JPH0514779B2 - - Google Patents
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- Publication number
- JPH0514779B2 JPH0514779B2 JP62070694A JP7069487A JPH0514779B2 JP H0514779 B2 JPH0514779 B2 JP H0514779B2 JP 62070694 A JP62070694 A JP 62070694A JP 7069487 A JP7069487 A JP 7069487A JP H0514779 B2 JPH0514779 B2 JP H0514779B2
- Authority
- JP
- Japan
- Prior art keywords
- metal
- particles
- composite material
- conductive composite
- dispersed
- 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
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- 229910052751 metal Inorganic materials 0.000 claims description 129
- 239000002184 metal Substances 0.000 claims description 129
- 239000002245 particle Substances 0.000 claims description 49
- 239000002131 composite material Substances 0.000 claims description 33
- 239000011159 matrix material Substances 0.000 claims description 12
- 229910052759 nickel Inorganic materials 0.000 claims description 12
- 238000004519 manufacturing process Methods 0.000 claims description 11
- 229910052787 antimony Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 16
- 229910052709 silver Inorganic materials 0.000 description 10
- 239000000463 material Substances 0.000 description 9
- 239000000498 cooling water Substances 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 238000002156 mixing Methods 0.000 description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 6
- 238000002844 melting Methods 0.000 description 6
- 230000008018 melting Effects 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- 239000011882 ultra-fine particle Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 238000005245 sintering Methods 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 238000005728 strengthening Methods 0.000 description 4
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- 239000000110 cooling liquid Substances 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 229910002804 graphite Inorganic materials 0.000 description 3
- 239000010439 graphite Substances 0.000 description 3
- 239000000155 melt Substances 0.000 description 3
- 238000000465 moulding Methods 0.000 description 3
- 238000007712 rapid solidification Methods 0.000 description 3
- 238000005299 abrasion Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 238000009689 gas atomisation Methods 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 239000007791 liquid phase Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 230000002787 reinforcement Effects 0.000 description 2
- 239000010979 ruby Substances 0.000 description 2
- 229910001750 ruby Inorganic materials 0.000 description 2
- 239000007790 solid phase Substances 0.000 description 2
- 229910000990 Ni alloy Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 229910052785 arsenic Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
Description
〔技術分野〕
この発明は、導電性複合材料およびその製法に
関する。
〔背景技術〕
Ag、Au、Cuなどの導電性材料に粒子を分散さ
せて強化する場合、粒子間距離が問題となる。外
力が働くと材料は変形するが、このとき転位が動
きながら変形する。転位を動きにくくすると変形
がしにくくなり、硬度も大きくなると言える。転
位を動かすのに必要な外力σは、
σ＝μb／2πλ μ：剛性率
ｂ：バーガスベクトル
λ：粒子間距離
で表される。
従つて、粒子間距離λを小さくすれば、転位を
動かそうとする力σが大きくなり、転位が動きに
くくなつて変形しにくい硬い導電性複合材料がで
きる。粒子間距離を小さくするためには、分散粒
子を小さく、粒子の含有量を多くすればよい。
真空中で金属を蒸発させてつくる0.01〜1μｍの
超微粒子が市販されている。２種のこのような超
微粒子を混合し、成形し、焼結し、そして機械的
に粉砕することにより分散強化粉末をつくること
ができる。0.07μｍのAg超微粒子と0.02μｍのNi
超微粒子を上記の方法で粉末とした場合の、Ag
中のNi粒子の分散状態を第２図に顕微鏡写真で
示した。Ni粒子は、Ag粒子およびNi粒子の合計
重量の５％を占める。第２図の写真で、小さな粒
状の部分がNi粒子、それらの周りをうめる海状
の部分がAgマトリツクスである。この写真にみ
るように、Ni超微粒子が多数凝集しており、超
