free barium combine to cause oxidation. This is because it changes into barium.
一方、850℃以上の温度では、電子放出能力の
ばらつきが大きくなつている。これは、金属超微
粉同志の焼結が開始し始めるため、アルカリ土類
炭酸塩中への均一な分散が行なわれにくくなり、
超微粉としての特徴が消失してしまうからであ
る。 On the other hand, at temperatures above 850°C, the variation in electron emission ability becomes large. This is because the ultrafine metal powder begins to sinter together, making it difficult to uniformly disperse it into the alkaline earth carbonate.
This is because the characteristics of ultrafine powder will disappear.
以上のことから、金属超微粉の熱処理温度は
400〜850℃が最も適切であることが明らかであ
る。 From the above, the heat treatment temperature for ultrafine metal powder is
It is clear that 400-850°C is most suitable.
なお、上記実施例では、電子管用陰極体につい
て説明したが、撮像管や送信管などの陰極体の製
造に適用しても、上記と同様な効果を奏する。 In the above embodiments, a cathode body for an electron tube has been described, but the same effects as described above can be obtained even if the present invention is applied to the manufacture of cathode bodies for image pickup tubes, transmission tubes, and the like.
以上のように、この発明によれば、金属超微粉
をアルカリ土類炭酸塩と混合する工程の前に、水
素雰囲気中で熱処理することにより、金属超微粉
の表面の酸化物の分解にともなう酸素ガスの発生
を抑制して、高い電子放出能力を発揮する陰極体
を製造することができる。 As described above, according to the present invention, by heat-treating the ultrafine metal powder in a hydrogen atmosphere before the step of mixing the ultrafine metal powder with the alkaline earth carbonate, the oxygen It is possible to manufacture a cathode body that suppresses gas generation and exhibits high electron emission ability.
第１図は電子管用陰極体の拡大断面図、第２図
は金属超微粉の水素雰囲気中での処理温度と電子
放出能力との関係を示した説明図である。
１……基体金属、２……アルカリ土類炭酸塩、
３……金属超微粉。
FIG. 1 is an enlarged sectional view of a cathode body for an electron tube, and FIG. 2 is an explanatory diagram showing the relationship between processing temperature of ultrafine metal powder in a hydrogen atmosphere and electron emission ability. 1... Base metal, 2... Alkaline earth carbonate,
3... Ultrafine metal powder.
Claims (1)
雰囲気中において450〜850℃の温度で熱処理する
工程と、その熱処理された金属超微粉をバリウム
を含むアルカリ土類炭酸塩粉に混合する工程と、
その混合体をニツケルを主成分とする基体金属上
に被着形成する工程とを備えたことを特徴とする
電子管などの陰極体の製造方法。 ２ 上記金属超微粉がニツケル粉末、コバルト粉
末、またはニツケル粉末とコバルト粉末の混合粉
末である特許請求の範囲第１項記載の電子管など
の陰極体の製造方法。[Scope of Claims] 1. A step of heat-treating ultrafine metal powder with a particle size of 0.3 microns or less at a temperature of 450 to 850°C in a hydrogen atmosphere, and converting the heat-treated ultrafine metal powder to an alkaline earth carbonate containing barium. The process of mixing into powder,
A method for producing a cathode body for an electron tube, etc., comprising the step of depositing the mixture on a base metal mainly composed of nickel. 2. The method for manufacturing a cathode body such as an electron tube according to claim 1, wherein the ultrafine metal powder is nickel powder, cobalt powder, or a mixed powder of nickel powder and cobalt powder.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58066517A JPS59191226A (en) | 1983-04-13 | 1983-04-13 | Cathode body of electron tube or the like |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP58066517A JPS59191226A (en) | 1983-04-13 | 1983-04-13 | Cathode body of electron tube or the like |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59191226A JPS59191226A (en) | 1984-10-30 |
| JPH0318287B2 true JPH0318287B2 (en) | 1991-03-12 |
Family
ID=13318123
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP58066517A Granted JPS59191226A (en) | 1983-04-13 | 1983-04-13 | Cathode body of electron tube or the like |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59191226A (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR900007751B1 (en) * | 1985-05-25 | 1990-10-19 | 미쯔비시덴끼 가부시기가이샤 | Electron tube cathode and method of the same |
| KR920008303B1 (en) * | 1990-11-02 | 1992-09-26 | 삼성전관 주식회사 | A method of coating of filament |
| KR20020063327A (en) * | 2001-01-27 | 2002-08-03 | 삼성에스디아이 주식회사 | Metal cathode and indirectly heated cathode assembly having the same |
| KR100768183B1 (en) * | 2001-10-30 | 2007-10-17 | 삼성에스디아이 주식회사 | Method for manufacturing pellet of cathod of electron gun |
| JP2007307670A (en) * | 2006-05-19 | 2007-11-29 | Imao Corporation:Kk | Clamping device |
-
1983
- 1983-04-13 JP JP58066517A patent/JPS59191226A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59191226A (en) | 1984-10-30 |
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