JPH0997561A - Manufacture of cathode for electron tube - Google Patents
Manufacture of cathode for electron tubeInfo
- Publication number
- JPH0997561A JPH0997561A JP7255420A JP25542095A JPH0997561A JP H0997561 A JPH0997561 A JP H0997561A JP 7255420 A JP7255420 A JP 7255420A JP 25542095 A JP25542095 A JP 25542095A JP H0997561 A JPH0997561 A JP H0997561A
- Authority
- JP
- Japan
- Prior art keywords
- metal
- cathode
- minutes
- metal layer
- base metal
- 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.)
- Granted
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 23
- 229910052751 metal Inorganic materials 0.000 claims abstract description 46
- 239000002184 metal Substances 0.000 claims abstract description 45
- 239000010953 base metal Substances 0.000 claims abstract description 40
- 238000010438 heat treatment Methods 0.000 claims abstract description 30
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 20
- 229910000287 alkaline earth metal oxide Inorganic materials 0.000 claims abstract description 17
- 230000001603 reducing effect Effects 0.000 claims abstract description 13
- 229910052788 barium Inorganic materials 0.000 claims abstract description 12
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910001404 rare earth metal oxide Inorganic materials 0.000 claims abstract description 12
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 11
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims description 17
- 239000000203 mixture Substances 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 abstract description 3
- 230000002829 reductive effect Effects 0.000 abstract description 3
- 239000011777 magnesium Substances 0.000 description 10
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 8
- 229910052710 silicon Inorganic materials 0.000 description 8
- 239000010703 silicon Substances 0.000 description 8
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 7
- 238000001994 activation Methods 0.000 description 7
- 229910052749 magnesium Inorganic materials 0.000 description 7
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 7
- 229910052721 tungsten Inorganic materials 0.000 description 7
- 239000010937 tungsten Substances 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- 238000009792 diffusion process Methods 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 230000004913 activation Effects 0.000 description 5
- 239000011575 calcium Substances 0.000 description 5
- 238000006722 reduction reaction Methods 0.000 description 5
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 4
- 229910052791 calcium Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000007796 conventional method Methods 0.000 description 4
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 4
- 229910052712 strontium Inorganic materials 0.000 description 4
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 229910004283 SiO 4 Inorganic materials 0.000 description 3
- QVQLCTNNEUAWMS-UHFFFAOYSA-N barium oxide Chemical group [Ba]=O QVQLCTNNEUAWMS-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 229910052916 barium silicate Inorganic materials 0.000 description 2
- HMOQPOVBDRFNIU-UHFFFAOYSA-N barium(2+);dioxido(oxo)silane Chemical compound [Ba+2].[O-][Si]([O-])=O HMOQPOVBDRFNIU-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000010894 electron beam technology Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007921 spray Substances 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 239000000020 Nitrocellulose Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000011230 binding agent Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 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
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 229920001220 nitrocellulos Polymers 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 238000005979 thermal decomposition reaction Methods 0.000 description 1
- 238000007740 vapor deposition Methods 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Landscapes
- Solid Thermionic Cathode (AREA)
Abstract
Description
【０００１】[0001]
【発明の属する技術分野】この発明は、ブラウン管など
に使用される電子管用陰極の製造方法に関するものであ
る。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for manufacturing a cathode for an electron tube used for a cathode ray tube or the like.
【０００２】[0002]
【従来の技術】図５は、たとえば特開平３−２５７７３
５号公報に開示されたテレビジョン用ブラウン管や撮像
管に用いられている電子管用陰極の一部拡大断面図であ
る。図６は、従来の電子管用陰極の製造方法を示す図で
ある。図５において、１は略円筒状のスリーブ、２はシ
リコン（Ｓｉ）、マグネシウム（Ｍｇ）などの還元性元
素を微量含有し、主成分がニッケル（Ｎｉ）からなる基
体金属であり、略円筒状のスリーブ１の一端に溶接固定
されている。３は基体金属２の頂部上面に被覆形成され
た金属層であり、基体金属２の還元性元素の少なくとも
一種より還元性が同等、または小さく、かつニッケル
（Ｎｉ）よりも還元性が大きい金属を主成分とする。４
は金属層３の上面に被着形成された電子放射物質層で、
バリウム（Ｂａ）、ストロンチウム（Ｓｒ）及びカルシ
ウム（Ｃａ）を含む３元のアルカリ土類金属酸化物４ａ
中に、酸化スカンジウムなどの希土類金属酸化物４ｂを
分散させて構成されている。５はスリーブ１内に配設さ
れたヒータであり、これを加熱することにより、基体金
属２が加熱され、電子放射物質層４から熱電子が放出さ
れる。2. Description of the Related Art FIG.
