JP4974834B2 - Brazing material - Google Patents
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- JP4974834B2 JP4974834B2 JP2007261376A JP2007261376A JP4974834B2 JP 4974834 B2 JP4974834 B2 JP 4974834B2 JP 2007261376 A JP2007261376 A JP 2007261376A JP 2007261376 A JP2007261376 A JP 2007261376A JP 4974834 B2 JP4974834 B2 JP 4974834B2
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- 239000000463 material Substances 0.000 title claims description 63
- 238000005219 brazing Methods 0.000 title claims description 50
- 238000002844 melting Methods 0.000 claims description 21
- 230000008018 melting Effects 0.000 claims description 21
- 239000011888 foil Substances 0.000 claims description 18
- 239000000843 powder Substances 0.000 claims description 17
- 229910052719 titanium Inorganic materials 0.000 claims description 17
- 229910052726 zirconium Inorganic materials 0.000 claims description 15
- 238000005304 joining Methods 0.000 claims description 11
- 229910001069 Ti alloy Inorganic materials 0.000 claims description 5
- 239000012535 impurity Substances 0.000 claims description 4
- 239000010936 titanium Substances 0.000 description 38
- 229910052751 metal Inorganic materials 0.000 description 20
- 239000002184 metal Substances 0.000 description 20
- 230000007797 corrosion Effects 0.000 description 19
- 238000005260 corrosion Methods 0.000 description 19
- 239000000203 mixture Substances 0.000 description 11
- 238000000034 method Methods 0.000 description 8
- 230000009466 transformation Effects 0.000 description 8
- 239000000919 ceramic Substances 0.000 description 7
- 229910045601 alloy Inorganic materials 0.000 description 6
- 239000000956 alloy Substances 0.000 description 6
- 230000000052 comparative effect Effects 0.000 description 6
- 238000010438 heat treatment Methods 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 150000002739 metals Chemical class 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 2
- 229910052581 Si3N4 Inorganic materials 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000011230 binding agent Substances 0.000 description 2
- 230000005496 eutectics Effects 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 238000007650 screen-printing Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- HQVNEWCFYHHQES-UHFFFAOYSA-N silicon nitride Chemical compound N12[Si]34N5[Si]62N3[Si]51N64 HQVNEWCFYHHQES-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 229910001374 Invar Inorganic materials 0.000 description 1
- NRTOMJZYCJJWKI-UHFFFAOYSA-N Titanium nitride Chemical compound [Ti]#N NRTOMJZYCJJWKI-UHFFFAOYSA-N 0.000 description 1
- 229910004696 Ti—Cu—Ni Inorganic materials 0.000 description 1
- 229910001315 Tool steel Inorganic materials 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 238000005280 amorphization Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 229910002056 binary alloy Inorganic materials 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000005548 dental material Substances 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000004455 differential thermal analysis Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009689 gas atomisation Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000007943 implant Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- 238000005551 mechanical alloying Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011224 oxide ceramic Substances 0.000 description 1
- 229910052574 oxide ceramic Inorganic materials 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000010791 quenching Methods 0.000 description 1
- 230000000171 quenching effect Effects 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- HBMJWWWQQXIZIP-UHFFFAOYSA-N silicon carbide Chemical compound [Si+]#[C-] HBMJWWWQQXIZIP-UHFFFAOYSA-N 0.000 description 1
- 229910010271 silicon carbide Inorganic materials 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009864 tensile test Methods 0.000 description 1
- 238000002076 thermal analysis method Methods 0.000 description 1
- PMTRSEDNJGMXLN-UHFFFAOYSA-N titanium zirconium Chemical compound [Ti].[Zr] PMTRSEDNJGMXLN-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Description
本発明は、ろう付け材料に関する。 The present invention relates to a brazing material.
セラミックス同士やセラミックスと金属との接合を行なう際に、いわゆる活性金属法が採用されている。活性金属法は、ＴｉやＺｒの活性金属粉末とＣｕやＮｉなどの比較的低融点の残部組成金属粉末とを混合して接合用ペーストとし、これを被接合部材の接合面に塗布して加熱し接合する方法である。しかし、この方法は、加熱前の接合用ペーストが活性金属粉末と残部組成金属粉末との単なる混合体であり、接合時の合金化が十分に進みにくく、強度的に不十分となりやすい問題がある。 A so-called active metal method is employed when joining ceramics or ceramics to a metal. In the active metal method, an active metal powder such as Ti or Zr and a residual metal powder having a relatively low melting point such as Cu or Ni are mixed to form a bonding paste, which is applied to the bonding surface of the member to be bonded and heated. And joining. However, this method has a problem that the bonding paste before heating is simply a mixture of the active metal powder and the remaining composition metal powder, and the alloying at the time of bonding is not sufficiently advanced, and the strength tends to be insufficient. .
