JPH0689424B2 - Shape memory alloys, superelastic alloys and vibration-proof alloys - Google Patents
Shape memory alloys, superelastic alloys and vibration-proof alloysInfo
- Publication number
- JPH0689424B2 JPH0689424B2 JP1913685A JP1913685A JPH0689424B2 JP H0689424 B2 JPH0689424 B2 JP H0689424B2 JP 1913685 A JP1913685 A JP 1913685A JP 1913685 A JP1913685 A JP 1913685A JP H0689424 B2 JPH0689424 B2 JP H0689424B2
- Authority
- JP
- Japan
- Prior art keywords
- alloys
- alloy
- niti
- weight
- shape memory
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
- 229910045601 alloy Inorganic materials 0.000 title claims description 43
- 239000000956 alloy Substances 0.000 title claims description 43
- 229910001285 shape-memory alloy Inorganic materials 0.000 title claims description 4
- 229910001000 nickel titanium Inorganic materials 0.000 claims description 29
- 230000009466 transformation Effects 0.000 claims description 18
- 229910000734 martensite Inorganic materials 0.000 claims description 9
- 229910052804 chromium Inorganic materials 0.000 claims description 5
- 229910052742 iron Inorganic materials 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- 150000002739 metals Chemical group 0.000 claims description 5
- 229910052759 nickel Inorganic materials 0.000 claims description 5
- 229910052720 vanadium Inorganic materials 0.000 claims description 5
- 229910052782 aluminium Inorganic materials 0.000 claims description 4
- 229910052726 zirconium Inorganic materials 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims 3
- 238000013016 damping Methods 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 16
- 229910052760 oxygen Inorganic materials 0.000 description 16
- 239000001301 oxygen Substances 0.000 description 16
- 239000000203 mixture Substances 0.000 description 6
- 230000008859 change Effects 0.000 description 5
- 239000011159 matrix material Substances 0.000 description 5
- KHYBPSFKEHXSLX-UHFFFAOYSA-N iminotitanium Chemical compound [Ti]=N KHYBPSFKEHXSLX-UHFFFAOYSA-N 0.000 description 4
- 239000006104 solid solution Substances 0.000 description 4
- 229910001069 Ti alloy Inorganic materials 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 238000005452 bending Methods 0.000 description 2
- 229910002056 binary alloy Inorganic materials 0.000 description 2
- 238000005266 casting Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000006698 induction Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000002844 melting Methods 0.000 description 2
- 230000008018 melting Effects 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 229910018107 Ni—Ca Inorganic materials 0.000 description 1
- 230000006399 behavior Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010309 melting process Methods 0.000 description 1
- 230000003446 memory effect Effects 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
Landscapes
- Powder Metallurgy (AREA)
- Manufacture And Refinement Of Metals (AREA)
Description
【発明の詳細な説明】 ［産業上の利用分野］ この発明は、NiTi系機能合金に関し、特にマルテンサイ
ト変態開始温度を高めるとともに、靱性を高めて成形加
工性を高めるために、微量の添加元素が含有されてなる
機能合金に関する。Description: TECHNICAL FIELD The present invention relates to a NiTi-based functional alloy, and in particular, in order to increase the martensitic transformation start temperature and toughness to improve moldability, a small amount of additional element is added. It relates to a functional alloy containing.
［従来の技術］ 形状記憶効果および超弾性挙動などを示す機能合金とし
ては、従来より種々のものが提案されているが、特にNi
Ti合金は、回復力、寿命および耐蝕性などの特性に最も
優れており、したがって最も実用化が進んでいるもので
ある。[Prior Art] Various functional alloys having a shape memory effect and superelastic behavior have been proposed in the past.
The Ti alloy is the most excellent in properties such as recoverability, life and corrosion resistance, and is thus most practically used.
［発明が解決しようとする問題点］ ところで、NiTi合金の製造は、工業的には黒鉛るつぼを
用いた高周波誘導真空溶解によって行なわれている。こ
の真空溶解の工程によっては、炉内の真空度によっても
その混入量は異なるが、通常、400〜500ppmの酸素が混
入するという問題があった。混入した酸素は、Ni−Tiマ
トリックス中に固溶したり、Ti4Ni2Oの酸化物となって
析出したりする。[Problems to be Solved by the Invention] Meanwhile, the production of NiTi alloy is industrially carried out by high frequency induction vacuum melting using a graphite crucible. Depending on the vacuum melting process, the mixed amount varies depending on the degree of vacuum in the furnace, but there is a problem that 400 to 500 ppm of oxygen is mixed. Entrained oxygen, or a solid solution in Ni-Ti matrix, or deposited as oxides of Ti 4 Ni 2 O.
