TW469462B - Cathode subassembly and color CRT equipped therewith - Google Patents
Cathode subassembly and color CRT equipped therewith Download PDFInfo
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- TW469462B TW469462B TW089112171A TW89112171A TW469462B TW 469462 B TW469462 B TW 469462B TW 089112171 A TW089112171 A TW 089112171A TW 89112171 A TW89112171 A TW 89112171A TW 469462 B TW469462 B TW 469462B
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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
- H01J1/20—Cathodes heated indirectly by an electric current; Cathodes heated by electron or ion bombardment
- H01J1/26—Supports for the emissive material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J29/00—Details of cathode-ray tubes or of electron-beam tubes of the types covered by group H01J31/00
- H01J29/02—Electrodes; Screens; Mounting, supporting, spacing or insulating thereof
- H01J29/04—Cathodes
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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
- H01J1/142—Solid thermionic cathodes characterised by the material with alkaline-earth metal oxides, or such oxides used in conjunction with reducing agents, as an emissive material
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Abstract
Description
469^62 五、發明説明(1) 發明領域: 本發明係有闕於一種陰極次組件與—種彩色陰極射線 管(CRT) ’且特別有關於一種陰極次組件,於高操作電 流時仍具有很長的使用壽命,而將其裝設於彩色陰極射線 管。 相關技術說明: 現今’幾乎所有彩色陰極射線管是由所謂的「氧化陰 極(oxide cathodes )」所組成。據了解,氧化陰極包含 特殊金屬材料所製成的陰極基底(base)與覆蓋於基底表 面的多孔,氧化膜。基底中的金屬材料包含主成份鎳(H )加上微量的還原劑(例如:矽(s i )和鎂(;多 孔隙氧化膜則由含鋇(Ba )的鹼土金屬氧化物所製成,膜 厚約為50微米至1〇〇微米。 、 ”氧化陰極在略低於溫度δ00 t:操作時能輕易活化,且 製作成本低β因此,已經被廣泛地實際應用。 接下來的說明係關於設計在彩色陰極射線管 極次 '紐件之氧化陰極習知技術。 # 第1圖係顯示含陰極次組件之氧化陰極習 第1圖所示,氧化陰極70習知技術包括:由包含主=二^ (亦即,鎳基材料)加上微量還原劑(例如:攻伤鎳 金屬材料,所製成的陰極基底71,此基底71外创鎂)之 狀。用於電子發射表面之基底71上表面,覆蓋二二帽 鹼土金屬氧化物所形成之多孔隙氧化膜72, 1二含鋇的 微米至100微米。 、2厚約為50469 ^ 62 V. Description of the invention (1) Field of the invention: The present invention relates to a cathode subassembly and a color cathode ray tube (CRT) ', and particularly to a cathode subassembly, which still has a high operating current. It has a long service life, and it is installed in a color cathode ray tube. Description of related technology: At present, almost all color cathode ray tubes are composed of so-called "oxide cathodes". It is understood that the oxidized cathode includes a cathode base made of a special metal material and a porous, oxide film covering the surface of the base. The metallic material in the substrate contains the main component nickel (H) plus a trace amount of reducing agent (for example: silicon (si) and magnesium (; porous oxide film is made of alkaline earth metal oxide containing barium (Ba)). The thickness is about 50 micrometers to 100 micrometers. "" The oxidation cathode is slightly lower than the temperature δ00 t: it can be easily activated during operation, and the production cost is low β. Therefore, it has been widely used in practice. The following description is about design Known technology of oxidized cathodes in color cathode ray tube extreme times. # Figure 1 shows the oxidized cathodes with cathode subassembly shown in Figure 1. The conventional technology of oxidized cathode 70 includes: ^ (That is, nickel-based material) plus a trace amount of reducing agent (for example, a cathode substrate 71 made by attacking a nickel metal material, and the substrate 71 is externally created by magnesium). The substrate 71 is used for an electron-emitting surface The surface is covered with a porous oxide film 72 formed by two-two-hat alkaline-earth metal oxides, one-two micrometers containing barium to 100 micrometers, and a thickness of about 50.
第5頁 46946 2 五、發明說明(2) ----- 陰極套管73置入於氡化膜72背側之基底π内,利用焊 接固定套管73與基底71。陰極7〇本身靠套管73内附之加熱 器74來加熱。基底71、膜72與套管73構成一陰極次組件… 79丄因此可說此陰極7〇係由次組件79與加熱器74所組成。 數字75表示基底71與膜72之間的界面。 陰極次組件79習知技術之缺點係於高操作電流密度約 1 A/cm2以上時,使用壽命從一般數萬小時減至數千小時以 下。換言之,次組件79之電子發射能力(亦即,發射率 (emissivity))於高操作電流密度約u/cm2以上操作數 千小時便大為降低,此乃氧化次組件7 9習知技術幾乎唯一 的缺點。接下來的原因被認為是導致次組件79發射率降低 的原因。 當陰極基底71由加熱器74往上加熱至8〇〇 °c左右,基 底71内含的矽與鎂(用於還原劑)於基底71内發生熱擴 散’然後與多孔隙膜72内的氧化鋇(Ba〇)在界面75處反 應。因此發生以下的化學反應(1 )與(2 ).Page 5 46946 2 V. Description of the invention (2) ----- The cathode sleeve 73 is placed in the substrate π on the back side of the tritium film 72, and the sleeve 73 and the substrate 71 are fixed by welding. The cathode 70 itself is heated by a heater 74 attached to the sleeve 73. The base 71, the membrane 72, and the sleeve 73 constitute a cathode subassembly ... 79 丄 Therefore, it can be said that the cathode 70 is composed of the subassembly 79 and the heater 74. The number 75 indicates an interface between the substrate 71 and the film 72. The disadvantage of the conventional technique of the cathode subassembly 79 is that when the high operating current density is about 1 A / cm2 or more, the service life is reduced from tens of thousands of hours to thousands of hours or less. In other words, the electron emission capability (ie, emissivity) of the sub-module 79 is greatly reduced when operating at a high operating current density of about u / cm2 for thousands of hours, which is almost the only known technology for oxidizing the sub-module 79. Shortcomings. The next reason is believed to be the cause of the reduced emissivity of the sub-module 79. When the cathode substrate 71 is heated up to about 800 ° C by the heater 74, the silicon and magnesium (for reducing agent) contained in the substrate 71 undergo thermal diffusion in the substrate 71, and then oxidize with the porous film 72. Barium (Ba0) reacts at the interface 75. Therefore, the following chemical reactions (1) and (2) occur.
BaO + ( l/2)Si —i>Ba r (l/2)Si〇 (1) j BaO + Mg —^ Ba + MgO (2) 反應(1)與(2)之結果使鎖原子產生低功函數,因 而電子從鋇原子發射。然而此種情況,反應(1)與(2) 所產生的生成物:氧化矽與氧化鎂,沈積一層狀物於界面 75處。因此,在界面75處形成一種由氧化矽與氧化鎂所造 成的中間層(未展示於圖中)。 中間層由於為一大電阻’阻礙電子流經次組件7 9,並BaO + (l / 2) Si —i> Ba r (l / 2) Si〇 (1) j BaO + Mg — ^ Ba + MgO (2) The result of reaction (1) and (2) makes the lock atom low Work function, so electrons are emitted from the barium atom. However, in this case, the products produced by reactions (1) and (2): silicon oxide and magnesium oxide, deposited a layer at the interface 75. Therefore, an intermediate layer made of silicon oxide and magnesium oxide is formed at the interface 75 (not shown in the figure). The middle layer is a large resistance ’which prevents electrons from flowing through the sub-components 7 9 and
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且阻礙基底71内的矽和鎂與臈之間的接觸,抑制反應 )與(2 )之進行。由於這兩個理由,當操作時間較 時’次組件79習知技術的電子發射率會降低。 上述之發射率降低機制與操作電流密度並盔 係。然而,若操作電流密度高於1A/Cm2時,會^ 發射率的降低。 d此而加連 〇當陰極次組件79的操作電流密度大時,中間層在門私 操作後快速形成。因此,操作於高電流密度時不管二^ 的阻礙,而在中間層產生焦耳熱。由於焦耳熱的產生I 作期間的界面75溫度高於操作溫度數十度。結果使鹿 (1)與(2)過度進行,中間層過度成長而變厚。因正向 反饋作用(positive feedback behavior ),使得一系^ 的現象加速發生。此為上述的陰極次組件79 射」 降低的機制。 电于發射千 早期的彩色陰極射線管尺寸小且操作電流密度低, 化陰極的使用壽命並未引起任何問題。相反地,現今的奢 色陰極射線管尺寸變得較大且使用i A/cm2以上的操作電流^ 密度。因此,上述中使用壽命短的缺點變得更為明顯。^ 解決此項缺點,已經完成許多改良方法讓氧化陰極在高操 作電流密度時有較長的使用壽命。 舉例說明,1 989年一月發表於日本未審查專利公報之 = 64-5417號,公開一種改良的氧化陰極,氧化陰極内的 夕孔隙膜由稀土金屬氧化物(例如:氧化銳(SC9〇3 )), 混入含鋇之鹼土金屬氧化物所製成。改良後的陰極在上述In addition, the contact between silicon, magnesium, and thallium in the substrate 71 is hindered, and the progress of the reactions (2) and (2) is suppressed. For these two reasons, the electron emission rate of the conventional technique of the sub-assembly 79 decreases when the operation time is relatively long. The above-mentioned emissivity reduction mechanism is compatible with the operating current density. However, if the operating current density is higher than 1A / Cm2, the emissivity will decrease. d In addition, when the operating current density of the cathode sub-assembly 79 is large, the intermediate layer is formed quickly after the private door operation. Therefore, Joule heat is generated in the intermediate layer regardless of the obstructions when operating at a high current density. Due to the generation of Joule heat, the temperature of the interface 75 during operation is tens of degrees higher than the operating temperature. As a result, deer (1) and (2) progressed excessively, and the middle layer grew excessively and became thick. Due to the positive feedback action, a series of phenomena are accelerated. This is the mechanism by which the above-mentioned cathode subassembly is lowered. The early color cathode ray tubes were small in size and low in operating current density, and the service life of the cathode did not cause any problems. In contrast, today's luxury color cathode ray tubes have become larger in size and use operating currents at a density higher than i A / cm2. Therefore, the shortcoming of the short service life described above becomes more apparent. ^ To address this shortcoming, many improvements have been made to allow the oxidation cathode to have a longer service life at high operating current densities. For example, published in Japanese Unexamined Patent Publication No. 64-5417 in January 1989, an improved oxidation cathode is disclosed. The pore film in the oxidation cathode is made of rare earth metal oxides (for example: Oxide sharp (SC9〇3 )), Mixed with barium-containing alkaline earth metal oxides. The modified cathode is above
