JPH03295562A - Shape memory alloy for living body - Google Patents

Shape memory alloy for living body

Info

Publication number
JPH03295562A
JPH03295562A JP2098980A JP9898090A JPH03295562A JP H03295562 A JPH03295562 A JP H03295562A JP 2098980 A JP2098980 A JP 2098980A JP 9898090 A JP9898090 A JP 9898090A JP H03295562 A JPH03295562 A JP H03295562A
Authority
JP
Japan
Prior art keywords
wire
pin
shape memory
alloy
memory alloy
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
Application number
JP2098980A
Other languages
Japanese (ja)
Other versions
JP3013384B2 (en
Inventor
Takasumi Shimizu
孝純 清水
Yoshiaki Shiyugo
守護 嘉朗
Yoshiyuki Niiyama
新山 善之
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Daido Steel Co Ltd
Original Assignee
Daido Steel Co Ltd
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Daido Steel Co Ltd filed Critical Daido Steel Co Ltd
Priority to JP2098980A priority Critical patent/JP3013384B2/en
Publication of JPH03295562A publication Critical patent/JPH03295562A/en
Application granted granted Critical
Publication of JP3013384B2 publication Critical patent/JP3013384B2/en
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61BDIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B17/00Surgical instruments, devices or methods, e.g. tourniquets
    • A61B17/56Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor
    • A61B17/58Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws, setting implements or the like
    • A61B17/68Internal fixation devices, including fasteners and spinal fixators, even if a part thereof projects from the skin
    • A61B17/72Intramedullary pins, nails or other devices
    • A61B17/7233Intramedullary pins, nails or other devices with special means of locking the nail to the bone
    • A61B17/7258Intramedullary pins, nails or other devices with special means of locking the nail to the bone with laterally expanding parts, e.g. for gripping the bone
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61BDIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B17/00Surgical instruments, devices or methods, e.g. tourniquets
    • A61B17/56Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor
    • A61B17/58Surgical instruments or methods for treatment of bones or joints; Devices specially adapted therefor for osteosynthesis, e.g. bone plates, screws, setting implements or the like
    • A61B17/68Internal fixation devices, including fasteners and spinal fixators, even if a part thereof projects from the skin
    • A61B17/72Intramedullary pins, nails or other devices
    • A61B17/7208Flexible pins, e.g. ENDER pins
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61BDIAGNOSIS; SURGERY; IDENTIFICATION
    • A61B17/00Surgical instruments, devices or methods, e.g. tourniquets
    • A61B2017/00831Material properties
    • A61B2017/00867Material properties shape memory effect

Abstract

PURPOSE:To prevent the generation of the harms of metals, such as Ni, on the human body and to allow the wide application of the above shape memory alloy to a medical field, etc., by forming a titanium oxide film on the surface of an alloy contg. 43 to 57wt.% Ni and the balance Ti and unavoidable impurities. CONSTITUTION:An intramedullary pin 1 is formed by mixing prescribed ratios of Mond Ni and sponge Ti, subjecting the mixture to vacuum melting or high-frequency melting, forging, and rolling followed by drawing to form a wire, cutting the wire to the prescribed length, then pickling the wire by an acid mixture composed of hydrogen fluoride acid and nitric acid and further immersing the wire for 30 seconds into nitric acid to form a titanium oxide film on the surface. The pin is thereafter formed to memorize the three-dimensional shape which is sized to have a bulge larger by about 10% than the medullary cavity diameter of the thigh 2 and has the same bow shape even when observed by changing the angle by 90 deg.. The intramedullary pin 1 deformed in the state of cooling in ice water is warmed by the bodily temp. and attains the working temp. when the pin inserted into the medulla of the thigh 2. The pin presses the bone wall from the inside by the curved part 1a and the curved part 1b, thereby stabilizing the thigh 2.

Description

【発明の詳細な説明】 (産業上の利用分野) 本発明は、医療機器等に使用する形状記憶合金に関する
DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to a shape memory alloy used in medical equipment and the like.

(従来の技術) 近年、形状記憶合金の特性を医療分野に応用するため種
々の試みが行われている。中でもT1Ni系合金につい
ては、耐食性が優れていること、生体との馴染が良いこ
と等から、医療等に広く用いられている。例えば、歯科
分野では、T1Ni系合金を歯列矯正用材料や、歯科鋳
造による補綴物に応用したり、また人工歯根としてイン
ブラント材に応用することも行われている。
(Prior Art) In recent years, various attempts have been made to apply the properties of shape memory alloys to the medical field. Among them, T1Ni alloys are widely used in medical applications and the like because of their excellent corrosion resistance and good compatibility with living organisms. For example, in the dental field, T1Ni alloys are being applied to orthodontic materials, prosthetics made by dental casting, and implant materials as artificial tooth roots.

