JPH0441638A - Shape memory alloy - Google Patents
Shape memory alloyInfo
- Publication number
- JPH0441638A JPH0441638A JP14456290A JP14456290A JPH0441638A JP H0441638 A JPH0441638 A JP H0441638A JP 14456290 A JP14456290 A JP 14456290A JP 14456290 A JP14456290 A JP 14456290A JP H0441638 A JPH0441638 A JP H0441638A
- Authority
- JP
- Japan
- Prior art keywords
- alloy
- shape memory
- memory alloy
- workability
- biological
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910001285 shape-memory alloy Inorganic materials 0.000 title claims abstract description 11
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 33
- 239000000956 alloy Substances 0.000 claims abstract description 33
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 5
- 230000032683 aging Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 11
- 229910052802 copper Inorganic materials 0.000 abstract description 4
- 238000005482 strain hardening Methods 0.000 abstract description 2
- 229910018054 Ni-Cu Inorganic materials 0.000 abstract 1
- 229910018481 Ni—Cu Inorganic materials 0.000 abstract 1
- 239000010949 copper Substances 0.000 description 15
- 230000009466 transformation Effects 0.000 description 14
- 238000002844 melting Methods 0.000 description 7
- 230000008018 melting Effects 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 238000005266 casting Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000002244 precipitate Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000010583 slow cooling Methods 0.000 description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 2
- 229910052804 chromium Inorganic materials 0.000 description 2
- 229910052742 iron Inorganic materials 0.000 description 2
- 230000003446 memory effect Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 229910001020 Au alloy Inorganic materials 0.000 description 1
- 229910001018 Cast iron Inorganic materials 0.000 description 1
- 229910010165 TiCu Inorganic materials 0.000 description 1
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 239000003353 gold alloy Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910000734 martensite Inorganic materials 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000035936 sexual power Effects 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 230000003313 weakening effect Effects 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
Abstract
Description
【発明の詳細な説明】 し産業上の利用分野〕 本発明は形状記憶合金に関するものである。[Detailed description of the invention] Field of industrial use] The present invention relates to shape memory alloys.
［従来の技術］
従来、Ｔ１Ｎｉ及びＴｉＮ１Ｘ （但し、 Ｘ−Ｆｅ、
Ｃｕ、Ｃｒ、Ｖ・・・）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及び超
弾性を示すことがよく知られている。[Prior art] Conventionally, T1Ni and TiN1X (however, X-Fe,
It is well known that Cu, Cr, V...) alloys exhibit remarkable shape memory effects and superelasticity accompanying the reverse transformation of thermoelastic martensitic transformation.
また ７ｉＮｉＣｕ合金については、形状記憶効果の出
現確認は、オランダ国より出願された特開昭４６−１５
０２号公報に示されている。Regarding the 7iNiCu alloy, the appearance of the shape memory effect was confirmed in Japanese Unexamined Patent Publication No. 46-15 filed by the Netherlands.
This is shown in Publication No. 02.
更に、Ｃｕ添加によってＮｉ濃度の変態温度依存性を鋭
くさせ、工業的に再現性のある製造を可能にできること
は、米国より出願された特開昭５３−２８５１８号公報
に示されている。Furthermore, Japanese Patent Laid-Open No. 53-28518, filed in the United States, shows that the dependence of Ni concentration on transformation temperature can be sharpened by adding Cu, thereby enabling industrially reproducible production.
また本発明者らは、Ｃ添加Ｔ１Ｎｉ合金が１本質的なＴ
１Ｎｉ合金の特性を損なわず、形状記憶特性の改善に役
立つことができることを見出だしている（東北大選研當
報Ｓ、５７．６第３８巻。The inventors also found that the C-added T1Ni alloy has one essential T1Ni alloy.
It has been found that it can help improve the shape memory properties of the 1Ni alloy without impairing its properties (Tohoku University Senken Report S, 57.6, Vol. 38).
特開昭６３−１１６３６号公報）。(Japanese Unexamined Patent Publication No. 11636/1983).
［発明が解決しようとする課題］
しかしながら１上述した従来のＴｉＮ１Ｃｕ合金は、Ｃ
ｕ添加量の増加と伴に、Ｔ１Ｃｕの析出物が増加し、加
工性が悪くな傾向を示す。特に。[Problems to be Solved by the Invention] However, the conventional TiN1Cu alloy described above is
As the amount of u added increases, the amount of T1Cu precipitates increases, and the workability tends to deteriorate. especially.
