JP2016006218A - High temperature shape memory alloy and method for producing the same - Google Patents
High temperature shape memory alloy and method for producing the same Download PDFInfo
- Publication number
- JP2016006218A JP2016006218A JP2014152847A JP2014152847A JP2016006218A JP 2016006218 A JP2016006218 A JP 2016006218A JP 2014152847 A JP2014152847 A JP 2014152847A JP 2014152847 A JP2014152847 A JP 2014152847A JP 2016006218 A JP2016006218 A JP 2016006218A
- Authority
- JP
- Japan
- Prior art keywords
- temperature
- shape memory
- memory alloy
- tipd
- mpa
- 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
Landscapes
- Heat Treatment Of Steel (AREA)
- Micromachines (AREA)
Abstract
Description
本発明は、高温形状記憶合金およびその製造方法に関し、より詳しくは、高温における仕事量と繰り返し特性を向上させた高温形状記憶合金およびその製造方法に関するものである。 The present invention relates to a high-temperature shape memory alloy and a method for producing the same, and more particularly to a high-temperature shape memory alloy having improved work volume and repetition characteristics at high temperatures and a method for producing the same.
ＴｉＮｉに代表される形状記憶合金は、動力を必要とせず温度変化を感知して動作するアクチュエイター等として利用されている。このような形状記憶合金に対する性能要求は様々であって、自動車エンジンやジェットエンジン等、数百℃〜千℃オーダーの高温部で使用するアクチュエイター等の部品には、そのような高温での使用環境でも動作する形状記憶合金が必要とされている。 Shape memory alloys typified by TiNi are used as actuators and the like that operate by sensing temperature changes without requiring power. Performance requirements for such shape memory alloys vary, and parts such as actuators used in high-temperature parts of the order of several hundreds of degrees C to 1000 C, such as automobile engines and jet engines, are used at such high temperatures. There is a need for shape memory alloys that work in the environment.
そこで、これまでにも、ＴｉＮｉにＺｒ、ＨｆやＰｄ、Ｐｔ等を添加することにより、形状記憶効果に関連するマルテンサイト変態温度を上昇させる試みが行われてきた。例えば、特許文献１には、Ｔｉが５０〜５２原子％であり、Ｐｔが１０〜２５原子％であり、５原子％以下のＡｕ、Ｐｄ、Ｃｕを１種以上含み、２原子％以下のＣを含み、残部がＮｉであり、Ｔｉ４（Ｎｉ、Ｐｔ）３型の析出物が生成する高温形状記憶合金が開示されている。 So far, attempts have been made to increase the martensitic transformation temperature related to the shape memory effect by adding Zr, Hf, Pd, Pt or the like to TiNi. For example, in Patent Document 1, Ti is 50 to 52 atomic%, Pt is 10 to 25 atomic%, and contains at least one kind of Au, Pd, or Cu of 5 atomic% or less, and C of 2 atomic% or less. , The balance being Ni, and a high temperature shape memory alloy in which a Ti 4 (Ni, Pt) 3 type precipitate is generated is disclosed.
一方で、ＴｉＰｔやＴｉＰｄを基本構成とした合金を用いた高温形状記憶合金の開発も行われてきた。例えば、特許文献２には、Ｐｔ-４２〜６３原子％Ｔｉ合金にＩｒが添加され、Ｐｔの一部が５０原子％未満のＩｒで置換される形状記憶特性と擬弾性を持ち合わせる合金が開示されている。特許文献３には、Ｐｄが４５〜５５原子％、Ｈｆ、Ｚｒ、Ｔａ、Ｎｂ、Ｖ、Ｍｏ、Ｗのうちの１種以上が０．１〜１５原子％、残部がＴｉと不可避不純物からなり、２００℃〜５５０℃までの温度範囲で形状回復を示す合金が開示されている。そして、非特許文献１には、ＴｉＰｄの形状回復率に対するＺｒの添加効果について示されている。 On the other hand, high temperature shape memory alloys using alloys based on TiPt or TiPd have been developed. For example, Patent Document 2 discloses an alloy having shape memory characteristics and pseudoelasticity in which Ir is added to a Pt-42 to 63 atom% Ti alloy and a part of Pt is replaced with less than 50 atom% Ir. ing. In Patent Document 3, Pd is 45 to 55 atomic%, one or more of Hf, Zr, Ta, Nb, V, Mo, and W are 0.1 to 15 atomic%, and the balance is Ti and inevitable impurities. Alloys exhibiting shape recovery in the temperature range from 200 ° C. to 550 ° C. are disclosed. Non-Patent Document 1 shows the effect of adding Zr on the shape recovery rate of TiPd.
これらのこれまで開発されてきた高温形状記憶合金は、マルテンサイト変態温度が３００℃以下のものが多かった。なかには３００℃以上のマルテンサイト変態温度を示す合金も示されているが、これらについては回復率が明確に示されておらず、実際に回復を起こすかどうかは明らかではなかった。 Many of these high-temperature shape memory alloys that have been developed so far have a martensitic transformation temperature of 300 ° C. or lower. Among them, alloys showing a martensitic transformation temperature of 300 ° C. or higher are also shown, but the recovery rate is not clearly shown for these, and it is not clear whether recovery actually occurs.
形状記憶合金は、マルテンサイト相を有する状態で変形が加えられた後、マルテンサイト変態温度以上に加熱されることによって、マルテンサイト相から母相であるオーステナイト相へと変態して形状が回復する。そのため、高温で形状回復を起こすためには、マルテンサイト変態温度を高くする必要がある。 The shape memory alloy is deformed in a state having a martensite phase, and is then heated to a temperature higher than the martensite transformation temperature, thereby transforming from the martensite phase to the austenite phase that is the parent phase to recover the shape. . Therefore, in order to cause shape recovery at a high temperature, it is necessary to increase the martensitic transformation temperature.
しかしながら、高いマルテンサイト変態温度近傍で変形、形状回復を繰り返すと、高温でマルテンサイト相に変形が加えられるため、しばしば永久に歪みが入る塑性変形を起こす。塑性変形を起こすと、永久歪みの分、形状が回復しないため回復率が落ちる。 However, when deformation and shape recovery are repeated in the vicinity of a high martensite transformation temperature, deformation is applied to the martensite phase at high temperatures, which often causes plastic deformation that is permanently distorted. When plastic deformation occurs, the recovery rate decreases because the shape does not recover due to permanent deformation.
以上のことから、高温形状記憶合金を開発するためには、マルテンサイト変態温度を上昇させ、かつ、マルテンサイト変態温度近傍での強度を向上させる必要がある。 From the above, in order to develop a high-temperature shape memory alloy, it is necessary to increase the martensitic transformation temperature and improve the strength in the vicinity of the martensitic transformation temperature.
本発明は、従来の高温形状記憶合金における上記の問題を解決するためになされたものであり、高温における仕事量と繰り返し特性を向上させた高温形状記憶合金およびその製造方法を提供することを課題としている。 The present invention has been made to solve the above-mentioned problems in conventional high-temperature shape memory alloys, and it is an object to provide a high-temperature shape memory alloy having improved work volume and repeatability at high temperatures and a method for producing the same. It is said.
