JPS6237707B2 - - Google Patents
Info
- Publication number
- JPS6237707B2 JPS6237707B2 JP5145483A JP5145483A JPS6237707B2 JP S6237707 B2 JPS6237707 B2 JP S6237707B2 JP 5145483 A JP5145483 A JP 5145483A JP 5145483 A JP5145483 A JP 5145483A JP S6237707 B2 JPS6237707 B2 JP S6237707B2
- Authority
- JP
- Japan
- Prior art keywords
- particle size
- molybdenum
- weight
- wire
- present
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired
Links
- 239000000463 material Substances 0.000 claims description 20
- 239000002245 particle Substances 0.000 claims description 17
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 11
- 229910052750 molybdenum Inorganic materials 0.000 claims description 11
- 239000011733 molybdenum Substances 0.000 claims description 11
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 3
- 229910021193 La 2 O 3 Inorganic materials 0.000 description 31
- 239000006185 dispersion Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000010406 cathode material Substances 0.000 description 4
- 238000005498 polishing Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 238000001953 recrystallisation Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 2
- 230000005484 gravity Effects 0.000 description 2
- 238000003754 machining Methods 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 238000005096 rolling process Methods 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 230000002706 hydrostatic effect Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- ZCUFMDLYAMJYST-UHFFFAOYSA-N thorium dioxide Chemical compound O=[Th]=O ZCUFMDLYAMJYST-UHFFFAOYSA-N 0.000 description 1
- 229910003452 thorium oxide Inorganic materials 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Landscapes
- Solid Thermionic Cathode (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Description
〔発明の技術分野〕
本発明は、La2O3粒子がMo中に均一に分散さ
れた構造材料用のモリブデンに関する。
〔発明の技術的背景とその問題点〕
La2O3を含有せるMo材は、主に電子管の陰極
材として、コイル状（スパイラル状）の線または
板を丸めた円筒として供される。
ところで、Mo中のLa2O3は酸化トリウム入り
タングステン（ThO2―Ｗ）中のThO2と同様に
Moと固溶したり化合物を形成することなく、Mo
中にLa2O3の粒子として分散されている。
このため、このようなモリブデン材料の諸特性
は、La2O3粒子の含有量のみならず、その分散状
態の影響を大きく受ける。
例えば、Mo中のLa2O3が凝集している等、
La2O3粒子の分散状態が悪い場合にはコイル状あ
るいは円筒状に賦形する等の二次加工を施す際
に、しばしば断線したり、亀裂を生じるという問
題が生じた。
また、上記の如くMo中のLa2O3の分散状態が
悪いと、電子管の陰極材として用いた場合には良
好な電子放出特性が得られにくく、しかも短寿命
となるという種々の問題があつた。
しかしながら、従来、モリブデン材料に添加す
べきLa2O3の適切な分散状態が知られていなかつ
たため、上記加工性、電子放射特性などの諸問題
を解決することができなかつた。
〔発明の目的〕
本発明の目的は、上記問題点を解消し、構造材
として用いた場合には容易に二次加工ができ、し
かも電子管の陰極材として用いた場合には長寿命
となるLa2O3を１〜５重量％含有するMo材を提
供することにある。
〔発明の概要〕
本発明者らは上記目的を達成すべく、鋭意研究
を重ねた結果、La2O3を１〜５重量％含有する
Mo材において、Mo中にLa2O3粒子を均一かつ微
細に分散せしめると、その二次加工性、電子放出
特性等の諸特性が改善されることを見出し、本発
明を完成した。
本発明の構造材用モリブデンは、モリブデン
（Mo）中に１〜５重量％の酸化ランタン
（La2O3）が均一に分散されており、該分散された
酸化ランタン（La2O3）の個々の平均粒径が３μ
ｍ以下であつて、かつ、最大粒径が７μｍ以下で
あることを特徴とする。
本発明において、La2O3は電子放出能を与え、
かつ、高温強度を高める成分である。
La2O3の含有量は１〜５重量％とする。La2O3
の含有量が１％未満の場合はLa2O3の添加効果が
得られにくく、純Moに近い特性を示し、５％を
超えた場合は、５％以下の添加効果と、さほど大
きな変化が認められず、しかも、二次加工性が悪
くなる等の問題点を生じる。
La2O3の粒子径は平均粒径で３μｍ以下であ
り、かつ、最大粒径で７μｍ以下でなければなら
ない。平均粒径が３μｍを超えるか、または最大
粒径が７μｍを超えると、線または板を二次加工
