JP4497473B2 - Metal fiber three-dimensional structure and manufacturing method thereof. - Google Patents
Metal fiber three-dimensional structure and manufacturing method thereof. Download PDFInfo
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本発明は、高い空隙率を有する金属繊維からなる三次元構造体、およびその製造方法に関し、さらに詳しくは冠動脈ステント、人工骨、人工歯根、電気機器の電極および空調機器などのフィルター用素材として用いられる高い空隙率を有し、かつ形状記憶特性を有する金属繊維三次元構造体、およびその製造方法に関する。 The present invention relates to a three-dimensional structure made of metal fibers having a high porosity and a method for producing the same, and more specifically, used as a filter material for coronary artery stents, artificial bones, artificial tooth roots, electrodes of electrical equipment, and air conditioners. The present invention relates to a metal fiber three-dimensional structure having a high porosity and shape memory characteristics, and a method for producing the same.
チタン系金属材料は、比強度が高く、耐食性、生体親和性にも優れていることから、工業分野では電気機器の電極や空調機器のフィルターとして、生体・医療分野では人工骨、人工歯根として使用されてきた。ところが、チタンは機械加工が困難な金属であり高精度の加工品や複雑な形状の部材を作成するには、粉末焼結法で仕様製品に近い製品を作成し、それを研削などで整形するなど無駄に消費する量が多く製品コストを高いものにしていた。 Titanium-based metal materials have high specific strength, excellent corrosion resistance and biocompatibility, so they are used as electrodes for electrical equipment and filters for air-conditioning equipment in the industrial field, and as artificial bones and dental roots in the biological and medical fields. It has been. However, titanium is a metal that is difficult to machine, and in order to create high-precision processed products and members with complex shapes, create a product close to the specified product by powder sintering and shape it by grinding or the like. The amount of wasteful consumption was high, and the product cost was high.
近年、チタン系金属材料の上記特質を生かすとともに、高い空隙率を有する部材が、例えば心臓外科分野では冠動脈ステントの素材として、再生医療では生体骨の足場材の素材として、また、歯科分野では人工歯根の素材として、さらには空調機器分野ではフィルターの素材として求められるようになってきた。高い空隙率を有する部材の作成にはレーザー加工などの特殊加工法を用いて加工するのが一般的におこなわれているが、それでも空隙率が３０％程度の製品が得られるのが限界であった。この問題を解決したチタン系金属部材として特許文献１にチタン繊維三次元構造焼結体が提案されている。該チタン繊維三次元構造焼結体は、空隙率が４０％を超え、再生医療における骨髄中の未分化間葉系幹細胞の成長を大きく促進できる素材として、また、歯根培養が容易である部材として、また、電極における電流密度を大きくできる部材として、さらには空調機器分野において流体の圧力損失が少なく、パーティクルの補足効果が高い素材として注目を集めている。 In recent years, a member having a high porosity, taking advantage of the above-mentioned properties of titanium-based metal materials, has been used as a material for coronary stents in the field of cardiac surgery, as a material for scaffolds of living bones in regenerative medicine, and as an artificial material in the dental field. It has been demanded as a material for roots, and further as a material for filters in the field of air conditioning equipment. In general, a member having a high porosity is processed by using a special processing method such as laser processing, but it is still the limit that a product with a porosity of about 30% can be obtained. It was. As a titanium-based metal member that solves this problem, Patent Document 1 proposes a titanium fiber three-dimensional structure sintered body. The titanium fiber three-dimensional structure sintered body has a porosity of more than 40%, and can be used as a material that can greatly promote the growth of undifferentiated mesenchymal stem cells in bone marrow in regenerative medicine, and as a member that can be easily cultivated by roots. In addition, as a member that can increase the current density in the electrode, and in the field of air-conditioning equipment, it has been attracting attention as a material that has a low fluid pressure loss and a high particle-capturing effect.
