JP2001003127A - Ti-Zr alloy - Google Patents

Abstract

(57) [Summary] [PROBLEMS] For general industrial use, excellent cold workability at room temperature, for medical use, further improvement of corrosion resistance, especially improvement of corrosion resistance in acidic solutions such as HCl solution,
Provided is a Ti-Zr-based alloy having flexibility, for example, a Young's modulus as low as that of bone. SOLUTION: 25-50% by mass of Ti, 25-Zr
60 mass%, 5-30 mass% of Nb and 5-40 mass% of Ta, and the mass ratio of Zr to Ti is 0.5
1.5 and the mass ratio of Nb to Ta is 0.1.
A Ti-Zr-based alloy having a particle size of 125 to 1.5.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has excellent high strength, low Young's modulus, sufficient ductility required when used as a structural member, and plastic working. The present invention relates to a Ti-Zr-based alloy having excellent properties.

[0002]

2. Description of the Related Art Ti-based alloys are made of Ti
It has excellent corrosion resistance by forming a dense oxide film of O ₂ , and has various excellent properties such as light and strong and large specific strength (quotient of tensile strength divided by specific gravity). Equipment materials, corrosion-resistant materials for the seawater utilization industry, camera shutter parts, communication equipment, optical equipment,
It is widely used as a material for consumer goods such as eyeglass frames, golf club drivers and iron heads. However, since the Ti-based alloy has a hard α-phase metal structure at normal temperature, machining such as rolling, forging or cutting is not easy, and only a β-phase region capable of being machined by precipitation at a high temperature region. The current situation is to do it. In addition, in terms of material, corrosion resistance and
Despite having good properties such as strength, there is a problem that workability is very poor. These drawbacks have hindered the expansion of conventional Ti-based alloys for general industrial use.

On the other hand, titanium (Ti), zirconium (Zr), niobium (Nb), tantalum (Ta), platinum (Pt), inorganic tin (inorganic Sn), and the like have become biocompatible based on the results of previous research. Known as an excellent element,
It is starting to attract attention as a medical material. However, when used as a medical material, stricter corrosion resistance is required as compared with general industrial use. That is,
Even if the elution amount of the components eluted from the material is very small, the adverse effect on the human body cannot be ignored in the case of medical materials, so the materials used for medical materials are It is required that the mother component has such a property that it does not elute through the oxide film which exhibits a passive state even when it comes into contact with body fluid or blood. In addition to the above properties, it is also very important that the medical material has an excellent affinity for surrounding tissues and that it is close to the Young's modulus of living bone.

In order to achieve the above characteristics,
Various Ti-based alloys have been reported so far, for example, titanium, about 10-20 wt% or about 35-50 w%.
% metal selected from the group consisting of niobium and tantalum, and alloys used in dental devices comprising zirconium sufficient to act as a beta stabilizer and reduce the rate of beta structure transformation in the alloy (especially Table 10-
No. 501719) and second metals selected from the group consisting of titanium, zirconium, hafnium and mixtures thereof, and niobium, tantalum,
Titanium alloys containing a predetermined composition of a third metal selected from the group consisting of vanadium and a mixture thereof (Japanese Unexamined Patent Publication No. 9-510501) are listed. However, the former alloy does not show the mass ratio of zirconium to titanium or the mass ratio of tantalum to niobium. Specifically, zirconium is most preferably 18% by mass or less, and tantalum refers only to the total amount of niobium, and only a part of niobium can be replaced with tantalum. Is assumed to be zero. Such alloys are unsatisfactory in terms of ductility, proof stress, and even very strong corrosion resistance.

The latter alloy forms a cermet or a ceramic body by being oxidized or oxidized, and is subjected to a heat treatment in a certain temperature range, and is oxidized by an oxidizing gas to change its properties. The alloy disclosed in Japanese Unexamined Patent Publication (Kokai) No. 9-510501 does not show a good beta phase at the time of alloying, is inferior in plasticity and workability at room temperature, and has poor corrosion resistance. There is a problem of insufficient.

Therefore, although there is a strong demand for the development of a Ti-based alloy having high strength, excellent corrosion / acid resistance, easy workability, low Young's modulus, and especially a Young's modulus close to that of living bone, all properties are satisfied. There was nothing to do before.

[0007]

Accordingly, an object of the present invention is to provide a high strength (σf) at normal temperature, a low Young's modulus (E),
That is, it is an object of the present invention to provide a general industrial Ti-Zr alloy having high elasticity, thereby being excellent in plasticity and workability at normal temperature and also excellent in corrosion resistance.

[0008] Another object of the present invention is to provide a medical Ti- alloy having excellent plasticity and workability at normal temperature, having corrosion resistance more than that of general industrial use, and having excellent compatibility with living tissues.
It is to provide a Zr-based alloy.

