WO2018047990A1

WO2018047990A1 - Method for preparing cu-zr alloy ingot from ba-zr-f compound

Info

Publication number: WO2018047990A1
Application number: PCT/KR2016/010014
Authority: WO
Inventors: 이종현; 하이크 네르시시얀; 이영준; 한슬기; 최정훈; 박동재; 주신형
Original assignee: 충남대학교산학협력단; 주식회사 엔에스이
Priority date: 2016-09-07
Filing date: 2016-09-07
Publication date: 2018-03-15

Abstract

A method for preparing a Cu-Zr alloy ingot from a Ba-Zr-F compound, according to the present invention, provides high energy efficiency and enables preparation of a Cu-Zr alloy ingot which can contain 28 wt % or more of Zr in a Cu base material by means of a simple process.

Description

Specification

Name of invention: CU-ZR alloy ingot from BA-ZR-F compound

How to make

Field of technology

[1] The present invention relates to a method for producing a Cu-Zr alloy ingot from a Ba-Zr-F compound.

Background

[2] Zirconium is very useful for nuclear energy-related engineering materials and nuclear materials because of its high permeability and its inherent properties such as corrosion resistance. In particular, zirconium has good strength and circulation at high temperatures. Because it is not easily corroded to coolant, does not form radioisotopes well, and has little mechanical damage by inductor irradiation, 90% of the world's zirconium production is used for the nuclear industry.Therefore, nuclear reactors, gratings, guides, It is very important for coating pipes, alloys with uranium, etc. covering heavy water pressure pipe materials and nuclear fuel rods.

[3] The Kroll method, a conventional method for smelting zirconium from zirconium ore, is mainly used for mass production processes, but it uses chlorine gas, which is highly toxic due to the multistage chlorination process. There is a limit to environmental friendliness.In addition, commercially available products are not separated from their coexisting hafnium, and contain 2 to 3% of hafnium, which is not high in purity, and thus requires an additional process for separation.

[4] Other techniques are described in US Patent Publication US2007-0003474A1.

Zirconium tetrafluoride (ZrF ₄ ) is known for recycling zirconia by recycling. ZirF ₄ is transformed into ZrF ₄ zirconia (ΖιΌ ₂ ) by heating based on solid ZrF ₄ and water. This method is not preferable because a large amount of harmful gases such as hydrofluoric acid and nitric acid, which are generated when heated to a high temperature, can be released in the air in large quantities.

[5] These zirconium alloys containing or containing dissimilar metals

For example, zirconium alloys can be used for special purposes such as welding electrodes, casting molds, electrical components, aerospace, etc., and are mainly made of Cu-Zr type master alloys. Various adjustments are made and supplied.

[6] United States Patent Application Publication No. 2015-0225818A1 uses a discharge plasma sintering method.

Zirconium and 5 to 8, weight ^«is a method for producing a Cu-Zr alloy containing a ¾ known. In addition, the parent company in Japan uses the hot extrusion method to add only about 0.1 at.% Of copper zirconium to up to about 50 times indium zirconium up to 5.0 at.%. We have developed a zirconium-copper alloy wire that realizes high conductivity.

[7] However, the above method has to be based on expensive manufacturing equipment, and has a large disadvantage in that the content of zirconium in the copper base material is extremely low.

Detailed description of the invention

Technical task

[8] The purpose of the present invention is to prepare a Qi-Zr alloy ingot from Ba-Zr-F compounds.

Is to provide a way.

[9] Specifically, the main object of the present invention is to provide a method for producing a zirconium-containing Cu-Zr-based alloy ingot from Ba-Zr-F-based compound through an environmentally simple heat treatment process.

Task solution

The present invention provides a method for producing a Cu-Zr alloy ingot.

[11] The method for producing a Cu-Zr alloy ingot according to the present invention comprises: a) mixing a Ba-Zr-F based compound, magnesium and copper, wherein the molar ratio of copper to the Ba-Zr-F based compound is 1: 3-10 and b) heat-treating the mixed mixture in step a) at 1,150-1,500 ° C. In this case, the product obtained in step b) is a fluorine-based compound and Cu. -Zr alloy ingot can be divided into two layers.

