CN103695814B - Zirconium-based amorphous alloy and its preparation method - Google Patents

Abstract

The present invention proposes a kind of zirconium-base amorphous alloy and preparation method.The component of described zirconium-base amorphous alloy meets following chemical formula (I): ZraCubAlcMdEre(I) wherein M represents one or more elements in Ni, Fe, Co, Mn, Cr, Ti, Hf, Ta, Nb; a, b, c, d, e are atomic percent; 40≤a≤70; 15≤b≤35; 5≤c≤15; 5≤d≤15,0 & lt; E≤2.5, and a+b+c+d+e=100.The preparation method of described zirconium-base amorphous alloy comprises the following steps: a) take the metal containing Zr, Al, Cu, M and Er according to the composition of above-mentioned chemical formula (I) and mix respectively, obtaining mixture; B) described mixture is placed in smelting furnace to smelt in a vacuum or inert atmosphere, obtains melt, wherein, smelting temperature is higher than the fusing point 50 ~ 400 DEG C of described zirconium-base amorphous alloy, and tap to tap time is 5 ~ 60 minutes; C) described melt is cast, obtain described zirconium-base amorphous alloy.According to zirconium-base amorphous alloy preparation method of the present invention, technical grade starting material can be adopted to prepare large critical size non-crystaline amorphous metal.

Description

Zirconium-based amorphous alloy and its preparation method

technical field

The invention relates to a zirconium-based amorphous alloy and a preparation method thereof.

Background technique

Amorphous alloys appeared in the 1960s. The initial amorphous alloys are difficult to be practically applied because the critical size (the largest size for forming amorphous crystals) can only reach the micron level. However, material properties such as high strength, high hardness, corrosion resistance, and excellent high-temperature fluidity have attracted a large number of scientific researchers and have been widely studied. Amorphous alloys with large critical sizes and suitable for industrial production have been continuously developed. The critical size is gradually increasing. From the micron level to the millimeter level and even to the centimeter level. Generally speaking, amorphous alloys whose critical cooling rate is less than 500°C/s and whose critical size is greater than 1 mm are called bulk amorphous alloys. The emergence of bulk amorphous alloys provides the possibility for industrial production.

The amorphous formation ability of amorphous alloys is easily affected by non-metallic elements or impurity elements, resulting in a significant reduction in the critical size of amorphous alloys or even the failure to form amorphous, especially non-metallic gas elements such as oxygen and nitrogen will greatly deteriorate the critical size. Therefore, usually the requirements for the purity of raw materials are very strict, and the requirements for the smelting environment are also very strict, and even high-vacuum preparation conditions are required, which greatly increases the production cost and makes it difficult to industrialize production.

Contents of the invention

The present invention aims at solving one of the above technical problems at least to a certain extent or at least providing a useful commercial choice.

Therefore, an object of the present invention is to provide a method for preparing a zirconium-based amorphous alloy.

Another object of the present invention is to provide a zirconium-based amorphous alloy.

According to the method for preparing a zirconium-based amorphous alloy according to the embodiment of the first aspect of the present invention, the composition of the zirconium-based amorphous alloy conforms to the following chemical formula (I):

ZraCubAlcMdEre (I)

Where M represents one or several elements in Ni, Fe, Co, Mn, Cr, Ti, Hf, Ta, Nb, a, b, c, d, e are atomic percentages, 40≤a≤70, 15≤ b≤35, 5≤c≤15, 5≤d≤15, 0<e≤2.5, and a+b+c+d+e=100, characterized in that the preparation method of the zirconium-based amorphous alloy includes the following step:

a) weighing metals containing Zr, Al, Cu, M and Er according to the composition of the above chemical formula (I) and mixing them to obtain a mixed material;

b) placing the mixed material in a smelting furnace for smelting under vacuum or an inert atmosphere to obtain a melt,

Wherein, the smelting temperature is 50-400°C higher than the melting point of the zirconium-based amorphous alloy, and the smelting time is 5-60 minutes;

c) casting the melt to obtain the zirconium-based amorphous alloy.

