JPH04105659A - Biological titanium alloy and manufacture thereof - Google Patents
Biological titanium alloy and manufacture thereofInfo
- Publication number
- JPH04105659A JPH04105659A JP2225520A JP22552090A JPH04105659A JP H04105659 A JPH04105659 A JP H04105659A JP 2225520 A JP2225520 A JP 2225520A JP 22552090 A JP22552090 A JP 22552090A JP H04105659 A JPH04105659 A JP H04105659A
- Authority
- JP
- Japan
- Prior art keywords
- titanium alloy
- heating
- alloy
- heat treatment
- total
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 229910001069 Ti alloy Inorganic materials 0.000 title claims abstract description 41
- 238000004519 manufacturing process Methods 0.000 title claims description 8
- 238000010438 heat treatment Methods 0.000 claims abstract description 22
- 239000002344 surface layer Substances 0.000 claims abstract description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001873 dinitrogen Inorganic materials 0.000 claims abstract description 5
- 230000009466 transformation Effects 0.000 claims abstract description 3
- 210000000988 bone and bone Anatomy 0.000 abstract description 15
- 238000009792 diffusion process Methods 0.000 abstract description 9
- 238000000034 method Methods 0.000 abstract description 8
- 229910045601 alloy Inorganic materials 0.000 abstract description 6
- 239000000956 alloy Substances 0.000 abstract description 6
- 239000012620 biological material Substances 0.000 abstract description 6
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000010410 layer Substances 0.000 abstract description 3
- 238000004458 analytical method Methods 0.000 description 5
- 239000007769 metal material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 239000002639 bone cement Substances 0.000 description 3
- 238000005260 corrosion Methods 0.000 description 3
- 230000007797 corrosion Effects 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 229910052588 hydroxylapatite Inorganic materials 0.000 description 2
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 description 2
- 238000004544 sputter deposition Methods 0.000 description 2
- 229910000967 As alloy Inorganic materials 0.000 description 1
- 229910000599 Cr alloy Inorganic materials 0.000 description 1
- 229910000883 Ti6Al4V Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000000975 bioactive effect Effects 0.000 description 1
- 239000005312 bioglass Substances 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000000919 ceramic Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000002241 glass-ceramic Substances 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 238000002233 thin-film X-ray diffraction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Landscapes
- Materials For Medical Uses (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は、人工骨などの生体用材料として使用される
生体親和性に優れたチタン合金とその製造方法に関する
。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) The present invention relates to a titanium alloy having excellent biocompatibility and used as a biomaterial such as an artificial bone, and a method for producing the titanium alloy.
（従来の技術）
病気や事故によって失われた骨の補強方法の一つに人工
骨を嵌植（Ｉｎｐｌａｎｔａｔｉｏｎ）する方法がある
。この人工骨の材料に求められる主要な性質は、■生体
適合性、■耐食性、０強度、および■骨との接合性であ
る。(Prior Art) One of the methods for reinforcing bones lost due to disease or accidents is the method of implanting artificial bones. The main properties required of this artificial bone material are: (1) biocompatibility, (2) corrosion resistance, zero strength, and (2) bondability with bone.
人工骨材の代表的なものにバイオグラス（Ｂｉ。Bioglass (Bi.
ｇｌａｓｓ）、水酸アパタイトセラミックス、Ａ−グラ
スセラミックス等があり、これらは生体活性（Ｂｉｏ−
ａｃｔｉｖｅ）であるが強度に乏しく、荷重のあまりか
からない部分のみに使用されている。大きな荷重のかか
る部分にはＣｏ−Ｃｒ合金、ステンレス鋼、チタン合金
等が用いられるが、これらは生体反応性がない（Ｂｉｏ
ｉｎｃｒｔである）ため、骨セメントを用いて人骨と接
合しなければならない、しかし、骨セメントの使用は、
その重合熱、毒性モノマー、生体親和性の不足などから
多くの問題が指摘されている。glass), hydroxyapatite ceramics, A-glass ceramics, etc., and these have bioactivity (Bio-
active), but it lacks strength and is used only in areas that are not subject to much load. Co-Cr alloys, stainless steel, titanium alloys, etc. are used for parts subject to large loads, but these have no bioreactivity (Bio
incrt), it must be connected to human bone using bone cement. However, the use of bone cement
Many problems have been pointed out, including its polymerization heat, toxic monomers, and lack of biocompatibility.