本発明は、上記の課題を解決するために、以下のことを特徴としている。
（１）４５〜５５原子％のＰｄ、および残部がＴｉと不可避不純物からなるＴｉＰｄ系高温形状記憶合金であって、前記Ｔｉの一部がＺｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｍｏ、Ｗのうちの１種以上で、全体組成に対して０．１〜１５原子％の範囲で置換されており、マルテンサイト双晶組織の、オーステナイト相に対するマルテンサイト相のバリアントの８０％以上が同一方向を示すＴｉＰｄ系高温形状記憶合金。
（２）上記ＴｉＰｄ系高温形状記憶合金において、前記Ｐｄの一部がＰｔ、Ｉｒのうちの１種以上で、全体組成に対して０．１〜５４．９原子％の範囲で置換されているＴｉＰｄ系高温形状記憶合金。
（３）上記ＴｉＰｄ系高温形状記憶合金において、マルテンサイト変態温度が４００℃〜１０００℃であるＴｉＰｄ系高温形状記憶合金。
（４）上記ＴｉＰｄ系高温形状記憶合金において、永久歪みが０．５％以下であるＴｉＰｄ系高温形状記憶合金。
（５）上記ＴｉＰｄ系高温形状記憶合金において、仕事量が０．５Ｊ／ｃｍ３以上であるＴｉＰｄ系高温形状記憶合金。
（６）上記いずれかのＴｉＰｄ系高温形状記憶合金を用いて作製されたＴｉＰｄ系高温形状記憶合金アクチュエイター。
（７）上記いずれかのＴｉＰｄ系高温形状記憶合金の製造方法であって、溶製した前記形状記憶合金の原料を、真空容器中に不活性ガスとともに封入した状態で、マルテンサイト変態温度以上のＢ２型立方晶領域の温度から前記形状記憶合金の液相を生じる温度より１００℃を下回る温度までの範囲内で、０．５時間以上保持する溶体化処理を施した後、０℃以下の冷媒に入れて焼き入れし、目的とする応力以上かつ４００ＭＰａ以下の応力下で、マルテンサイト相が安定な温度からオーステナイト相に変態が終了する温度以上の温度に上昇させた後、マルテンサイト相が安定な温度に降温させる加圧・熱サイクルを１回以上繰り返した後に目的とする応力下で加圧・熱サイクルを行うＴｉＰｄ系高温形状記憶合金の製造方法。
The present invention is characterized by the following in order to solve the above problems.
(1) TiPd-based high-temperature shape memory alloy consisting of 45 to 55 atomic% Pd and the balance being Ti and inevitable impurities, wherein a part of the Ti is Zr, Hf, Nb, Ta, Mo, W TiPd that is one or more and is substituted in the range of 0.1 to 15 atomic% with respect to the whole composition, and that 80% or more of the martensitic phase variant of the martensite twin structure has the same direction with respect to the austenite phase. High temperature shape memory alloy.
(2) In the TiPd-based high-temperature shape memory alloy, a part of the Pd is one or more of Pt and Ir, and is substituted in the range of 0.1 to 54.9 atomic% with respect to the entire composition. TiPd high temperature shape memory alloy.
(3) The TiPd high temperature shape memory alloy, wherein the martensitic transformation temperature is 400 ° C to 1000 ° C.
(4) The TiPd high temperature shape memory alloy, wherein the permanent deformation is 0.5% or less.
(5) The TiPd high temperature shape memory alloy, wherein the work amount is 0.5 J / cm 3 or more.
(6) A TiPd-based high-temperature shape memory alloy actuator manufactured using any one of the above TiPd-based high-temperature shape memory alloys.
(7) A method for producing any one of the above TiPd-based high-temperature shape memory alloys, wherein the melted raw material of the shape memory alloy is enclosed with an inert gas in a vacuum vessel and has a martensite transformation temperature or higher. In the range from the temperature of the B2 type cubic crystal region to the temperature lower than 100 ° C. than the temperature at which the liquid phase of the shape memory alloy is generated, a solution treatment for holding for 0.5 hour or more is performed, and then the refrigerant at 0 ° C. or lower The martensite phase is stabilized after the martensite phase is raised from the stable temperature to the austenite phase at a temperature equal to or higher than the temperature at which the transformation is completed under a stress of 400 MPa or less and higher than the target stress. A method for producing a TiPd-based high-temperature shape memory alloy in which a pressurization / thermal cycle is repeated under a target stress after repeating the pressurization / thermal cycle for lowering the temperature to one temperature at least once.
本発明のＴｉＰｄ系高温形状記憶合金によれば、一定応力下でマルテンサイト相が安定な温度から変態温度を超える温度の間で加圧・熱サイクルを行うことにより、高温における仕事量と繰り返し特性を向上させた高温形状記憶合金を提供することができる。 According to the TiPd-based high-temperature shape memory alloy of the present invention, the work and repetition characteristics at high temperatures can be achieved by pressing and thermal cycling between a temperature at which the martensite phase is stable and a temperature exceeding the transformation temperature under a constant stress. It is possible to provide a high-temperature shape memory alloy with improved
＜ＴｉＰｄ系高温形状記憶合金の合金組成＞
本発明のＴｉＰｄ系高温形状記憶合金は、ＴｉＰｄ化合物を基本的な構成としている。Ｔｉ、Ｐｄの二元系状態図によると、Ｐｄの割合が４５〜５５原子％の組成範囲でＴｉＰｄ化合物が安定に存在することが確認でき、Ｐｄの好ましい組成範囲は４５〜５５原子％であることがわかる。以上のことを前提として、以下に本発明のＴｉＰｄ系高温形状記憶合金の実施形態についてさらに詳細に説明する。
<Alloy composition of TiPd high temperature shape memory alloy>
The TiPd-based high-temperature shape memory alloy of the present invention is basically composed of a TiPd compound. According to the binary system phase diagram of Ti and Pd, it can be confirmed that the TiPd compound exists stably in the composition range where the ratio of Pd is 45 to 55 atomic%, and the preferable composition range of Pd is 45 to 55 atomic%. I understand that. Based on the above, embodiments of the TiPd-based high-temperature shape memory alloy of the present invention will be described in more detail below.
本発明のＴｉＰｄ系高温形状記憶合金の第一の実施形態では、ＴｉＰｄ化合物に対し、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｍｏ、Ｗのうちの１種以上が、全体組成に対して０．１〜１５原子％の範囲でＴｉの一部を置換するように添加される。 In the first embodiment of the TiPd-based high-temperature shape memory alloy of the present invention, at least one of Zr, Hf, Nb, Ta, Mo, and W is 0.1 to 0.1% of the total composition with respect to the TiPd compound. It is added so as to substitute a part of Ti in the range of 15 atomic%.
上記の元素は、ＴｉＰｄ化合物の高温強度を向上させるのに有効な元素である。また、これらの元素は、Ｔｉと似た性質を持つ、周期律表の４〜６族の元素であり、Ｔｉの一部を置換しても、結晶中に大きな欠陥は生成しない。 Said element is an element effective in improving the high temperature strength of a TiPd compound. These elements are elements of groups 4 to 6 in the periodic table having properties similar to Ti, and even if a part of Ti is substituted, no large defect is generated in the crystal.