According to the preparation method of the zirconium-based amorphous alloy according to the embodiment of the present invention, the zirconium-based amorphous alloy with a large critical size can be prepared by using industrial-grade raw materials, and the preparation method is convenient for production control, and the zirconium-based amorphous alloy can be obtained stably.

In addition, the method for preparing a zirconium-based amorphous alloy according to the embodiment of the present invention may also have the following distinguishing technical features:

According to some embodiments of the present invention, the raw material of Zr is an alloy with a total mass percentage of Zr and Hf greater than 99%, and the raw materials of Cu, Al, and M are elemental metals with an elemental mass percentage greater than 99%.

According to some embodiments of the present invention, the raw material of Er is an elemental metal with a purity greater than 98%.

According to other embodiments of the present invention, the raw material of Er is an AlEr master alloy.

According to some embodiments of the present invention, in the step b), the smelting temperature is 100° C. higher than that of the zirconium-based amorphous alloy.

According to some embodiments of the present invention, in the step b), the smelting time is 15-30 minutes.

The preparation method of zirconium-based amorphous alloy according to claim 1, characterized in that, in the step b), the smelting atmosphere adopts a vacuum atmosphere with a vacuum degree of less than 10 Pa.

According to some embodiments of the present invention, in the step b), the smelting atmosphere adopts an inert gas protective atmosphere.

The zirconium-based amorphous alloy according to the embodiment of the second aspect of the present invention is prepared according to the preparation method of the zirconium-based amorphous alloy according to any embodiment of the first aspect.

According to some embodiments of the present invention, the critical dimension of the zirconium-based amorphous alloy is greater than 3mm.

Additional aspects and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.

Description of drawings

The above and/or additional aspects and advantages of the present invention will become apparent and comprehensible from the description of the embodiments in conjunction with the following drawings, wherein:

Fig. 1 is a schematic flow chart of a method for preparing a zirconium-based amorphous alloy according to an embodiment of the present invention.

detailed description

Embodiments of the invention are described in detail below, examples of which are illustrated in the accompanying drawings. The embodiments described below by referring to the figures are exemplary and are intended to explain the present invention and should not be construed as limiting the present invention.

The method for preparing a zirconium-based amorphous alloy according to an embodiment of the present invention will first be described below with reference to FIG. 1 .

The composition of the zirconium-based amorphous alloy according to the embodiment of the present invention conforms to the following chemical formula (I):

ZraCubAlcMdEre (I)

Where M represents one or several elements in Ni, Fe, Co, Mn, Cr, Ti, Hf, Ta, Nb, a, b, c, d, e are atomic percentages, 40≤a≤70, 15≤ b≤35, 5≤c≤15, 5≤d≤15, 0<e≤2.5, and a+b+c+d+e=100.

As shown in Figure 1, the preparation method of the zirconium-based amorphous alloy according to the embodiment of the present invention comprises the following steps:

a) Weighing and mixing metals containing Zr, Al, Cu, M and Er respectively according to the composition of the above chemical formula (I) to obtain a mixed material.

The present invention finds that by adopting the preparation method of the present invention, industrial-grade raw materials can be used, wherein metal zirconium can adopt a metal whose total mass percentage of Zr and Hf is greater than 99%, that is, industrial-grade HZr-2 metal zirconium can be used for smelting non-ferrous metals. Crystal alloys, while Cu, Al, and M metals can be industrial metals with a purity of 99%, which greatly reduces the manufacturing cost of the alloy.