微粒子を１つ１つ分離して分散させることは難し
い。しかも、この凝集したかたまりの分布が不均
一で、Ni粒子の存在しないかなり広いAgだけの
領域が存在する。これは全体的には硬度の低下を
引き起こす原因となる。また、このようなもの
は、現在のところ高価であり、工業製品として採
用しにくいなどの欠点があつた。
Asを強化する場合、Agに固溶しにくいNi粒子
とAg粒子を混合し、成形し、焼結し、そして機
械的に粉砕して所定の大きさの粉末を作製する方
法もある。この場合、AsおよびNiの粒子は、一
般には、数〜50μｍの大きさ（350メツシユ以下）
のため、第３図に示すように、Ni粒子が一部凝
集したりして、１〜20μｍの大きさのNi粒子が分
散し、分散強化の効果は小さくなる。
特開昭61−147827号公報には、Ag中に、１〜
20ミクロンのNi粒子とサブミクロンのNi微粒子
が均一に分散されている電気接点材料およびこの
材料の製法が開示されている。前述したように、
分散強化の効果を上げるためには、分散粒子間の
距離を小さくする必要がある。しかし、前記公報
で開示されている発明では、２種の大きさのNi
粒子が分散されており、しかも、１〜20ミクロン
という大きな粒子が混じつている。このため、分
散強化の効果がより低くかつた。また、この材料
の製法は、AgとNiをNiの融点以上の温度で溶解
させ、これを噴霧して粉末を得、この粉末を成形
した後順次焼結、圧縮、熱間圧縮、押出加工して
いる。得られた接点材料は前記のようなものであ
るので、前記粉末は２種の大きさの分散粒子を有
している。
〔発明の目的〕
この発明は、以上のことに鑑みて、従来の導電
性複合材料に比べて電気特性をあまり変化させず
に硬度を大きくし、粘着性が少なく、摩耗性およ
び高温での変形の少ない導電性複合材料を提供す
るとともに、そのような導電性複合材料をつくる
方法を提供することを目的とする。
〔発明の開示〕
上記の目的を達成するために、第１の発明は、
マトリツクス金属(A)中に、この金属(A)と二相分離
する金属(B)からなる粒径0.01〜1μｍの粒子が１種
以上分散されており、かつ、金属(A)と金属(B)との
合計重量に対し金属(B)が0.5〜20％である導電性
複合材料を要旨とし、第２の発明は、金属(A)およ
びこれと二相分離する金属(B)を含み、金属(A)およ
び金属(B)の合計重量に対して金属(B)が0.5〜20％
という割合である溶湯を急冷凝固させることによ
り、金属(A)中に、金属(B)からなる粒径0.01〜1μｍ
の粒子が１種以上分散されており、かつ、金属(A)
と金属(B)との合計重量に対し金属(B)が0.5〜20％
である導電性複合材料を得る導電性複合材料の製
法を要旨とする。
以下に、これらの発明を詳しく説明する。
マトリツクス金属(A)と二相分離する金属(B)と
は、金属(A)と均一の固相をつくらない、すなわ
ち、固溶体をつくらないもの、（全くつくらない
ものに限定せず、固溶する程度の低いものをも含
める）を指す。金属(A)と金属(B)とが溶融状態で均
一の液相をつくるか否かは問わないが、均一の液
相をつくる方が、固相となつたときに、金属(B)が
微細な状態で均一に金属(A)中に分散されやすいの
で、好ましい。
金属(A)としては、特に限定はないが、たとえ
ば、Ag、Au、Cuなどが挙げられる。
金属(B)としては、マトリツクス金属(A)に応じて
種々選択され、特に限定はない。たとえば、金属
(A)がAgである場合、金属(B)としては、Ni、Cr、
Fe、Co、Si、Rh、Ｖからなる群の中から選ばれ
た少なくとも１種が好ましい。金属(A)がAuであ
る場合、金属(B)としては、Ge、Si、Sb、Rhから
なる群の中から選ばれた少なくとも１種が好まし
い。金属(A)がCuである場合、金属(B)としては、
Feが好ましい。金属(A)と金属(B)としてこれらの
組み合わせを選択すれば、金属(B)の分散がより微
細で均一にすることが容易である。
分散される金属(B)の量は、金属(A)および金属(B)
の合計重量に対して0.5〜20％とする必要がある。
0.5％を下回ると、分散粒子の量が少ないため粒
子の間隔が大きくなり、分散強化の効果が少なく
なる。20％を上回ると、金属(A)中に細かく分散し
ない単独の大きな粒子の量が多くなる。
金属(B)は、粒径0.01〜1μｍの粒子となつて金属
(A)中に分散されていることが必要である。0.01μ
ｍを下回ると、金属(A)の導電性が低下するという
問題が生じる。1μｍを上回ると、分散強化の効
果が小さいという問題が生じる。なお、現実に
は、粒径1μｍより大で5μｍ以下の金属(B)粒子が、
金属(A)マトリツクス中の金属(B)粒子全体に対し
て、約5wt％以下入つていても差支えない。
この発明の導電性複合材料は、種々の方法で製
造される。たとえば、急冷凝固法を用いるように
すると、金属(B)が上記粒径範囲内の粒子となつて
金属(A)のマトリツクス中に分散されやすく、この
ようにするために、厳密な条件設定を特に必要と
しない。
溶融した金属を、周囲に水の膜を張つた回転盤
（回転ドラム）の中に噴出させ、溶融金属を急冷
凝固させる方法で、アモルフアス繊維を作製する
ことが行われている。このような方法を実施する
のに使われる装置で回転盤の回転スピードなどを
変えることにより、粉末なども作製することがで
きる。従来は、互いに固溶する金属を融解し、急
冷凝固させていた。
この発明の製法では、常温で互いに固溶しない
金属を溶融し、混合したのち、急冷凝固させるこ
とにより、マトリツクス金属中にこれと固溶しな
い金属粒子が均一に細かく分散した粉末などを作
製できるところに特徴がある。
急冷凝固法としては、特に限定はないが、回転
液中噴霧法、高圧ガスアトマイズ法が好ましい。
これらの方法によれば、マトリツクス金属(A)中に
金属(B)が、より微細かつ均一に分散した導電性複
合材料を得ることができる。
より具体的に説明すると、たとえば、Ag−
4.6wt％Ni合金粉末を作製するには、Agおよび
Niを65.4wt％Ag、4.6wt％Niの割合で黒鉛るつ
ぼに入れ、高周波溶融によつて1650℃の溶湯温度
とする。回転液中噴霧法の場合には、この溶湯を
直径0.1〜0.2mmのノズル孔から、回転するドラム
内壁に形成された水膜中に噴出すればよい。ま
た、高圧ガスアトマイズ法の場合、直径0.1〜５
mmのノズルから噴出した金属流を50〜100Kg／cm2
の高圧不活性ガスで噴霧すればよい。
第４図および第５図は、回転液中噴霧法に用い
られる装置の１例をあらわす。これらの図中、１
は、一端を閉じた円筒状の回転ドラム、２は冷却
液体、３は噴出炉、４は噴出ノズル、５は溶融金
属（溶湯）、６は急冷粉末、７は加熱装置、８は
駆動装置である。駆動装置８により回転ドラム１
が回転する。回転ドラム１の内壁には遠心力によ
り内壁を覆うように冷却液体２が膜を形成してい
る。金属(A)および金属(B)は加熱装置７により噴出
炉３内で溶融する。この溶融金属５は、噴出炉３
の上部の穴からのガスの圧力により、噴出ノズル
４から冷却液体２中へ噴出されて急冷され、急冷
粉末６ができる。
この発明の導電性複合材料を急冷凝固法により
製造する場合、冷却速度は、104〜105℃/sec.程
度以上とするのが好ましい。冷却速度が104〜105
℃／ｓｅｃ．程度を下回ると、金属(B)粒子の分散性が
悪くなるおそれがある。溶湯（溶融金属）の温度
は、金属(B)の融点より100℃以上高いことが好ま
しく、200℃以上高いとより好ましい。金属(B)の
融点より100℃以上高くないと、金属(B)単相の大
きな粒子が現れることがある。回転液中噴霧法に
おいて、冷却速度を上記のものとするためには、
溶湯を瞬時に冷却水中に噴出することが好まし
く、ノズルなどの溶湯噴出口と冷却水の表面との
距離を10mm以下にすることが好ましく、５mm以下
であることがより好ましい。その距離を10mmより