FIG. 5 is a partially enlarged cross-sectional view of a cathode for an electron tube used in a television cathode ray tube or an imaging tube disclosed in Japanese Patent Publication No. FIG. 6 is a diagram showing a conventional method for manufacturing a cathode for an electron tube. In FIG. 5, reference numeral 1 denotes a substantially cylindrical sleeve, and 2 denotes a base metal containing a trace amount of a reducing element such as silicon (Si) or magnesium (Mg), the main component of which is nickel (Ni). Is fixed to one end of the sleeve 1 by welding. Reference numeral 3 denotes a metal layer formed on the top surface of the base metal 2 by covering at least one of the reducing elements of the base metal 2 with a reducing property equal to or smaller than that of at least one reducing element and a reducing property larger than nickel (Ni). Main component. Four
Is an electron emitting material layer formed on the upper surface of the metal layer 3;
Ternary alkaline earth metal oxide 4a containing barium (Ba), strontium (Sr) and calcium (Ca)
A rare earth metal oxide 4b such as scandium oxide is dispersed therein. Reference numeral 5 denotes a heater disposed in the sleeve 1. By heating the heater, the base metal 2 is heated, and thermoelectrons are emitted from the electron emitting material layer 4.
【０００３】次に、このように構成された電子管用陰極
において、従来の製造方法による基体金属２への金属層
３及び電子放射物質層４の被着形成方法について、図６
を用いて説明する。まず、基体金属２とスリーブ１を溶
接して（Ｓ１）、陰極基体部を形成した後、この陰極基
体部を、例えば電子ビーム蒸着装置内に配設し、１０-5
〜１０-8ｔｏｒｒ程度の真空雰囲気で、タングステン
（Ｗ）を電子ビームで加熱蒸着して、金属層３を形成す
る（Ｓ２）。その後、この陰極基体部を、例えば真空中
で８００〜１１００°Ｃの温度範囲で５分間未満の熱処
理する（Ｓ３）が、これは金属層３内部あるいは表面に
残存する酸素などの不純物を除去し、また金属層３を焼
結あるいは再結晶化あるいは基体金属２中へ拡散させる
ためである。[0003] Next, in the thus configured cathode for an electron tube, a method for forming a metal layer 3 and an electron emitting material layer 4 on a base metal 2 by a conventional manufacturing method will be described with reference to FIG.
This will be described with reference to FIG. First, the base metal 2 and the sleeve 1 are welded (S1) to form a cathode base portion, and then the cathode base portion is arranged in, for example, an electron beam vapor deposition apparatus, and 10 −5
Tungsten (W) is heated and evaporated by an electron beam in a vacuum atmosphere of about 10 −8 torr to form the metal layer 3 (S2). Thereafter, the cathode base is heat-treated in a vacuum at a temperature of 800 to 1100 ° C. for less than 5 minutes (S3) to remove impurities such as oxygen remaining inside or on the surface of the metal layer 3. The purpose is to sinter or recrystallize the metal layer 3 or to diffuse the metal layer 3 into the base metal 2.
【０００４】次に、上記熱処理後の陰極基体部上面に、
バリウム、ストロンチウム、カルシウムの３元系炭酸
塩、所定量の酸化スカンジウムとニトロセルロース等か
らなるバインダーの懸濁混合液を、例えばスプレー法な
どで塗布して、電子放射性物質層４となる膜を形成する
（Ｓ４）。ついで、この陰極を電子銃に組み込み、ブラ
ウン管の排気工程中にヒータ５によって加熱する。この
時、３元系炭酸塩は熱分解により、アルカリ土類金属酸
化物（４ａ）に変化する。排気工程の後に、さらに高温
に加熱して活性化工程を経るが、この時アルカリ土類金
属酸化物４ａの一部が還元されて、電子放射物質層４が
半導体的性質を有するようになり、金属層３上にアルカ
リ土類金属酸化物４ａと希土類金属酸化物４ｂとの混合
物からなる電子放射物質層４が形成される。Next, on the upper surface of the cathode base after the heat treatment,
A ternary carbonate of barium, strontium, and calcium, and a suspension mixture of a binder composed of a predetermined amount of scandium oxide and nitrocellulose are applied by, for example, a spray method to form a film that becomes the electron-emitting material layer 4. (S4). Then, this cathode is incorporated into an electron gun and heated by the heater 5 during the exhaust process of the cathode ray tube. At this time, the ternary carbonate is converted to the alkaline earth metal oxide (4a) by thermal decomposition. After the evacuation process, the material is further heated to a high temperature and undergoes an activation process. At this time, a part of the alkaline earth metal oxide 4a is reduced, and the electron emitting material layer 4 has semiconductor properties, On the metal layer 3, an electron emitting material layer 4 made of a mixture of an alkaline earth metal oxide 4a and a rare earth metal oxide 4b is formed.