Ｃｕ添加量が１０ａｔ％を越えると、極端に加工性は悪
くなる。このため、その溶解法としては、溶解後、急冷
銅鋳型等に鋳込み、Ｔ１Ｃｕの析出を抑える必要があっ
た。When the amount of Cu added exceeds 10 at%, workability becomes extremely poor. Therefore, as a melting method, it was necessary to suppress the precipitation of T1Cu by casting it into a quenched copper mold or the like after melting.
ところが、この溶解方法によれば、溶解インゴットを大
きくすることが不可能であった。すなわち、インゴット
を大きくすることは、急冷効果が弱くなることとなり１
本来抑えなければならないＴ１Ｃｕが析出してしまう欠
点がある。However, according to this melting method, it was impossible to increase the size of the melted ingot. In other words, increasing the size of the ingot weakens the quenching effect.
There is a drawback that T1Cu, which should originally be suppressed, precipitates.
更に、工業的な溶解法として、高周波真空溶解によって
得た合金を鉄等の鋳型に鋳込むことがよく用いられてい
る。Furthermore, as an industrial melting method, casting an alloy obtained by high frequency vacuum melting into a mold made of iron or the like is often used.
しかしこの方法では、Ｃｕ添加が、５ａｔ％程度で限界
となり、それ以上のＣｕ添加の合金では。However, in this method, the Cu addition reaches a limit at about 5 at%, and in alloys with more Cu addition.
殆んどの場合、熱間等による加工時点で、ワレ。In most cases, cracks occur during hot processing.
カケを生じさせることとなっていた。It was supposed to cause chips.
一方、ＴｉＮ１Ｃｕ合金は、工業的にはＮｉ濃度の変態
温度依存性を弱める効果はあるものの。On the other hand, although TiN1Cu alloy has the effect of weakening the dependence of Ni concentration on transformation temperature from an industrial perspective.
逆に、所望の変態温度を得難い難点があった。即ち、Ｔ
ｉ ５ｏＮ ｉ ５ｏ−ｘｃ ｕ ｘなる式でＸを変
化させても１合金の変態温度は、Ｍｓ点でほぼ５０℃前
後である。On the contrary, it was difficult to obtain the desired transformation temperature. That is, T
Even if X is changed according to the formula i5oNi5o-xcux, the transformation temperature of one alloy is approximately 50° C. at the Ms point.
また、変態温度を下げるために、Ｎ１ｍ度を化学量論値
（５０ａｔ％）より増加させることか考えられるが、加
工性は量論値よりはずれるに従い悪くなり、生体温度（
＝３７℃）以下で超弾性を示す温度、すなわち、Ｍｓ点
を３０℃以下とすることが困難となる。Also, in order to lower the transformation temperature, it may be possible to increase N1m degree above the stoichiometric value (50 at%), but the processability deteriorates as it deviates from the stoichiometric value, and the biological temperature (
= 37° C.) or lower, it becomes difficult to maintain the temperature at which superelasticity is exhibited, that is, the Ms point to be 30° C. or lower.
尚、これを解決する手段として、Ｃｒ、Ｆｅ等の第４元
素を添加することは、前記の特開昭５３−２８５１８号
公報に示されているが、変態温度を下げる効果は認めら
れるものの加工性の改善には至っていないのが現状であ
る。As a means to solve this problem, the addition of a fourth element such as Cr or Fe is shown in the above-mentioned Japanese Patent Application Laid-Open No. 53-28518, but although it is recognized to be effective in lowering the transformation temperature, it is difficult to process. The current situation is that sexual performance has not improved.
そこで１本発明の技術的課題は、上記欠点に鑑みＴｉＮ
１Ｃｕ合金の機能的特長を損わず、加工性を改善し、且
つ、生体温度で超弾性を示す領域まで十分に変態温度を
下げた形状記憶合金を提供することにある。Therefore, one technical problem of the present invention is to solve the problem of TiN in view of the above drawbacks.
The object of the present invention is to provide a shape memory alloy that does not impair the functional features of the 1Cu alloy, has improved workability, and has a transformation temperature sufficiently lowered to a region that exhibits superelasticity at biological temperatures.