4 6 9 4 6 2 五、發明說明⑷ ' 之兩操作電流密度下’使用壽命較長於之前的氧化陰極。 然而’卻已不足以符合實際應用。 另一種改良的氧化陰極公間發表於1 997年四月的日本 未審査專利公報之第9-1 06750號。改良的氧化陰極包括; 陰極基底、由稀土金屬氧化物(例如:氧化銃)混入含鋇 之驗土金屬氧化物所製成的多孔隙膜以及一層金屬(例 如:鎢(W ))位於基底和膜之間。改良後的陰極在上述 之高操作電流密度下,使用壽命較長於之前的氧化陰極。 然而,卻也已不足以符合實際應用。 公開於公報第64-54 1 7與9-1 06750號之改良氧化陰極 有一缺點,氧化陰極在上述之高操作電流 度近似於之前的氧化陰極。 卜雜作/里 另一方面,將浸潰陰極(impregnated cath〇des)併 入彩色陰極射線管非常麻煩^據瞭解,浸潰陰極通常使用 於微波管並且確定長期操作於上述之高操作電流密度。浸 潰陰極甚至於高電流密度時,電子發射率幾乎都沒有降 低所、’又有出現關於使用哥命的問題。然而,浸潰陰極 :-嚴:缺點就是活化時間&、操作溫度高以及製造成本 :二不會有這些問題。活化時間長需加長陰極 的時效線(aging line);操作溫度高則 '、,、需二改良:改變陰極次組件的材料、提高電子餘 的熱阻°這些需求或問題實際上十分難以解決 如上詳細解釋,為了滿足高操作電流密度下的需 已將氣化陰極改良過;另一方面亦將浸潰陰極4 6 9 4 6 2 V. Description of the invention ⑷ The service life at two operating current densities is longer than the previous oxidation cathode. However, 'is not enough to meet the practical application. Another improved oxidized cathode was publicly published in Japanese Unexamined Patent Publication No. 9-1 06750 in April, 1997. The improved oxidized cathode includes: a cathode substrate, a porous film made of a rare earth metal oxide (such as hafnium oxide) mixed with a barium-containing earth test metal oxide, and a layer of metal (such as tungsten (W)) on the substrate and Between the membranes. The improved cathode has a longer service life than the previous oxidized cathode at the above-mentioned high operating current density. However, it is no longer sufficient for practical applications. The improved oxidation cathodes disclosed in the publications Nos. 64-54 1 7 and 9-1 06750 have a disadvantage. The above-mentioned high operating current of the oxidation cathode is similar to that of the previous oxidation cathode. On the other hand, it is very troublesome to incorporate impregnated cathodes into color cathode ray tubes. It is understood that impregnated cathodes are usually used in microwave tubes and are determined to operate at the above-mentioned high operating current density for a long time. . When the cathode is immersed, even at a high current density, the electron emission rate is hardly reduced, and there is a problem about the use of the emissary. However, the impregnated cathode:-Yan: The disadvantages are the activation time & the high operating temperature and the manufacturing cost: Second, there will be no such problems. Long activation time requires lengthening the aging line of the cathode; high operating temperatures require improvement: changing the material of the cathode subassembly and increasing the thermal resistance of the electrons. These requirements or problems are actually very difficult to resolve Explain in detail that the gasification cathode has been modified in order to meet the needs at high operating current density; on the other hand, the cathode will be immersed
469462 五、發明說明(5) 應用於彩色陰極射線管。然而’上述改良之氧化陰極在高 操作電流密度下的使用壽命仍然有問題而無法滿足實際應 用。浸潰陰極有活化時間長、操作溫度高與製造成本高的 問題。因此,改良過之氧化陰極與浸潰陰極都無法取代展 不於第1圖中之氧化陰極70習知技術。 發明概述: 本發明之目的在於提出一種陰極次組件,其儘管具有 與傳統氧化陰極相等的活化時間以及操作温度,於彩色吟 極射線管一般,少之使用壽命期間,其電子發射率甚至: 大於lA/cm2之高操作電流密度中幾乎都沒有降低,並將此 陰極次组件裝設於彩色陰極射線管。 本發明另一目的在於提出一種陰極次組件,且 子,射率,可施行於簡化的製造過程,並裝設於彩色陰極 經由以下說明將 以上目的與其他未具體說明之目的 使熟習此技藝人士更為明瞭。 根據本發明第一形態,提出的陰極次組件包括: ) 一多孔隙陰極片,係由含鎳、氧化銳(s =材;之燒結物體所形成;此物體係使用熱均 ίΪΐί 氧化航ΜΙ)粉末以及電子發射材料粉 末/ ϋ物所製成;此陰極片具有電子發射表面。 Μ份片支撐物,用以支撐陰極片;此片支撐物一 i (Cr ) ^丢極片;此部份係由含主成份鎳與至少一種從 、鈕(Ta )、鉬(M〇 )、锆(Zr )、鎢)與469462 V. Description of the invention (5) Application to color cathode ray tubes. However, the service life of the above-mentioned improved oxidation cathode at high operating current density is still problematic and cannot satisfy practical applications. Impregnated cathodes have problems with long activation times, high operating temperatures, and high manufacturing costs. Therefore, neither the improved oxidation cathode nor the impregnated cathode can replace the conventional technique of the oxidation cathode 70 shown in FIG. 1. Summary of the invention: The object of the present invention is to propose a cathode subassembly, which has the same activation time and operating temperature as a conventional oxidized cathode, and is generally similar to a color-injection cathode-ray tube, and has a small lifetime. There is almost no decrease in the high operating current density of 1A / cm2, and this cathode subassembly is installed in a color cathode ray tube. Another object of the present invention is to provide a cathode sub-assembly, and the emissivity can be implemented in a simplified manufacturing process and installed in a color cathode. The above purpose and other unspecified purposes will be familiar to those skilled in the art through the following description More clear. According to the first aspect of the present invention, the proposed cathode sub-assembly includes:) A multi-porous cathode sheet, which is formed of a sintered object containing nickel and sharp oxide (s = material; this system uses a thermal homogenizer). Made of powder and electron emitting material powder / tritium; this cathode has an electron emitting surface. M pieces of sheet support to support the cathode sheet; this sheet support-i (Cr) ^ dipole sheet; this part is composed of the main component nickel and at least one slave, button (Ta), molybdenum (M〇) , Zirconium (Zr), tungsten) and
469462 五、發明說明(6) H)組群擇選出的金屬合金所製成;至少-種從鉻、 料之還原鎢與鈷組群擇選出的金屬用作於電子發射材 起雷勤奮地研究氧化陰極於高操作電流密度下引 的機制已有一段很長時曰。結果已成功 @搞Μ & A八有新結構之改良式氧化陰極次組件,於彩色 ^ 〜官一般至少之使用壽命期間,其電子發射率甚至 於1A/cm之南操作電流密度中幾乎都沒有降低。 特別地如以上之概述’本發明之陰極次組件包括一 δ鎳、氧化銳與電子發射材料之燒結物體所形成的多孔 隙陰極片,以及一種支撐陰極片之片支撐物□此物體係使 用熱均壓燒結鎳粉末、氧化銃粉末以及電子發射材料粉末 混合物所製成。片支撐物一部份接觸於陰極片,此部份係 由含主成份鎳與至少一種從鉻、鈕、鉬、锆、鎢與鈷組群 擇選出的金屬合金所製成;至少一種從鉻、鉅、鉬、錘、 鎢與鈷組群擇選出的金屬用作於電子發射材料之還原劑。 用作於陰極基底之多孔隙陰極片係由含鎳、氧化銳以 及電子發射材料之燒結物體所形成。因此,具有類似於錄 的格狀(grid-shaped)結構或組織,換言之,具有許多 的開放孔(open pores )。陰極片的孔洞被填入電子發射 材料與氧化銃。因此’介於陰極片(亦即,陰極基底)與 電子發射材料之間的界面總面積大大地增加,同時,形成 於每單位界面面積之中間層厚度大大地減少。 由於中間層厚度的減少’甚至在大&1A/cm2之高操作469462 V. Description of the invention (6) H) Made of metal alloys selected by the group; at least one metal selected from the group of chromium, reduced tungsten and cobalt is used in electron emission materials for diligent research The mechanism of the oxidation of the cathode at high operating current densities has been around for a long time. The result has been successfully @GANM & A has an improved structure of the oxidation cathode sub-module with a new structure. During the life span of the color ^ ~ at least general, its electron emission rate is almost even 1A / cm south operating current density. No reduction. In particular, as outlined above, the cathode sub-assembly of the present invention includes a porous cathode sheet formed of a sintered body of δ nickel, oxide oxide, and an electron-emitting material, and a sheet support for supporting the cathode sheet. This object system uses heat Equal pressure sintered nickel powder, hafnium oxide powder and electron emitting material powder mixture. A part of the sheet support is in contact with the cathode sheet, and this part is made of nickel as a main component and at least one metal alloy selected from the group consisting of chromium, button, molybdenum, zirconium, tungsten, and cobalt; at least one kind of chromium Metals selected from the group consisting of iron, giant, molybdenum, hammer, tungsten and cobalt are used as reducing agents for electron emission materials. A porous cathode sheet used as a cathode substrate is formed of a sintered object containing nickel, oxide oxide, and an electron-emitting material. Therefore, it has a grid-shaped structure or organization similar to a record, in other words, has many open pores. The holes of the cathode sheet are filled with an electron emitting material and thorium oxide. Therefore, the total area of the interface between the cathode sheet (that is, the cathode substrate) and the electron-emitting material is greatly increased, and at the same time, the thickness of the intermediate layer formed per unit interface area is greatly reduced. Due to the reduction in the thickness of the intermediate layer ’, even at large & 1A / cm2
第10頁 469462 五、發明說明(7) ί : f Ϊ下’中間層也不會加速形成。同樣地,填入孔泗 的氧=飢具有阻止中間層形成之功能,因而 用! 率於彩色陰極射線管-舣 至用可命期間,甚至在上述之大於u 流密度中幾乎都沒有降低。 η插作電 =外’由於電子發射機制與一般的氧化陰極相同,而 維持了活化時間短與操作溫度低的優點。 至;一種從鉻、钽、鉬、鍅、鎢與鈷組 屬用作於電子發射材料之還原劑。因此,加速 電子發射材料還原反應,提供了優良電子 簡 的製造過程。 竹「王興間1 再者,至少一t從鉻m、鎢與鈷組群擇遽 出的金屬經由電子發射材料還原反應不會產生高電阻♦中 間層。因此,可進一步抑制電子發射率的降低。 〜 如以上所述,根據本發明第一觀點之陰極次組哿 達成上述之目的。 根據本發日月之第二形態’所提出㈣色陰 包 括了第一形態所述之陰極次組件。毋需說,卜nI < 達成於陰極射線管中。 ㈣’上述目的亦哥 圖式之簡單說明: 為了讓本發明^上述和其他目的、特徵、和優點能更 明顯易懂,所附圖表說明如下: 第!圖顯示出包含陰極次組件之氣化陰極習知技術概 略結構剖面圖。 469462 五、發明說明(8) 第2圖顯示出包含本發明實施炼& 分解過程前之氧化陰極概略結構剖面圖'極-人組件於陰極 第3圖顯示出電子發射材料膜 成巧極片之電子發射表面之氧化陰極V略解结過構= 第4圖顯示出本發明實施例中,陰極次構^面圖。 間與分解溫度關係曲線圖。 之·刀解% 第5圖顯示出本發明實施例與習知技術中, 件之驅動電壓與發射電流關係曲線圖。 &極-人、、且 第6圖顯示出本發明實施例中,陰極次組件之 ^ 度特性與最大陰極電流.之函數關係曲線圖。 第7圖顯示出本發明實施例中,陰極次組件之 極電流改變量與操作時間之函數關係曲線圖。 [符號說明] 70、Ϊ0〜氧化陰極;7 1〜陰極基底; 72〜多孔隙氧化膜;73、14〜陰極套管; 74、15〜加熱器; 75〜基底和膜之間界面; 7 9、1 9〜陰極次組件;1卜多孔隙陰極片; 12〜片支掠物; 13〜發射表面; 17~孔洞; 23〜發射材料膜。 發明說明: 以下配合所附圖式詳細說明本發明之實施例。 先前於發明背景中提及公開於日本未審查專利公報之 第64-541 7與9-1 06 750號中的氧化陰極習知技術,可加入 一項反應於反應(1 )與(2 )以分解中間層而減緩一系列Page 10 469462 V. Description of the invention (7) ί: f Ϊ 下 ’intermediate layer will not accelerate to form. Similarly, the oxygen = hunger filled in Kongsi has the function of preventing the formation of the intermediate layer, so the rate of use from the color cathode ray tube to the serviceable life is almost not reduced even in the above-mentioned current density greater than u. η Interpolated Electricity = Outer 'maintains the advantages of short activation time and low operating temperature because the electron emission mechanism is the same as that of a general oxidation cathode. To; a reducing agent for chromium, tantalum, molybdenum, rhenium, tungsten, and cobalt used as an electron-emitting material. Therefore, the reduction reaction of the electron-emitting material is accelerated, and an excellent manufacturing process is provided. Bamboo "Wang Xingjian 1 In addition, at least one t of metals selected from the group consisting of chromium m, tungsten and cobalt will not generate high resistance through the reduction reaction of the electron emitting material. Therefore, the electron emission rate can be further suppressed. Reduction. ~ As mentioned above, the cathode sub-group according to the first aspect of the present invention achieves the above-mentioned objective. According to the second form of the sun and the moon, the color shade includes the cathode sub-assembly described in the first form. Needless to say, nI < is achieved in a cathode ray tube. ㈣ 'The above object is also a simple illustration of the schema: In order to make the present invention ^ above and other objects, features, and advantages more obvious and understandable, the attached The diagram is explained as follows: Figure! The figure shows a schematic cross-sectional view of the conventional structure of a gasification cathode including a cathode subassembly. 469462 V. Description of the invention (8) Figure 2 shows the oxidation before the decomposition & decomposition process of the present invention is included. Sectional view of the structure of the cathode. The pole-human component on the cathode. Figure 3 shows the oxidized cathode V of the electron-emitting surface of the electron-emitting material film into a pole piece. The structure V is slightly decomposed. Figure 4 shows the implementation of the present invention. Figure 5 shows the relationship between the cathode secondary structure and the decomposition temperature. Figure 5 shows the relationship between the driving voltage and the emission current of the device in the embodiment of the present invention and the conventional technology. &Amp; FIG. 6 is a graph showing the relationship between the characteristics of the cathode subassembly and the maximum cathode current in the embodiment of the present invention. FIG. 7 shows the cathode subassembly in the embodiment of the present invention. A graph of the relationship between the amount of electrode current change and operating time. [Symbols] 70, Ϊ0 ~ oxidized cathode; 7 1 ~ cathode substrate; 72 ~ porous oxide film; 73, 14 ~ cathode sleeve; 74, 15 ~ heated 75 ~ interface between substrate and membrane; 7, 9, 19 ~ cathode subassembly; 1 polyporous cathode sheet; 12 ~ sheet support; 13 ~ emitting surface; 17 ~ hole; 23 ~ emitting material film. Description of the invention: The embodiments of the present invention will be described in detail with reference to the attached drawings. The oxidation cathodes disclosed in Japanese Unexamined Patent Publication Nos. 64-541 7 and 9-1 06 750 were mentioned in the background of the invention. Technology, you can add a reaction to the reaction ( 1) and (2) slow down a series by decomposing the middle layer