(発明が解決しようとする課題) しかしながら、医療等に用いる従来のT1Ni系形状記
憶合金は、主成分のNiが細胞に対し毒性を有するとい
う報告もあり生体に対して信頼性が低い。また一部の人
には金属アレルギーを起こさせる場合もある。このため
、現在、前述したようなインブラント材への応用は、生
体に使用した場合の信頼性が比較的高い歯科分野に多く
、医療分野に広く応用されていない。
(Problems to be Solved by the Invention) However, conventional T1Ni-based shape memory alloys used for medical purposes have low reliability for living organisms, as there are reports that Ni, the main component, is toxic to cells. It may also cause metal allergies in some people. For this reason, at present, the implant materials described above are mostly applied in the dental field, where reliability is relatively high when used in living organisms, and are not widely applied in the medical field.

本発明は、このような問題点を解決するためになされた
もので、Ni等の金属の生体に対する害の発生を防止し
、医療分野等に広(応用することを可能とした生体用形
状記憶合金を提供することを目的とする。
The present invention was made in order to solve these problems, and it is a shape memory for living bodies that prevents metals such as Ni from causing harm to living bodies, and that can be widely applied in the medical field. The purpose is to provide alloys.

(課題を解決するための手段) そのために、本発明の生体用形状記憶合金は、Niが4
3〜57wt%、残部がTiと不可避不純物を含有する
合金の表面にチタン酸化膜を形成したことを特徴とする
(Means for solving the problem) For this purpose, the shape memory alloy for biological use of the present invention has a Ni content of 4
It is characterized in that a titanium oxide film is formed on the surface of an alloy containing 3 to 57 wt%, the balance being Ti and unavoidable impurities.

前記合金の成分がNi:43〜57wt%、Ti:35
〜45wt%、およびCo、Fe、Pd、Pt、B、A
r1、Si、■、Nb、Cuのうち少なくとも1種また
は2種以上の総量:1〜10wt%からなることを特徴
とする。
The components of the alloy are Ni: 43 to 57 wt%, Ti: 35
~45wt%, and Co, Fe, Pd, Pt, B, A
It is characterized in that the total amount of at least one or two or more of r1, Si, ■, Nb, and Cu is 1 to 10 wt%.

チタン酸化膜を形成する合金は、形状記憶特性または超
弾性を発揮させる作動温度(変態温度)を生体用として
使用可能な温度範囲に設定する。
For the alloy that forms the titanium oxide film, the operating temperature (transformation temperature) at which it exhibits shape memory properties or superelasticity is set within a temperature range that can be used for biological purposes.

Co、Fe、Pd、Pt、B、Aff、Si、V、Nb
、Cuのうち少なくとも1種を1wt%以上含ませるの
は、Cuを除いた残りの元素は変態温度を低下させる働
きがあり、この働きを応用して作動温度を望ましい温度
に調節するためであり、また、10wt%以下とするの
は、この値以上含むと合金が難加工になるためである。
Co, Fe, Pd, Pt, B, Aff, Si, V, Nb
The reason why at least one of Cu is included in an amount of 1 wt% or more is that the remaining elements other than Cu have a function of lowering the transformation temperature, and by applying this function, the operating temperature can be adjusted to a desired temperature. , and the reason why it is set at 10 wt% or less is that if it is contained above this value, the alloy becomes difficult to work.

合金の加工は、圧延したものを板状にしたり線引加工し
て線状にしたりして目的とする形状にすることができる
The alloy can be processed into a desired shape by rolling it into a plate shape or drawing it into a wire shape.

目的とする形状に加工された合金は、チタン酸化膜の形
成の前処理に硝酸等を用いて表面汚染層を酸洗除去する
The alloy processed into the desired shape is pickled to remove the surface contamination layer using nitric acid or the like as a pretreatment for forming a titanium oxide film.

チタン酸化膜の形成は、乾式あるいは湿式法で合金の表
面を強制酸化させて行う。例えば、酸洗処理後の合金を
硝酸に浸漬して行うと設備も比較的簡単なもので済むた
め望ましい。また乾式法では、一定の酸素分圧下、30
0〜600℃の間で加熱処理する。この方法では形状配
憶処理と同時に被膜処理できる特徴がある。
The titanium oxide film is formed by forcibly oxidizing the surface of the alloy using a dry or wet method. For example, it is desirable to immerse the alloy after pickling in nitric acid because it requires relatively simple equipment. In addition, in the dry method, under a constant oxygen partial pressure, 30
Heat treatment is performed between 0 and 600°C. This method has the feature that it can process the film at the same time as the shape memory process.

