KR20160082947A - Manufacture method for titanium-niobium alloy - Google Patents

Abstract

The present invention relates to a method for manufacturing a titanium-niobium (Ti-Nb) alloy from titanium-niobium oxide (TiNb_2O_7). The method for manufacturing a titanium-niobium (Ti-Nb) alloy comprises: a step where titanium dioxide (TiO_2) reacts with niobium pentoxide (Nb_2O_5) in an electric furnace to produce titanium-niobium oxide; a step of reducing the titanium-niobium oxide (TiNb_2O_7) using a metal reducing agent to produce a titanium-niobium (Ti-Nb) alloy; and a step of removing metal reducing agent oxide and a surplus metal reducing agent by an acid leaching process.

Description

TECHNICAL FIELD [0001] The present invention relates to a method of manufacturing a titanium-niobium alloy (Ti-Nb alloy)

The present invention relates to a method for producing a titanium-niobium alloy, and more particularly, to a method for producing a titanium-niobium alloy by reducing a titanium-niobium oxide produced from a reaction between titanium dioxide (TiO ₂ ) and niobium pentoxide (Nb ₂ O ₅ ) Titanium-niobium alloy (Ti-Nb alloy).

In general, titanium alloys are light, strong, and corrosion-resistant, and are widely used as materials for various parts.

In particular, titanium-niobium alloy (Ti-Nb alloy) among titanium alloys is a typical alloying-type superconducting material most commonly used for superconducting magnets since it has good plasticity and no electric resistance at low temperature.

Conventionally, an ingot is produced by mixing and melting titanium (Ti) and niobium (Nb) metals in a desired composition. At this time, the electron beam melting method is used to minimize impurities such as oxygen. The ingot can then be preformed and compounded with copper (Cu), which serves as a stabilizing role for the current and as a structural reinforcement. At this time, a majority of titanium-niobium (Ti-Nb) superconducting alloy wires are inserted into a copper (Cu) base to produce a multifilamentary wire. Such a multifilamentary wire can be used as a practical superconductor because the current distribution in the conductor is uniform and the alternating current loss is small.

However, such a manufacturing method requires an electron beam melting technique, resulting in an increase in production cost. In addition, the process up to the pre-shrinkage is repeatedly subjected to a complex procedure such as hot extrusion, cold working, heat treatment, and cold working, thereby complicating the process.

It is an object of the present invention to provide a method of manufacturing a titanium-niobium (Ti-Nb) alloy by a simpler process.

It is another object of the present invention to provide a method for producing a titanium-niobium alloy (Ti-Nb alloy) in powder form from titanium dioxide (TiO ₂ ) and niobium pentoxide (Nb ₂ O ₅ ).

Another object of the present invention is to provide a method for producing a titanium-niobium alloy (Ti-Nb alloy) at a melting point lower than the melting point of titanium dioxide (TiO ₂ ) and niobium pentoxide (Nb ₂ O ₅ ).

In order to achieve the object of the present invention, the present invention provides a method of producing a titanium-niobium oxide according to the above (1), wherein titanium oxide (TiO ₂ ) is reacted with niobium pentoxide (Nb ₂ O ₅ ) (2) in which the titanium-niobium oxide produced in the step (1) is reacted with the metal reducing agent to form the titanium-niobium alloy (Ti-Nb alloy) and the metal reductant oxide, And (3) removing excess metal reducing agent by an acid leaching process. The present invention also provides a method for producing a titanium-niobium alloy.

More specifically, the reaction in the above step (1) is represented by [Reaction Scheme 1].

[Reaction Scheme 1]

_{xTiO 2 + yNb 2 O 5 →} Ti x Nb 2y O (2x + 5y)

In this case, the mixing molar ratio (x: y) of the above Reaction Scheme 1 is 1: 9 to 9: 1.

The reaction in step (1) proceeds at a temperature of 1500 ° C. or higher.

More specifically, the metal reducing agent used in step (2) is calcium (Ca), aluminum (Al), or carbon (C).