469462 五、發明說明(9) 現象的進行’從而抑制電子發射率的降低。 不同於此,本發明者發現事實上若中間層的厚度薄於 氧化陰極習知技術’即使在高搡作電流密度大於1A/cm2且 不加入任何反應於反應(1)與(2)中,—系列的現象也 不會因正向反饋而加速進行β這件事實原因’被認為是中 間層厚度小’產生於中間層之總焦耳熱少且中間層不會被 過度加熱,因而防止正向反饋。 對照展示於第1圖中之氧化陰極次組件79習知技術, 由反應(1)與(2)在界面75面積中所產生之氧化矽和氧 化鎮總商數(亦即,總體積),明白表示出中間層的厚 度。因此’於較寬廣的界面75面積生長,中間層的厚度就 會較小。然而’從第1圖看來,界面75面積大約等於陰極 基底71之電子發射表面面積。依照推論,不改變次組件π 結構無法徹底增加界面75面積。 有鑑於此’本發明提供一種陰極次組件,係使两多孔 隙燒結物體所製成的「多孔隙陰極片」取代陰極基底。 片(亦即’物體)中的微孔填入電子發射村料,因此,片 中所有孔洞内壁可做電子發射材料的界面用。據瞭解通 常多孔隊燒結體表面積是相同物艘大小之平拓矣而接夕奴 千倍或數萬倍。意即電子發射村料之界面 習知技術之數千倍或數萬倍。換言之,本發明之次組件其 中間層厚度是次組件79習知技術的數千分之—或數萬分^ 一,徹底減少中間層單位面積所產生的焦耳熱◎相對2, 電子發射材料的界面不會被過度加熱且上述之正向反鎮作 469462469462 V. Description of the invention (9) Progress of phenomenon ', thereby suppressing the decrease of the electron emission rate. Unlike this, the present inventors found that if the thickness of the intermediate layer is thinner than the conventional technique of oxidizing the cathode, even if the current density is higher than 1A / cm2 at high operation and no reaction is added to reactions (1) and (2), —The phenomenon of series will not be accelerated due to the positive feedback. The fact that 'is considered to be a small thickness of the intermediate layer' produces less total Joule heat from the intermediate layer and the intermediate layer will not be overheated, thus preventing the forward direction. Feedback. Comparing the conventional technique of the oxidized cathode sub-assembly 79 shown in FIG. 1, the total quotient (ie, total volume) of silicon oxide and oxidized town generated by reactions (1) and (2) in the area of the interface 75, The thickness of the intermediate layer is clearly shown. Therefore, if the area grows over a wider interface 75, the thickness of the intermediate layer will be smaller. However, from the perspective of Fig. 1, the area of the interface 75 is approximately equal to the electron-emitting surface area of the cathode substrate 71. According to the inference, the area of the interface 75 cannot be completely increased without changing the π structure of the subassembly. In view of this, the present invention provides a cathode subassembly, which replaces the cathode substrate with a "porous cathode sheet" made of two porous sintered objects. The micro-holes in the film (that is, the 'object') are filled with the electron emission material. Therefore, the inner walls of all the holes in the film can be used as the interface of the electron-emitting material. It is understood that the surface area of the sintered body of the porous team is usually 1,000 times or tens of thousands of times as large as the size of the same ship. It means the interface of electron emission materials, thousands of times or tens of thousands of times of the known technology. In other words, the thickness of the intermediate layer of the secondary component of the present invention is one thousandth of the conventional technology of the secondary component 79—or tens of thousands of ^^, which completely reduces the Joule heat generated by the unit area of the intermediate layer. The interface will not be overheated and the above anti-reverse action is 469462
用也會停止,因而防止一系列現象加速進行。 "另一方面,本發明中的電子發射機制或次組件原理與 -人組件79習知技術相同。特別地,鋇原子經由反應(、 :(2 ) |生低功函數因而產生發射電子。導致活化時間 與刼作溫度和次組件79習知技術相同。 :下來’本發明中將電子發射材料填入陰極片 的方法如以下之說明。 將電子發射材料填入多孔隙片中孔洞並不容易,第一 種方法就是使用所謂的「熔融浸潰法」(f used impregnation method ),曾慣用於生產著名的浸潰陰 極β此法係將多孔隙片與電子發射材料保持接觸,然後往 上加熱至一特殊溫度使發射材料熔化β此情形中,熔化之 發射材料利用毛細作用自動浸潰於片中之孔洞。 嫁融浸潰法為何能應用於生產浸潰陰極之理由係陰極 基底之溶點高於電子發射材料熔點。舉例來說,若陰極基 底由鶴的燒結物體所製成且電子發射材料為鋇—鈣鋁酸鹽 aluminate),基底熔點約3300 °C而發射材料熔 點約為2 5 0 0 t。意即基底熔點高於發射材料熔點8 0 0度。 然而’參考之前,此例中的浸潰陰極有活化時間長與搡作 溫度高(例如,約1 0 0 0 °C )的缺點。此缺點係由使用的材 料(亦即’鎢與鋇-鈣鋁酸鹽)所造成,因此非常難以解 決。 為了不失去氧化陰極習知技術中活化時間短與操作溫 度低的特性,基底需要由含主成份鎳之合金(亦即’鎳基Use also stops, thus preventing a series of phenomena from accelerating. " On the other hand, the electron emission mechanism or sub-assembly principle in the present invention is the same as the conventional technique of the human assembly 79. In particular, the barium atom generates an emitted electron via the reaction (,: (2)) to generate a low work function. This results in the activation time being the same as the operating temperature and the conventional technique of the sub-assembly 79.: Down 'In the present invention, the electron emitting material is filled The method of entering the cathode sheet is described below. It is not easy to fill the holes in the porous sheet with the electron-emitting material. The first method is to use the so-called "f used impregnation method", which was used to produce The well-known impregnated cathode β method is to keep the porous sheet in contact with the electron emitting material, and then heat it up to a special temperature to melt the emitting material. In this case, the molten emitting material is automatically impregnated into the film by capillary action. The reason why the graft immersion immersion method can be used to produce impregnated cathodes is that the melting point of the cathode substrate is higher than the melting point of the electron emitting material. For example, if the cathode substrate is made of a sintered object of a crane and the electron emitting material is It is barium-calcium aluminate (alumminate), the melting point of the substrate is about 3300 ° C and the melting point of the emitting material is about 2 500 t. This means that the melting point of the substrate is 800 degrees higher than the melting point of the emissive material. However, before the reference, the impregnated cathode in this example has the disadvantages of long activation time and high operation temperature (for example, about 100 ° C). This disadvantage is caused by the materials used (i.e., 'tungsten and barium-calcium aluminate) and is therefore very difficult to resolve. In order not to lose the characteristics of short activation time and low operating temperature in the conventional technology of oxidized cathode, the substrate needs to be made of an alloy containing nickel as the main component (that is, a 'nickel-based
469462 五、發明說明(ΐϊ^ ---- 一·' t金)所製成且發射材料為含鋇鹼土金屬氧化物(亦即, 鎖氧化驗土金屬)。然而,由於鎳基合金與含鋇鹼土金 氧化物之疼點幾乎相等約為1 4 00 °c而無法應用熔融浸潰 第二種將電子發射材料填入多孔隙片中孔洞之方法’ ,均勻混合鎳基合金粉末與含鋇氧化鹼土金屬粉末於真空 或氮氣C1¾ )氛圍下做高溫燒結。然而,此法有一問題就 是無電子從陰極片中發射出。這是由於陰極片的生產過程 或彩色陰極射線管根據以下的化學方程式(3).469462 V. Description of the invention (ΐϊ ^ ---- 一 gold) and the emitting material is a barium-containing alkaline earth metal oxide (that is, a lock oxide earth test metal). However, because the pain points of nickel-based alloys and barium-containing alkaline-earth gold oxides are almost equal to about 1 400 ° c, it is not possible to apply melt impregnation. The second method of filling electron-emitting materials into holes in a porous sheet is uniform. The nickel-based alloy powder and the barium oxide-containing alkaline earth metal powder are mixed for high-temperature sintering in a vacuum or nitrogen atmosphere. One problem with this method, however, is that no electrons are emitted from the cathode. This is due to the production process of the cathode sheet or the color cathode ray tube according to the following chemical equation (3).
BaO + H20—> Ba(〇H)2 (3) 使陰極片中的氧化鋇(Ba〇 )與大氣中的水分發生反應而 變成氫氧化鋇(Ba(〇H)2)。 據瞭解’氫氧化銷經由任何還原反應也不會產生類似 於反應(1)與(2)的鋇原子。因此,燒結體在8〇〇〇c下 生產的多孔隙陰極片係為電中性而無電子發射。然而,若 ,片的製作至安裝於彩色陰極射線管之所有步驟是在無水 氛圍(例如’氮氣氛圍)中完成’則有可能在8 〇 〇艺時電 子從月中發射。此想法並不.可行,因為需要非常大型的設 備’導致第二種方法同樣無法應用。 回到第1圖中的氧化陰極79習知技術,可看見以下的 方法能巧妙地阻止化學反應(3 )發生於陰極79。 使用含銅鹼土金屬碳酸鹽(亦即,含鋇碳酸鹼土金屬 )取代含鎖氧化鹼土金屬。由於含鋇碳酸鹼土金屬在大氣 中很穩定’不會有任何類似反應(3 )之反應發生β將含BaO + H20— > Ba (〇H) 2 (3) Barium oxide (Ba0) in the cathode sheet reacts with moisture in the atmosphere to become barium hydroxide (Ba (〇H) 2). It is understood that the 'hydroxide pin' does not generate barium atoms similar to reactions (1) and (2) through any reduction reaction. Therefore, the porous cathode sheet produced by the sintered body at 800 ° C was electrically neutral without electron emission. However, if all the steps from the production of the film to the installation of the color cathode ray tube are completed in an anhydrous atmosphere (such as a 'nitrogen atmosphere'), electrons may be emitted from the moon at 800 hours. This idea is not feasible, because the need for very large equipment ’makes the second method equally unapplicable. Returning to the conventional technique of oxidizing the cathode 79 in FIG. 1, it can be seen that the following method can cleverly prevent the chemical reaction (3) from occurring at the cathode 79. The copper-containing alkaline earth metal carbonate (ie, the barium-containing alkaline earth metal) is used in place of the lock-oxidized alkaline earth metal. Since the alkaline earth metal containing barium carbonate is very stable in the atmosphere ’, there will not be any similar reaction (3).
