JPH0524209B2 - - Google Patents
Info
- Publication number
- JPH0524209B2 JPH0524209B2 JP59164694A JP16469484A JPH0524209B2 JP H0524209 B2 JPH0524209 B2 JP H0524209B2 JP 59164694 A JP59164694 A JP 59164694A JP 16469484 A JP16469484 A JP 16469484A JP H0524209 B2 JPH0524209 B2 JP H0524209B2
- Authority
- JP
- Japan
- Prior art keywords
- phase
- alloy
- metal
- particles
- amorphous
- 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
- 229910052751 metal Inorganic materials 0.000 claims description 37
- 239000002184 metal Substances 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 28
- 239000002923 metal particle Substances 0.000 claims description 26
- 238000000034 method Methods 0.000 claims description 19
- 239000011159 matrix material Substances 0.000 claims description 13
- 230000000171 quenching effect Effects 0.000 claims description 13
- 238000010791 quenching Methods 0.000 claims description 12
- 229910000808 amorphous metal alloy Inorganic materials 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 claims description 9
- 229910052737 gold Inorganic materials 0.000 claims description 7
- 238000004519 manufacturing process Methods 0.000 claims description 5
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229910052758 niobium Inorganic materials 0.000 claims description 4
- 229910052720 vanadium Inorganic materials 0.000 claims description 4
- 229910052790 beryllium Inorganic materials 0.000 claims description 3
- 229910052797 bismuth Inorganic materials 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- 229910052735 hafnium Inorganic materials 0.000 claims description 3
- 229910052745 lead Inorganic materials 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052727 yttrium Inorganic materials 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- 229910052796 boron Inorganic materials 0.000 claims description 2
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- 238000007712 rapid solidification Methods 0.000 claims description 2
- 229910045601 alloy Inorganic materials 0.000 description 29
- 239000000956 alloy Substances 0.000 description 29
- 239000002245 particle Substances 0.000 description 29
- 239000000463 material Substances 0.000 description 13
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000010949 copper Substances 0.000 description 9
- 229910052786 argon Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- 238000002844 melting Methods 0.000 description 5
- 230000008018 melting Effects 0.000 description 5
- 238000009987 spinning Methods 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000005096 rolling process Methods 0.000 description 4
- 238000005204 segregation Methods 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000010622 cold drawing Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000003507 refrigerant Substances 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- 239000000498 cooling water Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 150000001247 metal acetylides Chemical class 0.000 description 2
