JP2589125B2 - Manufacturing method of shape memory alloy - Google Patents
Manufacturing method of shape memory alloyInfo
- Publication number
- JP2589125B2 JP2589125B2 JP63037406A JP3740688A JP2589125B2 JP 2589125 B2 JP2589125 B2 JP 2589125B2 JP 63037406 A JP63037406 A JP 63037406A JP 3740688 A JP3740688 A JP 3740688A JP 2589125 B2 JP2589125 B2 JP 2589125B2
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- shape memory
- atomic percent
- memory alloy
- present
- 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 - Fee Related
Links
Description
【発明の詳細な説明】 ［産業上の利用分野］ 本発明は、チタン・ニッケル・銅基形状記憶合金の製
造に関するもので、特にヒステリシスの小さい、且つ、
低温時と高温時の荷重差の大きい形状記憶合金の製造方
法に関するものである。Description: TECHNICAL FIELD The present invention relates to the production of a titanium-nickel-copper-based shape memory alloy, and particularly has a small hysteresis and
The present invention relates to a method for manufacturing a shape memory alloy having a large load difference between a low temperature and a high temperature.
［従来の技術］ 一般にTiNi合金が熱弾性型マルテンサイト変態の逆変
態に付随して顕著な形状記憶効果を示すことはよく知ら
れている。[Prior Art] It is well known that TiNi alloys generally exhibit a remarkable shape memory effect accompanying the reverse transformation of thermoelastic martensitic transformation.
また、特公昭61−54850号公報のようにNiの一部をCu
で置換したTiNiCu合金が前記同様の形状記憶効果を示
し、かつ、組成に対し変態温度が殆んど無関係であるこ
とはMeleonらによって見出されている。Further, as in JP-B-61-54850, a part of Ni is converted to Cu.
It has been found by Meleon et al. That the TiNiCu alloy substituted with has the same shape memory effect as described above and that the transformation temperature is almost independent of the composition.
更に、このTiNiCu合金は、Cuの添加量が増えるにつ
れ、マルテンサイト変態温度と逆変態温度が近接し、マ
ルテンサイト相は、TiNi2元合金については、単斜晶で
あるのに対して、 Cu10原子パーセント以上のTiNiCu合金では斜方晶とな
ることが本間らによって見出されている。（東北大選研
索報37（1981）79） 本間らによって見出された特徴は、応力−温度ヒステ
リシスの小さなバネ製作を可能にし、これまで自動車用
バネ等に実用化されている。Furthermore, in this TiNiCu alloy, as the addition amount of Cu increases, the martensitic transformation temperature and the reverse transformation temperature become closer, and the martensitic phase is monoclinic for the TiNi binary alloy, whereas Cu10 atoms It has been found by Honma et al. That TiNiCu alloys having a percentage or more become orthorhombic. The feature discovered by Honma et al. Enables the production of springs with small stress-temperature hysteresis and has been put to practical use in automotive springs and the like.
［発明が解決しようとする課題］ TiNiCu合金は、Cu添加量を10原子パーセントから増加
されるに従ってマルテンサイト相の結晶構造の変化に伴
いTiCuが析出し始め、その結晶構造の変化量の増加と伴
に、TiCuの析出量は多くなる。このTiCuはTiNiCu合金を
脆くさせるので、TiNiCu合金の製造を困難にさせてい
る。このため、ヒステリシスの小さなバネを得るために
は、Cuを多く添加した方が良いが、前記TiCuの析出の増
大によってTiNiCu合金の製造は困難になり、これまでの
TiNiCu合金の製造方法ではTiNi合金の10原子パーセント
のCu添加が限度であった。[Problems to be Solved by the Invention] In the TiNiCu alloy, as the addition amount of Cu is increased from 10 atomic percent, TiCu begins to precipitate with a change in the crystal structure of the martensite phase, and the change in the crystal structure increases. Accordingly, the precipitation amount of TiCu increases. This TiCu makes the TiNiCu alloy brittle, which makes the production of the TiNiCu alloy difficult. For this reason, in order to obtain a spring with a small hysteresis, it is better to add a large amount of Cu, but it is difficult to produce a TiNiCu alloy due to an increase in the precipitation of TiCu.
In the production method of TiNiCu alloy, the addition of 10 atomic percent Cu of TiNi alloy was the limit.
