JPS6063334A - Manufacture of niobium alloy - Google Patents

Abstract

PURPOSE:To manufacture simply a high purity Nb alloy having a uniform composition by heating a niobium halide and other metallic halide together with metallic Al to reduce the halides. CONSTITUTION:A niobium halide such as niobium chloride or niobium bromide and other metallic halide such as the chloride or bromide of Ti, Zr or Hf are used in such a ratio as to give a desired alloy composition. They are reduced with metallic Al to obtain an alloy consisting of Nb and other metal such as Ti. The reduction begins at about 300 deg.C, and AlCl3 is produced as a by-product. It is, however, preferable that they are heated to about 600-1,500 deg.C when the reactivity, alloying action and the purity of the resulting alloy are taken into consideration. Chlorides are easily available as said halides, and an Nb-Ti alloy suitable for use as a superconductive material can be manufactured at a low cost by using niobium chloride and titanium chloride.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for producing a niobium-based alloy. For more information, see niobium halides and other halogenated gold fly gold jrA.
The present invention relates to the production of niobium-based alloys using aluminum alloys.

As superconducting materials, Nb-based alloys, such as A15 type compounds such as Nb5Ti alloy, Nb3Sn, and U3Ga, have been developed and have already been put into practical use as wire rods.

In particular, most practical wire rods are currently manufactured from Nb-Ti alloys because Nb-Ti alloys are inexpensive and can be made into wires with only fM.

The composition of commonly used Nb-Ti alloys is Nb3
0~6ow1. %, and its manufacturing method is as follows:
Electron beam melting or consumable electrode type arc melting of metal niobium and metal titanium is repeated twice to make the alloy composition uniform, and the Nt)-Ti alloy is cold worked into a round bar shape. This round bar is placed in a steel tube and rolled into a composite material.

Wire drawing knife Roe 2 The surface is insulated and made into a single core superconductor wire material.

A large number of these single-core wires are combined into multi-core wires, heat treated, and made into multi-core superconducting wires. In order to process the edge material without any problems, the purity of the Nb-Ti alloy becomes an issue, and oxygen, nitrogen,
The inclusion of interstitial impurities such as carbon and magnetic metals such as iron, nickel, and cobalt is also strictly restricted. Furthermore, since uniformity of the alloy composition is also an important condition, melting is usually performed twice as described above.

The present inventors conducted research on a method for obtaining a highly pure niobium-based alloy using only 1 klff, and as a result, they simultaneously reduced niobium halide and other gold halide/*3 using metallic aluminum, Discovered a method to obtain an alloy of niobium and other metals and completed the TC invention.

The niobium halides used in the present invention include niobium chloride and niobium bromide. Other metals that form alloys with niobium include titanium, zirconium, hafnium, etc., and their chlorides and bromides.

Next, the present invention will be described in detail with respect to the case where JJ%-compounds of niobium and titanium (hereinafter referred to as NbcLX and Tictx, respectively) are used.

NbC6x is made by A'jJ after oxidation of alloys such as ferro-niobium and ores containing niobium.
tx is also Jt, A of titanium alloys and ores containing titanium:
g conversion.

It can be obtained by purification.

For example, the reaction between a niobium tM compound, a titanium oxide, and a gold-plated aluminum is 315 Nb0z, +A4-+315 Nb in the case of Nb045, TiCL,
+ALCL33/4 TiC! 4 +A4-)3/A
Ti+TiC! Each reaction represented by z4 takes place, after which an N'b-Ti alloy is formed.

This removed Atff1 varies depending on the composition of the target Nb*Ti alloy, but basically it is
The total amount is sufficient.

These reactions start at about 300° C. and AtCl3 is produced, but AtCl3 is sublimed and discharged from the reaction system at this temperature. after that,? The reaction progresses as 1AEl''Z increases, and all of the wall by-product Atct3 produced by the Nb-Ti alloy escapes, so there is no decrease in the purity of the NbaTi alloy due to htct3.