大きくした場合、できた導電性複合材料におい
て、金属(B)粒子の分散性が悪くなるおそれがあ
る。また、冷却水の速度Ｖは、噴出流の速度ｖよ
り充分に速いことが必要で、1.5≦ｖ／ｖ≦2.0で
あることが好ましい。冷却水の速度と噴出流の速
度が同程度の場合、冷却水の速度の方が遅い場
合、あるいは、冷却水の速度の方が極端に速い場
合、できた導電性複合材料において、金属(B)粒子
の分散性が悪くなるおそれがある。さらに、この
よつなおそれを防ぐためには、冷却水の温度は10
℃以下であることが好ましく、４℃以下であるこ
とがより好ましい。なお、冷却水は、冷却効果の
点から、静止しているより流れている方が好まし
い。
つぎに、この発明の１実施例をあらわす顕微鏡
写真を参照しながら、さらに詳しく説明する。な
お、第１図ないし第３図の各顕微鏡写真におい
て、写真上の実測長さ6.5mmは、それぞれ、長さ
10μｍに対応している。
第１図は、この発明の導電性複合材料が粉末で
ある場合の１実施例の組織をあらわす顕微鏡写真
である。この導電性複合材料は、Ag−4.6Ni
（Ni：4.6wt％、残部Ag）の溶湯を上記のように
して急冷凝固して作製したものである。第２図
は、0.07μｍのAg超微粉末と0.02μｍのNi超微粉
末をNi5wt％、残部Agという割合で混合し、成
形し、そして焼結して作製した導電性粉末の組織
をあらわす顕微鏡写真である。第３図は、通常の
Ag−5Ni導電性粉末の組織をあらわす顕微鏡写
真である。この粉末は、数〜50μｍの電解Ag粉
と、同じ大きさのカーボニールNi粉を混合し、
成形し、そして焼結して作製したものである。
第１図の写真に見るように、急冷凝固粉末で
は、Niが約0.5μｍの大きさで分散している。大
きさの極端に異なる粒子はほとんどない。第２図
の写真に見るように、超微粉末から作製した粉末
では、Niが約１〜10μｍの大きさで凝集してい
る。第３図の写真に見るように、従来の粉末で
は、Niが１〜20μｍの大きさで分散している。こ
のように、この発明の導電性粉末は、他のものに
比べて、分散金属が非常に細かく分散しているこ
とがわかる。
上記実施例では、この発明の導電性複合材料を
粉末で得たものとして説明したが、この発明の導
電性複合材料は、粉末以外に、たとえば、帯状、
繊維状等の形でも得られ、その形状は特に限定さ
れない。
この発明にかかる導電性複合材料は、分散金属
(B)が非常に細かく金属(A)のマトリツクス中に分散
しているので、従来のものに比べて、硬度が大き
い。したがつて、この発明にかかる導電性複合材
料は変形しにくく、材料同士の粘着性が少なくな
つている。常温における硬度が高いので、摩耗性
および高温での変形の少ないものとなつている。
また、従来のものと比べて、電気特性があまり変
わつていない。この発明の導電性複合材料の電気
特性は、分散される金属(B)の導電率、含有量によ
つて種々異なるが、発明者らが確かめたところで
は、粒径0.01〜1μｍ程度の金属(B)粒子が、金属(A)
と金属(B)との合計重量に対し0.5〜20％分散した
場合、導電率の変化はほとんどなかつた。このた
め、この発明にかかる導電性複合材料は、電気部
品、導電ペーストなど幅広い応用に利用すること
ができる材料である。
以下、実施例を示すが、この発明は実施例に限
定されない。
実施例 １
AgおよびNiをAg95wt％、Ni5wt％の割合で
黒鉛るつぼに入れ、高周波溶解によつて1650℃で
の溶湯温度とした。直径120μｍのルビー製ノズ
ル孔からアルゴン背圧4.5Kg/cm2で、500rpmで回
転する直径600mmのドラム内壁に形成された４℃
の水膜中に噴出した。このときの水膜と噴出した
溶湯とのなす角度は60゜であり、ノズル下端と水
面との距離は４mmであつた。
このようにして、100〜200μｍの粉末状の導電
性複合材料を作製し、Ar雰囲気中で850℃、３時
間焼鈍した。
このようにして得られた試料の硬度を測定し、
分散強化の評価とした。
実施例 ２
AgおよびNiをAg80wt％、Ni20wt％の割合で
黒鉛るつぼに入れ、高周波溶解によつて1750℃の
溶湯温度とした。この溶湯を直径３mmのルビー製
ノズル孔からアルゴン背圧１Kg/cm2で噴出し、そ
の噴出流を70Kg/cm2の高圧アルゴンガスで噴霧し
て急冷凝固粉末を作製した。
このようにして作製した粉末を実施例１と同様
にして焼鈍した。
実施例 ３〜15
実施例１において金属Ａおよび金属Ｂの種類、
配合量を第１表に示すようにした以外は実施例１
と同様にして、粉末状の導電性複合材料を得て、
実施例１と同様にして焼鈍した。
比較例 １
350メツシユ以下の、Ag粉末およびNi粉末を
第１表に示す割合で混合しのち、この粉末を400
℃の金型に入れ、10トン／cm2で成形し、アルゴン
雰囲気中で850℃、３時間焼結した。
比較例 ２〜５
実施例１において金属(A)および金属(B)の種類、
配合量を第１表に示すようにした以外は実施例１
と同様にして、粉末状の導電性複合材料を得て、
実施例１と同様にして焼鈍した。
上記実施例および比較例で得られた焼鈍粉末お
よび焼結材料の硬度を、マイクロビツカース硬度
計を用いて測定した。100ｇの荷重を15秒間加え
た。結果を第１表に示した。
[Technical Field] The present invention relates to a conductive composite material and a method for producing the same. [Background Art] When particles are dispersed in a conductive material such as Ag, Au, or Cu to strengthen it, the distance between the particles becomes a problem. When an external force is applied, the material deforms, and at this time, the dislocations move as the material deforms. It can be said that making it difficult for dislocations to move makes it difficult to deform and increases hardness. The external force σ required to move the dislocation is expressed as follows: σ=μb/2πλμ: rigidity b: Vargas vector λ: interparticle distance. Therefore, if the interparticle distance λ is reduced, the force σ that attempts to move the dislocations becomes larger, making it difficult for the dislocations to move, resulting in a hard conductive composite material that is difficult to deform. In order to reduce the interparticle distance, the dispersed particles may be made smaller and the content of the particles may be increased. Ultrafine particles of 0.01 to 1 μm are commercially available, which are made by evaporating metal in vacuum. A dispersion strengthened powder can be made by mixing two such ultrafine particles, compacting, sintering, and mechanically crushing. 0.07μm Ag ultrafine particles and 0.02μm Ni
