CN106282851A - A kind of low cost zirconium-base amorphous alloy and preparation method thereof - Google Patents

Abstract

The invention provides a low-cost, reusable zirconium-based amorphous alloy and a preparation method thereof. The composition of the zirconium-based amorphous alloy is: (Zr _{a Cub Ni c Al d} Ti _e ) _100-x O _x , a, b, c, d, e, x are atomic percentages, where: 40≤a≤60, 34≤b≤50, 0≤c≤5, 2≤d≤14, 0≤e≤5, 50ppm ≤x≤5000ppm. The zirconium-based amorphous alloy has excellent mechanical properties and strong amorphous forming ability. Compared with the traditional amorphous alloy composition, the present invention relaxes the purity requirements of the real raw material metal, thereby reducing the cost of raw materials, and is suitable for industrial production. offers possibilities.

Description

A low-cost zirconium-based amorphous alloy and its preparation method

technical field

The invention relates to an amorphous alloy, and in particular provides a zirconium-based amorphous alloy with relatively high amorphous forming ability and a preparation method thereof.

Background technique

Amorphous alloys were first discovered in the Au-Si eutectic system in the 1960s. Since then, this material has been widely concerned due to its various excellent properties, and it is considered to lead the next material revolution. . Due to the characteristics of long-range disorder and short-range order in the structure of amorphous alloys, it has unique properties compared with traditional crystalline metal materials: for example, the strength of general Zr-based amorphous alloys is twice that of steel, and its corrosion resistance It is dozens or even hundreds of times that of stainless steel, and its elastic limit of up to 2% is three times that of ordinary traditional crystal metal materials. These excellent properties have brought broad development prospects for amorphous alloys in aerospace, IT electronics, machinery, chemical and other fields.

At present, the application of amorphous alloys in the world is mainly concentrated in the application of strips and transformer cores, and there are few examples of the application of bulk amorphous alloys. This is mainly due to the following reasons:

1. Lack of good amorphous alloy composition. Among many amorphous alloy systems, Zr-based alloys are considered to be the most applicable amorphous alloys due to their excellent properties and good amorphous forming ability. However, Zr-based amorphous alloys with good formability and excellent performance have been protected by patents in the world, and their high patent use or purchase costs have caused certain obstacles to the industrialization of amorphous alloys.

2. The impact of high cost of amorphous alloys. Because amorphous alloys have high requirements on the purity of raw materials, for example, Zr-based amorphous alloys require high-purity zirconium as raw materials, which is very expensive, which is currently a bottleneck problem restricting the wide application of amorphous alloys. In addition, the amorphous alloy also requires a high degree of vacuum in the production process, which further increases the cost of the amorphous alloy.

3. Lack of amorphous alloys with good repeatability in production. For a long time, amorphous alloys have been unable to achieve the docking of laboratory conditions and production conditions, that is, the quality of amorphous alloys obtained under laboratory conditions is unstable in production conditions, the repeatability is not good, and the obtained products are not completely amorphous. , cannot be mass-produced.

In view of the above problems, the present invention provides a low-cost, easy-to-use zirconium-based amorphous alloy composition and preparation method in industrial conditions, and strives to solve the problems that hinder the industrialization of zirconium-based amorphous alloys, so as to facilitate its future large-scale industrial production Lay the groundwork.

Contents of the invention

Aiming at the problem that the current production process of zirconium-based amorphous alloys requires high raw material purity and vacuum degree, the present invention provides a low-cost, reusable zirconium-based amorphous alloy and its preparation method. Amorphous alloys have excellent amorphous-forming ability and have excellent mechanical properties.

The present invention specifically provides a zirconium-based amorphous alloy, the zirconium-based amorphous alloy is (Zr _{a Cub Ni c Al d} Ti _e ) _100-x O _x , a, b, c, d, e, x is the atomic percentage, where: 40≤a≤60, 34≤b≤50, 0≤c≤5, 2≤d≤14, 0≤e≤5, 50ppm≤x≤5000ppm. Based on the total volume of the alloy, when the zirconium-based amorphous alloy is cast into a rod-shaped sample with a diameter greater than or equal to 4mm and a length of 50mm, the amorphous content is 30% to 99%, and the compression plastic deformation is greater than 3%.

The zirconium-based amorphous alloy of the present invention is characterized in that: the value ranges of a, b, c, d, e, x (atomic percentage) are preferably: 44≤a≤54, 40≤b≤50, 0≤ c≤5, 5≤d≤10, e=0, 400ppm≤x≤3500ppm. At this time, when the zirconium-based amorphous alloy is cast into a rod-shaped sample with a diameter greater than or equal to 4 mm and a length of 50 mm, its amorphous content is greater than 40%.