469^^2 五、發明說明(12) 鋇碳酸鹼土金屬塗佈於基底71表面,於陰極分解過程中真 空加熱至800 °C到lOOtre。由於受熱而發生以下的反應(4 ),導致碳酸鋇(BaC03 )分解出氧化鋇。469 ^^ 2 V. Description of the invention (12) The barium carbonate alkaline earth metal is coated on the surface of the substrate 71, and it is vacuum heated to 800 ° C to 100tre during the cathodic decomposition process. The following reaction (4) occurs due to heating, which causes barium carbonate (BaC03) to decompose into barium oxide.
BaC03—>BaO + C02 (4) 由於氧化鋇在真空中生成,不會與大氣中的水分發生 反應,所以不會據由反應(3 )而改變成氫氧化鋇。此結 果可使含鋇氧化鹼土金屬之多孔隙膜72形成於基底71上。 除了鎖之外的任何驗土金屬在基底71中,也會有類似反應 (4)的反應發生。然而,這對於本發明並不重要而忽略 不談。 本發明者打算結合將氧化陰極79習知技術中的含鋇氧 化驗土金屬改成含鋇碳酸驗土金屬之方法以及把電子發射 材料填入多孔隙片中孔洞之方法,結果討論出以下的方 法0 將錄基合金粉末與含鋇碳酸鹼土金屬粉末一起均勻混 合’然後於真空或氮氣氛圍中做高溫燒結。此方法中,因 ^錄基w金的溶點約為1400 °C而將燒結溫度設定在1〇〇〇。匚 然而據了解’若含铜碳酸驗土金属加熱至1000s C 3 )進^1 程式(4)而完全分解成氧化鋇,再據由方程式 二種方&步轉為氫氧化鋇。所以,陰極片與使用上述第 發射)1 :生產的一樣有相同問題(亦即,不會產生電子 多孔y ί即氧化陰極7 9習知技術中把電子發射材料填入 *、片中孔洞之方法無法被採用。 接下來’本發明者留意到由反應(4 )中的碳酸鋇所BaC03— > BaO + C02 (4) Because barium oxide is generated in a vacuum, it does not react with moisture in the atmosphere, so it does not change to barium hydroxide by reaction (3). As a result, a porous film 72 containing barium oxide alkaline earth metal can be formed on the substrate 71. Any soil test metal other than the lock will have a similar reaction (4) in the substrate 71. However, this is not important to the present invention and is ignored. The inventor intends to combine the method of changing the barium-containing oxidized soil test metal into the barium-containing carbonate test metal in the conventional technology of the oxidation cathode 79 and the method of filling the holes in the porous sheet with the electron-emitting material. Method 0: Mix the base alloy powder with the barium carbonate-containing alkaline earth metal powder uniformly, and then perform high temperature sintering in a vacuum or nitrogen atmosphere. In this method, the sintering temperature is set to 1000 because the melting point of the metal is about 1400 ° C.匚 However, it is understood that if the copper-containing carbonic acid soil test metal is heated to 1000s C 3) into the ^ 1 formula (4) and completely decomposed into barium oxide, then according to the two formulas of the equation & step to barium hydroxide. Therefore, the cathode sheet has the same problems as those produced using the above-mentioned No. 1 emission (ie, no electron porosity is generated, that is, the cathode 7 9 is filled with the electron-emitting material in the conventional technique, and the holes in the sheet are filled. The method cannot be adopted. Next, the present inventor noticed that it was caused by barium carbonate in reaction (4).
4 6 9 4 6 2 五、發明說明(13) 產生二氧化碳氣體。換言之,事實上根據勒沙特列定律 (Le Chatelier’s law) ’若含碳酸鋇粉末混合物之燒結 過程在高壓下執行,不會發生反應(4)。意即含碳酸鋇 粉末混合物受到在特定高壓下燒結約束’燒結出之鎳基合 金沒有分解的含鋇碳酸鹼土金屬。 為了在高壓下施行燒結,本發明者注意到所謂的熱均 壓(HIP)法,係公開發表於1996年二月曰本未審查專利 公報之第8-5 0849號的例子。公開於公報之第8-50849號中 之燒結物體’電子發射材料維持碳酸鹽之形式,所以電子 發射特性經由溼式切割、溼式研磨、清潔與烘乾(3 〇 〇 °C 以下)過程也不會退化。因此,具有燒結物體加工成片時 無嚴格限制條件與片的製造線(manufactUring lines) 容易構成之優點。 公開於公報之第8-50849號中,填入燒結物體孔洞中 的電子發射材料沒有限定是含鎖;5炭酸鹼土金屬。並且’含 鋇碳酸鹼土金屬沒有必要分解成含鋇氧化鹼土金屬。 由於後來的研究’本發明者發現以下的事實: (1 )電子發射材料必須是含鋇碳酸鹼土金屬。 (2 )含鋇碳酸驗土金屬必須分解成含鋇氧化驗土金 屬。 (3)由鋇(Ba)、銘(Sr)和釣(Ca)之共沈殿法 (co-precipitation)所產生的碳酸鹽(亦即,鋇/鹤/鈣 碳酸共沈物)以含鋇碳酸鹼土金屬較佳。鋇、勰和鈣較佳 的莫耳比為鋇:鳃:鈣=(45到65 ) : ( 30到5 0 ) : ( 24 6 9 4 6 2 V. Description of the invention (13) Generate carbon dioxide gas. In other words, according to Le Chatelier's law, in fact, if the sintering process of the barium carbonate-containing powder mixture is performed under high pressure, no reaction will occur (4). This means that the barium carbonate-containing powder mixture is constrained by sintering at a certain high pressure, and the nickel-based alloy sintered is a barium-containing alkaline earth metal containing barium carbonate that does not decompose. In order to perform sintering under high pressure, the present inventors noticed the so-called hot equalizing (HIP) method, which is an example published in February 1996 in Japanese Unexamined Patent Publication No. 8-5 0849. The sintered object disclosed in the bulletin No. 8-50849 'electron-emitting material maintains the form of carbonate, so the electron emission characteristics are also processed through wet cutting, wet grinding, cleaning and drying (below 300 ° C). No degradation. Therefore, there is an advantage that the sintered object is processed into a wafer without strict restrictions and the manufacturing lines of the wafer can be easily constructed. As disclosed in Gazette No. 8-50849, the electron-emitting material filled in the pores of the sintered object is not limited to contain a lock; 5 carbonic acid alkaline earth metal. And the 'barium-containing carbonate alkaline earth metal does not need to be decomposed into a barium-containing oxide alkaline earth metal. As a result of subsequent research, the inventors found the following facts: (1) The electron-emitting material must be a barium carbonate-containing alkaline earth metal. (2) Barium carbonate soil test metal must be decomposed into barium oxide soil test metal. (3) Carbonate (ie, barium / crane / calcium carbonate co-precipitate) produced by co-precipitation of barium (Ba), Sr, and Ca Alkaline earth metals are preferred. The preferred molar ratios for barium, scandium, and calcium are barium: gill: calcium = (45 to 65): (30 to 50): (2
第17頁 4 6 9 46 2 五、發明說明(14) 到15 (4+)含鋇氧化鹼土金屬必需在陰極分解過程中形成 Ϊ t Ϊ蓋於陰極片之發射表面。對此,鋇/錄/鈣氧化共沈 物為較佳的。 如同之前參考於方程式(1)與方程式(2)的解釋, 還原劑必需還原氧化鋇。在公開於上述刊物之第8_5〇849 號技術中’還原劑受到熱均壓約束而與鎳基合金粉末以及 ,子發射材料在一起。然而,卻發現部份的還原劑沒有顯 示出任何所要求的還原作用。這是因為部份還原劑已經在 熱均壓期間與鎳粉末反應,導致彩色陰極射線管上的陰極 片在操作中已經失去作用。為了補償還原作用之弱化,本 發明者發展出含有還原劑供應層於陰極片與片支撐物(例 如’陰極帽(cathode cap ))之間的新結構,並公開於 曰本未審查專利公報之第9-63459號。 公開於日本未審查專利公報之第9-63459號之陰極結 構雖然顯示出所要求之還原反應,卻有製造過程複雜的缺 點。為了排除此點’本發明者繼續研究並且發現含還原劑 之鎳基合金若位於片支撐物與陰極片接觸的部份,由於鎳 基合金含還原劑的關係而發生所要求的反應(1)與(2 )。舉例來說’月支撐物也許本身係由含還原劑的鎳基合 金所製成。若是如此’就能顯示所要求的還原反應,簡化 製造過程。 含還原劑的鏢基合金,最好至少要有一種金屬是從鉻 (Cr )、鈕(Ta )、鉬(Mo )、錘(zr )、鎢)以及 469^62 五、發明說明(15) ------- =3)之组重群量擇百選八出。還原劑對錄合成比較佳的範圍設定 1 ] 重量百刀比(wt% ),因為可以加強雷子於 射、機械以及熱特性。從 ( 。=毛 本的觀"來看,鉻疋最好的並且還原劑對錄較 設定於19到30之重量百分比。 们σ敗 若鉻以,成比範圍從1 9到30之重量百分比之方式混入 鎳基合金,氧化鋇的還原反應就會如以下方程式(5)。 aBaO + ^Cr Ba3(Cr04)2 + rBa (5) 幸運地,由反應(5 )所生成之Bas(Cr〇4)2副產物幾乎 沒有形成任何高電阻之中間層,而不同於由反應(1)與 (2 )所生成的氧化石夕和氧化鎮副產物。因此,幾乎沒有 形成具阻抗之中間層以及中間層之厚度因電子發射材料與 片之間的界面總面積增加而減少數千倍或數萬倍的影響, 導致電子發射效能之降低受到進一步的抑制。 最好於3 0 °C到800 °C的溫度範圍内,將陰極片(亦 即’燒結物體)的熱膨脹係數(亦即,線性膨脹係數)範 園設定於12χ 10-νκ到2〇χ 10-δ/κ。既然如此,將鉻對鎳之 合成比設定於19到30之重量百分比之片支撐物就具有一顯 著優點。這是因為此類型的支撐物於3 〇 °c到8 0 0 t:溫度範 園内具有13. 3 X 10-6/K到15 X 10-6/κ的熱膨脹係數(亦即, 線性膨脹係數),並且幾乎與陰極片的線性膨脹係數相 等。所以’陰極片與片支撐物之間沒有產生熱應力,從而 保證陰極次組件的穩定度與信賴度。 本發明者公開過一種含氧化稀土金屬(例如,氧化Page 17 4 6 9 46 2 V. Description of the invention (14) to 15 (4+) Barium oxide-containing alkaline earth metals must be formed during cathodic decomposition. Ϊ t Ϊ covers the emission surface of the cathode. In this regard, a barium / recording / calcium oxide coprecipitate is preferred. As explained earlier with reference to equations (1) and (2), the reducing agent must reduce barium oxide. In the technique disclosed in the above-mentioned publication No. 8_5 0849, the 'reducing agent is constrained by the heat equalizing pressure and is together with the nickel-based alloy powder and the subemissive material. However, it was found that some of the reducing agents did not show any required reduction. This is because part of the reducing agent has reacted with the nickel powder during the hot equalization, causing the cathode sheet on the color cathode ray tube to have lost its effect during operation. In order to compensate for the weakening of the reduction effect, the present inventors developed a new structure containing a reducing agent supply layer between the cathode sheet and the sheet support (such as a 'cathode cap') and disclosed in Japanese Unexamined Patent Publication No. 9-63459. Although the cathode structure disclosed in Japanese Unexamined Patent Publication No. 9-63459 shows a required reduction reaction, it has a drawback that the manufacturing process is complicated. In order to eliminate this point, the present inventors continued to study and found that if the nickel-based alloy containing the reducing agent is located at the portion where the sheet support is in contact with the cathode sheet, the required reaction occurs due to the relationship between the nickel-based alloy containing the reducing agent (1) With (2). For example, the moon support may itself be made of a nickel-based alloy containing a reducing agent. If so ', the required reduction reaction can be displayed and the manufacturing process can be simplified. Dart-based alloys containing reducing agents, preferably at least one metal is from chromium (Cr), button (Ta), molybdenum (Mo), hammer (zr), tungsten) and 469 ^ 62 5. Description of the invention (15) ------- = 3) Choose a group of eight out of 100. The setting range of the reducing agent for recording and synthesis is better. 1] Weight-to-blade ratio (wt%), because it can enhance the radiation, mechanical and thermal characteristics of the lightning. From the point of view of (. = Maoben), chromium is the best and the reducing agent ratio is set at a weight percentage of 19 to 30. We σ are worse than chromium, and the proportion ranges from 19 to 30 weight When mixed into nickel-based alloys as a percentage, the reduction reaction of barium oxide will be as shown in the following equation (5): aBaO + ^ Cr Ba3 (Cr04) 2 + rBa (5) Fortunately, Bas (Cr generated by reaction (5) 〇4) 2 The by-product hardly forms any high-resistance intermediate layer, which is different from the oxide stone and oxide town by-products generated by reactions (1) and (2). Therefore, almost no intermediate layer with resistance is formed. And the thickness of the intermediate layer is reduced by thousands of times or tens of thousands of times due to the increase in the total area of the interface between the electron-emitting material and the sheet, resulting in further reduction in the reduction of the electron emission efficiency. It is best to be 30 ° C to 800 In the temperature range of ° C, the thermal expansion coefficient (that is, the linear expansion coefficient) of the cathode sheet (that is, the sintered object) is set to 12χ 10-νκ to 2χ 10-δ / κ. In this case, we will Chromium-to-nickel composite ratio set at 19 to 30 weight percent It has a significant advantage. This is because this type of support has a thermal expansion coefficient of 13. 3 X 10-6 / K to 15 X 10-6 / κ in the temperature range ( That is, the coefficient of linear expansion), and it is almost equal to the coefficient of linear expansion of the cathode sheet. Therefore, 'there is no thermal stress between the cathode sheet and the sheet support, thereby ensuring the stability and reliability of the cathode sub-assembly. By a rare earth oxide-containing metal (for example, oxidized
