Technical Field
[0001] The present invention relates to a deoxidation method of an Al-Nb-Ti alloy for removing
oxygen from an Al-Nb-Ti alloy manufactured using an alloy material that is composed
of an aluminum material, a niobium material and a titanium material and contains oxygen
in a total amount of 0.5 mass% or more.
Background Art
[0002] In recent years, demand for a Ti-Al alloy as a metal material for airplanes or automobiles
is growing. Among others, demand for a Ti-Al-Nb alloy having more enhanced oxidation
resistance by adding Nb to Ti-Al is increasing. When titanium alloy of which main
component is titanium that is an active metal, such as Ti-Al-Nb alloy, is produced,
it is indispensable to prevent contamination by oxygen during melting, and a melting
method such as vacuum arc remelting method (VAR), electron beam melting method (EB),
plasma arc melting method (PAM), vacuum induction melting method (VIM) and cold crucible
induction melting method (CCIM) has been conventionally employed.
[0003] Among these melting methods, the melting method such as VAR, EB and VIM is a melting
method of melting an alloy in a vacuum atmosphere and when such a melting method is
employed for melting a Ti-Al-Nb alloy, not only Al or Nb as an alloy element but also
Ti are evaporated during melting to cause an element loss. More specifically, it is
very difficult in the current industrial process to control the Ti-Al-Nb alloy to
have a target composition, resulting in a rise of the production cost.
[0004] For the smelting of a Ti-Al-Nb alloy having a low oxygen content, production of
a Ti-Al-Nb alloy by use of a high-grade niobium or titanium material having a low
oxygen content is effective, but since the high-grade niobium material is expensive
and its price tends to rise particularly in recent years, a need to produce a Ti-Al-Nb
alloy by use of a relatively low-grade niobium material having a large oxygen content
and being inexpensive, such as lower niobium, niobium oxide ore (Nb
2O
5) and scrap raw material, is increasing day by day. As with the niobium material,
a high-grade titanium material is expensive, and needs for use of a relatively low-grade
titanium material, such as scrap raw material, is also increasing.
[0005] Ti is an active metal and has a very strong bonding force to oxygen present in the
melting atmosphere, and measures to deal with how to decrease the amount of oxygen
entering from the outside during melting and prevent contamination have been heretofore
taken. However, it is not easy to remove oxygen once dissolved in Ti, and although
little is known at present about the effort therefor itself, the related art includes
the following proposals.
[0006] Patent Document 1 discloses a method for melting a γ-titanium aluminide, including
a step of melting, in a calcium oxide-made crucible, a charging material composed
of a titanium aluminide alloy and a metal such as niobium in an amount effective for
reducing oxygen intake into the melt, but only a melting method for a Ti-Al-Nb alloy
is merely described, and a technique regarding a deoxidation method for a Ti-Al-Nb
alloy is neither described nor suggested. In addition, the niobium raw material used
is a high-purity material with a purity of 99.9% or more, and the oxygen concentration
of the Ti-Al-Nb alloy after melting is a concentration not requiring deoxidation.
[0007] Patent Document 2 describes a production method of a Ti-Al alloy, including melting
a Ti-Al alloy in a lime crucible in vacuum or in an inert atmosphere, adding Ca or
a Ca-containing alloy to the melted Ti-Al alloy, and performing a deoxidation treatment.
Patent Document 2 certainly describes a technique regarding the deoxidation method
of a Ti-Al alloy, but even use of a niobium material is neither described nor suggested,
let alone use of a niobium material with a high oxygen content.
[0008] Patent Document 3 describes a method for producing a high-purity and low-oxygen Ti-Al
alloy by, in the smelting of an alloy containing Ti-Al as its main component, deoxidizing
the alloy with Ca, evaporating/removing excess Ca, and performing contamination-free
uniform melting. However, in Patent Document 3 as well, even use of a niobium material
is not described, and the method for deoxidizing a Ti-Al-Nb alloy is neither described
not suggested. In addition, according to the technique described in Patent Document
3, two steps of adding/melting of Ca and melting for removal of Ca and homogenization
are required and moreover, remaining Ca cannot be completely removed, raising a concern
about the increase in the production cost/time and the change in various properties
due to remaining Ca.