In the zirconium-based amorphous alloy of the present invention, the value ranges of a, b, c, d, e, and x (atomic percentage) are preferably: 44≤a≤51, 40≤b≤50, 0≤c≤5, 5≤d≤10, 0.5≤e≤3, 400ppm≤x≤3500ppm. At this time, when the zirconium-based amorphous alloy is cast into a rod-shaped sample with a diameter greater than or equal to 6 mm and a length of 50 mm, its amorphous content is greater than 70%.

In the zirconium-based amorphous alloy of the present invention, the value ranges of a, b, c, d, e, x (atomic percentage) are preferably: 44≤a≤52, 38≤b+c≤48, 5≤d≤ 10, 1≤e≤3, 400ppm≤x≤3500ppm. At this time, when the zirconium-based amorphous alloy is cast into a rod-shaped sample with a diameter greater than or equal to 6mm and a length of 50mm, the amorphous content is greater than 70%, and the compressive plasticity is greater than 4%.

The present invention also provides a method for preparing the zirconium-based amorphous alloy, which is characterized in that: under the condition of a vacuum of 0.1-10 Pa, an inert protective gas is introduced to melt the raw material and rapidly cool it to an amorphous state, wherein The cooling rate is greater than 10K/s, the alloy melting temperature is 3000°C, each melting time is greater than 30 seconds, and repeated melting is greater than or equal to 4 times.

The preparation method of the zirconium-based amorphous alloy of the present invention is characterized in that the purity of the raw materials for preparing the amorphous alloy is low, and the purity of the raw materials is greater than 97%, and the oxygen content is required to be less than 10000ppm. The present invention adopts low-purity raw materials to prepare amorphous alloys through adjustment and control of alloy components, and the amorphous formation ability of the obtained alloys is comparable to that of amorphous alloys prepared by using high-purity raw materials, and the compressive plasticity is not reduced

detailed description

The purity of raw materials used in the following examples is >97%, the oxygen content is <1 at.%, and the purity of argon gas is greater than 95%.

Example 1

Composition: (Zr ₄₉ Cu _36.6 Ni _1.4 Al ₁₃ ) _99.8 O _0.2

Put the raw materials into the melting furnace according to the atomic percentage of the composition, evacuate to 1 Pa, then pass in argon as a protective gas, melt the alloy at 3000 degrees Celsius for 4 minutes, repeat the melting 4 times, and then cast the melt into the mold , to obtain a size of For rod-shaped samples, the volume percentage of the amorphous phase is greater than 30%.

Example 2

Composition: (Zr ₄₆ Cu ₄₆ Ti ₂ Al ₆ ) _99.8 O _0.2

Put the raw materials into the melting furnace according to the atomic percentage of the composition, evacuate to 1 Pa, then pass in argon as a protective gas, melt the alloy at 3000 degrees Celsius for 4 minutes, repeat the melting 4 times, and then cast the melt into the mold , to obtain a size of For rod-shaped samples, the volume percentage of the amorphous phase is greater than 40%.

Example 3

Composition: (Zr _47.75 Cu ₃₅ Ni ₅ Ti ₂ Al _10.25 ) _99.9 O _0.1

Put the raw materials into the melting furnace according to the atomic percentage of the composition, evacuate to 0.1 Pa, then pass in argon as a protective gas, melt the alloy at 3000 degrees Celsius for 4 minutes, repeat the melting 4 times, and then cast the melt into the mold , to obtain a size of The rod-shaped sample, the volume percentage of amorphous phase is greater than 90%, and its compression plasticity is 6%.

Example 4

Composition: (Zr _45.5 Cu _44.1 Ni _4.9 Al _5.5 ) _99.7 O _0.3

Put the raw materials into the melting furnace according to the atomic percentage of the composition, evacuate to 10 Pa, then pass in argon as a protective gas, melt the alloy at 3000 degrees Celsius for 4 minutes, repeat the melting 4 times, and then cast the melt into the mold , to obtain a size of For rod-shaped samples, the volume percentage of the amorphous phase is greater than 35%.

Example 5

Composition: (Zr ₅₁ Cu _35.55 Ni _3.95 Al _9.5 ) _99.8 O _0.2

Put the raw materials into the melting furnace according to the atomic percentage of the composition, evacuate to 0.1 Pa, then pass in argon as a protective gas, melt the alloy at 3000 degrees Celsius for 4 minutes, repeat the melting 4 times, and then cast the melt into the mold , to obtain a size of For rod-shaped samples, the volume percentage of the amorphous phase is greater than 60%.

