JPH0543761B2 - - Google Patents
Info
- Publication number
- JPH0543761B2 JPH0543761B2 JP60041518A JP4151885A JPH0543761B2 JP H0543761 B2 JPH0543761 B2 JP H0543761B2 JP 60041518 A JP60041518 A JP 60041518A JP 4151885 A JP4151885 A JP 4151885A JP H0543761 B2 JPH0543761 B2 JP H0543761B2
- Authority
- JP
- Japan
- Prior art keywords
- powder
- molybdenum
- nickel
- reduction
- temperature
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 28
- 239000000843 powder Substances 0.000 claims description 25
- 229910052759 nickel Inorganic materials 0.000 claims description 14
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 12
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical group O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 10
- 229910000476 molybdenum oxide Inorganic materials 0.000 claims description 9
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 229910052739 hydrogen Inorganic materials 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 7
- 238000000034 method Methods 0.000 description 10
- 230000005484 gravity Effects 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 238000005245 sintering Methods 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 3
- QXYJCZRRLLQGCR-UHFFFAOYSA-N dioxomolybdenum Chemical compound O=[Mo]=O QXYJCZRRLLQGCR-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000465 moulding Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 238000004663 powder metallurgy Methods 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000012190 activator Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000007429 general method Methods 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Description
【発明の詳細な説明】
（産業上の利用分野）
本発明は、粉末冶金法において使用されるモリ
ブデン粉末の製法に関するものである。DETAILED DESCRIPTION OF THE INVENTION (Industrial Field of Application) The present invention relates to a method for producing molybdenum powder used in powder metallurgy.
（従来の技術）
粉末冶金法の原料となる金属モリブデン粉末
は、酸化モリブデン粉末を比較的低温の一次還元
と比較的高温の二次還元の２回に分けて水素還元
して製造する（２段還元法）のが一般的である。
このような一般的な方法とは別に、例えば三酸化
モリブデン粉末（M0O3）を水素雰囲気炉中で最
高1100℃以上の温度まで時間をかけて徐々に昇温
し加熱することによつて１段で金属粉末に還元す
る方法（１段還元法）もある。(Prior art) Metallic molybdenum powder, which is a raw material for powder metallurgy, is produced by reducing molybdenum oxide powder with hydrogen in two stages: primary reduction at a relatively low temperature and secondary reduction at a relatively high temperature. (reduction method) is common.
Apart from such general methods, for example, molybdenum trioxide powder (M 0 O 3 ) is heated in a hydrogen atmosphere furnace by gradually raising the temperature to a maximum of 1100°C or more over time. There is also a method of reducing metal powder in one step (one-step reduction method).
（発明が解決しようとする問題点）
上記従来の製法のうち、２段還元法は、還元を
２回に分けて行なわなければならないので、それ
だけ手間がかかり、必要な装置も多くなるという
問題点があつた。また上記従来の１段還元法は、
２段還元法に較べて工程が簡単であるという利点
はあるが、得られる金属粉末の粒度が粗く、圧粉
体を焼結したときに十分な比重が得られないとい
う問題があり、通常のモリブデンワイヤ等の工業
生産に採用することができなかつた。(Problems to be Solved by the Invention) Among the conventional production methods mentioned above, the two-stage reduction method requires reduction to be carried out in two steps, which is time-consuming and requires more equipment. It was hot. In addition, the conventional one-stage reduction method described above is
Although it has the advantage that the process is simpler than the two-stage reduction method, there is a problem that the particle size of the obtained metal powder is coarse and sufficient specific gravity cannot be obtained when the green compact is sintered. It could not be adopted for industrial production of molybdenum wire, etc.
（問題点を解決するための手段）
本発明は、上記従来の製法の問題点を解決し、
粒度が細かく焼結時に高比重の得られる粉末を得
るため、次のような構成とした。(Means for solving the problems) The present invention solves the problems of the conventional manufacturing method described above,
In order to obtain a powder with fine particle size and high specific gravity upon sintering, the following configuration was adopted.
すなわち、本発明にかかるモリブデン粉末の製
法は、三酸化モリブデンを主成分とする酸化モリ
ブデン粉末に0.0025〜0.03重量％のニツケルを添
加した後、水素雰囲気中で600℃以下の低温から
徐々に1000℃以上の高温に加熱し、酸化モリブデ
ン粉末を還元して微量のニツケルを含有する金属
モリブデン粉末を得ることを特徴としている。 That is, the method for producing molybdenum powder according to the present invention involves adding 0.0025 to 0.03% by weight of nickel to molybdenum oxide powder whose main component is molybdenum trioxide, and then gradually increasing the temperature from a low temperature of 600°C or lower to 1000°C in a hydrogen atmosphere. It is characterized in that it is heated to a high temperature above and reduced the molybdenum oxide powder to obtain a metal molybdenum powder containing a trace amount of nickel.