ここで云うこれまでの方法では、前述特公昭61−5485
0号公報に記載されているものであって、黒鉛ルツボ内
でアルゴン雰囲気の誘導炉によって溶解し、黒鉛鋳型に
鋳造し、900℃で焼鈍を繰り返しながら、約10％ごとの
加工を行う方法である。この加工方法によれば、鋳造時
の溶湯凝固過程でのTiCu析出は避けられず、得られたTi
NiCu合金材料は脆く、Cu添加量が原子パーセント以上の
TiNiCu合金の鋳造後の加工工程すなわち、熱間および冷
間加工では素材にヒビ・クラックが入り、所要の寸法素
材は得られないという欠点を有した。In the conventional method referred to here, the aforementioned Japanese Patent Publication No. Sho 61-5485
No. 0, which is melted by an induction furnace in an argon atmosphere in a graphite crucible, cast into a graphite mold, and repeatedly annealed at 900 ° C. while performing a process of about every 10%. is there. According to this processing method, TiCu precipitation in the process of solidification of the molten metal during casting is inevitable, and the resulting Ti
NiCu alloy materials are brittle, and the Cu content is more than
In the working process after casting of the TiNiCu alloy, that is, in hot and cold working, the material has cracks and cracks, and has a disadvantage that a material of required dimensions cannot be obtained.
本発明は上記欠点に鑑みて行われており、バネ材料と
してヒステリシスの小さく、靭性のすぐれた形状記憶合
金製造方法を提供することを目的とする。The present invention has been made in view of the above drawbacks, and has as its object to provide a method of manufacturing a shape memory alloy having a small hysteresis and excellent toughness as a spring material.
［課題を解決するための手段］ 本発明によれば、Ti49〜51原子パーセント、Cu10〜30
原子パーセント、残部Niからなる合金インゴットを溶融
する溶融工程と、溶融状態の該合金を急冷凝固する急冷
工程とを有し、上記急冷工程は上記合金母相からのTiCu
の析出を抑制することを特徴とする形状記憶合金の製造
方法が得られる。[Means for Solving the Problems] According to the present invention, Ti49 to 51 atomic percent, Cu10 to 30
Atomic percent, a melting step of melting an alloy ingot consisting of the balance of Ni, and a quenching step of quenching and solidifying the alloy in a molten state, wherein the quenching step comprises TiCu from the alloy matrix.
Thus, a method for producing a shape memory alloy, characterized in that precipitation of aluminum is suppressed.
また、本発明によれば、Ti49〜51原子パーセント、Cu
10〜30原子パーセント、Cr、Fe、およびＶの内の少なく
とも１種0.01〜５原子パーセント、残部Niからなる合金
インゴットを溶融する溶融工程と、溶融状態の該合金を
急冷凝固する急冷工程とを有し、上記急冷工程は合金母
相からのTiCuの析出を抑制することを特徴とする形状記
憶合金の製造方法が得られる。Also, according to the present invention, Ti49-51 atomic percent, Cu
A melting step of melting an alloy ingot consisting of 10 to 30 atomic percent, at least one of Cr, Fe, and V, 0.01 to 5 atomic percent, and a balance of Ni; and a quenching step of rapidly solidifying the alloy in a molten state. The quenching step suppresses the precipitation of TiCu from the alloy matrix and provides a method for producing a shape memory alloy.
また、前記の急冷工程は、合金母相からのTiCuの析出
を抑え、このことにより所要寸法製作可能にし、さらに
溶融状態条または線状に急冷凝固させることが可能とな
る。In addition, the above-mentioned quenching step suppresses the precipitation of TiCu from the alloy matrix, thereby making it possible to produce required dimensions, and rapidly solidifying it into a molten strip or linear form.
本発明における典型的な形状記憶合金は、一般的に
は、次式によって表される。Ti50Ni50-xCux,およびTi50
Ni50-x-yCux,Yy、ここで、ＹはCr、Fe、およびＶの内の
少なくとも一種、ｘ＝10〜30,y＝0.01〜５である。ただ
し、Feについて、ｙは５未満である。A typical shape memory alloy in the present invention is generally represented by the following formula. Ti 50 Ni 50-x Cu x , and Ti 50
Ni 50-xy Cu x , Y y , where Y is at least one of Cr, Fe, and V, x = 10-30, y = 0.01-5. However, for Fe, y is less than 5.