［課題を解決するための手段］
本発明によれば＋ Ｔ ｉ ｓｏＮ ｉ ５Ｏ−ｘＣｕ
ｘ （但し。[Means for Solving the Problems] According to the present invention + T i soN i 5O-xCu
x (However.
ｘ−５〜１５）なる式で表されるＴｉＮ１Ｃｕ合金を含
み、当該Ｎｉ及びＴｉの少なくともどちらか一方を、
０．２５〜５．Ｏａｔ％の範囲内で、Ｃと置換されて成
ることを特徴とする形状記憶合金が得られる。x-5 to 15), containing at least one of Ni and Ti,
0.25-5. A shape memory alloy characterized in that C is substituted within the range of Oat% is obtained.
また１本発明によれば、前記形状記憶合金を。According to one aspect of the present invention, the shape memory alloy is provided.
加工硬化した後、実質的に４００〜５５０℃の範囲内で
１時効処理を施し、少なくとも生体温度で超弾性を示す
ことを特徴とする形状記憶合金の処理方法が得られる。After work hardening, a single aging treatment is performed substantially within the range of 400 to 550° C., thereby obtaining a method for processing a shape memory alloy characterized in that it exhibits superelasticity at least at biological temperature.
［実施例］ 次に本発明の実施例を図面を参照して説明する。[Example] Next, embodiments of the present invention will be described with reference to the drawings.
まず、高周波真空溶解法によって得た合金を。First, an alloy obtained by high frequency vacuum melting method.
鋳鉄鋳型による徐冷および水冷銅鋳型による急冷の２種
類の鋳込み方法をによって、インゴットを作成した。そ
れらを９００℃の容体化処理後、熱間加工を行った。Ingots were produced using two types of casting methods: slow cooling using a cast iron mold and rapid cooling using a water-cooled copper mold. After a 900° C. compacting treatment, they were subjected to hot working.
表−１に本発明合金の一例として阻１〜磁６゜比較合金
としてＮｏ、 ７〜１３の各々合金の熱間加工性のテス
ト結果を示した。Table 1 shows the hot workability test results of alloys No. 1 to No. 1 to Magnetic No. 6 as examples of the present invention alloys, and No. 7 to No. 13 as comparative alloys.
表−１
Ｏ・・・良好
△・・・やや難
×・・・不可
比較合金中、鋳込方法が徐冷によると、Ｃｕ添加１０ａ
ｔ％のＮＱ、 ８は、熱間加工でワレが生じ加工できな
かった。尚、急冷によるＮｏ、１０合金は十分に加工で
きたが、これは急冷によってＴｉ Ｃｕの析出を制御で
きたためと思われる。しかし、Ｃｕ添加１５ａｔ％はい
づれの方法によっても加工はできなかった。Table-1 O...Good △...Slightly difficult ×...Uncomparable Among the alloys, if the casting method is slow cooling, Cu addition 10a
t% NQ, 8 cracked during hot working and could not be processed. It should be noted that alloy No. 10 could be sufficiently processed by rapid cooling, but this is probably because the precipitation of TiCu could be controlled by rapid cooling. However, Cu addition of 15 at% could not be processed by any of the methods.
また、変態点を下げるために、Ｎｉ濃度をｌａｔ％増加
させたＮｏ、１３合金は急冷によっても、加工はできな
かった。Furthermore, alloy No. 13, in which the Ni concentration was increased by lat% in order to lower the transformation point, could not be processed even by rapid cooling.
一方７本発明合金よれば、徐冷によってもいづれの合金
をも加工することができた。尚、Ｃｕ濃度の高（・Ｃｕ
添加１５ａｔ％のＮα３及びＮｏ、６合金出は、ワレが
生じ易（、加工性は十分に改善されたとは云い難かった
。On the other hand, according to the seven invention alloys, any of the alloys could be processed by slow cooling. In addition, if the Cu concentration is high (・Cu
The Nα3 and No.6 alloys with an additive content of 15 at% were prone to cracking (and it was difficult to say that the workability was sufficiently improved).