する際に断線したり、亀裂が入る等、著じるしく
加工性が低下するばかりでなく、電子管の陰極材
料として用いた場合、長時間安定な電子放出特性
を得ることが困難となる。
更に、線あるいは板材の二次加工性は、La2O3
の含有量、分散形態の他に、モリブデン（Mo）
と酸化ランタン（La2O3）からなる焼結体からの
加工率（横断面積の変化率）に影響される。
本発明の構造材用モリブデンは、好ましくは、
焼結体からの加工率60％以上で加工されたもので
ある。Moの様に、もともとCu，Al等と比較して
脆い金属は、焼結によつて生じる方向性のない結
晶組織を、加工することによつて、その加工方向
に配向した結晶組織を形成させることができる。
このような集合組織を形成させることによつて構
造材用モリブデンの柔軟性が向上する。La2O31
〜５重量％含有せるMo材において、発明者の実
験結果によれば、焼結体からの加工率は、大きく
なる程二次加工性が容易となるが、60％以上の加
工率を有する線、あるいは板材であれば、実用上
問題ない。
〔発明の実施例〕
以下本発明のLa2O31〜５重量％含有せるMo材
の特徴を説明する。
粉末冶金法によつてLa2O3含有量を0.5，1.0，
2.0，4.0，6.0重量％、さらにLa2O3粒径に差が出
る様、添加量、混合方法を変え、機械プレスによ
り1.5ton／cm2の圧力で圧粉体を作り、この圧粉体
を1850℃で８時間水素雰囲気中で焼結した。この
時得られた焼結体は、比重が約9.50、断面が12×
12mm、長さ650mmの形状であつた。この焼結体を
温度を加えながら転打加工、引抜き加工を施し、
0.60mmφの線を得た。Mo線中のLa2O3粒子径の確
認は、線を熱硬化性樹脂の中に埋込み、通常の研
磨法により鏡面仕上後、５〜20重量％のNaOH水
溶液中で電解研磨する方法によりMo材のみを研
磨し、La2O3を研磨面に浮き上がらせる様に残留
させた後、走査型電子顕微鏡により観察した。
線径0.60mmφにおけるMo中のLa2O3含有量及
び、La2O3の最大粒子径と線の柔軟性、二次再結
晶温度との関連を第１表に示した。
TECHNICAL FIELD OF THE INVENTION The present invention relates to molybdenum for structural materials in which La 2 O 3 particles are uniformly dispersed in Mo. [Technical background of the invention and its problems] Mo material containing La 2 O 3 is mainly used as a cathode material for electron tubes, in the form of a coiled (spiral) wire or a cylinder formed by rolling a plate. By the way, La 2 O 3 in Mo is similar to ThO 2 in tungsten containing thorium oxide (ThO 2 -W).
Mo without forming a solid solution or forming a compound with Mo.
It is dispersed in the form of La 2 O 3 particles. Therefore, the various properties of such a molybdenum material are greatly influenced not only by the content of La 2 O 3 particles but also by their dispersion state. For example, La 2 O 3 in Mo is agglomerated, etc.
If the dispersion state of the La 2 O 3 particles is poor, problems often arise, such as wire breakage or cracking during secondary processing such as shaping into a coil or cylinder. In addition, as mentioned above, if the dispersion state of La 2 O 3 in Mo is poor, it is difficult to obtain good electron emission characteristics when used as a cathode material in an electron tube, and there are various problems such as short life. Ta. However, since the appropriate dispersion state of La 2 O 3 to be added to molybdenum materials has not been known, it has not been possible to solve the above-mentioned problems such as workability and electron emission characteristics. [Object of the Invention] The object of the present invention is to solve the above-mentioned problems, and to develop La that can be easily subjected to secondary processing when used as a structural material, and has a long life when used as a cathode material for electron tubes. An object of the present invention is to provide a Mo material containing 1 to 5% by weight of 2O3 . [Summary of the Invention] In order to achieve the above object, the present inventors have conducted intensive research and found that a product containing 1 to 5% by weight of La 2 O 3 has been developed.