これについて具体的に例を挙げて説明すれば、
以下の通りである。 To explain this with a concrete example,
It is as follows.
先ず原料である酸化モリブデン（M0Ox、通常
は三酸化モリブデンM0O3を主成分とするもの）
粉末にニツケルを添加するが、この方法として
は、ニツケルを含有する水溶性化合物、例えば硝
酸ニツケルを水に溶解させて得られる水溶液を酸
化モリブデン粉末にふりかけて充分混合し、乾燥
させる方法がある。添加するニツケルの量は、
0.0025〜0.03％（重量％、以下同じ）とするのが
好ましく、0.005〜0.03％とするのがより好まし
い。ニツケルの量が0.0025％より少ないと、所望
の効果を得ることができず、0.03％よりも多いと
焼結後の加工がきわめて困難となる。 First, the raw material is molybdenum oxide (M 0 Ox, usually molybdenum trioxide M 0 O 3 is the main component).
Nickel is added to the powder, and one method for this is to sprinkle a water-soluble compound containing nickel, such as an aqueous solution obtained by dissolving nickel nitrate in water, over molybdenum oxide powder, mix thoroughly, and dry. The amount of nickel added is
It is preferably 0.0025 to 0.03% (weight %, same hereinafter), more preferably 0.005 to 0.03%. If the amount of nickel is less than 0.0025%, the desired effect cannot be obtained, and if it is more than 0.03%, processing after sintering becomes extremely difficult.
所定量のニツケルを添加した粉末は、水素雰囲
気の還元炉を用いて１段還元を行なう。この還元
は、例えば、600〜800ｇの粉末をボートに入れ、
550℃程度の低温から1150℃程度の高温まで、出
口側の温度が次第に高くなるように温度勾配のつ
いた電気炉中を一定の速度で進行させる方法で行
なう。炉中での保持時間は、３時間以上とするの
が好ましい。この還元時に、粉末を600℃よりも
高い温度で急激に加熱すると、三酸化モリブデン
が昇華するので、600℃以下の温度で二酸化モリ
ブデンまたはそれよりも低級な酸化物に変えた
後、徐々に昇温するのが好ましい。 The powder to which a predetermined amount of nickel has been added is subjected to one-stage reduction using a reduction furnace in a hydrogen atmosphere. This reduction can be done, for example, by putting 600-800g of powder into a boat,
The process is carried out by moving at a constant speed through an electric furnace with a temperature gradient, from a low temperature of about 550°C to a high temperature of about 1150°C, so that the temperature on the exit side gradually increases. The holding time in the furnace is preferably 3 hours or more. During this reduction, if the powder is rapidly heated to a temperature higher than 600°C, molybdenum trioxide will sublimate, so after converting it to molybdenum dioxide or a lower oxide at a temperature below 600°C, the powder will be gradually sublimated. Preferably warm.
この還元によつて、ブレーン空気透過法による
比表面積が大きい（粒度が細かい）モリブデン金
属粉末が得られる。このように、１段還元で微細
な粉末が得られるのは、モリブデン中に微量に添
加されているニツケルが、還元中に活性化の働き
をなすからであろうと推測される。なお、この製
法で得られるモリブデン粉末を加圧成形して得ら
れる圧粉体を常法に従つて通電焼結した結果、通
常の２段還元で得られるものと同様な高比重の焼
結体を得ることができた。 This reduction yields a molybdenum metal powder with a large specific surface area (fine particle size) by the Blaine air permeation method. It is presumed that the reason why a fine powder is obtained in the one-stage reduction is that nickel, which is added in a small amount to molybdenum, acts as an activator during the reduction. Furthermore, as a result of electrification sintering of the green compact obtained by pressure-molding the molybdenum powder obtained by this manufacturing method according to a conventional method, a sintered compact with a high specific gravity similar to that obtained by normal two-stage reduction is obtained. I was able to get
（実施例および比較例）
ニツケルの添加量が0.005％(A)、0.0025％(B)、
0.0017％(C)の３種の酸化モリブデン粉末（M0O3
が主成分）と、ニツケルを添加しない同様な酸化
モリブデン粉末(D)を、入口側から順に550−850−
1050−1150℃と次第に高温となるように配置され
た４つのヒートゾーンをそなえた水素炉で還元し
た。還元は、ステンレス鋼製のボートに酸化物粉
末を入れ、該ボートを35分ごとにその１本分（１
つのヒートゾーンに対応）だけ高温側へ移動させ
ることによつて行なつた。水素流量はいずれも４
m3／Hrであり、ボートに対する粉末充填量は、
上記Ａ、Ｂ、Ｄが730ｇ、Ｃが800ｇであつた。(Example and Comparative Example) The amount of nickel added is 0.005% (A), 0.0025% (B),
Three types of molybdenum oxide powder (M 0 O 3
is the main component) and a similar molybdenum oxide powder (D) without adding nickel, in order from the inlet side to 550-850-
Reduction was carried out in a hydrogen furnace equipped with four heat zones arranged to gradually increase the temperature to 1050-1150°C. For reduction, oxide powder is placed in a stainless steel boat, and the boat is heated every 35 minutes.