（発明が解決しようとする課題）
上記のような現状から、強度の大きい金属材料であって
生体活性（生体親和性）に優れた材料の開発が強く要望
されている。(Problems to be Solved by the Invention) Under the current situation as described above, there is a strong demand for the development of a metal material with high strength and excellent bioactivity (biocompatibility).
本発明のｔ！Ｊ題は、強度が高く、人骨との接合に骨セ
メントを必要としない材料、およびその製造方法を提供
することにある。T of the present invention! The object of the present invention is to provide a material that has high strength and does not require bone cement for connection with human bone, and a method for manufacturing the same.
（課題を解決するための手段）
生体材料として使用される金属材料の一つにチタン合金
がある。これは軽量で且つ機械的性質および化学的性質
（耐食性）にも優れているから、生体材料としては極め
て望ましいものである。しかし、チタン合金そのものは
生体活性が乏しい。(Means for solving the problem) Titanium alloy is one of the metal materials used as biomaterials. This is extremely desirable as a biomaterial because it is lightweight and has excellent mechanical and chemical properties (corrosion resistance). However, titanium alloy itself has poor bioactivity.
本発明はこのチタン合金に生体活性を付与することを目
的としてなされたもので、その要旨は下記のとおりであ
る。The present invention was made for the purpose of imparting bioactivity to this titanium alloy, and the gist thereof is as follows.
（１） Ｓｉ、 Ｙを単独または合計で０，５〜１０
ＭＩ％含有することを特徴とする生体用チタン合金。(1) Si, Y alone or in total from 0.5 to 10
A titanium alloy for biological use characterized by containing MI%.
ｆ２） Ｓｉまたは／およびＹを表層部に濃化させた
上記（１）の生体用チタン合金。f2) The titanium alloy for biological use according to (1) above, in which Si and/or Y are enriched in the surface layer.
（３） Ｓｉ、Ｙを単独または合計で０５〜１０重量
％含有するチタン合金を７５０℃からβ変態点までの温
度域で加熱することを特（衣とする上記（２）の生体用
チタン合金の製造方法。(3) The titanium alloy for biological use according to (2) above, which is specially prepared by heating a titanium alloy containing 05 to 10% by weight of Si and Y alone or in total in a temperature range from 750°C to the β transformation point. manufacturing method.
（４１Ｓｉ、 Ｙを単独または合計で０．５〜１０重蓋
％含有するチタン合金の表面を高エネルギービーム、例
えばレーザービーム、プラズマビームで７５０℃以上に
加熱することを特徴とする上記（２）の生体用チタン合
金の製造方法。((2) above, characterized in that the surface of a titanium alloy containing 0.5 to 10% of 41Si and Y alone or in total is heated to 750°C or higher with a high-energy beam, such as a laser beam or a plasma beam. A method for producing titanium alloy for biological use.
上記（１）のチタン合金とは、純Ｔ己こＳｉまたは／お
よびＹを添加したもの、或いはＴｉ−６Ａｌ−４Ｖ合金
、Ｔｉ ３Ａｌ−２，５Ｖ合金、等（７） Ｔ ｉ合
金！、ｍＳｉマたは／およびＹを添加したものである。The titanium alloy mentioned in (1) above refers to pure Ti alloy with Si or/and Y added, Ti-6Al-4V alloy, Ti3Al-2,5V alloy, etc. (7) Ti alloy! , mSi or/and Y.