【０００５】この活性化工程において、アルカリ土類金
属酸化物４ａの一部は、次のような反応をする。すなわ
ち、基体金属２中に含有されるシリコン、マグネシウム
などの還元性元素は、拡散により金属層３とアルカリ土
類金属酸化物４ａの界面に移動し、アルカリ土類金属酸
化物４ａと反応する。たとえば、アルカリ土類金属酸化
物が酸化バリウムであれば次式（１）、（２）の様に反
応し、遊離バリウムを生成する。 ４ＢａＯ＋Ｓｉ→２Ｂａ＋Ｂａ2 ＳｉＯ4 ・・・・（１） ＢａＯ＋Ｍｇ→Ｂａ＋ＭｇＯ ・・・・（２） また、特開平３−２５７７３５号公報に開示されている
ように、電子放射物質層４が直接接している金属層３と
の反応も同時に進行し、金属層３の成分が例えばタング
ステンである場合は、式（３）のような反応が起こり、
遊離バリウムの生成の手助けとなる。 ２ＢａＯ＋１／３Ｗ→Ｂａ＋１／３Ｂａ3 ＷＯ6 ・・・・（３） これらの反応の結果、金属層３上に被着形成されている
アルカリ土類金属酸化物４ａの一部が還元されて、酸素
欠乏型の半導体となり、遊離バリウムからの電子放射が
容易になる。In this activation step, a part of the alkaline earth metal oxide 4a reacts as follows. That is, reducing elements such as silicon and magnesium contained in the base metal 2 move to the interface between the metal layer 3 and the alkaline earth metal oxide 4a by diffusion and react with the alkaline earth metal oxide 4a. For example, if the alkaline earth metal oxide is barium oxide, it reacts as in the following formulas (1) and (2) to generate free barium. 4BaO + Si → 2Ba + Ba 2 SiO 4 (1) BaO + Mg → Ba + MgO (2) Further, as disclosed in JP-A-3-257735, the electron-emitting material layer 4 is in direct contact with the electron-emitting material layer. The reaction with the metal layer 3 also proceeds at the same time, and when the component of the metal layer 3 is, for example, tungsten, a reaction as in the formula (3) occurs.
Helps generate free barium. 2BaO + ／ W → Ba + ／ Ba 3 WO 6 (3) As a result of these reactions, a part of the alkaline earth metal oxide 4a deposited and formed on the metal layer 3 is reduced and oxygen It becomes a deficient semiconductor, which facilitates electron emission from free barium.