ＴｉＰｄ化合物の高温強度を向上させるためには、Ｚｒ、Ｈｆ、Ｎｂ、Ｔａ、Ｍｏ、Ｗのうちの１種以上を、全体組成に対して０．１原子％以上添加する必要がある。一方で、ＴｉＰｄ化合物に固溶できる組成範囲は限られており、上記の元素の全体組成に対する割合が１５原子％を超えると、別の相の割合が多くなる場合がある。 In order to improve the high temperature strength of the TiPd compound, it is necessary to add one or more of Zr, Hf, Nb, Ta, Mo, and W in an amount of 0.1 atomic% or more based on the total composition. On the other hand, the composition range that can be dissolved in the TiPd compound is limited, and if the ratio of the above elements to the total composition exceeds 15 atomic%, the ratio of another phase may increase.
また、本発明のＴｉＰｄ系高温形状記憶合金の第二の実施形態では、上記のＴｉＰｄ系高温形状記憶合金に対し、Ｐｔ、Ｉｒのうちの１種以上が、全体組成に対して０．１〜５４．９原子％の範囲でＰｄの一部を置換するように添加されることが好ましい。 Moreover, in 2nd embodiment of the TiPd type | system | group high temperature shape memory alloy of this invention, 1 type or more of Pt and Ir with respect to said TiPd type | system | group high temperature shape memory alloy is 0.1-0.1 with respect to the whole composition. It is preferably added so as to substitute a part of Pd in the range of 54.9 atomic%.
上記の元素は、ＴｉＰｄ化合物の高温強度を向上させるのに有効な元素である。また、Ｐｔ、Ｉｒについては、Ｐｄと全率固溶するため、５４．９原子％までの範囲で添加可能である。 Said element is an element effective in improving the high temperature strength of a TiPd compound. Pt and Ir can be added in a range of up to 54.9 atomic% because they are completely dissolved with Pd.
＜ＴｉＰｄ系高温形状記憶合金の特性＞
本発明のＴｉＰｄ系高温形状記憶合金は、マルテンサイト変態温度が４００℃〜１０００℃であることが好ましい。また、本発明のＴｉＰｄ系高温形状記憶合金は、４００℃〜１０００℃のマルテンサイト変態温度近傍で変形、形状回復を繰り返した場合であっても、永久歪みが０．５％以下の繰り返し特性を有することが好ましい。そして、本発明のＴｉＰｄ系高温形状記憶合金は、４００℃〜１０００℃という高温のマルテンサイト変態温度であっても形状回復を起こし、０．５Ｊ／ｃｍ３以上の仕事量を有することが好ましい。
<Characteristics of TiPd high temperature shape memory alloy>
The TiPd high temperature shape memory alloy of the present invention preferably has a martensitic transformation temperature of 400 ° C to 1000 ° C. In addition, the TiPd-based high-temperature shape memory alloy of the present invention has a repetitive characteristic of a permanent set of 0.5% or less even when deformation and shape recovery are repeated near the martensitic transformation temperature of 400 ° C. to 1000 ° C. It is preferable to have. The TiPd-based high-temperature shape memory alloy of the present invention preferably undergoes shape recovery even at a high martensitic transformation temperature of 400 ° C. to 1000 ° C., and preferably has a work amount of 0.5 J / cm 3 or more.
＜ＴｉＰｄ系高温形状記憶合金の組織構造＞
本発明のＴｉＰｄ系高温形状記憶合金は、マルテンサイト双晶組織の、オーステナイト相に対するマルテンサイト相のバリアントの８０％以上が同一方向を示す。従来の製造方法によって製造された形状記憶合金では、マルテンサイト双晶組織におけるマルテンサイト相のバリアントの方向性にはバラつきがあり、一定の規則性は見出されていなかった。本発明のＴｉＰｄ系高温形状記憶合金では、バリアントの８０％以上が同一方向を示すことにより、マルテンサイト相からオーステナイト相への逆変態を促進することによって、合金の繰り返し特性が向上すると考えられる。
<Structure structure of TiPd-based high-temperature shape memory alloy>
In the TiPd-based high-temperature shape memory alloy of the present invention, 80% or more of the martensite phase variant with respect to the austenite phase in the martensite twin structure shows the same direction. In the shape memory alloy manufactured by the conventional manufacturing method, the direction of the variant of the martensite phase in the martensite twin structure varies, and no regularity has been found. In the TiPd-based high-temperature shape memory alloy of the present invention, it is considered that 80% or more of the variants show the same direction, thereby promoting the reverse transformation from the martensite phase to the austenite phase, thereby improving the repetition characteristics of the alloy.
このようなバリアントの規則的な配列は、本発明のＴｉＰｄ系高温形状記憶合金を製造する過程において、一定の応力を負荷することによってマルテンサイト相に変形が生じ、マルテンサイト双晶組織内のマルテンサイトバリアントの再配列が惹起され、一つの結晶粒を占めるバリアントが一定方向に優先的に成長するためであると考えられる。 Such a regular arrangement of variants causes deformation in the martensite phase by applying a certain stress in the process of manufacturing the TiPd-based high-temperature shape memory alloy of the present invention, and the martensite in the martensitic twin structure. This is probably because the rearrangement of site variants is induced, and the variants occupying one crystal grain preferentially grow in a certain direction.
＜ＴｉＰｄ系高温形状記憶合金の製造方法＞
以下に、本発明の高温形状記憶合金の製造工程の一実施形態について説明する。
<Method for producing TiPd-based high-temperature shape memory alloy>
Below, one Embodiment of the manufacturing process of the high temperature shape memory alloy of this invention is described.
まず、本発明の高温形状記憶合金の原料を溶解して溶製する。溶解には、一般的なＴｉ材料溶解に用いられる各種溶解法を採用することができ、特に制限されるものではなく、これらの方法としては、例えば、アーク溶解法、電子ビーム溶解法、高周波溶解法等の溶解法を挙げることができる。 First, the raw material of the high-temperature shape memory alloy of the present invention is melted and melted. Various melting methods used for general Ti material melting can be adopted for melting and are not particularly limited. Examples of these methods include arc melting, electron beam melting, and high-frequency melting. A dissolution method such as a method can be mentioned.
次に、溶製した原料を、真空容器中に、アルゴンガス等の不活性ガスとともに封入した状態で、マルテンサイト変態温度以上のＢ２型立方晶領域の温度から前記形状記憶合金の液相を生じる温度より１００℃を下回る温度までの範囲内で、０．５時間以上保持する溶体化処理を施す。 Next, a liquid phase of the shape memory alloy is generated from the temperature of the B2 cubic region above the martensite transformation temperature in a state where the melted raw material is sealed in an inert gas such as argon gas in a vacuum vessel. A solution treatment for holding for 0.5 hours or more is performed within a range from the temperature to a temperature lower than 100 ° C.
