JPS60224727A - Ti-zr sintered alloy - Google Patents
Ti-zr sintered alloyInfo
- Publication number
- JPS60224727A JPS60224727A JP8111984A JP8111984A JPS60224727A JP S60224727 A JPS60224727 A JP S60224727A JP 8111984 A JP8111984 A JP 8111984A JP 8111984 A JP8111984 A JP 8111984A JP S60224727 A JPS60224727 A JP S60224727A
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- sintered
- sintered alloy
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Abstract
Description
【発明の詳細な説明】
〔発明の利用分野〕
本発明は機械、機器等の構成材料ならびに医療用材料と
しても好適なＴｉ−Ｚｒ系焼結合金に関し、さらに詳し
くは、焼結が容易で、機械的性質および耐食・耐熱性に
すぐれたＴｉ−Ｚｒ系焼結合金、ならびに生体えの適合
性のよい多孔性Ｔｉ−Ｚｒ系焼結合金に関する。[Detailed Description of the Invention] [Field of Application of the Invention] The present invention relates to a Ti-Zr based sintered alloy that is suitable as a constituent material for machines, equipment, etc. and as a medical material. The present invention relates to a Ti-Zr based sintered alloy with excellent mechanical properties and corrosion and heat resistance, and a porous Ti-Zr based sintered alloy with good compatibility with living organisms.
近年、軽くて強靭で、そのうえ耐熱性ならびに耐食性の
すぐれた特性をもっＴ１およびＴｉ合金は、たとえば、
航空機、車輌および深海艇用構造材料、または化学装置
、公害防止機器および海水利用装置用耐食材料、あるい
は電解用電極、通信機器、光学器機および医療用部材等
、多くの産業分野で利用されるようになり、現在さらに
ＴｉおよびＴ１合金の特性を生かすための新しい用途開
発が積極的に行なわれつつある。In recent years, T1 and Ti alloys, which are light and strong and have excellent heat resistance and corrosion resistance, have been developed, for example.
It is used in many industrial fields, such as structural materials for aircraft, vehicles, and deep-sea boats, corrosion-resistant materials for chemical equipment, pollution prevention equipment, and seawater utilization equipment, electrodes for electrolysis, communication equipment, optical equipment, and medical components. Currently, new applications are being actively developed to take advantage of the properties of Ti and T1 alloys.
しかしながら、ＴｉおよびＴ１合金は溶解ならびに鋳造
が容易でなく、特に小物の溶解、鋳造についてはむすか
しく、そのうえ成形加工が非常に困難であるという問題
点がある。この問題を解決するために、消耗電極式アー
ク溶解法、電子ビーム溶解法、あるいはプラズマ・ビー
ム溶解法等の特殊溶解法の開発、および加工分野におい
ては、恒温鍛造法、超塑性成形方法などの加工方法の改
善、ならびに材料の製造分野においては、粉末冶金法に
よるＴＩおよびＴｉ合金の製造方法の研究開発か活発に
行なわれている。このなかで、特に鋳塊製造工程を経な
いで、Ｔｉ粉末と母合金粉末あるいは添加合金粉末を混
合して、かなり自由にＴ１合金成分の調整ができ、目的
とする所望の性質をそなえたＴｉ合金を容易に製造する
ことか可能な粉末冶金法は、次世代技術として大いに注
目を集めている。However, Ti and T1 alloys are not easy to melt and cast, and it is particularly difficult to melt and cast small items, and furthermore, there are problems in that they are extremely difficult to mold. In order to solve this problem, special melting methods such as consumable electrode arc melting, electron beam melting, or plasma beam melting have been developed, and in the processing field, methods such as isothermal forging and superplastic forming have been developed. In the field of improving processing methods and producing materials, active research and development is being carried out on methods for producing TI and Ti alloys using powder metallurgy. Among these, it is possible to adjust the T1 alloy composition quite freely by mixing Ti powder and master alloy powder or additive alloy powder without going through the ingot manufacturing process, and it is possible to produce Ti that has the desired properties. Powder metallurgy, which allows easy production of alloys, is attracting a lot of attention as a next-generation technology.
本発明者らは先に、上述の粉末冶金法によって、特に生
体組織の接着性がよく、生体組織に近い弾性係数を有し
、生体えの適合性のすぐれた、純Ｔ１゜Ｔｉ−ＰＬ、
Ｔｉ−ＰｄおよびＴｉ −Ｍｏ系の生体修復用の多孔性
焼結体の発明（特公昭５７−１０１６３号）を完成させ
て特許出願をしている。しかし、上記の発明における純
ＴｉおよびＴ１合金粉末は、粉末の焼結性が弱く、した
がって焼結体を成形してもその機械的強度が低いために
、生体への適合性の点ではすぐれているものの、生体修
復用材料として用いる範囲が限定され、生体への適合性
が狭いという問題点かあった。The present inventors have previously developed pure T1°Ti-PL, which has particularly good adhesion to living tissue, has an elastic modulus close to that of living tissue, and is excellent in compatibility with living organisms, using the powder metallurgy method described above.
He has completed the invention of Ti-Pd and Ti-Mo based porous sintered bodies for biological repair (Japanese Patent Publication No. 10163/1983) and has filed a patent application. However, the pure Ti and T1 alloy powders in the above invention have poor sinterability, and therefore have low mechanical strength even when formed into a sintered body, so they are not excellent in compatibility with living organisms. However, there were problems in that the scope of its use as a material for biological repair was limited and its compatibility with living organisms was narrow.
本発明の目的は、上述した従来のＴ１およびＴｉ合金粉
末の焼結性が弱いという問題点を改善するために、Ｔｉ
またはＴ１合金粉末にＺｒ粉末を添加することにより、
焼結が極めて容易で、機械的性質および耐食・耐熱性の
すぐれた、新規なＴｉ−Ｚｒ系焼結合金、ならびに生体
への適合性のすぐれた多孔質Ｔｉ−Ｚｒ系焼結合金を提
供するにある。An object of the present invention is to improve the problem of the weak sinterability of the conventional T1 and Ti alloy powders mentioned above.