11bC1x, TiC! The method of supplying tx to the reaction system and the reaction method are not particularly limited, but NbctX and Tic! Even if the reaction is carried out by mixing 4x and aluminum powder, Nbctx, Tlc
The reaction may be carried out by adding tX in liquid or gasified form, or by adding it in powder form or pellet form.

As the reaction atmosphere for the above reaction or the carrier gas for addition, it is preferable to use a gas containing less water, such as Ar, He, etc., since chlorides with strong hygroscopic properties are handled. Further, in order to quickly and completely remove aluminum halide produced as a by-product of the reaction from the reaction system, it is preferable to flow the carrier gas in a flow-through manner. However, the flow rate needs to be adjusted to minimize raw material loss.

In the unexploded January, ALi is the target 1 (b-Ti-i It varies depending on the composition of the gold, but it is practically sufficient to carry out the reaction according to the above reaction formula, and preferably an At-soluble state is required. The amount is in the range of 0.5 times or more and 3 times or less, more preferably 0.8 to 2.0 times the number of moles.

When using A4 powder i7J't, it is 0.5 times or more and 1.2 times or less, preferably 0.8 to 1.2 times the number of moles thereof.
1 times the range.

When used in the molten state of At, if it is less than 0.8 times the number of moles, the loss of NbC2X and TiCLX will increase, and if it is more than 5 times the number of moles, the amount of unreacted A4 will increase, and a large amount of alkali will be generated during Nb extraction. A solution is required.

When using At powder, if the number of moles is less than [15 times,
The loss of chloride increases, and if it is larger than 1.2 times, the recovered Nb
-Unreacted A4 in the Ti alloy remains, requiring a P1+8 treatment step.

Another feature of the present invention is that lower chlorides of both niobium chloride and titanium chloride can be utilized. For example, in the case of -4 chloride, NbC! 4. In addition, NbOt4rNbOt3.
．． 8. Nb062,6. , NbC12,1,, Nb
O12, titanium chloride, in addition to T i Ct4, Ti0
z3. Any TiO4 reaction method can be used, i.e. in liquid form.

It can be used depending on the method, gaseous or solid.

In addition, metal aluminum, which is a reducing agent, can be used in powder form, pellets, lumps, or sheets.
The advantage is that the reaction method can be selected depending on the shape of the material.

In particular, when At powder is used, it is generally used for in-phase reactions, and the A4 powder is preferably 100 meshes or less in order to increase the contact area with chloride.

Another feature of the present invention is that an alloy having a desired composition can be easily obtained by changing the amount of chloride added during the reduction reaction. The reaction temperature of the reduction reaction with At is not particularly limited as long as it is 300°C or higher, but from the viewpoint of reactivity 7 alloying 2 alloy purity etc.
o 'C is preferred. In addition, in order to improve the yield of the product, it is preferable to use a halide as a raw material because the reaction is good in the same phase.

The reaction is normally carried out under atmospheric pressure, but as long as the airtightness of li:1 is ensured, the reaction can be carried out satisfactorily even under reduced pressure or increased pressure.

The reaction can be carried out using metal, ceramic, or carbon wood as the wood for the reaction vessel.

In the present invention, the alloy composition can be freely changed by adjusting the amount of niobium halide, halogen compound 4 of 11ρ, and niobium compound can be easily obtained in a highly pure form. Therefore, since the obtained niobium-based alloy has a uniform composition, the N
Even in the case of b*Ti negative gold, a high purity alloy can be obtained without the need for treatments such as twice melting as in the conventional method.

Next, the present invention will be described in more detail with reference to Examples, but the invention is not limited thereto.

Example 1 As a niobium source, purified Nb0z was obtained by chlorinating ferro-niobium and passing through a process such as distillation to produce a ferrite sheath.

The composition of Nb0t is Nb: 34.4wt%,
ct: 65.6 wt%.

As a titanium source, purified Ti0t4 was obtained through a chloride lit j% process such as chlorination and distillation of synthetic rutile.

The composition of Ti c A4 is Ti: 25.3wt
%, az near 4.7vt%.