溶体化処理は、溶解中に生成した不均一な組織を均質にするために、マルテンサイト変態温度以上のＢ２型立方晶領域の温度で一定時間以上行う必要がある。 The solution treatment needs to be performed for a certain period of time at a temperature of the B2 type cubic crystal region at or above the martensite transformation temperature in order to homogenize the heterogeneous structure generated during dissolution.
マルテンサイト変態温度は合金組成によって異なるが、本発明の高温形状記憶合金が高融点の元素で構成されているため、オーステナイト相であるＢ２型立方晶領域の温度で熱処理することにより十分に拡散し、均質化が行われるため望ましい。また、Ｂ２型立方晶領域は融点まで続くが、融点近傍で熱処理をすると結晶の規則状態が保たれなくなる可能性があることから、溶体化処理温度は、その合金の液相を生じる温度から１００℃を下回る温度を上限とする。 Although the martensitic transformation temperature varies depending on the alloy composition, since the high-temperature shape memory alloy of the present invention is composed of a high melting point element, it can be sufficiently diffused by heat treatment at the temperature of the austenitic B2 cubic region. This is desirable because homogenization is performed. Further, although the B2 type cubic crystal region continues to the melting point, there is a possibility that the ordered state of the crystal may not be maintained if heat treatment is performed in the vicinity of the melting point. Therefore, the solution treatment temperature is 100 ° C. from the temperature at which the liquid phase of the alloy is generated. The upper limit is a temperature lower than ° C.
溶体化処理時間は０．５時間以上、好ましくは０．５〜５００時間の範囲である。溶体化時間が０．５時間以上であれば、均質化が十分に行われ、組織が均一状態となるため望ましい。一方、溶体化処理時間は構成元素が十分に拡散した後は、組織に変化が起こらないため、長すぎると不経済であることも考慮して、上限を５００時間とする。 The solution treatment time is 0.5 hours or more, preferably 0.5 to 500 hours. A solution time of 0.5 hour or longer is desirable because homogenization is sufficiently performed and the structure becomes uniform. On the other hand, since the solution treatment time does not change in the structure after the constituent elements have sufficiently diffused, the upper limit is set to 500 hours considering that it is uneconomical if it is too long.
次に、溶体化処理後、合金を０℃以下の氷水等の冷媒中へ導入して焼き入れを行う。 Next, after the solution treatment, the alloy is introduced into a coolant such as ice water at 0 ° C. or lower and quenched.
０℃以下の条件で焼き入れを行うことにより、マルテンサイト変態が起こり、Ｂ１９型斜方晶の相が生成することにより、ミクロ組織がマルテンサイト双晶組織となる。冷却速度が遅い場合、Ｂ２型立方晶の相が完全に変態せず残留することがあるため、できるだけ瞬時に０℃以下の冷媒中への焼き入れを行うことにより、Ｂ１９型斜方晶相が体積率で９０％以上を占める高温形状記憶合金を製造することができる。なお、残部の相はＴｉＰｄ系金属間化合物相領域から外れた際に生成する第二相で構成される。 When quenching is performed at a temperature of 0 ° C. or lower, martensitic transformation occurs, and a B19 orthorhombic phase is formed, so that the microstructure becomes a martensitic twin structure. When the cooling rate is slow, the phase of B2 cubic crystal may remain completely untransformed. Therefore, by quenching in a refrigerant at 0 ° C. or less as quickly as possible, the B19 orthorhombic phase is A high temperature shape memory alloy occupying 90% or more by volume ratio can be manufactured. The remaining phase is composed of a second phase that is generated when the phase deviates from the TiPd-based intermetallic compound phase region.
その後、目的とする応力以上かつ４００ＭＰａ以下の応力下でマルテンサイト相が安定な温度からオーステナイト相に変態が終了する温度以上の温度に上昇させた後、マルテンサイト相が安定な温度に降温させる加圧・熱サイクルを１回以上繰り返す。そして、目的とする応力下で加圧・熱サイクルを行うことにより、繰り返し特性向上に必要な双晶組織を生成することができる。４００ＭＰａ以上の応力をかけると、回復不可能な大きな歪みが導入される場合があることから、４００ＭＰａを上限とする。ここで、「目的とする応力」とは、本発明の高温形状記憶合金が仕事量と繰り返し特性を発揮する最大応力をいう。すなわち、本発明において、目的とする応力は、４００ＭＰａを上限として、所望の目的、用途等に応じて、種々設定することができる。目的とする応力としては、例えば、５０ＭＰａ、１００ＭＰａ、１５０ＭＰａなどと設定することができるが、これらに限定されない。 Thereafter, the temperature is increased from the temperature at which the martensite phase is stable to the austenite phase at a temperature equal to or higher than the target stress and 400 MPa or lower, and then the temperature at which the transformation is completed. Repeat the pressure / heat cycle one or more times. Then, by performing pressurization / thermal cycle under a target stress, it is possible to generate a twin structure necessary for repeated improvement of characteristics. When a stress of 400 MPa or more is applied, a large strain that cannot be recovered may be introduced, so 400 MPa is set as the upper limit. Here, the “target stress” refers to the maximum stress at which the high-temperature shape memory alloy of the present invention exhibits work and repetition characteristics. That is, in the present invention, the target stress can be variously set according to the desired purpose, application, etc. with an upper limit of 400 MPa. The target stress can be set to, for example, 50 MPa, 100 MPa, 150 MPa, etc., but is not limited thereto.
上記製造方法により、高温での仕事量と繰り返し特性に優れた本発明の高温形状記憶合金を製造することができる。 By the above production method, the high-temperature shape memory alloy of the present invention, which is excellent in the work amount at high temperature and the repeatability, can be produced.
以下に、実施例に基づいて本発明を具体的に説明する。もちろん本発明は、これらの例によって何ら限定されるものではない。 Hereinafter, the present invention will be specifically described based on examples. Of course, the present invention is not limited to these examples.
Ｔｉ−５０Ｐｄ−５Ｚｒ、Ｔｉ−５０Ｐｄ−５Ｈｆ、Ｔｉ−５０Ｐｄ−５Ｎｂ、Ｔｉ−３５Ｐｄ−１５Ｐｔ-５Ｚｒ（原子％）についての各合金組成の高純度元素を真空状態でアーク溶解法により溶解し、ボタン状の合金２０ｇを溶製した。 A high purity element of each alloy composition of Ti-50Pd-5Zr, Ti-50Pd-5Hf, Ti-50Pd-5Nb, Ti-35Pd-15Pt-5Zr (atomic%) is melted by an arc melting method in a vacuum state, and button 20 g of an alloy was melted.
次に、この溶製した合金をＴｉ箔で包み、真空にした石英管中にアルゴンガス雰囲気で封じ込めた。石英管中に封じ込めた合金を１０００℃で３時間溶体化処理後、氷水中で急冷して合金試料を作製した。 Next, this melted alloy was wrapped in Ti foil and sealed in a vacuumed quartz tube in an argon gas atmosphere. The alloy contained in the quartz tube was subjected to a solution treatment at 1000 ° C. for 3 hours, and then rapidly cooled in ice water to prepare an alloy sample.
