JPH03260037A - High strength amorphous alloy - Google Patents
High strength amorphous alloyInfo
- Publication number
- JPH03260037A JPH03260037A JP2059139A JP5913990A JPH03260037A JP H03260037 A JPH03260037 A JP H03260037A JP 2059139 A JP2059139 A JP 2059139A JP 5913990 A JP5913990 A JP 5913990A JP H03260037 A JPH03260037 A JP H03260037A
- Authority
- JP
- Japan
- Prior art keywords
- amorphous
- content
- elements
- crystalline phase
- rare earth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910000808 amorphous metal alloy Inorganic materials 0.000 title claims abstract description 31
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 26
- 239000011159 matrix material Substances 0.000 claims abstract description 8
- 229910052727 yttrium Inorganic materials 0.000 claims abstract description 5
- 229910052746 lanthanum Inorganic materials 0.000 claims abstract description 4
- 239000000654 additive Substances 0.000 claims description 28
- 230000000996 additive effect Effects 0.000 claims description 28
- 239000002184 metal Substances 0.000 claims description 22
- 239000006104 solid solution Substances 0.000 claims description 4
- 229910052684 Cerium Inorganic materials 0.000 claims description 2
- 229910052779 Neodymium Inorganic materials 0.000 claims description 2
- 229910052772 Samarium Inorganic materials 0.000 claims description 2
- 229910001122 Mischmetal Inorganic materials 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 7
- 229910052742 iron Inorganic materials 0.000 abstract description 2
- 229910052759 nickel Inorganic materials 0.000 abstract description 2
- 230000001105 regulatory effect Effects 0.000 abstract 4
- 239000007787 solid Substances 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 description 47
- 239000000956 alloy Substances 0.000 description 47
- 238000001816 cooling Methods 0.000 description 22
- 239000013078 crystal Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 6
- 238000002425 crystallisation Methods 0.000 description 6
- 230000008025 crystallization Effects 0.000 description 6
- 239000000463 material Substances 0.000 description 5
- 230000007423 decrease Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 229910001020 Au alloy Inorganic materials 0.000 description 3
- 239000003353 gold alloy Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000005280 amorphization Methods 0.000 description 2
- 238000007707 calorimetry Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000001771 impaired effect Effects 0.000 description 2
- 238000000034 method Methods 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 235000009852 Cucurbita pepo Nutrition 0.000 description 1
- 241000219104 Cucurbitaceae Species 0.000 description 1
- 229910000858 La alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 125000005843 halogen group Chemical group 0.000 description 1
- 238000001192 hot extrusion Methods 0.000 description 1
- 210000003127 knee Anatomy 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C45/00—Amorphous alloys
Abstract
Description
【発明の詳細な説明】
Ａ０発明の目的
（１）産業上の利用分野
本発明は高強度非晶質合金、特に、主金属元素、希土類
元素よりなる第１添加元素および希土類元素以外の元素
よりなる第２添加元素を含んでマトリックスを構成する
非晶質相と、前記主金属元素および第１．第２添加元素
を含み、且つそれら第１、第２添加元素を過飽和に固溶
して、前記非晶質相に均一に分散する結晶質相とより構
成される高強度非晶質合金の改良に関する。Detailed Description of the Invention A0 Object of the Invention (1) Industrial Field of Application The present invention relates to a high-strength amorphous alloy, particularly an alloy containing a main metal element, a first additive element consisting of a rare earth element, and an element other than the rare earth element. an amorphous phase constituting a matrix containing the second additive element; the main metal element and the first additive element; Improvement of a high-strength amorphous alloy that includes a second additive element and is composed of a crystalline phase that is uniformly dispersed in the amorphous phase by supersaturated solid solution of the first and second additive elements. Regarding.
（２）従来の技術
従来、この種非晶質合金としては、特開昭６４−４７８
３１号公報に記載された各種非晶質Ａｉ！合金が知られ
ているが、何れも高強度化を促進するために非晶質単相
化を狙ったものである。(2) Conventional technology Conventionally, this type of amorphous alloy was disclosed in Japanese Patent Application Laid-Open No. 64-478.
Various amorphous Ai! described in Publication No. 31! Alloys are known, but all of them are aimed at forming an amorphous single phase in order to promote high strength.
（３）発明が解決しようとする課題
しかしながら、従来の非晶質合金のように非晶質単相化
を狙った場合において、製造条件等により結晶質相が一
部混在すると、その結晶質相の現出に起因して合金全体
の強度および靭性が低下する、という問題がある。(3) Problems to be solved by the invention However, when aiming at amorphous single phase as in conventional amorphous alloys, if some crystalline phases are mixed due to manufacturing conditions etc., the crystalline phase There is a problem in that the strength and toughness of the entire alloy are reduced due to the appearance of .
本発明は前記に鑑み、非晶質相からなるマトリックス中
に混在する結晶質相に着目し、結晶貧相における主金属
元素の含有量および希土類元素成分値（第２添加元素含
有量との関係で決まる）を特定することにより、合金全
体の強度低下を防止すると共に非晶質単相合金よりも更
に強度を向上させ得るようにした前記非晶質合金を提供
することを目的とする。In view of the above, the present invention focuses on the crystalline phase mixed in the matrix consisting of the amorphous phase, and calculates the content of the main metal element and the rare earth element component value (in relation to the content of the second additive element) in the poorly crystalline phase. It is an object of the present invention to provide an amorphous alloy that prevents a decrease in the strength of the entire alloy and further improves the strength compared to an amorphous single-phase alloy by specifying the following.