[0009]

Means for Solving the Problems The present inventors have conducted intensive studies on Ti-Zr-based alloys in order to achieve the above objects, and as a result, have found that Ti, Zr, Nb and Ta have a specific composition.
Have been found to be excellent in plasticity and workability at room temperature, and also excellent in affinity with living tissue, and have completed the present invention based on the above findings. .

[0010] That is, the above objects are as follows:
This is achieved by (12).

(1) 25 to 50% by mass of Ti, Zr 2
5 to 60% by mass, Nb 5 to 30% by mass, and Ta 5 to 5% by mass.
Ti-Z comprising 40% by mass, wherein the mass ratio of Zr to Ti is 0.5 to 1.5, and the mass ratio of Nb to Ta is 0.125 to 1.5.
r-based alloy.

(2) The alloy according to (1), wherein the content of Ti is 30 to 40% by mass.

(3) The alloy according to (1) or (2), wherein the content of Zr is 25 to 45% by mass.

(4) The alloy according to any one of (1) to (3), wherein the content of Nb is 10 to 20% by mass.

(5) The alloy according to any one of (1) to (4), wherein the content of Ta is 10 to 30% by mass.

(6) In the Ti—Zr-based alloy according to any one of (1) to (5), at least one of Nb and Ta is Ni, Cu, Pd, Pt, Al,
Si, Cr, Mn, Co, V, Fe, Ag, Au, S
n, Mo, Hf, Zn, Ga, W, Tc, Ru, Rh,
A Ti-Zr-based alloy, wherein the Ti-Zr-based alloy is substituted with at least one substitution element selected from the group consisting of Cd and In.

(7) The substitution elements are V, Cr, Mn, F
e, Co, Ni, Cu, Zn, Ga, Mo, Pd, A
The alloy according to (6), wherein the alloy is at least one element selected from the group consisting of g, W, Pt, and Au.

(8) The alloy according to the above (6) or (7), wherein the content of the substitution element is 20 to 40% by mass based on the mass of all the constituent elements.

(9) Further, with respect to the total mass of the constituent elements,
0.01 to 5% by mass of Ni, Cu, Pd, Pt, Al,
Si, Cr, Mn, Co, O, N, V, Fe, Ag, A
(1) characterized in that it contains at least one additional element selected from the group consisting of u, Sn, Mo and Hf.
The Ti-Zr-based alloy according to any one of (1) to (5).

(10) The additional elements are V, Cr, Mn, F
e, Co, Ni, Cu, Zn, Ga, Mo, Pd, A
The alloy according to (9), wherein the alloy is at least one element selected from the group consisting of g, W, Pt, and Au.

(11) The alloy according to the above (9) or (10), wherein the content of the additional element is 1 to 4% by mass based on the mass of all the constituent elements.

(12) Assuming that the tensile strength is σf (Pa) and the Young's modulus is E (Pa), σf / E ≧ 0.016 and E
The alloy according to any one of the above (1) to (11), which satisfies ≦ 70 GPa.

[0023]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the present invention will be described in detail.

According to a first concept of the invention, Ti 25
-50 mass%, Zr 25-60 mass%, Nb 5-3
0% by mass and 5 to 40% by mass of Ta;
The mass ratio of Zr to 0.5 to 1.5, and T
A Ti-Zr-based alloy is provided, wherein the mass ratio of Nb to a is 0.125 to 1.5. In the above concept, the content (% by mass) of each constituent element is selected so that the sum of the constituent elements of the alloy becomes 100% by mass except for impurities and additives of 5% by mass or less.

Among the constituent elements constituting the alloy of the above concept, Ti has a hexagonal close-packed lattice structure (α phase) at room temperature and cannot be expected to have large ductility, but a body-centered cubic lattice structure (β Phase) and is known to exhibit greater ductility than the α phase. The Young's modulus of the pure Ti (grade 2) is 106GPa, to form a dense oxide film of TiO ₂ on the surface at 610 ° C. or higher, the TiO ₂
The film does not change in air at normal temperature, has excellent strength, has corrosion resistance, and generates TiCl ₄ at 300 ° C. or higher.
Since Ti has excellent specific strength (quotient of tensile strength divided by specific gravity), it is often used as a Ti-based alloy by utilizing this property. When alloyed, it becomes a solid solution and has a significant effect on ductility. If ductility is lost, forging cannot be performed, at least as an important means of improving the cast structure. Therefore, the condition for an excellent Ti-based alloy is that it has plasticity. At present, unfortunately, there are many examples in which even if a target element is added to a Ti-based alloy, it is brittle and has very poor workability and cannot be used. On the other hand, according to the present invention, Ti-Zr-Nb-Ta
It has been found that the above disadvantages can be overcome by using a quaternary alloy consisting of

In the above concept, the content of Ti is Zr
And at the same time satisfying the relationship shown below, and usually 25 to 50% by mass, preferably 30 to 40% by mass, and more preferably 30 to 35% by mass, based on the total mass of the constituent elements.
It is. At this time, when the content of Ti exceeds 50% by mass, the content of Ti becomes too high, and poor plasticity and workability, which are inherent defects of Ti, are remarkably exhibited. In addition, processing at room temperature cannot be performed, and steps such as heat treatment increase, which is not preferable. Conversely, if the content of Ti is less than 25% by mass, the amount of Ti is too small, and the excellent strength, specific strength, corrosion resistance and stability, which are also advantages of using Ti, are not sufficient. It does not show its excellent properties and can no longer be called a Ti-based alloy, which is still unfavorable.