また、ＴｉやＴｉ合金の接合にはＴｉ−Ｃｕ−Ｎｉの積層箔のろう材が使用されている。このろう材は、接合強度が高く、また耐食性にも優れているが、融点が９３０℃程度と高く、かつ単金属の箔を積層したタイプのろう材であるため、ろう材の加工性が極めて悪い欠点がある。また、ＴｉやＴｉ合金を被接合部材として（以下、Ｔｉ系被接合部材という）、その接合に使用する場合、Ｔｉのβ変態点が８８３℃であることから、上記ろう材では接合温度が該β変態点を超え、Ｔｉ系被接合部材の組織が変態により粗大化しやすく強度低下を招く問題がある。 In addition, a brazing material of a laminated foil of Ti—Cu—Ni is used for joining Ti and Ti alloys. This brazing material has high bonding strength and excellent corrosion resistance, but has a melting point as high as about 930 ° C. and is a brazing material in which single metal foils are laminated. There are bad drawbacks. Further, when Ti or a Ti alloy is used as a member to be joined (hereinafter referred to as a Ti-based member to be joined), and the β transformation point of Ti is 883 ° C., the brazing material has a joining temperature of There is a problem that the β transformation point is exceeded, and the structure of the Ti-based member is likely to be coarsened by transformation, leading to a decrease in strength.
そこで、Ｔｉを含有するろう材の加工性を改善するために、配合した合金原料を溶湯から急冷し、非晶質薄帯としたろう材が、例えば特許文献１，２に開示されている。また、特許文献３には、ＴｉとＺｒとからなる主成分金属に、副成分金属としてＣｕ及びＮｉの少なくともいずれかを含有させたろう材が開示されている。Ｎｉの添加により、ろう材の耐食性と強度とが双方とも向上する利点がある。 In order to improve the workability of the brazing material containing Ti, for example, Patent Documents 1 and 2 disclose brazing materials in which a blended alloy raw material is quenched from a molten metal to form an amorphous ribbon. Patent Document 3 discloses a brazing material in which a main component metal made of Ti and Zr contains at least one of Cu and Ni as a subcomponent metal. The addition of Ni has the advantage that both the corrosion resistance and strength of the brazing material are improved.
しかしながら、近年、金属成分としてのＮｉは生体への影響懸念から次第に敬遠されるようになってきており、Ｎｉを含有せずとも耐食性と強度とが双方とも優れた高性能のろう付け材料が望まれている。特に、Ｔｉ系被接合部材がめがねフレームなど人体に直接接触した状態で使用されるものについては、Ｎｉフリーな高強度及び高耐食性のろう付け材料の開発が切望されている。 However, in recent years, Ni as a metal component has gradually been shunned due to concerns about impact on the living body, and a high performance brazing material excellent in both corrosion resistance and strength is desired without containing Ni. It is rare. In particular, for materials used in a state where the Ti-based member is in direct contact with the human body, such as a spectacle frame, the development of a brazing material having high strength and high corrosion resistance that is Ni-free is eagerly desired.
本発明の課題は、Ｔｉ及びＺｒを含有したろう付け材料において、Ｎｉを含有せずとも強度と耐食性との双方に優れ、生体適合性の良好なろう付け材料を提供することにある。 An object of the present invention is to provide a brazing material containing Ti and Zr, which is excellent in both strength and corrosion resistance and has good biocompatibility without containing Ni.
上記の課題を解決するために、本発明のろう付け材料は、
Ｃｕ：１０質量％以上３０質量％以下、
Ｃｏ：５質量％以上２０質量％以下、をそれぞれ含有し、
残部が、３０質量％以上のＴｉ、２０質量％以上のＺｒ及び不可避不純物からなり、Ｔｉ＋とＺｒとの合計を６０質量％以上８０質量％以下となしたことを特徴とする。
In order to solve the above problems, the brazing material of the present invention comprises:
Cu: 10% by mass or more and 30% by mass or less,
Co: 5% by mass or more and 20% by mass or less, respectively,
The balance is 30% by mass or more of Ti, 20% by mass or more of Zr and inevitable impurities, and the total of Ti + and Zr is 60% by mass or more and 80% by mass or less.