しかし、上記引用文献1に記載のチタン繊維三次元構造焼結体は、不織布状に展開したチタン系繊維を焼成したにとどまることから、人工骨、人工歯根、電極或いは空調機器のフィルターとして使用している内に、繊維の脱落が起こり、これらの部材が変形し、寿命が短いなどの欠点があった。その上、前記チタン繊維三次元構造焼結体では冠動脈ステントで必要とされる可撓性、高屈曲抵抗などの条件を満足させることができなかった。その上、前記チタン繊維三次元構造焼結体は加工が難しいことから所望の形状の部材を容易に作成できないなどの問題もあった。 However, the titanium fiber three-dimensional structure sintered body described in the above cited document 1 is used only as a filter for artificial bones, artificial tooth roots, electrodes, or air conditioners because it only burns titanium-based fibers developed in a nonwoven fabric. In the meantime, there was a drawback that the fibers dropped out, these members were deformed, and the life was short. Moreover, the titanium fiber three-dimensional structure sintered body could not satisfy the conditions such as flexibility and high bending resistance required for the coronary stent. In addition, since the titanium fiber three-dimensional structure sintered body is difficult to process, there is a problem that a member having a desired shape cannot be easily formed.
上記冠動脈ステントへの摘要からみるならば純チタンと純ニッケルとの金属間化合物であるTiNi形状記憶合金は優れた素材といえるが、従来のTiNi形状記憶合金ではレーザー加工などで空隙率を高めようとしても上記冠動脈ステント、人工骨、人工歯根、電極或いは空調機器のフィルター用素材として満足する空隙率を有する素材の作成が困難であるなどの問題があった。
こうした現状に鑑み、本発明者は、鋭意研究を続けた結果、２種類以上の金属繊維を不織布状に積層体或いは混合展開し、それを特定の条件で加熱し、二種類以上の金属繊維間の接触部分を固相接合し、さらに規則化処理で金属間化合物を形成することで任意の形状の部材が容易に作成できる上に、金属繊維同士が堅固に固定され型崩れがなく安定した高い空隙率を有する三次元構造体が得られること、さらに、チタン繊維とニッケル繊維を用いて三次元構造体を得た場合には、それがTiNi形状記憶合金の特徴を有することをも見出して、本発明を完成したものである。すなわち、 In view of the current situation, the present inventor has conducted earnest research, and as a result, laminated or mixed two or more types of metal fibers into a nonwoven fabric, heated under specific conditions, and between two or more types of metal fibers. In addition to solid-phase bonding of the contact parts, and forming an intermetallic compound by a regularization process, members of any shape can be easily created, and metal fibers are firmly fixed to each other, without being out of shape and stable. It is found that a three-dimensional structure having a porosity can be obtained, and further, when a three-dimensional structure is obtained using titanium fibers and nickel fibers, it has characteristics of a TiNi shape memory alloy, The present invention has been completed. That is,
本発明は、金属繊維の接触部に金属間化合物が形成され形状記憶特性、超弾性特性に優れ、高い空隙率を有する金属繊維三次元構造体を提供することを目的とする。 An object of the present invention is to provide a metal fiber three-dimensional structure having an intermetallic compound formed at a contact portion of a metal fiber, excellent in shape memory characteristics and superelastic characteristics, and having a high porosity.
また、本発明は、可撓性、屈曲抵抗性に優れた金属繊維三次元構造体を提供することを目的とする。 Another object of the present invention is to provide a metal fiber three-dimensional structure excellent in flexibility and bending resistance.
また、本発明は、上記金属繊維三次元構造体の製造方法を提供することを目的とする。 Moreover, an object of this invention is to provide the manufacturing method of the said metal fiber three-dimensional structure.
上記目的を達成する本発明は、純チタン繊維と純ニッケル繊維が空隙率４０〜９５％の三次元構造をなし、かつ両繊維の接触部に金属間化合物が形成されていることを特徴とする金属繊維三次元構造体及びその製造方法に係る。 The present invention that achieves the above object is characterized in that pure titanium fibers and pure nickel fibers have a three-dimensional structure with a porosity of 40 to 95%, and an intermetallic compound is formed at the contact portion of both the fibers. The present invention relates to a metal fiber three-dimensional structure and a manufacturing method thereof.