- 238000005191 phase separation Methods 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910000881 Cu alloy Inorganic materials 0.000 description 1
- 229910017263 Mo—C Inorganic materials 0.000 description 1
- 229910008423 Si—B Inorganic materials 0.000 description 1
- 239000011358 absorbing material Substances 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000005266 casting Methods 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002425 crystallisation Methods 0.000 description 1
- 230000008025 crystallization Effects 0.000 description 1
- 239000010432 diamond Substances 0.000 description 1
- 229910003460 diamond Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000012770 industrial material Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- -1 oxides Chemical class 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000010979 ruby Substances 0.000 description 1
- 229910001750 ruby Inorganic materials 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000007711 solidification Methods 0.000 description 1
- 230000008023 solidification Effects 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
Landscapes
- Soft Magnetic Materials (AREA)
Description
本発明は、母相中に微細な第２相金属粒子が均
一に分散してなる組織を有する第２相金属粒子分
散型非晶質合金の製造法に関するものである。
近年、新規金属材料を製造するプロセスとして
注目を集めている液体急冷法は、従来にない急冷
速度104〜106℃／secという急冷プロセスであり、
非晶質合金あるいは非平衡結晶質合金を容易に製
造することが可能である。
この液体急冷法の特徴である急冷効果を用い
て、非晶質あるいは結晶質合金中に第２相粒子を
分散させるという試みを行つた発明に特開昭59−
47341号公報及び特開昭59−47352号公報がある。
通常、母相中に炭化物、酸化物を分散させると、
母相の硬さ、耐摩耗性を向上させることができる
が、鋳造する際の冷却速度が非常に遅いために、
第２相粒子の偏析が大きく、特性のバラツキが大
きかつた。その偏析を少しでも小さくするため
に、液体急冷法を用い、第２相粒子分散型非晶質
合金を製造しようとしたのが、上記発明である。
この方法によると、従来材に比べて分散性は改
善される傾向にあつたが、上記発明の実施例にも
あるように、第２相粒子として用いられているも
のは、粒径1μｍのWC、TiC、BN、粒径2μｍの
ThO2、粒径3μｍのSiC、NbN、粒径5μｍのFe粒
子であり、その第２相粒子の粒径は、１〜5μｍ
と非常に大きく、また分散性についても最近接粒
子間隔が１〜100μｍとバラツキ、偏析が多く、
特性にもバラツキを生じる傾向にあつた。この理
由は、上記発明の製造法が、溶湯を相溶しない第
２相粒子（例えば炭化物、酸化物、金属、合金）
を溶湯と混合した状態から液体急冷法により急冷
凝固しているためであると考えられる。すなわ
ち、溶湯と第２相粒子の濡れ性が悪く、また溶湯
と第２相粒子が全く相溶しないために、偏席をお
こしやすく、凝固後の母相中の第２相粒子の粒径
は、溶湯と混合する前の粒径と変わらず大きく、
さらに第２相粒子の形状が角型であるため、応力
集中源になりやすい傾向にあつた。
本発明者らは、従来の第２相粒子分散型非晶質
合金よりもさらに微細な第２相金属粒子を母相中
に均一に分散させた非晶質合金を製造することを
目的として鋭意検討した結果、特定の２相分離す
る合金を相溶した液体単相の溶湯状態から液体急
冷法により急冷凝固させると、母相は非晶質相と
なり、さらに母相中に微細な第２相金属粒子が均
一に分散した組織を有する第２相金属粒子分散型
非晶質合金が得られることを見出し、得られた合
金が機械的性質、電気的性質、磁気的性質、耐食
性等の優れた特性を有しており、その特性もバラ
ツキがないことを見出し、本発明を完成した。
すなわち本発明は、式；MaXbYc（式中Ｍ、Ｘ
は非晶質相を形成する母相金属元素で、ＭはFe、
Co、Ni、Cr、Mo、Ｖからなる群より選ばれた
１種又は２種以上の元素、ＸはＢ、Ｐ、Si、Ｃ、
Ge、Zr、Hf、Nbからなる群より選ばれた１種
又は２種以上の元素であり、Ｙは急冷凝固後、第
２相金属粒子となる金属元素で、Cu、Ag、Au、
Pb、Bi、Sn、Beからなる群より選ばれた１種又
は２種以上の元素であり、ａは100−（ｂ＋ｃ）で
与えられる原子％で、ｂは10〜35原子％で、ｃは
１〜10原子％である。）で示される合金を溶融さ
せて相溶した液体単相の溶湯を得、次いで得られ
た溶湯を液体急冷法で急冷凝固させることを特徴
とする母相中に微細な第２相金属粒子が均一に分
散してなる組織を有する第２相金属粒子分散型非
晶質合金の製造法である。
本発明に適用する合金は、式；MaXbYcで示
される合金であることが必要である。ここで、
Ｍ、Ｘとは、非晶質合金母相を形成する元素で、
ＭはFe、Ni、Co、Mo、Ｖからなる群より選ば
れた１種又は２種以上の元素であり、ＸはＢ、