[12] In one embodiment of the present invention, a method of manufacturing a Cu-Zr alloy ingot is provided in c), b).

The method may further include separating the Cu—Zr alloy ingot from the product obtained in the step.

[13] In an example of the present invention, the heat treatment of step b) is preferably performed.

May be performed at 1,200-1,500 ° C.

In an example of the present invention, the heat treatment of step b) may be specifically performed for 0.5 to 10 hours.

[15] In one embodiment of the present invention, the molar ratio of copper to Ba-Zr-F compounds is

Specifically 1: 3-5.

[16] In an example of the present invention, the molar ratio of magnesium to Ba-Zr-F compound is

As long as magnesium can reduce the Ba-Zr-F compound as a reducing agent, it may be 1: 0.5 to 10, for example.

[17] In one embodiment of the present invention, the Ba-Zr-F-based compound is specifically BaZrF ₆ , Ba ₂ ZrF

8, Ba ₅ Zr ₂ F, ₃ and BaZr ₂ F ₁₀ and the like may include any one or more.

[18] In one embodiment of the present invention, the Cu-Zr alloy ingot specifically includes any one or two or more selected from CuZr, CuZr ₂ , Cu ₈ Zr ₃ , Cu ₁₀ Zr ₇ and Cu _5l Zr, _4, and the like. And preferably one or more selected from Cu ₁₀ Zr ₇ and Cu _5l Zr ₁₄ .

[19] In one embodiment of the present invention, the Cu-Zr alloy ingot is the entire Cu-Zr alloy ingot. It can contain 1 to 30% by weight of zirconium by weight.

Effects of the Invention

[20] The production method of Cu-Zr alloy ingot from Ba-Zr-F compound of the present invention has the effect of producing Cu-Zr alloy ingot with high energy efficiency and simple process.

In particular, the manufacturing method has the advantage of producing a Cu-Zr alloy that can contain up to 30% by weight of zirconium base material in an eco-friendly simple heat treatment process.

[22] Notwithstanding the effects not expressly stated herein, it is noted that the effects described in the following specification, which are expected by the technical features of the present invention, and their potential effects, shall be treated as described in the present specification.

Brief description of the drawings

1 is an image of a product obtained according to Examples 1 to 3, Comparative Example 1, and Comparative Example 2, and is in the order from the upper left to the right and the lower left to the right in order. 2, Example 3 The images for Comparative Example 1 and Comparative Example 2. FIG.

FIG. 2 is an image of a product obtained according to Examples 1 to 3, Comparative Example 1, and Comparative Example 2. FIG.

3 is a spectrum showing the results obtained by measuring the Cu-Zr alloy ingot obtained according to Examples 1 to 3, Comparative Example 1 and Comparative Example 2 by X-ray diffraction analysis.

4 shows a scanning electron microscope of a Cu—Zr alloy ingot obtained according to Example 4;

Data measured using Energy Dispersive X-ray Spectroscopy (EDS). (a is an image of ingot cutting section, b is an image of the cutting section observed by scanning microscope, b-1 is an image of the distribution of Cu elements by EDS, b-2 is an analysis of the distribution of Zr elements by EDS Image.)

Best Mode for Carrying Out the Invention

Hereinafter, a method of manufacturing a Cu-Zr alloy ingot from the Ba-Zr-F compound of the present invention will be described in detail with reference to the accompanying drawings.

[28] The drawings described in the present invention are provided as examples to ensure that the idea of the present invention is sufficiently communicated to those skilled in the art. Thus, the present invention may be embodied in other forms without being limited to the drawings presented. The drawings may be exaggerated to clarify the spirit of the invention.

[29] In addition, unless otherwise defined in the technical and scientific terms used in the present invention, it has the meaning commonly understood by a person of ordinary knowledge in the technical field to which the present invention belongs, as shown in the following description and accompanying drawings. Descriptions of known functions and configurations that may unnecessarily obscure the subject matter of the invention are omitted.

In addition, in the present invention, the unit of% used unclearly without special mention means% by weight. [31] The present invention provides a method for producing a Cu-Zr alloy ingot.

[32] The method for producing a Cu-Zr alloy ingot according to the present invention comprises the steps of: a) mixing Ba-Zr-F based compounds, magnesium and copper, and b) heat treating the mixed mixture in step a). Include.