本発明のろう付け材料は、上記組成を採用することにより、比較的低融点でセラミックスや、特にＴｉ系被接合部材との濡れ性に優れ、かつ高強度であり、また、耐食性（特に塩化物中での耐食性）に優れる。そして、Ｎｉが不可避不純物レベルに抑えられ、実質的に含有されないので、歯科用材料やインプラント材など、生体用材料としての適合性も良好である。生体用以外にも、例えば海水との接触環境下で使用される部材（例えば熱交換器等）の接合にも好適に採用できる。Ｎｉ含有量は、１００ｐｐｍ未満であることが望ましい。 By adopting the above composition, the brazing material of the present invention has a relatively low melting point, excellent wettability with ceramics, particularly Ti-based bonded members, and high strength, and also has corrosion resistance (especially chloride). Excellent corrosion resistance. And since Ni is suppressed to an inevitable impurity level and is not substantially contained, compatibility as a biomaterial such as a dental material or an implant material is also good. In addition to the living body, it can be suitably used for joining members (for example, heat exchangers) used in a contact environment with seawater, for example. The Ni content is desirably less than 100 ppm.
特に、Ｔｉ系被接合部材に適用する場合、すなわちＴｉ又はＴｉ合金の接合に使用する場合は、ろう付け材料の融点が８８３℃（すなわち、Ｔｉのβ変態点）未満にすることが、ろう付け処理時にＴｉ系被接合部材の組織がβ変態により粗大化することを防止する観点において望ましい。なお、ろう付け材料の融点は、材料の示差熱分析を行なったとき、その分析曲線上に現れる吸熱ピーク点を示す温度として定義する。 In particular, when applied to a Ti-based member to be joined, that is, when used for joining of Ti or Ti alloy, the brazing material should have a melting point lower than 883 ° C. (that is, the β transformation point of Ti). This is desirable from the viewpoint of preventing the structure of the Ti-based member to be coarsened due to β transformation during processing. The melting point of the brazing material is defined as a temperature indicating an endothermic peak point appearing on the analysis curve when the differential thermal analysis of the material is performed.
以下、本発明のろう付け材料の組成限定理由について説明する。
（１）Ｃｕ：１０質量％以上３０質量％以下
Ｃｕはろう付け材料の濡れ性を改善し、また、Ｔｉ，Ｚｒとの共晶形成によりろう付け材料の低融点化に寄与する。ただし、Ｃｕ含有量が３０質量％を超えると耐食性が損なわれることにつながる。他方、Ｃｕ含有量が１０質量％未満では、ろう付け材料の低融点化（特に、Ｔｉのβ変態点である８８３℃以下にすること）とが困難になり、ろう付け強度の低下を招きやすくなる。Ｃｕ含有量は、より望ましくは１０質量％以上２０質量％以下とするのがよい。
Hereinafter, the reasons for limiting the composition of the brazing material of the present invention will be described.
(1) Cu: 10% by mass or more and 30% by mass or less Cu improves the wettability of the brazing material and contributes to lowering the melting point of the brazing material by forming a eutectic with Ti and Zr. However, if the Cu content exceeds 30% by mass, the corrosion resistance is impaired. On the other hand, if the Cu content is less than 10% by mass, it becomes difficult to lower the melting point of the brazing material (particularly, to be 883 ° C. or less, which is the β transformation point of Ti), and the brazing strength is likely to be lowered. Become. The Cu content is more preferably 10% by mass or more and 20% by mass or less.
（２）Ｃｏ：５質量％以上２０質量％以下
Ｃｏはろう付け材料の耐食性を向上させ、また、Ｃｕと同様にろう付け材料の低融点化に寄与する。ただし、Ｃｏ含有量が５質量％未満では耐食性改善効果が顕著でなくなる。また、Ｃｏ含有量が２０質量％を超えると濡れ性が悪化し、接合後の強度低下を招く。Ｃｏ含有量は、より望ましくは１０質量％以上２０質量％以下とするのがよい。
(2) Co: 5% by mass or more and 20% by mass or less Co improves the corrosion resistance of the brazing material and contributes to lowering the melting point of the brazing material in the same manner as Cu. However, if the Co content is less than 5% by mass, the effect of improving corrosion resistance is not significant. On the other hand, when the Co content exceeds 20% by mass, the wettability deteriorates and the strength after bonding is reduced. More preferably, the Co content is 10% by mass or more and 20% by mass or less.