Ｐ、Si、Ｃ、Ge、Zr、Hf、Nbからなる群より選
ばれた１種又は２種以上の元素であり、Ｙとは第
２相金属粒子を形成する元素で、Cu、Ag、Au、
Pb、Bi、Sn、Beからなる群より選ばれた１種又
は２種以上の元素である。またａは100−（ｂ＋
ｃ）で与えられた原子％であり、ｂは10〜35原子
％であることが必要で、ｃは１〜10原子であるこ
とが必要である。ｂが10原子％未満、35原子％を
超える場合には、液体急冷法によつても非晶質形
成能が低下するため、母相は結晶化し、脆くな
り、またｃが１原子以下では、第２相金属粒子は
観察されず、さらにｃが10原子％を超える場合に
は、第２相金属粒子が粗大化し、不均一な分散と
なり、実用上有用性の乏しい材料をなる。また、
Ta、Ti、Ｗからなる群より選ばれた１種又は２
種以上の元素を５原子％以下で添加すると、得ら
れる合金の機械的性質や結晶化温度の上昇による
耐熱性の向上が見られるので好ましい。
本発明では、まず上記の合金を溶融させて相溶
した液体単相の溶湯を得ることが必要である。そ
のためには、冷えば、上記合金を、その合金の融
点よりも20〜250℃の高い温度で溶融させればよ
い。この場合、溶湯噴出用ノズル内で合金を溶解
する際、溶湯撹拌作用のある高周波加熱がよい
が、超音波振動を溶湯に与えて２相分離を抑える
方法、又は溶解用の高周波コイルとは別に内側に
用湯撹拌用コイルを併設して合金の２相分離を抑
える方法も好ましい結果を与える。また、用湯噴
出用ノズル内で合金を溶解したあと、噴出孔まで
の経路の中で堰又はセラミツクフイルターを設置
し、溶湯中の合金成分の偏析を抑えることも効果
がある。
次に上記で得た液体単相の溶湯を液体急冷法で
急冷凝固させる。この液体急冷法とは、溶融した
金属、合金を急速に冷却して過冷させ、その構造
を凍結させてアモルフアスとする方法をいい、例
えば、片ロール法、双ロール法及び回転液中紡糸
法が特に有効であり、これらの方法は104〜106
℃／secの冷却速度を有している。この片ロール
法、双ロール法等により薄帯材料を製造するに
は、例えば溶湯中に液々分離、固液分離の状態が
全くない、すなわち完全に相溶した液体単相の状
態の温度より、ノズル孔を通して約300〜
1000rpmで回転している直径30〜3000mmの例えば
銅あるいはCr鋼製のロールに噴出して幅が約１
〜300mmで厚さが約５〜500μｍの薄帯材料を容易
に得ることができる。また、回転液中紡糸法によ
り細線材料を製造するには、例えば溶湯中に液々
分離、固液分離した状態が全くない、すなわち完
全に相溶した液体単相の状態の温度より、ノズル
鋼を通してアルゴンガス背圧にて、50〜500rpm
で回転するドラム内に遠心力により深さ１〜10cm
の冷媒膜中に噴出して細線状材料を容易に得るこ
とができる。この際のノズルからの噴出溶湯と冷
媒面とのなす角度は、約20〜100度、噴出溶解湯
と冷媒面の速度比は0.7〜0.9であることが好まし
い。
このように相溶した液体単相の溶湯状態から液
体急冷法により急冷凝固させると、例えば、母相
中に粒径が１〜100nｍ程度の非常に微細で、か
つ１〜100nｍ程度の間隔に均一に分散した第２
相金属粒子を含む組織となり、第２相金属粒子の
粒径と第２相金属粒子間の間隔はほぼ同じである
といつた非常に優れた微細化及び分散の均一性が
見られる。例えば、70Fe−5Cr−10Si−13B−
2Auの合金は、粒径15nｍのAuの第２相金属粒子
が25nｍの粒子間隔で分散しているという極めて
微細で均一な組織を有している。また、70Fe−
10Cr−18B−2Cu合金は、粒径10nｍのCuの第２
相粒子が30nｍの粒子間隔で均一に分散されてい
る。このように本発明により得られた第２相金属
粒子分散型非晶質合金は、従来の第２相粒子分散
型非晶質合金と比較して第２相粒子の微細性、分
散の均一性は非常に優れている。
このような第２相金属粒子分散型非晶質合金、
例えば上記した70Fe−5Cr−10Si−13B−2Au合
金は、破断強度にしてもAuを含まない非晶質単
相合金と比較して335Kg／mm2から370Kg／mm2と大幅
な向上が見られる。また、上記70Fe−10Cr−
18B−2Cu合金は、硬さにおいて、Cuを含まない
非晶質単相合金と比較して290DPNから345DPN
と向上する。
本発明により得られた上記の組織を有する第２
相粒子分散型非晶質合金は、高い引張速度、良好
な靭性を有し、また良好な硬さ、耐摩耗性、耐疲
労性に優れており、電気抵抗も高く、電磁気特
性、電気的特性も良好なうえ、その特性もバラツ
キがないことから、各種工業用材料、複合材料、
フイルター及びストレーナ用材料、吸音材用繊
維、液体ヘリウムの液面センサー等のセンサー材
料、高抵抗線等に広く用いられ、工業的に非常に
有用な材料である。
以下、本発明を実施例により具体的に説明す
る。
実施例１〜15、比較例１〜６
表−１に示す各種組成よりなるFe−Cr−（Si、
Ｂ）−（Nb、Ta、Ｖ）＋（Cu、Au）、Fe−（Zr、
Hf）−Ｂ＋（Cu、Au）、Co−Si−Ｂ＋（Cu、Au）
及びFe−Mo−Ｃ＋（Cu、Au）系合金をアルゴン
ガス雰囲気中で溶融させて相溶した液体単相の溶
湯を得た。次いで溶湯温度を1300℃に保ち、アル
ゴンガス噴出圧3.5Kg／mm2で、孔径0.3mmの石英ノ
ズルより500rpmで回転している直径100mmの銅製
ロールに噴出して急冷凝固させて連続した表面形
状の均一な幅1.5mm、厚さ30μｍの薄帯材料を得
た。
これらの薄帯の組織観察を透過電子顕微鏡によ
り測定した。また破断強度をインストロン型引張
試験機、硬度をビツカース硬度計を用いて室温で
測定した。
その結果を表−１にまとめて示す。
The present invention relates to a method for producing a second phase metal particle dispersed amorphous alloy having a structure in which fine second phase metal particles are uniformly dispersed in a matrix. The liquid quenching method, which has recently attracted attention as a process for manufacturing new metal materials, is a rapid cooling process with an unprecedented quenching rate of 10 4 to 10 6 °C/sec.
