JPH0558798A - Production of copper oxide whisker - Google Patents
Production of copper oxide whiskerInfo
- Publication number
- JPH0558798A JPH0558798A JP24646291A JP24646291A JPH0558798A JP H0558798 A JPH0558798 A JP H0558798A JP 24646291 A JP24646291 A JP 24646291A JP 24646291 A JP24646291 A JP 24646291A JP H0558798 A JPH0558798 A JP H0558798A
- Authority
- JP
- Japan
- Prior art keywords
- whiskers
- copper oxide
- copper
- alloy
- group
- 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.)
- Pending
Links
Abstract
Description
【産業上の利用分野】本発明はプラスチックの充填材、
補強材、その他各種用途に利用することができる酸化銅
ウイスカーの製造方法に関する。FIELD OF THE INVENTION The present invention relates to a plastic filler,
The present invention relates to a method for producing a copper oxide whisker that can be used for a reinforcing material and various other purposes.
【従来の技術】金属酸化物は板状、針状、あるいはブロ
ック状等の各種形状を示し、中でもウイスカーと呼ばれ
る針状単結晶をするものもある。ウイスカーを形成する
金属酸化物としては、酸化亜鉛、酸化ベリリウム等が知
られている。又、酸化物ではないが炭化物として炭化ケ
イ素、窒化物として窒化チタン等がウイスカーとしてよ
く知られ、現在プラスチックの充填材、補強材として有
望視されているものの、高価であったり製造に多大な労
力を要したりするため、必ずしも満足のいくものではな
かった。2. Description of the Related Art Metal oxides have various shapes such as a plate shape, a needle shape, or a block shape, and among them, there are some which form a needle-shaped single crystal called whiskers. Zinc oxide, beryllium oxide and the like are known as metal oxides forming whiskers. Also, although not an oxide, silicon carbide as a carbide and titanium nitride as a nitride are well known as whiskers, which are currently regarded as promising fillers and reinforcing materials for plastics, but are expensive and require a great deal of labor for production. Was not always satisfactory.
【発明の目的】このように各種の金属化合物のウイスカ
ーが知られていたが、酸化銅がウイスカーとして生成す
ることは、未だ知られていなかった。本発明者らは、先
に特願平２−３０４０３０号において、新規な酸化銅ウ
イスカーと、それを製造する方法を提案した。本発明
は、この新規な酸化銅ウイスカーを更に効率よく製造す
る方法を提供することを目的とする。さらに、金属銅か
ら確実に酸化銅ウイスカーを生成せしめることを目的と
する。さらに、安価な金属銅を主原料とすることにより
経済性に富む酸化銅ウイスカーを提供することを目的と
する。さらに、比較的簡単な手法をもって酸化銅ウイス
カーを生成させ、提供することを目的とする。さらに他
の目的は、以下の説明から明らかになるだろう。OBJECTS OF THE INVENTION Whiskers of various metal compounds have been known as described above, but it has not been known yet that copper oxide is produced as whiskers. The present inventors previously proposed a novel copper oxide whisker and a method for producing the same in Japanese Patent Application No. 2-304030. An object of the present invention is to provide a method for more efficiently producing this novel copper oxide whisker. Furthermore, it is intended to surely form copper oxide whiskers from metallic copper. Another object of the present invention is to provide an economical copper oxide whisker by using inexpensive metallic copper as a main raw material. Furthermore, it aims at producing and providing a copper oxide whisker with a comparatively simple method. Still other objects will become apparent from the description below.
