JPS59177305A - Production of molybdenum powder and molybdenum material - Google Patents

Production of molybdenum powder and molybdenum material

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Publication number
JPS59177305A
JPS59177305A JP58051453A JP5145383A JPS59177305A JP S59177305 A JPS59177305 A JP S59177305A JP 58051453 A JP58051453 A JP 58051453A JP 5145383 A JP5145383 A JP 5145383A JP S59177305 A JPS59177305 A JP S59177305A
Authority
JP
Japan
Prior art keywords
powder
molybdenum
la2o3
sintered body
lanthanum
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP58051453A
Other languages
Japanese (ja)
Other versions
JPS6227123B2 (en
Inventor
Tadashi Shimizu
忠 清水
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toshiba Corp
Original Assignee
Toshiba Corp
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Toshiba Corp filed Critical Toshiba Corp
Priority to JP58051453A priority Critical patent/JPS59177305A/en
Publication of JPS59177305A publication Critical patent/JPS59177305A/en
Publication of JPS6227123B2 publication Critical patent/JPS6227123B2/ja
Granted legal-status Critical Current

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  • Powder Metallurgy (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)

Abstract

PURPOSE:To produce an Mo sintered body having excellent processability by adding a specific amt. of lanthanum nitrate to powder of Mo then heating the powder to disperse uniformly the lanthanum nitrate into Mo as lanthanum oxide and molding and sintering the powder. CONSTITUTION:La(NO3)3 is added and mixed at 1-5wt% expressed in terms of La2O3 to powder of Mo or MoO3 having 2-5mum average grain size and the mixture thereof is subjected to a heat treatment to decompose thermally the La (NO3)3 to La2O3. The powder is further reduced in a hydrogen atmosphere if necessary to produce the powder mixture consisting of the powder of La2O3 dispersed uniformly in the Mo powder. Such powder is molded under pressure by a mechanical press, hydrostatic press, etc. and is then sintered at >=1,700 deg.C in a non-oxidative atmosphere. While such sintered body is heated, the sintered body is subjected to rolling and drawing at >=60% reduction ratio with respect to the cross-sectional area, and the Mo material which is deposited thereon with La2O3, is free from disconnection and cracking in the state of secondary processing and has excellent processability is produced.

Description

【発明の詳細な説明】 〔発明の技術分野〕 本発明は、構造用材料として用いる酸化ランタン(以下
L8203 と記す)を均一にモリブデン(以下Moと
記す)中に分散させるMoの製造法に関する。
Detailed Description of the Invention [Technical Field of the Invention] The present invention relates to a method for producing Mo in which lanthanum oxide (hereinafter referred to as L8203) used as a structural material is uniformly dispersed in molybdenum (hereinafter referred to as Mo).

〔発明の技術的背景とその問題点J La20Bを含有したMoは、主に電子管の陰極相料と
して線あるいは板状にした後、線はコイル状(ス/?イ
ラル状)に鈑は曲げ加工等、二次加工して用いるr、 
Mo中のLa2O3は、酸化トリウム入りタングステン
(Th02−W )中のThO2と同様にMOに固溶し
た9、Moと化合物を作ること々く、La20.。
[Technical Background of the Invention and Its Problems J Mo containing La20B is mainly used as a cathode phase material in electron tubes after being made into a wire or plate shape. etc., used by secondary processing,
Like ThO2 in tungsten containing thorium oxide (Th02-W), La2O3 in Mo often forms a compound with 9 and Mo dissolved in MO. .

の粒子として分散している。It is dispersed as particles.

このため、Mo中のLa2O3微粉の分散性が不良の場
合には、線せたは板状に加工する際、断線したり、割れ
たりするため加工が非常に困難であった。
For this reason, if the dispersibility of the La2O3 fine powder in Mo is poor, it is very difficult to process the wire or plate because it may break or crack.

また、Moはもともと銅、アルミニウム等と比較し、非
常に脆い金属であり、コイル状にしたり、板全曲けたす
する等、二次加工をすることがむずかしい材料である。
Moreover, Mo is originally a very brittle metal compared to copper, aluminum, etc., and is a material that is difficult to perform secondary processing, such as forming into a coil shape or completely bending a plate.