It is possible to easily produce amorphous alloys or non-equilibrium crystalline alloys. Japanese Patent Laid-Open No. 1983-1999 was an invention in which an attempt was made to disperse second phase particles in an amorphous or crystalline alloy by using the quenching effect, which is a characteristic of this liquid quenching method.
There are No. 47341 and JP-A-59-47352.
Usually, when carbides and oxides are dispersed in the matrix,
Although the hardness and wear resistance of the matrix can be improved, the cooling rate during casting is very slow, so
The segregation of the second phase particles was large, and the characteristics varied widely. In order to reduce the segregation as much as possible, the above invention attempts to produce a second phase particle-dispersed amorphous alloy using a liquid quenching method. According to this method, the dispersibility tended to be improved compared to conventional materials, but as shown in the examples of the above invention, the particles used as the second phase particles were WC with a particle size of 1 μm. , TiC, BN, particle size 2μm
ThO 2 , SiC with a particle size of 3 μm, NbN, Fe particles with a particle size of 5 μm, and the particle size of the second phase particles is 1 to 5 μm.
It is very large, and its dispersibility varies from 1 to 100 μm, with a large amount of segregation.
There was also a tendency for variations in characteristics to occur. The reason for this is that the production method of the above invention uses second phase particles (e.g. carbides, oxides, metals, alloys) that are incompatible with the molten metal.
This is thought to be due to the fact that the mixture is mixed with the molten metal and then rapidly solidified using the liquid quenching method. In other words, the wettability of the molten metal and the second phase particles is poor, and the molten metal and the second phase particles are not compatible at all, so uneven distribution tends to occur, and the particle size of the second phase particles in the matrix after solidification is , the particle size is as large as before mixing with the molten metal,
Furthermore, since the second phase particles had a rectangular shape, they tended to become a stress concentration source. The present inventors have worked diligently with the aim of producing an amorphous alloy in which second-phase metal particles, which are even finer than conventional second-phase particle-dispersed amorphous alloys, are uniformly dispersed in the matrix. As a result of our investigation, we found that when a specific two-phase-separating alloy is rapidly solidified using a liquid quenching method from a molten state of a compatible liquid single phase, the parent phase becomes an amorphous phase, and a fine second phase is formed in the parent phase. It has been discovered that a second-phase metal particle-dispersed amorphous alloy having a structure in which metal particles are uniformly dispersed can be obtained, and the resulting alloy has excellent mechanical properties, electrical properties, magnetic properties, corrosion resistance, etc. The present invention was completed based on the discovery that these characteristics have the same characteristics and that there is no variation in the characteristics. That is, the present invention provides the formula; MaXbYc (wherein M,
is a matrix metal element that forms an amorphous phase, M is Fe,
One or more elements selected from the group consisting of Co, Ni, Cr, Mo, and V, X is B, P, Si, C,
One or more elements selected from the group consisting of Ge, Zr, Hf, and Nb, and Y is a metal element that becomes second phase metal particles after rapid solidification, including Cu, Ag, Au,
One or more elements selected from the group consisting of Pb, Bi, Sn, and Be, where a is atomic % given by 100-(b+c), b is 10 to 35 atomic %, and c is It is 1 to 10 atom%. ) is melted to obtain a compatible liquid single-phase molten metal, and then the obtained molten metal is rapidly solidified by a liquid quenching method, in which fine second phase metal particles are present in the matrix. This is a method for producing a second phase metal particle-dispersed amorphous alloy having a uniformly dispersed structure. The alloy applied to the present invention needs to be an alloy represented by the formula: MaXbYc. here,
M and X are elements that form an amorphous alloy matrix,
M is one or more elements selected from the group consisting of Fe, Ni, Co, Mo, and V; X is B;