（３）Ｔｉ，Ｚｒ：不可避不純物を除く残部
ただし、Ｔｉ：３０質量％以上、Ｚｒ：２０質量％以上、
ＴｉとＺｒの合計が６０質量％以上８０質量％以下、
ＴｉとＺｒは、活性金属として本発明のろう付け材料の主成分をなすものである。ＴｉとＺｒの合計が６０質量％未満になると、残部組成をなすＣｕ及びＣｏを上記組成範囲を充足するように選択したとき、ろう付け材料の融点が高くなりすぎ、ろう付け強度の低下を招くことにつながる。また、ＴｉとＺｒの合計が８０質量％を超えると、低融点化に寄与するＣｕ及びＣｏの含有代が圧迫され、ろう付け材料の融点の上昇を招きやすくなるほか、濡れ性悪化によるろう付け強度低下にもつながる。また、Ｔｉ−Ｚｒ二元系は、３０原子％Ｚｒ付近に共融点が存在し、Ｔｉ単体金属と比較して約１００℃、Ｚｒ単体金属と比較して約２４０℃、融点が下がることが知られており、ＴｉとＺｒとを適当な比率で共配合してろう付け材料に適用することにより、ろう付け材料の低融点化に寄与する。しかし、ＴｉとＺｒの合計が６０質量％以上に確保されることから、Ｔｉが３０質量％未満になるか、Ｚｒが２０質量％未満になるとＴｉ側ないしＺｒ側に組成が偏り、ろう付け材料の融点が高くなりすぎることにつながる。
(3) Ti, Zr: remainder excluding inevitable impurities However, Ti: 30% by mass or more, Zr: 20% by mass or more,
The total of Ti and Zr is 60% by mass or more and 80% by mass or less,
Ti and Zr form the main components of the brazing material of the present invention as active metals. When the total of Ti and Zr is less than 60% by mass, the melting point of the brazing material becomes too high when Cu and Co constituting the remaining composition are selected so as to satisfy the above composition range, resulting in a decrease in brazing strength. It leads to things. Moreover, if the total of Ti and Zr exceeds 80% by mass, the content of Cu and Co, which contributes to lowering the melting point, is pressed, and the melting point of the brazing material is likely to increase, and brazing due to deterioration of wettability. It also leads to a decrease in strength. In addition, the Ti—Zr binary system has a eutectic point near 30 atomic% Zr, and it is known that the melting point is lowered by about 100 ° C. compared to a single Ti metal and about 240 ° C. compared to a Zr single metal. Therefore, Ti and Zr are co-blended in an appropriate ratio and applied to the brazing material, which contributes to lowering the melting point of the brazing material. However, since the total of Ti and Zr is secured to 60% by mass or more, when Ti is less than 30% by mass or Zr is less than 20% by mass, the composition is biased to the Ti side or Zr side, and the brazing material Leads to the melting point of being too high.
本発明によるろう付け材料は、材料形態として粉末及び急冷箔帯のいずれも採用でき、被接合部材の形態に適宜選択することができる。急冷箔帯は結晶質箔と異なり柔軟性に富み、加工も容易である。いずれも、単体金属の粉末や箔の複合体ではなく、溶融状態を一旦経由して合金化した状態となっている必要がある。急冷箔帯の場合は、被接合部材に挟み込んで加熱するだけでろう付けできる。このような急冷薄帯は、例えば、母合金を石英などのるつぼで溶解し、スリットあるいは微細孔から高速回転しているＣｕ等の冷却ロール上に噴射することにより、非晶質薄帯として製造できる。このときの冷却速度は、１０５Ｋ／秒以上１０６Ｋ／秒以下に設定するのがよい。また、急冷箔帯の厚さは、例えば１０μｍ以上５０μｍ以下に設定するのがよい。急冷箔帯の厚さが１０μｍ未満では連続した均質な薄帯の製造が困難となり、箔が断続化したり孔が多数形成された箔となる不都合があり、３０μｍを超えると冷却速度が不十分となり、非晶質化が進まず脆弱な箔となる不都合がある。 The brazing material according to the present invention can employ either a powder or a quenched foil strip as a material form, and can be appropriately selected as a form of a member to be joined. Unlike the crystalline foil, the quenched foil strip is rich in flexibility and easy to process. In any case, it is not a complex of a single metal powder or foil, but must be in an alloyed state once through a molten state. In the case of a quenched foil strip, brazing can be achieved by simply sandwiching and heating between the members to be joined. Such a quenched ribbon is manufactured as an amorphous ribbon by, for example, melting a mother alloy with a crucible such as quartz and spraying it onto a cooling roll such as Cu rotating at high speed from a slit or a fine hole. it can. The cooling rate at this time is preferably set to 10 5 K / second or more and 10 6 K / second or less. Further, the thickness of the quenched foil strip is preferably set to, for example, 10 μm or more and 50 μm or less. If the thickness of the quenching foil strip is less than 10 μm, it is difficult to produce a continuous and homogeneous thin strip, and there is a disadvantage that the foil is intermittently formed or a foil having a large number of holes. If it exceeds 30 μm, the cooling rate is insufficient. However, there is a disadvantage that the amorphization does not proceed and a fragile foil is formed.