本実施例においては、合金試料に関する各種物性の測定、評価は、それぞれ以下のようにして行った。
＜マルテンサイト変態温度の測定＞
各合金試料の試験片を、大気中で、１分間に１０℃の昇温降温速度の条件でＤＳＣ（示差走査型熱分析装置）により示差熱分析を行い、マルテンサイト変態温度を測定した。
＜永久歪みの測定＞
各合金試料の試験片について、一定の応力下でマルテンサイト相が安定な温度からオーステナイト相に変態が終了する温度以上の温度に上昇させた後、マルテンサイト相が安定な温度に降温させた（永久歪み測定試験）結果から温度−歪み曲線を作成し、試験前後の歪みの差（％）を測定した。なお、加圧・熱サイクルの結果からも同様の温度−歪み曲線を作成することができる。
＜仕事量の測定＞
各合金試料の試験片について、上記の永久歪み測定試験の結果から温度−歪み曲線を作成し、昇温時のマルテンサイト変態開始温度における歪みと、昇温時のマルテンサイト変態終了温度における歪みとの差を算出し、変態歪み（％）を測定した。この変態歪み（％）に対して、負荷した応力（ＭＰａ）を乗算することにより、単位面積当たりの仕事量（J/cm３）を算出した。
In this example, measurement and evaluation of various physical properties related to the alloy samples were performed as follows.
<Measurement of martensitic transformation temperature>
The specimen of each alloy sample was subjected to differential thermal analysis by DSC (differential scanning thermal analyzer) under the condition of a temperature rising / falling rate of 10 ° C. per minute in the air, and the martensitic transformation temperature was measured.
<Measurement of permanent strain>
The specimen of each alloy sample was raised from a temperature at which the martensite phase was stable under constant stress to a temperature at which the transformation was completed to an austenite phase, and then the temperature was lowered to a temperature at which the martensite phase was stable ( Permanent strain measurement test) A temperature-strain curve was created from the results, and the strain difference (%) before and after the test was measured. A similar temperature-strain curve can be created from the results of pressurization and thermal cycling.
<Measurement of work volume>
For each specimen of the alloy sample, a temperature-strain curve is created from the result of the permanent strain measurement test, and the strain at the martensitic transformation start temperature at the time of temperature rise and the strain at the martensite transformation end temperature at the time of temperature rise The transformation strain (%) was measured. The work per unit area (J / cm 3 ) was calculated by multiplying this transformation strain (%) by the applied stress (MPa).
［比較例１］
図１に、加圧・熱サイクルを行っていないＴｉ−５０Ｐｄ−５Ｚｒに対して、２５ＭＰａ、５０ＭＰａ、１００ＭＰａ、１５０ＭＰａ、２００ＭＰａおよび２５０ＭＰａの応力下で、室温から昇温時の変態終了温度（Ａｆ）＋３０℃の間で永久歪み測定試験を行った結果を示す。試験片は３x３x６mmの角柱を用いた。マルテンサイト変態温度は４４０から５００℃であった。すべての応力条件において、永久歪みが残り、永久歪みは２５ＭＰａで１％程度、２５０ＭＰａで５％程度であった。
[Comparative Example 1]
FIG. 1 shows the transformation end temperature (A f) when the temperature is raised from room temperature under stress of 25 MPa, 50 MPa, 100 MPa, 150 MPa, 200 MPa, and 250 MPa with respect to Ti-50Pd-5Zr that is not subjected to pressurization / thermal cycle. ) The result of a permanent strain measurement test performed between + 30 ° C. The test piece used was a 3 × 3 × 6 mm prism. The martensitic transformation temperature was 440 to 500 ° C. Under all the stress conditions, permanent strain remained, and the permanent strain was about 1% at 25 MPa and about 5% at 250 MPa.
［実施例１］
図２に、２５ＭＰａ、５０ＭＰａ、１００ＭＰａ、１５０ＭＰａ、２００ＭＰａおよび２５０ＭＰａの応力下で、室温から昇温時の変態終了温度（Ａｆ）＋３０℃の間で加圧・熱サイクルを１回ずつ行った後に、５０ＭＰａまたは１００ＭＰａの応力下で、室温から昇温時の変態終了温度（Ａｆ）＋３０℃の間で加圧・熱サイクルを１回行ったＴｉ−５０Ｐｄ−５Ｚｒ、Ｔｉ−５０Ｐｄ−５Ｈｆ、Ｔｉ−５０Ｐｄ−５Ｎｂの、５０ＭＰａまたは１００ＭＰａの応力下での永久歪み測定試験の結果を示す。試験片は３x３x６mmの角柱を用いた。これらのマルテンサイト変態温度は４００〜５００℃の間であった。Ｔｉ−５０Ｐｄ−５ＺｒおよびＴｉ−５０Ｐｄ−５Ｎｂでは、温度−歪み曲線は完全なクローズループを形成し、永久歪みを残さずに回復した。Ｔｉ−５０Ｐｄ−５Ｈｆでは０．３％程度の永久歪みが残った。また、このグラフから計算された仕事量（負荷した応力（ＭＰａ）×変態歪み（％））は、Ｔｉ−５０Ｐｄ−５Ｚｒでは１．９１J/cm３、Ｔｉ−５０Ｐｄ−５Ｈｆでは１．１７J/cm３、Ｔｉ−５０Ｐｄ−５Ｎｂでは０．６J/cm３であった。この結果から、目的とする一定の応力以上の加圧条件で加圧・熱サイクルを１回以上行った後に目的とする応力下で加圧・熱サイクルを行うことによって、目的とする応力下で永久歪みが０．５％以下の、４００℃以上の高温で仕事量を示す合金が得られることがわかった。なお、「永久歪みを残さない」とは、永久歪みが全く生じないか、または永久歪みが０．１％未満であることをいうものとする。
[Example 1]
FIG. 2 shows a state in which a pressurization / thermal cycle is performed once between room temperature and a transformation end temperature (A f ) + 30 ° C. under a stress of 25 MPa, 50 MPa, 100 MPa, 150 MPa, 200 MPa and 250 MPa. Ti-50Pd-5Zr, Ti-50Pd-5Hf, and Ti-50Pd-5Hf, which were subjected to one pressurization and thermal cycle between room temperature and transformation end temperature (A f ) + 30 ° C. under a stress of 50 MPa or 100 MPa. The result of the permanent strain measurement test under 50MPa or 100MPa stress of -50Pd-5Nb is shown. The test piece used was a 3 × 3 × 6 mm prism. These martensitic transformation temperatures were between 400-500 ° C. For Ti-50Pd-5Zr and Ti-50Pd-5Nb, the temperature-strain curve formed a complete closed loop and recovered without leaving permanent set. In Ti-50Pd-5Hf, a permanent strain of about 0.3% remained. Moreover, the work amount (load stress (MPa) × transformation strain (%)) calculated from this graph is 1.91 J / cm 3 for Ti-50Pd-5Zr and 1.17 J / cm for Ti-50Pd-5Hf. 3 for Ti-50Pd-5Nb was 0.6 J / cm 3 . From this result, under the target stress, the pressure / thermal cycle is performed under the target stress after performing the pressurization / thermal cycle at least once under the pressurizing condition of the target constant stress or more. It was found that an alloy having a permanent strain of 0.5% or less and showing a work amount at a high temperature of 400 ° C. or higher can be obtained. “No permanent distortion” means that no permanent distortion occurs or the permanent distortion is less than 0.1%.