第１図にＴｉ５゜Ｎｉ４ｏ−ｙｃＬＪ＋ｏｃ）’ ｔ：
ｙ−ｉ〜５）およびＴ ｉ ５Ｏ−ＹＮ ｉ ４Ｏ−Ｆ
ＣＬｌ １ｏ （Ｖ −１〜２）の各々の合金のＭｓ点
とＣ添加量の関係を示した。In Figure 1, Ti5゜Ni4o-ycLJ+oc)'t:
y-i~5) and T i 5O-YN i 4O-F
The relationship between the Ms point and the amount of C added for each alloy of CLl 1o (V -1 to 2) is shown.
図中、ａはＮｉをＣに置換したものであり、ｂはＴｉに
Ｃを置換したものの結果である。In the figure, a shows the result of replacing Ni with C, and b shows the result of replacing C with Ti.
ａシリーズは、Ｃ添加による変態温度低下効果は薄い。In the a series, the effect of lowering the transformation temperature due to the addition of C is weak.
一方、ｂシリーズはＴｉとの置換であるため、変態温度
の低下効果は強＜、２ａｔ％添加すると、Ｍｓ点は約１
０℃程度まで低下し、３７℃での超弾性が十分に得られ
ることが分かる。On the other hand, since the b series is replaced with Ti, the effect of lowering the transformation temperature is strong. When 2 at% is added, the Ms point is approximately 1
It can be seen that the temperature decreases to about 0°C, and sufficient superelasticity can be obtained at 37°C.
添加したＣはマトリックス中のＴｉと主に反応して、Ｔ
ｉｃの析出物を形成することは１本発明者らの研究によ
って明らかにされている。The added C mainly reacts with Ti in the matrix, resulting in T
The formation of IC precipitates has been clarified by research conducted by the present inventors.
このことは、ＴｉＮ１Ｃ合金についても同様のことが云
えると考えられる。ａシリーズのようにＮｉに置換して
も変態温度に作用するＮｉ量は（Ｎ ｉ ＋Ｃ）量と見
ることができるため、顕著には効かない。しかし、Ｔｉ
に置換すると（Ｎ ｉ ＋Ｃ）ｊｉはＴｉに対して多く
なるために変態温度への影響は大きくなる。また、溶解
中に生成したＴｉＣがＴ１Ｃｕの析出を抑える効果を持
つために表−１に示すような加工性の改善が図られるも
のと思われる。It is thought that the same can be said of the TiN1C alloy. Even if it is replaced with Ni as in the a series, the amount of Ni that acts on the transformation temperature can be seen as the amount of (N i +C), so it does not have a significant effect. However, Ti
When it is replaced with (N i +C) ji becomes larger than Ti, the influence on the transformation temperature becomes greater. In addition, since the TiC produced during melting has the effect of suppressing the precipitation of T1Cu, it is thought that the workability is improved as shown in Table 1.
しかし、Ｃ添加量は０．２５ａｔ％以下の場合、加工性
の改善効果は認め難い、また５ａｔ％を越えても。However, if the amount of C added is less than 0.25 at%, it is difficult to see any improvement in workability, and even if it exceeds 5 at%.
加工性の著しい改善は認められない。No significant improvement in workability was observed.
即ち２本発明の最適Ｃ添加量は０，５〜１．５ ａｔ％
である。また、Ｃｕ量が、１５ａｔ％程度の場合には、
Ｃ添加を大きくしても加工性は改善するものの、工業的
に供し得難＜、Ｃｕ添加の限度は１５ａｔ％未満と思わ
れる。That is, the optimum amount of C added in the present invention is 0.5 to 1.5 at%.
It is. Moreover, when the Cu amount is about 15 at%,
Although processability is improved even if the addition of C is increased, it is difficult to use it industrially, and the limit of addition of Cu is thought to be less than 15 at%.
次に、熱間加工によって得た本発明に係わるＮｏ。Next, No. according to the present invention obtained by hot working.
５合金を冷間加工によって約φ１ ｍの線材とし。5 alloy was cold-worked into a wire rod with a diameter of approximately 1 m.
３７℃での超弾性測定用試料とした。時効温度を４００
℃、５００および６００℃とし、それぞれ３０分の処理
時間とした。その結果、４００℃および５００℃では、
従来のＴ１Ｎｉ２元合金同様の超弾性が得られたが、６
００℃では、超弾性は示すものの若干繰り返しに劣るこ
とが分かった。This was used as a sample for superelasticity measurement at 37°C. Aging temperature 400
℃, 500 and 600℃, and the treatment time was 30 minutes each. As a result, at 400℃ and 500℃,
Superelasticity similar to the conventional T1Ni binary alloy was obtained, but 6
At 00°C, it was found that although superelasticity was exhibited, the repeatability was slightly inferior.