上記チタン繊維又はニッケル繊維は、ＪＩＳ規格の第１種、第２種、第３種に定められた純金属チタン又はニッケルの１種又はそれ以外を削り出す切削法（特許文献２、３）や、チタン又はニッケル金属母材を伸線加工する伸線法などで製造された金属繊維であって、少なくともアスペクト比が１５以上の短繊維又は長繊維である。前記アスペクト比が１５未満では、繊維同士の絡み合いがなく不織布としての機能を果たさず、高い空隙率を有する三次元構造体を得ることができない。さらに、前記金属繊維はその断面を顕微鏡で観測する測定法で直径１０〜３００μｍであるのがよい。直径が１μｍ未満では三次元構造体の製造時に充填密度が過度になり空隙率の高い構造体が得られず、直径が３００μｍを越えると剛性が大きくなり過ぎ繊維の形枠への充填が困難となる。 The titanium fiber or nickel fiber is a pure metal titanium or nickel specified in JIS standard type 1, type 2, type 3, or a cutting method for scraping one or the other (Patent Documents 2 and 3) A metal fiber manufactured by a wire drawing method for drawing a titanium or nickel metal base material, and is a short fiber or a long fiber having an aspect ratio of 15 or more. When the aspect ratio is less than 15, the fibers do not entangle and do not function as a nonwoven fabric, and a three-dimensional structure having a high porosity cannot be obtained. Further, the metal fiber is preferably 10 to 300 μm in diameter by a measuring method in which the cross section is observed with a microscope. If the diameter is less than 1 μm, the packing density becomes excessive at the time of manufacturing the three-dimensional structure, and a structure having a high porosity cannot be obtained. If the diameter exceeds 300 μm, the rigidity becomes too high and it is difficult to fill the fiber formwork. Become.
本発明の金属繊維三次元構造体は、純チタン繊維と純ニッケル繊維とが原子組成比で０.７〜２：１の割合で混合展開又は積層された不織布状をなし、両金属繊維の接触部分が金属間化合物を形成し形状記憶特性、超弾性特性を有するとともに、空隙率が４０〜９５％と高い立体形状をなす上に、可撓性、屈曲抵抗性にも優れた三次元構造体である。このように本発明の三次元構造体は金属繊維の接触部分がTiNi金属間化合物となっていることから冠動脈ステント、人工骨、人工歯根、電気機器の電極および空調機器などのフィルターとして使用中に金属繊維の脱落がなく長期間の使用ができる。さらに、形状記憶特性、超弾性特性、可撓性、屈曲抵抗性などに優れていることから、従来の形状記憶合金線或いは形状記憶薄板では製造困難な形状の部材も容易に製造できる。前記空隙率は、数式（１） The metal fiber three-dimensional structure of the present invention is a nonwoven fabric in which pure titanium fibers and pure nickel fibers are mixed and expanded or laminated in an atomic composition ratio of 0.7 to 2: 1. A three-dimensional structure in which the portion forms an intermetallic compound, has shape memory characteristics and superelasticity, has a high three-dimensional shape with a porosity of 40 to 95%, and is excellent in flexibility and bending resistance It is. As described above, since the contact portion of the metal fiber is a TiNi intermetallic compound, the three-dimensional structure of the present invention is being used as a filter for coronary stents, artificial bones, artificial tooth roots, electrodes of electrical equipment, and air conditioners. It can be used for a long time without falling off of metal fibers. Furthermore, since it is excellent in shape memory characteristics, superelastic characteristics, flexibility, bending resistance, etc., it is possible to easily manufacture members having shapes that are difficult to manufacture with conventional shape memory alloy wires or shape memory thin plates. The porosity is expressed by Equation (1).
（式中、Ｒｐは空隙率（％）、ｍは構造体の質量（ｇ）、Ｖは構造体の体積（ｃｍ３）、ρは密度（ｇ／ｃｍ３）を表わす。）
で表わされる値であり、製品の用途により適宜選定される。たとえば人工骨の場合には空隙率４０〜９５％が、人工歯根の場合には６０〜９５％が、電気機器の場合には４０〜６０％が、フィルター材料の場合には空隙率７０〜９０％などがよい。
(In the formula, Rp represents the porosity (%), m represents the mass (g) of the structure, V represents the volume (cm 3 ) of the structure, and ρ represents the density (g / cm 3 ).)