この二次加工性を改善する為には、Moの焼結体あるい
m:溶融したインゴットを高い加工率(減面率)で加工
し、加工方向に繊維組織を発達させ(遷移温度を室温以
下にし)、線あるいは板の柔軟性全向上せしめているの
が最も一般的な方法である。
In order to improve this secondary workability, the Mo sintered body or molten ingot is processed at a high processing rate (area reduction rate), and a fiber structure is developed in the processing direction (the transition temperature is set at room temperature). The most common method is to completely improve the flexibility of the wire or plate.

本発明者らは、上記問題点に着目し、La2O3が1〜
5亜量係含有するMOについて、その線材をコイル状に
したり、板を曲けたすする等、二次加工性を容易にせし
める為には、焼結体からの加工率が60%以上にするこ
とが必要であることを実験研究によりつきとめた1、又
この加工率60fo以上に容易に加工するだめには、M
o中に微細なL a20゜全均一に分散させることが必
要であり、その為には、Mo粉末中にLa2O3k凝集
させることなく均一に分散埒せることが必要であった。
The present inventors focused on the above-mentioned problems and determined that La2O3 is 1 to 1.
In order to facilitate secondary processing of MO containing MO, such as making the wire into a coil or bending a plate, the processing rate from the sintered body should be 60% or more. Through experimental research, we have found that it is necessary to have a processing rate of 60fo or higher.
It was necessary to uniformly disperse the fine La20° in the Mo powder, and for that purpose, it was necessary to uniformly disperse La2O3k in the Mo powder without agglomerating it.

しかしながら、機械的な方法でLa、、03微粉末をM
o中に均一に分散せしめる従来の方法は、L a203
が微細になればなるほど、凝集しやすくなるという問題
があった。
However, by mechanical method, La, 03 fine powder is
The conventional method for uniformly dispersing L a203
There was a problem in that the finer the particles, the more likely they were to aggregate.

〔発明の目的〕[Purpose of the invention]

本発明の目的は、上記の問題点を解消し、微細なLa2
O3’?r: Mo中に均一に分散せしめる酸化ランタ
ンを含有したモリブデンの製造方法を提供し、りって、
線、あるいは板状に容易に力j4工できる様な、焼結体
を提供し7、さらにこれら線あるいは板状のLa2O3
が1〜5爪量重量含むMoの二次加工性′fi:ネi′
易にせしめることにある。
The purpose of the present invention is to solve the above-mentioned problems and to
O3'? r: Provides a method for producing molybdenum containing lanthanum oxide that is uniformly dispersed in Mo,
We provide a sintered body that can be easily machined into a wire or plate shape, and furthermore, we provide a sintered body that can be easily machined into a wire or plate shape.
Secondary workability of Mo containing 1 to 5 claw weight 'fi: Nei'
It's about making it easier.

〔発明の概要〕[Summary of the invention]

本発明のモリブデンの製造方法(は、MOもしくは1v
Io酸化物の粉末に、Mo粉末の重量に対して硝酸ラン
タンをLa2O3で1〜5亜量係含有させ、1.20℃
以上で加熱分解し、硝酸ランタンf La2O3に変え
、さらに、水累雰囲気中で還元し、Mo粉末中に均一分
散したLa2Q3担持のMo粉末全得る1、こうして得
られた粉末を機械プレス、あるいは静水圧プレスで、加
圧成型後、非酸化性雰凹気中で、1700℃以上で焼結
する。この焼結体を、熱を加えながらロール加工あるい
は引抜き加工等をほどこし、焼結体の4717断面積に
対し60%以上加工することを特徴とするLa2Q3担
持Mo棒、線、あるいは板の製造方法である。
The method for producing molybdenum of the present invention (is MO or 1v
The Io oxide powder contains 1 to 5 parts of lanthanum nitrate based on the weight of the Mo powder, and the temperature is 1.20°C.
The above process is thermally decomposed and converted into lanthanum nitrate f La2O3, and further reduced in an aqueous atmosphere to obtain the entire Mo powder supporting La2Q3 uniformly dispersed in the Mo powder1.The thus obtained powder is mechanically pressed or statically After pressure molding using a hydraulic press, it is sintered at 1700°C or higher in a non-oxidizing atmosphere. A method for manufacturing a La2Q3-supported Mo rod, wire, or plate, characterized in that the sintered body is subjected to rolling or drawing processing while applying heat, thereby processing 60% or more of the 4717 cross-sectional area of the sintered body. It is.