The reduction reaction in the step (2) is carried out at a temperature of 1500 ° C or higher.

More specifically, acetic acid (CH ₃ COOH), hydrochloric acid (HCl), nitric acid (HNO ₃ ), or sulfuric acid (H ₂ SO ₄ ) is used as the acid leaching reaction in the step (3).

According to the method for manufacturing a titanium-niobium alloy (Ti-Nb alloy) according to an embodiment of the present invention, the following effects can be expected.

In an embodiment of the present invention, a titanium-niobium alloy (Ti-Nb alloy) can be manufactured from a more simplified process.

In an embodiment of the present invention, a titanium-niobium alloy (Ti-Nb alloy) having a larger volume than the titanium-niobium alloy powder is produced from the titanium-niobium oxide, can do.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 is a flow chart schematically illustrating a method of manufacturing a titanium-niobium alloy (Ti-Nb alloy) according to an embodiment of the present invention.
FIG. 2 is a melting-point diagram according to a mixed molar ratio of titanium dioxide (TiO ₂ ) and niobium pentoxide (Nb ₂ O ₅ ).
3 is an Ellingham diagram for indicating the reactivity of the metal reducing agent.
4 is a photograph of a titanium-niobium alloy (Ti-Nb alloy) obtained by reducing the titanium-niobium oxide produced according to an embodiment of the present invention.

Hereinafter, a method for fabricating a titanium-niobium alloy (Ti-Nb alloy) according to an embodiment of the present invention will be described in detail with reference to the accompanying drawings.

FIG. 1 is a flowchart schematically showing a method for producing a titanium-niobium alloy according to an embodiment of the present invention. FIG. 2 is a graph showing a mixed molar ratio of titanium dioxide (TiO ₂ ) and niobium pentoxide (Nb ₂ O ₅ ) FIG. 4 is a photograph of a titanium-niobium alloy (Ti-Nb alloy) obtained by reducing titanium-niobium oxide produced according to an embodiment of the present invention.

Referring to FIG. 1, the present invention provides a method of manufacturing a titanium-niobium oxide, comprising the steps of: (1) forming titanium-niobium oxide; (2) forming a titanium-niobium alloy; (Ti-Nb) alloy including a metal reductant oxide as a by-product of step S20 and an excess metal reducing agent in an acid leaching step (3) (S30) .

More specifically, in step (1) (S10), titanium dioxide (TiO ₂ ) is reacted with niobium pentoxide (Nb ₂ O ₅ ) in an electric furnace to produce titanium-niobium oxide. The reaction formula in which the titanium-niobium oxide is produced can be represented by the following Reaction Scheme 1.

[Reaction Scheme 1]

_{xTiO 2 + yNb 2 O 5 →} Ti x Nb 2y O (2x + 5y)

At this time, the mixing molar ratio (x: y) of the above Reaction Scheme 1 may be determined within the range of 1: 9 to 9: 1. However, when the molar ratio of the titanium dioxide (TiO ₂ ) is relatively low as compared with the niobium pentoxide (Nb ₂ O ₅ ), the efficiency of the reaction is decreased. If the molar ratio of the niobium pentoxide (Nb ₂ O ₅ ) is relatively high as compared with the titanium dioxide (TiO ₂ ), a high melting point is required, so that the caustic ratio is reduced. Also, referring to FIG. 2, TiNb ₂ O ₇ is produced without a surplus of reactant when the mixing molar ratio of titanium dioxide (TiO ₂ ) to niobium pentoxide (Nb ₂ O ₅ ) is 1: 1 within the above range, Preferably, the mixing molar ratio may be 1: 1.

The titanium-niobium oxide has a melting point of 1500 ° C under the condition that the mixing molar ratio of titanium dioxide (TiO ₂ ) and niobium pentoxide (Nb ₂ O ₅ ) is 1: 1. Accordingly, the reaction in the step (1) may be carried out at a temperature of 1500 ° C. or higher in a state where the partial pressure of an inert gas such as argon (Ar) gas in the furnace is controlled.