In addition, the purity of the metal Er can also be selected from low-purity rare earth elements, and the purity of the rare earth elements is preferably greater than 98%. Considering that rare earth elements are easy to oxidize elements, and in order to facilitate smelting and mixing with the master alloy, it is preferable to add them in the form of master alloys, more preferably AlEr alloys.

b) Put the mixed material in a melting furnace for smelting under vacuum or an inert atmosphere to obtain a melt, wherein the smelting temperature is 50-400°C higher than the melting point of the zirconium-based amorphous alloy, and the smelting time is 5-400°C. 60 minutes.

The inventors of the present invention have found through a lot of research that the smelting process has an important influence on obtaining an amorphous alloy with a large critical size. When the smelting temperature is below the above temperature range, the critical size of the amorphous alloy will be significantly reduced, and when the smelting temperature is higher than the above temperature range, it is not conducive to cost reduction. In the present invention, the preferred smelting temperature is 100°C higher than the melting point.

In addition, when the smelting time is lower than the above range, the uniformity of the amorphous alloy components will become low, and the harmful impurities and harmful gases in the raw materials cannot be removed by slagging through sufficient reaction with rare earth elements. After a large number of tests, the present invention finds that when the smelting time is longer than 10 minutes, it is more beneficial to prepare the amorphous alloy with a critical size larger than 3mm. At the same time, considering the requirement of cost reduction, the preferred smelting time is 15-30 minutes.

In addition, in the step b), the smelting atmosphere may adopt a vacuum atmosphere with a vacuum degree of less than 10 Pa, or may also adopt an inert gas protective atmosphere.

c) casting the melt to obtain the zirconium-based amorphous alloy.

There is no specific limitation on the specific casting method, for example, the commonly used method of the present invention can be used, such as casting by suction casting, etc.

According to the method for preparing a zirconium-based amorphous alloy according to the above-mentioned embodiments of the present invention, the critical dimension of the prepared zirconium-based amorphous alloy can be larger than 3 mm.

Because the amorphous alloy has excellent mechanical properties of high strength and high hardness, the amorphous alloy of the present invention and its manufacturing method are particularly suitable for preparing high-precision thin-walled amorphous products, especially structural parts of electronic products, and have great commercial value. .

In the following, the zirconium-based amorphous alloy of the present invention and its preparation method will be described in detail through specific examples and comparative examples.

Example 1

Proportion according to Zr51.9Al10Cu30Ni7Er1.1. Metal zirconium adopts elemental metal with a metal purity greater than 99%, and Al, Cu, Ni, Er adopts elemental metal with a purity greater than 99%.

After the proportioning is completed, put it into a vacuum melting furnace, and fill it with 99.99% argon for atmosphere protection, and carry out alloying smelting. The smelting temperature is 1000°C, and the smelting time is 15Min. The smelting temperature in the smelting process is obtained by infrared temperature measurement. The melting point of amorphous alloy is tested by STA409C synchronous thermal analyzer, the temperature rise rate is 20°/Min, and the protective gas is argon.

After the smelting is completed, the melt is cast into a metal mold to obtain a metal casting with a diameter ranging from 0.5mm to 15mm, and the casting is cut to obtain a metal cross section for critical dimension testing. The critical dimension is measured by the D/Max2500PCXRD diffractometer of Rigaku Co., Ltd. The diffraction angle is 2theta between 20°~60°, the scanning speed is 4°/min, the scanning voltage is 40Kv, and the current is 200mA.

The preparation conditions and test results of amorphous alloys are listed in Table 1.

Example 2

Proportion according to Zr51.5Al10Cu30Ni7HfEr0.5. Metal zirconium adopts metal (Zr+Hf) elemental metal with a purity greater than 99%, and Al, Cu, Ni, Hf, Er adopts elemental metal with a purity greater than 99%.

After the proportioning is completed, put it into a vacuum melting furnace, and fill it with 99.99% argon for atmosphere protection, and carry out alloying smelting. The smelting temperature is 1000°C, and the smelting time is 15Min. The smelting temperature in the smelting process is obtained by infrared temperature measurement. The melting point of amorphous alloy is tested by STA409C synchronous thermal analyzer, the temperature rise rate is 20°/Min, and the protective gas is argon.