We have completed the present invention by discovering that in Mo materials, when La 2 O 3 particles are uniformly and finely dispersed in Mo, various properties such as secondary processability and electron emission characteristics are improved. The molybdenum for structural materials of the present invention has 1 to 5% by weight of lanthanum oxide ( La 2 O 3 ) uniformly dispersed in molybdenum (Mo). Individual average particle size is 3μ
m or less, and the maximum particle size is 7 μm or less. In the present invention, La 2 O 3 provides electron emission ability,
Moreover, it is a component that increases high-temperature strength. The content of La 2 O 3 is 1 to 5% by weight. La 2 O 3
When the content of La 2 O 3 is less than 1%, it is difficult to obtain the effect of adding La 2 O 3 and the properties are close to those of pure Mo, and when it exceeds 5%, the effect of adding La 2 O 3 is less than 5%, and there is no significant change. This is not acceptable and causes problems such as poor secondary processability. The particle size of La 2 O 3 must be 3 μm or less in average particle size and 7 μm or less in maximum particle size. If the average grain size exceeds 3 μm or the maximum grain size exceeds 7 μm, not only will the wire or plate be broken or cracked during secondary processing, but the workability will be significantly reduced. When used as a cathode material for an electron tube, it is difficult to obtain stable electron emission characteristics over a long period of time. Furthermore, the secondary workability of wire or plate material is La 2 O 3
In addition to the content and dispersion form of molybdenum (Mo)
It is influenced by the processing rate (rate of change in cross - sectional area) from a sintered body made of The molybdenum for structural materials of the present invention preferably has:
Processed from a sintered body at a processing rate of 60% or more. Metals like Mo, which are inherently more brittle than Cu, Al, etc., can be processed to form a crystal structure that is oriented in the processing direction by processing the non-directional crystal structure created by sintering. be able to.
By forming such a texture, the flexibility of molybdenum for structural materials is improved. La 2 O 3 1
According to the inventor's experimental results, in a Mo material containing ~5% by weight, the larger the machining rate from the sintered body, the easier the secondary workability, but the line with a machining rate of 60% or more , or a plate material, there is no practical problem. [Embodiments of the Invention] The characteristics of the Mo material containing 1 to 5% by weight of La 2 O 3 of the present invention will be described below. The La 2 O 3 content was reduced to 0.5, 1.0,
2.0, 4.0, 6.0% by weight, and the addition amount and mixing method were changed to create a difference in La 2 O 3 particle size, and a compact was made using a mechanical press at a pressure of 1.5 ton/cm 2 . was sintered at 1850°C for 8 hours in a hydrogen atmosphere. The sintered body obtained at this time has a specific gravity of approximately 9.50 and a cross section of 12×
It had a shape of 12 mm and a length of 650 mm. This sintered body is subjected to rolling and drawing processing while applying temperature,
A line of 0.60 mmφ was obtained. The La 2 O 3 particle size in the Mo wire can be confirmed by embedding the wire in a thermosetting resin, polishing it to a mirror finish using a normal polishing method, and then electrolytically polishing it in a 5-20% NaOH aqueous solution. After polishing only the material and leaving La 2 O 3 floating on the polished surface, it was observed using a scanning electron microscope. Table 1 shows the La 2 O 3 content in Mo at a wire diameter of 0.60 mmφ and the relationship between the maximum particle diameter of La 2 O 3 , wire flexibility, and secondary recrystallization temperature.