Or by adding Zr powder to T1 alloy powder,
To provide a novel Ti-Zr-based sintered alloy that is extremely easy to sinter and has excellent mechanical properties, corrosion resistance, and heat resistance, and a porous Ti-Zr-based sintered alloy that is highly compatible with living organisms. It is in.
要するに本発明は、公知である通常の方法によって製造
された、ＴｉおよびＴｉ合金系粉末にＺｒ粉末を添加し
て、成形ならびに焼結して、Ｚｒを５〜９０重量％（以
下単にチという）含有させることによって、Ｔ１合金の
もつ本来の特性を損なわずに、機械的強度、特に引張強
さおよび圧縮強度が大きく、耐食・耐熱性にすぐれたＴ
ｉ −Ｚｒ系焼結合金、ならびに生体への適合性のよい
多孔質Ｔｉ−Ｚｒ系燻焼合金ある。In short, the present invention adds Zr powder to Ti and Ti alloy powder produced by a known conventional method, and molds and sinters the powder to form a powder containing 5 to 90% by weight of Zr (hereinafter simply referred to as "Chi"). By including T1, it has high mechanical strength, especially tensile strength and compressive strength, and excellent corrosion and heat resistance without impairing the original properties of T1 alloy.
There are i-Zr based sintered alloys and porous Ti-Zr based sintered alloys which are highly compatible with living organisms.
本発明者らは、Ｔ１およびＴ１合金粉末にＺｒ粉末を添
加して焼結すると、（１）合金粉末間の拡散が促進され
、かつＴ１とＺｒの強固な固溶体が形成されること、（
２）およびＺｒ粉末は軟質の金属であるために、加圧成
形時にその成形体の密度が高くなり、したがって焼結体
の密度が上昇するという、二つの相剰効果とによって、
引張強さならびに圧縮強度の大きな、強固なＴｉ−Ｚｒ
系焼結合金が得られることを、研究の過程で知見し本発
明を完成するに至った。そして本発明者らは、Ｔｉまた
はＴ１合金粉末に４０〜７０％のＺｒ粉末を含有させた
焼結体の密度は、真密度に対して９５％以上のものが得
られ、これは溶解法によって製造されたＴ１合金に匹敵
する強度があることを実験の結果確認している。The present inventors found that when Zr powder is added to T1 and T1 alloy powder and sintered, (1) diffusion between the alloy powders is promoted and a strong solid solution of T1 and Zr is formed;
2) and Zr powder is a soft metal, so the density of the compact increases during pressure molding, and therefore the density of the sintered body increases.
Strong Ti-Zr with high tensile and compressive strength
In the course of research, it was discovered that a system sintered alloy could be obtained, and the present invention was completed. The present inventors have found that the density of a sintered body containing 40 to 70% Zr powder in Ti or T1 alloy powder is 95% or more of the true density, and this is due to the melting method. Experiments have confirmed that it has strength comparable to the manufactured T1 alloy.
本発明によるＴｉ−Ｚｒ系焼結合金の原料であるＴ１な
らびにＴｉ合金粉末は、ＴｉまたはＴ１合金から公知の
金属粉末製造方法、すなわち、還元法、噴霧法、電解法
、熱分解法、機械的粉砕法または合金化法あるいは蒸発
凝縮法によって製造されるものであってもよい。そして
、Ｔ１またはＴ１合金粉末の種類としては、純゛ｒ１金
属、およびＴｉのα合金系では、Ｔｉ−５Ａ／−２，５
Ｓｎ、 Ｔｉ−２，５Ｃｕ等、αリッチα−β合金系で
は、Ｔｉ−８Ａ／−Ｉ Ｍｏ−ＩＶ、Ｔｉ−１１ｓｎ−
２，２５ＡＩ！−５Ｚｒ−ＩＭｏ−０，２５Ｓｉ、Ｔｉ
Ｔｉ−６Ａｅ−２Ｓｎ−４Ｚｒ−２，Ｔｉ−６Ａ／−２
Ｓｎ−４Ｚｒ−２Ｍｏ、Ｔｌ −５Ａｌ −５Ｓｎ−２
Ｚｒ−２Ｍｏ−０，２５Ｓｉ、Ｔｉ−６Ａｊ？−２Ｎｂ
−ＩＴａ−Ｑ８Ｍｏ、Ｔｉ−６ＡＩ！−２Ｓｎ−１，５
Ｚｒ−ＩＭｏ−０，３５Ｂｉ−０，ｌＳｉ、 Ｔｉ−６
Ａ／−５Ｚｒ −０，５Ｍｏ−０，２３ｉ、Ｔｉ−５，
５Ａ／−３，５Ｓｎ−３Ｚｒ−Ｉ Ｎｂ −０，３Ｍｏ
−０，３Ｓｉ、およびＴｌ ５Ａ／−６Ｓｎ−２Ｚｒ
−ＩＭｏ−０，２５Ｓｉ等、Ｔ１のα−β合金系では、
ＴＩ−８Ｍｎ 、 Ｔｉ−３ＡＩ！−２，５Ｖ、Ｔｉ
−６Ａｌ−４Ｖ、Ｔｉ−６Ａ／−６Ｖ−２Ｓｎ、 Ｔｉ
−７Ａｊ？−４Ｍｏ、 Ｔｉ−６Ａ／−２Ｓｎ−４Ｚｒ
−６ＭＯ１Ｔｉ −６ＡＩ！−２Ｓｎ −２Ｚｒ−２Ｍ
ｏ−２Ｃｒ−０，２５Ｓｉ、Ｔｉ−１０Ｖ−２Ｆｅ−３
Ａ／、 Ｔｉ−４ＡＩ！−２Ｓｎ−４Ｍｏ−０，５Ｓｉ
、Ｔｉ−４ＡＩ！−４Ｓｎ−４Ｍｏ−Ｑ、５ＳｉＳ Ｔ