一方、粉末の場合は、該粉末を有機溶剤やバインダーと混練してペースト状とし、被接合部材の適用面に塗布して使用することができる。この場合、スクリーン印刷法等を採用すれば、適用面が微小な場合、あるいは多数の個所を一度に接合する場合のいずれにおいても好適であり、ディスペンサーを用いて適用面にろう付け材料を自動供給することも可能である。粉末の粒径は、標準ふるい通過径にて２５０μｍ以下となっているのが塗布均一性を確保する観点にて望ましく、１５０μｍ以下であればより好ましい。特に、スクリーン印刷に適用する場合は、上記粒径は４５μｍ以下となっていることが望ましい。他方、金属粉末の化学安定性や取り扱い性を考慮すれば、該粒径は、平均粒径にて２５μｍ以上であることが望ましい。なお、このようなろう付け材料の粉末は、例えば、アトマイズ法や混合法（例えば、メカニカルアロイング法）などにより製造できる。 On the other hand, in the case of powder, the powder can be kneaded with an organic solvent or binder to form a paste, which can be applied to the application surface of the member to be joined. In this case, adopting a screen printing method, etc., is suitable for applications where the application surface is very small, or when joining a large number of locations at once. Brazing material is automatically supplied to the application surface using a dispenser. It is also possible to do. The particle diameter of the powder is preferably 250 μm or less at the standard sieve passage diameter from the viewpoint of ensuring coating uniformity, and more preferably 150 μm or less. In particular, when applied to screen printing, the particle size is desirably 45 μm or less. On the other hand, considering the chemical stability and handleability of the metal powder, the particle size is desirably 25 μm or more in terms of average particle size. Such a powder of brazing material can be produced by, for example, an atomizing method or a mixing method (for example, a mechanical alloying method).
本発明によるろう付け材料によりろう付け可能な被接合部材の材質は、該ろう付け材料より高融点の金属及びセラミックスのいずれも採用できる。金属の場合は、Ｔｉ、Ｚｒ、Ｗ、Ｍｏ（あるいはそれらを主成分とする合金）や、ステンレス鋼、工具鋼、インバー等のＦｅ系合金を例示できる。また、セラミックスの場合は、酸化アルミニウムや酸化ジルコニウムあなどの酸化物系セラミックス、炭化珪素などの炭化物系セラミックス、窒化珪素、窒化チタンなどの窒化物系セラミックスなどを例示できる。ただし、いずれも上記のものに限定されない。 As the material of the member to be joined that can be brazed with the brazing material according to the present invention, any of metals and ceramics having a melting point higher than that of the brazing material can be adopted. In the case of metals, examples thereof include Ti, Zr, W, Mo (or alloys containing them as main components), and Fe-based alloys such as stainless steel, tool steel, and invar. In the case of ceramics, oxide ceramics such as aluminum oxide and zirconium oxide, carbide ceramics such as silicon carbide, and nitride ceramics such as silicon nitride and titanium nitride can be exemplified. However, none is limited to the above.