［発明の効果コ
以上１本発明によれば、ＴｉＮ１Ｃｕ合金の加工性を改
善し、且つ３７℃以下での超弾性を示すＴｉＮ１Ｃｕ合
金を得ることが出来るため、感温バネおよび歯列矯正線
、ガイドワイヤー等医療用バネ材として適用が可能とな
る。[Effects of the Invention] 1. According to the present invention, it is possible to improve the workability of the TiN1Cu alloy and to obtain a TiN1Cu alloy that exhibits superelasticity at temperatures below 37°C. It can be applied as a medical spring material such as guide wires.
第１図はＴｉ５ｏＮｆ４ｏ−ｙｃｕ＋ｏｃＹ （ｙ−０
〜５）１合金、およびＴ ｉ ５ｏ−ｙＮ ｉ ４０Ｃ
ｕ ＋ｏＣＹ（ｙ−０−２）合金のＭｓ点とＣ添加量の
関係を示す図である。
図中（ａ）はＴ ｉ ５ｏＮ ｉ ４０−、Ｃｕ １６
Ｃｙ合金を示しくｂ）はＴ ｉ ５ｏ−ｙＮ ｉ ４ｏ
Ｃｕ ＋ｏ金合金示している。Figure 1 shows Ti5oNf4o-ycu+ocY (y-0
~5) 1 alloy, and T i 5o-yN i 40C
It is a figure which shows the relationship between the Ms point of u+oCY(y-0-2) alloy and the amount of C added. In the figure (a) is Ti 5oN i 40-, Cu 16
Indicates Cy alloy; b) is T i 5o-yN i 4o
Cu + o gold alloy is shown.
Claims (2)
し、ｘ＝５〜１５）なる式で表されるＴｉＮｉＣｕ合金
を含み、当該Ｎｉ及びＴｉの少なくともどちらか一方を
、０．２５〜５．０ａｔ％の範囲内で、Ｃと置換されて
成ることを特徴とする形状記憶合金。(1) Contains a TiNiCu alloy represented by the formula Ti_5_0Ni_5_0_-_xCu_x (where x = 5 to 15), and contains at least one of Ni and Ti within the range of 0.25 to 5.0 at%, A shape memory alloy characterized by being substituted with C.
後、実質的に４００〜５５０℃の範囲内で、時効処理を
施し、少なくとも生体温度で超弾性を示すことを特徴と
する形状記憶合金の処理方法。(2) The shape memory alloy according to claim 1 is work-hardened and then subjected to an aging treatment at a temperature of substantially 400 to 550°C, so that the shape exhibits superelasticity at least at biological temperature. How to process memory alloys.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14456290A JPH0441638A (en) | 1990-06-04 | 1990-06-04 | Shape memory alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP14456290A JPH0441638A (en) | 1990-06-04 | 1990-06-04 | Shape memory alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH0441638A true JPH0441638A (en) | 1992-02-12 |
Family
ID=15365137
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP14456290A Pending JPH0441638A (en) | 1990-06-04 | 1990-06-04 | Shape memory alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0441638A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019073754A1 (en) * | 2017-10-10 | 2019-04-18 | 株式会社古河テクノマテリアル | Ti-Ni ALLOY, WIRE, ELECTRIFICATION ACTUATOR AND TEMPERATURE SENSOR USING SAME, AND METHOD FOR MANUFACTURING Ti-Ni ALLOY MATERIAL |
-
1990
- 1990-06-04 JP JP14456290A patent/JPH0441638A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2019073754A1 (en) * | 2017-10-10 | 2019-04-18 | 株式会社古河テクノマテリアル | Ti-Ni ALLOY, WIRE, ELECTRIFICATION ACTUATOR AND TEMPERATURE SENSOR USING SAME, AND METHOD FOR MANUFACTURING Ti-Ni ALLOY MATERIAL |
| US11313732B2 (en) | 2017-10-10 | 2022-04-26 | Furukawa Techno Material Co., Ltd. | Ti—Ni-based alloy; wire, electrically conductive actuator, and temperature sensor, each using this alloy; and method of producing a Ti—Ni-based alloy |
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