Ｂ１発明の構成
（１）課題を解決するための手段
本発明は、主金属元素、希土類元素よりなる第１添加元
素および希土類元素以外の元素よりなる第２添加元素を
含んでマトリックスを構成する非晶質相と、前記主金属
元素および第１．第２添加元素を含み、且つそれら第１
．第２添加元素を過飽和に固溶して、前記非晶質相に均
一に分散する結晶質相とより構成される高強度非晶質合
金において、前記結晶質相における前記主金属元素の含
有量を８５原子％以上、９９．８原子％以下に設定し、
前記第１添加元素である希土類元素の含有量をａ原子％
、前記第２添加元素の含有量をｂ原子％とした場合の前
記結晶質相における希土類元素成分値Ｃ，を、
Ｃ１＝
ａ十す
と定義したとき、希土類元素成分値ｃ、ｌを０．５以下
に設定したことを特徴とする。B1 Structure of the Invention (1) Means for Solving the Problem The present invention provides a non-containing material that constitutes a matrix including a main metal element, a first additive element consisting of a rare earth element, and a second additive element consisting of an element other than the rare earth element. a crystalline phase, the main metal element and the first. contains a second additive element, and the first
．． In a high-strength amorphous alloy comprising a crystalline phase uniformly dispersed in the amorphous phase with a supersaturated solid solution of a second additive element, the content of the main metal element in the crystalline phase is set to 85 atomic % or more and 99.8 atomic % or less,
The content of the rare earth element, which is the first additional element, is a atomic %.
, when the rare earth element component value C, in the crystalline phase when the content of the second additive element is b atomic %, is defined as C1=a+, the rare earth element component values c and l are 0. It is characterized by being set to 5 or less.
（２）作 用
マトリックスとし、ての非晶質相に分散している結晶質
相における主金属元素の含有量および希土類元素成分値
を前記のように特定すると、非晶質合金全体の強度を一
層向上させることができる。(2) If the main metal element content and rare earth element component values in the crystalline phase dispersed in the amorphous phase are specified as described above, the strength of the entire amorphous alloy can be determined as follows. This can be further improved.
た＼し、主金属元素の含有量が８５原子％未満では、非
晶質合金製造時に結晶質相中に化合物が生成され易く、
また化合物が単独で現出し易くなり、その結果、非晶質
合金全体の脆化を招く。However, if the content of the main metal element is less than 85 atomic %, compounds are likely to be generated in the crystalline phase during the production of an amorphous alloy.
Further, the compound tends to appear alone, resulting in embrittlement of the entire amorphous alloy.
方、９９．８原子％を上回ると、通常の冷却速度では非
晶質相と結晶質相との混相を得ることが困難であり、そ
こで冷却速度を極端に上げたのでは量産性が著しく損わ
れる。その上、非晶質合金自体の耐熱性が悪化する、と
いった問題もある。こＸで主金属元素とは、Ａｆまたは
Ｍｇをいう。On the other hand, when it exceeds 99.8 atomic percent, it is difficult to obtain a mixed phase of amorphous and crystalline phases at normal cooling rates, and if the cooling rate is increased extremely, mass productivity will be significantly impaired. be exposed. Furthermore, there is also the problem that the heat resistance of the amorphous alloy itself deteriorates. The main metal element in X means Af or Mg.
希土類元素は非晶質化達成のために必要な元素であるが
、その希土類元素は比較的大きな原子半径を有するため
、結晶質相を構成する主金属元素の結晶格子に規定量以
上の希土類元素が侵入すると、その格子定数が増加して
跪くなる。Rare earth elements are necessary elements to achieve amorphization, but because the rare earth elements have a relatively large atomic radius, a specified amount or more of rare earth elements is added to the crystal lattice of the main metal element constituting the crystalline phase. When it invades, its lattice constant increases and it falls to its knees.
そこで、結晶質相における希土類元素成分値Ｃつを０．
５以下に設定するもので、このように設定することによ
って結晶格子の格子定数を純粋な主金属元素のそれに近
似させることが可能となる。Therefore, the rare earth element component value C in the crystalline phase is set to 0.
By setting it to 5 or less, it becomes possible to approximate the lattice constant of the crystal lattice to that of the pure main metal element.
このように構成すると、高い硬さを有する非晶質相に比
較的軟らかい結晶質相が分散することになるので、その
結晶質相がそれと非晶質相間の界面歪を吸収するため、
非晶質合金全体の靭性が改善されるものと思われる。With this structure, a relatively soft crystalline phase is dispersed in a highly hard amorphous phase, and the crystalline phase absorbs the interfacial strain between it and the amorphous phase.
It is believed that the toughness of the entire amorphous alloy is improved.
（３）実施例
第１図は、単ロール方式を採用した非晶質合金製造装置
の概略を示す、その装置は、同図時計方向に回転する純
銅製冷却ロール１と、その冷却ロールｌの周囲に、出口
を冷却ロール１外周面に近接させて固定された石英製ノ
ズル２と、ノズル２の下端部を囲繞するように起設され
た高周波加熱用コイル３とを備えている。冷却ロール１
の直径は２００ｍ、ノズル２の出口における口径は０．
３瓢、その出口と冷却ロール１外周面とのギャップは０
．３ ｗｍにそれぞれ設定されている。(3) Example Figure 1 shows an outline of an amorphous alloy manufacturing apparatus employing a single roll system.The apparatus consists of a pure copper cooling roll 1 rotating clockwise in the figure, It is provided with a quartz nozzle 2 fixed with its outlet close to the outer circumferential surface of the cooling roll 1 and a high-frequency heating coil 3 raised so as to surround the lower end of the nozzle 2. cooling roll 1
The diameter of the nozzle 2 is 200 m, and the aperture at the exit of the nozzle 2 is 0.
3 gourds, the gap between the outlet and the outer peripheral surface of the cooling roll 1 is 0.