【問題点を解決するための手段】本発明は、金属銅に少
なくとも１種の三族ｂ亜属の元素をそ添加した合金を、
酸素含有雰囲気下で加熱することを特徴とする酸化銅ウ
イスカーの製造方法を提供する。理由は明らかではない
が、三族ｂ亜属元素を添加した合金を、酸素含有雰囲気
下で加熱することにより酸化銅ウイスカーが効率よく製
造できることが見出されたのである。三族ｂ亜属元素と
しては、ホウ素、アルミニウム、ガリウム又はインジウ
ムの単独又は２種以上の組合わせが好ましく、中でもア
ルミニウムが好ましい。金属銅に三族ｂ亜属元素以外の
金属や元素を加えると、酸化銅ウイスカーが生成しなか
ったり、生成してもわずかであるので、好ましくない。
三族ｂ亜属元素の添加量は０.０４乃至２.６０重量％の
範囲が好ましく、特に好ましい範囲は０.４０乃至２.２
０重量％である。銅合金中の三族ｂ亜属元素の含有量が
０.０４重量％以下の場合はウイスカーの生成は困難で
ある。又２.６０重量％よりも多くなるとウイスカーを
生成しないか又は生成しても僅かな量であるので好まし
くない。酸化銅ウイスカーを製造する具体的手法として
は先づ銅と三族ｂ亜属の元素のいずれか１種、又は２種
以上の組み合わせをルツボに入れ、真空炉、マツフル
炉、高周波炉、あるいはアーク炉等で熔融し銅合金を得
る。この時、あらかじめ三族ｂ亜属の元素を銅と一緒に
加えておいて溶解してもよいし、或いは炉の構造によっ
ては銅をあらかじめ溶解し、熔融している銅に三族ｂ亜
属の元素を加えてもよい。いずれにしても銅にこれらの
元素が混然一体となった合金であればよい。このように
して得られた合金をヤスリ、グラインダー等で機械的に
削って粉末を得るか、又は、アトマイズ法と呼ばれる方
法、即ち合金を熔融して噴霧し、粉末にしいも良い。こ
の粉末を酸素が５〜１００％の割合で含まれる雰囲気
中、例えば酸素と窒素の混合気体中で２５０〜７００℃
で加熱することにより、酸化銅ウイスカーを安定的に得
ることが出来る。加熱のための好ましい温度条件は、２
５０乃至７００℃である。温度が２５０℃以下の場合で
はウイスカーが生成しないか、または、ウイスカーが生
成しても極く微量であったり、極めて細かいウイスカー
であったりして、好ましくない。また、７００℃を越え
るとウイスカーが溶融状態となり、好ましくない。上記
のような雰囲気及び温度条件下で銅合金を０.５〜３０
時間加熱する。さらに、詳しくは以下の実施例をもって
明らかになるであろう。SUMMARY OF THE INVENTION The present invention provides an alloy in which at least one element of Group IIIb subgroup is added to metallic copper.
Provided is a method for producing a copper oxide whisker, which comprises heating in an oxygen-containing atmosphere. Although the reason is not clear, it has been found that a copper oxide whisker can be efficiently produced by heating an alloy to which a Group 3 subgroup b element is added in an oxygen-containing atmosphere. As the Group 3 subgroup b element, boron, aluminum, gallium, or indium is preferably used alone or in combination of two or more, and aluminum is particularly preferable. It is not preferable to add a metal or an element other than the Group 3 subgroup b element to the metallic copper, because copper oxide whiskers are not formed, or even if they are formed, only slightly.
The addition amount of Group III group b element is preferably in the range of 0.04 to 2.60% by weight, and particularly preferably in the range of 0.40 to 2.2.
It is 0% by weight. When the content of the Group 3 subgroup b element in the copper alloy is 0.04% by weight or less, it is difficult to form whiskers. Further, if it exceeds 2.60% by weight, whiskers are not formed, or even if they are formed, it is a slight amount, which is not preferable. As a concrete method for producing a copper oxide whisker, any one of the elements of the Group 3 subgroup b and the combination of two or more elements are put into a crucible first, and then a vacuum furnace, a pineapple furnace, a high frequency furnace, or an arc is produced. Melt in a furnace to obtain a copper alloy. At this time, an element of Group 3b subgroup may be added in advance together with copper to be melted, or depending on the structure of the furnace, copper may be previously melted and the molten copper may be added to Group 3b group b. You may add the element of. In any case, it may be an alloy in which these elements are mixed and integrated with copper. The alloy thus obtained may be mechanically ground with a filer, a grinder or the like to obtain powder, or a method called atomization method, that is, the alloy may be melted and sprayed to obtain powder. This powder is contained in an atmosphere containing oxygen in a ratio of 5 to 100%, for example, in a mixed gas of oxygen and nitrogen at 250 to 700 ° C.
By heating at 1, the copper oxide whiskers can be stably obtained. The preferred temperature condition for heating is 2
It is 50 to 700 ° C. When the temperature is 250 ° C. or lower, no whiskers are formed, or even if the whiskers are formed, the amount is very small or the particles are extremely fine, which is not preferable. Further, if the temperature exceeds 700 ° C., the whiskers are in a molten state, which is not preferable. Under the above atmosphere and temperature conditions, the copper alloy is added in an amount of 0.5 to 30.
Heat for hours. Further details will be made clear by the following examples.