第19頁 ^ S 9 46 2 五、發明說明(16) 航’SqO3)之陰極片於上述公報之第8_5〇849號中β更進 一步在1 9 99年二月公開一種生產燒結物體之方法並發表於 曰本未審查專利公報之第1 1 -400 46號,即是把鎳粉末與氧 化稀土金屬粉末一起均勻混合,混合物並於氫氣(η2 )氛 圍中加”、、電子發射材料混於混合物中因而受熱,並且含 有電子發射材料之混合物受到熱均壓約束,因此形成了燒 結物體。此處,本發明者公開以下這兩種未曾公開之新結 果發表。 特別地,當氧化銃(Sc2〇3 )從許多氧化稀土金屬擇選 出時’氧化鏡對全部之電子發射材料粉末與鎳粉末,較佳 的混合比範圍是從1到7之重量百分比(w t % ^此限制與 陰極分解過程中’陰極片上的發射表面形成一2〇微米到 150微来厚之電子發射材料緊緊相關。以下是詳細的 釋0 、,在陰極分解過程之前,陰極片之發射表面如鏡子表面 般平坦並且無膜位於其上。分解過程期間,多孔隙片中之 電子發射材料(例如,鋇/锶/鈣之氧化共沈物)經由孔洞 從發射表面滲出。當分解過程完成時,發射表面係 層電子發射枯料膜。 本發明者發現發射表面上形成之電子發射材料膜與加 入陰極片中之氧化钪總量幾乎呈反比。此項新結果並未公 開於上述公報第8_5〇849與H—40 046號中以及其他發表或^ 文件。若氧化銃總量少於% ,發射材料膜的厚度會1 於150微米;若氧化釩總量多於7wt% ,發射材料膜的厚度Page 19 ^ S 9 46 2 V. Description of the invention (16) The cathode sheet of the aircraft (SqO3) was published in the above-mentioned bulletin No. 8_5〇849. Β further disclosed in February 1999 a method for producing sintered objects and Published in Japanese Unexamined Patent Publication No. 1 1-400 46, that is, nickel powder and rare earth oxide powder are uniformly mixed together, the mixture is added in a hydrogen (η2) atmosphere, and the electron emitting material is mixed into the mixture. Therefore, the mixture containing the electron-emitting material is constrained by the heat equalizing pressure, thereby forming a sintered body. Here, the present inventors have disclosed the following two unpublished new results. In particular, when scandium oxide (Sc20 3) When selected from many rare earth oxide metals, 'The best mixing ratio range for oxide mirrors for all electron-emitting material powders and nickel powders is from 1 to 7 weight percent (wt% ^ This limitation is in the process of cathode decomposition') The emission surface on the cathode sheet forms an electron-emitting material with a thickness of 20 micrometers to 150 micrometers. The following is a detailed explanation. Before the cathode decomposition process, the emission of the cathode sheet is closely related. The surface is as flat as a mirror surface with no film on it. During the decomposition process, electron-emitting materials in the porous sheet (eg, barium / strontium / calcium oxide co-precipitates) seep from the emitting surface through the holes. When the decomposition process is complete At the time, the emitting surface layer is an electron-emitting dry film. The inventors found that the film of the electron-emitting material formed on the emitting surface is almost inversely proportional to the total amount of thorium oxide added to the cathode sheet. 8_5〇849 and H-40 046 and other published or ^ documents. If the total amount of hafnium oxide is less than%, the thickness of the emissive material film will be 1 to 150 microns; if the total amount of vanadium oxide is more than 7wt%, the emissive material film thickness of
第20頁 4 6 9 4t> ^Page 20 4 6 9 4t > ^
五、發明說明(17) 於20微米。當發射材料膜厚度大於15〇微米時,片中 電子難以朝膜外發射而減少電子發射。當發射材 =:厚度小於20微米時,發射表面所產生的電子數量少或 ’同樣地減少電子發射。因此,將氧化銃總量設定於 1 ^ ^ i到7耐%的範圍所得到的發射材料膜厚為20微米到 Ϊ50微米是最好的。 陰極片之發射表面之表面粗糙度(In )最好設定於3 下。意即發射表面可以反射,換言1,大體上為一 拋光鏡面。此會產生以下的優點。 燒結物體具有鎳的微格(minute grid_like)結構, ίΐΐϋ中填有發射材料與氧化銳。此燒結物體被切片或 Γΐΐί形狀與尺寸’從而形成陰極片。由於鍊是硬金 2 物體剖面圖傾向形成所謂的凹陷,覆蓋一部份 :區二因此,填入發射材料與氧化銃的孔洞覆蓋於凹陷 冰叔=二况Γ、’縱使發射材料(例如,鋇/锶/鈣之氧化共 二矣$恭t解過程期間分解,分解的發射材料也不能從發 電子。,即發射材料臈無法形成於整個表面上 磨至3微乎從以發下射的表:徹底移除凹陷。可將片的發射表面研 愿主~ 3獨^水以下的表^面ϊέΡ I、》Αλ 1 J衣回祖糙度以解決這個問題。 極片之;二末對鎳粉末之適當重量比乃決定於陰 Ϊ = 以及燒結物體之機械強度。特別地, ,丨、道& ϋ i里過少,易明瞭地,發射電子數目就 ’導致電子發射啟能柄 。 I過多,組&I& g M 另一方面,若發射材料粉末總 •多、成格構之鎳顆粒總量就不足,導致燒結物體5. Description of the invention (17) is at 20 microns. When the thickness of the emissive material film is greater than 15 micrometers, it is difficult for the electrons in the sheet to emit toward the outside of the film and reduce the electron emission. When the emitter =: thickness is less than 20 micrometers, the number of electrons generated from the emitting surface is small or the electron emission is likewise reduced. Therefore, it is best to set the total thickness of the erbium oxide in the range of 1 ^^ i to 7% resistance to a film thickness of 20 micrometers to Ϊ50 micrometers. The surface roughness (In) of the emission surface of the cathode sheet is preferably set to 3 or less. This means that the emitting surface is reflective, in other words, approximately a polished mirror surface. This has the following advantages. The sintered object has a minute grid_like structure of nickel, which is filled with an emissive material and an oxide sharp. This sintered object is sliced or shaped to form a cathode sheet. Because the chain is hard gold2, the cross-sectional view of the object tends to form a so-called depression, covering a part: area two. Therefore, the hole filled with the emitting material and thorium oxide covers the depression. The oxidation of barium / strontium / calcium has a total amount of 矣 2. It is decomposed during the solution process, and the decomposed emissive material cannot emit electrons. That is, the emissive material can not be formed on the entire surface. Table: The depression is completely removed. The emission surface of the film can be applied to the surface of the surface ~ 3 ^ 水 ϊ Ρ Ρ Ρ I, I, Αλ 1 J clothing ancestral roughness to solve this problem. The appropriate weight ratio of the nickel powder is determined by the yin Ϊ = and the mechanical strength of the sintered object. In particular, 、, 道, &; ϋ i are too small, and it is easy to understand that the number of emitted electrons will cause the electron emission energizing handle. I Too much, the group & I & g M On the other hand, if the total amount of powder of the emitting material is large, the total amount of nickel particles in the lattice structure is insufficient, resulting in sintered objects
第21頁 469^6 2-Page 21 469 ^ 6 2-
五、發明說明(18) _ 機械強度不足以形成陰極片。者磨々 末對鎳粉末的重量比最好在4〇 t ^ : ’發射材料粉 錄粉末與電子發射材;=到9/:t%範圍之中。 物)粉末之適當平均粒徑乃決& f t鈣之碳酸共沈 及格狀結構之孔洞尺寸4Ϊ:於度以 大’燒結:體之格結構較粗糙因而機械強低。 此,機械製造過程就難以得到所要形狀與尺寸之如 若鎳粉末平均粒徑過小,燒結物體之格結構較緊;因 法提供電子發射。考慮這”射材料無 u微来到9微米範圍之^事實鎳粉末平均粒徑最好在 為了改良電子發射特性,鋇/鋰/鈣之碳酸共沈物 平均粒徑最好近似於鎳顆粒。其理由如禾5. Description of the invention (18) _ The mechanical strength is not sufficient to form a cathode sheet. The weight ratio of the ground powder to the nickel powder is preferably in the range of 40 t ^: ′ emitting material powder and electron emitting material; = to 9 /: t%. The appropriate average particle size of the powder is determined by the co-precipitation of calcium carbonate and the pore size of the lattice structure 4Ϊ: Larger than the degree sintering: The lattice structure of the body is rough and the mechanical strength is low. Therefore, it is difficult to obtain the desired shape and size in the mechanical manufacturing process. If the average particle diameter of the nickel powder is too small, the lattice structure of the sintered object is tight; therefore, electron emission is provided. Considering the fact that the radioactive material is not in the range of 9 micrometers, the fact that the average particle diameter of the nickel powder is preferably in order to improve the electron emission characteristics, and the average particle diameter of the barium / lithium / calcium carbonate co-precipitate is preferably similar to the nickel particles. The reason
II
孔洞尺寸係近似於鎳粉末平均粒徑。因此,若鋇/ 鈣之碳酸共沈物粉末平均粒徑近似於鎳顆粒平均粒徑" 入孔洞的鋇/鏍/鈣之碳酸共沈物顆粒不會太多亦不會太 ;。,有利於排除在鋇/鳃/鈣之碳酸共沈物顆粒中所產生 異常晶體應力。導致鋇/鳃/鈣之碳酸共沈物粉末平均粒俨 最好在0.9微米到7微米範圍之中D 對本發明來說’從四幾基鎮(nickel carbonyl)中 以所謂的「羰基法(carb〇nyi ffletho(i)」(或稱為熱分 解法)所生成的鎳粉末最好。「四羰基鎳」這字另一名稱 係Ni(CO)4 ’由鎳與一氧化碳(c〇)反應於溫度42〇κ以下 所生成《由於溫度453Κ以上四羰基鎳會分解成鎳與—氣化The pore size is approximate to the average particle diameter of nickel powder. Therefore, if the average particle size of the barium / calcium co-precipitate powder is similar to the average particle size of nickel particles, the barium / 钡 / calcium co-precipitate particles into the pores will not be too much or too large. It is beneficial to exclude the abnormal crystal stress generated in the barium / gill / calcium carbonate precipitates. The average particle size of the barium / gill / calcium carbonate coprecipitate powder is preferably in the range of 0.9 micrometers to 7 micrometers. D For the present invention, from the nickel carbonyl, the so-called "carb method 〇nyi ffletho (i) ”(also called thermal decomposition method) is the best nickel powder. Another name for the word“ nickel tetracarbonyl ”is Ni (CO) 4 'which is reacted by nickel with carbon monoxide (c). When the temperature is below 42 ° K, the tetracarbonyl nickel will be decomposed into nickel and-gasification due to the temperature above 453K.