本発明の最大の特ぞりは、La2O3の添加方法として
、4i!l酸ランタンでドーf後、とn−e熱分解によ
って、La2O3に変えることにある。この方法を用い
ることによ、 q O,粉末の混合方法に比較し、より
微細なLa20.、粉末ヲMO中に均一に分散させるこ
とができる3、この結果、以後、棒線あるいは板等に加
工する81合、断線、割れ等が極めて少なく、これらを
容易に二次加工することができる。又、この様にして得
られMo棒、線あるいは板は、Mo中に微細なLa20
.1が均一に分散している為、例えは、it(子骨の陰
極椙料に使用した場合、極めて良好な電子放出特性を得
ることができる。
The greatest feature of the present invention is that the method of adding La2O3 is 4i! After doping with lanthanum acid, it is converted to La2O3 by thermal decomposition. By using this method, finer La20. , the powder can be uniformly dispersed in the MO3. As a result, there are extremely few wire breaks, cracks, etc. when processing the powder into wire rods or plates, etc., and these can be easily subjected to secondary processing. . Moreover, the Mo rod, wire or plate obtained in this way has fine La20 in the Mo.
.. 1 is uniformly dispersed, for example, when it is used as a cathode material for an osseous bone, extremely good electron emission characteristics can be obtained.

本発明にお−いて、Mo粉末中に分散させたL a20
3の粒径は、平均粒径で0.5μm以下で、最大粒径が
1.0μm以下であることが望ましく、もしこれ以上の
粒径をイ丁するLa20aが入った場合、棒、線あるい
は板等にする際の加工性が著しるしく悪くなるばかりで
なく、構造材料として用いた場合、その特性を低下させ
る等さまざまな障否をひきおこしやすい。又、Mo粉本
の平均粒径は2〜5μmηが望ましく、この範囲外のM
o粉末全使用した場合圧粉体に亀裂が入ったり、焼結体
をロール加工、ハンマー加工、転打加工あるいは引き抜
き加工をする場合、加工性に支障を生じやすい。
In the present invention, L a20 dispersed in Mo powder
The particle size of No. 3 is desirably 0.5 μm or less in average particle size and 1.0 μm or less in maximum particle size. If La20a with a particle size larger than this is included, it is preferable to use a bar, wire or Not only does it have a markedly poor workability when it is made into plates, etc., but when used as a structural material, it tends to cause various problems such as deterioration of its properties. In addition, the average particle diameter of Mo powder is preferably 2 to 5 μmη, and M
o If all the powder is used, the green compact may crack, and when the sintered compact is rolled, hammered, rolled or drawn, workability is likely to be impaired.

La2O3の添加量を1〜5i!S′量係とするのは、
」W t %以下で1l−1l:構造材としての特性例
えば、十分な電子放出特性が得られにくくなり、又5重
帛°係を超えると、加工性に゛悪影響を及はしやすいた
めである。
The amount of La2O3 added is 1 to 5i! The S' quantity is
1l-1l below Wt%: Characteristics as a structural material For example, it becomes difficult to obtain sufficient electron emission characteristics, and if it exceeds a 5-layer ratio, it tends to have a negative effect on workability. be.

〔発明の実施例〕[Embodiments of the invention]

以下、本発明のIVfoの製造方法について、実施例に
沿って説明する3、 実施例1 平均粒径2.5μmのM o 02粉末に、あらかじめ
、分析して硝酸ランタン中のLa’5確認した硝酸ラン
タンLa (NOs )s ・6 H2O’l:、La
、、0.換算で3%水を加えながら泥状になる様に添加
した。
The method for producing IVfo of the present invention will be described below with reference to Examples 3. Example 1 Mo 02 powder with an average particle size of 2.5 μm was analyzed in advance to confirm La'5 in lanthanum nitrate. Lanthanum nitrate La (NOs)s ・6 H2O'l:, La
,,0. The mixture was added to form a slurry while adding 3% water (calculated as 3%).

これを温浴中で攪拌しながら十分乾燥させた後、電気ヒ
ータで200℃で2時間加熱しLa(NOs)、+ 全
La20.、に分解させた(乾燥温度を高くし、La(
NO3)sの分解と乾燥を同時に行っても良い)。
After sufficiently drying this in a hot bath while stirring, it was heated with an electric heater at 200°C for 2 hours to form La(NOs), + total La20. , (by increasing the drying temperature and decomposing La(
The decomposition and drying of NO3)s may be performed at the same time).

