JPS59116302A - Method for reducing hyperfine metallic particle - Google Patents
Method for reducing hyperfine metallic particleInfo
- Publication number
- JPS59116302A JPS59116302A JP57208500A JP20850082A JPS59116302A JP S59116302 A JPS59116302 A JP S59116302A JP 57208500 A JP57208500 A JP 57208500A JP 20850082 A JP20850082 A JP 20850082A JP S59116302 A JPS59116302 A JP S59116302A
- Authority
- JP
- Japan
- Prior art keywords
- particles
- hyperfine
- reducing
- reduction
- hydrogen
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 238000000034 method Methods 0.000 title claims description 16
- 239000013528 metallic particle Substances 0.000 title abstract 4
- 239000002245 particle Substances 0.000 claims abstract description 17
- 239000011164 primary particle Substances 0.000 claims abstract description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000007789 gas Substances 0.000 claims abstract description 9
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 239000002923 metal particle Substances 0.000 claims description 13
- 238000005245 sintering Methods 0.000 abstract description 7
- 238000010438 heat treatment Methods 0.000 abstract 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 10
- 239000002184 metal Substances 0.000 description 10
- 229910052751 metal Inorganic materials 0.000 description 10
- 229910052759 nickel Inorganic materials 0.000 description 5
- 239000010419 fine particle Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 230000004580 weight loss Effects 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- OAKJQQAXSVQMHS-UHFFFAOYSA-N Hydrazine Chemical compound NN OAKJQQAXSVQMHS-UHFFFAOYSA-N 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 229910001111 Fine metal Inorganic materials 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 229910001873 dinitrogen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011163 secondary particle Substances 0.000 description 1
- 238000007873 sieving Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 230000002269 spontaneous effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/20—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds
- B22F9/22—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from solid metal compounds using gaseous reductors
Abstract
Description
【発明の詳細な説明】
本発明は１次粒子平均粒径が１０００ Ａ以下の金Ｆｉ
ｌ１ｖ（微粒子の還元方法に関する。DETAILED DESCRIPTION OF THE INVENTION The present invention uses gold Fi having an average primary particle diameter of 1000 A or less.
l1v (Relating to a method for reducing fine particles.
１次粒子平均粒子径が１０００Å以下の金属超微れ′１
子は磁気記篩付料、導電性ペーストなどの電子材料、粉
末冶金材ｆ′１１化学反応試剤、触媒等に優れた性質を
示１ことが知られている。Ultra-fine metal particles with an average primary particle diameter of 1000 Å or less'1
It is known that the powder exhibits excellent properties in magnetic sieving materials, electronic materials such as conductive pastes, powder metallurgy materials, chemical reaction reagents, catalysts, etc.
従来の金Ｅｉ ＜”ｈ扮（１；Ｉｊえば１ミクロン以上
）の製法としては、金属を機械的に粉砕したり、あるい
は溶液中で金属含有化学試剤を適当な貸元剤により処理
干ることにより製造されてきた。捷だ、金属超微粒子（
通常１ミクロン以下の粒径の粒子）の製法としては、（
１）真空（１０−’ ｔＯｒｒ以下）中で金属を加熱蒸
発させる真空蒸発法、（２）数１００ｔｏｒｒ以下のア
ルゴン、窒素、水素等の雰囲気ガス中で金属を加熱蒸発
させるガス中蒸発法により製造する方法が開発されてき
た。Conventional methods for producing gold (1; if Ij is 1 micron or more) include mechanically crushing the metal, or processing and drying metal-containing chemical reagents in a solution with an appropriate base agent. It has been manufactured by.
The manufacturing method for (usually particles with a particle size of 1 micron or less) is (
1) Vacuum evaporation method in which the metal is heated and evaporated in a vacuum (10-' tOrr or less), (2) Manufactured by the in-gas evaporation method in which the metal is heated and evaporated in an atmospheric gas such as argon, nitrogen, hydrogen, etc. at several 100 torr or less. A method has been developed to do so.