[33] In step b), the melting point of the mixture containing Ba-Zr-F-based compound, magnesium, and copper to be melted at a temperature above the melting point of l, 085 ^o C (The melting point of copper is

1,085 ° C) As a result of the heat treatment, the mixture is in the form of a liquid melt. Thus, the mixture in the molten state can be phase separated by the density difference of the respective components.

[34] The method for producing a Cu-Zr alloy ingot may further include cooling the product, which is a mixture of molten state produced in step b). In one embodiment, the cooling step is not particularly limited, for example, 25 It may be performed at ~ 300 ° C, specifically 50-200 ° C, more specifically at 75-150 ^° C.

[35] The condensed product includes a Cu-Zr compound and a by-product Ba-Mg-F compound. Thus, the method for producing a Qi-Zr alloy ingot is based on c) from the product obtained in step b). It may further comprise a step of separating the Zr alloy ingot.

[36] However, if the molar ratio and heat treatment temperature of each component described below are not satisfied,

Since Cu-Zr compound and by-product Ba-Mg-F compound are not automatically separated and formed, it may not be possible to manufacture Cu-Zr alloy ingot separated from Ba-Mg-F compound. It is as follows.

In the step b), the magnesium is heat-treated at a melting point or higher.

As a reducing agent, Ba-Zr-F compounds are reduced to reduce barium fluoride, magnesium barium and

Si) reaction to produce zirconiumol, s2) reaction to generate Cu-Zr compound by reaction of generated zirconium and copper, and reaction of produced barium fluoride and produced magnesium barium to produce Ba-Mg-F compound S3) a reaction is carried out. This is a specific example, which can be described as Scheme 1 below when the Ba-Zr-F compound is Ba ₂ ZrF ₈ .

[38] [Bandungsik 1]

[39] si) Ba ₂ ZrF ₈ + 2Mg → 2BaF ₂ + 2MgF ₂ + Zr

[40] s2) xCu + Zr → Cu _x Zr

[41] s3) BaF ₂ + gF ₂ → BaMgF ₄

[42] As in Reaction 1, in step b), the Ba-Zr-F-based compound, the magnet and the copper react at a melting point temperature, and finally, the Cu-Zr-based compound and BaMgF containing Cu _x Zr. A product containing a Ba-Mg-F based compound including ₄ is produced.

[43] At this time, the molar ratio of copper to Ba-Zr-F based compound which is initially mixed is 1: 3 ~ 10,

Specifically, in the case of 3 to 5, that is, when 1 m of the Ba-Zr-F-based compound is mixed to 3 mol or more, a Cu-Zr-based composition having a higher density than that of the Ba-Mg-F-based compound The compound is produced, and the product obtained in the state separated into two layers by the density difference can be obtained. It is possible to manufacture Cu-Zr alloy ingot easily.

On the other hand, when the copper content of less than 1 mol of the Ba-Zr-F-based compound is less than 3 mol, the density difference of each compound is lower than that of the Ba-Mg-F-based compound or the actual dissociation may occur. It is not possible to manufacture the Cu-Zr alloy ingot separated from the Ba-Mg-F based compound itself, and the upper limit of the copper can be controlled according to the content of zirconium, which is required for the Cu-Zr alloy ingot and is not greatly limited. For example, may be 10 m.

[45] In other words, for 1 m of the Ba-Zr-F-based compound, when the copper is 3 mol or more, specifically 3-10 mol, and more specifically, 3 to 5 m, the resulting Cu-Zr-based compound and

Phase separation occurs due to the density difference of Ba-Mg-F-based compounds, and it is possible to separate and manufacture Cu-Zr-based alloy ingots separated from Ba-Mg-F-based compounds.

[46] In addition, the Cu-Zr alloy ingot produced when the above molar ratio is satisfied up to 30 wt% ^< z / 4 of zirconium, specifically 1-30 wt%, more specifically 5-30 wt% of the total weight of the alloy. There is a possible effect.

In a further preferred embodiment, the heat treatment in step b) is performed at 1,150-1,500 ° C.