第22頁 469 Αδ 2 五、發明說明(19) 碳,所以天然鎳以此反應生產高純度鎳。羰基法已經被廣 泛使用於此目的。所生成的高純度鎳被稱作「羰鎳」。根 據本發明者的研究,羰鎳粉末最好以電子發射能力與特性 的觀點來看,理由未曾完全明瞭過。然而,從一氧化碳中 所產生留下的碳(C),被認為是鎳中的雜質並且影響到 電子發射能力。 由於以下的理由,燒結物體密度最好在理論密度(假 定燒結物體不.含孔洞下所計算& )的82 %以上。 若燒結物體的密度低於理論密度的82% ,鎳之格結構 不具有足夠的機械強度,因而燒結物體無法具有所要尺 寸。此外’密度量測方便於檢視燒結過程是否正常地完成 於熱均壓法。 下文特舉一較佳實施例’並配合所附圖式2到7,作詳 細說明如下: 第2圖展示出根據本發明之實施例所設計於彩色陰極 射線管中,内含陰極次组件之陰極。 如第2圖所示’陰極1〇包括:近似於圓柱狀的陰極套 管14 '以焊接固定於套管14上方之帽狀片支撐物12以及以 焊接固定於片支撐物12之圓盤狀陰極片^。陰極片η完全 下壓於片支撐物1 2。根據本發明之實施例,由陰極片1 1、 片支撐物12以及陰極套管丨4絚成一陰極次組件19 ^ 陰極片11形成於鎳粉末、氧化銃粉末以及電子發射材 料粉末之混合物所製成的燒結物體。特別地,這三種粉末 均勻地混合成特殊粉體或粉混合物。形成的粉體或混合Page 22 469 Αδ 2 V. Description of the invention (19) Carbon, so natural nickel uses this reaction to produce high-purity nickel. The carbonyl method has been widely used for this purpose. The resulting high-purity nickel is called "nickel carbonyl". According to the research by the present inventors, it is preferable that the nickel carbonyl powder is not completely understood from the viewpoint of electron emission ability and characteristics. However, the carbon (C) remaining from carbon monoxide is considered an impurity in nickel and affects the electron emission ability. For the following reasons, the density of the sintered object is preferably more than 82% of the theoretical density (assuming that the sintered object does not contain & calculated with holes). If the density of the sintered object is lower than 82% of the theoretical density, the lattice structure of nickel does not have sufficient mechanical strength, so the sintered object cannot have the required size. In addition, the 'density measurement is convenient to check whether the sintering process is normally performed by the hot equalizing method. In the following, a preferred embodiment is specifically described, and it is described in detail in conjunction with the attached drawings 2 to 7: FIG. 2 shows a color cathode ray tube designed according to an embodiment of the present invention, which contains a cathode subassembly cathode. As shown in FIG. 2, “cathode 10 includes a cathode casing 14 that is approximately cylindrical” and a cap-shaped sheet support 12 fixed to the top of the tube 14 by welding and a disc shape fixed to the sheet support 12 by welding. Cathode sheet ^. The cathode sheet η is completely pressed against the sheet support 12. According to the embodiment of the present invention, the cathode sheet 11, the sheet support 12 and the cathode sleeve 4 are formed into a cathode subassembly 19 ^ The cathode sheet 11 is formed of a mixture of nickel powder, hafnium oxide powder and electron emission material powder Into a sintered object. In particular, these three powders are uniformly mixed into a special powder or powder mixture. Formed powder or mix
第23頁 469 厶6 2 五、發明說明(20) 物’以熱均壓法燒結成一燒結物體。之後,燒結物體受到 適當的機械製造加工,因而形成陰極片U。因為适原因, 陰極片11具有類似於鎳之格結構之多孔隙結構並且有許多 微小孔洞在裡面。孔洞被填入氧化銃與電子發射材料。陰 極片Π具有展示於第一圖中陰極70習知技術之陰極基底71 的功用。 由含主成份錄以及至少一種從鉻、組、翻、結、鶴與 鈷組群擇選出的金屬合金所製成之片支撐物12,用以作^ 電子發射材料的還原劑。 固定於套管14内之加熱器15是用來加熱陰極次組件 19 加熱器1 5之結構與一般氧化陰極所用的相同 包括根據本發明之上述結構之陰極次組件丨9在内,陰 極片11具有多孔隙或格結構或組織並且陰極片j ^中之孔洞 17填有發射材料與氧化叙。因&,發射材料與陰極片η之 丄= 大大地增加。同時,形成於每單位界面面積 之中間層厚度大大地減少。 =二次組件79習知技術,中間I (未展示於圖中) f細作期間形成於發射材料與陰極片u之間的界面。缺 積增加’每單位面積之中間層厚度大:地 間二Ui在i於1A/cm2之高操作電流密度時,中 不會加速發生。同樣地,氧化銃被填入 到拙岳丨 巾間層形成。因此,中間層之形成本身可受 2抑:。於疋,就彩色陰極射之 …子發射能力(亦即,發射率…在上Page 23 469 厶 6 2 V. Description of the invention (20) The object 'is sintered into a sintered body by a hot equalizing method. Thereafter, the sintered object is subjected to appropriate mechanical manufacturing processing, thereby forming a cathode sheet U. For proper reasons, the cathode sheet 11 has a porous structure similar to the lattice structure of nickel and has many minute holes therein. The holes are filled with hafnium oxide and an electron-emitting material. The cathode sheet Π has the function of the cathode substrate 71 shown in the conventional technique of the cathode 70 shown in the first figure. A sheet support 12 made of a main component and at least one metal alloy selected from the group consisting of chromium, group, turn, knot, crane and cobalt is used as a reducing agent for the electron emitting material. The heater 15 fixed in the sleeve 14 is used to heat the cathode sub-assembly 19. The structure of the heater 15 is the same as that used for a general oxidation cathode, including the cathode sub-assembly according to the above structure of the present invention. It has a multi-porous or lattice structure or organization and the holes 17 in the cathode sheet ^ are filled with emitting materials and oxides. Because of &, 丄 = of the emitting material and the cathode η is greatly increased. At the same time, the thickness of the intermediate layer formed per unit interface area is greatly reduced. = Secondary component 79 conventional technology, intermediate I (not shown in the figure) f is the interface formed between the emitting material and the cathode sheet u during the fine work. The increase in the defect 'has a large thickness of the intermediate layer per unit area: when the ground Ui is at a high operating current density of 1A / cm2, the middle does not accelerate. Similarly, dysprosium oxide was filled into Zhuo Yue and the interstitial layer was formed. Therefore, the formation of the intermediate layer itself can be affected by 2:. Yu Xun, the color cathode radiates ... the sub-emission capability (that is, the emissivity ... above
五、發明說明(21) 作電流密度下幾乎都沒有降低。 此外’電子發射機制與一般氧化陰極相同,維持了活 化時間短以及操作溫度低的優點。 ' 至少一種從鉻、鈕、鉬、錯 '鎢與钴組群擇選出的金 屬於片支樓物12材料組成部分中,用以作為發射材科的還 原劑。因此’填入孔洞丨7之發射材料加速還原反應,提供 一優良電子發射特性於簡化的製造過程。 至少一種從鉻、鈕、鉬、鍅、鎢與鈷組群擇選出的金 屬’不會形成具有阻抗之中間層於電子發射材料之還原反 應期間。因此,電子發射能力或發射率之降低可以被進一 步抑制。 較佳地,形成之陰極片11是用發射材料粉末對錄粉末 之重量比設定於40 %到9 6 %範圍中的方式所產出的燒結物 體’鎳粉末的平均粒徑設定於〇·8微米到9微米範圍之中, 且銻粉末係由羰基法分解四羰基鎳所產生。既然如此,就 能達到優良的電子發射特性。同時,保證燒結物體於生產 陰極片的機械製造加工中具有高機械強度。 陰極片11密度最好在理論密度的82%以上,因為低於 理論密度的82%以下沒有足夠的機械強度。 較佳地’陰極片11熱膨脹係數(亦即,線性膨脹係數 )範圍乃設定於12x 1〇-6/£到2〇>< 10-VK。若陰極片^熱膨 脹係數於此範圍内’就會與片支撐物12幾乎相等,因而抑 制陰極片11與片支稽·物;[2間之熱應力。因此,可保證次組 件1 9之穩定度與信賴度。V. Description of the invention (21) There is almost no decrease in operating current density. In addition, the electron emission mechanism is the same as that of a general oxidation cathode, and the advantages of short activation time and low operating temperature are maintained. 'At least one kind of gold selected from the group consisting of chromium, button, molybdenum, tungsten and tungsten is a material component of the 12 branch materials and is used as a reducing agent for the family of emitting materials. Therefore, the emissive material filled in the holes 7 accelerates the reduction reaction and provides an excellent electron emission characteristic in a simplified manufacturing process. At least one metal selected from the group consisting of chromium, button, molybdenum, thorium, tungsten, and cobalt 'will not form an intermediate layer having an impedance during the reduction reaction of the electron-emitting material. Therefore, a reduction in electron emission ability or emissivity can be further suppressed. Preferably, the formed cathode sheet 11 is an average particle diameter of a sintered object 'nickel powder produced by setting the weight ratio of the emitting material powder to the recording powder in the range of 40% to 96%, set to 0.8. In the range of micrometers to 9 micrometers, antimony powder is generated by the decomposition of nickel tetracarbonyl nickel by the carbonyl method. In this case, excellent electron emission characteristics can be achieved. At the same time, it ensures that the sintered object has high mechanical strength in the mechanical manufacturing process of producing the cathode sheet. The density of the cathode sheet 11 is preferably more than 82% of the theoretical density because the mechanical density is not sufficient below 82% of the theoretical density. Preferably, the range of the coefficient of thermal expansion (i.e., the coefficient of linear expansion) of the 'cathode sheet 11 is set to 12x10-6 / £ to 20 > < 10-VK. If the thermal expansion coefficient of the cathode sheet is within this range, it will be almost equal to the sheet support 12, thereby suppressing the thermal stress between the cathode sheet 11 and the sheet support [2]. Therefore, the stability and reliability of the subassembly 19 can be guaranteed.