【０００６】しかしながら、（１）式の反応で生成した
珪酸バリウム（Ｂａ2 ＳｉＯ4 ）は、陰極動作中に金属
層３と電子放射物質層４の界面に蓄積され、基体金属２
からのマグネシウムあるいはシリコンの拡散が抑制さ
れ、還元反応の低下による遊離バリウムの生成を抑える
ため、希土類金属酸化物４ｂを電子放射物質層４中に添
加することにより、式（４）（５）のように反応して珪
酸バリウムを分解し、継続したマグネシウムあるいはシ
リコンの拡散を可能にさせる。この場合、陰極温度が７
００〜８００°Ｃの動作温度で３．０Ａ／ｃｍ2 以上の
電流密度動作が可能となる。 １／２Ｓｃ2 Ｏ3 ＋３／２Ｍｇ→Ｓｃ＋３／２ＭｇＯ ・・・・（４） １／２Ｂａ2 ＳｉＯ4 ＋４／３Ｓｃ→Ｂａ＋１／２Ｓｉ＋２／３Ｓｃ2 Ｏ３ ・・・・（５） なお、金属層３が無く、希土類金属酸化物４ｂの添加の
みの場合は、１．３２〜２．６４Ａ／ｃｍ２ である。However, barium silicate (Ba 2 SiO 4 ) generated by the reaction of the formula (1) is accumulated at the interface between the metal layer 3 and the electron emitting material layer 4 during the operation of the cathode, and the base metal 2
In order to suppress the diffusion of magnesium or silicon from silicon and suppress the production of free barium due to the reduction of the reduction reaction, the rare-earth metal oxide 4b is added to the electron-emitting material layer 4 to obtain the following formulas (4) and (5). In this manner to decompose the barium silicate to allow continued diffusion of magnesium or silicon. In this case, when the cathode temperature is 7
A current density operation of 3.0 A / cm 2 or more can be performed at an operating temperature of 00 to 800 ° C. 1/2 Sc 2 O 3 +3/2 Mg → Sc + 3/2 MgO (4) 1 / 2Ba 2 SiO 4 +4/3 Sc → Ba + 1 / 2Si + 2/3 Sc 2 O 3 (5) Metal layer 3 And when only the rare earth metal oxide 4b is added, it is 1.32 to 2.64 A / cm 2 .
【０００７】[0007]
【発明が解決しようとする課題】このような従来の電子
管用陰極の製造方法においては、金属層３の形成前に基
体金属２の熱処理を実施しておらず、また、金属層３形
成後の熱処理においても、処理時間が通常５分間未満で
あったため、金属層３の焼結、再結晶化、基体金属２へ
の拡散、基体金属２との接合強度の状態にバラツキが生
じ易く、その結果、初期の電子放射特性のバラツキが大
きいという欠点があった。In such a conventional method for manufacturing a cathode for an electron tube, the heat treatment of the base metal 2 is not performed before the formation of the metal layer 3, and the method for manufacturing the cathode for the electron tube is not performed. Also in the heat treatment, the treatment time is usually less than 5 minutes, so that the sintering, recrystallization, diffusion into the base metal 2 and the bonding strength with the base metal 2 are apt to vary, as a result. However, there is a disadvantage that the dispersion of the initial electron emission characteristics is large.
【０００８】この発明は、このような従来の電子管用陰
極の製造方法のもつ課題を解決するためになされたもの
で、初期の電子放射特性のバラツキの少ない電子管用陰
極の製造方法を得ることを目的としている。The present invention has been made in order to solve the problems of the conventional method for manufacturing a cathode for an electron tube, and it is an object of the present invention to obtain a method for manufacturing a cathode for an electron tube with a small variation in initial electron emission characteristics. Has an aim.
【０００９】[0009]
【課題を解決するための手段】この発明に係わる電子管
用陰極の製造方法においては、ニッケルを主成分とし還
元剤を含有する基体金属上に、基体金属の還元剤より還
元性が同等または小さく且つニッケルより還元性が大き
い金属を主成分とする金属層を形成した後、基体金属と
金属層を、真空または還元性雰囲気中で、８００〜１１
００℃の温度範囲で、５分以上６０分以下の熱処理を行
い、次いで金属層上に、少なくともバリウムを含むアル
カリ性土類金属酸化物と希土類金属酸化物との混合物か
らなる電子放射物質層を塗布するものである。基体金属
上に金属層を形成する前に、基体金属を還元性雰囲気中
で、８００〜１１００℃の温度範囲で熱処理するもので
ある。熱処理に要する時間を、５分以上６０分以下とす
るものである。In the method for manufacturing a cathode for an electron tube according to the present invention, a reducing agent having the same or smaller reducibility than the reducing agent of the base metal is formed on the base metal containing nickel as a main component and containing the reducing agent. After forming a metal layer containing a metal having a reducibility higher than that of nickel as a main component, the base metal and the metal layer are heated to 800 to 11 in a vacuum or a reducing atmosphere.
Heat treatment is performed for 5 minutes or more and 60 minutes or less in a temperature range of 00 ° C., and then an electron emitting material layer made of a mixture of an alkaline earth metal oxide containing at least barium and a rare earth metal oxide is applied on the metal layer. To do. Before forming a metal layer on the base metal, the base metal is heat-treated in a reducing atmosphere in a temperature range of 800 to 1100 ° C. The time required for the heat treatment is 5 minutes or more and 60 minutes or less.