ｉ−５Ａ／−２Ｓｎ−２Ｚｒ−４Ｍ。T1 and Ti alloy powder, which are the raw materials for the Ti-Zr sintered alloy according to the present invention, can be produced using known metal powder manufacturing methods from Ti or T1 alloy, such as reduction method, spraying method, electrolytic method, pyrolysis method, mechanical method, etc. It may be manufactured by a crushing method, an alloying method, or an evaporation condensation method. As for the type of T1 or T1 alloy powder, pure r1 metal and Ti α alloy type include Ti-5A/-2,5
In α-rich α-β alloy systems such as Sn, Ti-2,5Cu, etc., Ti-8A/-I Mo-IV, Ti-11sn-
2,25 AI! -5Zr-IMo-0,25Si,Ti
Ti-6Ae-2Sn-4Zr-2, Ti-6A/-2
Sn-4Zr-2Mo, Tl-5Al-5Sn-2
Zr-2Mo-0,25Si, Ti-6Aj? -2Nb
-ITa-Q8Mo, Ti-6AI! -2Sn-1,5
Zr-IMo-0,35Bi-0,lSi, Ti-6
A/-5Zr-0,5Mo-0,23i, Ti-5,
5A/-3,5Sn-3Zr-I Nb-0,3Mo
-0,3Si, and Tl 5A/-6Sn-2Zr
-In T1 α-β alloy systems such as IMo-0,25Si,
TI-8Mn, Ti-3AI! -2,5V, Ti
-6Al-4V, Ti-6A/-6V-2Sn, Ti
-7Aj? -4Mo, Ti-6A/-2Sn-4Zr
-6MO1Ti -6AI! -2Sn -2Zr-2M
o-2Cr-0,25Si, Ti-10V-2Fe-3
A/, Ti-4AI! -2Sn-4Mo-0,5Si
, Ti-4AI! -4Sn-4Mo-Q, 5SiS T
i-5A/-2Sn-2Zr-4M.
−４Ｃｒ、 Ｔｉ−４，５Ａｊ？−５Ｍｏ−］、５Ｃｒ
、およびＴｉ−５Ａｚ’−２Ｃｒ−ＩＦｅ等、Ｔｉのβ
合金系では、Ｔｉ−１３Ｖ−］ｌＣｒ−３Ａ／、Ｔｉ−
８Ｍｏ−８Ｖ−２Ｆｅ−３Ａ／Ｓ Ｔｉ−３Ａ／−８Ｖ
−６Ｃｒ−４Ｍｏ−４Ｚｒ、Ｔｉ−１１，５Ｍｏ−６Ｚ
ｒ−４，５Ｓｎ、Ｔｉ−１１Ｖ−１１Ｚｒ−２Ｎ！−２
Ｓｎ、 Ｔｉ−１５Ｍｏ−５Ｚｒ、およびＴｉ−１５Ｍ
。-4Cr, Ti-4,5Aj? -5Mo-], 5Cr
, and Ti-5Az'-2Cr-IFe, etc., β of Ti
In the alloy system, Ti-13V-]lCr-3A/, Ti-
8Mo-8V-2Fe-3A/S Ti-3A/-8V
-6Cr-4Mo-4Zr, Ti-11,5Mo-6Z
r-4,5Sn, Ti-11V-11Zr-2N! -2
Sn, Ti-15Mo-5Zr, and Ti-15M
.
−５Ｚｒ−３Ｍ等をあげることができるが、必要によっ
ては上記以外の池の元素を含むＴ１合金粉末を使用して
もよい。-5Zr-3M etc., but if necessary, T1 alloy powder containing elements other than those mentioned above may be used.
また、Ｔ１または１１合金粉末に添加するＺｒ粉末もＴ
ｉの場合と同様に、純ＺｒまたはＺｒ合金から製造され
た粉末でよ＜、ＴｌまたはＺｒ以外の他の添加元素（Ｎ
ｉ、 Ｃｏ、 Ｐｄ、 Ｐｔ等）についても、その純金
属または合金から製造された粉末を使用することができ
る。In addition, Zr powder added to T1 or 11 alloy powder is also T.
As in the case of i, the powder manufactured from pure Zr or Zr alloy may be used, and other additive elements other than Tl or Zr (N
Powders made from pure metals or alloys thereof can also be used for the metals (I, Co, Pd, Pt, etc.).
第１図に、本発明によるＴ１粉末とＺｒ粉末を添加して
、成形し焼結した場合のＴｉ−Ｚｒ系焼結合金のＺｒ含
有量（重量％）と圧縮強度（ＭＰａ・・・メガパスカル
）の関係を示す。第２図は、第１図のＴ巨Ｚｒ系合金に
おけるＺｒ含有量（重量％）と引張強さくＭＰａ）との
関係を示すグラフである。Figure 1 shows the Zr content (wt%) and compressive strength (MPa...megapascal) of a Ti-Zr based sintered alloy that is formed and sintered by adding T1 powder and Zr powder according to the present invention. ). FIG. 2 is a graph showing the relationship between Zr content (weight %) and tensile strength (MPa) in the T giant Zr alloy shown in FIG.
第３図オヨび第４図は、Ｔｉ−６Ａ／−４ＶおよびＴｉ
−１５Ｍｏ−５Ｚｒ合金粉末に、それぞれＺｒ粉末を加
えて加圧成形し焼結した場合のＺｒ含有量（重量％）と
引張強さく ＭＰａ ）との関係を示す。Figure 3 and Figure 4 show Ti-6A/-4V and Ti
The relationship between Zr content (weight %) and tensile strength (MPa) when Zr powder is added to -15Mo-5Zr alloy powder, pressure molded, and sintered is shown.