ここで、本発明においてはCu添加量10原子パーセント
未満では、従来法によっても容易に合金は加工され、か
つ、本発明の目的であるヒステリシスの小さい合金素子
を得ることはできない。また、Cu添加量が30原子パーセ
ントを越えると、TiCu析出は顕著に認めらないが、曲げ
特性が悪くなる。Here, in the present invention, if the added amount of Cu is less than 10 atomic percent, the alloy can be easily processed even by the conventional method, and the alloy element with small hysteresis, which is the object of the present invention, cannot be obtained. On the other hand, if the added amount of Cu exceeds 30 atomic percent, no remarkable TiCu precipitation is observed, but the bending properties deteriorate.
更に、本発明においては、Cr,Fe,およびＶ添加はいず
れも変態温度を低下される効果を有するが、５原子パー
セントを越えると、曲げ特性の劣化と同時に変態温度が
−100℃以下となり、バネ材料としては実用的ではな
い。Further, in the present invention, the addition of Cr, Fe, and V all have the effect of lowering the transformation temperature.However, if it exceeds 5 atomic percent, the transformation temperature becomes -100 ° C. or lower simultaneously with the deterioration of bending characteristics, It is not practical as a spring material.
［実施例］ 以下、本発明の実施例を図面を参照して説明する。[Example] Hereinafter, an example of the present invention will be described with reference to the drawings.
第１図は本発明の実施例に係る形状記憶合金の製造方
法を示す。FIG. 1 shows a method for manufacturing a shape memory alloy according to an embodiment of the present invention.
図のような片ロール装置で、アルゴン雰囲気中にて黒
鉛ノズル１中で表−１の化学組成の合金インゴット小片
を再溶解し、1.0気圧の噴出圧で、1000rpmの速度で回転
するステンレス製ロール３の表面に噴出させ巾5mm厚さ
0.02mmの薄帯を製造した。In a single roll apparatus as shown in the figure, a small piece of alloy ingot having the chemical composition shown in Table 1 was redissolved in a graphite nozzle 1 in an argon atmosphere, and a stainless steel roll rotated at a speed of 1000 rpm at an ejection pressure of 1.0 atm. Spouting on the surface of 3 5mm thick
A 0.02 mm ribbon was manufactured.
表２はこのように合金インゴット１〜19より得られた
薄帯10を室温でＶ字型に曲げ、Ｙ曲げ破断の有無を調べ
た結果で、表２の薄帯試料番号は表１のインゴット番号
にそれぞれ対応している。 Table 2 shows the results obtained by bending the ribbon 10 thus obtained from the alloy ingots 1 to 19 into a V-shape at room temperature and examining the presence or absence of Y-bending breakage. Each corresponds to a number.
表−２に示すように、参考例の薄帯番号１〜２および
本発明の薄帯番号３〜6,番号８〜10,番号12〜13,番号16
〜18はいずれも破断は認められなかった。 As shown in Table 2, the ribbon numbers 1-2 of the reference example and the ribbon numbers 3-6, 8-10, 12-13, and 16 of the present invention were used.
No break was observed in any of Nos. To 18.
次に上と同じ番号１〜２、３〜６、８〜10、12〜13お
よび16〜18の薄帯を示差走査熱量計（DSC）によってマ
ルテンサイト変態温度（MS），および逆変態温度（AS）
を測定した。その結果を表−２に示す。Next, the ribbons of the same numbers 1-2, 3-6, 8-10, 12-13 and 16-18 were subjected to differential scanning calorimetry (DSC) to determine the martensitic transformation temperature (MS) and reverse transformation temperature (MS). AS)
Was measured. Table 2 shows the results.
また、薄帯試料１〜6,薄帯試料８〜10,薄接12〜13,薄
帯16〜18はいずれもマルテンサイト変態温度と逆変態温
度の近傍が認められた。従って本発明の実施例による方
法により得られた番号３〜６、８〜10、12〜13および16
〜18の形状記憶合金を感温素子として使用する場合、参
考例１〜２のものと同様にヒステリシスの小さい素子の
提供が可能である。また、TiCu析出物の有無を調べるた
めに、光学顕微鏡およびＸ線マイクロアナライザーで形
状記憶合金薄帯を調べたが、いずれも顕著なTiCuの析出
は認められなかった。表−２は、試料番号は表−１の合
金の化学組成を示す試料番号と同じでこの合金の試料は
次のように製造された。Further, in all of the ribbon samples 1 to 6, the ribbon samples 8 to 10, the thin junctions 12 to 13, and the ribbons 16 to 18, the vicinity of the martensitic transformation temperature and the reverse transformation temperature were observed. Accordingly, the numbers 3 to 6, 8 to 10, 12 to 13 and 16 obtained by the method according to the embodiment of the present invention.