Prior Art Document
Patent Document
Summary of Invention
Technical Problem
[0010] The present invention has been made to solve the above-described conventional problems,
and an object of the present invention is, by focusing attention first on the production
of an Al-Nb-Ti alloy containing Al as its main component and having a low oxygen content,
to provide a deoxidation method of a Al-Nb-Ti alloy, in which a Ti-Al-Nb alloy having
a target composition and a low oxygen content can be easily produced without creating
a high vacuum atmosphere.
Solution to Problem
[0011] The method for deoxidizing an Al-Nb-Ti alloy in the present invention includes melting
and holding an Al-Nb-Ti alloy containing from 50 to 75 mass% of Al, from 5 to 30 mass%
of Nb, and 80 mass% or less in total of Al and Nb by a melting method using a water-cooled
copper vessel in an atmosphere of 1.33 Pa to 2.67×10
5 Pa at a temperature of 1,900 K or more, thereby decreasing an oxygen content thereof,
the Al-Nb-Ti alloy being prepared using an alloy material composed of an aluminum
material, a niobium material and a titanium material and containing oxygen in a total
amount of 0.5 mass% or more.
[0012] It is preferred that a CaO-CaF
2 flux obtained by blending from 0 mass% to 95 mass% of calcium fluoride with calcium
oxide is added during melting of the Al-Nb-Ti alloy by the melting method using the
water-cooled copper vessel.
[0013] It is preferred that the melting method using the water-cooled copper vessel is any
one of an arc melting method, a plasma arc melting method and an induction melting
method.
Advantageous Effects of Invention
[0014] According to the deoxidation method of an Al-Nb-Ti alloy of the present invention,
the content of Al in the melt is set to a high concentration of 50 to 75 mass%, so
that even when a high vacuum atmosphere is not created, an Al-Nb-Ti alloy having a
target composition and a low oxygen content can be easily produced by using a low-grade
inexpensive niobium material having a high oxygen content while causing substantially
no volatilization loss of Al, Nb and Ti during melting. An appropriate amount of this
Al-Nb-Ti alloy having a low oxygen content is mixed with Ti having a low oxygen content,
whereby a desired Ti-Al-Nb alloy containing Ti as its main component can be obtained
at a relatively low cost.
Brief Description of Drawings
[0015]
[FIG. 1] A graph diagram illustrating the relationship between the Al content in an
Al-Nb-Ti alloy and the oxygen content before and after melting.
[FIG. 2] A graph diagram enlarging the region surrounded by a square of FIG. 1 illustrating
the relationship between the Al content in an Al-Nb-Ti alloy and the oxygen content
before and after melting.
[FIG. 3] A graph diagram illustrating the relationship between the Al content in an
Al-Nb-Ti alloy and the oxygen content before and after melting, including addition
or no addition of flux.
[FIG. 4] A graph diagram enlarging the region surrounded by a square of FIG. 3 illustrating
the relationship between the Al content in an Al-Nb-Ti alloy and the oxygen content
before and after melting.
Description of Embodiments
[0016] The present inventors have made intensive studies to obtain a Ti-Al-Nb alloy (a Ti-Al-Nb
alloy of which main component being titanium that is an active metal) having a target
composition and a low oxygen content by using the above-described low-grade niobium
material having a high oxygen content.
[0017] As a result, they have conceived that while it is difficult for technical and cost
reasons to reduce the oxygen content in conjunction with previously controlling the
alloy to a desired composition, i.e., to an alloy composition containing titanium
as its main component, when the process thereof is divided and after an Al-Nb-Ti alloy
having a low oxygen content and containing aluminum as its main component is prepared,
the Al-Nb-Ti alloy having a low oxygen content is mixed with an appropriate amount
of pure Ti having a low oxygen content obtained by a normal production method, a Ti-Al-Nb
alloy having a desired composition and containing titanium as its main component may
be obtained relatively in an easy and low-cost manner.