．． 3 wm respectively.
非晶質合金である非晶質Ａ１合金の製造時には、／ｌよ
りなる主金属元素、希土類元素よりなる第１添加元素お
よび希土類元素以外の元素よりなる第２添加元素を含む
溶融合金ｍが、ノズル２の出口から冷却ロールｌ外周面
に、アルゴンガス圧（例えば、０．４ｋｇ／ｄ）により
噴出され、その冷却ロール１の回転に伴いノズル２と冷
却ロール１との間よりそのロール１外周面に添着して薄
いリボン状に引出されると同時に急冷され、これにより
非晶質Ａｉ金合金得られる。When manufacturing an amorphous A1 alloy, which is an amorphous alloy, a molten alloy m containing a main metal element consisting of /l, a first additive element consisting of a rare earth element, and a second additive element consisting of an element other than the rare earth element, Argon gas pressure (for example, 0.4 kg/d) is ejected from the outlet of the nozzle 2 onto the outer peripheral surface of the cooling roll 1, and as the cooling roll 1 rotates, the outer periphery of the cooling roll 1 is ejected from between the nozzle 2 and the cooling roll 1. The amorphous Al-gold alloy is obtained by attaching it to a surface and drawing it out into a thin ribbon, and at the same time rapidly cooling it.
この場合、冷却ロール１の回転速度を、非晶質単相Ａｆ
ｆｉ合金（非晶質成分の体積分率が１００％の合金）を
得るときよりも下げて、溶融合金の冷却速度を遅くする
と、溶融合金において結晶質相が現出する。In this case, the rotational speed of the cooling roll 1 is set to the amorphous single phase Af
If the cooling rate of the molten alloy is lower than that used to obtain a fi alloy (an alloy in which the volume fraction of the amorphous component is 100%), a crystalline phase will appear in the molten alloy.
このような手法を採用することによって、主金属元素お
よび第１．第２添加元素を含んでマトリックスを構成す
る非晶質相と、前記主金属元素および第１．第２添加元
素を含み、且つそれら第１゜第２添加元素を過飽和に固
溶して、非晶質相に均一に分散する微細な結晶質相とよ
り構成された高強度非晶ｉｉ、１合金が得られる。By adopting such a method, the main metal element and the first metal element. an amorphous phase constituting a matrix containing a second additive element, the main metal element and the first additive element; High-strength amorphous ii, 1 that contains a second additive element and is composed of a fine crystalline phase that is uniformly dispersed in the amorphous phase by supersaturated solid solution of the first and second additive elements; An alloy is obtained.
主金属元素であるＡｌの結晶質相における含有量は８５
原子％以上、９９．８原子％以下に設定される。たりし
、Ａｆの含有量が８５原子％未満では、非晶質／１合金
製造時に結晶質相中に化合物（Ａｆｚ Ｙ、Ａｌｓ Ｎ
Ｌ ＡｆＮＬ Ｙａ等）が生成され易く、また化合物が
単独で現出し易くなり、その結果、非晶質Ａｉ！合金全
体のｆｆ１（ヒを招く。The content of Al, the main metal element, in the crystalline phase is 85
It is set to be at least atomic % and at most 99.8 atomic %. However, if the Af content is less than 85 at%, compounds (Afz Y, Als N
(L AfNL Ya, etc.) are likely to be generated, and the compound is likely to appear alone, resulting in amorphous Ai! ff1 of the entire alloy.
一方、９９．８原子％を上回ると、通常の冷却速度では
非晶質相と結晶質相との混和を得ることが困難であり、
そこで冷却速度を極端に上げたのでは量産性が著しく損
われる。その上、非晶質Ａｆ合金自体の耐熱性が悪化す
る、といった問題もある。On the other hand, when it exceeds 99.8 atomic %, it is difficult to obtain miscibility between the amorphous phase and the crystalline phase at a normal cooling rate;
Therefore, if the cooling rate is extremely increased, mass productivity will be significantly impaired. Furthermore, there is also the problem that the heat resistance of the amorphous Af alloy itself deteriorates.
第１添加元素である希土類元素としては、Ｙ、Ｌａ、Ｃ
ｅＳ Ｓｍ、Ｎｄ、Ｍｍ （ミツシュメタル）から選択
される少なくとも一種が該当し、その含有量は０．１原
子％以上、５原子％以下に設定される。たりし、希土類
元素の含有量がｏ、ｌ原子％未満では非晶質相と結晶質
相との混相を得ることが不可能となり、一方、５原子％
を上回ると、結晶質相が脆化し、結果的に非晶質Ａｎ合
金自体が脆くなる。The rare earth elements that are the first additive elements include Y, La, and C.
eS At least one selected from Sm, Nd, and Mm (Mitshu Metal) corresponds to this, and its content is set to 0.1 atomic % or more and 5 atomic % or less. However, if the content of rare earth elements is less than o, l atomic %, it is impossible to obtain a mixed phase of an amorphous phase and a crystalline phase;
If it exceeds , the crystalline phase becomes brittle, and as a result, the amorphous An alloy itself becomes brittle.
第２添加元素としては、Ｎｉ、Ｆｅ、Ｃｏから選択され
る少なくとも一種が該当し、その含有量は１０原子％以
下に設定される。た父′シ、第２添加元素の含有量が１
０原子％を上回ると、結晶質相中に化合物が現出し易く
なると共に希土類元素の含有量との相関により合金全体
として非晶質相形威能が低下する。第２添加元素の下限
値は、好ましくは５原子％である。５原子％未満では、
製造条件が厳しくなる。The second additive element is at least one selected from Ni, Fe, and Co, and its content is set to 10 atomic % or less. The content of the second additive element is 1
When it exceeds 0 atomic %, compounds tend to appear in the crystalline phase, and the amorphous phase power of the alloy as a whole decreases due to the correlation with the rare earth element content. The lower limit of the second additive element is preferably 5 at.%. At less than 5 atom%,
Manufacturing conditions will become stricter.