When ultrafine particles are made into powder using the above method, Ag
Figure 2 shows a micrograph showing the dispersion state of the Ni particles inside. Ni particles account for 5% of the total weight of Ag and Ni particles. In the photograph in Figure 2, the small granular parts are Ni particles, and the sea-like part surrounding them is the Ag matrix. As seen in this photo, many ultrafine Ni particles are aggregated, and it is difficult to separate and disperse the ultrafine particles one by one. Moreover, the distribution of these agglomerated masses is non-uniform, and there is a fairly wide region containing only Ag and no Ni particles. This causes an overall decrease in hardness. Furthermore, such products currently have drawbacks such as being expensive and difficult to adopt as industrial products. When reinforcing As, there is also a method of mixing Ni particles and Ag particles that are difficult to dissolve in Ag, molding, sintering, and mechanically crushing to produce powder of a predetermined size. In this case, As and Ni particles generally have a size of several to 50 μm (350 mesh or less).
Therefore, as shown in FIG. 3, some of the Ni particles aggregate, and Ni particles with a size of 1 to 20 μm are dispersed, reducing the effect of dispersion strengthening. JP-A-61-147827 discloses that in Ag, 1 to
An electrical contact material in which 20 micron Ni particles and submicron Ni particles are uniformly dispersed and a method for manufacturing this material are disclosed. As previously mentioned,
In order to increase the dispersion strengthening effect, it is necessary to reduce the distance between dispersed particles. However, in the invention disclosed in the above publication, two sizes of Ni
The particles are dispersed, and large particles ranging from 1 to 20 microns are mixed in. Therefore, the effect of dispersion reinforcement was lower. The manufacturing method for this material is to melt Ag and Ni at a temperature higher than the melting point of Ni, spray this to obtain a powder, mold this powder, and then sequentially sinter, compress, hot press, and extrude. ing. Since the contact material obtained is as described above, the powder has two different sizes of dispersed particles. [Objective of the Invention] In view of the above, the present invention has been developed to increase hardness without significantly changing electrical properties compared to conventional conductive composite materials, and to reduce tackiness, abrasion resistance, and deformation at high temperatures. It is an object of the present invention to provide a conductive composite material with a small amount of conductive material, and to provide a method for producing such a conductive composite material. [Disclosure of the invention] In order to achieve the above object, the first invention
In the matrix metal (A), one or more particles with a particle size of 0.01 to 1 μm made of a metal (B) that separates into two phases from the metal (A) are dispersed, and the metal (A) and the metal (B) are dispersed in the matrix metal (A). ), the second invention includes a metal (A) and a metal (B) that separates into two phases from the metal (A), Metal (B) is 0.5 to 20% of the total weight of metal (A) and metal (B).