Preferably 1,200-1, 500 ° C, more preferably l, 300 ~ l, 500 ^o may be performed on the C. When the heat treatment temperature is less than 1,200 ° C, the Ba of the density difference, even if satisfying the above molar ratio Phase separation of Cu-Zr compounds from Mg-F compounds may not occur.

[48] More preferably, the heat treatment temperature can be 1,300 ~ 1,500 ° C, and if it is satisfied, the concentration of impurities such as oxide can be minimized, so that a higher purity Cu-Zr alloy ingot can be obtained, and the content of zirconium There is an effect that can be increased than this. Specifically, the heat treatment temperature is

At 1,300 ~ 1,500 ° C, the content of oxygen-based impurities such as oxygen or oxygen compounds is 0.2% by weight or less, more specifically, 0.01-0.2% by weight, more specifically 0.01, based on the total weight of the Cu-Zr alloy ingot. It may be ~ 0.16% by weight.

[49] As described above, the separation of the Ba-Mg-F-based compound and the Cu-Zr-based compound depends on the copper concentration during initial mixing, so that the molar ratio and heat treatment of each component described above are performed at the same time to satisfy the degree. Separation of high-purity Cu-Zr alloy ingots is more effective, and the zirconium content of the Cu-Zr alloy ingots produced can be further increased if the molar ratio and heat treatment temperature of each component described above are satisfied.

[50] The Ba-Mg-F compound and the Cu-Zr compound were formed in two layers.

As the step c), which separates the product, proceeds, the surface of Ba-Mg-F-based and Cu-Zr-based compounds in the solid product formed by cooling the melt (molten compound) is cut and And / or can be separated into a Ba-Mg-F-based compound and a Cu-Zr-based alloy ingot by grinding or the like. In step c), the separation can be performed by the flow of each layer, such as pouring up or down the melt before cooling. But besides that Ba-Mg-F-based compounds and Cu-Zr-based compounds are not limited because various methods may be used to separate the two-layered product.

In an example of the present invention, the heat treatment time may be such that phase separation may occur due to the density difference between the Cu-Zr compound and the Ba-Mg-F compound, for example, 0.5-10. Hour, specifically 0.5-5 hours.

[52] In one embodiment of the present invention, the molar ratio of magnesium to Ba-Zr-F compound is

Magnesium may be enough to reduce the Ba-Zr-F-based compound as a reducing agent, for example 1: 0.5-10, specifically 1: 0.5-5, and 1: 2 in one embodiment.

In an example of the present invention, the Ba-Zr-F-based compound may be one or two or more selected from BaZrF ₆ , Ba ₂ ZrF 8, Ba ₅ Zr ₂ F _13, and BaZr ₂ F ₁₀ . And may preferably be Ba ₂ ZrF _s . When the Ba-Zr-F compound is Ba ₂ ZrI ¾, a reaction such as the reaction formula 1 above is carried out to form Cu-Zr from the Ba-Mg-F compound. The alloy ingot can be effectively separated and obtained.

In an example of the present invention, the Cu-Zr alloy ingot includes at least one selected from CuZr, CuZr ₂ , Cu ₈ Zr ₃ , Cu ₁₀ Zr _7, and Cu ₅₁ Z _ri4. Cu-Zr alloy ingot Cu _lu Zr ₇ , more preferably _{5 | As} the content of ₄ increases, the phase separation due to the density difference proceeds more efficiently.

Cu-Zr alloy ingots can be effectively separated and obtained from Ba-Mg-F based compounds.

In an example of the present invention, the separated Ba-Mg-F based compounds can also be separated with very high purity. Therefore, the isolated Ba-Mg-F based compounds can also be used in various industrial fields.

[56] Hereinafter, the present invention will be described in detail by way of examples, but they will be described in more detail.

For the sake of clarity, the scope of the present invention is not limited to the following examples.

[Example 1]

[58] Ba ₂ ZrF ₈ , magnesium and copper in order of 1: 2: 5 molar ratio to alumina crucible

The mixture was added and mixed for 12 minutes to produce a mixture. The crucible was sealed to prevent oxidation of magnesium by oxygen. The crucible was then placed in a furnace and heat treated at 1,200 ° C. for 2 hours. By gravity and density difference, Ba-Mg-F compound is separated into the upper layer and Cu-Zr compound is separated into the lower layer. Next, the melt was cooled to room temperature, and the product obtained at this time is shown in Fig. 1. The product was then layered on top of a Ba-Mg-F-based compound (volume).