図から明らかなごとく、本発明によるＴｉ −Ｚｒ系焼
結合金は、Ｚｒの含有量の増加とともに急速に機械的性
質の改善が見られ、添加の効果のある好ましい範囲は５
〜９０チである。そして、より顕著な圧縮強さならびに
引張強度を得るためのより好ましい範囲は３０〜７０チ
であり、機械的強度がピークに達する最も好ましいＺｒ
添加の範囲は４０〜６０チである。As is clear from the figure, the mechanical properties of the Ti-Zr sintered alloy according to the present invention rapidly improve as the Zr content increases, and the preferable range in which the addition is effective is 5.
~90chi. A more preferable range for obtaining more significant compressive strength and tensile strength is 30 to 70 inches, and the most preferable range is Zr at which the mechanical strength reaches its peak.
The addition range is 40 to 60 inches.
次に本発明に関する実施例を二三あげ、さらに詳細に説
明する。Next, a few examples relating to the present invention will be given and explained in more detail.
（実施例１）
純Ｔｉおよび純Ｚｒの球形粉を、公知の回転電極法（Ｒ
ＥＰ ） ニよッテ製造し、４２０〜５００μｍの大き
さの球形粉を篩にかけ選別した。このＴｉおよびＺ「の
球形粉は、■形混合器によって十分に混合するとともに
、添加するＺｒ球形粉は、焼結合金中のＺｒ含有量とし
て５〜９０％の範囲まで変化させた。(Example 1) Pure Ti and pure Zr spherical powders were prepared using a known rotating electrode method (R
EP) Niyotte was produced, and spherical powder with a size of 420 to 500 μm was sieved and sorted. The spherical powders of Ti and Z were thoroughly mixed in a ■-shaped mixer, and the Zr spherical powder added was varied within the range of 5 to 90% as the Zr content in the sintered alloy.
次に、この所定量のＺｒ球形粉を含有するＴｉ球形粉と
の混合物を、アルミナ製の型に入れて約ｉｏｏ。Next, a mixture of a predetermined amount of Zr spherical powder and Ti spherical powder was placed in an alumina mold and heated to about 100 ml.
℃の温度で、真空度約１Ｏ−５Ｔｏｒｒの高真空中で焼
結した。そしてアルミナの型から取り出した試料を、再
び約１４００°Ｃの温度で、３〜２４ｈｒ、高真空中で
焼結した。試料の圧縮試験は、インストロン（Ｉｎ５ｔ
ｒ−ｏｎ）型の万能試験機を用いて、クロスヘッドスピ
ードＱ、５ｍｍ／ｍｉｎで行なった。試験片の大きさは
、４φＸ８ｍｍである。この多孔性Ｔｉ−Ｚｒ焼結合金
の表面と断面は、走査型電子顕微鏡（ＳＥＭ）とＸ線マ
イクロアナライザ（ＥＰＭＡ）で観察し分析した。It was sintered at a temperature of 0.degree. C. in a high vacuum with a degree of vacuum of about 10@-5 Torr. Then, the sample taken out from the alumina mold was sintered again in a high vacuum at a temperature of about 1400°C for 3 to 24 hours. The compression test of the sample was performed using an Instron (In5t
The test was carried out using a universal testing machine (R-ON) type at a crosshead speed Q of 5 mm/min. The size of the test piece is 4φ×8mm. The surface and cross section of this porous Ti-Zr sintered alloy were observed and analyzed using a scanning electron microscope (SEM) and an X-ray microanalyzer (EPMA).
ポロシティ（多孔率）と空孔径は画像解析装置で測定し
た。Porosity and pore diameter were measured using an image analysis device.
第１図に、Ｚｒ含有量（重量％）と圧縮強度（ＭＰａ）
との関係を示す。本実施例による多孔性Ｔｉ−Ｚｒ合金
の圧縮強度は、Ｚ［の含有量の増加と共に急速に増加し
、そして５０〜６０％Ｚｒでピークを示し、圧縮強度は
最大となる。この組成での圧縮強度は、多孔性綿Ｔｉあ
るいは純Ｚｒ焼結合金の４〜８倍であり、人間の骨の２
倍以上の値を示す。また、Ｚｒを５０〜６０チ含有する
多孔性Ｔｉ −Ｚｒ焼結合金のヤング率は、圧縮テスト
の結果から４゜６〜７．４ＧＰａ（ギガパスカル）であ
った。そして圧縮破壊歪は７チ以上であった。Figure 1 shows the Zr content (weight%) and compressive strength (MPa).
Indicates the relationship between The compressive strength of the porous Ti-Zr alloy according to the present example increases rapidly with the increase of the Z[ content, and shows a peak at 50-60% Zr, and the compressive strength becomes maximum. The compressive strength of this composition is 4 to 8 times that of porous cotton Ti or pure Zr sintered alloy, and 2 times that of human bone.
Indicates a value that is more than double. The Young's modulus of the porous Ti-Zr sintered alloy containing 50 to 60 Zr was 4°6 to 7.4 GPa (gigapascal) from the results of a compression test. The compressive fracture strain was 7 inches or more.
第２図に、Ｚｒ含有量（重量％）と引張強さくＭＰａ）
。Figure 2 shows the Zr content (weight%) and tensile strength (MPa).
.
との関係を示す。第１図に示した圧縮強度の変化と同様
な傾向を示し、Ｚｒを５チ含有させても引張強さの上昇
が見られ、Ｚｒ含有量が３０％付近を超えると顕著に引
張強さが上昇し、６０％付近でピークに達する。Indicates the relationship between The same trend as the change in compressive strength shown in Fig. 1 was observed, and an increase in tensile strength was observed even when 5% of Zr was added, and when the Zr content exceeded around 30%, the tensile strength significantly decreased. It increases and reaches its peak at around 60%.