One or more elements selected from the group consisting of P, Si, C, Ge, Zr, Hf, and Nb, and Y is an element that forms second phase metal particles, including Cu, Ag, and Au. ,
One or more elements selected from the group consisting of Pb, Bi, Sn, and Be. Also, a is 100−(b+
c), b needs to be 10 to 35 atoms, and c needs to be 1 to 10 atoms. If b is less than 10 atomic % and exceeds 35 atomic %, the ability to form an amorphous state is reduced even by liquid quenching, so the matrix becomes crystallized and brittle, and if c is less than 1 atom, No second phase metal particles are observed, and if c exceeds 10 atomic %, the second phase metal particles become coarse and non-uniformly dispersed, resulting in a material with poor practical utility. Also,
One or two selected from the group consisting of Ta, Ti, and W
It is preferable to add more than 5 atomic % of the above elements, since the mechanical properties of the resulting alloy and the heat resistance are improved by increasing the crystallization temperature. In the present invention, it is first necessary to melt the above-mentioned alloy to obtain a compatible single-phase liquid molten metal. To this end, once cooled, the alloy may be melted at a temperature 20 to 250°C higher than the melting point of the alloy. In this case, when melting the alloy in the molten metal spouting nozzle, high-frequency heating with a molten metal stirring effect is preferable, but it is also recommended to apply ultrasonic vibration to the molten metal to suppress two-phase separation, or to use a method separate from the high-frequency coil for melting. A method of suppressing two-phase separation of the alloy by installing a hot water stirring coil inside also gives favorable results. It is also effective to install a weir or a ceramic filter in the path to the spout hole after melting the alloy in the hot water spouting nozzle to suppress segregation of alloy components in the molten metal. Next, the liquid single-phase molten metal obtained above is rapidly solidified by a liquid quenching method. This liquid quenching method refers to a method in which a molten metal or alloy is rapidly cooled and supercooled to freeze its structure and become amorphous. Examples include the single roll method, twin roll method, and rotating liquid spinning method. are particularly effective, and these methods are 10 4 to 10 6
It has a cooling rate of °C/sec. To produce a ribbon material by this single roll method, double roll method, etc., for example, the temperature must be lower than the temperature at which there is no liquid-liquid separation or solid-liquid separation state in the molten metal, that is, a completely compatible liquid single phase state. , about 300 ~ through the nozzle hole
Spray onto a roll made of copper or Cr steel, for example, with a diameter of 30 to 3000 mm, rotating at 1000 rpm, and the width is about 1 mm.
A ribbon material of ~300 mm and a thickness of about 5-500 μm can be easily obtained. In addition, in order to produce fine wire materials by spinning in a rotating liquid, for example, the nozzle steel is heated at a temperature lower than the temperature at which there is no liquid-liquid separation or solid-liquid separation in the molten metal, that is, a completely compatible liquid single phase. 50-500 rpm with argon gas back pressure through
A depth of 1 to 10 cm is created by centrifugal force inside the rotating drum.
A thin wire-like material can be easily obtained by ejecting it into a refrigerant film. At this time, it is preferable that the angle between the molten metal jetted from the nozzle and the refrigerant surface be about 20 to 100 degrees, and the speed ratio between the jetted molten metal and the refrigerant surface be 0.7 to 0.9. When a molten state of a single phase of mutually dissolved liquid is rapidly solidified by the liquid quenching method, for example, very fine particles with a diameter of about 1 to 100 nm are formed in the matrix, and they are uniformly spaced at intervals of about 1 to 100 nm. The second distributed in
The structure contains phase metal particles, and the grain size of the second phase metal particles and the spacing between the second phase metal particles are almost the same, showing excellent refinement and uniformity of dispersion. For example, 70Fe−5Cr−10Si−13B−
The 2Au alloy has an extremely fine and uniform structure in which Au second phase metal particles with a particle size of 15 nm are dispersed at a particle interval of 25 nm. Also, 70Fe−
The 10Cr-18B-2Cu alloy is a secondary Cu alloy with a grain size of 10 nm.