マトリックスである非晶質相における主金属元素、第１
．第２添加元素の含有量は、結晶質相におけるそれら元
素の含有量よりも多い方が好ましい。この含有量の関係
が逆転すると、結晶質相中に化合物が現出し易くなり、
合金全体の脆化の原因となる。The main metal element in the amorphous phase that is the matrix, the first
．． The content of the second additional element is preferably greater than the content of those elements in the crystalline phase. When this content relationship is reversed, compounds tend to appear in the crystalline phase,
This causes embrittlement of the entire alloy.
前記手法を採用し、その際冷却ロール１の回転速度を変
えてＡ １２ ＠ｇＹ５ Ｎ ｉ ｂ （数値は原子
％、以下各合金について同じ）の組成を有する非晶質／
１合金Ａ−Ｄを製造し、冷却ロール１の回転速度と結晶
質相の含有量との関係を調べたところ下表の結果が得ら
れた。なお、結晶質相の結晶構造は、Ａｆに起因してｆ
ｃｃ（面心立方構造）であり、またその結晶質相の平均
直径は３００Å以上、８００Å以下であった。By employing the above method and changing the rotational speed of the cooling roll 1, an amorphous/
1 Alloys A to D were manufactured and the relationship between the rotational speed of the cooling roll 1 and the content of the crystalline phase was investigated, and the results shown in the table below were obtained. Note that the crystal structure of the crystalline phase is f due to Af.
cc (face-centered cubic structure), and the average diameter of the crystalline phase was 300 Å or more and 800 Å or less.
第２〜第４図は非晶質ＡＩ１合金Ａ〜ＤのＸ線回折図を
それぞれ示す、測定に用いられたＸ線管の対陰極はＣｕ
であり、Ｋα線が使用された。Figures 2 to 4 show the X-ray diffraction patterns of amorphous AI1 alloys A to D, respectively.The anticathode of the X-ray tube used in the measurement was Cu.
and Kα radiation was used.
非晶質Ａ１合金Ａは、冷却速度が速いため非晶質単相Ａ
１合金となり、第２図において、急峻なピークの無い非
晶質特有のハローパターンが見られる。Amorphous A1 Alloy A is amorphous single phase A because of its fast cooling rate.
1 alloy, and in FIG. 2, a halo pattern characteristic of amorphous materials without steep peaks can be seen.
非晶質合金Ｂは、冷却速度を前記合金六の場合よりも１
．００ｏ ｒｐｍ＋下げたものであり、第３図に示すよ
うに僅かな結晶質相の現出に伴いピークｐ。Amorphous alloy B has a cooling rate of 1 more than that of alloy 6.
．． 00o rpm+, and as shown in FIG. 3, the peak p occurs with the appearance of a slight crystalline phase.
が現れる。このピークｐ、はｆｃｃの（１１１）面に対
応する。appears. This peak p corresponds to the (111) plane of fcc.
非晶質Ａｆｆ合金Ｃは、冷却速度を前記合金への場合の
２分の１に下げたものであり、略３割が結晶質相である
。したがって、第４図に示すように結晶質相の現出に伴
い高いピークＰ１および低いピーク２２〜ｐ４が現れる
。これらピークｐｔ〜ｐ４において、ピークｐｉはｒ
ｅｃ（７）（２００）面に、ピークＰ３はｆｃｃの（２
２０）面に、ピークｐ４はｆｅｃの（３１１）面にそれ
ぞれ対応する。Amorphous Aff alloy C has a cooling rate lowered to one-half of that for the above alloy, and has approximately 30% crystalline phase. Therefore, as shown in FIG. 4, a high peak P1 and low peaks 22 to p4 appear as a crystalline phase appears. In these peaks pt to p4, the peak pi is r
On the ec(7)(200) plane, peak P3 is on the fcc(2
20) plane, and peak p4 corresponds to the (311) plane of fec, respectively.
非晶質Ａｆｆｉ合金りは、冷却速度を前記合金Ｃの場合
よりも、さらに下げたものであり、略４割が結晶質相で
ある。したがって、第５図に示すように結晶質相の現出
に伴い高いピークＩ）＋、Ｐｚと低いピークＰｓ、ｐａ
とが現れる。The amorphous Affi alloy has a cooling rate lower than that of Alloy C, and approximately 40% of the alloy is a crystalline phase. Therefore, as shown in FIG. 5, with the appearance of the crystalline phase, a high peak I)+, Pz and a low peak Ps, pa
appears.
第６図は三種の非晶質Ａ１合金における結晶質相の含有
量と引張強さとの関係を示す０図中、線Ｘ、が前述のＡ
ＩＶ、＠ｑ Ｙ ５ Ｎ ｉ ｂ合金に、また線Ｘ２
がＡ ｊＱ ６Ｂ Ｙ ｚ Ｎ ｌ ｌａ合金に、さら
に線Ｘ、がＡＥ、。ＹａＮｉ４合金にそれぞれ該当する
。Figure 6 shows the relationship between crystalline phase content and tensile strength in three types of amorphous A1 alloys.
IV, @q Y 5 N i b alloy, and line X2
is the A jQ 6B Y z N l la alloy, and the line X is AE. Each corresponds to YaNi4 alloy.