これらのいずれの方法においても、製造される金漢扮の
粒径がミクロンオーダー程度より小さくなると、空気中
では、その高い比表面積、酸素との強い親和性のために
自然発火にいたる性質がある。そのために、製造時に金
属微粒子表面を除重化し、これを貯蔵・運搬する方法が
採用されている。勿論製造時に金属に対して不活性なガ
スあるいは液による密封等の方法により自然発火を防止
することはｎＪ能であるが、製造、貯蔵、運搬における
煩雑さ及び危険性が倍加するだめ、金属超微粒子を応用
使用することが制約されてきた。表面す飲酸化、された
金属超微粒子をその特性を摸う（例えば粒子間の焼結に
より粒径が増大する）ことなく、還元する方法が確立す
るならば産業的価値は大きい。In any of these methods, if the particle size of the produced Jinhange becomes smaller than the micron order, it has the tendency to spontaneously ignite in the air due to its high specific surface area and strong affinity for oxygen. . For this purpose, a method has been adopted in which the surface of metal fine particles is deweighted during production and then stored and transported. Of course, it is possible to prevent spontaneous ignition by sealing the metal with an inert gas or liquid during manufacturing, but this would double the complexity and danger of manufacturing, storage, and transportation. Applications of fine particles have been restricted. It would be of great industrial value if a method could be established for reducing ultrafine metal particles whose surface has been oxidized without altering their properties (for example, increasing the particle size due to sintering between particles).
本発明はこの間！、ＩＩＩ点を）・イ決ぜんとするもの
であり、その目的は表面が酸化物層で覆われた金属超微
粒子をその特性を４’ｔ１うことなく還元する方法を提
供するにある。This invention is now available! , III), and its purpose is to provide a method for reducing ultrafine metal particles whose surfaces are covered with an oxide layer without changing their properties.
本発明者は前記目的を達成すべく種々のい４元方法につ
いて研冗を重ねだ結果、水、アルコール等の溶媒中に金
属ｌ５−１微粒子を分散させ、還元剤例えば水素化ホウ
岩ナトリウノ１．ヒドラジン、ポルマリン等を添１川す
ることにより５元し得られることが分った。しかし、こ
の方法によると、金属の悸ン）１によっては、ゴ頑元剤
が強力でありすき゛だり、微弱でありすぎたり、斗た溶
媒の関与による還元された表面の、Ｊ＋）劣化が起った
ｌ）、還元７晶度、処理時間の条件設定に手数がかかる
等の間穎点がある。In order to achieve the above object, the present inventor has repeatedly studied various quaternary methods, and as a result, the metal l5-1 fine particles are dispersed in a solvent such as water or alcohol, and a reducing agent such as borohydride sodium 15-1 is used. ．． It was found that a 5-component solution can be obtained by adding hydrazine, polymerine, etc. However, according to this method, depending on the concentration of the metal, the hardening agent may be too strong or too weak, and the reduced surface may deteriorate due to the involvement of the solvent. There are some disadvantages such as low crystallinity, reduction of crystallinity, and the time required to set the processing time.
外だ、金属超微粒子を固定床とし、Ｊｑ元ガス雰囲包下
で’ｉｉ１． ’ｉ局するＪ二、−１除去の不完全、ガ
ス流のかだ、しり等によりＩり１（公的ハ゛＾結が進行
し／ζりあるいけ不十分なバ元部分が生ずる間顕点があ
ることが分った。Outside, 'ii1. 'i station J2, -1 removal is incomplete, gas flow rafts, tails, etc. cause I-1 (official high condensation progresses / It turns out that there is.
川に６１Ｆ究を車ね、金属超微粒子を水素含有ガス流に
より流動化し、昇温するときは極めて容易に、且つ焼結
することなく、均一に還元［７得られることが分った。After conducting a 61F study, it was found that when ultrafine metal particles are fluidized by a hydrogen-containing gas flow and heated, they can be uniformly reduced extremely easily and without sintering [7].
この知見に基いて本発明を完成した。The present invention was completed based on this knowledge.
本発明の要旨は、表面が酸化物層に晋われた１次粒子平
均粒径が１０００Å以下の金属超微粒子を水素含有ガス
流により流動化させながら昇温して還元する方法にある
。The gist of the present invention is a method for reducing ultrafine metal particles whose surfaces are covered by an oxide layer and whose primary particle average diameter is 1000 Å or less by raising the temperature while fluidizing them with a hydrogen-containing gas flow.
本発明において汀う１次粒子平均粒径１０００Å以下と
は、粒子平均粒径１０００Å以下の粒子が物理力、化学
力により集合した例えばそれらの粒子が繊維状に繋がっ
た２次粒子の形ｒ１号のものも含んだものを総称する。In the present invention, the primary particle average particle size of 1000 Å or less refers to the form of secondary particles No. A general term for things that include things like.
そして金属は種類を問わず、Ａｇ舌の貴金属、紺。And regardless of the type of metal, it is a precious metal with Ag tongue, and navy blue.
ニッケル、コバルト等の卑金属にすべて適用し得られる
。It can be applied to all base metals such as nickel and cobalt.