【００１０】[0010]
実施の形態１．図１は、この発明の実施の形態１による
電子管用陰極の製造方法を示す図である。図２は、図１
の製造方法を適用した電子管用陰極の活性化後の電子放
射特性を示すグラフである。なお、電子管用陰極の構造
は、図５に示すものと同じであるので、図５を援用す
る。基体金属２の主成分はニッケルであり、少なくとも
１種、通常２〜４種の還元剤を含有したものが用いら
れ、例えば、シリコン、マグネシウム、タングステン等
の還元剤の割合が、通常０．０１〜３％（重量％、以下
同様）のものが用いられるが、実施の形態１では、基体
金属２として、ニッケル中に０．０５％のシリコンと、
０．０５％のマグネシウムを含有させた。金属基体２上
には、例えばタングステン、モリブデン、タンタル、ク
ロム等から選ばれた少なくとも１種以上の金属元素を含
む金属層３を形成する。金属層３の厚さは、２．０μｍ
以下であることが好ましく、０．８μｍ以下であれば更
に良い。Embodiment 1. FIG. 1 is a diagram showing a method for manufacturing an electron tube cathode according to Embodiment 1 of the present invention. FIG. 2 shows FIG.
6 is a graph showing electron emission characteristics after activation of a cathode for an electron tube to which the method of (1) is applied. Since the structure of the cathode for an electron tube is the same as that shown in FIG. 5, FIG. 5 will be referred to. The main component of the base metal 2 is nickel, and one containing at least one, usually two to four, reducing agents is used. For example, the ratio of the reducing agent such as silicon, magnesium, and tungsten is usually 0.01%. In the first embodiment, 0.05% of silicon in nickel is used as the base metal 2;
It contained 0.05% magnesium. On the metal base 2, a metal layer 3 containing at least one or more metal elements selected from, for example, tungsten, molybdenum, tantalum, chromium and the like is formed. The thickness of the metal layer 3 is 2.0 μm
Or less, and more preferably 0.8 μm or less.
【００１１】金属層３上に形成される電子放射物質層４
は、少なくともバリウムを含み、他にストロンチウム、
カルシウム等が含まれるアルカリ土類金属酸化物４ａ
と、たとえば酸化スカンジウム、酸化イットリウム等の
希土類金属酸化物４ｂの混合物からなる層である。電子
放射物質層４中のアルカリ土類金属酸化物４ａの割合
は、９０〜９９％が好ましく、希土類金属酸化物４ｂの
割合は、１〜１０％が好ましいが、実施の形態１ではバ
リウム、ストロンチウム、カルシウムを含むアルカリ土
類金属酸化物９３％と、希土類金属酸化物として酸化ス
カンジウム７％を含む混合物を、スプレー法により被着
形成している。Electron emitting material layer 4 formed on metal layer 3
Contains at least barium, as well as strontium,
Alkaline earth metal oxide 4a containing calcium and the like
And a layer made of a mixture of rare earth metal oxides 4b such as scandium oxide and yttrium oxide. The proportion of the alkaline earth metal oxide 4a in the electron emitting material layer 4 is preferably 90 to 99%, and the proportion of the rare earth metal oxide 4b is preferably 1 to 10%. In the first embodiment, barium and strontium are used. A mixture containing 93% of an alkaline earth metal oxide containing calcium and 7% of scandium oxide as a rare earth metal oxide is formed by spraying.
【００１２】図１の電子管用陰極の製造方法について説
明する。まず基体金属２とスリーブ１が溶接された（Ｓ
１１）後に、基体金属２の頂部上面にスパッタリング蒸
着法により、タングステンの金属層３を被着形成し（Ｓ
１２）、その後、金属層３の焼結、再結晶化、基体金属
２中への拡散を行うため、真空中で１０００°Ｃの熱処
理を１０分間実施した（Ｓ１３）。電子放射物質層４に
ついては、Ｓ１３の熱処理後に、スプレー法により約１
００μｍの厚さで塗布を行っている（Ｓ１４）。なお、
比較例として、Ｓ１３の熱処理時間を、２分間、５分
間、２０分間、６０分間としたものも同様に電子放射特
性を評価した。図２は、実施の形態１による電子管用陰
極の初期電子放射特性であり、電子管用陰極を電子銃に
組み込み、更に排気工程、活性化工程を経たブラウン管
において、８００°Ｃの陰極温度に設定して評価した結
果である。比較のためのＳ１３の熱処理時間を、２分
間、５分間、２０分間、６０分間としたものも同様に記
載したが、図からも判るように熱処理時間が、５分間未
満では特性のバラツキが大きく、１０分間以上では安定
している。A method for manufacturing the cathode for an electron tube of FIG. 1 will be described. First, the base metal 2 and the sleeve 1 were welded (S
11) Then, a tungsten metal layer 3 is formed on the top surface of the base metal 2 by sputtering deposition (S).