第６図から明らかなように各合金において、非晶質単相
（結晶質相の含有量−〇）の場合に比べ結晶質相の含有
量が増加するに従って強度が高くなるもので、特に、結
晶質相の含有量５体積％以上、４０体積％以下の範囲が
好適である。As is clear from Figure 6, in each alloy, the strength increases as the crystalline phase content increases compared to the case of an amorphous single phase (crystalline phase content - ○). The content of the crystalline phase is preferably in the range of 5% by volume or more and 40% by volume or less.
この場合、線ＸＩ＋ χ！で示すＡ Ｉ ｌ１９Ｙ５
Ｎ ４６合金、Ａ Ｐ−ｅｓＹｚ Ｎ ｉ Ｈ０合金
においては結晶質相の含有量４０体積％近傍にて脆化が
始まる。In this case, the line XI+χ! A I l19Y5 shown as
In N46 alloy and AP-esYzNiH0 alloy, embrittlement begins when the crystalline phase content is around 40% by volume.
方、線Ｘ、で示すＡｆ、。Ｙ６Ｎｉａ合金においては、
結晶質相の含有量２０体積％近傍にて脆化が始まるもの
で、この合金は組成上、本発明には含まれない。On the other hand, Af, indicated by line X. In Y6Nia alloy,
Embrittlement begins when the crystalline phase content is around 20% by volume, and this alloy is not included in the present invention due to its composition.
結晶質相の平均直径は、前記のように３００Å以上、８
００λ以下が適当である。その平均直径が３００人未満
では、結晶質相を現出させることの意義が失われ、一方
、８００λを上回ると、結晶質相の安定化が図れず、ま
た均一な分散が不可能となり、非晶質ＡＩ！合金全体の
強度が低下する。The average diameter of the crystalline phase is 300 Å or more, 8
00λ or less is appropriate. If the average diameter is less than 300 λ, the significance of making the crystalline phase appear is lost, while if it exceeds 800 λ, the crystalline phase cannot be stabilized and uniform dispersion becomes impossible, resulting in non-uniformity. Crystalline AI! The overall strength of the alloy decreases.
希土類元素は非晶質化達成のために必要な元素であるが
、その希土類元素は比較的大きな原子半径（例えば、Ｙ
では１．８人）を有するため、結晶質相を構成するＡｆ
ｆｉの結晶格子（ｆｃｃ）に規定量以上の希土類元素が
侵入すると、その格子定数（α＝４．０５人）が増加し
て跪くなる。Rare earth elements are necessary elements to achieve amorphization, but the rare earth elements have a relatively large atomic radius (for example, Y
1.8 people), the Af constituting the crystalline phase
When more than a specified amount of rare earth elements invades the crystal lattice (fcc) of fi, its lattice constant (α=4.05) increases and it collapses.
こ＼で、希土類元素の含有量をａ原子％、第２添加元素
の含有量をｂ原子％とした場合の結晶質相における希土
類元素成分値ＣＲを、
Ｃ，ｌ ＝
ａ＋ｂ
と定義すると、希土類元素成分値Ｃｍは０．５以下に設
定される。Here, if the rare earth element content CR in the crystalline phase is defined as C, l = a + b, where the content of the rare earth element is a atomic % and the content of the second additive element is b atomic %, then the rare earth element The elemental component value Cm is set to 0.5 or less.
結晶質相における希土類元素成分値Ｃ３を前記のように
設定することによって結晶格子の格子定数を純粋なＡｆ
のそれに近似させることが可能となる。By setting the rare earth element component value C3 in the crystalline phase as described above, the lattice constant of the crystal lattice becomes pure Af.
It becomes possible to approximate that of .
このように構成すると、高い硬さを有する非晶質相に比
較的軟らかい結晶質相が分散することになるので、その
結晶質相がそれと非晶質相間の界面歪を吸収するため、
非晶質合金全体の靭性が改善されるものと思われる。With this structure, a relatively soft crystalline phase is dispersed in a highly hard amorphous phase, and the crystalline phase absorbs the interfacial strain between it and the amorphous phase.
It is believed that the toughness of the entire amorphous alloy is improved.
第７〜第９図は、結晶質相の含有量２０体積％のＡＮ−
Ｙ−Ｎｉ系非晶質合金におけるＹｔ２分値Ｃ＊ （ａ
／ ａ ＋ ｂ、た＼し、ａ−Ｙ、ｂ−・・Ｎｉ）と
、結晶質相における結晶格子の格子定数、引張強さおよ
びヤング率との関係をそれぞれ示す。Figures 7 to 9 show AN- with a crystalline phase content of 20% by volume.
Yt2-minute value C* (a
/ a + b, \, a-Y, b-...Ni) and the lattice constant, tensile strength, and Young's modulus of the crystal lattice in the crystalline phase, respectively.
第７図から明らかなように、Ｙ成分値ＣＲ＋を０゜５以
下に設定することにより、格子定数を、純Ａｌのそれ（
４，０５人）に近似させることができる。As is clear from Fig. 7, by setting the Y component value CR+ to 0°5 or less, the lattice constant can be changed to that of pure Al (
4.05 people).
また第８．第９図から明らかなように、Ｙ成分値ＣＲを
０．５以下に設定することにより、引張強さおよびヤン
グ率を高い値に保つことができる。Also the 8th. As is clear from FIG. 9, by setting the Y component value CR to 0.5 or less, the tensile strength and Young's modulus can be maintained at high values.
前記ａ ／ ａ ＋ ｂ≦０．５よりａ≦ｂの関係が成
立し、これは、Ｙ、Ｌａ、Ｃｅ等の高価な希土類元素を
減少させ得ることを意味するので、非晶質Ａ１合金のコ
ストを低減する上に有効である。From the above a/a + b≦0.5, the relationship a≦b is established, which means that expensive rare earth elements such as Y, La, Ce, etc. can be reduced. This is effective in reducing costs.