This value is appropriately selected according to the application of the product. For example, the porosity is 40 to 95% in the case of an artificial bone, 60 to 95% in the case of an artificial tooth root, 40 to 60% in the case of an electric device, and the porosity 70 to 90 in the case of a filter material. % Etc. are good.
本発明の金属繊維三次元構造体は、純チタン繊維と純ニッケル繊維とを、型枠に原子組成比が０.７〜２；１の範囲で混合展開又は積層し、それを不活性ガス又は真空雰囲気下、好ましくは１×１０−３Ｐａ以下の減圧雰囲気下で、８００〜１２００℃の温度で加熱し、固相拡散による金属間化合物を形成したのち、さらに、１×１０−４Ｐａ以下の高度真空雰囲気下、８００〜１２００℃で規則化処理して製造される。前記型枠としては、高融点を有し、チタンやニッケルと反応性がない材質、例えばＭｏ、Ｗ、Ｔａなどの高融点金属材料、アルミナ、ジルコニア、窒化珪素、サイアロンなどのセラミックス材料が好適に使用される。金属繊維三次元構造体の形状としては、円柱、角錐、円筒、円錐第、角錐台、球体、それらの組合せ体などが挙げられる。 In the metal fiber three-dimensional structure of the present invention, pure titanium fiber and pure nickel fiber are mixed and expanded or laminated in a mold within an atomic composition ratio range of 0.7 to 2; After heating at a temperature of 800 to 1200 ° C. in a vacuum atmosphere, preferably under a reduced pressure atmosphere of 1 × 10 −3 Pa or less to form an intermetallic compound by solid phase diffusion, further 1 × 10 −4 Pa or less In an advanced vacuum atmosphere at 800 to 1200 ° C. As the mold, a material having a high melting point and not reactive with titanium or nickel, for example, a high melting point metal material such as Mo, W, or Ta, or a ceramic material such as alumina, zirconia, silicon nitride, or sialon is suitable. used. Examples of the shape of the metal fiber three-dimensional structure include a cylinder, a pyramid, a cylinder, a first cone, a truncated pyramid, a sphere, a combination thereof, and the like.
また、加熱炉としては、電気加熱式炉、ガス加熱式炉、通電加熱式炉、誘導加熱式炉等が挙げられる。 Examples of the heating furnace include an electric heating furnace, a gas heating furnace, an electric heating furnace, an induction heating furnace, and the like.
本発明の金属繊維三次元構造体は、純チタン繊維と純ニッケル繊維とが不織布状をなし、高空隙率を有する上に、純チタン繊維と純ニッケル繊維の接触部分が金属間化合物を形成し高い保形性を有し、かつ形状記憶特性、超弾性特性を有することから冠動脈ステント、人工骨、人工歯根、電気機器の電極および空調機器などのフィルターなど複雑な形状の部材も容易に作成できる。 In the metal fiber three-dimensional structure of the present invention, pure titanium fibers and pure nickel fibers form a non-woven fabric, have a high porosity, and contact portions between pure titanium fibers and pure nickel fibers form an intermetallic compound. Due to its high shape retention and shape memory and superelastic properties, it is easy to create members with complex shapes such as coronary stents, artificial bones, artificial tooth roots, electrical equipment electrodes and air conditioner filters. .
本発明をさらに実施例に基づいて詳述するが、本発明はこれに限定されるものではない。 The present invention is further described in detail based on examples, but the present invention is not limited thereto.