合金中における酸化物の含有量が高くなると、熱間加工
に際し割れが生じたり、あるいは最終部材への成形加工
中にクラックが入ったりするおそれがある。When the content of oxides in the alloy is high, cracks may occur during hot working, or cracks may occur during forming of the final member.
また、酸素の固溶によって格子定数が変化し、その結果
変態点が変化するおそれがある。あるいは、酸化物が析
出することによりNi−Tiマトリックスの組成が変化し、
その結果変態点が低下するおそれもあった。このこと
は、溶解条件が微妙に変化した場合、混入酸素量の変化
により変態点が移動することを意味し、これが所望の変
態点を有するインゴットの溶製を困難にしている原因で
あるとも考えられる。Further, the solid solution of oxygen may change the lattice constant, resulting in a change in the transformation point. Alternatively, the composition of the Ni-Ti matrix changes due to the precipitation of oxides,
As a result, the transformation point may be lowered. This means that when the melting conditions change subtly, the transformation point moves due to the change in the amount of mixed oxygen, which is also considered to be the cause that makes it difficult to produce an ingot having the desired transformation point. To be
さらに、酸素混入量は、高変態点となるようなTi過剰組
成の合金ほど多く、したがってTi過剰組成の合金ほど理
論的に予想される変態点より低い変態点の合金しか得ら
れないことになる。In addition, the oxygen content is higher in alloys with a Ti-rich composition that results in a higher transformation point, so that alloys with a Ti-rich composition can only yield alloys with transformation points lower than the theoretically expected transformation point. .
上述のように、機能合金として種々の特性上優れている
といわれているNiTi合金においても、酸素の混入によ
り、成形加工性になお問題を残しており、また２元合金
ではMs点（マルテンサイト変態開始温度）の上限はせい
ぜい80℃であり、より高いMs点の機能合金を構成するこ
とは極めて困難であった。As described above, NiTi alloy, which is said to be excellent in various properties as a functional alloy, still has a problem in formability due to the mixing of oxygen, and in the binary alloy, the Ms point (martensite) The upper limit of the transformation initiation temperature) is at most 80 ° C, and it was extremely difficult to construct a functional alloy with a higher Ms point.
それゆえに、この発明の目的は、成形加工性に優れ、か
つ高マルテンサイト変態開始温度を有する機能合金を提
供することにある。Therefore, an object of the present invention is to provide a functional alloy which is excellent in formability and has a high martensite transformation start temperature.
［問題点を解決するための手段］ 本願発明者達は、上記問題点を種々検討した結果、NiTi
合金中に400〜500ppmもの酸素が混入するのはTiと酸素
との親和力が強いためであるとの認識に基づき、Tiより
も酸素との親和力に勝る元素を添加すれば、混入酸素量
を低減し得ると考え、種々の元素が添加されたNiTi合金
につき多数の実験を繰返した。その結果、Niを50〜60重
量％含み、残部がTiよりなる熱弾性型マルテンサイト変
態を生じるNiTi合金、または該NiもしくはTiの一部がC
u,Al,V,Zr,Fe,CrおよびCoからなる群から選択される１
種以上の金属で置換されたNiTi合金に、0.001〜0.5重量
％のCaを含有させれば、上述の問題点が解決されること
を見出した。[Means for Solving Problems] As a result of various studies on the above problems, the inventors of the present application have found that NiTi
Based on the recognition that 400 to 500 ppm of oxygen is mixed in the alloy because Ti has a strong affinity with oxygen, the amount of mixed oxygen can be reduced by adding an element that has a higher affinity with oxygen than Ti. Considering that it is possible, many experiments were repeated for NiTi alloys to which various elements were added. As a result, a NiTi alloy containing 50 to 60% by weight of Ni, the remainder being thermoelastic martensitic transformation consisting of Ti, or a part of the Ni or Ti being C
1 selected from the group consisting of u, Al, V, Zr, Fe, Cr and Co
It has been found that the above-mentioned problems can be solved by adding 0.001 to 0.5% by weight of Ca to a NiTi alloy substituted with one or more metals.
［作用］ この発明では、Caが、NiTi溶湯の脱酸剤として機能す
る。すなわち、添加されているCaは酸素と結合してCaO
に変化し、したがってNi−Tiマトリックス中への酸素の
固溶およびTi4Ni2O酸化物の析出力が抑制される。[Operation] In this invention, Ca functions as a deoxidizing agent for the molten NiTi. That is, the added Ca combines with oxygen to form CaO.
Therefore, the solid solution of oxygen in the Ni—Ti matrix and the precipitation force of Ti 4 Ni 2 O oxide are suppressed.