[0018] The present inventors have found that the soluble oxygen concentration (solubility
limit) decreases in a composition range of containing high-concentration Al in an
alloy, and made intensive studies to find a method where even when a high vacuum atmosphere
is not created, an Al-Nb-Ti alloy having a target composition and a low oxygen content
can be easily produced by using a low-grade niobium or titanium material containing
a lot of oxygen, such as lower niobium, niobium oxide ore (NbO
x) and scrap raw material, while causing no volatilization losses of Al, Nb and Ti.
[0019] More specifically, it has been found that when the content of Al in the melt is set
as high as 50 to 75 mass%, even in an Al-Nb-Ti alloy prepared using a low-grade niobium
or titanium material, a deoxidation reaction proceeds during melting in a water-cooled
copper vessel without creating a high vacuum atmosphere and a low-oxygen Al-Nb-Ti
alloy having a target composition can be easily produced while causing substantially
no volatilization loss of Al, Nb and Ti. The present invention has been accomplished
based on this finding.
[0020] In addition, it has also been found that when a CaO-CaF
2 flux not dissolving in titanium and having a specific component composition is added
as a deoxidation reaction accelerator before or during melting of an Al-Nb-Ti alloy,
the deoxidation reaction proceeds more unfailingly.
[0021] The present invention is described in more detail below based on embodiments.
[0022] The deoxidation method of an Al-Nb-Ti alloy of the present invention is a method
where an Al-Nb-Ti alloy containing from 50 to 75 mass% of Al, from 5 to 30 mass% of
Nb, and 80 mass% or less in total of Al and Nb, prepared using an alloy material composed
of an aluminum material, a niobium material and a titanium material and containing
oxygen in a total amount of 0.5 mass% or more is melted and held by a melting method
using a water-cooled copper vessel, such as arc melting method, plasma arc melting
method and induction melting method, in an atmosphere of 1.33 Pa to 2.67×10
5 Pa at a temperature of 1,900 K or more and the oxygen content is thereby decreased.
A low-grade niobium material such as lower niobium, niobium oxide ore (NbO
x) and scrap raw material may be used as the niobium material, and titanium oxide (TiO
x), scrap raw material, etc., may be used as the titanium material.
[0023] As the reason why a low-grade niobium material having a high oxygen content, such
as lower niobium, niobium oxide ore (NbO
x) and scrap raw material, is used for the preparation of an Al-Nb-Ti alloy, these
niobium materials are inexpensive and easy to procure, compared with a high-grade
raw material. As the reason why the total content of oxygen in an alloy material composed
of an aluminum material, a niobium material and a titanium material is set to be 0.5
mass% or more, when the total content of oxygen in the alloy material is less than
0.5 mass%, the oxygen content is slight and a low-oxygen Al-Nb-Ti alloy can be easily
obtained by performing dilution or simple refining. In the present invention, the
upper limit of the oxygen content is not specified, but the upper limit of the total
content of oxygen actually contained in the alloy material above is considered to
be about 30.0 mass%.
[0024] As the reason why in an Al-Nb-Ti alloy prepared using the alloy material composed
of an aluminum material, a niobium material and a titanium material, the Al content
is set to be from 50 to 75 mass%, the Nb content is set to be from 5 to 30 mass%,
and the total content of Al and Nb is set to be 80 mass% or less, when the Al content
in the Al-Nb-Ti alloy is 50 mass% or more and the Nb content is 5 mass% or more, a
deoxidation reaction of the Al-Nb-Ti alloy is allowed to proceed by a melting method
using a water-cooled copper vessel, such as arc melting method, plasma arc melting
method and induction melting method, even in an atmosphere of 1.33 Pa to 2.67×10
5 Pa and not in a high vacuum atmosphere. In addition, as the reason why the pressure
during melting is set to be from 1.33 Pa to 2.67×10
5 Pa, at the pressure in this range, volatilization loss of Al, Nb and Ti is not caused
and reduction in the yield due to scattering of molten metal can be prevented.