第１０図は、Ａ１．。。−ＸＹｘ系非晶質合金（線ｙ＋
）および” ｑｓ−ｘＹｘ Ｎ ｉ Ｚ系非晶質合金（
線ｙ２）において、それらの結晶質相の含有量を５〜４
０体積％に設定したときの各結晶質相における結晶格子
の格子定数とＹ含有量との関係を示す。FIG. 10 shows A1. . . -XYx amorphous alloy (line y+
) and “qs-xYx N i Z-based amorphous alloy (
In line y2), the content of those crystalline phases is 5 to 4
The relationship between the lattice constant of the crystal lattice and Y content in each crystalline phase when set to 0 volume % is shown.
第１０図Ｈｙ＋ 、）’ｚ より、Ｙ含有量が２原子％
以下であれば格子定数は略一定であるが、２原子％を上
回ると格子定数が増加する。From Figure 10 Hy+,)'z, the Y content is 2 atomic%.
If it is below, the lattice constant is approximately constant, but if it exceeds 2 atomic %, the lattice constant increases.
したがって、Ａ ｉＬ ９ｌ−ＸＹＸ Ｎ ｊ ｚ系非
晶質合金においては、その強度確保−ヒ、Ｙ含有量は０
．５原子％以上、２原子％以下に設定される。Therefore, in the A iL 9l-XYX Nj z-based amorphous alloy, ensuring its strength, the Y content is 0.
．． The content is set to 5 atomic % or more and 2 atomic % or less.
第１１〜第１３図は、非晶質Ａｆ金合金ある三種のＡ
ｌ １１９Ｙｓ Ｎ ｌ ｂ合金の示差熱量分析図を示
す。第１１図は非晶質単相の場合に、また第１２図は結
晶質相の含有量が２６体積％の場合に、さらに第１３図
は結晶質相の含有量が３７体積％の場合にそれぞれ該当
する。Figures 11 to 13 show three types of amorphous Af gold alloys.
1 shows a differential calorimetry analysis diagram of l 119Ys N l b alloy. Figure 11 shows the case of an amorphous single phase, Figure 12 shows the case where the crystalline phase content is 26% by volume, and Figure 13 shows the case where the crystalline phase content is 37% by volume. Applicable to each.
第１１図に示す非晶質単相ＡＰ、合金の結晶化温度Ｔｘ
は８９°Ｃであるが、結晶質相の含有量が増加するに従
って結晶化温度Ｔｘが高くなる傾向があり、そのため第
１２図に示す非晶質Ａｆｆ合金の結晶化温度Ｔｘは９９
゛ｃに、また第１３図に示す非晶質Ａ１合金の結晶化温
度Ｔｘは１０９℃にそれぞれ上昇する。Crystallization temperature Tx of amorphous single phase AP and alloy shown in Figure 11
is 89°C, but the crystallization temperature Tx tends to increase as the content of the crystalline phase increases, so the crystallization temperature Tx of the amorphous Aff alloy shown in Fig. 12 is 99°C.
The crystallization temperature Tx of the amorphous A1 alloy shown in FIG.
また結晶化温度Ｔｘを超えた後における発熱量、したが
って山の高さを比較すると、第１１図の非晶質単相Ａ１
合金の場合が最も高く、結晶質相の含有量の増加に伴い
山の高さが低くなることが判る。これは結晶化により生
じる結晶質相の量が少ないことを意味する。Moreover, when comparing the calorific value after exceeding the crystallization temperature Tx, and therefore the height of the peak, we find that the amorphous single phase A1 in Fig. 11
It is seen that the height is highest for alloys, and the height of the peak decreases as the content of crystalline phase increases. This means that the amount of crystalline phase produced by crystallization is small.
したがって、第１２．第１３図に示すような熱的特性を
有する非晶質Ａ１合金より素材を形威し、その素材を用
いて熱間塑性加工、例えば熱間押出し加工を行う場合、
素材に対する熱的管理が比較的容易となる。Therefore, the 12th. When forming a material from an amorphous A1 alloy having thermal properties as shown in FIG. 13 and performing hot plastic working, such as hot extrusion, using the material,
Thermal management of the material becomes relatively easy.
なお、非晶質単相Ａｆ金合金熱処理を施した場合にも結
晶質相が現出するが、この場合の結晶質相は結晶粒成長
が速いために粗大化し、また分散状態が不均一となり、
その上結晶質相の偏析が生しるため、本発明に係る非晶
質ＡＩ！、合金に比べて強度および靭性が低くなる。ま
た本発明には、主金属元素をＭｇとする非晶ｔＭｇ合金
も包含される。Note that a crystalline phase also appears when an amorphous single-phase Af gold alloy is heat-treated, but the crystalline phase in this case becomes coarse due to rapid crystal grain growth, and the dispersion state becomes non-uniform. ,
Moreover, since segregation of the crystalline phase occurs, the amorphous AI according to the present invention! , lower strength and toughness compared to alloys. The present invention also includes an amorphous tMg alloy in which Mg is the main metal element.
Ｃ１発明の効果
本発明によれば、マトリックスである非晶質相に特定の
結晶質相を均一に分散させた非晶質合金において、結晶
質相における主金属元素の含有量および希土類元素成分
値を前記のように特定することにより、強度が高く、ま
た熱間塑性加工性の良好な非晶質合金を提供することが
できる。C1 Effect of the invention According to the invention, in an amorphous alloy in which a specific crystalline phase is uniformly dispersed in an amorphous phase that is a matrix, the content of the main metal element and the rare earth element component value in the crystalline phase can be reduced. By specifying as described above, it is possible to provide an amorphous alloy with high strength and good hot plastic workability.