なお、この発明において、Caの添加量を0.001〜0.5重量
％としたのは、通常予想される酸素混入量（少なくとも
400〜500ppm）を考慮したものである。すなわち、0.001
重量％未満では十分な脱酸することができず、他方0.5
重量％以下でも十分な脱酸効果が奏され得るからであ
る。In the present invention, the addition amount of Ca is set to 0.001 to 0.5% by weight because the normally expected amount of oxygen mixture (at least
400-500ppm) is taken into consideration. Ie 0.001
If it is less than wt%, sufficient deoxidation cannot be achieved, while 0.5%
This is because a sufficient deoxidizing effect can be obtained even if the content is less than or equal to wt%.
Caの添加方法としては、Ca単独でもしくはNi−Ca母合金
の形で、予め現材料中に添加しておいてもよく、あるい
はNiTi溶湯中に添加してもよい。また、鋳造前に表面に
浮いた酸化物を除去すること、あるいはフィルタで濾過
することによりCaOのNiTi合金中への混入を防止するこ
とができ、したがって低酸素のNiTi合金インゴットを容
易に製造することが可能である。As a method of adding Ca, Ca alone or in the form of a Ni—Ca master alloy may be added in advance to the current material or may be added to the molten NiTi. Further, it is possible to prevent CaO from being mixed into the NiTi alloy by removing oxides floating on the surface before casting, or by filtering with a filter, and thus easily produce a low oxygen NiTi alloy ingot. It is possible.
また、CaOは、少量であればNiTi合金中に残存していた
としても、機能効果を損うことはない。In addition, CaO does not impair the functional effect even if it remains in the NiTi alloy in a small amount.
［実施例の説明］ 実施例１ スポンジTiと電解Niを原料としてAf点（逆変態終了温
度）が110℃となるような合金を、高周波誘導真空溶解
し、全体が溶け落ちた後にCaを0.5重量％添加し、浮遊
酸化物を除去し、鋳造した。[Explanation of Examples] Example 1 An alloy of sponge Ti and electrolytic Ni having an A f point (reverse transformation end temperature) of 110 ° C. was melted by high frequency induction vacuum, and Ca was melted after the whole melted down. 0.5 wt% was added, the floating oxide was removed, and casting was performed.
このようにして得られたインゴットを、熱間加工と冷間
加工とにより線材とし、しかる後コイル状のアクチュエ
ータを作成したところ、Af＝110℃の温度で温度ヒステ
リシスが25deg以下の動作をすることが確められた。The ingot thus obtained was made into a wire rod by hot working and cold working, and then a coil-shaped actuator was created. At a temperature of A f = 110 ° C, a temperature hysteresis of 25deg or less It was confirmed.
なお、Caを含有しないNiおよびTi2元合金の場合、Af＝1
10℃での温度ヒステリシスは30degであった。In the case of Ni and Ti binary alloys that do not contain Ca, A f = 1
The temperature hysteresis at 10 ℃ was 30deg.
実施例２ Caを0.3重量％添加したNi−45重量％Ti合金を熱間加工
および冷間加工し、厚さ0.2mmの条材とした。この条材
は、靱性に富み180°完全密着曲げが可能であった。Example 2 A Ni-45% by weight Ti alloy containing 0.3% by weight of Ca was hot worked and cold worked to obtain a strip material having a thickness of 0.2 mm. This strip was rich in toughness and capable of 180 ° perfect contact bending.
なお、Caを含有しないNi−45重量％Ti合金の同一工程に
より得られた試料は、同一条件で曲げ試験したところ折
損した。A sample obtained by the same step of a Ni-45 wt% Ti alloy containing no Ca was broken when subjected to a bending test under the same conditions.
［発明の効果］ 以上のように、この発明によれば、Niを50〜60重量％含
み、残部がTiよりなる熱弾性型マルテンサイト変態を生
じるNiTi合金、またはNiもしくはTiの一部がCu,Al,V,Z
r,Fe,CrおよびCoからなる群から選択される１種以上の
金属で置換されてなるNiTi合金に、0.001〜0.5重量％Ca
が含有されているため、Ni−Tiマトリックス中への酸素
の固溶およびTi4Ni2O酸化物の析出が効果的に抑制さ
れ、したがって成形加工性に優れた機能合金を実現する
ことが可能となる。また、混入酸素量を効果的に低減す
ることができるため、NiTiマトリックスの組成が所望の
組成から変化しにくく、したがって変態点の制御が容易
であり、さらにMs点を80℃以上の温度にすることが可能
であるため、（Af−Ms）で表わされる温度ヒステリシス
が小さくなり100℃近傍の高温で動作可能な機能合金を
実現することも可能となる。[Advantages of the Invention] As described above, according to the present invention, a NiTi alloy containing 50 to 60% by weight of Ni, the balance being Ti and causing a thermoelastic martensitic transformation, or Ni or a part of Ti being Cu , Al, V, Z
0.001 to 0.5% by weight of Ca is added to a NiTi alloy that is substituted with one or more metals selected from the group consisting of r, Fe, Cr and Co.