【表】【table】
【表】
これから明らかな如く、La2O3の含有量は1.0〜
５重量％が最も良く、本発明者らの実験結果によ
れば２〜３重量％が最も適正な量である。又、
La2O3の粒子径は小さい方が良く、８μｍを超え
ると二次加工性は急激に低下する。
また、上記圧粉体を2ton／cm2の静水圧でプレス
し、圧粉体を成形し、水素雰囲気中にて1850℃×
８時間焼結して得られた比重9.45、直径60mm〓、
長さ400mmの形状の焼結体をハンマー加工、ロー
ル加工し厚さ0.2mmの板を得た。この時、中間
で、水素雰囲気中にて二次再結晶温度以上で熱処
理した。熱処理する板材の寸法は、板厚0.2mmに
加工する迄の加工率が40％，60％，80％とした。
この時の板材の柔軟性について調査した結果を第
２表に示す。[Table] As is clear from this, the content of La 2 O 3 is 1.0~
The best amount is 5% by weight, and according to the experimental results of the present inventors, the most appropriate amount is 2 to 3% by weight. or,
The smaller the particle size of La 2 O 3 , the better; if it exceeds 8 μm, the secondary processability will drop sharply. In addition, the green compact was pressed with a hydrostatic pressure of 2 ton/cm 2 to form a green compact, and was heated at 1850°C in a hydrogen atmosphere.
Specific gravity 9.45, diameter 60mm obtained by sintering for 8 hours,
A sintered body with a length of 400 mm was hammered and rolled to obtain a plate with a thickness of 0.2 mm. At this time, in the middle, heat treatment was performed in a hydrogen atmosphere at a temperature equal to or higher than the secondary recrystallization temperature. The dimensions of the plate material to be heat treated were set at processing rates of 40%, 60%, and 80% until the plate thickness was 0.2 mm.
Table 2 shows the results of an investigation regarding the flexibility of the plate material at this time.
【表】
この結果から明らかな如く60％以上加工を施工
された板材の柔軟性が良いことがわかる加工率に
よる柔軟性効果は、線の場合もまつたく同様であ
る。
次に電力管（線径0.2mm〓）を用いMo中の
La2O3含有量と、電子放出特性との関連性を第３
表に示す。第３表によると、La2O3の含有量は1.0
重量％以上必要であり、6.0重量％を超えても電
子放出特性は良くならず、むしろ２重量％の特性
に比較して若干、低下傾向がある。[Table] As is clear from this result, it is clear that the flexibility of the plate material processed by 60% or more is good.The flexibility effect depending on the processing rate is also the same in the case of wire. Next, using a power tube (wire diameter 0.2 mm),
The relationship between La 2 O 3 content and electron emission characteristics was investigated in the third section.
Shown in the table. According to Table 3, the content of La 2 O 3 is 1.0
At least 6.0% by weight does not improve the electron emission characteristics, and in fact tends to deteriorate slightly compared to the properties at 2% by weight.
以上の説明から明らかな様に本発明の構造材用
モリブデンは、
その二次加工性が良好であること、二次再
結晶温度が高く、従つて高温強度が高いこと、
電子放出特性が安定で、かつ、優れること等の効
果を奏し、その工業的価値は極めて大である。
As is clear from the above description, the molybdenum for structural materials of the present invention has good secondary processability, a high secondary recrystallization temperature, and therefore high high-temperature strength.
It exhibits effects such as stable and excellent electron emission characteristics, and its industrial value is extremely large.