本発明の方法は、これらの金属超微粒子を流動層反応器
に仕込み、通常は純水素ガスを月１い、還元速度を抑え
る場合は不活性ガスで稀釈した水素ガスを使用して流動
化させる。流入させるガスの空す速度（空塔基準）はＧ
Ｈ８ｖテ５００〜１００００１／ｈｒがよいが、分留り
をよくする上からは１０００〜５０００１．／ｈｒであ
ることが好機しい。還元温度は１００〜３００℃がよい
。この温度より低いと還元速度がおそく、３００℃を超
えると焼結を起こす恐れがある。金属超微粒子の滞留時
間は０．１〜１０分間、好機しくは帆１〜１分である。In the method of the present invention, these ultrafine metal particles are charged into a fluidized bed reactor, and normally pure hydrogen gas is supplied once a month, but if the reduction rate is to be suppressed, hydrogen gas diluted with an inert gas is used to fluidize the particles. . The emptying speed of the inflowing gas (empty tower standard) is G
H8vte 500-100001/hr is good, but 1000-50001/hr is recommended for better fractionation. /hr is preferred. The reduction temperature is preferably 100 to 300°C. If the temperature is lower than this, the reduction rate is slow, and if it exceeds 300°C, there is a risk of sintering. The residence time of the ultrafine metal particles is 0.1 to 10 minutes, preferably 1 to 1 minute.
これらの条件は金属の種類、所望する還元程度により選
定する。These conditions are selected depending on the type of metal and the desired degree of reduction.
実施例１
１次粒子平均粒径が３００人である表面が酸化されたニ
ッケル超微粒子０゜１ｙを外径１０關φの流動層反応器
に仕込み、予め窒素ガスで系内を置換した後、水素ガス
で流動化させた。水素ガス量は常温常圧で１２０ｍ（７
分で供給し、層高は１８ｍｍであった。常温から１７５
℃まで昇温し、１７５℃で０．２５分間保持した後、反
応器外壁を急冷した。Example 1 Ultrafine nickel particles 0゜1y with an oxidized surface and an average primary particle diameter of 300 mm were charged into a fluidized bed reactor with an outer diameter of 10 mm, and after purging the system with nitrogen gas in advance, Fluidized with hydrogen gas. The amount of hydrogen gas is 120 m (7 m) at normal temperature and pressure.
The layer height was 18 mm. From room temperature to 175
After raising the temperature to 175°C and holding it for 0.25 minutes, the outer wall of the reactor was rapidly cooled.
得られた蹟元ニッケル超微粒子の比表面積は２７．０ｍ
２／２であシ、還元前の比表面積２７．３ ｍ２／ ｔ
と比較すると焼結の防止が達成されていることが分かる
。水蒸気発生を伴う還元による酸素損失のためによる重
量減は０．００５ Ｆであった。The specific surface area of the obtained ultrafine nickel particles was 27.0 m
2/2 size, specific surface area before reduction 27.3 m2/t
It can be seen that the prevention of sintering has been achieved when compared with the above. The weight loss due to oxygen loss due to reduction with steam generation was 0.005 F.
実施例２
１次粒子平均粒径が５００人である表面が酸化されたニ
ッケル超微粒子を用いて実施例１と同様な方法で還元し
た。還元前の比表面積は２．２ ｍ２／Ｓ’、還元後の
比表面積は２．１ｍ２／ｆ’であり、才だ重量減は０．
００６９であった。Example 2 Reduction was carried out in the same manner as in Example 1 using ultrafine nickel particles with an oxidized surface and an average primary particle diameter of 500 nm. The specific surface area before reduction was 2.2 m2/S', the specific surface area after reduction was 2.1 m2/f', and the weight loss was 0.
It was 0069.
実施例３
１次粒子平均粒径が１００ＯＡである表面が酸化された
ニッケル超微粒子を用いて実施例と同様な方法で還元し
た。還元前の比表面積は２．２ ｍ２／ ｆで還元後の
比表面積は２．１ ｍ２／２であり、重量減は０．００
０３ ｆであった。Example 3 Reduction was carried out in the same manner as in Example using ultrafine nickel particles with an oxidized surface and an average primary particle diameter of 100 OA. The specific surface area before reduction is 2.2 m2/f, the specific surface area after reduction is 2.1 m2/2, and the weight loss is 0.00
It was 03 f.