次に、粒子表面にLa20gを分散させたMoO2を水
素雰囲気中で温度1000℃、4時間還元し、平均粒径
3μmのLa2O3担持Mo粉末を得た。この時、電子
顕微鏡で観察したL A20sの粒径は0.1〜0.4
μmであった。
Next, MoO2 with 20 g of La dispersed on the particle surface was reduced in a hydrogen atmosphere at a temperature of 1000° C. for 4 hours to obtain a La2O3-supported Mo powder with an average particle size of 3 μm. At this time, the particle size of LA20s observed with an electron microscope was 0.1 to 0.4.
It was μm.

このLa、、Os担持MO粉末を、機械プレスにより1
.5ton/iの圧力で、圧粉体を成形し、このま才で
は取扱いが困難なため、水素雰囲気中で1200℃で1
時間仮焼結後1850℃で8時間焼結し、形状が断面積
12X12+m++、長さ650問、比重が9.5の焼
結体を得た。
This La,,Os-supported MO powder was mechanically pressed into 1
.. The green compact was molded at a pressure of 5 tons/i, and since it was difficult to handle at this stage, it was heated at 1200°C in a hydrogen atmosphere.
After temporary sintering, sintering was carried out at 1850° C. for 8 hours to obtain a sintered body having a cross-sectional area of 12×12+ m++, a length of 650 pieces, and a specific gravity of 9.5.

次に、この焼結体を、温度を加えながらロール〃u工、
転打加工、さらに引抜き加工を施し、020闘φの線を
得た。
Next, this sintered body is rolled while applying temperature.
After rolling and drawing, a line with a diameter of 020 mm was obtained.

実施例2 Mo粉末を、静水圧で2 ton/lriの圧力でプレ
スし、圧粉体を成型した。次に、これを水素雰囲気中で
1850℃×8時間焼結して、寸法70rMlφ×60
0晒、比重9,450焼結体を得た。
Example 2 Mo powder was hydrostatically pressed at a pressure of 2 ton/lri to form a green compact. Next, this was sintered in a hydrogen atmosphere at 1850°C for 8 hours, and the dimensions were 70rMlφ x 60mm.
A sintered body with a specific gravity of 9,450 was obtained.

この焼結体を加熱しながら、ノ・ンマーで加工後、熱間
、冷間ロール加工を施し、厚さ30μmのシー ト 不
−得た。
This sintered body was worked with a thermometer while being heated, and then subjected to hot and cold rolling to obtain a sheet having a thickness of 30 μm.

この様にして得られた線あるいはシートは、スパイラル
状または円筒状に二次力0工する場合、純Moの線、あ
るいはシートと同様、二次加工性はきわめて良好であっ
た。
When the wire or sheet thus obtained was processed into a spiral or cylindrical shape without any secondary force, the wire or sheet had extremely good secondary workability, similar to pure Mo wire or sheet.

〔発明の効果〕〔Effect of the invention〕

以上の説明から明らかな通り、本発明の方法は、■ 1
a203の添加fi” La(NOs)3・6H20に
よシ溶液の形で行うため、Mo中に均一に、しかも微細
に分散させることができること、 ■ したがって線、あるいは板状に容易に加工できるこ
とと、これに伴い、焼結体からの加工率を大きくとるこ
とができ、この結果、線あるい上板の二次加工性が、純
MOと比較し、はぼ同等であること、 ■ La20*がMo中に均一に分散させることができ
ることにより、構造材としての特性が太きく IFiJ
上したこと、 等の効果を秦し、その工業的価値は極めて犬である1、 なお、本発明に係る溶液分散の方法は、La(NOs)
3に代えて加熱によってLaの酸化物を生成する、他の
6f溶性化合物を用いても同様の効果力:イ4)られ、
ること番コ、いう賛でもない。
As is clear from the above explanation, the method of the present invention includes: (1)
Since the addition of a203 is carried out in the form of a solution of La(NOs)3.6H20, it can be uniformly and finely dispersed in Mo. ■ Therefore, it can be easily processed into a wire or plate shape. Accordingly, the processing rate from the sintered body can be increased, and as a result, the secondary workability of the wire or upper plate is almost the same as that of pure MO. ■ La20 * can be uniformly dispersed in Mo, giving it great properties as a structural material.IFiJ
The industrial value of the above effects is extremely low1.The solution dispersion method according to the present invention can be applied to La(NOs).
Similar effects can be obtained by using other 6f-soluble compounds that generate La oxides by heating in place of 3.
It's not even a compliment.