Molten salt) to obtain a Cu-Zr alloy ingot (Example 1).

An image of the Cu-Zr alloy ingot is shown in FIG. 2. In addition, to analyze its composition, X-ray diffraction analysis (PANalytical X'Pert PRO XRPD, Netherlands) was used. Is shown in Figure 3. [60] [Example 2]

[61] The molar ratio of Ba ₂ ZrF ₈ , magnesium and copper in Example 1 was set to 1: 2: 4 in order.

The same procedure as in Example 1 was conducted except that a Cu-Zr alloy ingot (Example 2) was obtained.

[Example 3]

In Example 1, the molar ratio of Ba ₂ ZrF ₈ , magnesium and copper was 1: 2: 3 in order.

The same procedure as in Example 1 was conducted except that a Cu-Zr alloy ingot (Example 3) was obtained.

[64] [Comparative Example 1]

[65] In Example 1, the molar ratio of B ZrF ₈ , magnesium and copper was set to 1: 2: 2 in order.

Except for preparing a Cu-Zr-based product (Example 4), it was carried out in the same manner as in Example 1.

[66] [Comparative Example 2]

In Example 1, the molar ratio of Ba ₂ ZrF ₈ , magnesium and copper was set to 1: 2: 1 in order.

The same procedure as in Example 1 was conducted except that the product (Example 5) was prepared.

[Example 4]

[69] was carried out, except that the Cu-Zr alloy ingot obtained by the heat treatment temperature is 1, 200 ° C instead of l, 300 ^o C in Example 3 and performed in the embodiment 3 gwadong.

[70] [Comparative Example 3]

Example 3 was carried out in the same manner as in Example 3, except that the product was manufactured at a heat treatment temperature of 1,100 ° C. instead of 1,200 ° C.

[72] The products prepared in Examples 1 to 4 were composed of fluorine-based compounds (BaMgF ₄ ) and

As the Cu-Zr compound was formed in two layers, a very high purity Cu-Zr alloy ingot was obtained.

[73] On the other hand, the products prepared in Comparative Examples 1 to 3 were fluorine-based compounds (BaMgF ₄ ) and

As Cu-Zr-based compounds were mixed and formed without separation, Cu-Zr-based alloy ingots could not be obtained. Specifically, as shown in Fig. 1, Comparative Examples 1 to Comparative Examples.

The product prepared in 2 did not have a large difference in density of each compound, so that the Cu-Zr compound did not form as a lower layer and existed in a mixed state. Therefore, the Cu-Zr alloy ingot could not be obtained.

[74] This result is attributed to the fact that the difference in density between the Ba-Mg-F-based compound and the Cu-Zr-based compound is not so large that the two layers are separated from each other.

The density of copper is higher than the density of 8.92 g / cm ³ rozirconium, 6.5 g / cm ^{3. The} intermediate products BaF ₂ and MgF ₂ , which form Ba-Mg-F compounds, are 4.893 g / cm ³ and 3.15 g, respectively. / cm ^3. Thus, Cu-Zr-based compounds content is higher composition of copper is brought to a higher density than relative to another component separation downstairs can be an ingot form of a Cu-Zr based alloy ol obtained, that is, In the case of Examples 1 to 3 having a high mixing ratio of initial copper to increase the copper composition (density) of the Cu-Zr compound, specifically Ba ₂ ZrF ₈ Note: When the molar ratio of copper is 1: 3 or more, it can be seen that the Cu-Zr compound is separated and obtained in the form of ingot having high purity.

[75] Thus, when the molar ratio of Ba ₂ ZrF ₈ : copper is 1: 3 or more, the Cu-Zr compound is high.

The reason for the separation in the form of ingot of purity is also shown by the XRD spectrum of FIG. 3. From Examples 3 to 3, it can be seen that the high density Cu _5L Zr _M compound is the main component, whereas Ba ₂ ZrF _{8 In the case of} Comparative Example 2 in which the molar ratio of copper is 1: 1, it can be confirmed that the low density Cu _s Zr compound is the main component.