以下、本発明の効果を確認するために行なった実験結果について説明する。
（実施例１）
表１のＮｏ．１〜１４（Ｎｏ１〜６が実施例、他は比較例である）の各種組成となるように原料を配合し、ボタン型アーク溶解炉で溶解して合金化した。それら合金を石英ノズルに入れ、Ａｒ減圧雰囲気下高周波で溶解後、周速約３０ｍ／秒で回転するＣｕ製ロール上に噴射して急冷箔帯を得た。箔帯の厚みは２０〜３０μｍであり、幅は２０ｍｍである。また、Ｎｏ１〜６の実施例箔帯は全て柔軟性があり、Ｘ線回折によりアモルファスであることを確認している。他方、比較例のＮｏ．７〜Ｎｏ．１４については、Ｎｏ．８の組成においては箔帯化ができなかったが、他は箔帯が製造できた。
Hereinafter, experimental results performed to confirm the effects of the present invention will be described.
Example 1
No. in Table 1 The raw materials were blended so as to have various compositions of 1 to 14 (Nos. 1 to 6 are Examples and others are comparative examples), and melted and alloyed in a button type arc melting furnace. These alloys were put in a quartz nozzle, melted at a high frequency under an Ar reduced pressure atmosphere, and then sprayed onto a Cu roll rotating at a peripheral speed of about 30 m / sec to obtain a quenched foil strip. The thickness of the foil strip is 20-30 μm and the width is 20 mm. Moreover, the Example foil strips of Nos. 1 to 6 are all flexible and have been confirmed to be amorphous by X-ray diffraction. On the other hand, no. 7-No. For No. 14, no. In the composition of No. 8, a foil band could not be formed, but in the other cases, a foil band could be manufactured.
上記材料については熱分析を行ない、融点を測定した。結果を表１に示す。Ｎｏ１〜６の実施例材の融点は、いずれもＴｉのβ変態温度（８８３℃）以下であることがわかる。なお、比較例材のＮｏ．９は９８０℃と上記β変態温度を超える融点を示し、ＴｉやＴｉ合金の接合には適さないことがわかる。 About the said material, the thermal analysis was conducted and melting | fusing point was measured. The results are shown in Table 1. It turns out that melting | fusing point of the Example material of No1-6 is all below (beta) transformation temperature (883 degreeC) of Ti. The comparative material No. No. 9 shows a melting point exceeding 980 ° C. and the β transformation temperature, which is not suitable for joining Ti or Ti alloy.
次に、純Ｔｉの丸棒（平行部φ６ｍｍ）の端面間に上記各ろう付け材料薄帯を挟み込んで突き合わせ、高周波通電により９００℃で５分加熱することによりろう付けを行なった。なお、加熱時には、材料がずれないよう、圧力約１ＭＰａにて加圧保持した。ろう付け後の部材は、所定の試験片形状に加工して室温にて引張試験を行ない、引張強度を測定した。なお、被接合部材として使用した純Ｔｉ丸棒の引張強度は３６０ＭＰａである。結果を表１に示す。Ｎｏ．８，１３，１４を除き実施例材及び比較例材ともに、接合面ではなく被接合部材（母材）側にて破断した。そして、実施例材の強度は、いずれも上記母材強度（３６０ＭＰａ）の９０％以上の高強度を示すことがわかる。他方、Ｃｏ含有量が不足するＮｏ．７では、引張強度がやや劣っている。また、Ｎｏ．８，１３，１４の比較例は接合面での破壊がみられ、強度は極めて低いことがわかる。 Next, the brazing material ribbons were sandwiched between end faces of pure Ti round bars (parallel portion φ6 mm), and brazed by heating at 900 ° C. for 5 minutes by high-frequency energization. During heating, the pressure was maintained at a pressure of about 1 MPa so that the material would not shift. The member after brazing was processed into a predetermined test piece shape, subjected to a tensile test at room temperature, and measured for tensile strength. In addition, the tensile strength of the pure Ti round bar used as a member to be joined is 360 MPa. The results are shown in Table 1. No. Except for 8, 13 and 14, both the example material and the comparative example material were broken on the joined member (base material) side, not on the joining surface. And it turns out that the intensity | strength of an Example material shows the high intensity | strength of 90% or more of the said base material intensity | strength (360 MPa) all. On the other hand, no. In No. 7, the tensile strength is slightly inferior. No. It can be seen that the comparative examples 8, 13, and 14 show breakage at the joint surface and the strength is extremely low.