(作用) 本発明の生体用形状配憶合金によると、実際に生体に接
触する合金の表面に、生体に対して安定なチタン酸化膜
を形成したため、合金中に含まれるNi等の金属の溶出
を防止するとともにNi等の金属と生体との接触を妨げ
る。
(Function) According to the shape-memory alloy for living organisms of the present invention, a titanium oxide film that is stable to living organisms is formed on the surface of the alloy that actually comes into contact with living organisms, so metals such as Ni contained in the alloy are eluted. It also prevents contact between metals such as Ni and living bodies.

(実施例) 以下、本発明の実施例を図面にもとづいて説明する。(Example) Embodiments of the present invention will be described below based on the drawings.

本実施例は、生体用形状記憶合金をインブラント材とし
て整形外科分野に応用する。
In this example, a biomedical shape memory alloy is applied to the field of orthopedics as an implant material.

第1図は、大腿骨の転子部が骨折した場合にその骨折部
を補強結合させるため髄内ビン1を骨髄内に挿入した大
腿骨2を示す。
FIG. 1 shows a femur 2 in which an intramedullary bottle 1 has been inserted into the bone marrow in order to reinforce and connect the fractured trochanteric region of the femur.

次に、この髄内ビン1の製造方法を説明する。Next, a method of manufacturing this intramedullary bottle 1 will be explained.

まず、モンドNiとスポンジTiの所定量を混合し、真
空溶解または高周波溶解する。鍛造、圧延後、線引加工
を行い、ワイヤーを形成する。このワイヤーを所定の長
さに切断した後、適当な濃度に調整したフッ化水素酸と
硝酸の混酸により酸洗処理を行い、さらに硝酸に30秒
間浸漬して表面にチタン酸化膜を形成する。その後、こ
のワイヤーを所定に設定された形状に記憶させる。この
形状は、大腿骨2の髄腔径よりも約IO%大きな張りを
もつ寸法で、しかも90”角度を変えて観察しても同じ
ような弓形をもつ3次元的な形状にする。また、髄内ビ
ン1のMs点は、16℃に設定されている。
First, predetermined amounts of Mondo Ni and sponge Ti are mixed and melted in vacuum or by high frequency. After forging and rolling, wire is drawn to form a wire. After cutting this wire to a predetermined length, it is pickled with a mixed acid of hydrofluoric acid and nitric acid adjusted to an appropriate concentration, and then immersed in nitric acid for 30 seconds to form a titanium oxide film on the surface. This wire is then memorized into a predetermined shape. This shape has a tension approximately IO% larger than the diameter of the medullary canal of the femur 2, and is a three-dimensional shape that has a similar arcuate shape even when observed at different angles of 90". The Ms point of intramedullary bottle 1 is set at 16°C.

前述したよう方法で製造された髄内ビン1は、氷水中で
冷却することにより比較的容易に形状を変化させること
ができる。このため、冷却した状態で変形した髄内ビン
1を、第2図(A )、(B)に示すように、大腿骨2
の骨髄内に挿入すると、体温により髄内ビン1は温めら
れ作動温度に達し、第1図(A)、(B)に示すように
、元の形状に戻ろうとする。ここに第1図(A)と第2
図(A)が対応し、第1図(B)と第2図(B)が対応
する。しかし、静的ピン1は、大腿骨2の腔径よりも約
10%大きな張りをもっているため、元の形状に戻るこ
とができず、曲部1aおよび曲部1bにより大腿骨2の
骨壁を内部から圧迫し骨折した大腿骨2を安定させる。
The shape of the intramedullary bottle 1 manufactured by the method described above can be changed relatively easily by cooling it in ice water. Therefore, the deformed intramedullary bottle 1 in a cooled state is inserted into the femur 2 as shown in FIGS. 2(A) and (B).
When inserted into the bone marrow of the patient, the intramedullary bottle 1 is warmed by body temperature and reaches the operating temperature, and attempts to return to its original shape as shown in FIGS. 1(A) and 1(B). Here, Figure 1 (A) and Figure 2
Figure (A) corresponds, and Figure 1 (B) and Figure 2 (B) correspond. However, since the static pin 1 has a tension approximately 10% larger than the cavity diameter of the femur 2, it cannot return to its original shape, and the bony wall of the femur 2 is stretched by the curved portions 1a and 1b. The fractured femur 2 is stabilized by compression from the inside.