After the smelting is completed, the melt is cast into a metal mold to obtain a metal casting with a diameter ranging from 0.5mm to 15mm, and the casting is cut to obtain a metal cross section for critical dimension testing. The critical dimension is measured by the D/Max2500PCXRD diffractometer of Rigaku Co., Ltd. The diffraction angle is 2theta between 20°~60°, the scanning speed is 4°/min, the scanning voltage is 40Kv, and the current is 200mA.

The preparation conditions and test results of amorphous alloys are listed in Table 1.

Example 3

Proportion according to Zr50Al10Cu30Ni7HfTi0.5Er1.5. Metal zirconium adopts elemental metal with metal (Zr+Hf) purity greater than 99%, and Al, Cu, Ni, Hf, Ti, Er adopts elemental metal with purity greater than 99%.

After the proportioning is completed, put it into a vacuum melting furnace, and fill it with 99.99% argon for atmosphere protection, and carry out alloying smelting. The smelting temperature is 1000°C, and the smelting time is 15Min. The smelting temperature in the smelting process is obtained by infrared temperature measurement. The melting point of amorphous alloy is tested by STA409C synchronous thermal analyzer, the temperature rise rate is 20°/Min, and the protective gas is argon.

After the smelting is completed, the melt is cast into a metal mold to obtain a metal casting with a diameter ranging from 0.5mm to 15mm, and the casting is cut to obtain a metal cross section for critical dimension testing. The critical dimension is measured by the D/Max2500PCXRD diffractometer of Rigaku Co., Ltd. The diffraction angle is 2theta between 20°~60°, the scanning speed is 4°/min, the scanning voltage is 40Kv, and the current is 200mA.

The preparation conditions and test results of amorphous alloys are listed in Table 1.

Example 4

Proportion according to Zr51Al8Cu27Ni7Co3Hf0.8Fe2.5Ti0.5Er0.2. Metal zirconium adopts metal (Zr+Hf) elemental metal with a purity greater than 99%, and Al, Cu, Ni, Co, Hf, Fe, Ti, Er adopts elemental metal with a purity greater than 99%.

After the proportioning is completed, put it into a vacuum melting furnace, and fill it with 99.99% argon for atmosphere protection, and carry out alloying smelting. The smelting temperature is 1000°C, and the smelting time is 15Min. The smelting temperature in the smelting process is obtained by infrared temperature measurement. The melting point of amorphous alloy is tested by STA409C synchronous thermal analyzer, the temperature rise rate is 20°/Min, and the protective gas is argon.

After the smelting is completed, the melt is cast into a metal mold to obtain a metal casting with a diameter ranging from 0.5mm to 15mm, and the casting is cut to obtain a metal cross section for critical dimension testing. The critical dimension is measured by the D/Max2500PCXRD diffractometer of Rigaku Co., Ltd. The diffraction angle is 2theta between 20°~60°, the scanning speed is 4°/min, the scanning voltage is 40Kv, and the current is 200mA.

The preparation conditions and test results of amorphous alloys are listed in Table 1.

Comparative example 1

Proportion according to Zr52Al10Cu30Ni7Hf. Metal zirconium adopts metal Zr with a purity greater than 99.9%, and Al, Cu, Ni, and Hf use elemental metals with a purity greater than 99.9%.

After the proportioning is completed, put it into a vacuum melting furnace, and fill it with 99.99% argon for atmosphere protection, and carry out alloying smelting. The smelting temperature is 1000°C, and the smelting time is 15Min. The smelting temperature in the smelting process is obtained by infrared temperature measurement. The melting point is tested by STA409C synchronous thermal analyzer, the temperature rise rate is 20°/Min, and the protective gas is argon.