次の、表１の各組成のうち、比較例材のＮｏ．９を除く各組成について、同様に材料を配合してマグネシアるつぼに入れ、高周波加熱で溶融し、その溶湯を直径４ｍｍのノズルから落下させつつ、２ＭＰａの圧力にてアルゴンガスを吹きつけ、ガスアトマイズ法により合金粉末を作製した。得られた粉末は目開き１５０μｍのふるいを通し、通過した粉末を試料として得た。いずれの粉末もほぼ球形であり、Ｘ線回折により結晶質であることを確認している。 Of the following compositions in Table 1, the comparative material No. For each composition except 9, the materials were similarly mixed and put in a magnesia crucible, melted by high frequency heating, and the molten metal was dropped from a nozzle with a diameter of 4 mm, and argon gas was blown at a pressure of 2 MPa, and the gas atomization method Thus, an alloy powder was prepared. The obtained powder was passed through a sieve having an opening of 150 μm, and the passed powder was obtained as a sample. All the powders are almost spherical and confirmed to be crystalline by X-ray diffraction.
この粉末を、周知のバインダー及び有機溶剤と混練してペーストに調製した。該ペーストを、肉厚１ｍｍ、外径１４ｍｍ、長さ６ｍｍの純Ｔｉ製のパイプの端面と、直径２５ｍｍの純Ｔｉ製の円板との間に塗布して重ね合わせ、真空ろう付け炉内にて９００℃で２０分加熱してろう付けを行なった。接合後の各試験品は、６質量％ＦｅＣｌ３水溶液中にて、５０℃で２４時間浸漬し、その後取り出して腐食減量を測定した。なお、腐食減量は、腐食前試験片重量をＷ０、腐食後試験片重量をＷとして、｛（Ｗ０−Ｗ）／Ｗ０｝×１００（％）にて算出した。該腐食減量が３％未満のものを良好（◎）、３％以上５％未満のものを可(○）、５％以上のものを不可(△）として評価した。結果を表１に示す。実施例材はいずれも耐食性は良好であり、接合時の濡れ性も良好であった。他方、Ｃｏの含有が不十分な比較例材であるＮｏ．７、Ｎｏ．１０は、いずれも耐食性が不十分である。 This powder was kneaded with a known binder and an organic solvent to prepare a paste. The paste is applied between the end face of a pure Ti pipe having a wall thickness of 1 mm, an outer diameter of 14 mm, and a length of 6 mm and a pure Ti disk having a diameter of 25 mm, and is placed in a vacuum brazing furnace. And brazing was carried out by heating at 900 ° C. for 20 minutes. Each test article after joining was immersed in a 6 mass% FeCl 3 aqueous solution at 50 ° C. for 24 hours, and then taken out to measure corrosion weight loss. Corrosion weight loss was calculated as {(W0−W) / W0} × 100 (%), where W0 is the weight of the specimen before corrosion and W is the weight of the specimen after corrosion. The corrosion weight loss of less than 3% was evaluated as good (◎), 3% or more but less than 5% was acceptable (◯), and 5% or more was evaluated as unacceptable (Δ). The results are shown in Table 1. All of the example materials had good corrosion resistance and good wettability during bonding. On the other hand, No. 1 which is a comparative material with insufficient Co content. 7, no. No. 10 has insufficient corrosion resistance.
以上のごとく、本発明の実施例材にかかるＮｏ．１〜Ｎｏ．６の各ろう付け材料は、いずれもＮｉを含有したＮｏ．１１，Ｎｏ．１２のろう付け材料と、強度及び耐食性ともまったく遜色ない結果が得られており、Ｔｉ及びＺｒを含有したろう付け材料において、Ｎｉを含有せずとも強度と耐食性との双方に優れ、生体適合性の良好なろう付け材料が実現していることが明らかである。 As mentioned above, No. concerning the example material of the present invention. 1-No. Each brazing material of No. 6 contains Ni. 11, no. 12 brazing materials and strength and corrosion resistance were obtained, and the brazing material containing Ti and Zr is excellent in both strength and corrosion resistance and biocompatibility without containing Ni. It is clear that a good brazing material is realized.
Claims (4)
Ｃｏ：５質量％以上２０質量％以下、をそれぞれ含有し、
残部が、３０質量％以上のＴｉ、２０質量％以上のＺｒ及び不可避不純物からなり、ＴｉとＺｒとの合計を６０質量％以上８０質量％以下となしたことを特徴とするろう付け材料。 Cu: 10% by mass or more and 30% by mass or less,
Co: 5% by mass or more and 20% by mass or less, respectively,
A brazing material characterized in that the balance is 30% by mass or more of Ti, 20% by mass or more of Zr and inevitable impurities, and the total of Ti and Zr is 60% by mass or more and 80% by mass or less.
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