Further, Zr which is a constituent element of the alloy of the present invention is used.
Has a hexagonal close-packed lattice structure (α phase) at room temperature,
Transforms to body-centered cubic structure (β-phase) above ℃. Also, Zr
Produces a dense oxide film in the air and has excellent corrosion resistance, especially in high temperature water, which is significantly higher than other metals.
It has the property that it is difficult to react even in molten alkali.
As described above, since Zr has excellent corrosion resistance and acid resistance,
Used for various mechanical applications. The Young's modulus of pure Zr is 94.5 GPa.

In the above concept, the content of Zr is in the range of 25 to 60% by mass with respect to the total mass of the constituent elements, and the mass ratio of Zr to Ti is 0.5 to 1.
It is essential that the condition satisfying the range of 5 is satisfied. Preferably, the content of Zr is based on the total mass of the constituent elements.
It is 25 to 45% by mass, more preferably 30 to 35% by mass. Further, the mass ratio of Zr to Ti is preferably 0.5 to 1.5, and more preferably 0.8 to 1.2. At this time, if the Zr content is less than 25% by mass or the mass ratio of Zr to Ti is less than 0.5, the α phase of Ti precipitates in the alloy, and the plasticity and workability are significantly reduced. In addition, the Young's modulus increases, and the affinity with the living tissue deteriorates, which is not preferable. On the other hand, when the content of Zr is 60
Mass% or the mass ratio of Zr to Ti is 1.
When it exceeds 5, no improvement in corrosion resistance is observed, and only the specific gravity of the obtained alloy increases, and the Young's modulus also increases, and the plasticity and workability decrease, which is also unfavorable. By setting the content of Zr in the specific range as described above, Zr forms a dense oxide film without changing Ti in room temperature air, and the characteristics of both are improved. Synergistically, it can show good corrosion resistance and acid resistance.

Further, N, which is a constituent element of the alloy of the present invention,
b indicates extensibility, its Young's modulus is 105 GPa, its hardness is almost the same as that of wrought iron, and other constituent elements T
It is a metal softer than a. Therefore, by adding Nb, it is possible to impart flexibility (low elasticity) to the obtained alloy. Nb is a metal which forms an oxide film in the air and exhibits corrosion resistance, is insoluble in acids other than hydrofluoric acid, does not dissolve in alkaline aqueous solutions, and contains various alloys (for example, heat-resistant alloys). Widely used as an additive element. Therefore, by using Nb as a component of the Ti-Zr-based alloy of the present invention, corrosion resistance and acid resistance can be improved in cooperation with Zr.

In the above concept, the content of Nb is in the range of 5 to 30% by mass with respect to the total mass of the constituent elements, and the mass ratio of Nb to Ta is 0.125 to 30%.
It is indispensable to satisfy the condition of 1.5.
Preferably, the content of Nb is 10 to 20% by mass, more preferably 10 to 15% by mass, based on the total mass of the constituent elements. Further, the mass ratio of Nb to Ta is preferably 0.3 to 1.5, more preferably 0.5 to 1.0. At this time, if the content of Nb is less than 5% by mass or the mass ratio of Nb to Ta is less than 0.125, the resulting alloy is not sufficiently flexible, plasticity is reduced, and Young's modulus is increased. Problem arises. Conversely, if Nb is added in excess of 30% by mass or the mass ratio of Nb to Ta exceeds 1.5, no improvement in corrosion resistance or suppleness can be expected, and improvement in corrosion resistance is not apparent. However, the specific gravity only increases, and no improvement is seen in the affinity with the living tissue, which is also not preferable.

Further, Ta, which is a constituent element of the alloy of the present invention, is rich in malleability and elastic as in Nb. Ta is a metal harder than Nb, and its Young's modulus is 187 GPa. Therefore, by adding Ta, it is possible to increase the elasticity of the alloy, but it is not possible to impart flexibility. Also, Ta
Is a metal that forms an oxide film in the air and exhibits corrosion resistance, and has a characteristic of extremely strong corrosion resistance. Therefore, by using Ta as a component of the Ti-Zr-based alloy of the present invention, the corrosion resistance can be improved in cooperation with Zr.