[0025] The deoxidation reaction is a phenomenon developed only in a high Al content region
with low oxygen solubility, and it is suggested in the following ternary phase diagram
of Ti-Al-O (
X. L. Li, R. Hillel, F. Teyssandier, S. K. Choi, and F. J. J. Van Loo, Acta Metall.
Mater., 40 [11] 3147-3157 (1992)) that as the Al content is higher, the oxygen solubility limit decreases. In addition,
the deoxidation reaction is a phenomenon developed in a liquid phase and in the case
of an Al-Nb-Ti alloy, when Al activity in the alloy melt becomes high, the deoxidation
reaction proceeds more significantly. When the Al-Nb-Ti alloy has an Al content of
50 to 75 mass%, an Nb content of 5 to 30 mass% and a total amount of Al and Nb of
80 mass% or less, the deoxidation reaction proceeds basically at a temperature of
1,900 K or more.
[0026] In the Al-Nb-Ti alloy, as the reason why the upper limit of the Al content is set
to be 75 mass%, the upper limit of the Nb content is set to be 30 mass%, and the total
amount of Al and Nb is set to be 80 mass% or less, since the Al-Nb-Ti alloy contains
other alloy elements in addition to Nb and Ti or impurities such as oxygen, if the
contents of Al and Nb are too large, the proportion of Ti decreases and the alloy
cannot be an Al-Nb-Ti alloy.
[0027] The deoxidation method of an Al-Nb-Ti alloy of the present invention is described
as a method of reducing the oxygen content without causing substantially no volatilization
loss of Al, Nb and Ti, and the term "substantially no volatilization loss" indicates
that between before and after melting, the difference in Al content is 1.0 mass% or
less and the difference in Nb content is 0.5 mass% or less.
[0028] In the deoxidation of an Al-Nb-Ti alloy, a flux of CaO alone or a CaO-CaF
2 flux obtained by blending more than 0 mass% and 95 mass% or less of calcium fluoride
with calcium oxide is added as a deoxidation reaction accelerator, whereby the deoxidation
reaction is more promoted.
[0029] By the addition of a flux of CaO alone or a CaO-CaF
2 flux obtained by blending more than 0 mass% and 95 mass% or less of calcium fluoride
with calcium oxide, which does not dissolve in the Al-Nb-Ti alloy, Al
2O
3 as a deoxidation product produced during melting of the Al-Nb-Ti alloy produces a
compound with CaO or dissolves in CaO-CaF
2, causing reduction in Al
2O
3 activity and in turn, the deoxidation reaction is further promoted.
[0030] In order for the deoxidation reaction to proceed, it is considered that Al
2O
3 present in the Al-Nb-Ti alloy must be put into contact with the added flux. It is
presumed that since Nb having high specific gravity is added, the specific gravity
of the Al-Nb-Ti alloy is larger than the specific gravity of a Ti-Al binary alloy
and separation of the Al-Nb-Ti alloy from Al
2O
3 and the added flux is prompted, consequently facilitating the contact of Al
2O
3 with the flux.
[0031] In the case of 0 mass% of calcium fluoride, i.e., CaO alone, the flux has a high
melting point and does not melt at a temperature around the melting point of the Al-Nb-Ti
alloy but when put into contact with Al
2O
3 present in the Al-Nb-Ti alloy, produces a CaO-Al
2O
3 compound having a low melting point to reduce the Al
2O
3 activity, making it possible to further promote deoxidation. Accordingly, this flux
can be used, though its melting point is higher than that of the Al-Nb-Ti alloy.
[0032] On the other hand, if the blending amount of calcium fluoride exceeds 95 mass%, contamination
by fluorine is generated. Accordingly, in the present invention, a flux of CaO alone
or a CaO-CaF
2 flux obtained by blending more than 0 mass% and 95 mass% or less of calcium fluoride
with calcium oxide is employed.
Examples
[0033] The present invention is described in greater detail below by referring to Examples,
but the present invention is not limited to these Examples and can be implemented
by appropriately adding changes as long as they comply with the gist of the present
invention, and these changes all are included in the technical scope of the present
invention.
(Relationship between Al content in Al-Nb-Ti alloy and oxygen content before and after
melting)
[0034] Al-Nb-Ti alloys having an oxygen content of 4 to 30 mass% and having various alloy
element contents were prepared using an alloy material composed of an aluminum material,
a niobium material and a titanium material (titanium oxide or metallic titanium).
Deoxidation of each of the prepared Al-Nb-Ti alloys was conducted by melting and then
holding the alloy in a 100 kW plasma arc furnace using a water-cooled copper vessel.