In the embodiment of the present invention, the metal reducing agent in step (2) (S20) may be calcium (Ca), aluminum (Al), or carbon (C). Of these, calcium (Ca) is preferable. As shown in FIG. 3, calcium (Ca) has a relatively low G because it has a good reactivity, so that it can be rapidly reduced. Such limitations are not absolute but refer to metal reducing agents mainly used in embodiments of the present invention. Accordingly, a metal reducing agent which is not melted at the reaction temperature of the embodiment of the present invention can be included in the metal reducing agent.

In step (2) (S20), the temperature and time conditions of the reduction reaction may be the same as the limiting conditions of step (1) in the continuous process of step (1).

In an embodiment of the present invention, the titanium-niobium oxide reacts with the metal reducing agent so that the titanium-niobium alloy is reduced to produce a titanium-niobium alloy and a metal reducing agent oxide. Substantially in the step (2) (S20), in addition to the titanium-niobium oxide and the metal reducing agent oxide, a surplus metal reducing agent may remain.

That is, in the step (3) (S30), the metal reducing agent oxide and the excess metal reducing agent generated after the titanium-niobium oxide is reduced in the step (2) may be removed by an acid leaching process . Therefore, only the titanium-niobium alloy (Ti-Nb alloy) can be selectively recovered by removing the metal reducing agent oxide and the excess metal reducing agent.

In an embodiment of the present invention, the acid leaching reaction may be an aqueous acid solution of acetic acid (CH ₃ COOH), hydrochloric acid (HCl), nitric acid (HNO ₃ ) or sulfuric acid (H ₂ SO ₄ ). Such limitations are by no means absolute, but are limiting in nature to acids that are primarily used to remove reaction by-products in embodiments of the present invention. Therefore, the reaction by-product of the present invention does not generate additional by-products during the acid leaching reaction, and all acids capable of removing reaction by-products can be included in the reaction product.

In the embodiment of the present invention thus constructed, as shown in FIG. 4, a titanium-niobium alloy (Ti-Nb alloy) is produced in a concentrated form rather than in a powder form (see FIG. Accordingly, the Ti-Nb alloy in the aggregated form has a lower oxidation reaction rate of the Ti-Nb alloy than the Ti-Nb alloy in powder form, The corrosion of the titanium-niobium alloy (Ti-Nb alloy) can be relatively prevented.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the present invention as defined by the appended claims and their equivalents. .

Claims (6)

(1) titanium dioxide (TiO ₂ ) is reacted with niobium pentoxide (Nb ₂ O ₅ ) in an electric furnace to produce titanium-niobium oxide;
(2) the titanium-niobium oxide produced in the step (1) reacts with the metal reducing agent to produce a titanium-niobium alloy and a metal reducing agent oxide; And
(3) removing the metal reducing agent oxide and excess metal reducing agent, which are produced as reaction by-products in the step (2), by an acid leaching process; (Ti-Nb) alloy.
The method according to claim 1,
Wherein the reaction of step (1) is represented by [Reaction Scheme 1], and the Reaction Scheme 1 satisfies the following mixing molar ratio condition.

[Reaction Scheme 1]
_{xTiO 2 + yNb 2 O 5 →} Ti x Nb 2y O (2x + 5y)
(Wherein x: y is 1: 9 to 9: 1)
The method according to claim 1,
In the step (1), the reaction proceeds at a temperature of 1500 ° C. or higher, and the Ti-Nb alloy is produced.
The method according to claim 1,
Wherein the metal reducing agent is calcium (Ca), aluminum (Al), or carbon (C) in the step (2).
The method according to claim 1,
Wherein the reduction reaction in the step (2) is performed at a temperature of 1500 ° C or higher.
The method according to claim 1,
The above-mentioned (3) acid leaching step reaction is acetic acid (CH ₃ COOH), hydrochloric acid (HCl), nitric acid (HNO ₃₎ or sulfuric acid (H ₂ SO ₄₎ the titanium is used as aqueous acid solution-niobium alloy (Ti-Nb alloy ).

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