コイル材切削法により換算直径４６μｍの純チタン繊維と換算直径４６μｍの純ニッケル繊維を製造し、洗浄・脱脂した。前記純チタン繊維と純ニッケル繊維とを原子組成比１：１で形枠内に均一に分散し、１×１０−３Ｐａの減圧雰囲気下、８５０℃で１０時間加熱し、そのまま冷却し、縦１４ｃｍ、横１４ｃｍ、厚さ１ｍｍ、質量１８．４ｇの角柱状の金属不織布を得た。この金属不織布をさらに真空熱処理炉内で１×１０−４Ｐａの真空雰囲気下、８５０℃で１０時間加熱し、室温まで冷却し規則化処理を行った。得られた金属繊維三次元構造体の接合部を観察したところ図１、２にみるようにＴｉＮｉ金属間化合物が形成されていた。さらに、同金属繊維三次元構造体について示差走査熱量測定をおこなったとこる、図３にみるようにマルチンサイト変態と逆変態とが見られ形状記憶特性を有することが確認された。この金属繊維三次元構造体についてニッケルの密度を８．８５（ｇ／ｃｍ３）、チタンの密度を４．５（ｇ／ｃｍ３）として、式（１）を使用して空隙率を計算したところ８６％であった。前記金属繊維三次元構造体は、形状記憶特性、超弾性特性、可撓性、屈曲抵抗などが良好で、冠動脈ステント用素材として有用であった。 Pure titanium fibers having a converted diameter of 46 μm and pure nickel fibers having a converted diameter of 46 μm were produced by a coil material cutting method, and washed and degreased. The pure titanium fiber and the pure nickel fiber are uniformly dispersed in the form frame at an atomic composition ratio of 1: 1, heated at 850 ° C. for 10 hours in a reduced pressure atmosphere of 1 × 10 −3 Pa, cooled as it is, A prismatic metal nonwoven fabric having a size of 14 cm, a width of 14 cm, a thickness of 1 mm, and a mass of 18.4 g was obtained. The metal nonwoven fabric was further heated in a vacuum heat treatment furnace in a vacuum atmosphere of 1 × 10 −4 Pa at 850 ° C. for 10 hours, cooled to room temperature, and subjected to ordering treatment. When the joint part of the obtained metal fiber three-dimensional structure was observed, a TiNi intermetallic compound was formed as shown in FIGS. Furthermore, when the differential scanning calorimetry was performed on the metal fiber three-dimensional structure, as shown in FIG. 3, the multisite transformation and the reverse transformation were observed, and it was confirmed that they had shape memory characteristics. With respect to this metal fiber three-dimensional structure, the porosity was calculated using Equation (1), assuming that the density of nickel was 8.85 (g / cm 3 ) and the density of titanium was 4.5 (g / cm 3 ). However, it was 86%. The metal fiber three-dimensional structure has good shape memory characteristics, superelastic characteristics, flexibility, bending resistance, and the like, and was useful as a coronary stent material.
本発明の金属繊維三次元構造体は、純チタン繊維と純ニッケル繊維とからなる三次元構造体で耐熱性、耐薬品性に優れている上に、高い空隙率を有し、かつ形状記憶特性、超弾性特性、可撓性、屈曲抵抗性に優れ、心臓外科、再生医療、歯科治療、電気機器の電極、空調用フィルターなどの素材として有用である。 The metal fiber three-dimensional structure of the present invention is a three-dimensional structure composed of pure titanium fiber and pure nickel fiber, which is excellent in heat resistance and chemical resistance, has a high porosity, and has shape memory characteristics. It has excellent superelastic properties, flexibility, and bending resistance, and is useful as a material for cardiac surgery, regenerative medicine, dental treatment, electrical equipment electrodes, air conditioning filters, and the like.
１：チタン繊維
２：ニッケル繊維
３：チタン・ニッケル金属間化合物
1: Titanium fiber 2: Nickel fiber 3: Titanium / nickel intermetallic compound
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| JPH0949004A (en) * | 1995-08-09 | 1997-02-18 | Furukawa Electric Co Ltd:The | Shape memory plate |
| JP2000080591A (en) * | 1998-09-04 | 2000-03-21 | Tomoegawa Paper Co Ltd | Metal fiber sheet, metal fiber sheet laminate, and method for manufacturing metal fiber sheet |
| JP3735712B2 (en) * | 2002-03-12 | 2006-01-18 | 独立行政法人産業技術総合研究所 | Method for producing porous material and molded body thereof |
| JP2004018951A (en) * | 2002-06-17 | 2004-01-22 | Nv Bekart Sa | Titanium fiber three-dimensional structure sintered body and method of manufacturing the same |
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