Here, only Ar was used as the plasma gas, and the pressure during melting was 1.20×10
5 Pa.
[0035] In order to examine the effect of the Al content of the Al-Nb-Ti alloy on the deoxidation
reaction caused by melting, samples were prepared using Al-Nb-Ti alloys having an
Al content of 30 mass%, 45 mass%, and 60 mass%, respectively. With respect to the
sample using an Al-Nb-Ti alloy having an Al content of 30 mass% or 60 mass%, both
a sample using, as the titanium material, titanium oxide and a sample using metallic
titanium were made, but with respect to the sample using an Al-Nb-Ti alloy having
an Al content of 45 mass%, only a sample using titanium oxide as the titanium material
was made. In FIGs. 1 and 2, the sample using titanium oxide and the sample using metallic
titanium are denoted by a filled circle mark and a filled square mark, respectively.
In these Al-Nb-Ti alloys, as shown in Table 1, the Nb content is from 10 to 20 mass%.
[0036] The relationship between the Al concentration (Al content) in the Al-Nb-Ti alloy
and the oxygen concentration (oxygen content) before and after melting is illustrated
in FIGs. 1 and 2. The upper side (proximal end side) and the lower side (distal end
side) of the arrow indicate before melting and after melting, respectively. In FIGs.
1 and 2, with respect to the sample using an Al-Nb-Ti alloy having an Al content of
30 mass% or 60 mass%, the plots are shifted slightly to the left or right for making
the filled circle mark and the filled square mark more visible.
[0037] The Al-Nb-Ti alloy is basically required to have an oxygen content of 0.1 mass%
or less, but according to FIGs. 1 and 2, in all of the samples having an Al content
of 30 mass% and 45 mass%, the oxygen content after melting is not 0.1 mass% or less,
failing in satisfying the condition that the oxygen content is 0.1 mass% or less.
On the other hand, in the sample having an Al content of 60 mass%, the oxygen content
after melting is 0.1 mass% or less in the case of using titanium oxide as the titanium
material as well as in the case of using metallic titanium, thus satisfying the condition
that the oxygen content is 0.1 mass% or less.
[0038] The Al deoxidation is governed by Al activity in the titanium alloy, and the Al activity
is supposed to have a logarithmic correlation with the Al content. According to
M. Maeda et al., Material Science and Engineering, A239-240 (1997), 276-280, the relationship between the oxygen content and the Al content after melting is
assumed to become the relationship denoted by the dashed line in FIG. 1. Extrapolating
from this dashed line, it is considered that the oxygen content drops to 0.1 mass%
or less after peaking at an Al content of 50 mass%.
(Relationship between blended alloy concentration before melting and alloy concentration
after nelting)
[0039] In addition, the relationship between the blended alloy concentration before melting
(deoxidation) of the Al-Nb-Ti alloy and the alloy concentration after melting (deoxidation)
was examined. The relationship between the contents of Al and Nb before melting of
the Al-Nb-Ti alloy and the contents of Al and Nb after melting are shown in Table
1. Here, those denoted by No. with suffix "a" indicate a sample using titanium oxide
as the titanium material, and those denoted by No. with suffix "b" indicate a sample
using metallic titanium as the titanium material.
Table 1
| No. |
Before Melting (mass%) |
After Melting (mass%) |
Remarks |
| Al |
Nb |
Al |
Nb |
| 1a |
30 |
10 |
32 |
8.6 |
Comparative Example |
| 1b |
30 |
10 |
27.8 |
10.8 |
Comparative Example |
| 2a |
45 |
15 |
45.8 |
15.4 |
Comparative Example |
| 3a |
60 |
20 |
59.6 |
20.2 |
Invention Example |
| 3b |
60 |
20 |
60.7 |
20.3 |
Invention Example |
[0040] In the case of an Al-Nb-Ti alloy having an Al content of 30 mass%, the difference
in the content was from 2.0 to 2.2 mass% for Al and from 0.8 to 1.4 mass% for Nb,
and deviation from the target composition was thus caused after melting. In the case
of an Al-Nb-Ti alloy having an Al content of 45 mass%, the difference in the content
was 0.8 mass% for Al and 0.4 mass% for Nb, and the deviation from the target composition
was small after melting, but as described above, since the Al content was small, the
oxygen content was not reduced to 0.1 mass% or less.