実施例４
１次粒子平均粒径が５００八である表面が酸化された銅
超微粒子を用いて実施例１と同様な方法で還元した。還
元前の比表面積は７．６ ｍ２／ｆ’で、還元後の比表
面積は７．３ｍ２７７であり、重量減は０．００３ ｒ
であった。Example 4 Reduction was carried out in the same manner as in Example 1 using surface-oxidized ultrafine copper particles having an average primary particle diameter of 500. The specific surface area before reduction was 7.6 m2/f', the specific surface area after reduction was 7.3 m277, and the weight loss was 0.003 r
Met.
以上のように、本発明の方法によると、金属超微粒子の
表面酸化層を全く焼結させることなく、１だ均一に容易
に還元し得られる効果を有する。As described above, the method of the present invention has the effect of easily and uniformly reducing the surface oxidized layer of ultrafine metal particles without sintering them at all.
特許用１人 新技術開発事業団
同 出卯人 林 ＠ 治手続補正書
昭和５９年１月３０１」
特許庁長官若杉和夫 殿
１、事件の表示
昭和５７年 特 許 願第２０８５００５２ 発明ｏ
名ｍ 金属超微粒子。還元方法３ 補正をする者
事件との関係 特許出願人
古、□＋１２ｊｌ 東京都千代田区永田町２丁目５番
２号氏 名（７山、）新技術開発事業団
（ほか１名）
４° 代 理 人 〒１６０電話５５６−６０９０
６ 補正により増加する発明の数 なし７ 補正の対象
明細書の発明の詳細な説明の欄
８ 補正の内容
（１）明細書第６頁６行「２．２ｍ２／り」を［２０，
３ｍ２／Ｓ’ｊと訂正する。1 person for patent use, New Technology Development Corporation, Ishuto Hayashi @ Administrative Procedures Amendment Document, January 1982, 301'' Kazuo Wakasugi, Commissioner of the Japan Patent Office, 1, Indication of Case 1982 Patent Application No. 20850052 Invention o
Name: ultrafine metal particles. Reduction method 3 Relationship with the person making the amendment Patent applicant Furu, □+12jl 2-5-2 Nagatacho, Chiyoda-ku, Tokyo Name (7 mountains) New Technology Development Corporation (and 1 other person) 4° Representation Person 160 Phone number 556-6090
6 Number of inventions increased by the amendment None 7 Column 8 for detailed explanation of the invention in the specification subject to the amendment Contents of the amendment (1) Change “2.2 m2/litre” on page 6, line 6 of the specification to [20,
Corrected to 3m2/S'j.
（２）同第６頁７ｔコ［２，１ｍ２／’ｉｉ’ Ｊを１
１９ 、７ ｍ／ｙｌと訂正する。(2) Same page 6 7t [2,1m2/'ii' J to 1
19, corrected to 7 m/yl.
Claims (1)
０００Å以下の金属超微粒子の還元処理工程において、
水素含有ガス流により金属超微粒子を流動化し昇温還元
することを特徴とする金属超微粒子の還元方法。1. The average particle size of primary particles whose surface is covered with an oxide layer is 1.
In the reduction treatment process of ultrafine metal particles of 000 Å or less,
A method for reducing ultrafine metal particles, which is characterized by fluidizing ultrafine metal particles using a hydrogen-containing gas flow and reducing the ultrafine metal particles by increasing the temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57208500A JPS59116302A (en) | 1982-11-30 | 1982-11-30 | Method for reducing hyperfine metallic particle |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP57208500A JPS59116302A (en) | 1982-11-30 | 1982-11-30 | Method for reducing hyperfine metallic particle |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS59116302A true JPS59116302A (en) | 1984-07-05 |
| JPH0232321B2 JPH0232321B2 (en) | 1990-07-19 |
Family
ID=16557180
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP57208500A Granted JPS59116302A (en) | 1982-11-30 | 1982-11-30 | Method for reducing hyperfine metallic particle |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS59116302A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5626645A (en) * | 1995-09-27 | 1997-05-06 | The United States Of America As Represented By The Department Of Energy | Process for making silver metal filaments |
| JP2007092099A (en) * | 2005-09-27 | 2007-04-12 | Nippon Steel Corp | Method for producing iron particle for producing hydrogen and method for producing gaseous hydrogen |
-
1982
- 1982-11-30 JP JP57208500A patent/JPS59116302A/en active Granted
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5626645A (en) * | 1995-09-27 | 1997-05-06 | The United States Of America As Represented By The Department Of Energy | Process for making silver metal filaments |
| JP2007092099A (en) * | 2005-09-27 | 2007-04-12 | Nippon Steel Corp | Method for producing iron particle for producing hydrogen and method for producing gaseous hydrogen |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0232321B2 (en) | 1990-07-19 |
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