Target Nb*Ti, alloy is generally superconducting Nb
Nb 55wt%-Ti used as eTi
The content was set at 45 wt%.

Tict4 bay to obtain the target Nb-Ti alloy.

Evaporation kA # of NbCl6 53.9 f shown in Figure-1
I put them separately in B. In addition, there are 2 At grains in the iron crucible.
5y (1.63 times the required At:fn:i), the reaction system was sufficiently purged with argon, the cock (a) was closed, and Ar was added from evaporator B at a rate of 100 d/M. The temperature of only the reaction vessel was raised to 800°C.

The reaction vessel was kept at 800℃, then Nb0z, ,
In order to match the evaporation amount of TiC4 per unit time, first, the temperature of NbC1 evaporator B was raised to 200° C. over 60 minutes. 20 minutes after heating the evaporator B, open the cock (a) and while flowing Ar at 1o 4, T i OA4
The temperature of evaporator A was raised to 90°C in 10 minutes, and NbC'5*
The reaction was carried out for 3 hours with approximately the same amount of evaporated Ticz4.
．． I got 1. After the reaction, the reactor was cooled while flowing Ar.

4Jt' of Nb-Ti alloy and unreacted AL from an iron crucible.
htat3 from Gastrap approx. c) sy IEI
I got it.

Recovered Nb-Ti alloy and unreacted At mixture approximately 43.25'
was ground and unreacted At was removed with 40% sodium hydroxide solution.
It was partially melted and the Nb-Ti alloy was recovered.

As a result of X-ray diffraction, this alloy was found to form a complete Nb.1.1 alloy. In addition, as a result of one analysis, the constants are Nb: 54.9wt% - T1: 45.0wt%, and the gas components are also oxygen 5Qpyn, nitrogen 8pμ, carbon 511
111, total component is iron 25p, At 15ppII
It was found that the alloy can be used as a superconducting Ml)-Ti alloy.

Example 2 As a niobium source, Nb3cA8(
Nb: 49.6 wt%, C6: 50.4 wt%
) is 302, and the titanium source is TiCl2 (
Ti: 31.0wt%, at: 69.0wt%)
After thoroughly mixing 9.2y and A4 stamp powders with 10.72 (chemical h (-stoichiometric amount) required for the reaction) in a glove box with an Ar atmosphere, pelletize the powder, and place the pellet in a quartz glass boat. This boat was further placed in a quartz glass reaction tube, and then taken out from the glove box.

Installed in a horizontal tank air furnace maintained at 700'C, Ar
After reacting for 2 hours while flowing Ar into the reaction tube at 100 J/2.4, the reactor was taken out of the furnace and cooled while flowing Ar.

After cooling to room temperature, the quartz glass boat was recovered.
Inside the boat, NbeTi alloy was formed in the form of a pellet.

As a result of constant 9 analysis, the target Nb: 55wt%-T1'
55.1w of Nb per 45wt%1 alloy
"i: 45.0 wt%, other components include Fe 2
011FI, At25 ppi.

Si, 511F, 030ppm, C8pp+i,
N was 10 ppm.

[Brief explanation of drawings]

FIG. 1 is a diagram showing the device 1 used in Example 1 of the invention. 1: Raw material heating section A 7: Molten aluminum 2: Raw material charging section 8 Nil crucible 3: Cutting cock (a) 9: Vertical 1; 6 vessel 4: Raw material heating section B 10: Reaction section heater 5: Raw material container Entry 1i: A
TCT3 extractor 6: Switching cock (b) 12: Thermocouple Patent applicant Toyo Soda Kogyo Co., Ltd.

Claims (1)

[Claims] 1. A method for producing a niobium-based alloy, which comprises heating niobium halides, other metal halides, and metal aluminum. 2. As niobium and other halides of Imaka 8,
Use these chloride proboscises! Item 1 of Section 1 of Section 1 of the request for permission. 5. 'l:J' using titanium as a metal other than niobium
1) The method according to claim 1 or 2.