第５図（ａ）は、Ｚｒ含有量が５０％のときの多孔性Ｔ
ｉ −Ｚｒ焼結合金の表面状態を示す顕微鏡写真であり
、第５図（ｂｌは、第５図ｆａ）におけるＴｉとＺｒの
結合状態を示すスケッチ図である。第６図（ａｌは第５
図＋ａ）の多孔性Ｔｉ −Ｚｒ焼結合金の断面状態を示
す顕微鏡写真であり、第６図（ｂｌは第６図（ａ）にお
けるＴｉとＺｒの結合状態を示すスケッチ図である。図
から明らかなごと（、Ｔｉ粒子とＺｒ粒子は拡散して固
溶体を形成し、強固に結合されており、その結果５０〜
６０９６ Ｚｒを含有する多孔性Ｔｉ −Ｚｒ焼結合金
の圧縮強度が最大になることがわかる。一方、Ｔ１とＴ
ｌ。Figure 5(a) shows the porous T when the Zr content is 50%.
It is a micrograph showing the surface state of the i-Zr sintered alloy, and is a sketch diagram showing the bonding state of Ti and Zr in FIG. 5 (bl is FIG. 5 fa). Figure 6 (al is the fifth
This is a micrograph showing the cross-sectional state of the porous Ti-Zr sintered alloy in Figure +a), and Figure 6 (bl is a sketch diagram showing the bonding state of Ti and Zr in Figure 6(a). From the figure As is clear (the Ti particles and Zr particles diffuse to form a solid solution and are strongly bonded, as a result, 50~
It can be seen that the compressive strength of the porous Ti-Zr sintered alloy containing 6096 Zr is maximized. On the other hand, T1 and T
l.
ＺｒとＺｒとの粒子間の結合は比較的ゆるやかである。The bond between Zr and Zr particles is relatively loose.
５０％Ｚｒを含有する多孔性Ｔｉ −Ｚｒ焼結合金の断
面の画像解析によれば、多孔率は２８〜３８チで、空孔
径は１６７〜２０４μｍであった。このような大きな空
孔中には骨が非常によく成長することが期待され、Ｚ「
が５０〜６０チ含有するＴｉ −Ｚｒ焼結合金の機械的
性質ならびに多孔空孔構造から考えて、骨とインブラン
トの固定に対して非常に好適であることを示している。According to image analysis of a cross section of a porous Ti-Zr sintered alloy containing 50% Zr, the porosity was 28 to 38 cm, and the pore diameter was 167 to 204 μm. It is expected that bones will grow very well in such large pores, and Z'
Considering the mechanical properties and porous structure of the Ti--Zr sintered alloy containing 50 to 60 Ti, it is shown to be very suitable for fixing bone and implants.
（実施例２）
Ｔｉ−６Ａ／−４Ｖ合金の粉末を回転電極法によって製
造し、−２００メツシユの大きさの粉末を篩にかけ選別
した。それに、−２００メツシユのＺｒ粉末を所定量加
え、これを■型ミキサーに入れて十分に混合した。この
Ｔｉ −６ＡＩ！−４Ｖ合金粉末とＺｒ粉末の混合粉を
、金型に入れて５ｔ／ｃｉの圧力で加圧成形してとり出
し、約１４００℃の温度で、真空度１Ｏ−５Ｔｏ汀で、
１時間焼結した。第３図に、Ｚｒ含有量（重量％）と引
張強さくＭＰａ）の関係を示す。図から明らかなごとく
、Ｚｒ含有量の増加と共に引張強さは急激に上昇し、５
〜９０％Ｚｒ含有量の範囲においてＺｒ添加の効果が現
れ、Ｚ［含有量が２０〜７０％の範囲で、母合金である
Ｔｉ−６ｆｉＪ！−４Ｖ焼結合金の約３倍以上の引張強
さを示し、４０〜６０チでピークに達し、９００ ＭＰ
ａ以上の引張強さが得られた。そしてＺ［含有量４０〜
７０チのＴｉ−Ｚｒ焼結合金の密度は、真密度に対して
９５チ以上のものが得られ、これは溶解法によって作ら
れたＴｉ−Ｚｒ合金に匹敵する引張強さのあることを発
明者らは確認している。その理由として、Ｔｉ −Ｚｒ
系焼結合金の密度は、Ｚｒを添加することによって拡散
が促進されること、あるいはＺｒは軟かいため、成形時
に密度が上昇し、したがって焼結合金の密度が高くなり
、このために焼結合金の圧縮強度が著しく上昇するもの
と考えられる。また、Ｔ１−Ｚｒ系焼結合金の引張強さ
＋よ。(Example 2) Ti-6A/-4V alloy powder was produced by a rotating electrode method, and the -200 mesh size powder was sieved and sorted. A predetermined amount of -200 mesh Zr powder was added thereto, and this was placed in a type mixer and thoroughly mixed. This Ti-6AI! A mixed powder of -4V alloy powder and Zr powder was put into a mold, pressure-molded at a pressure of 5t/ci and taken out, and at a temperature of about 1400℃ and a vacuum degree of 1O-5To.
It was sintered for 1 hour. FIG. 3 shows the relationship between Zr content (weight %) and tensile strength (MPa). As is clear from the figure, the tensile strength increases rapidly as the Zr content increases, and
The effect of Zr addition appears in the range of ~90% Zr content, and the mother alloy Ti-6fiJ! It exhibits a tensile strength that is about 3 times more than -4V sintered alloy, reaching a peak at 40 to 60 inches, and 900 MP
A tensile strength of a or more was obtained. and Z [content 40~
The inventor discovered that the density of a Ti-Zr sintered alloy of 70 cm is higher than the true density of 95 cm, and that this has a tensile strength comparable to that of a Ti-Zr alloy made by the melting method. They have confirmed that. The reason is that Ti-Zr
The density of the sintered alloy is determined by the fact that diffusion is promoted by the addition of Zr, or because Zr is soft, the density increases during molding, and the density of the sintered alloy increases. It is thought that the compressive strength of gold increases significantly. Also, the tensile strength of T1-Zr based sintered alloy is +.