実施例１ 電解銅板（同和鉱業（株）小坂鉱山、黒鉱より精錬）を
約１cm角位の大きさにブリキバサミを使って切断した。
この銅板１９.８ｇを、金属アルミニウム棒（模型工作
用アルミニウム棒：直径８mm、長さ１mm程度の市販品）
を削り出して得たアルミニウム粉末０.２ｇと一緒に、
ルツボ（ＴＯＰ，ＳＳＡ−Ｈ，Ｃ型）に入れ高周波電解
炉（イタリア製ＭＵＬＴＩＨＥＲＴＺＡＵＲＵＭ０５／
０Ｃ）に装着し、ルツボの開口部にはアルゴンガスを２
０ｍｌ／ｍｉｎの流量で流し不活性雰囲気とし、温度
℃で３００秒加熱溶解した。中の銅合金が固化した
のを肉眼で確かめ、ルツボを取り出し、水中に入れ完全
に冷却した。このルツボを割り、中の合金をを取り出
し、ヤスリで削り合金粉末を約１.２ｇ得た。この銅合
金粉末を１０mg採取し、真空理工（株）製示差熱分析計
（ＴＧＤ−７０００）を電気炉として、酸素を８０ｍｌ
／ｍｉｎの流量で流した環境の中で５５０℃で３時間加
熱処理をした。この熱処理後の粉末を走査型顕微鏡（日
本電子（株）製Ｔ−２０型）を用いて観察すると図１に
示すように明らかにウイスカーが生成していた。この時
のウイスカーは直径０.２μｍ、長さ２.０〜５.０μｍ
であった。又、重量計算から生成量を求めると５２.８
％であった。 比較例１ アルミニウムを加えない以外は全く実施例１と同様に操
作を行ったところ、単に酸化された表面が露出していた
だけで図１に示すような酸化銅ウイスカーは生成してい
なかった。 実施例２ 実施例１と同様にしてアルミニウムを別の三族ｂ亜属元
素に替え、表−１に示す様な組成で酸化銅ウイスカーの
生成を行った。結果を表−１に合わせて記載する。 比較例２ 実施例１と全く同様にしてアルミニウムの替りに三族ｂ
亜属以外の金属を表−１に併記した組成で酸化銅ウイス
カーの生成を行った。結果を表−１に合わせて記載する
が全く酸化銅ウイスカーの生成はなかった。なお、ここ
で使用した金属は総て和光純薬工業（株）の試薬１級と
記載されていたものである。Example 1 An electrolytic copper plate (refined from Kuroko ore, Kosaka mine, Dowa Mining Co., Ltd.) was cut into about 1 cm square pieces using tinplate scissors.
19.8 g of this copper plate is used as a metal aluminum rod (aluminum rod for model work: a commercial product having a diameter of 8 mm and a length of about 1 mm).
With 0.2g of aluminum powder obtained by shaving
Put in a crucible (TOP, SSA-H, C type) high frequency electrolysis furnace (MULTIHERTZAURUM05 / made in Italy)
0C), and 2 argon gas in the opening of the crucible.
Flow at a flow rate of 0 ml / min to create an inert atmosphere,
It was heated and melted at 300C for 300 seconds. It was visually confirmed that the copper alloy in the inside had solidified, and the crucible was taken out, put in water and completely cooled. The crucible was broken, the alloy inside was taken out, and scraped with a file to obtain about 1.2 g of alloy powder. 10 mg of this copper alloy powder was sampled and 80 ml of oxygen was used by using a differential thermal analyzer (TGD-7000) manufactured by Vacuum Riko Co., Ltd. as an electric furnace.
The heat treatment was performed at 550 ° C. for 3 hours in an environment of flowing at a flow rate of / min. When the powder after the heat treatment was observed with a scanning microscope (T-20 type manufactured by JEOL Ltd.), whiskers were clearly formed as shown in FIG. The whiskers at this time have a diameter of 0.2 μm and a length of 2.0 to 5.0 μm.
Met. Also, when the amount of product is calculated from the weight calculation, it is 52.8
%Met. Comparative Example 1 When the same operation as in Example 1 was carried out except that aluminum was not added, only the oxidized surface was exposed and the copper oxide whiskers as shown in FIG. 1 were not formed. Example 2 In the same manner as in Example 1, aluminum was replaced with another Group 3 subgroup b element, and copper oxide whiskers having the composition shown in Table 1 were produced. The results are also shown in Table 1. Comparative Example 2 In exactly the same manner as in Example 1, instead of aluminum, Group III b
Copper oxide whiskers were produced with the composition shown in Table 1 for metals other than subgenus. The results are also shown in Table 1, but no copper oxide whiskers were formed. In addition, all the metals used here were described as the first grade reagent of Wako Pure Chemical Industries, Ltd.