［実施例２］
図３に、２５ＭＰａ、５０ＭＰａ、１００ＭＰａ、１５０ＭＰａ、２００ＭＰａおよび２５０ＭＰａの応力下で、室温から昇温時の変態終了温度（Ａｆ）＋３０℃の間で加圧・熱サイクルを１回ずつ行った後に、１００ＭＰａの応力下で、加圧・熱サイクルを１回行ったＴｉ-５０Ｐｄ-５Ｚｒに対して、１００ＭＰａの応力下で永久歪み測定試験を５回行った結果を示す。試験片は３x３x６mmの角柱を用いた。この結果から、温度−歪み曲線において一度クローズループが得られると、そのあとも安定してクローズループが得られることがわかり、目的とする一定の応力以上の加圧条件で加圧・熱サイクルを１回以上行った後に目的とする応力下で加圧・熱サイクルを行うことによって、目的とする応力下での繰り返し特性が向上した合金が得られることがわかった。
[Example 2]
FIG. 3 shows a state in which a pressurization / thermal cycle is performed once under a stress of 25 MPa, 50 MPa, 100 MPa, 150 MPa, 200 MPa and 250 MPa between room temperature and a transformation end temperature (A f ) + 30 ° C. The results of five permanent strain measurement tests under a stress of 100 MPa are shown for Ti-50Pd-5Zr that was subjected to a pressurization / thermal cycle once under a stress of 100 MPa. The test piece used was a 3 × 3 × 6 mm prism. From this result, it can be seen that once a closed loop is obtained in the temperature-strain curve, a stable closed loop is obtained after that. It was found that an alloy having improved repetitive characteristics under the target stress can be obtained by performing pressurization and thermal cycling under the target stress after performing the test once or more.
［比較例２］
図４に、加圧・熱サイクルを行っていないＴｉ−３５Ｐｄ−１５Ｐｔ-５Ｚｒに対して、１５ＭＰａ、５０ＭＰａ、１００ＭＰａ、１５０ＭＰａおよび２００ＭＰａの応力下で、室温から昇温時の変態終了温度（Ａｆ）＋３０℃の間で永久歪み測定試験を行った結果を示す。試験片は３x３x６mmの角柱を用いた。マルテンサイト変態温度は５００℃近傍であり、Ｔｉ−５０Ｐｄ−５Ｚｒ、Ｔｉ−５０Ｐｄ−５Ｈｆ、Ｔｉ−５０Ｐｄ−５Ｎｂよりも高かった。すべての応力条件において、１．５％以下の永久歪みが残った。１５ＭＰａの小さい応力条件の場合であっても、永久歪みは０．５％を超えていた。
[Comparative Example 2]
FIG. 4 shows the transformation end temperature (A f at the time of temperature increase from room temperature under stresses of 15 MPa, 50 MPa, 100 MPa, 150 MPa, and 200 MPa with respect to Ti-35Pd-15Pt-5Zr that was not subjected to pressurization / thermal cycle. ) The result of a permanent strain measurement test performed between + 30 ° C. The test piece used was a 3 × 3 × 6 mm prism. The martensitic transformation temperature was around 500 ° C., which was higher than that of Ti-50Pd-5Zr, Ti-50Pd-5Hf, and Ti-50Pd-5Nb. Under all stress conditions, a permanent set of 1.5% or less remained. Even in the case of a small stress condition of 15 MPa, the permanent set exceeded 0.5%.
［実施例３］
図５に、１５ＭＰａ、５０ＭＰａ、１００ＭＰａ、１５０ＭＰａおよび２００ＭＰａの応力下で、室温から昇温時の変態終了温度（Ａｆ）＋３０℃の間で加圧・熱サイクル試験を１回ずつ行った後に、１５０ＭＰａの応力下で、加圧・熱サイクルを１回行ったＴｉ-３５Ｐｄ-１５Ｐｔ-５Ｚｒの、１５０ＭＰａの応力下での永久歪み測定試験の結果を示す。試験片は３x３x６mmの角柱を用いた。グラフ中の数字は永久歪み測定試験の回数を示す。この結果から、目的とする一定の応力以上の加圧条件で加圧・熱サイクルを１回以上行った後に目的とする応力下で加圧・熱サイクルを行うことによって、温度−歪み曲線においてクローズループを示し、目的とする応力下で永久歪みを残さずに仕事量を示す合金が得られることがわかった。仕事量は１．８J/ｃｍ３であった。
[Example 3]
In FIG. 5, under a stress of 15 MPa, 50 MPa, 100 MPa, 150 MPa, and 200 MPa, a pressure / thermal cycle test was performed once between room temperature and a transformation end temperature (A f ) + 30 ° C. at the time of temperature increase. The result of the permanent strain measurement test under the stress of 150MPa of Ti-35Pd-15Pt-5Zr which performed the pressurization and the heat cycle once under the stress of 150MPa is shown. The test piece used was a 3 × 3 × 6 mm prism. The numbers in the graph indicate the number of permanent strain measurement tests. From this result, it is possible to close in the temperature-strain curve by performing the pressure / thermal cycle under the target stress after performing the pressure / thermal cycle at least once under the pressure condition of the target constant stress or higher. It was found that an alloy showing a loop and showing a work amount without leaving a permanent set under a target stress was obtained. The work amount was 1.8 J / cm 3 .
［実施例４］
図６に、１００ＭＰａ、２００ＭＰａまたは３００ＭＰａの応力下で室温から昇温時の変態終了温度（Ａｆ）＋３０℃の間で加圧・熱サイクルを１回行った後、１００ＭＰａの応力下で、室温から昇温時の変態終了温度（Ａｆ）＋３０℃の間で加圧・熱サイクルを１０回行ったＴｉ-３５Ｐｄ-１５Ｐｔ-５Ｚｒの、永久歪み測定試験の結果を示す。試験片は３x３x６mmの角柱を用いた。グラフ中の数字は、試験片に対して行った加圧・熱サイクルの回数を示す。各図面の一番下のグラフは、加圧・熱サイクル前の試験片に対する１００ＭＰａ、２００ＭＰａまたは３００ＭＰａの応力下での永久歪み測定試験の結果である。この段階では、永久歪みの程度が大きかった。しかし、その後、１００ＭＰａで加圧・熱サイクルを１回行うことによって、温度−歪み曲線はクローズループを形成し、このクローズループはそれ以降の永久歪み測定試験中安定していた。また、このグラフから計算された仕事量（負荷した応力（ＭＰａ）×変態歪み（％））は、２．０J/cm３であった。この結果から、目的とする一定の応力以上の加圧条件で加圧・熱サイクルを１回以上行った後に目的とする応力下で加圧・熱サイクルを行うことによって、目的とする応力下での合金の繰り返し特性が向上し、４００℃以上の高温で仕事量を示す合金が得られることがわかった。
[Example 4]
In FIG. 6, after one pressurization / thermal cycle was performed between room temperature and a transformation end temperature (A f ) + 30 ° C. under a stress of 100 MPa, 200 MPa, or 300 MPa, a room temperature was obtained under a stress of 100 MPa. 3 shows the results of a permanent strain measurement test of Ti-35Pd-15Pt-5Zr that was subjected to pressurization / thermal cycle 10 times between A and the transformation end temperature (A f ) + 30 ° C. during temperature rise. The test piece used was a 3 × 3 × 6 mm prism. The numbers in the graph indicate the number of pressurization / thermal cycles performed on the test piece. The graph at the bottom of each drawing shows the results of a permanent strain measurement test under a stress of 100 MPa, 200 MPa, or 300 MPa on a test piece before pressurization / thermal cycle. At this stage, the degree of permanent distortion was large. However, after that, by performing one pressurization and thermal cycle at 100 MPa, the temperature-strain curve formed a closed loop, and this closed loop was stable during the subsequent permanent strain measurement test. Further, the work amount (loaded stress (MPa) × transformation strain (%)) calculated from this graph was 2.0 J / cm 3 . From this result, under the target stress, the pressure / thermal cycle is performed under the target stress after performing the pressurization / thermal cycle at least once under the pressurizing condition of the target constant stress or more. It has been found that the repetitive characteristics of the alloy are improved, and an alloy showing a work amount at a high temperature of 400 ° C. or higher can be obtained.