焼結合金の密度が上昇することと、Ｚｒの固溶効果とに
よって顕著に上昇するものと考えられる。It is thought that this remarkable increase is due to the increase in the density of the sintered alloy and the solid solution effect of Zr.
（実施例３）
実施例２と全く同様な条件で、Ｔｉ−１５Ｍｏ−５Ｚｒ
合金粉末を製造し、これにＺｒ粉末を添加混合、成形し
て焼結した。第４図に、Ｚｒ含有量（重量％）と引張強
さくＭＰａ）の関係を示す。図から明らかなどと＜、Ｚ
ｒ含有量約５逅ですでに母合金焼結体（Ｔｉ−１５Ｍｏ
−５Ｚｒ） （７）引張強さの２倍以上に達し、Ｚｒ含
有量が２０〜７０％の範囲では、母合金焼結体の引張強
さに対して、実に４倍以上の値を示し、４０〜６０％Ｚ
ｒでピークに達し、９００ Ｍ Ｐａ以上の引張強さを
示している。そして、Ｚｒ含有量が４０〜７０％の時に
、溶解法によって得られるＴｉ −１５Ｍｏ−５Ｚｒ合
金の真密度に対して９５％以上の密度の焼結合金が得ら
れたことは、実施例２におけるＴｉ−６Ａ／−４Ｖ−Ｚ
ｒ焼結合金の場合と全く同様であった。(Example 3) Under exactly the same conditions as Example 2, Ti-15Mo-5Zr
An alloy powder was produced, Zr powder was added thereto, mixed, molded, and sintered. FIG. 4 shows the relationship between Zr content (weight %) and tensile strength (MPa). It is clear from the figure that <, Z
The master alloy sintered body (Ti-15Mo
-5Zr) (7) It reaches more than twice the tensile strength, and in the range of Zr content from 20 to 70%, it shows a value that is actually more than four times the tensile strength of the master alloy sintered body, 40-60%Z
The tensile strength reaches a peak at r, and shows a tensile strength of 900 MPa or more. The fact that a sintered alloy with a density of 95% or more of the true density of the Ti-15Mo-5Zr alloy obtained by the melting method was obtained when the Zr content was 40 to 70% was confirmed in Example 2. Ti-6A/-4V-Z
It was exactly the same as the case of r sintered alloy.
以上詳細に説明したごとく本発明は、ＴＩおよびＴｉ合
金粉末にＺｒ粉末を添加するだけで、成形・−焼結が容
易となり、かつＴｉおよびＴｉ合金のもつ、軽くて強靭
で耐食・耐熱性がよいという特性を劣化させないで、機
械的性質のすぐれたＴｉ−Ｚｒ系焼結合金を容易に製造
することができるから、ジェットエンジン等の航空機用
構造部品、または各種反応器、熱交換器、耐酸・耐熱ポ
ンプおよびノクルブ等の化学装置用部材、あるいは精密
機械等に用いられる小物部品、海水利用産業用耐食部材
、電解用電極材などへの用途が期待される。As explained in detail above, the present invention facilitates molding and sintering by simply adding Zr powder to Ti and Ti alloy powders, and has the light, strong, corrosion and heat resistance properties of Ti and Ti alloys. Because Ti-Zr sintered alloys with excellent mechanical properties can be easily produced without deteriorating their properties, they can be used for structural parts for aircraft such as jet engines, various reactors, heat exchangers, and acid-resistant・It is expected to be used as parts for chemical equipment such as heat-resistant pumps and noclubs, small parts used in precision machinery, corrosion-resistant parts for industries that use seawater, and electrode materials for electrolysis.
また、生体に対して毒性がな（、組織接着性がよく、そ
のうえ機械的性質にすぐれ、生体組織に近い弾性係数を
もつ、生体への適合性のよい多孔性Ｔｉ −Ｚｒ系焼結
合金をも製造することができるので、歯科用または整形
外科用生体修復材料等としても利用することができ、実
用上の価値は大きい。In addition, we have developed a porous Ti-Zr-based sintered alloy that is non-toxic to living organisms (has good tissue adhesion, excellent mechanical properties, and has an elastic modulus close to that of living tissues) and is highly compatible with living organisms. Since it can also be produced as a biorepair material for dental or orthopedic surgery, it has great practical value.