第１図は非晶質合金製造装置の概略図、第２〜第５図は
非晶質Ａ４２合金のＸ線回折図、第６図は非晶質合金に
おける結晶質相の含有量と引張強さとの関係を示すグラ
フ、第７図はＹ成分値と格子定数との関係を示すグラフ
、第８図はＹ成分値と引張強さとの関係を示すグラフ、
第９図はＹ成分値とヤング率との関係を示すグラフ、第
１０図はＹ含有量と格子定数との関係を示すグラフ、第
１１図〜第１３図は非晶ｆＡＩ！、合金の示差熱量分析
図を示す。
ｍ・・・溶融合金、１・・・冷却ロール、２・・・ノズ
ル、３・・・高周波加熱用コイル
第１図Figure 1 is a schematic diagram of the amorphous alloy manufacturing equipment, Figures 2 to 5 are X-ray diffraction diagrams of the amorphous A42 alloy, and Figure 6 is the content of crystalline phase and tensile strength in the amorphous alloy. 7 is a graph showing the relationship between Y component value and lattice constant, FIG. 8 is a graph showing the relationship between Y component value and tensile strength,
FIG. 9 is a graph showing the relationship between Y component value and Young's modulus, FIG. 10 is a graph showing the relationship between Y content and lattice constant, and FIGS. 11 to 13 are graphs showing amorphous fAI! , shows a differential calorimetry diagram of the alloy. m... Molten alloy, 1... Cooling roll, 2... Nozzle, 3... High frequency heating coil Fig. 1
Claims (4)
よび希土類元素以外の元素よりなる第２添加元素を含ん
でマトリックスを構成する非晶質相と、前記主金属元素
および第１、第２添加元素を含み、且つそれら第１、第
２添加元素を過飽和に固溶して、前記非晶質相に均一に
分散する結晶質相とより構成される高強度非晶質合金に
おいて、前記結晶質相における前記主金属元素の含有量
を８５原子％以上、９９．８原子％以下に設定し、前記
第１添加元素である希土類元素の含有量をａ原子％、前
記第２添加元素の含有量をｂ原子％とした場合の前記結
晶質相における希土類元素成分値Ｃ＿Ｒを、Ｃ＿Ｒ＝ａ
／ａ＋ｂ と定義したとき、希土類元素成分値Ｃ＿Ｒを０．５以下
に設定したことを特徴とする高強度非晶質合金。(1) An amorphous phase constituting a matrix containing a main metal element, a first additive element consisting of a rare earth element, and a second additive element consisting of an element other than the rare earth element; A high-strength amorphous alloy comprising an additive element and a crystalline phase uniformly dispersed in the amorphous phase with the first and second additive elements in supersaturated solid solution; The content of the main metal element in the qualitative phase is set to 85 atomic % or more and 99.8 atomic % or less, the content of the rare earth element that is the first additional element is set to a atomic %, and the content of the second additional element is set to a The rare earth element component value C_R in the crystalline phase when the amount is b atomic % is expressed as C_R=a
A high-strength amorphous alloy characterized in that a rare earth element component value C_R is set to 0.5 or less when defined as /a+b.
％以上、５原子％以下のＹ、Ｌａ、Ｃｅ、Ｓｍ、Ｎｄ、
Ｍｍ（ミッシュメタル）から選択される少なくとも一種
であり、前記第２添加元素が１０原子％以下のＮｉ、Ｆ
ｅ、Ｃｏから選択される少なくとも一種である、第（１
）項記載の高強度非晶質合金。(2) Y, La, Ce, Sm, Nd in which the rare earth element as the first additive element is 0.1 atomic % or more and 5 atomic % or less;
At least one kind selected from Mm (misch metal), and the second additive element is 10 atomic % or less of Ni, F
e, Co.
) High-strength amorphous alloy described in item 2.
％以下に設定した、第（１）または第（２）項記載の高
強度非晶質合金。(3) The high-strength amorphous alloy according to item (1) or item (2), wherein the content of the crystalline phase is set to 5% by volume or more and 40% by volume or less.
Å以下に設定した、第（１）、第（２）または第（３）
項記載の高強度非晶質合金。(4) The average diameter of the crystalline phase is 300 Å or more, 800 Å or more
(1), (2) or (3) set below Å
High-strength amorphous alloy described in Section 1.