In the above concept, the content of Ta is Nb
At the same time as satisfying the above-mentioned relationship with the content of
It is 30% by mass, more preferably 15 to 25% by mass.
At this time, if the content of Ta is less than 5% by mass, the resulting alloy has an increased Young's modulus, reduced ductility, and inferior proof stress, which is not preferable. On the other hand, 40% by mass of Ta
Even if added in excess of the above, not only can corrosion resistance not be improved, but only the specific gravity is increased, and the suppleness is gradually lost, and the resulting alloy becomes brittle and difficult to process. Therefore, it is not preferable.

The method for producing a Ti—Zr alloy according to the present invention comprises:
The method is not particularly limited as long as it can produce an alloy having a specific composition as described above. For example, desired elements (for example, titanium, sponge titanium, pure titanium grades 1 to 4, etc .; Zr, sponge zirconium, Pure zirconium; pure niobium for Nb; pure tantalum for Ta; a material that does not limit its shape and whose purity does not affect its properties is made to have a predetermined composition (% by mass). Weigh it, arc-melt it in a water-cooled copper hearth, alloy it and make it into an ingot; melt it in a crucible, alloy it and make it into a powder by atomization; And ingots; and methods commonly used in the industry such as mechanical alloying, sputtering, and plasma methods, and various research institutions. And methods published in literatures and the like.

As described above, although the Ti—Zr-based quaternary alloy of the present invention defined in the above range is an alloy containing Ti and Zr as main components, its metal structure is β at room temperature.
Since it shows a phase, rolling, forging, machining, or the like can be performed at room temperature, and it shows extremely excellent workability. As an example, FIG. 1 shows an X-ray diffraction diagram showing the β phase of the quaternary Ti—Zr-based alloy produced in Example 2 below.

In the present invention, Nb and / or Ta, which are constituents of the Ti—Zr-based alloy according to the first concept, are Ni, Cu, Pd, Pt, Al, Si, C
r, Mn, Co, V, Fe, Ag, Au, Sn, Mo,
Hf, Zn, Ga, W, Tc, Ru, Rh, Cd and I
n may be substituted with at least one substituent element selected from the group consisting of Ti-Zr having such a composition.
Base alloys are also novel and form another concept of the present invention. That is, according to the second concept of the present invention, in the Ti—Zr-based alloy according to the first concept of the present invention, at least one of Nb and Ta is Ni, Cu, Pd,
Pt, Al, Si, Cr, Mn, Co, V, Fe, A
g, Au, Sn, Mo, Hf, Zn, Ga, W, Tc,
T is substituted with at least one kind of substitution element selected from the group consisting of Ru, Rh, Cd and In.
An i-Zr-based alloy is provided.

In the second concept, the content of the at least one substitution element is determined by the type and the content of the substitution element.

Of the substitution elements used for substituting Nb and / or Ta in the alloy of the above concept, P
t, Au and Pd are elements having excellent corrosion resistance, and by replacing Nb and / or Ta with these elements, the corrosion resistance of the base material can be improved. In addition, since these substitution elements do not adversely affect living tissue and have excellent biocompatibility, they are particularly preferably used when the alloy of the present invention is used for medical applications. Further, substitution elements other than Pt, Au and Pd are effective components for increasing the mechanical strength of the base material, but all of the substitution elements lower the corrosion resistance of the obtained alloy, This material is not suitable for medical use because it is inferior. Therefore, when an element other than Pt, Au and Pd is used as a substitution element, the obtained Ti-Zr-based alloy is used for general industry, for example, a marine material exposed to salt (metal such as a fishing rod or reel). Material or metal fishing line), an eyeglass frame to which sweat containing salt adheres, a club head of a golf club driver requiring specific strength, or an iron face material.

[0038] Specific examples of the composition of the alloy according to the above embodiment are not particularly limited as long as they satisfy the above composition conditions.

Ti _a1 Zr _b1 Nb _c1 (Ni, Cu, P
d, Pt, Al, Si, Cr, Mn, Co, V, Fe,
Ag, Au, Sn, Mo, Hf, Zn, Ga, W, T
c, Ru, Rh, at least one substitution element selected from the group consisting of Cd and In) a multicomponent alloy of _d1 (in this case, a
1 represents the content (% by mass) of Ti in the range of 25 to 50, b1 represents the content (% by mass) of Zr, in the range of 25 to 60, and c1 represents the content of Nb. Amount (% by mass), in the range of 5 to 30, and d1
Represents the total content (% by mass) of the substitution elements,
0, and b1 / a1 is 0.5 to 1.5, and c1 / d1 is 0.125 to 1.5); Ti _a2 Zr _b2 (Ni, Cu, Pd, Pt, Al, S
i, Cr, Mn, Co, V, Fe, Ag, Au, Sn,
Mo, Hf, Zn, Ga, W, Tc, Ru, Rh, Cd
And at least one substitution element) _c2 multiple alloy Ta _d2 (this time, a2, the content of Ti (wt%) selected from the group consisting of In represents, in the range of 25 to 50, b
2 represents the Zr content (% by mass) and ranges from 25 to 60, and c2 represents the total content (% by mass) of the substitution element.
Represents a range of 5 to 30, and d2 represents a content (% by mass) of Ta, a range of 5 to 40, b2 / a2 is 0.5 to 1.5, and c2 / d2
Is 0.125 to 1.5); and Ti _a3 Zr _b3 (Ni, Cu, Pd, Pt, Al, S
i, Cr, Mn, Co, V, Fe, Ag, Au, Sn,
Mo, Hf, Zn, Ga, W, Tc, Ru, Rh, Cd
And at least one substitution element selected from the group consisting of In and In) a multi-element alloy of _{c3 + d3} (where a3 represents the Ti content (% by mass) and ranges from 25 to 50, and b3
Represents the content (% by mass) of Zr and is in the range of 25 to 60, and c3 + d3 represents the total content (% by mass) of the substitution elements, is in the range of 10 to 50, and b
3 / a3 is 0.5 to 1.5).