Claims (1)

【特許請求の範囲】 1 モリブデン(Mo)もしくはモリブデン酸化物の粉
末に、モリブデン重量に対して、酸化ランタン(La2
Q3 )の量に換算して1〜5重量係となる様に硝酸ラ
ンタンを添加した後、120℃以上で加熱分解せしめる
ことを特徴とした酸化ランタンを含有したモリブデン粉
末の製造方法、1 2 モリブデン(Mo)もしくはモリブデン酸化物の粉
末に、モリブデン重量に対して、酸化ランタン(La2
O5)の量に換算して1〜5M量チとなる様に硝酸ラン
タンを添加した後、】20℃以上で加熱分解せしめて得
られた酸化ランタンを含有(7たモリブデン粉末全水素
雰囲気中で還元し、圧粉成形した後、非酸化性葵囲気中
で1700℃以上で焼結し、得られた・gεε鉢体焼結
体の横断面積に対し加工率60%以上で加工する酸化ラ
ンタンを含有したモリブデン材の製造方法。
[Claims] 1 Molybdenum (Mo) or molybdenum oxide powder is added with lanthanum oxide (La2) based on the weight of molybdenum.
Q3) A method for producing molybdenum powder containing lanthanum oxide, characterized by adding lanthanum nitrate in an amount of 1 to 5 by weight, and then thermally decomposing it at 120°C or higher, 12 molybdenum (Mo) or molybdenum oxide powder, lanthanum oxide (La2
After adding lanthanum nitrate to an amount of 1 to 5M (converted to the amount of After reducing and compacting, lanthanum oxide is sintered at 1700°C or higher in a non-oxidizing hollyhock atmosphere and processed at a processing rate of 60% or more with respect to the cross-sectional area of the obtained ・gεε pot body sintered body. A method for producing molybdenum-containing material.
JP58051453A 1983-03-29 1983-03-29 Production of molybdenum powder and molybdenum material Granted JPS59177305A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP58051453A JPS59177305A (en) 1983-03-29 1983-03-29 Production of molybdenum powder and molybdenum material

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP58051453A JPS59177305A (en) 1983-03-29 1983-03-29 Production of molybdenum powder and molybdenum material

Publications (2)

Publication Number Publication Date
JPS59177305A true JPS59177305A (en) 1984-10-08
JPS6227123B2 JPS6227123B2 (en) 1987-06-12

Family

ID=12887344

Family Applications (1)

Application Number Title Priority Date Filing Date
JP58051453A Granted JPS59177305A (en) 1983-03-29 1983-03-29 Production of molybdenum powder and molybdenum material

Country Status (1)

Country Link
JP (1) JPS59177305A (en)

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104439267A (en) * 2014-12-17 2015-03-25 崇义章源钨业股份有限公司 Material boat turnover material collection device
CN110359043A (en) * 2019-07-27 2019-10-22 西北师范大学 Dielectric soaks the preparation method of the titanium-based lanthana nano flower film of low-voltage response
CN110976900A (en) * 2019-11-21 2020-04-10 金堆城钼业股份有限公司 Production method of composite alloy molybdenum powder
CN113802025A (en) * 2021-09-16 2021-12-17 西安交通大学 Method for micro-doping TZM alloy and TZM alloy

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104439267A (en) * 2014-12-17 2015-03-25 崇义章源钨业股份有限公司 Material boat turnover material collection device
CN110359043A (en) * 2019-07-27 2019-10-22 西北师范大学 Dielectric soaks the preparation method of the titanium-based lanthana nano flower film of low-voltage response
CN110359043B (en) * 2019-07-27 2021-03-26 西北师范大学 Preparation method of titanium-based lanthanum oxide nanoflower film with dielectric wetting low-voltage response
CN110976900A (en) * 2019-11-21 2020-04-10 金堆城钼业股份有限公司 Production method of composite alloy molybdenum powder
CN113802025A (en) * 2021-09-16 2021-12-17 西安交通大学 Method for micro-doping TZM alloy and TZM alloy

Also Published As

Publication number Publication date
JPS6227123B2 (en) 1987-06-12

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