【表１】 但し、表−１中、 ×・・・生成を確認出来ず △・・・生成を認めるが明らかにウイスカーとは断定出
来ない 〇・・・明らかにウイスカーが生成している 実施例３ 実施例１と全く同様にしてアルミニウムの替りに表−２
に記載する様な三族ｂ亜属元素を組み合わせて合金を作
成し、酸化銅ウイスカーの生成を試みた。結果を表−２
に合わせて記載する[Table 1] However, in Table 1, × ... Generation cannot be confirmed. Δ ... Generation is recognized, but it cannot be clearly determined to be whiskers. ◯ ... Clearly whiskers are generated. Example 3 Example 1 In the same way as in Table 2 instead of aluminum
An alloy was prepared by combining the Group 3 b subgroup elements as described in 1 above and an attempt was made to form copper oxide whiskers. The results are shown in Table-2.
Enter according to
【表２】 実施例４ 実施例１と全く同様にして表−３のようにアルミニウム
の組成比率を変え、その他は全く替えずに酸化銅ウイス
カーの生成を試みた。結果を表−３に合わせて記載す
る。[Table 2] Example 4 The production of copper oxide whiskers was tried in exactly the same manner as in Example 1 except that the aluminum composition ratio was changed as shown in Table 3 and the others were not changed. The results are also shown in Table 3.
【表３】 比較例４ 実施例１と同様にしてアルミニウムを０.８％、鉄を０.
２％加え、それ以外は全く同様にしたところ、ウイスカ
ーの生成は認められなかった。実施例４のＮｏ．９に示
すように、アルミニウムを０.８％添加した場合はウイ
スカーの生成を認められるにも関わらず、これに三族ｂ
亜属以外の元素がわずかに添加されただけで、ウイスカ
ーの生成は認められなかった。[Table 3] Comparative Example 4 As in Example 1, aluminum was 0.8% and iron was 0.8%.
When 2% was added and the other conditions were exactly the same, the formation of whiskers was not observed. No. 4 of the fourth embodiment. As shown in Fig. 9, whisker formation was observed when 0.8% of aluminum was added.
No elements other than subgenus were added, and whiskers were not formed.
【発明の効果】以上、説明した様に本発明によれば酸化
銅ウイスカーを効率よく、かつ合理的に得ることが出来
る。このウイスカーはプラスチツクの充填材や強化材等
として利用出来るし、又酸化銅ウイスカーが導電性であ
ることに着目し、ＥＭＩ対策用材料として極めて有効で
もある。酸化銅ウイスカーの特性を利用した他の様々な
応用が期待出来る。As described above, according to the present invention, copper oxide whiskers can be obtained efficiently and rationally. This whisker can be used as a filler or a reinforcing material for plastics, and attention is paid to the fact that the copper oxide whisker is conductive, and is also extremely effective as an EMI countermeasure material. Various other applications can be expected utilizing the characteristics of copper oxide whiskers.
【図１】図１は、本発明の実施例１によって得られた酸
化銅ウイスカー（繊維）の形状を示す電子顕微鏡写真で
ある。FIG. 1 is an electron micrograph showing the shape of a copper oxide whisker (fiber) obtained according to Example 1 of the present invention.
─────────────────────────────────────────────────────
─────────────────────────────────────────────────── ───
【手続補正書】[Procedure amendment]
【提出日】平成３年１０月３１日[Submission date] October 31, 1991
【手続補正１】[Procedure Amendment 1]
【補正対象書類名】明細書[Document name to be amended] Statement
【補正対象項目名】発明の詳細な説明[Name of item to be amended] Detailed explanation of the invention
【補正方法】変更[Correction method] Change
【補正内容】[Correction content]
【発明の詳細な説明】Detailed Description of the Invention
【０００１】[0001]
【産業上の利用分野】本発明はプラスチックの充填材、
補強材、その他各種用途に利用することができる酸化銅
ウイスカーの製造方法に関する。FIELD OF THE INVENTION The present invention relates to a plastic filler,
The present invention relates to a method for producing a copper oxide whisker that can be used for a reinforcing material and various other purposes.
【０００２】[0002]
【従来の技術】金属酸化物は板状、針状、あるいはブロ
ック状等の各種形状を示し、中でもウイスカーと呼ばれ
る針状単結晶をするものもある。2. Description of the Related Art Metal oxides have various shapes such as a plate shape, a needle shape, or a block shape, and among them, there are some which form a needle-shaped single crystal called whiskers.