In the present invention, the substitution element is appropriately selected depending on the intended use and desired properties in consideration of the above characteristics. For example, 1. In general industrial use, the substitution element When used in place of Nb and of one type, V, Cr, M
n, Fe, Co, Ni, Cu, Zn, Ga, Mo, T
c, Ru, Rh, Pd, Ag, Cd, In, Sn are preferably used; 2. In general industrial applications, when the substitution element is used in place of Nb and is a mixed form of two or more types. Is preferably used, for example, Sn-Pt, Cu-Ni, Co-Cr and Al-V; 3. In medical applications, when the substitution element is used instead of Nb and is one type, V, Cr, Co, A
g, Sn, Au, Pd, Pt, Ni, Al are preferably used; 4. In medical applications, when the substitution element is used in place of Nb and is a mixed form of two or more, V,
A combination of elements selected from the group consisting of Cr, Mo, Pd, Ag, Sn, Pt, and Au is preferably used; 5. In general industrial applications, the substitution element is used in place of Ta and used in one kind. Sometimes, V, Cr, M
n, Fe, Co, Ni, Cu, Zn, Ga, Mo, T
c, Ru, Rh, Pd, Ag, Cd, In, Sn are preferably used; 6. In general industrial applications, when the substitution element is used in place of Ta and is a mixed form of two or more kinds. Is preferably used, for example, Al-Ni, Cu-Co, Sn-Pd and Cu-Al; 7. In medical applications, when the substitution element is used instead of Ta and is one type, V, Cr, Co, A
g, Sn, Au, Pd, Pt, Ni, Al are preferably used; 8. In medical applications, when the substitution element is used in place of Ta and is a mixed form of two or more, V,
A combination of elements selected from the group consisting of Cr, Mo, Pd, Ag, Sn, Pt, and Au is preferably used; 9. In general industrial applications, a substitution element is used instead of Nb and Ta and When the type is V,
Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, M
o, Tc, Ru, Rh, Pd, Ag, Cd, In, Sn
10. In general industrial applications, when the substitution element is used in place of Nb and Ta and is a mixed form of two or more, V, Cr, Mn, Fe, Co, Ni , C
u, Zn, Ga, Mo, Tc, Ru, Rh, Pd, A
Preferably, a combination of elements selected from the group consisting of g, Cd, In, and Sn is used; 11. In medical applications, the replacement elements are Nb and Ta.
V and C when used in place of
r, Co, Ag, Sn, Au, Pd, Pt, Ni, Al
Are preferably used; and 12. In medical applications, the replacement elements are Nb and Ta.
And when it is used in a mixed form of two or more, V, Cr, Mo, Pd, Ag, Sn, Pt, Au
A combination of elements selected from the group consisting of is preferably used.

The method for producing a Ti—Zr alloy according to the above concept of the present invention is not particularly limited as long as it can produce an alloy having a specific composition as described above, and the same method as described above can be applied. , Desired elements (for example, titanium, sponge titanium, pure titanium grades 1-4, etc .; Z
For r, sponge zirconium, pure zirconium, etc .;
For Nb, pure niobium and for Ta, pure tantalum,
Without limiting the shape, the purity of which does not affect the properties is weighed so as to have the specified composition (% by mass), and this is arc-melted in a water-cooled copper hearth, alloyed, and ingoted. Melting in a crucible, alloying, and powdering by atomization; casting in the same manner;
Floating melting, alloying and ingot method; and mechanical alloying method, sputtering method, plasma method, etc.
Examples of the method include methods generally used in industrial practice, and methods published in various research institutions and literatures. At this time, the form of the desired substitution element is the same as that in the known method without any particular limitation. For example, Ni is pure nickel, Cu is pure copper, oxygen-free copper, phosphorus deoxidized copper, tough pitch In the case of Al such as copper, other substitution elements such as pure aluminum are used in a pure metal state.