第25頁 469462 五、發明說明(22) 片支樓物12之合金中,至少一種從鉻、钽、鉬、锆、 鎢與鈷組群擇選出的金屬對鎳之重量比最好設定於丨% "到 33%範圍中。既然如此,就可保證電子發射、機械以及熱 特性》特別地,因鉻之獲取成本低而選擇鉻。鉻對鎳之重 量比最好設定於19%到30%範圍中。 、 電子發射材料粉末,最好使用鋇、鳃與鈣之共沈物 (亦即,鋇/鳃/鈣碳酸共沈物)所產生之碳酸鹽^。既 然如此’礙酸鹽粉末平均粒徑最好在〇. 9微米到7微米的範 圍中,近似於錄粉末平均粒徑。額外的優點係填入孔洞1 7 的,射材料不會太多也不會太少,致使發射材料不會發生 異常應力’而提供了優良電子發射特性。另外地,既然如 此’鎖、錄與鈣之莫耳比最好分別是:鋇從45到65 ; &從 30到50 ;鈣從2到1 5 (亦即,鋇:鳃:鈣=(45-65 ): ^30 50) : (2-15))。這是因為展示於第3圖中,由電 子發射材料所製造的膜23容易在陰極分解過程之後成形於 陰極片11之發射表面13。 如同以上解釋,燒結物體經機械加工所形成之陰極片 11具有特殊形狀’卻也因而在陰極片U發射表面13形成鎳 所造成之凹陷(未示於圖中)。由於鎳凹陷通常覆蓋於表 面13 ’表面13上的孔洞17緊密而阻止發射材料向外發射。 為解決此問題並促進發射材料膜23之形成’最好將表面13 之表面粗糙度(Rnax )研磨至3微米以下’從而除去凹陷。 / 為了強化電子發射能力,膜23厚最好是20微米到150 微米。若厚於150微米’陰極片11内部所產生的電子難以Page 25 469462 V. Description of the invention (22) Among the alloys of the supporting structure 12, at least one metal selected from the group consisting of chromium, tantalum, molybdenum, zirconium, tungsten and cobalt is preferably set to 丨% &Quot; to 33%. In this case, the electron emission, mechanical and thermal characteristics can be guaranteed. In particular, chromium is selected because of its low acquisition cost. The weight ratio of chromium to nickel is preferably set in the range of 19% to 30%. For the electron-emitting material powder, it is best to use the carbonate produced by barium, gill and calcium coprecipitate (ie, barium / gill / calcium carbonate coprecipitate ^). Even so, the average particle diameter of the hindering acid powder is preferably in the range of 0.9 to 7 m, which is similar to the average particle diameter of the powder. An additional advantage is that the holes 17 are filled in, and there is not too much or too little emitter material, so that the emitter material does not undergo abnormal stress' and provides excellent electron emission characteristics. In addition, in this case, the molar ratios of lock, record, and calcium are preferably: barium from 45 to 65; & from 30 to 50; calcium from 2 to 1 5 (that is, barium: gill: calcium = ( 45-65): ^ 30 50): (2-15)). This is because, as shown in FIG. 3, the film 23 made of an electron-emitting material is easily formed on the emission surface 13 of the cathode sheet 11 after the cathode decomposition process. As explained above, the cathode sheet 11 formed by the sintered object by machining has a special shape ', but thus also forms a depression (not shown) caused by nickel on the cathode sheet U emitting surface 13. Since the nickel depressions usually cover the holes 17 on the surface 13 ', the emitting material is prevented from emitting outwardly. In order to solve this problem and promote the formation of the emissive material film 23 ', it is preferable to grind the surface roughness (Rnax) of the surface 13 to 3 m or less' to remove the depression. / In order to enhance the electron emission ability, the thickness of the film 23 is preferably 20 to 150 microns. If it is thicker than 150 microns, it is difficult to generate electrons inside the cathode sheet 11.
第26頁 4 6 9 46 2 五、發明說明(23) 穿透膜23到外界’而減少電子發射數量。另一方面,若薄 於20微米,表面13所產生的雷子數詈; 座王刃电于聚里不足,同樣會減少電 子發射數量。 陰極片11中,燒結物體内的氧化敍粉末對結合發射材 料與錄粉末之重量比在1%到7%範圍中,可使膜23 到 20微米到150微米。 實施例: 本發明者確實地依據本發明.生產陰極片丨丨 於下列方法中。 b 首先,生產陰極片11於下列步驟(J )到(4 ) ·· (1)提供平均粒徑為5微米之錄粉末,以及由鋇、錄 ,鈣共沈物所產生的碳酸鹽(亦即,鋇/鏍/鈣碳酸共沈物 '分末)’其平均粒徑為1微米到2微米且鋇:鳃:妈之莫耳 ,,5〇 : 40 : 1〇。一起均勻混合1〇〇公克之鎳粉末、6公克 化銃粉末以及6〇公克之鋇/鏍/鈣碳酸共沈物粉末,形 成一粉末混合物。 (2 )粉末混合物於室溫中受壓力成形加工約束,而 形成—塑形體。 被拙(3)將成形之塑形體置入玻璃容器’容器内之空氣 離扣離而形成特殊真空氛圍。容器壓力設定於1〇_4 pa。抽 =體同時,在5〇 0艺左右,將存在於塑形體與容器中之 乳體除去。 結 (4 )將内含塑形體之容器置入熱均壓機做燒結’燒 u件為最高壓設在15〇 MPa,最高溫設在1100 °C,且於Page 26 4 6 9 46 2 V. Description of the invention (23) Penetrating the film 23 to the outside world 'and reducing the number of electron emission. On the other hand, if it is thinner than 20 microns, the number of thunders generated on the surface 13 will be 詈; the lack of electricity for the king blade will also reduce the number of electrons emitted. In the cathode sheet 11, the weight ratio of the oxide powder to the combined emission material and recording powder in the sintered object is in the range of 1% to 7%, and the film can be 23 to 20 microns to 150 microns. Example: The present inventors did according to the present invention to produce a cathode sheet in the following method. b First, the cathode sheet 11 is produced in the following steps (J) to (4) .... (1) Provide a powder with an average particle size of 5 microns, and a carbonate (also That is, the barium / gadolinium / calcium carbonate co-precipitate 'minutes)' has an average particle diameter of 1 micrometer to 2 micrometers and barium: gill: mother's mole, 50: 40: 10. 100 g of nickel powder, 6 g of hafnium powder, and 60 g of barium / rhenium / calcium carbonate coprecipitate powder were uniformly mixed together to form a powder mixture. (2) The powder mixture is constrained by pressure forming processing at room temperature to form a plastic body. (3) The formed plastic body is placed in a glass container ’and the air is released from the container to form a special vacuum atmosphere. The vessel pressure was set at 10-4 Pa. At the same time, the breasts in the plastic body and the container were removed at about 500 times. (4) Put the container containing the plastic body into a hot equalizer for sintering. The highest pressure is set to 15 MPa, the highest temperature is set to 1100 ° C, and
4.69 46 2 五、發明說明(24) 最高溫持溫30分鐘。 燒結過程中’只有錄粉末被實際地燒結成含有許多孔 洞1 7的格結構。氧化銳粉末以及鋇/勰/鈣碳酸共沈物粉末 未被燒結並留存於鎳結構之孔洞i 7。形成之孔洞1 7彼此互 通’因此稱作「開放孔」。存在於孔洞1 7之物質或物體可 在相鄰孔洞1 7之間移動或流動並且到達燒結物體的表面。 燒結過程期間,由於以上所述之高壓(亦即,最高壓丨5 〇 MPa )供於燒結物體上,鋇/鋰/鈣碳酸共沈物粉末不可能 分解成鋇/勰/鈣氧化物。 (5) 熱均壓機冷卻後,從機器取出容器,再由容器 中取出燒結物體。此燒結物體的密度為理論密度之85%且 室溫之線性膨脹係數為1 3. 0 X ΙΟ-6/K、100 t:時為13. 5 X 10_6/K、20 0 °C 時為 13. 6 X 1 0-6/K、5 0 0 °C 時為 15. 5 X 10-VK 以及80 0 °C 時為 18. 0 X ΙΟ-6/κ。 (6) 燒結物體以鑽石刀切成片,形成厚度為〇.5釐米 之薄片。切片過程係使用本發明者於1 997年公開發表於曰 本未審查專利公報之第9-14 7742號中之方法。每一薄片表 面用鑽石漿料研磨’所形成的研磨薄片厚度為0.22釐米且 表面粗糖度為1微米。然後’每個研磨薄片以黏結碳化物 所製成之金屬打孔模具打孔成型,形成直徑為1.1釐米, 厚度0· 22釐米之圓盤狀陰極片11。 接著’陰極10之製造係使用其中一種製造陰極片11的 方式。另一方面,50微米厚的鎳鉻合金盤(鎳:80 wt % ’絡·20 wt% )受到抽拉加工,形成一内徑1.1釐米且4.69 46 2 V. Description of the invention (24) The highest temperature is kept for 30 minutes. During the sintering process, only the recording powder is actually sintered into a lattice structure containing many holes 17. The oxidized sharp powder and the barium / rhenium / calcium carbonate coprecipitate powder were not sintered and remained in the holes i 7 of the nickel structure. The formed holes 17 communicate with each other 'and are therefore called "open holes". The substance or object existing in the holes 17 can move or flow between adjacent holes 17 and reach the surface of the sintered object. During the sintering process, the barium / lithium / calcium carbonate co-precipitate powder cannot be decomposed into barium / rhenium / calcium oxide due to the high pressure (i.e., the highest pressure 500 MPa) supplied to the sintered object as described above. (5) After the heat equalizer has cooled down, remove the container from the machine and remove the sintered object from the container. The density of this sintered object is 85% of the theoretical density and the linear expansion coefficient at room temperature is 1 3. 0 X IO-6 / K, 100 t: 13. 5 X 10_6 / K, 13 at 20 0 ° C 6 X 1 0-6 / K, 15. 5 X 10-VK at 500 ° C, and 18. 0 X ΙΟ-6 / κ at 80 ° C. (6) The sintered object is cut into pieces with a diamond knife to form a sheet having a thickness of 0.5 cm. The slicing process uses a method publicly published by the present inventor in Japanese Unexamined Patent Publication No. 9-14 7742 in 1997. The surface of each sheet was ground with diamond slurry 'to form an abrasive sheet having a thickness of 0.22 cm and a surface coarseness of 1 micron. Then, each of the abrasive flakes was punched with a metal punching mold made of cemented carbide to form a disc-shaped cathode sheet 11 having a diameter of 1.1 cm and a thickness of 0.22 cm. Next, the cathode 10 is manufactured by using one of the methods for manufacturing the cathode sheet 11. On the other hand, a 50-micron-thick nickel-chromium alloy disc (nickel: 80 wt% ′ and 20 wt%) was subjected to drawing processing to form an inner diameter of 1.1 cm and
第28頁 ^69462 五、發明說明(25) 深為0 · 2釐米之帽狀金屬部份。此金屬部份用作片支撐物 12。此外’50微米厚的鎳鉻合金盤(鎳:80wt % ,鉻: 20 wt % )受到另一抽拉加工,形成一内徑1. 2釐米到2釐 米且長度為8釐米之圓柱金屬部份。此金屬部份則用作套 管14。 陰極1 0係由以下方法組裝。 首先’將陰極片11置入片支撐物12内。然後,將含有 陰極片11之片支撐物12置入套管14頂端。套管14頂端受到 焊接加工的阻力影響,從而固定陰極片11與片支撐物12於 套管頂端。因此,陰極次組件1 9組裝完成。 最後,將加熱器15經由底端置入於套管14。因此,展 示於第2圖之陰極10結構就此完成。 跟隨此步驟,以一般方法將陰極10裝設於彩色射線 管’然後根據展示於第4圖中,一般分解過程之特殊溫度 量變曲線分解陰極片11約五分鐘。經由分解過程,陰極片 11中之鋇/錯/妈破酸共沈物因受熱而分解,產生鎖/錄/弼 氧化物。部份鋇/鑛/約氧化物經由陰極片11之微孔1 7漸漸 地從發射表面13發射。導致,由鋇/魏/釣氧化物所製成且 厚為50微米的膜23,形成於表面13上,如第3圖所示。 在此階段,先前所述之反應(5)並沒有充分進行, 因此’少許的電子發射被觀測到。然後,陰極片1 1分解乃 受到1 0 8 0 °C,1 5分鐘之活化過程影響從而加逮反應(5 )。導致產生充足之低功函數鋇原子並觀測到充足的電子 發射。觀測到結果展示於第5圖與第6圖。Page 28 ^ 69462 V. Description of the invention (25) A hat-shaped metal part with a depth of 0.2 cm. This metal portion is used as a sheet support 12. In addition, a 50-micrometer-thick nickel-chromium alloy disc (nickel: 80wt%, chromium: 20wt%) was subjected to another drawing process to form a cylindrical metal portion having an inner diameter of 1.2 cm to 2 cm and a length of 8 cm . This metal part is used as the sleeve 14. The cathode 10 is assembled by the following method. First, the cathode sheet 11 is placed in a sheet support 12. Then, a sheet support 12 containing the cathode sheet 11 is placed into the top end of the sleeve 14. The top end of the sleeve 14 is affected by the resistance of the welding process, so that the cathode sheet 11 and the sheet support 12 are fixed to the top end of the sleeve. Therefore, the cathode subassembly 19 is assembled. Finally, the heater 15 is inserted into the sleeve 14 via the bottom end. Therefore, the structure of the cathode 10 shown in FIG. 2 is completed. Following this step, the cathode 10 is installed in a color ray tube by a general method, and then the cathode sheet 11 is decomposed for about five minutes according to the special temperature variation curve of the general decomposition process shown in Fig. 4. Through the decomposition process, the barium / wrong / macroacid co-precipitate in the cathode sheet 11 is decomposed due to heat, resulting in lock / record / tritium oxide. Part of the barium / mineral / approximate oxide is gradually emitted from the emission surface 13 through the micropores 17 of the cathode sheet 11. As a result, a film 23 made of barium / Wei / fishing oxide and having a thickness of 50 m is formed on the surface 13, as shown in FIG. At this stage, the reaction (5) described earlier did not proceed sufficiently, so 'a little electron emission was observed. Then, the decomposition of the cathode sheet 11 was affected by the activation process at 1080 ° C for 15 minutes to increase the trapping reaction (5). As a result, sufficient low work function barium atoms were generated and sufficient electron emission was observed. The observed results are shown in Figures 5 and 6.