第１図は、本発明によるＴｉ粉末にＺｒ粉末を添加し、
成形・焼結した場合のＴｉ−Ｚｒ系焼結合金のＺｒ含有
量と圧縮強度の関係を示すグラフで、第２図は第１図の
Ｔｉ −Ｚｒ系焼結合金のＺｒ含有量と引張強さの関係
を示すグラフである。第３図は、本発明によるＴｉ−６
Ａ／−４Ｖ合金粉末にＺｒ粉末を添加して加圧成形し焼
結したＴｉ −Ｚｒ系焼結合金のＺｒ含有量と引張強さ
の関係を示すグラフであり、第４図は、Ｔｉ −１５Ｍ
ｏ−５Ｚｒ合金粉末にＺｒ粉末を添加して加圧成形し焼
結したＴｉ −Ｚｒ系焼結合金のＺｒ含有量と引張強さ
の関係を示すグラフである。第５図（ａｌは本発明の実
施例１におけるＺｒ含有量か５０チの時のＴｉ −Ｚｒ
系焼結合金の表面状態を示す顕微鏡写真で、第５図（ｂ
ｌは第５図（ａｌにおけるＴｉとＺｒの結合状態を示す
スケッチ図である。第６図（ａｌは第５図（ａ）のＴｉ
−Ｚｒ系焼結合金の断面状態を示す顕微鏡写真であり、
第６図ｆｂ）は第６図（ａｌにおけるＴｉとＺ、ｒの結
合状態を示すスケッチ図である。
代理人弁理士 中村純之助
５ｊＰ１図
Ｚｒ含；ｆ４童（＊１ｚ）
１Ｆ２図
Ｚｒ含有量 （＊ｔ％）
７３図
Ｚｒ含有量 （重量２）
ｔ４図
Ｚｒ含看童 （重ＩＸ）
（α）２．５．
０．５ｍｍ
（ｂ）
’Ｑ、５ｍｍ
手続補正書（麓）
特許庁長官 志 賀 学 殿
１、事件の表示 昭和５９年特許願第８１１１９号２、
発明の名称 Ｔｉ−Ｚｒ系焼結合金３、補正をする者
事件との関係 特許出願人
氏 名 川 原 春 幸
氏 名 三 浦 維 四
４、代理人
氏名 （６８３５） 弁理士 中村 純之助５、補正命
令の日付 昭和５９年７月３１日補正の内容
１、明細書の図面の簡単な説明の欄を次のとおりに訂正
する。
（１） 明細書の第１６頁第９行〜第１０行の［顕微鏡
写真」の後にｒ （Ｘ３４）Ｊを挿入する。
（２） 明細書の第１６頁第１３行の「顕微鏡写真」の
後にｒ （Ｘ３４）Ｊを挿入する。
（３） 明細書の第１６頁第９行の「表面状態」を「表
面組織」と訂正する。
（４） 明細書の第１６頁第１２行の「断面状態」を「
断面組織」と訂正する。FIG. 1 shows that Zr powder is added to Ti powder according to the present invention,
This is a graph showing the relationship between the Zr content and the compressive strength of the Ti-Zr sintered alloy when molded and sintered. Figure 2 shows the relationship between the Zr content and the tensile strength of the Ti-Zr sintered alloy shown in Figure 1. It is a graph showing the relationship between FIG. 3 shows a Ti-6 according to the present invention.
FIG. 4 is a graph showing the relationship between Zr content and tensile strength of a Ti--Zr based sintered alloy obtained by adding Zr powder to A/-4V alloy powder, press-forming and sintering; FIG. 15M
1 is a graph showing the relationship between Zr content and tensile strength of a Ti--Zr-based sintered alloy obtained by adding Zr powder to o-5Zr alloy powder, press-forming, and sintering. FIG. 5 (Al is Ti-Zr when the Zr content in Example 1 of the present invention is 50
Figure 5 (b) is a micrograph showing the surface condition of the sintered alloy.
5(a) is a sketch diagram showing the bonding state of Ti and Zr in FIG. 5(a).
- A micrograph showing a cross-sectional state of a Zr-based sintered alloy,
Figure 6 fb) is a sketch diagram showing the bonding state of Ti, Z, and r in Figure 6 (al).Representative Patent Attorney Junnosuke Nakamura 5jP1 Figure Zr included; f4 Child (*1z) 1F2 Figure Zr content ( *t%) Figure 73 Zr content (weight 2) Figure 73 Zr content (weight 2) Figure 4 Zr content (heavy IX) (α) 2.5. 0.5mm (b) 'Q, 5mm Procedural amendment (foot) Director General of the Patent Office Manabu Ka 1, Indication of the case 1981 Patent Application No. 81119 2,
Title of the invention Ti-Zr based sintered alloy 3, Relationship with the case of the person making the amendment Patent applicant name Haruyuki Kawahara Name Tsuyoshi Miura 44, name of agent (6835) Patent attorney Junnosuke Nakamura 5, amendment Date of order: July 31, 1980 Contents of amendment 1: The column of the brief explanation of the drawings in the specification is corrected as follows. (1) Insert r (X34)J after "Microphotograph" on page 16, lines 9 to 10 of the specification. (2) Insert r (X34)J after "micrograph" on page 16, line 13 of the specification. (3) "Surface condition" on page 16, line 9 of the specification is corrected to "surface texture." (4) Change “Cross-sectional condition” on page 16, line 12 of the specification to “
"Cross-sectional tissue" is corrected.