The phase particles are uniformly dispersed with a particle interval of 30 nm. As described above, the second-phase metal particle-dispersed amorphous alloy obtained by the present invention has fineness of the second-phase particles and uniformity of dispersion compared to conventional second-phase metal particle-dispersed amorphous alloys. is very good. Such a second phase metal particle dispersed amorphous alloy,
For example, the 70Fe-5Cr-10Si-13B-2Au alloy mentioned above shows a significant improvement in breaking strength from 335Kg/mm 2 to 370Kg/mm 2 compared to an amorphous single-phase alloy that does not contain Au. . In addition, the above 70Fe−10Cr−
18B−2Cu alloy has a hardness of 290DPN to 345DPN compared to amorphous single-phase alloy without Cu.
and improve. A second product having the above-mentioned structure obtained by the present invention
Phase particle dispersed amorphous alloy has high tensile rate, good toughness, and also has good hardness, wear resistance, fatigue resistance, high electrical resistance, electromagnetic properties, electrical properties Because of its good properties and consistent properties, it can be used for various industrial materials, composite materials,
It is widely used as a material for filters and strainers, fibers for sound absorbing materials, sensor materials such as liquid helium level sensors, high resistance wires, etc., and is an extremely useful material industrially. Hereinafter, the present invention will be specifically explained with reference to Examples. Examples 1 to 15, Comparative Examples 1 to 6 Fe-Cr-(Si,
B) - (Nb, Ta, V) + (Cu, Au), Fe - (Zr,
Hf)-B+ (Cu, Au), Co-Si-B+ (Cu, Au)
and Fe-Mo-C+ (Cu, Au) based alloy were melted in an argon gas atmosphere to obtain a compatible liquid single-phase molten metal. Next, the molten metal was kept at a temperature of 1300℃, and at an argon gas injection pressure of 3.5Kg/ mm2 , it was ejected from a quartz nozzle with a hole diameter of 0.3mm onto a copper roll with a diameter of 100mm rotating at 500rpm, and was rapidly solidified to create a continuous surface shape. A thin strip material with a uniform width of 1.5 mm and a thickness of 30 μm was obtained. The structure of these thin strips was observed using a transmission electron microscope. Further, the breaking strength was measured using an Instron type tensile tester, and the hardness was measured using a Vickers hardness tester at room temperature. The results are summarized in Table-1.
【表】
実施例１〜15は、本発明により得られた第２相
金属粒子分散型非晶質合金であり、粒径約10〜
50nｍの第２相金属粒子が約20〜65nｍの間隔で
均一に分散した組織を有していた。このような非
常に微細で均一に第２相粒子が分散した第２相金
属粒子分散型非晶質合金は、比較例１〜６の第２
相金属粒子を含まない非晶質合金と比較して破断
強度及び硬さの点において大きな向上が見られ
た。
実施例16〜24、比較例７〜10
非晶質母相中に微細かつ均一に分散した第２相
金属粒子が、超電導特性に及ぼす効果について検
討するために、実施例１と同一の装置及び条件に
より薄帯材料を製造した。
次にクライオスタツトを用いて、直流四端子法
により電気抵抗を測定し、超伝導特性の一つであ
るTc（超電導臨界温度）を測定した。
その結果を表−２に示す。[Table] Examples 1 to 15 are second phase metal particle dispersed amorphous alloys obtained according to the present invention, and have a particle size of about 10 to
It had a structure in which 50 nm second phase metal particles were uniformly dispersed at intervals of about 20 to 65 nm. Such a second phase metal particle-dispersed amorphous alloy in which second phase particles are very fine and uniformly dispersed is
Significant improvements in breaking strength and hardness were observed compared to amorphous alloys without phase metal particles. Examples 16 to 24, Comparative Examples 7 to 10 In order to study the effect of second phase metal particles finely and uniformly dispersed in the amorphous matrix on superconducting properties, the same equipment and equipment as in Example 1 were used. A thin ribbon material was produced according to the conditions. Next, the electrical resistance was measured using a cryostat using the DC four-terminal method, and Tc (superconducting critical temperature), which is one of the superconducting properties, was measured. The results are shown in Table-2.