By rapidly cooling and solidifying the molten metal at a ratio of
One or more types of particles are dispersed, and metal (A)
Metal (B) is 0.5 to 20% of the total weight of
The gist of this paper is a method for manufacturing a conductive composite material that obtains a conductive composite material having the following properties. These inventions will be explained in detail below. A metal (B) that separates into two phases from the matrix metal (A) is one that does not form a uniform solid phase with the metal (A), that is, one that does not form a solid solution (not limited to one that does not form at all), (including those to a lesser extent). It does not matter whether metal (A) and metal (B) form a uniform liquid phase in the molten state, but it is better to create a uniform liquid phase when metal (B) becomes a solid phase. It is preferable because it is easily dispersed uniformly in the metal (A) in a fine state. The metal (A) is not particularly limited, and examples thereof include Ag, Au, and Cu. The metal (B) can be selected from various types depending on the matrix metal (A), and is not particularly limited. For example, metal
When (A) is Ag, the metal (B) is Ni, Cr,
At least one selected from the group consisting of Fe, Co, Si, Rh, and V is preferred. When the metal (A) is Au, the metal (B) is preferably at least one selected from the group consisting of Ge, Si, Sb, and Rh. When metal (A) is Cu, metal (B) is
Fe is preferred. If these combinations are selected as metal (A) and metal (B), it is easy to make the metal (B) more finely and uniformly dispersed. The amount of metal (B) dispersed is the amount of metal (A) and metal (B)
It should be 0.5 to 20% of the total weight.
When it is less than 0.5%, the amount of dispersed particles is small, so the spacing between the particles becomes large, and the effect of dispersion strengthening is reduced. When it exceeds 20%, the amount of individual large particles that are not finely dispersed in the metal (A) increases. Metal (B) is a metal in the form of particles with a particle size of 0.01 to 1 μm.
(A) must be dispersed in 0.01μ
If it is less than m, a problem arises in that the conductivity of the metal (A) decreases. If it exceeds 1 μm, a problem arises in that the effect of dispersion strengthening is small. In reality, metal (B) particles with a particle size of more than 1 μm and less than 5 μm are
There is no problem even if it is contained in an amount of about 5 wt% or less based on the total metal (B) particles in the metal (A) matrix. The conductive composite material of this invention can be manufactured by various methods. For example, if a rapid solidification method is used, the metal (B) becomes particles within the above particle size range and is likely to be dispersed in the metal (A) matrix. Not particularly necessary. Amorphous fibers are produced by jetting molten metal into a rotating disk (rotating drum) surrounded by a film of water, and rapidly cooling and solidifying the molten metal. Powders can also be produced by changing the rotational speed of the rotary disk in the equipment used to carry out such methods. Conventionally, metals in solid solution with each other were melted and rapidly solidified. In the manufacturing method of this invention, metal particles that do not dissolve in solid solution with each other at room temperature are melted, mixed, and then rapidly solidified to produce a powder in which metal particles that do not dissolve in solid solution with each other are uniformly and finely dispersed in the matrix metal. There are characteristics. The rapid solidification method is not particularly limited, but a rotating liquid spray method and a high-pressure gas atomization method are preferred.
According to these methods, it is possible to obtain a conductive composite material in which the metal (B) is more finely and uniformly dispersed in the matrix metal (A). To explain more specifically, for example, Ag−
To make 4.6wt%Ni alloy powder, Ag and
Ni is placed in a graphite crucible at a ratio of 65.4wt%Ag and 4.6wt%Ni, and the melt temperature is brought to 1650℃ by high frequency melting. In the case of the spraying method in a rotating liquid, this molten metal may be jetted from a nozzle hole with a diameter of 0.1 to 0.2 mm into a water film formed on the inner wall of a rotating drum. In addition, in the case of high-pressure gas atomization method, the diameter is 0.1 to 5
The metal flow ejected from the mm nozzle is 50 to 100Kg/ cm2.
It can be sprayed with high-pressure inert gas. FIGS. 4 and 5 show an example of an apparatus used in the rotating liquid spray method. In these figures, 1
is a cylindrical rotating drum with one end closed, 2 is a cooling liquid, 3 is a blowing furnace, 4 is a blowing nozzle, 5 is a molten metal (molten metal), 6 is a quenched powder, 7 is a heating device, and 8 is a driving device. be. Rotating drum 1 by drive device 8
rotates. A film of cooling liquid 2 is formed on the inner wall of the rotating drum 1 by centrifugal force so as to cover the inner wall. Metal (A) and metal (B) are melted in the ejection furnace 3 by the heating device 7. This molten metal 5 is
Due to the pressure of the gas from the hole in the upper part of the gas, it is ejected from the ejection nozzle 4 into the cooling liquid 2 and is quenched to form a quenched powder 6. When producing the conductive composite material of the present invention by a rapid solidification method, the cooling rate is preferably about 10 4 to 10 5 °C/sec. or more. Cooling rate is 10 4 ~ 10 5
°C/sec. If it is below this level, the dispersibility of the metal (B) particles may deteriorate. The temperature of the molten metal (molten metal) is preferably 100°C or more higher than the melting point of the metal (B), more preferably 200°C or more higher. If the temperature is not 100°C or more higher than the melting point of metal (B), large single-phase particles of metal (B) may appear. In order to achieve the above cooling rate in the rotating liquid spray method,
It is preferred that the molten metal is instantaneously jetted into the cooling water, and the distance between the molten metal spout such as a nozzle and the surface of the cooling water is preferably 10 mm or less, more preferably 5 mm or less. If the distance is greater than 10 mm, the dispersibility of metal (B) particles in the resulting conductive composite material may deteriorate. Further, the velocity V of the cooling water needs to be sufficiently faster than the velocity v of the jet flow, and it is preferable that 1.5≦v/v≦2.0. When the velocity of the cooling water and the velocity of the jet stream are similar, when the velocity of the cooling water is slower, or when the velocity of the cooling water is extremely faster, metal (B ) Particle dispersibility may deteriorate. Furthermore, to prevent this further fear, the temperature of the cooling water should be 10
The temperature is preferably below 4°C, more preferably below 4°C. In addition, from the point of view of the cooling effect, it is preferable that the cooling water is flowing rather than being stationary. Next, an embodiment of the present invention will be explained in more detail with reference to a photomicrograph showing one embodiment of the present invention. In addition, in each of the micrographs in Figures 1 to 3, the actual measured length of 6.5 mm in the photograph is the length
Compatible with 10μm. FIG. 1 is a microscopic photograph showing the structure of an example in which the conductive composite material of the present invention is a powder. This conductive composite material is made of Ag−4.6Ni
(Ni: 4.6wt%, balance Ag) molten metal was rapidly solidified as described above. Figure 2 shows the microscopic structure of conductive powder prepared by mixing 0.07 μm ultrafine Ag powder and 0.02 μm ultrafine Ni powder in a ratio of 5wt% Ni and the balance being Ag, molding, and sintering. It's a photo. Figure 3 shows the normal
It is a micrograph showing the structure of Ag-5Ni conductive powder. This powder is made by mixing electrolytic Ag powder of several to 50 μm and carbonyl Ni powder of the same size.