Claims (1)
ランタン（La2O3）が均一に分散されており、該
分散された酸化ランタン（La2O3）の個々の平均
粒径が３μｍ以下であつて、かつ、最大粒径が７
μｍ以下であることを特徴とする構造材用モリブ
デン。1 1 to 5% by weight of lanthanum oxide (La 2 O 3 ) is uniformly dispersed in molybdenum (Mo), and the individual average particle size of the dispersed lanthanum oxide (La 2 O 3 ) is 3 μm or less and the maximum particle size is 7
Molybdenum for structural materials, which is characterized by having a particle size of less than μm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5145483A JPS59177345A (en) | 1983-03-29 | 1983-03-29 | Molybdenum for structural material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP5145483A JPS59177345A (en) | 1983-03-29 | 1983-03-29 | Molybdenum for structural material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59177345A JPS59177345A (en) | 1984-10-08 |
| JPS6237707B2 true JPS6237707B2 (en) | 1987-08-13 |
Family
ID=12887375
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP5145483A Granted JPS59177345A (en) | 1983-03-29 | 1983-03-29 | Molybdenum for structural material |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59177345A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0518650Y2 (en) * | 1987-09-22 | 1993-05-18 |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS63157832A (en) * | 1986-12-19 | 1988-06-30 | Tokyo Tungsten Co Ltd | Molybdenum plate and its production |
| AT386612B (en) * | 1987-01-28 | 1988-09-26 | Plansee Metallwerk | CRISP-RESISTANT ALLOY FROM MELTING-MELTING METAL AND METHOD FOR THEIR PRODUCTION |
| JPS63192850A (en) * | 1987-02-05 | 1988-08-10 | Tokyo Tungsten Co Ltd | Molybdenum plate and its production |
| JPS63235445A (en) * | 1987-03-25 | 1988-09-30 | Tokyo Tungsten Co Ltd | Molybdenum wire rod and its production |
| JPS63238237A (en) * | 1987-03-25 | 1988-10-04 | Tokyo Tungsten Co Ltd | Molybdenum wire rod and its production |
| US5134039A (en) * | 1988-04-11 | 1992-07-28 | Leach & Garner Company | Metal articles having a plurality of ultrafine particles dispersed therein |
| CN111187958B (en) * | 2020-02-19 | 2021-01-19 | 西安交通大学 | Mo powder/MoO2Method for preparing nano lanthanum-molybdenum oxide alloy by doping with lanthanum ammonium molybdate powder |
-
1983
- 1983-03-29 JP JP5145483A patent/JPS59177345A/en active Granted
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0518650Y2 (en) * | 1987-09-22 | 1993-05-18 |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS59177345A (en) | 1984-10-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4950327A (en) | Creep-resistant alloy of high-melting metal and process for producing the same | |
| US3069759A (en) | Production of dispersion strengthened metals | |
| JP4886199B2 (en) | Method for producing high-temperature stable niobium wire | |
| JPH0925526A (en) | Production of oxide grain dispersed metal matrix composite | |
| JPH0455800B2 (en) | ||
| JPS6237707B2 (en) | ||
| CN108941547B (en) | Preparation method of copper-doped graphene reinforced aluminum-based composite material | |
| JP4659278B2 (en) | Tungsten sintered body and manufacturing method thereof, tungsten plate material and manufacturing method thereof | |
| JPH08109422A (en) | Production of alumina dispersion strengthened copper | |
| EP0765949B1 (en) | Tungsten-lanthana alloy wire for a vibration resistant lamp filament | |
| US4594217A (en) | Direct powder rolling of dispersion strengthened metals or metal alloys | |
| JP2539018B2 (en) | Al Lower 2 O Lower 3 Base ceramics | |
| JP2531701B2 (en) | Manufacturing method of dispersion strengthened copper alloy | |
| JPH0448863B2 (en) | ||
| JPS59177305A (en) | Production of molybdenum powder and molybdenum material | |
| JP2607643B2 (en) | Electrode wire for wire electric discharge machining | |
| JP3121400B2 (en) | Manufacturing method of tungsten sintered body | |
| CN112430763A (en) | Al (aluminum)2O3Preparation method of dispersion-strengthened copper-based composite material | |
| JPH0477057B2 (en) | ||
| JPH0325499B2 (en) | ||
| RU2769344C1 (en) | Material for arc-quenching and breaking electrical contacts based on copper and method of its production | |
| JP2000178721A (en) | Ruthenium sputtering target, ruthenium raw material powder for producing the target and production thereof | |
| JPH053430B2 (en) | ||
| US3551992A (en) | Method of producing ductile-tungsten base sheet alloy | |
| JP2628235B2 (en) | Method for producing high heat-resistant aluminum alloy wire for conductive use |