Claims (1)
結したＴｉ−Ｚｒ系焼結合金であって。 Ｚｒを５〜９０重量％ 含有し、残部か不可避的に混入する不純物およびＴｉか
らなることを特徴とする、機械的性質、耐食性、耐熱性
、または生体への適合性のすぐれたＴ１−Ｚｒ系焼結合
金。 ２、Ｔ１またはＴ１合金粉末に、ＺｒまたはＺｒ合金粉
末を混合して、成形ならびに焼結したＴｉ −Ｚｒ系焼
結合金であって、重量％で。 Ｚｒ ５〜９０％。 および Ａ／１６％以下。 Ｖ ２６チ以下。 ５ｎ２２％以下。 Ｍｎ １６％以下。 ＭＯ３０％以下。 Ｔａ １０チ以下。 Ｐｄ ３０チ以下。 Ｎｉ ２チ以下。 Ｓｉ １チ以下。 Ｃｕ ５％以下。 Ｎｂ ２％以下。 Ｆｅ ３０％以下。 Ｃｒ ３０％以下。 Ｃｏ ９チ以下。 Ｐｔ ２０チ以下。 のうちから選ばれる１種以上の元素を含有し、残部が不
可避的に混入する不純物およびＴｉからなることを特徴
とする、機械的性質、耐食性、耐熱性、または生体への
適合性のすぐれたＴｉ−Ｚｒ系焼結合金。 ３、Ｚｒ含有量が３０〜７０重量％であることを特徴と
する特許請求の範囲第１項および第２項いずれか記載の
Ｔｉ−Ｚｒ系焼結合金。 ４、Ｚｒ含有量が４０〜６０重量％であることを特徴と
する特許請求の範囲第１項および第２項記載のＴｉ−Ｚ
ｒ系焼結合金。[Claims] 1. A Ti-Zr based sintered alloy obtained by mixing T1 powder with Zr powder, forming and sintering the mixture. A T1-Zr system with excellent mechanical properties, corrosion resistance, heat resistance, and compatibility with living organisms, characterized by containing 5 to 90% by weight of Zr, with the remainder consisting of unavoidably mixed impurities and Ti. Sintered alloy. 2. A Ti-Zr based sintered alloy formed by mixing T1 or T1 alloy powder with Zr or Zr alloy powder, molding and sintering, expressed as % by weight. Zr 5-90%. and A/16% or less. V 26 inches or less. 5n22% or less. Mn 16% or less. MO30% or less. Ta less than 10 inches. Pd 30 inches or less. Ni 2 or less. Si less than 1 inch. Cu 5% or less. Nb 2% or less. Fe 30% or less. Cr 30% or less. Co 9 inches or less. Pt 20 inches or less. Contains one or more elements selected from the following, with the remainder consisting of unavoidable impurities and Ti, and has excellent mechanical properties, corrosion resistance, heat resistance, or compatibility with living organisms. Ti-Zr based sintered alloy. 3. A Ti-Zr based sintered alloy according to any one of claims 1 and 2, characterized in that the Zr content is 30 to 70% by weight. 4. Ti-Z according to claims 1 and 2, characterized in that the Zr content is 40 to 60% by weight
r-based sintered alloy.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8111984A JPS60224727A (en) | 1984-04-24 | 1984-04-24 | Ti-zr sintered alloy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP8111984A JPS60224727A (en) | 1984-04-24 | 1984-04-24 | Ti-zr sintered alloy |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPS60224727A true JPS60224727A (en) | 1985-11-09 |
Family
ID=13737490
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP8111984A Pending JPS60224727A (en) | 1984-04-24 | 1984-04-24 | Ti-zr sintered alloy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPS60224727A (en) |
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| CN113249615A (en) * | 2021-06-11 | 2021-08-13 | 湖南大学 | Biomedical iron-containing refractory titanium-niobium alloy and preparation method thereof |
| CN115948676A (en) * | 2022-12-13 | 2023-04-11 | 西安九洲生物材料有限公司 | Self-adaptive implant for bone insufficiency, titanium-zirconium-iron alloy and preparation method thereof |
-
1984
- 1984-04-24 JP JP8111984A patent/JPS60224727A/en active Pending
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| US5019337A (en) * | 1990-02-16 | 1991-05-28 | American Dental Association Health Foundation | Ductile intermetallic compounds for dental applications |
| JPH051342A (en) * | 1991-06-24 | 1993-01-08 | Sumitomo Heavy Ind Ltd | Production of titanium alloy and sintered titanium alloy |
| KR100211097B1 (en) * | 1997-04-22 | 1999-07-15 | 박원훈 | Ti-based implant alloy with good biocompatibility |
| JPH11229058A (en) * | 1998-02-13 | 1999-08-24 | Sumitomo Metal Ind Ltd | Titanium alloy excellent in oxidation resistance and cold workability |
| JP2005048235A (en) * | 2003-07-28 | 2005-02-24 | National Institute For Materials Science | beta TYPE TITANIUM ALLOY FOR LIVING BODY |
| US20120135265A1 (en) * | 2009-07-07 | 2012-05-31 | Eurocoating S.P.A | Laser process for producing metallic objects, and object obtained therefrom |
| JP2011021257A (en) * | 2009-07-16 | 2011-02-03 | Yonosuke Murayama | Low-elastic titanium alloy |
| CN104762526A (en) * | 2015-03-26 | 2015-07-08 | 河北工程大学 | Low-cost and high-strength Ti-Zr-Al-F2 alloy |
| US10807164B2 (en) | 2015-11-02 | 2020-10-20 | Hi-Lex Corporation | Nitrogen solid solution titanium sintered compact and method for producing same |
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| US11802324B2 (en) | 2015-11-02 | 2023-10-31 | Hi-Lex Corporation | Nitrogen solid solution titanium sintered compact and method for producing same |
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| CN107190177A (en) * | 2017-05-05 | 2017-09-22 | 燕山大学 | A kind of zirconium Ti-Ni alloy and preparation method thereof |
| CN107099697A (en) * | 2017-05-22 | 2017-08-29 | 暨南大学 | A kind of Ni-free super elastic Ti-based shape memory alloy and its preparation method and application |
| CN108380890A (en) * | 2018-01-30 | 2018-08-10 | 中南大学 | A kind of low-elasticity-modulus titanium zirconium dentistry implant material and preparation method thereof |
| CN108103354A (en) * | 2018-02-02 | 2018-06-01 | 贾红琴 | A kind of medical titanium alloy bone implant and preparation method thereof |
| CN109097623A (en) * | 2018-08-03 | 2018-12-28 | 中鼎特金秦皇岛科技股份有限公司 | A kind of erosion resistant titanium alloy and preparation method thereof |
| CN112481521B (en) * | 2020-04-13 | 2021-08-31 | 国核宝钛锆业股份公司 | High-strength zirconium alloy and preparation method of bar for high-strength zirconium alloy fastener |
| CN112481521A (en) * | 2020-04-13 | 2021-03-12 | 国核锆铪理化检测有限公司 | High-strength zirconium alloy and preparation method of bar for high-strength zirconium alloy fastener |
| CN113249615A (en) * | 2021-06-11 | 2021-08-13 | 湖南大学 | Biomedical iron-containing refractory titanium-niobium alloy and preparation method thereof |
| CN115948676A (en) * | 2022-12-13 | 2023-04-11 | 西安九洲生物材料有限公司 | Self-adaptive implant for bone insufficiency, titanium-zirconium-iron alloy and preparation method thereof |
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