Priority Applications (7)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2059139A JP2639455B2 (en) | 1990-03-09 | 1990-03-09 | High strength amorphous alloy |
| NO910906A NO180205C (en) | 1990-03-09 | 1991-03-07 | High-strength aluminum-based, amorphous alloy |
| FR9102831A FR2659355B1 (en) | 1990-03-09 | 1991-03-08 | HIGH RESISTANCE AMORPHOUS ALLOY. |
| AU72751/91A AU634866B2 (en) | 1990-03-09 | 1991-03-08 | High strength amorphous alloy |
| CA002037818A CA2037818C (en) | 1990-03-09 | 1991-03-08 | High strength amorphous alloy |
| DE4107532A DE4107532C2 (en) | 1990-03-09 | 1991-03-08 | High strength amorphous body |
| GB9104956A GB2243617B (en) | 1990-03-09 | 1991-03-08 | High strength amorphous alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2059139A JP2639455B2 (en) | 1990-03-09 | 1990-03-09 | High strength amorphous alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH03260037A true JPH03260037A (en) | 1991-11-20 |
| JP2639455B2 JP2639455B2 (en) | 1997-08-13 |
Family
ID=13104688
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2059139A Expired - Lifetime JP2639455B2 (en) | 1990-03-09 | 1990-03-09 | High strength amorphous alloy |
Country Status (7)
| Country | Link |
|---|---|
| JP (1) | JP2639455B2 (en) |
| AU (1) | AU634866B2 (en) |
| CA (1) | CA2037818C (en) |
| DE (1) | DE4107532C2 (en) |
| FR (1) | FR2659355B1 (en) |
| GB (1) | GB2243617B (en) |
| NO (1) | NO180205C (en) |
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|---|---|---|---|---|
| JPH0693393A (en) * | 1992-08-05 | 1994-04-05 | Takeshi Masumoto | Aluminum-base alloy with high strength and corrosion resistance |
| JPH06316738A (en) * | 1992-02-07 | 1994-11-15 | Toyota Motor Corp | High strength aluminum alloy |
| CN103290340A (en) * | 2013-05-30 | 2013-09-11 | 济南大学 | Rare earth-based bulk metallic glass with adjustable rear earth ingredient content |
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|---|---|---|---|---|
| JP2945205B2 (en) * | 1992-03-18 | 1999-09-06 | 健 増本 | Amorphous alloy material and manufacturing method thereof |
| EP0564998B1 (en) * | 1992-04-07 | 1998-11-04 | Koji Hashimoto | Amorphous alloys resistant against hot corrosion |
| JPH0673479A (en) * | 1992-05-06 | 1994-03-15 | Honda Motor Co Ltd | High strength and high toughness al alloy |
| JPH0617161A (en) * | 1992-06-30 | 1994-01-25 | Honda Motor Co Ltd | Production of metallic material excellent in mechanical characteristic, etc. |
| EP0584596A3 (en) * | 1992-08-05 | 1994-08-10 | Yamaha Corp | High strength and anti-corrosive aluminum-based alloy |
| JP3852805B2 (en) * | 1998-07-08 | 2006-12-06 | 独立行政法人科学技術振興機構 | Zr-based amorphous alloy excellent in bending strength and impact strength and its production method |
| EP1111079A1 (en) * | 1999-12-20 | 2001-06-27 | Alcoa Inc. | Supersaturated aluminium alloy |
| US7520944B2 (en) * | 2003-02-11 | 2009-04-21 | Johnson William L | Method of making in-situ composites comprising amorphous alloys |
| US8333924B2 (en) * | 2006-03-20 | 2012-12-18 | National University Corporation Kumamoto University | High-strength and high-toughness magnesium alloy and method for manufacturing same |
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| DE3524276A1 (en) * | 1984-07-27 | 1986-01-30 | BBC Aktiengesellschaft Brown, Boveri & Cie., Baden, Aargau | Aluminium alloy for producing ultrafine-grained powder having improved mechanical and microstructural properties |
| JPH0637695B2 (en) * | 1988-03-17 | 1994-05-18 | 健 増本 | Corrosion resistant aluminum base alloy |
| JPH01240631A (en) * | 1988-03-17 | 1989-09-26 | Takeshi Masumoto | High tensile and heat-resistant aluminum-based alloy |
-
1990
- 1990-03-09 JP JP2059139A patent/JP2639455B2/en not_active Expired - Lifetime
-
1991
- 1991-03-07 NO NO910906A patent/NO180205C/en unknown
- 1991-03-08 DE DE4107532A patent/DE4107532C2/en not_active Expired - Fee Related
- 1991-03-08 CA CA002037818A patent/CA2037818C/en not_active Expired - Fee Related
- 1991-03-08 FR FR9102831A patent/FR2659355B1/en not_active Expired - Fee Related
- 1991-03-08 GB GB9104956A patent/GB2243617B/en not_active Expired - Fee Related
- 1991-03-08 AU AU72751/91A patent/AU634866B2/en not_active Ceased
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH01127641A (en) * | 1987-11-10 | 1989-05-19 | Takeshi Masumoto | High tensile and heat-resistant aluminum-based alloy |
| JPH01275732A (en) * | 1988-04-28 | 1989-11-06 | Takeshi Masumoto | High strength and heat-resistant aluminum-based alloy |
| JPH024902A (en) * | 1988-06-17 | 1990-01-09 | Takeshi Masumoto | Aluminum alloy powder used for coating material and coating material |
| JPH0375344A (en) * | 1989-08-15 | 1991-03-29 | Honda Motor Co Ltd | Connecting member |
| JPH03100130A (en) * | 1989-09-13 | 1991-04-25 | Honda Motor Co Ltd | Manufacture of structural member made of amorphous alloy |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH06316738A (en) * | 1992-02-07 | 1994-11-15 | Toyota Motor Corp | High strength aluminum alloy |
| JPH0693393A (en) * | 1992-08-05 | 1994-04-05 | Takeshi Masumoto | Aluminum-base alloy with high strength and corrosion resistance |
| CN103290340A (en) * | 2013-05-30 | 2013-09-11 | 济南大学 | Rare earth-based bulk metallic glass with adjustable rear earth ingredient content |
Also Published As
| Publication number | Publication date |
|---|---|
| AU7275191A (en) | 1991-09-12 |
| DE4107532A1 (en) | 1991-09-12 |
| CA2037818A1 (en) | 1991-09-10 |
| CA2037818C (en) | 1998-07-07 |
| NO910906D0 (en) | 1991-03-07 |
| GB9104956D0 (en) | 1991-04-24 |
| FR2659355B1 (en) | 1993-11-26 |
| NO180205C (en) | 1997-03-05 |
| GB2243617A (en) | 1991-11-06 |
| GB2243617B (en) | 1994-02-09 |
| DE4107532C2 (en) | 1996-08-29 |
| NO180205B (en) | 1996-11-25 |
| NO910906L (en) | 1991-09-10 |
| AU634866B2 (en) | 1993-03-04 |
| FR2659355A1 (en) | 1991-09-13 |
| JP2639455B2 (en) | 1997-08-13 |
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