即ち、Ｓｉ、Ｙが、単独もしくは合計で０．５〜１０重
量％含有されていることが必須であるが、Ｓｌ、Ｙ以外
の合金成分として、前記Ａ２、■、Ｚｒ、 Ｍｏ等、通
常のチタン合金に添加される成分が含有されていてもよ
い、これらの合金成分は、材料に要求される機械的性質
、化学的性質（耐食性）等に応して選択し、適当量添加
すればよい。That is, it is essential that Si and Y are contained individually or in a total of 0.5 to 10% by weight, but as alloy components other than Sl and Y, the above-mentioned A2, ■, Zr, Mo, etc. Components added to the titanium alloy may be included. These alloy components may be selected according to the mechanical properties, chemical properties (corrosion resistance), etc. required for the material, and added in appropriate amounts. .
（作用）
金属材料に生体活性を与えるということは、人骨と接合
したときに拡散相が形成させるようにするということで
ある。即ち、骨の主要゛成分であるＣａまたはＰが金属
材料に拡散浸透するようにすればよいのであるが、Ｃａ
、 ＰはＴｉには全く固溶しない、ところが、本発明者
はチタン合金にＳｉ、 Ｙの適当量を含有させておけば
、Ｃａ、 Ｐの拡散がおこることを［認した。特に、Ｓ
ｔ、 Ｙを表層部に濃化させておけば、この拡散現象が
顕著になり、骨との接合性が著しく高まる。(Function) Providing biological activity to a metal material means that a diffusion phase is formed when it is bonded to human bone. In other words, it is sufficient to allow Ca or P, which is the main component of bone, to diffuse and permeate into the metal material.
However, the present inventors have recognized that if appropriate amounts of Si and Y are contained in a titanium alloy, diffusion of Ca and P will occur. In particular, S
If t and Y are concentrated in the surface layer, this diffusion phenomenon will become noticeable, and the bonding property with bone will be significantly improved.
ＳｉもしくはＹｌまたはこれらの合計の含有量が０．５
重量％未満では上記の拡散現象が明確にならない、また
、その含有量が１０重量％を超えるとチタン合金本来の
機械的、化学的性質が積なわれて生体用材料として不適
当になる。Si or Yl or their total content is 0.5
If the content is less than 10% by weight, the above-mentioned diffusion phenomenon will not become clear, and if the content exceeds 10% by weight, the inherent mechanical and chemical properties of the titanium alloy will be accumulated, making it unsuitable as a biological material.
本発明のチタン合金は、必要な形状に加工した後、熱処
理して表層部にＳｉ、 Ｙの濃化層を形成させるのが望
ましい、その熱処理の一つの方法は、７５０℃からβ変
態点までの温度域で０．５〜４時間加熱することである
。７５０℃より低温、あるいは０．５時間より短時間の
加熱では濃化層の形成が不十分であり、一方あまりに高
温で、或いは過度に長時間加熱するとチタン合金の機械
的性質が劣化する。After processing the titanium alloy of the present invention into the required shape, it is desirable to heat-treat it to form a concentrated layer of Si and Y on the surface layer. One method for this heat treatment is to process the titanium alloy from 750°C to the β-transformation point. It is to heat in the temperature range of 0.5 to 4 hours. Heating at a temperature lower than 750° C. or for a shorter time than 0.5 hours will result in insufficient formation of a concentrated layer, while heating at too high a temperature or for an excessively long time will deteriorate the mechanical properties of the titanium alloy.
もう一つの方法は、レーザービーム、プラズマビーム等
の高エネルギービームで表面を加熱する方法である。こ
の場合の加熱温度は７５０℃以上とする。Another method is to heat the surface with a high energy beam such as a laser beam or plasma beam. The heating temperature in this case is 750°C or higher.