12) Then, a heat treatment at 1000 ° C. was performed in vacuum for 10 minutes in order to perform sintering, recrystallization, and diffusion into the base metal 2 of the metal layer 3 (S13). About the electron emitting material layer 4, after the heat treatment of S13, about 1
The coating is performed with a thickness of 00 μm (S14). In addition,
As a comparative example, electron emission characteristics were similarly evaluated when the heat treatment time of S13 was set to 2 minutes, 5 minutes, 20 minutes, and 60 minutes. FIG. 2 shows the initial electron emission characteristics of the cathode for an electron tube according to the first embodiment, in which the cathode for an electron tube was incorporated into an electron gun, and the cathode temperature was set to 800 ° C. in the cathode ray tube after the exhaust process and the activation process. This is the result of evaluation. For comparison, the heat treatment time of S13 is set to 2 minutes, 5 minutes, 20 minutes, and 60 minutes, but the same description is given. It is stable for more than 10 minutes.
【００１３】なお、実施の形態１ではＳ１３の熱処理工
程を真空中で行っているが、水素雰囲気のような還元性
雰囲気中で行った場合も同様の結果が得られている。ま
た、６０分間を超える熱処理を行った場合には、基体金
属２中の還元剤の蒸発による消耗が大きくなり、長期間
動作中の還元効果低下、遊離バリウム減少を引き起こす
ため、電子放射の寿命特性の劣化が顕著となる。また、
Ｓ１３の熱処理温度を１０００°Ｃにしているが、８０
０〜１１００°Ｃの熱処理温度であれば、同様の効果が
得られる。Although the heat treatment step of S13 is performed in a vacuum in the first embodiment, similar results are obtained when the heat treatment step is performed in a reducing atmosphere such as a hydrogen atmosphere. In addition, when the heat treatment is performed for more than 60 minutes, the consumption of the reducing agent in the base metal 2 due to evaporation increases, causing a reduction in reduction effect and a decrease in free barium during long-term operation. Degradation becomes remarkable. Also,
Although the heat treatment temperature of S13 is set to 1000 ° C.,
A similar effect can be obtained with a heat treatment temperature of 0 to 1100 ° C.
【００１４】実施の形態２．図３は、この発明の実施の
形態２による電子管用陰極の製造方法を示す図である。
図４は、図３の製造方法を適用した電子管用陰極の活性
化後の電子放射特性を示すグラフである。なお、電子管
用陰極の構造は、図５に示すものと同じであり、図５を
援用して説明する。実施の形態２では、タングステンの
金属層３を形成（Ｓ２３）前に、基体金属２を水素雰囲
気中１０００°Ｃで２０分間熱処理し（Ｓ２２）、基体
金属２の表面に付着した有機化合物等の異物の除去およ
び基体金属２の成分であるニッケル、シリコン、マグネ
シウムの表面酸化膜を還元し、清浄な金属面を形成させ
た。金属層３の形成については、基体金属２の頂部上面
にスパッタリング蒸着法により、タングステンの金属層
３を被着形成し（Ｓ２３）、その後、金属層３の焼結、
再結晶化、基体金属２中への拡散を行うため、真空中で
１０００°Ｃの熱処理を、１０分間実施している（Ｓ２
４）。電子放射物質層４については、Ｓ２４の熱処理後
にスプレー法により、約１００μｍの厚さで塗布を行っ
ている（Ｓ２５）。なお、比較例として、金属層３の形
成前のＳ２２の熱処理時間を２分間、５分間、１０分
間、６０分間としたものも、同様に電子放射特性を評価
した。Embodiment 2 FIG. FIG. 3 is a diagram showing a method of manufacturing an electron tube cathode according to Embodiment 2 of the present invention.