【表】
比較例７〜10は、第２相金属粒子を含まない非
晶質単相合金であり、Tcが1.5以下と超電導特性
を全く示さなかつた。
そのような組成の合金に第２相金属粒子を分散
させた実施例16〜34の第２相金属粒子分散型非晶
質合金は、第２相金属粒子が約25〜50nｍという
微細な粒径で、また粒子間隔が約25〜55nｍと極
めて均一に分散した組織を有しており、超伝導特
性であるTcに大きな向上が見られた。
実施例 25
70.5Fe−12.5P−10C−5Cr−2Cuの組成よりな
るアルゴンガス雰囲気中で溶融させて相溶した液
体単相の溶湯を得た。次いでこの溶湯をアルゴン
ガス噴出圧4.5Kg／cm2で孔径0.11mmのルビー製紡
糸ノズルにより、295rpmで回転している内径500
mmの円筒ドラム内に形成された温度５℃、深さ
2.5cmの回転冷却水中に噴出して急冷凝固させて
円形断面を有する連続細線を製造した。
このとき、紡糸ノズルと回転冷却水面との距離
は１mmに保持し、紡糸ノズルより噴出された溶融
金属流とその回転冷却面とのなす角度は65°であ
つた。
次に、この細線を一般に用いられているダイヤ
モンドダイスを用い、中間焼なましを行うことな
く連続して冷間線引加工を行つた。
この細線を、実施例１と同様な方法で観察・測
定したところ、分散した第２相金属粒子の粒径は
45nｍ、粒子間隔は、65nｍで、母相は非晶質相
であつた。この細線の破断強度は、第２相金属粒
子を含まない非晶質単相合金と比較して、急冷凝
固材では、20Kg／mm2、70％冷間伸線後では35Kg／
mm2向上し、急冷凝固材で295Kg／mm2、70冷間伸線
後で340Kg／mm2の破断強度を有していた。[Table] Comparative Examples 7 to 10 were amorphous single-phase alloys containing no second phase metal particles, and had a Tc of 1.5 or less and did not exhibit any superconducting properties. The second phase metal particle-dispersed amorphous alloys of Examples 16 to 34, in which second phase metal particles are dispersed in an alloy having such a composition, have second phase metal particles with a fine particle size of about 25 to 50 nm. It also has an extremely uniformly dispersed structure with particle spacing of approximately 25 to 55 nm, and a significant improvement in Tc, which is a superconducting property, was observed. Example 25 A compatible single-phase liquid molten metal was obtained by melting in an argon gas atmosphere and having a composition of 70.5Fe-12.5P-10C-5Cr-2Cu. Next, this molten metal was passed through a ruby spinning nozzle with an inner diameter of 500 mm rotating at 295 rpm at an argon gas injection pressure of 4.5 Kg/cm 2 and a hole diameter of 0.11 mm.
Temperature 5℃, depth formed in mm cylindrical drum
A continuous thin wire with a circular cross section was produced by squirting it into 2.5 cm of rotating cooling water and rapidly solidifying it. At this time, the distance between the spinning nozzle and the rotating cooling water surface was maintained at 1 mm, and the angle between the molten metal flow jetted from the spinning nozzle and the rotating cooling surface was 65°. Next, this fine wire was subjected to continuous cold drawing using a commonly used diamond die without intermediate annealing. When this thin wire was observed and measured in the same manner as in Example 1, the particle size of the dispersed second phase metal particles was found to be
The grain size was 45 nm, the particle spacing was 65 nm, and the parent phase was an amorphous phase. The breaking strength of this fine wire is 20Kg/mm 2 in the rapidly solidified material and 35Kg/mm 2 after 70% cold drawing, compared to an amorphous single-phase alloy that does not contain second phase metal particles.
mm 2 and had a breaking strength of 295 Kg/mm 2 as a rapidly solidified material and 340 Kg/mm 2 after 70 cold drawings.
Claims (1)
する母相金属元素で、ＭはFe、Co、Ni、Cr、
Mo、Ｖからなる群より選ばれた１種又は２種以
上の元素、ＸはＢ、Ｐ、Si、Ｃ、Ge、Zr、Hf、
Nbからなる群より選ばれた１種又は２種以上の
元素であり、Ｙは急冷凝固後、第２相金属粒子と
なる金属原子で、Cu、Ag、Au、Pb、Bi、Sn、
Beからなる群より選ばれた１種又は２種以上の
元素であり、ａは100−（ｂ＋ｃ）で与えられる原
子％で、ｂは10〜35原子％で、ｃは１〜10原子％
である。）で示される合金を溶融させて相溶させ
て液体単相の溶湯を得、次いで得られた溶湯を液
体急冷法で急冷凝固させることを特徴とする母相
中に微細な第２相金属粒子が均一に分散してなる
組織を有する第２相金属粒子分散型非晶質合金の
製造法。1 Formula; MaXbYc (in the formula, M and X are matrix metal elements that form an amorphous phase, and M is Fe, Co, Ni, Cr,
One or more elements selected from the group consisting of Mo, V, X is B, P, Si, C, Ge, Zr, Hf,
One or more elements selected from the group consisting of Nb, Y is a metal atom that becomes second phase metal particles after rapid solidification, Cu, Ag, Au, Pb, Bi, Sn,
One or more elements selected from the group consisting of Be, where a is the atomic % given by 100-(b+c), b is 10 to 35 atomic %, and c is 1 to 10 atomic %.