【０００３】ウイスカーを形成する金属酸化物として
は、酸化亜鉛、酸化ベリリウム等が知られている。又、
酸化物ではないが炭化物として炭化ケイ素、窒化物とし
て窒化チタン等がウイスカーとしてよく知られ、現在プ
ラスチックの充填材、補強材として有望視されているも
のの、高価であったり製造に多大な労力を要したりする
ため、必ずしも満足のいくものではなかった。Zinc oxide, beryllium oxide and the like are known as metal oxides forming whiskers. or,
Although not an oxide, silicon carbide as a carbide and titanium nitride as a nitride are well known as whiskers, and although they are currently promising as fillers and reinforcing materials for plastics, they are expensive and require a lot of labor for manufacturing. It wasn't always satisfactory.
【０００４】[0004]
【発明の目的】このように各種の金属化合物のウイスカ
ーが知られていたが、酸化銅がウイスカーとして生成す
ることは、未だ知られていなかった。OBJECTS OF THE INVENTION Whiskers of various metal compounds have been known as described above, but it has not been known yet that copper oxide is produced as whiskers.
【０００５】本発明者らは、先に特願平２−３０４０３
０号において、新規な酸化銅ウイスカーと、それを製造
する方法を提案した。The present inventors have previously proposed Japanese Patent Application No. 2-30403.
In No. 0, a novel copper oxide whisker and a method for producing it were proposed.
【０００６】本発明は、この新規な酸化銅ウイスカーを
更に効率よく製造する方法を提供することを目的とす
る。An object of the present invention is to provide a method for more efficiently producing this novel copper oxide whisker.
【０００７】さらに、金属銅から確実に酸化銅ウイスカ
ーを生成せしめることを目的とする。Another object of the present invention is to reliably produce copper oxide whiskers from metallic copper.
【０００８】さらに、安価な金属銅を主原料とすること
により経済性に富む酸化銅ウイスカーを提供することを
目的とする。Another object of the present invention is to provide a copper oxide whisker which is economically rich by using inexpensive metallic copper as a main raw material.
【０００９】さらに、比較的簡単な手法をもって酸化銅
ウイスカーを生成させ、提供することを目的とする。Another object of the present invention is to produce and provide copper oxide whiskers by a relatively simple method.
【００１０】さらに他の目的は、以下の説明から明らか
になるだろう。Still other objects will become apparent from the description below.
【００１１】[0011]
【問題点を解決するための手段】本発明は、金属銅に少
なくとも１種の三族ｂ亜属の元素をそ添加した合金を、
酸素含有雰囲気下で加熱することを特徴とする酸化銅ウ
イスカーの製造方法を提供する。理由は明らかではない
が、三族ｂ亜属元素を添加した合金を、酸素含有雰囲気
下で加熱することにより酸化銅ウイスカーが効率よく製
造できることが見出されたのである。SUMMARY OF THE INVENTION The present invention provides an alloy in which at least one element of Group IIIb subgroup is added to metallic copper.
Provided is a method for producing a copper oxide whisker, which comprises heating in an oxygen-containing atmosphere. Although the reason is not clear, it has been found that a copper oxide whisker can be efficiently produced by heating an alloy to which a Group 3 subgroup b element is added in an oxygen-containing atmosphere.
【００１２】三族ｂ亜属元素としては、ホウ素、アルミ
ニウム、ガリウム又はインジウムの単独又は２種以上の
組合わせが好ましく、中でもアルミニウムが好ましい。
金属銅に三族ｂ亜属元素以外の金属や元素を加えると、
酸化銅ウイスカーが生成しなかったり、生成してもわず
かであるので、好ましくない。As the Group IIIb element, boron, aluminum, gallium or indium is preferably used alone or in combination of two or more, and aluminum is particularly preferable.
When metals or elements other than Group 3 b subgroup elements are added to metallic copper,
It is not preferable because copper oxide whiskers are not produced or are little produced.
【００１３】三族ｂ亜属元素の添加量は０．０４乃至
２．６０重量％の範囲が好ましく、特に好ましい範囲は
０．４０乃至２．２０重量％である。銅合金中の三族ｂ
亜属元素の含有量が０．０４重量％以下の場合はウイス
カーの生成は困難である。又２．６０重量％よりも多く
なるとウイスカーを生成しないか又は生成しても僅かな
量であるので好ましくない。The addition amount of the Group 3 subgroup b element is preferably in the range of 0.04 to 2.60% by weight, and particularly preferably in the range of 0.40 to 2.20% by weight. Group III b in copper alloys
When the content of the subgenus element is 0.04% by weight or less, it is difficult to form whiskers. On the other hand, if it exceeds 2.60% by weight, whiskers are not formed, or even if they are formed, it is a small amount, which is not preferable.