When the shape memory alloys of Nos. 1 to 18 are used as the temperature-sensitive element, it is possible to provide an element having a small hysteresis as in the case of Reference Examples 1 and 2. Further, in order to examine the presence or absence of TiCu precipitates, the shape memory alloy ribbon was examined with an optical microscope and an X-ray microanalyzer. In Table 2, the sample numbers are the same as the sample numbers indicating the chemical compositions of the alloys in Table 1, and the samples of this alloy were manufactured as follows.
高周波真空溶解によって溶融され、鉄板上に鋳込まれ
たTiNiCu合金インゴットを２分割した。一方は本発明の
ための供試材とされた。表−１に実施に用いられた合金
インゴットの組成を示している。比較の為に同様な方法
により得られたTiNiCu合金インゴットの他方を従来法に
よって熱間加工および冷間加工（900℃での焼なまし、
および10％の冷間加工率）し、加工性の良否判定した。The TiNiCu alloy ingot melted by high-frequency vacuum melting and cast on an iron plate was divided into two parts. One was a test material for the present invention. Table 1 shows the composition of the alloy ingot used in the embodiment. For comparison, the other TiNiCu alloy ingot obtained by the same method was subjected to hot working and cold working (annealing at 900 ° C,
And a cold working rate of 10%) to determine the workability.
すなわち、表−１に示される化学組成の合金インゴッ
ト試料１〜19を900℃で２時間の均一化処理分、900℃の
温度で熱間加工を行った。その結果、試料1,2は容易に
加工された。試料３は耳割れを生じたがかろうじて加工
された。また試料４〜19は全く加工されなかった。That is, alloy ingot samples 1 to 19 having the chemical compositions shown in Table 1 were subjected to hot working at a temperature of 900 ° C for a homogenization treatment at 900 ° C for 2 hours. As a result, Samples 1 and 2 were easily processed. Sample 3 had ear cracks but was barely processed. Samples 4 to 19 were not processed at all.
次に加工率10％毎に900℃で30分間の焼なましを繰り
返しながら0.02mmの板厚まで加工された。試料1,2は容
易に加工されたが、試料３はかろうじて加工された。Next, the sheet was machined to a sheet thickness of 0.02 mm by repeating annealing at 900 ° C. for 30 minutes every 10% of the working rate. Samples 1 and 2 were easily processed, while Sample 3 was barely processed.
それらの結果を表２に示している。 The results are shown in Table 2.
以上のことから、従来の方法ではほとんど加工できな
かった試料番号３〜６、８〜10、12〜13および16〜18の
形状記憶合金も、本発明の方法によれば、容易に、薄帯
や線材として得られることが分かる。From the above, the shape memory alloys of Sample Nos. 3 to 6, 8 to 10, 12 to 13 and 16 to 18, which could hardly be processed by the conventional method, can be easily thinned according to the method of the present invention. It can be seen that it can be obtained as a wire rod.
第２図は本発明の他の実施冷に係る急冷凝固薄帯を得
る方法の説明図である。FIG. 2 is an explanatory view of a method for obtaining a rapidly solidified ribbon according to another embodiment of the present invention.
この図において、黒鉛ノズル11中から実施例に係る形
状記憶合金の溶湯12を噴出させて、噴出した溶湯は、１
対のロール13及び13′間に挾まれて急冷凝固薄帯とな
る。In this drawing, a molten metal 12 of the shape memory alloy according to the embodiment is ejected from a graphite nozzle 11 and the ejected molten metal becomes 1
The rapidly solidified ribbon is sandwiched between the pair of rolls 13 and 13 '.
第３図は本発明のもう１つの実施例に係る急冷凝固薄
帯を得る方法の説明図である。FIG. 3 is an explanatory view of a method for obtaining a rapidly solidified ribbon according to another embodiment of the present invention.
この図において、黒鉛ノズル１中から、本発明の実施
例に係る形状記憶合金の溶湯22を噴出させて、噴出した
溶湯は、回転するカップ状の内壁に反射して薄帯とな
る。In this figure, a molten metal 22 of the shape memory alloy according to the embodiment of the present invention is ejected from the graphite nozzle 1, and the ejected molten metal is reflected on a rotating cup-shaped inner wall to form a ribbon.
以上、本発明の実施例に係る形状記憶合金の製造方法
は、第１図〜第３図のようであるが、これらに限定され
ない。As described above, the manufacturing method of the shape memory alloy according to the embodiment of the present invention is as shown in FIGS. 1 to 3, but is not limited thereto.