上記の熱処理の加熱雰囲気として窒素ガスを使用すれば
、合金の表面にＴｉＮが形成されて、チタン合金を人工
関節などに使用する場合に問題になる耐摩耗性をも向上
させることができる。If nitrogen gas is used as the heating atmosphere for the above heat treatment, TiN is formed on the surface of the alloy, and the wear resistance, which is a problem when using titanium alloys for artificial joints, can also be improved.
（実施例１）
純チタンに５重量％のＹを含有させたチタン合金に窒素
ガス中８００℃で３０分および１時間の熱処理を施した
。二〇熱処理前後の試料表面についてＲＢＳ解析（１，
５ＭｅＶ、’１（ｅ）を行った。−その結果を第１図に
示す。(Example 1) A titanium alloy containing 5% by weight of Y in pure titanium was heat-treated at 800° C. for 30 minutes and 1 hour in nitrogen gas. 20 RBS analysis of the sample surface before and after heat treatment (1,
5MeV, '1(e) was performed. -The results are shown in Figure 1.
第１図から明らかなように、８００℃で３０分、および
１時間熱処理した試料の表層部にはＹが濃化している。As is clear from FIG. 1, Y is concentrated in the surface layer of the sample heat-treated at 800° C. for 30 minutes and 1 hour.
また、薄膜Ｘ線回折の結果、表面にはＴｉＮの形成が認
められた。Further, as a result of thin film X-ray diffraction, formation of TiN was observed on the surface.
上北熱処理後の試料を、−例として水酸アパタイト７ｇ
を懸濁させたリンゲルｉ’ｆＩ （Ｎａ”１４７、Ｋ’
４、Ｃａ”４．５、ＩＪ−１５５，５、ｓＥｑ／ Ｅ
） ５３ｍ ｌに浸漬し３７℃で保持した。４週間保持
したのち試料を溶液から取り出し、アセトン中で超音波
洗浄し、ＳＩＮ’Ｉｓ分析を行った。その結果を第２図
に示す。The sample after Kamikita heat treatment is - as an example, 7 g of hydroxyapatite.
Ringer's i'fI (Na"147, K'
4, Ca”4.5, IJ-155,5, sEq/E
) and kept at 37°C. After holding for 4 weeks, the samples were removed from the solution, ultrasonically cleaned in acetone, and subjected to SIN'Is analysis. The results are shown in FIG.
第２図から試料のチタン合金表面にはリンゲル液のＣａ
およびＰが拡散していることが明らかである。これは、
チタン合金中のＹがＣａおよびＰと化合物をつくるため
と推定される。Figure 2 shows that the surface of the titanium alloy sample contains Ca in Ringer's solution.
It is clear that and P are diffused. this is,
It is presumed that this is because Y in the titanium alloy forms a compound with Ca and P.
なお第２図の横軸はスパッタリング時間であり、１分の
スパッタリング時間は１０００人の深さに相当する。The horizontal axis in FIG. 2 is the sputtering time, and one minute of sputtering time corresponds to a depth of 1000 people.
（実施例２）
第１表に示す各種のチタン合金に実施例１と同じ熱処理
（ただし、加熱時間は３０分）を施し、実施例１と同し
リンゲル液への浸漬保持（６７２時間）を行った。その
試料についてＣａとＰの拡散状態を実施例１の方法で調
べた。また、表面のレーザービームによる加熱（加熱温
度２９５０″Ｃ１加熱深さ３００μ暖、出力２．８ Ｋ
Ｗ、窒素ガス雰囲気）も試みた（Ｎα１１）。(Example 2) Various titanium alloys shown in Table 1 were subjected to the same heat treatment as in Example 1 (however, the heating time was 30 minutes), and immersed in Ringer's solution (672 hours) as in Example 1. Ta. The state of diffusion of Ca and P in the sample was investigated using the method of Example 1. In addition, the surface was heated by a laser beam (heating temperature 2950"C1 heating depth 300μ warm, output 2.8K)
W, nitrogen gas atmosphere) was also tried (Nα11).