第29頁 4 6 9 46 2 ----------- 五、發明說明(26) " — 第5圖展示出陰極次組件79習知技術以及本發明之陰 極次組件的初始發射電流特性與驅動電壓函數關係。橫座 標代表驅動電壓(伏特),縱座標代表發射電流(微安培 )° 〇 從第5圖來看,次組件?9與19之初始發射電流特性大 體上並無不同,換言之,本發明的次組件19大體上與次組 件79具有相同的初始發射電流特性。考慮次組件?9習知技 術實際使用之全阻抗(fuUy resistant)性,發現本發 明之次組件1 9於初始發射電流特性上亦具有實際使用之全 阻抗性質。 第6圖展示出本發明之陰極次組件19之初始溫度特 性。橫座標代表陰極溫度几(t 縱座標代表最大陰極 電流MIk (微安培) 從第6圖來看,最大陰極電流M Ik於780 °C時飽和,換 言之,陰極次組件19的操作溫度為78〇 〇c。此與次組件79 習知技術幾乎相同。因此,套管14之熱阻相等於次組件79 習知技術之套管73,所以可將套管73應用於套管14。由於 -人组件1 9的操作溫度與次組件79相同,電子鎗組件無需任 何熱測。這些要點在實用中具有相當價值。 第7圖展示出本發明之陰極次組件19之最大陰極電流 MIk改變量,此乃經由次組件19於電流密度3A/c#連續操 作21 ’ 0 0 0小時所獲得。橫座標代表操作時間(小時),縱 座標代表最大陰極電流Μ丨k與初始最大陰極電流Mlk之比Page 29 4 6 9 46 2 ----------- 5. Description of the invention (26) " — Figure 5 shows the conventional technology of the cathode subassembly 79 and the initial stage of the cathode subassembly of the present invention. The emission current characteristic is a function of the driving voltage. The horizontal axis represents the driving voltage (volts), and the vertical axis represents the emission current (microamperes) ° 〇 From Figure 5, the secondary component? The initial emission current characteristics of 9 and 19 are not substantially different, in other words, the sub-assembly 19 of the present invention has substantially the same initial emission current characteristics as the sub-assembly 79. Considering subcomponents? The fuUy resistance of 9 conventional technologies is actually used, and it is found that the secondary component 19 of the present invention also has the full-impedance property of practical use in terms of the initial emission current characteristics. Fig. 6 shows the initial temperature characteristics of the cathode sub-assembly 19 of the present invention. The horizontal axis represents the temperature of the cathode (t The vertical axis represents the maximum cathode current MIk (microamperes). From Figure 6, the maximum cathode current M Ik is saturated at 780 ° C. In other words, the operating temperature of the cathode subassembly 19 is 78 °. 〇c. This is almost the same as the conventional technique of the sub-assembly 79. Therefore, the thermal resistance of the casing 14 is equivalent to the casing 73 of the sub-assembly 79, so the casing 73 can be applied to the casing 14. The operating temperature of the module 19 is the same as that of the sub-module 79, and the electron gun module does not need any thermal measurement. These points are of practical value. Figure 7 shows the maximum cathode current MIk change of the cathode sub-module 19 of the present invention. Obtained through continuous operation of the sub-assembly 19 at a current density of 3A / c # for 21 '0 0 0 hours. The horizontal coordinate represents the operating time (hours), and the vertical coordinate represents the ratio of the maximum cathode current M 丨 k to the initial maximum cathode current Mlk.
第30頁 46946 2 五、發明說明(27) --- 從第7圖來看’電流MIk於21,〇〇〇小時内最大減少鲁4 於5 % 。考慮如此小的電流Μ I k減少量’可以說螢幕之亮氐 與聚焦效能(亦即’解析度)幾乎相等於操作2丨,〇 〇 〇 ^ 後的初始值。此外’次組件1 9甚至從未於大尺寸之彩色 極射線管中以3 A / c m2電流密度之嚴格條件下連續操作。^ 此看來,至少在一般彩色陰極射線管螢幕操作期間不會 察到可辨認的電子發射降低量。 規 如同以上所解釋,根據本發明實施例之陰極次組件 19,甚至於彩色陰極射線管一般至少之使用壽命期間,其 電子發射能力(亦即,發射率)在大於1A/cm2之高操作電、 流密度中幾乎沒有降低。意即裝設有次組件丨9之彩色陰杨 射線管,螢幕上之亮度與解析度在長時間下來不會顯^出 =何可辨認之減低量’並且適用於大尺寸電視或電腦顯示 器。 、 本發明實施例於上述解釋中,整個片支撐物〗2係成形 於含主成份鎳與至少一種從鉻、钽、鉬、錯、鎢與鈷紐群 擇選出的金屬合金。然而’本發明並未受限於此結構只 要片支撑物12與陰極片11接觸之部份係成形於含主成份^ 與至少一種從鉻、鈕、鉬、锆、鎢與鈷組群擇選出的金屬 合金即可。既然如此,毋需說,便具有與上述實施例相 的優點。 本發明雖以較佳實施例揭露如上,然其熟悉此技藝人 士在不脫離本發明之精神和範圍内,當可做些許的更動與 潤飾’因此本發明之保護範圍當視後附之申請專利範圍所Page 30 46946 2 V. Description of the invention (27) --- From the view in Fig. 7, the current MIk can be reduced by a maximum of 4% to 5% within 21,000 hours. Considering such a small amount of reduction of the current M I k ′, it can be said that the brightness of the screen and the focusing efficiency (that is, the “resolution”) are almost equal to the initial values after the operation of 2, 〇 〇 〇 ^. In addition, the 'subassembly 19' has never been operated continuously under the strict conditions of a current density of 3 A / cm2 in a large-sized color polar tube. ^ It seems that at least no identifiable reduction in electron emission is observed during normal color cathode ray tube screen operation. As explained above, the cathode sub-assembly 19 according to the embodiment of the present invention, even the color cathode ray tube, generally has at least a lifetime during which its electron emission capability (ie, emissivity) is higher than 1A / cm2. There is almost no decrease in flow density. This means that a color yin-yang tube with a subassembly 9 is installed, and the brightness and resolution on the screen will not be displayed for a long time ^ = what is the identifiable reduction? And it is suitable for large-sized TVs or computer monitors. In the above explanation of the embodiment of the present invention, the entire sheet support 2 is formed from a main alloy containing nickel and at least one metal alloy selected from chromium, tantalum, molybdenum, tungsten, tungsten, and cobalt. However, the present invention is not limited to this structure, as long as the portion where the sheet support 12 and the cathode sheet 11 are in contact is formed with a main component ^ and at least one selected from the group consisting of chromium, button, molybdenum, zirconium, tungsten and cobalt Metal alloy is sufficient. In this case, it is needless to say that there are advantages compared with the above embodiment. Although the present invention is disclosed as above with a preferred embodiment, those skilled in the art can make some modifications and retouching without departing from the spirit and scope of the present invention. Range
第31頁Page 31
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JP17500999A JP2001006521A (en) | 1999-06-22 | 1999-06-22 | Cathode body structure and color picture tube |
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JP (1) | JP2001006521A (en) |
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CN111243917A (en) * | 2020-01-19 | 2020-06-05 | 中国科学院电子学研究所 | Cathode heater assembly and preparation method thereof |
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US6624578B2 (en) * | 2001-06-04 | 2003-09-23 | Extreme Devices Incorporated | Cathode ray tube having multiple field emission cathodes |
FR2840450A1 (en) | 2002-05-31 | 2003-12-05 | Thomson Licensing Sa | CATHODO-EMISSIVE BODY FOR CATHODE IMPREGNATED WITH ELECTRONIC TUBE |
JP2011076753A (en) * | 2009-09-29 | 2011-04-14 | Denki Kagaku Kogyo Kk | Electron source and electronic equipment |
JP5063715B2 (en) * | 2010-02-04 | 2012-10-31 | 株式会社日立ハイテクノロジーズ | Electron source, electron gun, electron microscope apparatus and electron beam drawing apparatus using the same |
CN113808892B (en) * | 2021-09-22 | 2023-10-20 | 中国科学院空天信息创新研究院 | Composite thermal subassembly and method of making the same |
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GB1076229A (en) * | 1963-10-08 | 1967-07-19 | Sylvania Electric Prod | Cathodes |
US3719856A (en) * | 1971-05-19 | 1973-03-06 | O Koppius | Impregnants for dispenser cathodes |
KR900007751B1 (en) * | 1985-05-25 | 1990-10-19 | 미쯔비시덴끼 가부시기가이샤 | Electron tube cathode and method of the same |
JPS6460938A (en) * | 1987-09-01 | 1989-03-08 | Hitachi Ltd | Cathode for electron tube |
JPH0690907B2 (en) * | 1988-02-02 | 1994-11-14 | 三菱電機株式会社 | Electron tube cathode |
JPH01307134A (en) * | 1988-06-02 | 1989-12-12 | Mitsubishi Electric Corp | Impregnated cathode |
JPH02106843A (en) * | 1988-10-14 | 1990-04-18 | Nec Corp | Cathode for electron tube |
DE4114856A1 (en) * | 1991-05-07 | 1992-11-12 | Licentia Gmbh | STOCK CATHODE AND METHOD FOR THE PRODUCTION THEREOF |
JPH05114352A (en) * | 1991-10-24 | 1993-05-07 | Toshiba Corp | Impregnated type cathode body structure and its manufacture |
JPH07235254A (en) * | 1994-02-21 | 1995-09-05 | Tokyo Kasoode Kenkyusho:Kk | Impregnated cathode |
KR100252817B1 (en) * | 1996-02-29 | 2000-04-15 | 모리 가즈히로 | Electrode for electronic tube |
JP3216579B2 (en) * | 1997-07-23 | 2001-10-09 | 関西日本電気株式会社 | Method for manufacturing cathode member and electron tube using this cathode member |
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1999
- 1999-06-22 JP JP17500999A patent/JP2001006521A/en active Pending
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CN111243917A (en) * | 2020-01-19 | 2020-06-05 | 中国科学院电子学研究所 | Cathode heater assembly and preparation method thereof |
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