Example 6

Composition: (Zr ₄₉ Cu _35.55 Ni _3.95 Ti ₂ Al _9.5 ) _99.8 O _0.2

Put the raw materials into the melting furnace according to the atomic percentage of the composition, evacuate to 0.1 Pa, then pass in argon as a protective gas, melt the alloy at 3000 degrees Celsius for 4 minutes, repeat the melting 4 times, and then cast the melt into the mold , to obtain a size of The rod-shaped sample, the volume percentage of the amorphous phase is greater than 75%.

Example 7

Composition: (Zr _45.5 Cu _41.8 Ni _2.2 Ti ₅ Al _5.5 ) _99.8 O _0.2

Put the raw materials into the melting furnace according to the atomic percentage of the composition, evacuate to 0.1 Pa, then pass in argon as a protective gas, melt the alloy at 3000 degrees Celsius for 4 minutes, repeat the melting 4 times, and then cast the melt into the mold , to obtain a size of The rod-shaped sample, the volume percentage of the amorphous phase is 45%.

Comparative example 1

Zr ₅₅ Cu ₃₀ Al ₁₀ Ni ₅ bulk amorphous alloy, under low oxygen content (oxygen content less than 200ppm), its amorphous formation critical size is 30mm, and when the oxygen content reaches 1300ppm, its amorphous formation critical size decreases When the oxygen content reaches 2800ppm, the critical dimension of amorphous formation is further reduced to 3mm, and the plastic deformation is about 2%.

Comparative example 2

Zr ₆₅ Cu _17.5 Al _7.5 Ni ₁₀ bulk amorphous alloy, at low oxygen content (oxygen content less than 200ppm), its amorphous formation critical size is 16mm, and when the oxygen content reaches 2800ppm, its amorphous formation critical size decreases It is 3mm, and its plastic deformation is about 2%.

Comparative example 3

Zr _52.5 Cu _17.9 Ni _14.6 Al ₁₀ Ti ₅ bulk amorphous alloy, at low oxygen content (oxygen content less than 200ppm), its amorphous formation critical size is 10mm, and when the oxygen content reaches 590ppm, its amorphous formation critical size The size is reduced to 6.5mm, and when the oxygen content reaches 2000ppm, the critical dimension of amorphous formation is further reduced to 3.5mm, and the plastic deformation is about 3%.

The above-mentioned embodiments are only to illustrate the technical concept and characteristics of the present invention, and the purpose is to enable those skilled in the art to understand the content of the present invention and implement it accordingly, and not to limit the protection scope of the present invention. All equivalent changes or modifications made according to the spirit of the present invention shall fall within the protection scope of the present invention.

Claims (10)

1. a zirconium-base amorphous alloy, it is characterised in that: described zirconium-base amorphous alloy is (Zr_aCu_bNi_cAl_dTi_e)_100-xO_x, a, b, c, d, e, x are atomic percent, wherein: 40≤a≤60,34≤b≤50,0≤c≤5,2≤d≤14,0≤e≤5,50ppm≤x≤5000ppm.

2. according to zirconium-base amorphous alloy described in claim 1, it is characterised in that: the span of a, b, c, d, e, x is: 44≤a≤54,40≤b≤50,0≤c≤5,5≤d≤10, e=0,400ppm≤x≤3500ppm.

3. according to zirconium-base amorphous alloy described in claim 1, it is characterised in that: the span of a, b, c, d, e, x is: 44≤a≤51,40≤b≤50,0≤c≤5,5≤d≤10,0.5≤e≤3,400ppm≤x≤3500ppm.

4. according to zirconium-base amorphous alloy described in claim 1, it is characterised in that: the span of a, b, c, d, e, x is: 44≤a≤52,38≤b+c≤48,5≤d≤10,1≤e≤3,400ppm≤x≤3500ppm.

5. the preparation method of the arbitrary described zirconium-base amorphous alloy of Claims 1 to 4; it is characterized in that: under protective gas atmosphere, by raw material melting and be cooled to amorphous state, the smelting temperature of alloy is 3000 DEG C; smelting time is more than 30 seconds, and melt back is more than or equal to 4 times.

6. according to the preparation method of zirconium-base amorphous alloy described in claim 5, it is characterised in that: prepare the material purity of non-crystaline amorphous metal > 97%.

7. according to the preparation method of zirconium-base amorphous alloy described in claim 5, it is characterised in that: prepare the oxygen content < 1at.% of non-crystaline amorphous metal raw material.

8. according to the preparation method of zirconium-base amorphous alloy described in claim 5, it is characterised in that: molten alloy under vacuum, required vacuum is 0.1-10 handkerchief.

9. according to the preparation method of zirconium-base amorphous alloy described in claim 5, it is characterised in that: melting protective gas is noble gas.

10. according to the preparation method of zirconium-base amorphous alloy described in claim 5, it is characterised in that: being cooled to amorphous state after alloy melting, cooldown rate is more than 10K/s.