髄内ビン1の表面には、生体に対して安定なチタン酸化
膜が形成されている。このため、骨髄内では、髄内ビン
1に含まれるNi等の金属と骨髄内の細胞とが直接接触
することはなく、またNi等の金属の溶出も抑えられて
いる。
A titanium oxide film that is stable to living organisms is formed on the surface of the intramedullary bottle 1. Therefore, within the bone marrow, metals such as Ni contained in the intramedullary bottle 1 do not come into direct contact with cells within the bone marrow, and elution of metals such as Ni is also suppressed.

第3図は、生体用形状記憶合金を人工関節ステムに応用
した例を示す。この関節ステム3は、形状配憶合金を円
柱状に加工し、ワイヤー放電加工機によりその外周面に
120°間隔で長さ方向へ切り込みを入れ爪部3aを形
成し、次いで長さ方向にズラした円柱を60°、回転さ
せて再び同様な切り込みを入れる操作を繰り返し、長さ
方向に5列の爪部3aを施したものである。チタン酸化
膜は加工後に形成した。爪部3aを径外側に起こした状
態を記憶させ、第3図に示すように、爪部3aを寝かし
た状態で生体内に挿入して使用する。
FIG. 3 shows an example in which a biomedical shape memory alloy is applied to an artificial joint stem. This joint stem 3 is made by machining a shape memory alloy into a cylindrical shape, using a wire electric discharge machine to cut the outer peripheral surface in the length direction at 120° intervals to form claw portions 3a, and then sliding it in the length direction. The cylinder was rotated by 60° and the same operation of making incisions was repeated, thereby forming five rows of claws 3a in the length direction. The titanium oxide film was formed after processing. A state in which the claw portion 3a is raised radially outward is memorized, and as shown in FIG. 3, the claw portion 3a is inserted into a living body in a lying state for use.

体温により関節ステムlが温められると、爪部3aは径
外側に起きるため、関節ステム3が外れないようにスト
ッパの役割を果たす。
When the joint stem 1 is warmed by body temperature, the claw portion 3a rises radially outward, and thus serves as a stopper to prevent the joint stem 3 from coming off.

また、第4図は、生体用形状記憶合金を骨結合用ステー
プルに応用した例を示す。ステープル4は、第4図のよ
うに背部4aと腕部4bとのなす角θを75°になるよ
うに形状配憶しである。そして、骨折部を結合する場合
には、腕部4bを背部4aに対して垂直にして腕部4b
を骨折部に差込む。体温によりステープル4の温度が上
昇すると、形状記憶効果により、腕部4bは骨折部を圧
迫し結合を安定させる。
Moreover, FIG. 4 shows an example in which the biomedical shape memory alloy is applied to a staple for bone attachment. The staple 4 is shaped so that the angle θ between the back portion 4a and the arm portion 4b is 75°, as shown in FIG. When joining the fractured part, the arm part 4b is made perpendicular to the back part 4a.
Insert into the fracture. When the temperature of the staple 4 rises due to body temperature, the arm portion 4b presses the fractured part due to the shape memory effect and stabilizes the bond.

その他、整形外科の分野では前述したものに限らず、髄
内釘やボーンブレー十等にも使用できる。
In addition, in the field of orthopedics, it can be used not only for the above-mentioned nails but also for intramedullary nails, bone braces, etc.

また形状記憶合金の超弾性を応用した骨折部締結用ワイ
ヤー等にも使用することができる。
It can also be used for wires for fastening bone fractures, etc., which utilizes the superelasticity of shape memory alloys.

他の実施例としては、整形外科の分野に限らず、その他
の医療、例えば、耳鼻咽喉科分野に使用する耳小骨連鎖
形成のためのブローテーゼ等に応用してもよい。また、
歯科分野での歯根等に使用できることはもちろんである
Other embodiments may be applied not only to the field of orthopedic surgery but also to other medical treatments, such as brothesis for forming the ossicular chain used in the field of otorhinolaryngology. Also,
Of course, it can be used for tooth roots etc. in the dental field.

(発明の効果) 以上説明したように、本発明の生体用形状記憶合金によ
れば、合金の表面に安定なチタン酸化膜を形成したため
、Ni等の金属の生体に対する悪影響を防止し、医療等
に安心して形状配憶合金の特性を応用できるという効果
がある。
(Effects of the Invention) As explained above, according to the shape memory alloy for living bodies of the present invention, since a stable titanium oxide film is formed on the surface of the alloy, it is possible to prevent the adverse effects of metals such as Ni on living bodies, and to use the shape memory alloy for medical purposes. This has the effect of allowing the properties of shape memory alloys to be applied with confidence.