それらの結果を第１表中に併記する。なお、第１表の拡
散の有無の欄で「有り」は、リンゲル液浸漬前の試料に
対して、浸漬後の試料の表面から１０００人の位置のＣ
ａがＳＩＭＳ分析の２次イオン強度で５０倍以上になっ
ているものである。「なし」は、５０倍未満のものであ
る。The results are also listed in Table 1. In Table 1, in the presence/absence of diffusion column, "Present" means that the sample was immersed in Ringer's solution before it was immersed in C, at a position 1,000 people from the surface of the sample.
a is 50 times or more higher than the secondary ion intensity in SIMS analysis. "None" means less than 50 times.
（以下、余白）
第 １
表
（発明の効果）
本発明のチタン合金は、チタン合金本来の優れた機械的
、化学的性質と前記のような生体活性をもつことにより
、人工骨その他の生体材料としてきわめて有用なもので
ある。(The following is a blank space) Table 1 (Effects of the Invention) The titanium alloy of the present invention has the excellent mechanical and chemical properties inherent to titanium alloys and the above-mentioned bioactivity, so it can be used as an artificial bone and other biomaterials. It is extremely useful.
第１図は、Ｔ１−５重量％Ｙ合金の窒素ガス中熱処理前
後の試料のＲＢ Ｓ （Ｒａｔｈｅｒｆｏｒｄ Ｂａｃ
ｋｓｃａｔｔｅｒ：ｎｇ ５ｐｅｃｔｒａ）解析結果で
ある。
第２図は、上記熱処理後の試料をリンゲル液に４週間浸
漬した後のＳＩ？ＩＳ分析結果である。
注、 ＊はレーザービーム加熱
第１表に示すとおり、Ｓｉまたは／およびＹを０．５〜
１０重量％含有するチタン合金には全てＣａおよびＰの
拡散が認められ、生体（骨）との親和性が大きいことが
明らかである。Figure 1 shows the RBS (Ratherford Bac
kscatter:ng5pectra) analysis results. FIG. 2 shows the SI? after the heat-treated sample was immersed in Ringer's solution for 4 weeks. These are the IS analysis results. Note: * indicates laser beam heating, as shown in Table 1, Si or/and Y is 0.5~
Diffusion of Ca and P was observed in all titanium alloys containing 10% by weight, and it is clear that they have a high affinity with living organisms (bones).
Claims (5)
含有することを特徴とする生体用チタン合金。(1) 0.5 to 10% by weight of Si and Y alone or in total
A titanium alloy for biological use characterized by containing.
項（１）の生体用チタン合金。(2) The titanium alloy for biological use according to claim (1), wherein Si and/or Y are concentrated in the surface layer.
含有するチタン合金を７５０℃からβ変態点までの温度
域で加熱することを特徴とする請求項（２）の生体用チ
タン合金の製造方法。(3) 0.5 to 10% by weight of Si and Y alone or in total
The method for producing a titanium alloy for biological use according to claim 2, characterized in that the titanium alloy contained therein is heated in a temperature range from 750° C. to a β transformation point.
含有するチタン合金の表面を高エネルギービームにより
７５０℃以上の温度域に加熱することを特徴とする請求
項（２）の生体用チタン合金の製造方法。(4) 0.5 to 10% by weight of Si and Y alone or in total
The method for producing a titanium alloy for biological use according to claim 2, characterized in that the surface of the titanium alloy containing the titanium alloy is heated to a temperature range of 750° C. or higher using a high-energy beam.