It is made by molding and sintering. As seen in the photograph in Figure 1, Ni is dispersed in the rapidly solidified powder with a size of approximately 0.5 μm. There are very few particles with extremely different sizes. As seen in the photograph of FIG. 2, in the powder made from ultrafine powder, Ni aggregates with a size of about 1 to 10 μm. As seen in the photograph in FIG. 3, in the conventional powder, Ni is dispersed in a size of 1 to 20 μm. Thus, it can be seen that in the conductive powder of the present invention, the dispersed metal is very finely dispersed compared to other powders. In the above embodiments, the conductive composite material of the present invention was explained as being obtained in the form of powder, but the conductive composite material of the present invention can be used in other forms other than powder, for example, in the form of a strip,
It can also be obtained in the form of fibers, etc., and the shape is not particularly limited. The conductive composite material according to the present invention has dispersed metal
Since (B) is very finely dispersed in the matrix of metal (A), it has greater hardness than conventional products. Therefore, the conductive composite material according to the present invention is difficult to deform, and the adhesiveness between the materials is reduced. Since it has high hardness at room temperature, it has low abrasion and deformation at high temperatures.
Furthermore, the electrical characteristics have not changed much compared to conventional ones. The electrical properties of the conductive composite material of this invention vary depending on the conductivity and content of the dispersed metal (B), but the inventors have confirmed that the metal (B) with a particle size of about 0.01 to 1 μm B) The particles are metal (A)
When dispersed in a proportion of 0.5 to 20% based on the total weight of the metal (B) and the metal (B), there was almost no change in conductivity. Therefore, the conductive composite material according to the present invention is a material that can be used in a wide range of applications such as electrical parts and conductive pastes. Examples will be shown below, but the present invention is not limited to the examples. Example 1 Ag and Ni were placed in a graphite crucible at a ratio of 95 wt% Ag and 5 wt% Ni, and the melt temperature was brought to 1650°C by high frequency melting. A temperature of 4°C was formed on the inner wall of a 600mm diameter drum rotating at 500rpm with an argon back pressure of 4.5Kg/ cm2 through a 120μm diameter ruby nozzle hole.
It erupted into a film of water. At this time, the angle between the water film and the spouted molten metal was 60°, and the distance between the lower end of the nozzle and the water surface was 4 mm. In this way, a powdery conductive composite material of 100 to 200 μm was produced and annealed at 850° C. for 3 hours in an Ar atmosphere. Measure the hardness of the sample obtained in this way,
It was evaluated as dispersion reinforcement. Example 2 Ag and Ni were placed in a graphite crucible at a ratio of 80 wt% Ag and 20 wt% Ni, and the melt temperature was brought to 1750°C by high frequency melting. This molten metal was spouted from a ruby nozzle hole with a diameter of 3 mm at an argon back pressure of 1 Kg/cm 2 , and the spouted flow was atomized with high-pressure argon gas at 70 Kg/cm 2 to produce a rapidly solidified powder. The powder thus produced was annealed in the same manner as in Example 1. Examples 3 to 15 In Example 1, the types of metal A and metal B,
Example 1 except that the blending amount was as shown in Table 1.
In the same manner as above, a powdered conductive composite material was obtained,
Annealing was performed in the same manner as in Example 1. Comparative Example 1 After mixing Ag powder and Ni powder of 350 mesh or less in the ratio shown in Table 1, this powder was mixed with 400 mesh
℃ mold, molded at 10 tons/cm 2 , and sintered at 850℃ for 3 hours in an argon atmosphere. Comparative Examples 2 to 5 In Example 1, the types of metal (A) and metal (B),
Example 1 except that the blending amount was as shown in Table 1.
In the same manner as above, a powdered conductive composite material was obtained,
Annealing was performed in the same manner as in Example 1. The hardness of the annealed powders and sintered materials obtained in the above examples and comparative examples was measured using a micro-Vickers hardness meter. A load of 100 g was applied for 15 seconds. The results are shown in Table 1.