Further, in the present invention, 0.01 to 5% by mass of Ni, Cu, Pd, Pt, A is added to the Ti-Zr-based alloy according to the first conception based on the total mass of the constituent elements.
1, Si, Cr, Mn, Co, O, N, V, Fe, A
g, Au, Sn, Mo and Hf, at least one additional element selected from the group consisting of
-Zr-based alloys are also novel and form another concept of the present invention. That is, according to the third concept of the present invention,
Furthermore, 0.01 to 5% by mass relative to the total mass of the constituent elements
Ni, Cu, Pd, Pt, Al, Si, Cr, Mn,
Ti according to the first aspect of the present invention, characterized by containing at least one additional element selected from the group consisting of Co, O, N, V, Fe, Ag, Au, Sn, Mo and Hf.
A -Zr-based alloy is provided. In this manner, the mechanical strength of the base material can be increased by further adding the above-described additive element to the Ti-Zr-based alloy of the first concept at a predetermined ratio. The same as the second concept, but among these additional elements, Pt, Au and P
d is an element having excellent corrosion resistance. By replacing Nb or Ta with these elements, the corrosion resistance of the base material can be improved. In addition, since these added elements do not adversely affect living tissues and have excellent biocompatibility, they are particularly preferably used when the alloy of the present invention is used for medical applications. Furthermore, elements other than Pt, Au, and Pd are effective components for increasing the mechanical strength of the base material, but since all of the added elements are materials with poor biocompatibility,
Pt, Au and Pd are unsuitable materials for medical use
When an element other than the above is used as an additional element, the obtained Ti-Zr-based alloy is used for general industry, for example, a marine material (a metal material such as a fishing rod or a reel or a metal fishing line) exposed to salt, It is used as an eyeglass frame to which sweat is attached, a club head of a golf club driver requiring specific strength, or an iron face material.

In the above concept, the content of the additional element is
It is essential that the content be 0.01 to 5% by mass relative to the total mass of the constituent elements, but it is preferably 1 to 4% by mass, more preferably 2 to 3% by mass. At this time, when the content of the additional element is less than 0.01% by weight, the effect of adding the additional element is not so much recognized, and it is in the range of impurities as in the case of the remaining trace element, which is not preferable. If the content of the additional element exceeds 5% by mass, properties different from desired properties appear, which is also not preferable.

In the above concept, the additive element is N
i, Cu, Pd, Pt, Al, Si, Cr, Mn, C
o, O, N, V, Fe, Ag, Au, Sn, Mo and H
At least one selected from the group consisting of f, preferably at least one selected from the group consisting of Ni, Pd, Cr, Co, and Fe. When the additive element is in a mixed form of two or more selected from the above group, the combination is Ti,
Although it depends on the content of Zr, Nb, and Ta, the application to be used, the desired properties, and the like, general industrial applications include, for example, a combination of Cr, Mo, Ni, and Co. A combination of Cr and Mo is preferred. In medical applications, for example, Pd, Pt, A
Examples include combinations of u, Sn, Ni, Al, and V. Of these, combinations of Pt, Pd, and Sn are preferable.

The method for producing a Ti—Zr-based alloy according to the above concept of the present invention is not particularly limited as long as it can produce an alloy having a specific composition as described above, and the same method as described above can be applied. , Desired elements (for example, titanium, sponge titanium, pure titanium grades 1-4, etc .; Z
For r, sponge zirconium, pure zirconium, etc .;
For Nb, pure niobium and for Ta, pure tantalum,
Without limiting the shape, the purity of which does not affect the properties is weighed so as to have the specified composition (% by mass), and this is arc-melted in a water-cooled copper hearth, alloyed, and ingoted. Melting in a crucible, alloying, and powdering by atomization; casting in the same manner;
Floating melting, alloying and ingot method; and mechanical alloying method, sputtering method, plasma method, etc.
Examples of the method include methods generally used in industrial practice, and methods published in various research institutions and literatures. At this time, the form of the desired additive element is the same as that in the known method without any particular limitation. For example, Ni is pure nickel, Cu is pure copper, oxygen-free copper, phosphorus deoxidized copper, tough pitch In the case of Al such as copper, other additive elements such as pure aluminum are used in a pure metal state.

[0046]

The present invention will now be described more specifically with reference to examples.

Examples 1 to 4 and Comparative Examples 1 to 7 Sponge titanium, sponge zirconium, pure niobium and pure tantalum were respectively weighed so as to have the ratios shown in Table 1 below, and these were arc melted in a water-cooled copper hearth. And alloyed to form an ingot. No heat treatment was performed after alloying.

The following mechanical properties of these alloys were evaluated as follows.

The tensile strength and Young's modulus were measured using an Instron tensile tester according to JISZ2201-1980.
The test piece of the No. 6 test was subjected to a strain rate of 1.67 × 10 ⁻³ S ^−1.
Was measured.