It is. ) is melted and made compatible to obtain a liquid single-phase molten metal, and then the obtained molten metal is rapidly solidified by a liquid quenching method. Fine second phase metal particles in the matrix. A method for producing a second phase metal particle-dispersed amorphous alloy having a structure in which metal particles are uniformly dispersed.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59164694A JPS6141733A (en) | 1984-08-06 | 1984-08-06 | Manufacture of amorphous alloy containing metallic particle dispersed as second phase |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59164694A JPS6141733A (en) | 1984-08-06 | 1984-08-06 | Manufacture of amorphous alloy containing metallic particle dispersed as second phase |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS6141733A JPS6141733A (en) | 1986-02-28 |
| JPH0524209B2 true JPH0524209B2 (en) | 1993-04-07 |
Family
ID=15798085
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59164694A Granted JPS6141733A (en) | 1984-08-06 | 1984-08-06 | Manufacture of amorphous alloy containing metallic particle dispersed as second phase |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS6141733A (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2593674B2 (en) * | 1987-12-29 | 1997-03-26 | ヤマハ発動機株式会社 | Parallel multi-cylinder engine with overhead camshaft |
| JP2792916B2 (en) * | 1989-06-16 | 1998-09-03 | 日立フェライト電子株式会社 | Noise filter |
-
1984
- 1984-08-06 JP JP59164694A patent/JPS6141733A/en active Granted
Also Published As
| Publication number | Publication date |
|---|---|
| JPS6141733A (en) | 1986-02-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US4478791A (en) | Method for imparting strength and ductility to intermetallic phases | |
| CA1223139A (en) | Amorphous iron-based alloy excelling in fatigue property | |
| JPH0336243A (en) | Amorphous alloy with excellent mechanical strength, corrosion resistance, and workability | |
| JPH0579750B2 (en) | ||
| JPH0621326B2 (en) | High strength, heat resistant aluminum base alloy | |
| JPH07122120B2 (en) | Amorphous alloy with excellent workability | |
| JPS61130451A (en) | Aluminum/iron/vanadium alloy having high strength at high temperature | |
| JPH0499244A (en) | High strength magnesium base alloy | |
| CA1222893A (en) | Nickel-based alloy | |
| JP3604308B2 (en) | Raw material alloy for nanocomposite magnet, powder and manufacturing method thereof, and nanocomposite magnet powder and magnet manufacturing method | |
| JPH06235040A (en) | High-strength, heat-resistant aluminum alloy, assembled solidified material thereof, and manufacturing method thereof | |
| EP0540055B1 (en) | High-strength and high-toughness aluminum-based alloy | |
| JPH05239583A (en) | High strength heat resistant aluminum alloy, its compacted and caked material and its production | |
| KR890003180B1 (en) | Magnetic Head for VTR | |
| US4710247A (en) | Rapidly solidified tri-nickel aluminide base alloy | |
| JPS6141733A (en) | Manufacture of amorphous alloy containing metallic particle dispersed as second phase | |
| JP3346861B2 (en) | High strength copper alloy | |
| JPH0524210B2 (en) | ||
| KR100784915B1 (en) | Zirconium / Titanium Based Amorphous Amorphous Alloys | |
| KR880000158B1 (en) | The method of manufacturing of super cooling alloy | |
| US4668311A (en) | Rapidly solidified nickel aluminide alloy | |
| EP0540054B1 (en) | High-strength and high-toughness aluminum-based alloy | |
| JPH05311359A (en) | High-strength aluminum-based alloy and its solidified material | |
| EP0175130B1 (en) | Method for imparting strength to intermetallic phases | |
| JP4374633B2 (en) | Method for producing raw material alloy for nanocomposite magnet, and method for producing nanocomposite magnet powder and magnet |