[0041] On the other hand, in the case of an Al-Nb-Ti alloy having an Al content of 60 mass%,
the deviation after melting was kept to a level where the change in content was from
0.4 to 0.7 mass% for Al and from 0.2 to 0.3 mass% for Nb. This result indicates that
in the case of an Al-Nb-Ti alloy having an Al content of 60 mass%, the Al content
was large enough to reduce all Nb oxide.
· Examples with addition of flux
(Relationship between Al content in Al-Nb-Ti alloy and oxygen content before and after
melting)
[0042] With respect to each of two kinds of Al-Nb-Ti alloys (Ti-60 mass% Al-20 mass% Nb
alloy, Ti-40 mass% Al-10 mass% of Nb alloy), a total of 5 alloys were prepared to
have various blended oxygen concentrations as shown in Table 2 by using an alloy material
composed of an aluminum material, a niobium material (niobium oxide) and a titanium
oxide. The blended oxygen concentration of each alloy is shown in Table 2. Five Al-Nb-Ti
alloys prepared were melted in a 10 kW plasma arc furnace using a water-cooled copper
vessel, and after adding flux as a deoxidation reaction accelerator to each melt (in
No. 1, the flux was not added), they were held to conduct deoxidation of the Al-Nb-Ti
alloy. Here, only Ar was used as the plasma gas, and the pressure during melting was
1.20×10
5 Pa.
[0043] As for the flux added, two kinds of fluxes, i.e., a CaO-CaF
2 flux obtained by blending 80 mass% of calcium fluoride with calcium oxide and a flux
of CaO alone not blended by calcium fluoride, were used.
[0044] The relationship between the Al concentration (Al content) and the oxygen concentration
(oxygen content) after melting of the Al-Nb-Ti alloy is illustrated in FIGs. 3 and
4 and shown in Table 2. In FIGs. 3 and 4, the results of Example without addition
of flux are illustrated together, and the results of Example (Ti-33 mass% Al-10 mass%
Nb alloy, blended oxygen concentration: 4.0 mass%) without addition of flux, which
is not shown in Table 2, are also illustrated.
[0045] As described above, the Al-Nb-Ti alloy is basically required to have an oxygen content
of 0.1 mass% or less. In the sample of No. 1 without addition of flux, since the Al
content is 60 mass%, the oxygen content after melting is 0.076 mass%, and the condition
that the oxygen content is 0.1 mass% or less is satisfied, but in the sample of No.
4 added with a flux of CaO alone, the oxygen content after melting was 0.036 mass%
and in the sample of No. 5 added with a CaO-CaF
2 flux obtained by blending 80 mass% of calcium fluoride with calcium oxide, the oxygen
content after melting was 0.018 mass%, revealing that deoxidation was further promoted.
Table 2
| No. |
Alloy Species |
Flux |
Blended Oxygen Concentration (mass%) |
Oxygen Concentration After Melting (mass%) |
| 1 |
Ti-60 mass% Al-20 mass% Nb |
none |
7.3 |
0.076 |
| 2 |
Ti-40 mass% Al-10 mass% Nb |
CaO |
2.4 |
0.16 |
| 3 |
Ti-40 mass% Al-10 mass% Nb |
CaO-CaF2 (CaF2: 80 mass%) |
0.8 |
0.14 |
| 4 |
Ti-60 mass% Al-20 mass% Nb |
CaO |
2.5 |
0.036 |
| 5 |
Ti-60 mass% Al-20 mass% Nb |
CaO-CaF2 (CaF2: 80 mass%) |
2.5 |
0.018 |
[0046] While the invention has been described in detail and with reference to specific embodiments
thereof, it will be apparent to one skilled in the art that various changes and modifications
can be made therein without departing from the spirit and scope of the invention.
Industrial Applicability
[0048] According to the present invention, an Al-Nb-Ti alloy having a low oxygen content
can be produced at a low cost, and this alloy is mixed with Ti having a small oxygen
content, whereby a Ti-Al-Nb alloy containing Ti as its main component can be produced
at a relatively low cost.