＜組織構造の解析＞
図７に、加圧・熱サイクル前（a）、および１５ＭＰａ、５０ＭＰａ、１００ＭＰａ、１５０ＭＰａおよび２００ＭＰａの応力下での加圧・熱サイクルを１回ずつ行った後に１５０ＭＰａの応力下で加圧・熱サイクルを１回行った後（b）のＴｉ-３５Ｐｄ-１５Ｐｔ-５Ｚｒの電子線後方散乱回折から得られた方位マップおよび逆極点図を示す。試験片は３x３x６mmの角柱を用い、試験片の任意の３ヶ所を選択して方位マップを作成した。ここでは、結晶方向をより視覚的に捉えやすくするために、結晶方向が同じものを同じ色で着色し、結晶方向の異なるものを別の色で示している。加圧・熱サイクル前の組織は、様々なマルテンサイトバリアントによりランダムに双晶が形成されていたが、加圧・熱サイクル後は一つの結晶粒を占めるバリアントの方位の８０％以上が同じ方位となっており、加圧・熱サイクル中にある方向のバリアントが優先的に成長したことがわかる。方位マップの右に、結晶方位の割合を示す逆極点図を示す。赤が８０％以上の割合を示し、青は、その方位がほとんど存在しないことを示す。加圧・熱サイクル前は、場所により様々な方位のマルテンサイトバリアントが生成していることがわかるが、加圧・熱サイクル後は、[０１０]に近い方向に赤い色が示され、ほとんどのバリアントが[０１０]に近い方向を向いていることがわかる。詳細に解析すると、マルテンサイトの[０１０]方向は、圧縮応力に対して応力を緩和する方向であった。マルテンサイト相は変形中にバリアントの再配列を起こすことが知られており、加圧・熱サイクル中にバリアントの再配列を起こしたと考えられる。このようにバリアントが再配列した組織がマルテンサイト相からオーステナイト相への逆変態を促進することによって、合金の繰り返し特性が向上すると考えられる。
<Analysis of organizational structure>
FIG. 7 shows a state before pressurization / thermal cycle (a), and after one pressurization / thermal cycle under stresses of 15 MPa, 50 MPa, 100 MPa, 150 MPa and 200 MPa, and then pressurization / heat under a stress of 150 MPa. The orientation map and reverse pole figure obtained from the electron beam backscattering diffraction of Ti-35Pd-15Pt-5Zr after (b) one cycle are shown. The test piece used was a 3 × 3 × 6 mm prism, and an arbitrary map of the test piece was selected to create an orientation map. Here, in order to make it easier to visually grasp the crystal direction, the same crystal direction is colored with the same color, and the different crystal directions are indicated with different colors. In the structure before pressurization / thermal cycle, twins were randomly formed by various martensite variants, but after pressurization / thermal cycle, more than 80% of the orientation of the variant occupying one crystal grain is the same orientation. It can be seen that variants in a certain direction during the pressurization / thermal cycle grew preferentially. A reverse pole figure showing the ratio of crystal orientation is shown on the right side of the orientation map. Red indicates a ratio of 80% or more, and blue indicates that there is almost no orientation. It can be seen that martensite variants with various orientations are generated depending on the location before pressurization / thermal cycle, but after pressurization / thermal cycle, red color is shown in the direction close to [010] It can be seen that the variant faces in a direction close to [010]. When analyzed in detail, the [010] direction of martensite was a direction to relieve stress against compressive stress. The martensite phase is known to cause rearrangement of variants during deformation, and is thought to have caused rearrangement of variants during pressurization and thermal cycling. It is considered that the structure in which the variants are rearranged in this way promotes the reverse transformation from the martensite phase to the austenite phase, thereby improving the repetition characteristics of the alloy.
本発明のＴｉＰｄ系高温形状記憶合金は、高温で起こるマルテンサイト変態を利用して形状回復を起こす材料であり、自動車やジェットエンジン等の高温部のアクチュエイター等に利用可能である。また、これら以外にも１０００℃以下の温度範囲で動作するアクチュエイター、高温流体の流量や圧力制御部等に使用することも可能である。
The TiPd-based high-temperature shape memory alloy of the present invention is a material that recovers its shape by utilizing martensitic transformation that occurs at high temperatures, and can be used for actuators in high-temperature parts such as automobiles and jet engines. In addition to these, it can be used for an actuator operating in a temperature range of 1000 ° C. or lower, a flow rate of a high-temperature fluid, a pressure control unit, and the like.