この発明にかかる導電性複合材料は、以上にみ
てきたように、マトリツクス金属(A)中に、この金
属(A)と二相分離する金属(B)からなる粒径0.01〜1μ
ｍの粒子が１種以上分散されており、かつ、金属
(A)と金属(B)との合計重量に対し金属(B)が0.5〜20
％であるので、硬度が大きく、粘着性が少なく、
摩耗性および高温での変形の少ないものである。
この発明にかかる導電性複合材料の製法は、以
上にみてきたように、金属(A)およびこれと二相分
離する金属(B)を含み、金属(A)および金属(B)の合計
重量に対して金属(B)が0.5〜20％という割合であ
る溶湯を急冷凝固させることにより、金属(A)中
に、金属(B)からなる粒径0.01〜1μｍの粒子が１種
以上分散されており、かつ、金属(A)と金属(B)との
合計重量に対し金属(B)が0.5〜20％である導電性
複合材料を得るので、前記のような導電性複合材
料を容易につくることができる。
As described above, the conductive composite material according to the present invention is composed of a matrix metal (A) containing a metal (B) that separates into two phases from the metal (A), and has a particle size of 0.01 to 1 μm.
One or more types of particles m are dispersed, and metal
Metal (B) is 0.5 to 20% of the total weight of (A) and metal (B)
%, so the hardness is high and the stickiness is low.
It is less abrasive and less deformed at high temperatures. As seen above, the method for producing a conductive composite material according to the present invention includes a metal (A) and a metal (B) that separates into two phases from this, and the total weight of the metal (A) and metal (B) is On the other hand, by rapidly cooling and solidifying a molten metal containing 0.5 to 20% metal (B), one or more particles of metal (B) with a particle size of 0.01 to 1 μm are dispersed in metal (A). In addition, the conductive composite material as described above can be easily produced because the metal (B) is 0.5 to 20% of the total weight of the metal (A) and the metal (B). be able to.
第１図、第２図および第３図は金属の組織の顕
微鏡写真であり、第１図は１実施例のもの、第２
図は比較例のもの、第３図は従来の１例、第４図
は回転液中噴霧法に利用する装置の１例の断面
図、第５図はその斜視図である。
Figures 1, 2, and 3 are micrographs of the metal structure, with Figure 1 being of one example, and Figure 2 being of the second example.
The figures are of a comparative example, FIG. 3 is a conventional example, FIG. 4 is a sectional view of an example of an apparatus used in the rotating liquid spray method, and FIG. 5 is a perspective view thereof.
Claims (1)
分離する金属(B)からなる粒径0.01〜1μｍの粒子が
１種以上分散されており、かつ、金属(A)と金属(B)
との合計重量に対し金属(B)が0.5〜20％である導
電性複合材料。 ２ 金属(A)がAgあり、金属(B)がNi、Cr、Fe、
Co、Si、RhおよびＶからなる群の中から選ばれ
た少なくとも１種である特許請求の範囲第１項記
載の導電性複合材料。 ３ 金属(A)がAuであり、金属(B)がGe、Si、Sbお
よびRhからなる群の中から選ばれた少なくとも
１種である特許請求の範囲第１項記載の導電性複
合材料。 ４ 金属(A)がCuであり、金属(B)がFeである特許
請求の範囲第１項記載の導電性複合材料。 ５ 金属(A)およびこれと二相分離する金属(B)を含
み、金属(A)および金属(B)の合計重量に対して金属
(B)が0.5〜20％という割合である溶湯を急冷凝固
させることにより、金属(A)中に、金属(B)からなる
粒径0.01〜1μｍの粒子が１種以上分散されてお
り、かつ、金属(A)と金属(B)との合計重量に対し金
属(B)が0.5〜20％である導電性複合材料を得る導
電性複合材料の製法。 ６ 金属(A)がAgであり、金属(B)がNi、Cr、Fe、
Co、Si、RhおよびＶからなる群の中から選ばれ
た少なくとも１種である特許請求の範囲第５項記
載の導電性複合材料の製法。 ７ 金属(A)がAuであり、金属(B)がGe、Si、Sbお
よびRhからなる群の中から選ばれた少なくとも
１種である特許請求の範囲第５項記載の導電性複
合材料の製法。 ８ 金属(A)がCuであり、金属(B)がFeである特許
請求の範囲第５項記載の導電性複合材料の製法。[Scope of Claims] 1. In the matrix metal (A), one or more particles having a particle size of 0.01 to 1 μm made of a metal (B) that separates into two phases from the metal (A) are dispersed, and (A) and metal (B)
A conductive composite material in which metal (B) is 0.5 to 20% based on the total weight of 2 Metal (A) is Ag, metal (B) is Ni, Cr, Fe,
The conductive composite material according to claim 1, which is at least one member selected from the group consisting of Co, Si, Rh, and V. 3. The conductive composite material according to claim 1, wherein the metal (A) is Au, and the metal (B) is at least one selected from the group consisting of Ge, Si, Sb, and Rh. 4. The conductive composite material according to claim 1, wherein the metal (A) is Cu and the metal (B) is Fe. 5 Contains metal (A) and metal (B) that separates into two phases from it, and the metal is
By rapidly solidifying a molten metal containing (B) at a ratio of 0.5 to 20%, one or more particles of metal (B) with a particle size of 0.01 to 1 μm are dispersed in metal (A), and , A method for producing a conductive composite material in which the content of metal (B) is 0.5 to 20% based on the total weight of metal (A) and metal (B). 6 Metal (A) is Ag, metal (B) is Ni, Cr, Fe,
The method for producing a conductive composite material according to claim 5, which is at least one member selected from the group consisting of Co, Si, Rh, and V. 7. The conductive composite material according to claim 5, wherein the metal (A) is Au and the metal (B) is at least one selected from the group consisting of Ge, Si, Sb and Rh. Manufacturing method. 8. The method for producing a conductive composite material according to claim 5, wherein the metal (A) is Cu and the metal (B) is Fe.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62070694A JPS63238230A (en) | 1987-03-25 | 1987-03-25 | Conducting composite material and its production |