The hardness was measured using a micro Vickers hardness tester, and the indentation after holding 10 S at a test load of 50 g was measured as Vickers hardness.

Table 1 shows the alloys of Examples 1 to 4 of the present invention,
As comparative examples, the mechanical properties of pure Ti and typical Ti alloys are shown. In Table 1, the content of each constituent element is represented by mass%.

Also, the quaternary Ti—
FIG. 1 shows an X-ray diffraction diagram showing the β phase of the Zr-based alloy.

[0053]

[Table 1]

As shown in Table 1 above, Examples 1 to 4
The alloy obtained by the method has a sufficiently low Young's modulus of 70 GPa or less as compared with pure Ti and other comparative examples, and has a tensile strength (P
a) / A Young's modulus (Pa) of 0.016 or more is not only supple but also has sufficient tensile strength, which is the stress when the sample breaks. Therefore, the alloy of the present invention is particularly suitable for golf clubs. It is the most suitable material as a medical material because it is most suitable for the head and can be used not only as other industrial materials, but also close to that of living bone.

When these alloys were cold-rolled, all of the alloys of Examples 1 to 4 could be rolled to a rolling reduction of 98%, without cracking or cracking during the rolling, and excellent cold plasticity. Workability was shown. On the other hand, when the alloys of Comparative Examples 1 to 6 were cold-rolled in the same manner, cracks and cracks occurred during the rolling. From this, the alloy of the present invention is excellent in cold plastic workability even in general industrial use as compared with conventionally known Ti-based alloys,
Regardless of cold or heat treatment, it can be easily processed into the desired shape.
It can be formed and opens the way for future industrial materials of Ti-based alloys.

Example 5 Sponge titanium, sponge zirconium, pure niobium, pure tantalum and pure gold were weighed so as to have the ratios shown in Table 2 below, which were arc-melted in a water-cooled copper hearth, alloyed, and ingoted. And

Next, the mechanical properties of this alloy were evaluated in the same manner as in Examples 1 to 4, and the results were shown in Table 2 below.
Shown in

The alloy of Example 5 is obtained by further adding Au as an additional element to a quaternary alloy composed of Ti, Zr, Nb and Ta, and is extremely excellent in corrosion resistance. Since it is a metal with excellent affinity and harmless to the human body, the resulting alloy is also considered to be excellent in biocompatibility and harmless to the human body, and can be expected to be applied to medical applications

[0059]

[Table 2]

Example 6 For the alloys obtained in Examples 2 to 4 and 5 and the pure Ti of Comparative Example 1, a platinum wire was used as a counter electrode and an Ag / AgCl electrode was used as a reference electrode in 1N hydrochloric acid under open air. Using a glass electrolysis cell equipped with a potentio / galvanostat and a function generator, an electrokinetic anodic polarization curve was measured,
The corrosion resistance to acids was evaluated. In this example, the electrolytic cell was held in a constant temperature water bath at 298K. The results are shown in FIG.

As apparent from FIG. 2, the alloys of the present invention and the pure Ti obtained in Examples 2 to 4 and 5 were all passivated, while the alloys of Examples 2 to 4 and 5 were all passivated. It was found that the passivation current density was lower than that of Ti, and that it had better corrosion resistance than pure Ti. Examples 2 to 4 and 5
In particular, the alloy of Example 2 showed the lowest passivation current density and was shown to have the best high corrosion resistance.

Example 7 Titanium sponge, sponge zirconium, pure niobium and pure tantalum were each weighed so as to have the proportions shown in Table 3 below, and were arc-melted in a water-cooled copper hearth to form an alloy to form an ingot. .

Next, the obtained alloys are described in Examples 1 to 3.
The mechanical properties were evaluated in the same manner as in Example 4, and the results are shown in Table 3 below.

The alloy of Example 7 is an alloy in which the content of Ta is relatively reduced among the constituents of the quaternary alloy consisting of Ti, Zr, Nb and Ta. The alloy of Example 7 is suitable as a material for artificial bones because it exhibits the pliability closest to living bone, and typical Ti-6Al-4V, which is currently attracting attention as a medical metal alloy, Ti-
13Nb-13Zr, Ti-29Nb-13Ta-4.
Compared to 6Zr or the like (see Table 1), it shows more excellent numerical values in terms of corrosion resistance and mechanical properties such as strength, Young's modulus and hardness, and is most suitable as a metal alloy for medical use.

[0065]

[Table 3]

Example 8 Titanium sponge, sponge zirconium, pure niobium, and inorganic tin were weighed so as to have the ratios shown in Table 4 below, and were arc-arc-melted in a water-cooled copper hearth to form an alloy to form an ingot. .

Next, the obtained alloys are described in Examples 1 to 3.
The mechanical properties were evaluated in the same manner as in Example 4, and the results are shown in Table 4 below.