Claims (7)
It is a manufacturing method of the TiPd type high temperature shape memory alloy as described in any one of Claims 1-5, Comprising: The state which enclosed the raw material of the said shape memory alloy melted with inert gas in the vacuum vessel In the range from the temperature of the B2 cubic crystal region above the martensitic transformation temperature to the temperature below 100 ° C. from the temperature at which the liquid phase of the shape memory alloy is generated, a solution treatment is performed for 0.5 hours or more. After that, it is quenched in a refrigerant of 0 ° C. or lower, and the temperature is increased from a temperature at which the martensite phase is stable to a temperature at which the transformation is completed to an austenite phase at a temperature higher than the target stress and 400 MPa or lower. The TiPd system is characterized in that after the pressurization / thermal cycle in which the martensite phase is cooled to a stable temperature is repeated one or more times, the pressurization / thermal cycle is performed under the target stress. Method for producing a shape memory alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014152847A JP6422113B2 (en) | 2014-05-29 | 2014-07-28 | High temperature shape memory alloy and method for producing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2014111525 | 2014-05-29 | ||
| JP2014111525 | 2014-05-29 | ||
| JP2014152847A JP6422113B2 (en) | 2014-05-29 | 2014-07-28 | High temperature shape memory alloy and method for producing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2016006218A true JP2016006218A (en) | 2016-01-14 |
| JP6422113B2 JP6422113B2 (en) | 2018-11-14 |
Family
ID=55224792
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2014152847A Expired - Fee Related JP6422113B2 (en) | 2014-05-29 | 2014-07-28 | High temperature shape memory alloy and method for producing the same |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JP6422113B2 (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018141207A (en) * | 2017-02-28 | 2018-09-13 | 国立研究開発法人物質・材料研究機構 | High temperature shape memory alloy and method for producing the same |
| JP2020084244A (en) * | 2018-11-21 | 2020-06-04 | 国立研究開発法人物質・材料研究機構 | High temperature shape memory alloy, method for producing the same, and actuator and engine using the same |
| CN114570948A (en) * | 2022-02-15 | 2022-06-03 | 中南大学 | Post-processing method for shape control of shape memory alloy part manufactured by additive manufacturing |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07207390A (en) * | 1994-01-14 | 1995-08-08 | Tokin Corp | Super elastic spring |
| JPH07233432A (en) * | 1994-02-24 | 1995-09-05 | Tokin Corp | Shape memory alloy and its production |
| US20090162243A1 (en) * | 2007-12-21 | 2009-06-25 | Cook Incorporated | Radiopaque alloy and medical device made of this alloy |
| WO2013011959A1 (en) * | 2011-07-15 | 2013-01-24 | 独立行政法人物質・材料研究機構 | High-temperature shape memory alloy and method for producing same |
| WO2014078670A1 (en) * | 2012-11-16 | 2014-05-22 | The Texas A&M University System | Self-adaptive, ultra-low elastic modulus shape memory alloys |
-
2014
- 2014-07-28 JP JP2014152847A patent/JP6422113B2/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH07207390A (en) * | 1994-01-14 | 1995-08-08 | Tokin Corp | Super elastic spring |
| JPH07233432A (en) * | 1994-02-24 | 1995-09-05 | Tokin Corp | Shape memory alloy and its production |
| US20090162243A1 (en) * | 2007-12-21 | 2009-06-25 | Cook Incorporated | Radiopaque alloy and medical device made of this alloy |
| WO2013011959A1 (en) * | 2011-07-15 | 2013-01-24 | 独立行政法人物質・材料研究機構 | High-temperature shape memory alloy and method for producing same |
| WO2014078670A1 (en) * | 2012-11-16 | 2014-05-22 | The Texas A&M University System | Self-adaptive, ultra-low elastic modulus shape memory alloys |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2018141207A (en) * | 2017-02-28 | 2018-09-13 | 国立研究開発法人物質・材料研究機構 | High temperature shape memory alloy and method for producing the same |
| JP2020084244A (en) * | 2018-11-21 | 2020-06-04 | 国立研究開発法人物質・材料研究機構 | High temperature shape memory alloy, method for producing the same, and actuator and engine using the same |
| JP7176692B2 (en) | 2018-11-21 | 2022-11-22 | 国立研究開発法人物質・材料研究機構 | High temperature shape memory alloy, manufacturing method thereof, actuator and engine using same |
| CN114570948A (en) * | 2022-02-15 | 2022-06-03 | 中南大学 | Post-processing method for shape control of shape memory alloy part manufactured by additive manufacturing |
Also Published As
| Publication number | Publication date |
|---|---|
| JP6422113B2 (en) | 2018-11-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Velmurugan et al. | Review on phase transformation behavior of NiTi shape memory alloys | |
| Cao et al. | Precipitation-hardened high-entropy alloys for high-temperature applications: A critical review | |
| Tseng et al. | Effects of crystallographic orientation on the superelastic response of FeMnAlNi single crystals | |
| Xue et al. | The effect of aging on the B2-R transformation behaviors in Ti-51at% Ni alloy | |
| JP2015504487A (en) | Nickel-base alloy heat treatment, nickel-base alloy, and articles containing nickel-base alloy | |
| Yang et al. | Microstructure characterization, stress–strain behavior, superelasticity and shape memory effect of Cu–Al–Mn–Cr shape memory alloys | |
| JP6422113B2 (en) | High temperature shape memory alloy and method for producing the same | |
| KR100807393B1 (en) | Process for making Ti-Ni based functionally graded alloys and Ti-Ni based functionally graded alloys produced thereby | |
| Shamsolhodaei et al. | Enhancement of mechanical and functional properties of welded NiTi by controlling nickel vapourisation | |
| CN101333611B (en) | Shape memory material and method of making the same | |
| JP5911072B2 (en) | High temperature shape memory alloy and manufacturing method thereof | |
| Aboutalebi et al. | Influences of aging and thermomechanical treatments on the martensitic transformation and superelasticity of highly Ni-rich Ti-51.5 at.% Ni shape memory alloy | |
| Niendorf et al. | Direct microstructure design by hot extrusion–high-temperature shape memory alloys with bamboo-like microstructure | |
| Zhang et al. | Effect of annealing temperature on martensitic transformation of Ti49. 2Ni50. 8 alloy processed by equal channel angular pressing | |
| KR101604598B1 (en) | Ni-based superalloy with excellent oxidization-resistance and creep property and method of manufacturing the same | |
| JP6156865B2 (en) | Super elastic alloy | |
| Zhao et al. | Effect of aging treatment on superelasticity of a Ti 48.8 Ni 50.8 V 0.4 alloy | |
| ur Rehman et al. | Quaternary alloying of copper with Ti50Ni25Pd25 high temperature shape memory alloys | |
| Yang et al. | Microstructure, martensitic transformation and shape memory effect of Ni38Co12Mn41In9 alloy | |
| RU2524888C1 (en) | THERMAL TREATMENT OF MONOCRYSTALS OF Fe-Ni-Co-Al-Ti FERROMAGNETIC ALLOY WITH SHAPE MEMORY EFFECT AND SUPERELASTICITY ORIENTED IN [001] DIRECTION AT STRETCHING STRAIN | |
| RU2495946C1 (en) | METHOD OF THERMAL TREATMENT OF Fe-Ni-Co-Al-Nb FERROMAGNETIC ALLOY MONOCRYSTALS WITH THERMOELASTIC CONVERSIONS | |
| JP6883818B2 (en) | High temperature shape memory alloy and its manufacturing method | |
| Bhaumik et al. | Nickel–Titanium shape memory alloy wires for thermal actuators | |
| JP2014058711A (en) | TiPt BASED HIGH TEMPERATURE SHAPE MEMORY ALLOY AND MANUFACTURING METHOD THEREOF | |
| JPH07233432A (en) | Shape memory alloy and its production |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20170519 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20170519 |
|
| A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20180228 |
|
| A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20180403 |
|
| A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20180530 |
|
| TRDD | Decision of grant or rejection written | ||
| A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20180918 |
|
| A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20181011 |
|
| R150 | Certificate of patent or registration of utility model |
Ref document number: 6422113 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |
|
| R250 | Receipt of annual fees |
Free format text: JAPANESE INTERMEDIATE CODE: R250 |
|
| LAPS | Cancellation because of no payment of annual fees |