【００１４】酸化銅ウイスカーを製造する具体的手法と
しては先づ銅と三族ｂ亜属の元素のいずれか１種、又は
２種以上の組み合わせをルツボに入れ、真空炉、マツフ
ル炉、高周波炉、あるいはアーク炉等で熔融し銅合金を
得る。この時、あらかじめ三族ｂ亜属の元素を銅と一緒
に加えておいて溶解してもよいし、或いは炉の構造によ
っては銅をあらかじめ溶解し、熔融している銅に三族ｂ
亜属の元素を加えてもよい。いずれにしても銅にこれら
の元素が混然一体となった合金であればよい。As a concrete method for producing the copper oxide whiskers, any one of the elements of the Group 3 subgroup b, or a combination of two or more elements, is first put in a crucible, and a vacuum furnace, a pine-furnace furnace, and a high-frequency furnace are put together. Alternatively, it is melted in an arc furnace or the like to obtain a copper alloy. At this time, an element of Group IIIb subgroup may be added in advance together with copper to be melted, or depending on the structure of the furnace, copper may be previously melted and the molten copper may be group IIIb.
Subgenus elements may be added. In any case, it may be an alloy in which these elements are mixed and integrated with copper.
【００１５】このようにして得られた合金をヤスリ、グ
ラインダー等で機械的に削って粉末を得るか、又は、ア
トマイズ法と呼ばれる方法、即ち合金を熔融して噴霧
し、粉末にしいも良い。The alloy thus obtained may be mechanically ground with a filer, a grinder or the like to obtain powder, or a method called atomization method, that is, the alloy may be melted and sprayed to obtain powder.
【００１６】この粉末を酸素が５〜１００％の割合で含
まれる雰囲気中、例えば酸素と窒素の混合気体中で２５
０〜７００℃で加熱することにより、酸化銅ウイスカー
を安定的に得ることが出来る。This powder is used in an atmosphere containing oxygen in a ratio of 5 to 100%, for example, in a mixed gas of oxygen and nitrogen.
By heating at 0-700 degreeC, a copper oxide whisker can be obtained stably.
【００１７】加熱のための好ましい温度条件は、２５０
乃至７００℃である。温度が２５０℃以下の場合ではウ
イスカーが生成しないか、または、ウイスカーが生成し
ても極く微量であったり、極めて細かいウイスカーであ
ったりして、好ましくない。また、７００℃を越えると
ウイスカーが溶融状態となり、好ましくない。The preferred temperature condition for heating is 250
To 700 ° C. When the temperature is 250 ° C. or lower, no whiskers are formed, or even if the whiskers are formed, the amount is very small or the particles are extremely fine, which is not preferable. Further, if the temperature exceeds 700 ° C., the whiskers are in a molten state, which is not preferable.
【００１８】上記のような雰囲気及び温度条件下で銅合
金を０．５〜３０時間加熱する。The copper alloy is heated for 0.5 to 30 hours under the above atmosphere and temperature conditions.
【００１９】さらに、詳しくは以下の実施例をもって明
らかになるであろう。Further details will be made clear by the following embodiments.