は（４）の生体用チタン合金の製造方法。(5) The method for producing a titanium alloy for biological use according to claim (3) or (4), wherein the heating is performed in a nitrogen gas atmosphere.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2225520A JPH04105659A (en) | 1990-08-27 | 1990-08-27 | Biological titanium alloy and manufacture thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2225520A JPH04105659A (en) | 1990-08-27 | 1990-08-27 | Biological titanium alloy and manufacture thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04105659A true JPH04105659A (en) | 1992-04-07 |
Family
ID=16830598
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2225520A Pending JPH04105659A (en) | 1990-08-27 | 1990-08-27 | Biological titanium alloy and manufacture thereof |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04105659A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0820737A2 (en) * | 1996-07-25 | 1998-01-28 | Injex Corporation | Artificial dental implant |
| EP0853938A1 (en) * | 1997-01-20 | 1998-07-22 | Injex Corporation | Prosthetic restoration and manufacturing method thereof |
| JP2002129265A (en) * | 2000-10-23 | 2002-05-09 | National Institute Of Advanced Industrial & Technology | Ti ALLOY FOR HUMAN BODY |
| EP1726669A1 (en) * | 2005-05-23 | 2006-11-29 | Deutsche Titan Gmbh | Titanium alloy |
| WO2007114218A1 (en) * | 2006-03-30 | 2007-10-11 | Kabushiki Kaisha Kobe Seiko Sho | Titanium alloy and engine exhaust pipes |
| JP2008506838A (en) * | 2004-07-13 | 2008-03-06 | エルケム アクシエセルスカプ | High strength, oxidation resistance, wear resistance titanium-silicon substrate alloy |
| JP2009097064A (en) * | 2007-10-19 | 2009-05-07 | Piolax Medical Device:Kk | Ti-BASE ALLOY |
-
1990
- 1990-08-27 JP JP2225520A patent/JPH04105659A/en active Pending
Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0820737A2 (en) * | 1996-07-25 | 1998-01-28 | Injex Corporation | Artificial dental implant |
| EP0820737A3 (en) * | 1996-07-25 | 1998-05-13 | Injex Corporation | Artificial dental implant |
| US5967782A (en) * | 1996-07-25 | 1999-10-19 | Injex Coporation | Artificial dental implant |
| EP0853938A1 (en) * | 1997-01-20 | 1998-07-22 | Injex Corporation | Prosthetic restoration and manufacturing method thereof |
| US5984683A (en) * | 1997-01-20 | 1999-11-16 | Injex Corporation | Prosthetic restoration and manufacturing method thereof |
| JP2002129265A (en) * | 2000-10-23 | 2002-05-09 | National Institute Of Advanced Industrial & Technology | Ti ALLOY FOR HUMAN BODY |
| JP4617451B2 (en) * | 2000-10-23 | 2011-01-26 | 独立行政法人産業技術総合研究所 | Ti alloy for living body |
| JP2008506838A (en) * | 2004-07-13 | 2008-03-06 | エルケム アクシエセルスカプ | High strength, oxidation resistance, wear resistance titanium-silicon substrate alloy |
| WO2006125776A1 (en) * | 2005-05-23 | 2006-11-30 | Thyssenkrupp Titanium Gmbh | Titanium alloy |
| EP1726669A1 (en) * | 2005-05-23 | 2006-11-29 | Deutsche Titan Gmbh | Titanium alloy |
| US8021605B2 (en) | 2005-05-23 | 2011-09-20 | Thyssfnkrupp VDM GmbH | Titanium alloy |
| WO2007114218A1 (en) * | 2006-03-30 | 2007-10-11 | Kabushiki Kaisha Kobe Seiko Sho | Titanium alloy and engine exhaust pipes |
| US20100173171A1 (en) * | 2006-03-30 | 2010-07-08 | Kabushiki Kaisha Kobe Seiko Sho (Kobe Steel, Ltd.) | Titanium alloy and engine exhaust pipes |
| US8431231B2 (en) * | 2006-03-30 | 2013-04-30 | Kobe Steel, Ltd. | Titanium Material and Exhaust Pipe for Engine |
| JP2009097064A (en) * | 2007-10-19 | 2009-05-07 | Piolax Medical Device:Kk | Ti-BASE ALLOY |
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