【図面の簡単な説明】[Brief explanation of the drawing]

第1図および第2図は骨髄内に挿入された生体用記憶合
金を表わす図、第3図は生体用記憶合金を適用した人工
関節ステムを表わす図、第4図は生体用形状記憶合金を
適用した骨結合用ステーブルを表わす図である。 1・・・髄内ピン (生体用形状記憶合金) (A) CB) 第1図
Figures 1 and 2 are diagrams showing a biological memory alloy inserted into the bone marrow, Figure 3 is a diagram showing an artificial joint stem to which the biological memory alloy is applied, and Figure 4 is a diagram showing a biological memory alloy. It is a figure showing the applied osteointegration stable. 1... Intramedullary pin (shape memory alloy for biological use) (A) CB) Figure 1

Claims (2)

【特許請求の範囲】[Claims] (1)Niが43〜57wt%、残部がTiと不可避不
純物を含有する合金の表面にチタン酸化膜を形成したこ
とを特徴とする生体用形状記憶合金。
(1) A shape memory alloy for biological use, characterized in that a titanium oxide film is formed on the surface of an alloy containing 43 to 57 wt% Ni, the balance being Ti and unavoidable impurities.
(2)前記合金の成分がNi:43〜57wt%、Ti
:35〜45wt%、およびCo、Fe、Pd、Pt、
B、Al、Si、V、Nb、Cuのうち少なくとも1種
または2種以上の総量:1〜10wt%からなることを
特徴とする請求項1に記載の生体用形状記憶合金。
(2) The components of the alloy are Ni: 43 to 57 wt%, Ti
: 35 to 45 wt%, and Co, Fe, Pd, Pt,
The shape memory alloy for living bodies according to claim 1, characterized in that the total amount of at least one or more of B, Al, Si, V, Nb, and Cu is 1 to 10 wt%.
JP2098980A 1990-04-13 1990-04-13 Biomedical shape memory alloy Expired - Fee Related JP3013384B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2098980A JP3013384B2 (en) 1990-04-13 1990-04-13 Biomedical shape memory alloy

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP2098980A JP3013384B2 (en) 1990-04-13 1990-04-13 Biomedical shape memory alloy

Publications (2)

Publication Number Publication Date
JPH03295562A true JPH03295562A (en) 1991-12-26
JP3013384B2 JP3013384B2 (en) 2000-02-28

Family

ID=14234163

Family Applications (1)

Application Number Title Priority Date Filing Date
JP2098980A Expired - Fee Related JP3013384B2 (en) 1990-04-13 1990-04-13 Biomedical shape memory alloy

Country Status (1)

Country Link
JP (1) JP3013384B2 (en)

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WO1998036699A3 (en) * 1997-02-25 1998-11-19 Manfred Hinze Fracture nail for intramedullary nailing of long shaft bones
EP0882431A1 (en) * 1997-06-05 1998-12-09 Claudio Di Bartolomei Device for the elastic intramedullary synthesis of bone fractures
WO2000040784A3 (en) * 1999-01-08 2000-12-07 Scimed Life Systems Inc Methods for coating metallic articles
WO2001013969A1 (en) * 1999-08-23 2001-03-01 Shinhan Machinery Co., Ltd. Apparatus and method for manufacturing an artificial porous titanium nickel medulla by using a hot rotational synthesis method
JP2002065709A (en) * 2000-08-23 2002-03-05 Tokyo Bio Ceramics Kenkyusho:Kk Fixture of tooth or bone
US6638372B1 (en) * 1990-12-18 2003-10-28 Advanced Cardiovascular Systems, Inc. Superelastic guiding member
CN100462473C (en) * 2007-04-11 2009-02-18 北京航空航天大学 Medical TiNi shape memory alloy sputtered by TiTaCo composite film on surface and its production
CN105296800A (en) * 2014-08-01 2016-02-03 中国石油大学(北京) TiNiCuNb memory alloy and preparation method thereof
CN109468519A (en) * 2018-11-29 2019-03-15 湖北第二师范学院 Yield strength is greater than the titanium silicon europium marmem and its production method, application and material of 800MPa
CN109602957A (en) * 2018-12-19 2019-04-12 云南大学 A kind of bio-medical porous titanium niobium copper orthopedic implanting material and its preparation method and application
CN114875294A (en) * 2022-06-07 2022-08-09 上海工程技术大学 Titanium-nickel-based alloy material and preparation method and application thereof

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