【００２０】[0020]
【実施例】 実施例１ 電解銅板（同和鉱業（株）小坂鉱山、黒鉱より精錬）を
約１ｃｍ角位の大きさにブリキバサミを使って切断し
た。この銅板１９．８ｇを、金属アルミニウム棒（模型
工作用アルミニウム棒：直径８ｍｍ、長さ１ｍｍ程度の
市販品）を削り出して得たアルミニウム粉末０．２ｇと
一緒に、ルツボ（ＴＯＰ，ＳＳＡ−Ｈ，Ｃ型）に入れ高
周波電解炉（イタリア製ＭＵＬＴＩＨＥＲＴＺ ＡＵＲ
ＵＭ０５／０Ｃ）に装着し、ルツボの開口部にはアルゴ
ンガスを２０ｍｌ／ｍｉｎの流量で流し不活性雰囲気と
し、温度１，４７０℃で３００秒加熱溶解した。中の銅
合金が固化したのを肉眼で確かめ、ルツボを取り出し、
水中に入れ完全に冷却した。このルツボを割り、中の合
金をを取り出し、ヤスリで削り合金粉末を約１．２ｇ得
た。この銅合金粉末を１０ｍｇ採取し、真空理工（株）
製示差熱分析計（ＴＧＤ−７０００）を電気炉として、
酸素を８０ｍｌ／ｍｉｎの流量で流した環境の中で５５
０℃で３時間加熱処理をした。この熱処理後の粉末を走
査型顕微鏡（日本電子（株）製Ｔ−２０型）を用いて観
察すると図１に示すように明らかにウイスカーが生成し
ていた。Example 1 An electrolytic copper plate (refined from Kuroka, Kosaka mine, Dowa Mining Co., Ltd.) was cut into about 1 cm square pieces using tin scissors. This copper plate (19.8 g) was used together with 0.2 g of aluminum powder obtained by cutting a metal aluminum rod (a commercial model aluminum rod having a diameter of 8 mm and a length of about 1 mm) together with a crucible (TOP, SSA-H). , C type) high frequency electrolysis furnace (MULTIHERTZ AUR made in Italy
UM05 / 0C), an argon gas was caused to flow through the opening of the crucible at a flow rate of 20 ml / min to make an inert atmosphere, and the mixture was heated and melted at a temperature of 1,470 ° C. for 300 seconds. Visually confirm that the copper alloy inside has solidified, take out the crucible,
It was placed in water and cooled completely. The crucible was broken, the alloy inside was taken out, and scraped with a file to obtain about 1.2 g of alloy powder. 10 mg of this copper alloy powder was sampled and manufactured by Vacuum Riko Co., Ltd.
A differential thermal analyzer (TGD-7000) manufactured as an electric furnace,
55 in an environment of flowing oxygen at a flow rate of 80 ml / min
Heat treatment was performed at 0 ° C. for 3 hours. When the powder after the heat treatment was observed with a scanning microscope (T-20 type manufactured by JEOL Ltd.), whiskers were clearly formed as shown in FIG.
【００２１】この時のウイスカーは直径０．２μｍ、長
さ２．０〜５．０μｍであった。又、重量計算から生成
量を求めると５２．８％であった。At this time, the whiskers had a diameter of 0.2 μm and a length of 2.0 to 5.0 μm. Further, the amount produced was calculated from the weight calculation and found to be 52.8%.
【００２２】比較例１ アルミニウムを加えない以外は全く実施例１と同様に操
作を行ったところ、単に酸化された表面が露出していた
だけで図１に示すような酸化銅ウイスカーは生成してい
なかった。Comparative Example 1 When the same operation as in Example 1 was carried out except that aluminum was not added, only the oxidized surface was exposed and copper oxide whiskers as shown in FIG. 1 were not formed. It was
【００２３】実施例２ 実施例１と同様にしてアルミニウムを別の三族ｂ亜属元
素に替え、表−１に示す様な組成で酸化銅ウイスカーの
生成を行った。結果を表−１に合わせて記載する。Example 2 In the same manner as in Example 1, aluminum was replaced with another Group 3 subgroup b element, and copper oxide whiskers having the composition shown in Table 1 were produced. The results are also shown in Table 1.
【００２４】比較例２ 実施例１と全く同様にしてアルミニウムの替りに三族ｂ
亜属以外の金属を表−１に併記した組成で酸化銅ウイス
カーの生成を行った。Comparative Example 2 In exactly the same manner as in Example 1, instead of aluminum, Group III b
Copper oxide whiskers were produced with the composition shown in Table 1 for metals other than subgenus.
【００２５】結果を表−１に合わせて記載するが全く酸
化銅ウイスカーの生成はなかった。なお、ここで使用し
た金属は総て和光純薬工業（株）の試薬１級と記載され
ていたものである。The results are also shown in Table 1, but no copper oxide whiskers were formed. In addition, all the metals used here were described as the first grade reagent of Wako Pure Chemical Industries, Ltd.
【００２６】[0026]
【表１】 但し、表−１中、 ×・・・生成を確認出来ず △・・・生成を認めるが明らかにウイスカーとは断定出
来ない ○・・・明らかにウイスカーが生成している[Table 1] However, in Table 1, x ... formation was not confirmed. △ ... formation was recognized, but it could not be clearly determined to be whiskers. O ... clearly whiskers were formed.