FIG. 4 is a graph showing electron emission characteristics after activation of the cathode for an electron tube to which the manufacturing method of FIG. 3 is applied. The structure of the cathode for an electron tube is the same as that shown in FIG. 5, and will be described with reference to FIG. In the second embodiment, before forming the tungsten metal layer 3 (S23), the base metal 2 is heat-treated at 1000 ° C. for 20 minutes in a hydrogen atmosphere (S22), and an organic compound or the like attached to the surface of the base metal 2 is removed. Removal of foreign matter and reduction of the surface oxide film of nickel, silicon, and magnesium, which are components of the base metal 2, formed a clean metal surface. Regarding the formation of the metal layer 3, a tungsten metal layer 3 is formed on the top surface of the base metal 2 by sputtering deposition (S23).
In order to perform recrystallization and diffusion into the base metal 2, a heat treatment at 1000 ° C. is performed for 10 minutes in a vacuum (S2).
4). The electron-emitting material layer 4 is applied with a thickness of about 100 μm by a spray method after the heat treatment in S24 (S25). In addition, as a comparative example, the electron emission characteristics were similarly evaluated when the heat treatment time of S22 before forming the metal layer 3 was 2 minutes, 5 minutes, 10 minutes, and 60 minutes.
【００１５】図４は、このようにして形成された電子管
用陰極を電子銃に組み込み、更に排気工程、活性化工程
を経たブラウン管において、８００°Ｃの陰極温度に設
定して評価した結果である。また、比較のための金属層
３の形成前のＳ２２の熱処理時間を、２分間、５分間、
１０分間、６０分間としたものも同様に記載したが、図
からも判るように、熱処理時間が５分間以上では、特に
バラツキが小さく、その効果が顕著に現れ、また、基体
金属２上への金属層３の接合強度も向上している。ま
た、Ｓ２２の熱処理を６０分を超えて施した場合には、
実施の形態１と同様の理由で寿命特性が低下する。FIG. 4 shows the results of evaluating the cathode for an electron tube formed in this manner in an electron gun, setting the cathode temperature to 800 ° C. in a cathode ray tube having undergone an exhausting step and an activating step. . In addition, the heat treatment time of S22 before forming the metal layer 3 for comparison was 2 minutes, 5 minutes,
Although 10 minutes and 60 minutes are also described in the same manner, as can be seen from the figure, when the heat treatment time is 5 minutes or more, the variation is particularly small, the effect is remarkable, and the effect on the base metal 2 is large. The bonding strength of the metal layer 3 is also improved. When the heat treatment of S22 is performed for more than 60 minutes,
The life characteristics deteriorate for the same reason as in the first embodiment.
【００１６】なお、実施の形態２では、Ｓ２２の熱処理
温度を１０００°Ｃにしているが、８００〜１１００°
Ｃの熱処理温度であれば、同様の効果が得られる。ま
た、Ｓ２４の熱処理温度も同様である。更に、Ｓ２４の
熱処理を真空中で行っているが、水素雰囲気のような還
元性雰囲気中で行った場合でも同様の効果が得られる。In the second embodiment, the heat treatment temperature of S22 is set to 1000 ° C., but 800 to 1100 ° C.
The same effect can be obtained if the heat treatment temperature is C. The same applies to the heat treatment temperature of S24. Further, although the heat treatment of S24 is performed in a vacuum, the same effect can be obtained when the heat treatment is performed in a reducing atmosphere such as a hydrogen atmosphere.
【図１】 この発明の実施の形態１による電子管用陰極
の製造方法を示す図である。FIG. 1 is a view showing a method of manufacturing an electron tube cathode according to Embodiment 1 of the present invention.
【図２】 図１の製造方法を適用した電子管用陰極の活
性化後の電子放射特性を示す図である。FIG. 2 is a diagram showing electron emission characteristics after activation of a cathode for an electron tube to which the manufacturing method of FIG. 1 is applied.
【図３】 この発明の実施の形態２による電子管用陰極
の製造方法を示す図である。FIG. 3 is a view showing a method for manufacturing an electron tube cathode according to Embodiment 2 of the present invention.
【図４】 図３の製造方法を適用した電子管用陰極の活
性化後の電子放射特性を示す図である。4 is a diagram showing electron emission characteristics after activation of a cathode for an electron tube to which the manufacturing method of FIG. 3 is applied.
【図５】 従来の電子管用陰極の一部拡大断面図であ
る。FIG. 5 is a partially enlarged sectional view of a conventional electron tube cathode.
【図６】 従来の電子管用陰極の製造方法を示す図であ
る。FIG. 6 is a diagram showing a conventional method for manufacturing a cathode for an electron tube.