However, as in the case of Comparative Example 3, when the heat treatment is performed at 1 or less than 100 ° C., the Ba-Mg-F system is satisfied even when the molar ratio of Ba ₂ ZrF ₈ : copper is 1: 3 or more. Since the compound and the Cu-Zr compound were not separated into two layers, the Cu-Zr alloy ingot could not be obtained. Thus, the Ba-Mg-F compound containing Cu-Zr compound

Separation and obtaining of Cu-Zr-based compounds from the product in the form of high-purity Cu-Zr-based ingots showed that the mixing ratio of copper and the heat treatment temperature were in close contact with each other.

[77] As a result of EDS analysis, all of Cu-Zr alloy ingots obtained in Examples 1 to 4 were obtained.

Fluoride molten salts such as Ba-Mg-F compounds are not included. In addition, the total impurity content of the Cu-Zr alloy ingot is about 10,000 ppm or less, and the Cu-Zr alloy ingot has an extremely 99 weight ^< ¾ or more weight. In addition, the oxygen concentration of the Cu-Zr alloy ingot was in the range of about 0.15-0.35% by weight.

In particular, in the case of Example 4 heat-treated at a temperature of 1,300 ° C. or higher, the oxygen content was significantly reduced from about 0.30 wt% to 0.16 \ vt% compared to Examples 1 to 3. Thus, the degree of silver higher than 1,300 ° C. The heat treatment can be further reduced in impurities such as oxides.

The above results are shown in Table 1 below.

[80] [Table I]

In addition, as shown in FIG. 2, as the molar ratio of copper decreases, the color of the product changes from dark gold to white.

Further, in the case of Examples 1 to 4, the Ba-Mg-F-based compound isolated

It was confirmed that BaM _g F ₄ was a very high purity molten salt composition, and therefore, the isolated Ba-Mg-F based compound could be used for various industrial fields.

In particular, all of the Cu-Zr alloy ingots prepared in Examples 1 to 4 contained zirconium in a high content, specifically, the Cu-Zr alloy ingots prepared in Example 4 were as shown in FIG. It was confirmed that the Cu-Zr alloy ingot containing 28 wt% zirconium based on some areas (zone 1) of the ingot.

Claims

Claim

[Claim 1] a) Ba-Zr-F-based compound, magnesium and copper are mixed, the Ba-Zr-F-based

Mixing the molar ratio of the copper to the compound in a ratio of 1: 3 to 10 and b) heat treating the complex mixed in the step a) at l, 150 to l, 500 ^° C.,

The product obtained in the step b) is a fluorine-based compound and a Cu-Zr alloy ingot is divided into two layers present method of manufacturing a Cu-Zr alloy ingot.

[Claim 2] In paragraph 1,

c) separating the Cu-Zr alloy ingot from the fluorine compound in the product obtained in step b).

[Claim 3] In paragraph 2,

The heat treatment of step b) is a method of manufacturing a Cu-Zr alloy ingot is carried out at 1, 200-1, 500 ° C.

[Claim 4] In paragraph 2,

A method for producing a Cu-Zr alloy ingot, wherein the molar ratio of copper to Ba-Zr-F compound is 1: 3-5.

[Claim 5] In Section I,

A method for producing a Cu-Zr alloy ingot wherein the molar ratio of magnesium to Ba-Zr-F compound is 1: 0.5 to 10.

[Claim 6] In paragraph 1,

The heat treatment of step b) is performed for 0.5-10 hours Cu-Zr alloy ingot manufacturing method.

Claim 7 In paragraph 1,

The Ba-Zr-F-based compound is BaZrF ₆ , Ba ₂ ZrF ₈ , Ba ₅ Zr ₂ F _L , and BaZr ₂ F _{10 A} method for producing a Cu-Zr alloy ingot containing any one or more selected from.

[Claim 8] In paragraph 1,

Method of producing a Cu-Zr based alloy ingot of the Cu-Zr-based alloy ingot comprising a Cu-Zr based compound on any one or two selected from Cu and Cu ₅₁ Zr ₇ _l0 Zr _l4.

[Claim 9] In any of the paragraphs 1 to 8,

Manufacturing method of Cu-Zr alloy ingot containing 1 to 30% by weight of zirconium based on the total weight of Cu-Zr alloy ingot.