As a result, since the solid solution of oxygen and the precipitation of Ti 4 Ni 2 O oxide in the Ni-Ti matrix are effectively suppressed, it is possible to realize a functional alloy with excellent formability. Becomes In addition, since the amount of mixed oxygen can be effectively reduced, the composition of the NiTi matrix is unlikely to change from the desired composition, and therefore the transformation point is easily controlled, and the Ms point is set to a temperature of 80 ° C or higher. Therefore, the temperature hysteresis represented by (A f −Ms) becomes small, and it becomes possible to realize a functional alloy that can operate at a high temperature near 100 ° C.
この発明は、熱弾性型マルテンサイト変態を生じるNiTi
機能合金一般に適用され得るものであり、したがって形
状記憶合金のほか超弾性合金あるいは防振合金としても
用いることが可能である。This invention is a NiTi that causes thermoelastic martensitic transformation.
It can be applied to functional alloys in general, and thus can be used not only as a shape memory alloy but also as a superelastic alloy or vibration-proof alloy.
Claims (6)
熱弾性型マルテンサイト変態を生じるNiTi合金に、0.00
1〜0.5重量％のCaを含有させたことを特徴とする、形状
記憶合金。1. A NiTi alloy containing 50 to 60% by weight of Ni, the balance being Ti, which produces a thermoelastic martensitic transformation,
A shape memory alloy containing 1 to 0.5% by weight of Ca.
がCu、Al、Ｖ、Zr、Fe、CrおよびCoからなる群から選択
される１種以上の金属で置換されたNiTi合金であること
を特徴とする、特許請求の範囲第１項記載の形状記憶合
金。2. The NiTi alloy is a NiTi alloy in which a part of the Ni or Ti is substituted with one or more metals selected from the group consisting of Cu, Al, V, Zr, Fe, Cr and Co. The shape memory alloy according to claim 1, wherein
熱弾性型マルテンサイト変態を生じるNiTi合金に、0.00
1〜0.5重量％のCaを含有させたことを特徴とする、超弾
性合金。3. A NiTi alloy containing 50 to 60% by weight of Ni, the balance being Ti, which causes a thermoelastic martensitic transformation, is added to 0.00
A superelastic alloy containing 1 to 0.5% by weight of Ca.
がCu、Al、Ｖ、Zr、Fe、CrおよびCoからなる群から選択
される１種以上の金属で置換されたNiTi合金であること
を特徴とする、特許請求の範囲第３項記載の超弾性合
金。4. The NiTi alloy is a NiTi alloy in which a part of the Ni or Ti is substituted with one or more metals selected from the group consisting of Cu, Al, V, Zr, Fe, Cr and Co. The superelastic alloy according to claim 3, characterized in that
熱弾性型マルテンサイト変態を生じるNiTi合金に、0.00
1〜0.5重量％のCaを含有させたことを特徴とする、防振
合金。5. A NiTi alloy containing 50 to 60% by weight of Ni, the balance being Ti, which causes a thermoelastic martensitic transformation, has a 0.00
A vibration-proof alloy characterized by containing 1 to 0.5% by weight of Ca.
がCu、Al、Ｖ、Zr、Fe、CrおよびCoからなる群から選択
される１種以上の金属で置換されたNiTi合金であること
を特徴とする、特許請求の範囲第５項記載の防振合金。6. The NiTi alloy is a NiTi alloy in which a portion of the Ni or Ti is substituted with one or more metals selected from the group consisting of Cu, Al, V, Zr, Fe, Cr and Co. The vibration-damping alloy according to claim 5, characterized in that it is present.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1913685A JPH0689424B2 (en) | 1985-02-01 | 1985-02-01 | Shape memory alloys, superelastic alloys and vibration-proof alloys |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP1913685A JPH0689424B2 (en) | 1985-02-01 | 1985-02-01 | Shape memory alloys, superelastic alloys and vibration-proof alloys |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS61177346A JPS61177346A (en) | 1986-08-09 |
| JPH0689424B2 true JPH0689424B2 (en) | 1994-11-09 |
Family
ID=11991041
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP1913685A Expired - Lifetime JPH0689424B2 (en) | 1985-02-01 | 1985-02-01 | Shape memory alloys, superelastic alloys and vibration-proof alloys |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0689424B2 (en) |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH0776401B2 (en) * | 1988-04-16 | 1995-08-16 | 株式会社トーキン | Superelastic alloy material and superelastic element |
-
1985
- 1985-02-01 JP JP1913685A patent/JPH0689424B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| JPS61177346A (en) | 1986-08-09 |
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