１ スリーブ、２ 基体金属、３ 金属層、４ 電子放
射物質層、４ａ アルカリ土類金属酸化物、４ｂ 希土
類金属酸化物、５ ヒータREFERENCE SIGNS LIST 1 sleeve, 2 base metal, 3 metal layer, 4 electron emitting material layer, 4a alkaline earth metal oxide, 4b rare earth metal oxide, 5 heater
───────────────────────────────────────────────────── フロントページの続き (72)発明者 近藤 利一 富山市晴海台８番５号 菱北電子株式会社 内 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Toshikazu Kondo 8-5 Harumidai, Toyama City Ryohoku Electronics Co., Ltd.
Claims (3)
基体金属上に基体金属の還元剤より還元性が同等または
小さく且つニッケルより還元性が大きい金属を主成分と
する金属層を形成する工程、上記基体金属と金属層を、
真空または還元性雰囲気中において、８００〜１１００
℃の温度範囲で、５分以上６０分以下の熱処理を行う工
程、上記金属層上に少なくともバリウムを含むアルカリ
性土類金属酸化物と希土類金属酸化物との混合物からな
る電子放射物質層を塗布する工程を含むことを特徴とす
る電子管用陰極の製造方法。1. A step of forming a metal layer containing, as a main component, a metal whose reducibility is equal to or smaller than that of a reducing agent of a base metal and which has a reducibility larger than that of nickel on a base metal containing nickel as a main component and containing a reducing agent. , The base metal and the metal layer,
800 to 1100 in vacuum or reducing atmosphere
A step of performing a heat treatment for 5 minutes or more and 60 minutes or less in a temperature range of 0 ° C., and applying an electron emitting material layer made of a mixture of an alkaline earth metal oxide containing at least barium and a rare earth metal oxide on the metal layer. A method for manufacturing a cathode for an electron tube, comprising the steps of:
に、基体金属を還元性雰囲気中で、８００〜１１００℃
の温度範囲で熱処理する工程を含むことを特徴とする請
求項１記載の電子管用陰極の製造方法。2. Prior to the step of forming a metal layer on the base metal, the base metal is heated at 800 to 1100 ° C. in a reducing atmosphere.
The method for producing a cathode for an electron tube according to claim 1, further comprising a step of performing heat treatment in the temperature range of.
に行われる熱処理工程に要する時間は、５分以上６０分
以下であることを特徴とする請求項２記載の電子管用陰
極の製造方法。3. The method according to claim 2, wherein the time required for the heat treatment step performed before the step of forming the metal layer on the base metal is 5 minutes to 60 minutes. Method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7255420A JP2835023B2 (en) | 1995-10-02 | 1995-10-02 | Manufacturing method of cathode for electron tube |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7255420A JP2835023B2 (en) | 1995-10-02 | 1995-10-02 | Manufacturing method of cathode for electron tube |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH0997561A true JPH0997561A (en) | 1997-04-08 |
| JP2835023B2 JP2835023B2 (en) | 1998-12-14 |
Family
ID=17278520
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7255420A Expired - Fee Related JP2835023B2 (en) | 1995-10-02 | 1995-10-02 | Manufacturing method of cathode for electron tube |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2001035435A1 (en) * | 1999-11-12 | 2001-05-17 | Orion Electric Co., Ltd. | Electron tube cathode and method for manufacturing the same |
| KR100357947B1 (en) * | 1999-11-05 | 2002-10-25 | 삼성에스디아이 주식회사 | Cathode for electron tube and preparing method therefor |
| US6641450B2 (en) | 1999-11-05 | 2003-11-04 | Samsung Sdi Co., Ltd. | Method of making a cathode for an electron tube |
-
1995
- 1995-10-02 JP JP7255420A patent/JP2835023B2/en not_active Expired - Fee Related
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100357947B1 (en) * | 1999-11-05 | 2002-10-25 | 삼성에스디아이 주식회사 | Cathode for electron tube and preparing method therefor |
| US6641450B2 (en) | 1999-11-05 | 2003-11-04 | Samsung Sdi Co., Ltd. | Method of making a cathode for an electron tube |
| WO2001035435A1 (en) * | 1999-11-12 | 2001-05-17 | Orion Electric Co., Ltd. | Electron tube cathode and method for manufacturing the same |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2835023B2 (en) | 1998-12-14 |
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