| US07/171,700 US4911769A (en) | 1987-03-25 | 1988-03-22 | Composite conductive material |
| GB8806756A GB2203167B (en) | 1987-03-25 | 1988-03-22 | Composite conductive material and method for manufacturing same |
| FR8803980A FR2613117B1 (en) | 1987-03-25 | 1988-03-25 | COMPOSITE CONDUCTIVE MATERIAL, METHOD FOR MANUFACTURING THE SAME, AND USE THEREOF IN A MATERIAL FOR ELECTRICAL CONTACTS |
| KR1019880003232A KR910006038B1 (en) | 1987-03-25 | 1988-03-25 | Composite conductive material |
| DE3810218A DE3810218C3 (en) | 1987-03-25 | 1988-03-25 | Process for producing a conductive composite material and electrical contact material obtainable therefrom |
| US07/468,210 US5022932A (en) | 1987-03-25 | 1990-01-22 | Rapid solidification of metal-metal composites having Ag, Au or Cu atrix |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP62070694A JPS63238230A (en) | 1987-03-25 | 1987-03-25 | Conducting composite material and its production |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS63238230A JPS63238230A (en) | 1988-10-04 |
| JPH0514779B2 true JPH0514779B2 (en) | 1993-02-25 |
Family
ID=13438995
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP62070694A Granted JPS63238230A (en) | 1987-03-25 | 1987-03-25 | Conducting composite material and its production |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS63238230A (en) |
Families Citing this family (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2821742B2 (en) * | 1987-10-22 | 1998-11-05 | 株式会社徳力本店 | Hard Ag alloy |
| JPH0826425B2 (en) * | 1988-09-16 | 1996-03-13 | 旭化成工業株式会社 | Conductive fiber and manufacturing method thereof |
| JP2702796B2 (en) * | 1990-02-23 | 1998-01-26 | 旭化成工業株式会社 | Silver alloy conductive paste |
| JPH03245405A (en) * | 1990-02-23 | 1991-11-01 | Asahi Chem Ind Co Ltd | Silver group alloy powder and conductive paste using same |
| JPH0791608B2 (en) * | 1990-06-21 | 1995-10-04 | 松下電工株式会社 | Contact material and manufacturing method thereof |
| JP2613966B2 (en) * | 1990-10-09 | 1997-05-28 | 松下電工株式会社 | Manufacturing method of contact material |
| KR20020028368A (en) * | 2000-10-09 | 2002-04-17 | 김수경 | Conductor of manufacturing method using gold and ceramic compound matter and the Conductor thereof |
| DE60227159D1 (en) * | 2001-03-06 | 2008-07-31 | Kiyohito Ishida | ELEMENT WITH SEPARATION STRUCTURE AND METHOD FOR THE PRODUCTION THEREOF |
| JP2006302525A (en) * | 2005-04-15 | 2006-11-02 | Kyoto Elex Kk | Conductive paste composition |
| JP4987558B2 (en) * | 2007-05-09 | 2012-07-25 | 京都エレックス株式会社 | Conductive paste composition |
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| JPS6141748A (en) * | 1984-08-06 | 1986-02-28 | Takeshi Masumoto | Second phase metal particle dispersion type alloy |
| JPS61147827A (en) * | 1984-12-21 | 1986-07-05 | Tanaka Kikinzoku Kogyo Kk | Ag-ni electrical contact material and its manufacture |
| JPS61149449A (en) * | 1984-12-24 | 1986-07-08 | Sumitomo Electric Ind Ltd | Composite material for lead frame for semiconductor device and its production |
| JPS6270683A (en) * | 1985-09-25 | 1987-04-01 | Jidosha Kiki Co Ltd | Screw rotor |
-
1987
- 1987-03-25 JP JP62070694A patent/JPS63238230A/en active Granted
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS56156743A (en) * | 1980-05-06 | 1981-12-03 | Nippon Telegr & Teleph Corp <Ntt> | Manufacture of electrical contact material |
| JPS58221245A (en) * | 1982-06-16 | 1983-12-22 | Matsushita Electric Ind Co Ltd | Manufacture of contact material |
| JPS6141748A (en) * | 1984-08-06 | 1986-02-28 | Takeshi Masumoto | Second phase metal particle dispersion type alloy |
| JPS61147827A (en) * | 1984-12-21 | 1986-07-05 | Tanaka Kikinzoku Kogyo Kk | Ag-ni electrical contact material and its manufacture |
| JPS61149449A (en) * | 1984-12-24 | 1986-07-08 | Sumitomo Electric Ind Ltd | Composite material for lead frame for semiconductor device and its production |
| JPS6270683A (en) * | 1985-09-25 | 1987-04-01 | Jidosha Kiki Co Ltd | Screw rotor |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS63238230A (en) | 1988-10-04 |
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