【００２７】実施例３ 実施例１と全く同様にしてアルミニウムの替りに表−２
に記載する様な三族ｂ亜属元素を組み合わせて合金を作
成し、酸化銅ウイスカーの生成を試みた。Example 3 In the same manner as in Example 1, Table 2 was used instead of aluminum.
An alloy was prepared by combining the Group 3 b subgroup elements as described in 1 above and an attempt was made to form copper oxide whiskers.
【００２８】結果を表−２に合わせて記載する。The results are shown in Table 2 together.
【００２９】[0029]
【表２】 [Table 2]
【００３０】実施例４ 実施例１と全く同様にして表−３のようにアルミニウム
の組成比率を変え、その他は全く替えずに酸化銅ウイス
カーの生成を試みた。Example 4 In exactly the same manner as in Example 1, the composition ratio of aluminum was changed as shown in Table 3 and the production of copper oxide whiskers was tried without changing anything else.
【００３１】結果を表−３に合わせて記載する。The results are shown in Table 3 together.
【００３２】[0032]
【表３】 [Table 3]
【００３３】比較例４ 実施例１と同様にしてアルミニウムを０．８％、鉄を
０．２％加え、それ以外は全く同様にしたところ、ウイ
スカーの生成は認められなかった。COMPARATIVE EXAMPLE 4 When 0.8% of aluminum and 0.2% of iron were added in the same manner as in Example 1 and the other conditions were the same, formation of whiskers was not observed.
【００３４】実施例４のＮｏ．９に示すように、アルミ
ニウムを０．８％添加した場合はウイスカーの生成を認
められるにも関わらず、これに三族ｂ亜属以外の元素が
わずかに添加されただけで、ウイスカーの生成は認めら
れなかった。No. 4 of the fourth embodiment. As shown in Fig. 9, whiskers were formed when 0.8% of aluminum was added, but whiskers were not formed when only elements other than Group 3 b subgenus were slightly added to the whiskers. I was not able to admit.
【００３５】[0035]
【発明の効果】以上、説明した様に本発明によれば酸化
銅ウイスカーを効率よく、かつ合理的に得ることが出来
る。As described above, according to the present invention, copper oxide whiskers can be obtained efficiently and rationally.
【００３６】このウイスカーはプラスチツクの充填材や
強化材等として利用出来るし、又酸化銅ウイスカーが導
電性であることに着目し、ＥＭＩ対策用材料として極め
て有効でもある。This whisker can be used as a filler or a reinforcing material for plastics, and attention is paid to the fact that the copper oxide whisker is conductive, and is also extremely effective as an EMI countermeasure material.
【００３７】酸化銅ウイスカーの特性を利用した他の様
々な応用が期待出来る。Various other applications can be expected utilizing the characteristics of the copper oxide whiskers.
Claims (3)
元素を添加した合金を、酸素含有雰囲気下で加熱するこ
とを特徴とする酸化銅ウイスカーの製造方法。1. A method for producing a copper oxide whisker, which comprises heating an alloy obtained by adding at least one element of Group IIIb subgroup to metallic copper in an oxygen-containing atmosphere.
ｂ亜属元素を含有する、請求項１に記載の酸化銅ウイス
カーの製造方法。2. The method for producing a copper oxide whisker according to claim 1, wherein the alloy contains 0.04 to 2.60% by weight of a Group 3 subgroup b element.
請求項１に記載の酸化銅ウイスカーの製造方法。3. The heating temperature is 250 to 700 ° C.
The method for producing the copper oxide whiskers according to claim 1.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24646291A JPH0558798A (en) | 1991-09-02 | 1991-09-02 | Production of copper oxide whisker |
| CA002068437A CA2068437A1 (en) | 1991-09-02 | 1992-05-12 | Copper oxide whiskers and process for producing the same |
| EP92107989A EP0530440A1 (en) | 1991-09-02 | 1992-05-12 | Copper oxide whiskers and process for producing the same |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP24646291A JPH0558798A (en) | 1991-09-02 | 1991-09-02 | Production of copper oxide whisker |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0558798A true JPH0558798A (en) | 1993-03-09 |
Family
ID=17148788
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP24646291A Pending JPH0558798A (en) | 1991-09-02 | 1991-09-02 | Production of copper oxide whisker |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0558798A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8640414B2 (en) | 2006-05-24 | 2014-02-04 | II Robert A. Reyes | Fully insulated glass panel rolling door |
-
1991
- 1991-09-02 JP JP24646291A patent/JPH0558798A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8640414B2 (en) | 2006-05-24 | 2014-02-04 | II Robert A. Reyes | Fully insulated glass panel rolling door |
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