［発明の効果］ 以上説明したように、本発明によれば、TiNiCu合金の
溶融状態からの急冷工程によって、TiNiCu合金母相から
ヒステリシスの小さな形状記録バネを容易に製造できる
とともに、安価なアクチュエータ等の靭性のすぐれた形
状記憶合金の製造方法の提供が可能である。[Effects of the Invention] As described above, according to the present invention, a shape recording spring with small hysteresis can be easily manufactured from a TiNiCu alloy matrix by a quenching process from the molten state of the TiNiCu alloy, and inexpensive actuators and the like can be manufactured. It is possible to provide a method for producing a shape memory alloy having excellent toughness.
第１図は本発明の一実施例に係る形状記憶合金の急冷凝
固薄帯を製造する方法を示す説明図、第２図および第３
図は本発明の他の実施例に係る形状記憶合金の急冷凝固
薄帯を製造する方法を示す説明図である。 １……ノズル、２……溶湯、3,3′……ロール、10,20,3
0……薄帯。FIG. 1 is an explanatory view showing a method for producing a rapidly solidified ribbon of a shape memory alloy according to one embodiment of the present invention, FIG. 2 and FIG.
The figure is an explanatory view showing a method for producing a rapidly solidified ribbon of a shape memory alloy according to another embodiment of the present invention. 1 ... Nozzle, 2 ... Molten, 3,3 '... Roll, 10,20,3
0 ... thin ribbon.
Claims (3)
ーセント、残部Niからなる合金インゴットを溶融する溶
融工程と、溶融状態の該合金を急冷凝固する急冷工程と
を有し、上記急冷工程は上記合金母相からのTiCuの析出
を抑制することを特徴とする形状記憶合金の製造方法。The present invention further comprises a melting step of melting an alloy ingot consisting of 49 to 51 atomic percent of Ti, 10 to 30 atomic percent of Cu and the balance of Ni, and a quenching step of rapidly solidifying the alloy in a molten state. A method for producing a shape memory alloy, comprising suppressing precipitation of TiCu from the alloy matrix.
ーセント、Cr、Fe、およびＶの内の少なくとも１種0.01
〜５原子パーセント、残部Niからなる合金インゴットを
溶融する溶融工程と、溶融状態の該合金を急冷凝固する
急冷工程とを有し、上記急冷工程は合金母相からのTiCu
の析出を抑制することを特徴とする形状記憶合金の製造
方法。2. At least one of 49 to 51 atomic percent of Ti, 10 to 30 atomic percent of Cu, Cr, Fe, and V.
A melting step of melting an alloy ingot consisting of about 5 atomic percent and the balance of Ni, and a quenching step of rapidly solidifying the alloy in a molten state.
A method for producing a shape memory alloy, characterized by suppressing the precipitation of iron.
回転する円筒面に噴出して急冷凝固して条又は線状に成
形する工程を有することを特徴とする第１および第２の
請求項のいずれかに記載の形状記憶合金の製造方法。3. The quenching step includes the step of:
3. The method for producing a shape memory alloy according to claim 1, further comprising a step of injecting into a rotating cylindrical surface, rapidly solidifying, and forming into a strip or a line.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63037406A JP2589125B2 (en) | 1988-02-22 | 1988-02-22 | Manufacturing method of shape memory alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63037406A JP2589125B2 (en) | 1988-02-22 | 1988-02-22 | Manufacturing method of shape memory alloy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH01212728A JPH01212728A (en) | 1989-08-25 |
| JP2589125B2 true JP2589125B2 (en) | 1997-03-12 |
Family
ID=12496644
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63037406A Expired - Fee Related JP2589125B2 (en) | 1988-02-22 | 1988-02-22 | Manufacturing method of shape memory alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP2589125B2 (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CA2559121A1 (en) | 2004-03-11 | 2005-09-22 | Japan Science And Technology Agency | Bulk solidified quenched material and process for producing the same |
| CN116005035A (en) * | 2022-12-30 | 2023-04-25 | 西安理工大学 | Shape memory alloy and preparation method thereof |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH076047B2 (en) * | 1982-12-07 | 1995-01-25 | 住友電気工業株式会社 | Shape memory alloy manufacturing method |
-
1988
- 1988-02-22 JP JP63037406A patent/JP2589125B2/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| JPH01212728A (en) | 1989-08-25 |
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