This was done by moving the temperature to the high temperature side by 200°C (corresponding to 1 heat zone). The hydrogen flow rate is 4 in both cases.
m 3 /Hr, and the powder filling amount for the boat is
The weight of A, B, and D was 730g, and the weight of C was 800g.
この還元によつて得られた金属粉末の比表面積
SBと、この粉末を加圧成形した圧粉体を最高電流
4600Aで通電焼結した場合の比重（計算比重）
SGは第１図に示すようであつた。なお、棒状の
焼結体の両端部は細くしてあるので、実際の比重
は図示されているものより0.2程度大きくなる。 Specific surface area of metal powder obtained by this reduction
S B and a green compact formed by pressure molding this powder at the highest current.
Specific gravity when sintered with electricity at 4600A (calculated specific gravity)
The SG was as shown in Figure 1. Note that since both ends of the rod-shaped sintered body are made thinner, the actual specific gravity is approximately 0.2 larger than that shown.
同図からわかるように、本発明の実施例である
Ａ、Ｂは、ニツケルを添加しないもの(D)およびニ
ツケル量の少ないものに較べて、粉末粒度が細か
く、焼結したときに高比重が得られる。 As can be seen from the figure, Examples A and B of the present invention have a finer powder particle size and a higher specific gravity when sintered than those with no nickel added (D) and those with a small amount of nickel. can get.
（効果）
以上に説明した如く、本発明にかかるモリブデ
ン粉末の製法は、１段の還元で、粒度が細かく、
焼結後に高比重の得られる粉末を得ることのでき
るすぐれたものとなつた。(Effects) As explained above, the method for producing molybdenum powder according to the present invention uses one-stage reduction to produce fine particle size.
This was an excellent product in that it was possible to obtain a powder with a high specific gravity after sintering.
第１図は金属モリブデン粉末の比表面積と焼結
後の比重をあらわすグラフである。
FIG. 1 is a graph showing the specific surface area and specific gravity of metal molybdenum powder after sintering.
Claims (1)
デン粉末に0.0025〜0.03重量％のニツケルを添加
した後、水素雰囲気中で600℃以下の低温から
徐々に1000℃以上の高温に加熱し、酸化モリブデ
ン粉末を還元して、微量のニツケルを含有する金
属モリブデン粉末を得ることを特徴とするモリブ
デン粉末の製法。1 After adding 0.0025 to 0.03% by weight of nickel to molybdenum oxide powder whose main component is molybdenum trioxide, the molybdenum oxide powder is heated from a low temperature of 600°C or less to a high temperature of 1000°C or higher in a hydrogen atmosphere. A method for producing molybdenum powder, which comprises reducing it to obtain a metallic molybdenum powder containing a trace amount of nickel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4151885A JPS61201708A (en) | 1985-03-01 | 1985-03-01 | Manufacture of molybdenum powder |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP4151885A JPS61201708A (en) | 1985-03-01 | 1985-03-01 | Manufacture of molybdenum powder |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61201708A JPS61201708A (en) | 1986-09-06 |
| JPH0543761B2 true JPH0543761B2 (en) | 1993-07-02 |
Family
ID=12610593
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP4151885A Granted JPS61201708A (en) | 1985-03-01 | 1985-03-01 | Manufacture of molybdenum powder |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS61201708A (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US7276102B2 (en) | 2004-10-21 | 2007-10-02 | Climax Engineered Materials, Llc | Molybdenum metal powder and production thereof |
| US7524353B2 (en) | 2004-10-21 | 2009-04-28 | Climax Engineered Materials, Llc | Densified molybdenum metal powder and method for producing same |
| CN109848431B (en) * | 2019-02-27 | 2022-05-10 | 金堆城钼业股份有限公司 | Preparation method of fine molybdenum powder |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5835561A (en) * | 1981-08-26 | 1983-03-02 | Fuji Xerox Co Ltd | Device for preventing contamination of optical system in copying machine |
-
1985
- 1985-03-01 JP JP4151885A patent/JPS61201708A/en active Granted
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5835561A (en) * | 1981-08-26 | 1983-03-02 | Fuji Xerox Co Ltd | Device for preventing contamination of optical system in copying machine |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61201708A (en) | 1986-09-06 |
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