[0068]

[Table 4]

[0069]

As described above, the Ti-Zr-based alloy of the present invention contains 25 to 50% by mass of Ti, 25 to 60% by mass of Zr, 5 to 30% by mass of Nb, and 5 to 40% by mass of Ta.
And the mass ratio of Zr to Ti is 0.5 to
1.5 and the mass ratio of Nb to Ta is 0.1
25 to 1.5. Therefore, the metal structure of the Ti—Zr alloy of the present invention is Ti
Despite being an alloy containing Zr and Zr as its main component, its metallographic structure shows a β phase at room temperature without special heat treatment, so that rolling, forging or machining can be performed at room temperature. , Exhibiting excellent workability, and also exhibiting such excellent plastic workability at room temperature, thus opening up a new avenue for Ti-based alloys as general industrial materials, Zr, Ta, and Nb, which are constituent elements, are all dense and strong oxide film constituent elements and have excellent biocompatibility, and therefore are optimal as medical alloys.

In the quaternary Ti—Zr alloy, at least one of Nb and Ta is Ni, C
u, Pd, Pt, Al, Si, Cr, Mn, Co, V,
Fe, Ag, Au, Sn, Mo, Hf, Zn, Ga,
A Ti-Zr-based alloy characterized by being substituted with at least one substitution element selected from the group consisting of W, Tc, Ru, Rh, Cd and In; and the quaternary Ti-Z
0.01% based on the total mass of the constituent elements in the r-based alloy.
~ 5% by mass of Ni, Cu, Pd, Pt, Al, Si, C
r, Mn, Co, O, N, V, Fe, Ag, Au, S
A Ti-Zr-based alloy characterized by containing at least one additional element selected from the group consisting of n, Mo and Hf has more excellent corrosion resistance and acid resistance of the base material and mechanical strength of the base material. Therefore, it is used as a Ti-Zr alloy for general industrial use and also for medical use.

[Brief description of the drawings]

FIG. 1 is an X-ray diffraction graph showing a β phase of a quaternary Ti—Zr-based alloy produced in Example 2.

FIG. 2 is a graph showing a comparison of the corrosion resistance of the Ti—Zr alloys obtained in Examples 2 to 5 and pure Ti in Example 6.

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[Procedure amendment]

[Submission date] January 12, 2000 (2000.1.1)
2)

[Procedure amendment 1]

[Document name to be amended] Drawing

[Correction target item name] Fig. 1

[Correction method] Change

[Correction contents]

FIG.

[Procedure amendment 2]

[Document name to be amended] Drawing

[Correction target item name] Figure 2

[Correction method] Change

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FIG. 2

 ──────────────────────────────────────────────────続 き Continuation of the front page (72) Inventor Zhang Tong 3-17-30, Kongozawa, Taishiro-ku, Sendai-shi, Miyagi (72) Inventor Kazuya Sato 1-15-110, Oritate, Aoba-ku, Sendai, Miyagi Japan Material Co., Ltd. (72) Inventor Takashi Kurosaka 1-15-10 Oritate, Aoba-ku, Sendai City, Miyagi Prefecture Japan Material Co., Ltd. (72) Inventor Yuji Ogata 1-15-10, Oritate, Aoba-ku, Sendai City, Miyagi Japan Material (72) Inventor: Shin Satoshi Wang 1-15-10 Oritate, Aoba-ku, Sendai City, Miyagi Prefecture Within Japan Material Co., Ltd. (72) Inventor: Takashi Kaneko 1500, Inokuchi, Nakai-cho, Ashigara-gun, Kanagawa Prefecture Terumo Corporation Inventor Hiroshi Kasori 1500 Inoguchi, Nakai-machi, Ashigara-gun, Kanagawa Prefecture Terumo Corporation F-term (reference) 4C059 AA01 AA08 4C081 AB01 AB06 CG03 CG06

Claims (3)

[Claims] 1. 25 to 50% by mass of Ti, 25 to 25% of Zr
60 mass%, 5-30 mass% of Nb and 5-40 mass% of Ta, and the mass ratio of Zr to Ti is 0.5
1.5 and the mass ratio of Nb to Ta is 0.1.
A Ti-Zr-based alloy having a particle size of 125 to 1.5. 2. The Ti—Zr-based alloy according to claim 1, wherein at least one of Nb and Ta is Ni,
Cu, Pd, Pt, Al, Si, Cr, Mn, Co,
V, Fe, Ag, Au, Sn, Mo, Hf, Zn, G
A Ti-Zr-based alloy characterized by being substituted with at least one substitution element selected from the group consisting of a, W, Tc, Ru, Rh, Cd and In. 3. The method according to claim 1, further comprising:
01 to 5% by mass of Ni, Cu, Pd, Pt, Al, S
i, Cr, Mn, Co, O, N, V, Fe, Ag, A
The Ti-Zr-based alloy according to claim 1, comprising at least one additional element selected from the group consisting of u, Sn, Mo, and Hf.