After the smelting is completed, the melt is cast into a metal mold to obtain a metal casting with a diameter ranging from 0.5mm to 15mm, and the casting is cut to obtain a metal cross section for critical dimension testing. The critical dimension is measured by the D/Max2500PCXRD diffractometer of Rigaku Co., Ltd. The diffraction angle is 2theta between 20°~60°, the scanning speed is 4°/min, the scanning voltage is 40Kv, and the current is 200mA.

The preparation conditions and test results of amorphous alloys are listed in Table 1.

Comparative example 2

The alloy ratio is carried out according to Zr52Al10Cu30Ni7Hf. Metal zirconium adopts metal (Zr+Hf) elemental metal with a purity greater than 99%, and Al, Cu, Ni, Hf, Er adopts elemental metal with a purity greater than 99%.

After the proportioning is completed, put it into a vacuum melting furnace, and fill it with 99.99% argon for atmosphere protection, and carry out alloying smelting. The smelting temperature is 1000°C, and the smelting time is 15Min. The smelting temperature in the smelting process is obtained by infrared temperature measurement. The melting point is tested by STA409C synchronous thermal analyzer, the temperature rise rate is 20°/Min, and the protective gas is argon.

After the smelting is completed, the alloy melt is cast into a metal mold to obtain a metal casting with a diameter ranging from 0.5mm to 15mm, and the casting is cut to obtain a metal cross section for critical dimension testing. The critical dimension is measured by the D/Max2500PCXRD diffractometer of Rigaku Co., Ltd. The diffraction angle is 2theta between 20°~60°, the scanning speed is 4°/min, the scanning voltage is 40Kv, and the current is 200mA.

The preparation conditions and test results of amorphous alloys are listed in Table 1.

Comparative example 3

Proportion according to Zr50Al10Cu30Ni7Er3. Metal zirconium adopts metal (Zr+Hf) elemental metal with a purity greater than 99%, and Al, Cu, Ni, Er adopts elemental metal with a purity greater than 99%.

After the proportioning is completed, put it into a vacuum melting furnace, and fill it with 99.99% argon for atmosphere protection, and carry out alloying smelting. The smelting temperature is 1000°C, and the smelting time is 15Min. The smelting temperature in the smelting process is obtained by infrared temperature measurement. The melting point is tested by STA409C synchronous thermal analyzer, the temperature rise rate is 20°/Min, and the protective gas is argon.

After the smelting is completed, the melt is cast into a metal mold to obtain a metal casting with a diameter ranging from 0.5mm to 15mm, and the casting is cut to obtain a metal cross section for critical dimension testing. The critical dimension is measured by the D/Max2500PCXRD diffractometer of Rigaku Co., Ltd. The diffraction angle is 2theta between 20°~60°, the scanning speed is 4°/min, the scanning voltage is 40Kv, and the current is 200mA.

The preparation conditions and test results of amorphous alloys are listed in Table 1.

Comparative example 4

Proportion according to Zr51.9Al10Cu30Ni7Er1.1. Metal zirconium adopts metal Zr with a purity greater than 99%, and Al, Cu, Ni, and Er adopts elemental metal with a purity greater than 99%.

After the proportioning is completed, put it into a vacuum melting furnace, and fill it with 99.99% argon for atmosphere protection, and carry out alloying smelting. The smelting temperature is 900°C, and the smelting time is 15Min. The smelting temperature in the smelting process is obtained by infrared temperature measurement. The melting point is tested by STA409C synchronous thermal analyzer, the temperature rise rate is 20°/Min, and the protective gas is argon.

After the smelting is completed, the melt is cast into a metal mold to obtain a metal casting with a diameter ranging from 0.5mm to 15mm, and the casting is cut to obtain a metal cross section for critical dimension testing. The critical dimension is measured by the D/Max2500PCXRD diffractometer of Rigaku Co., Ltd. The diffraction angle is 2theta between 20°~60°, the scanning speed is 4°/min, the scanning voltage is 40Kv, and the current is 200mA.

The preparation conditions and test results of amorphous alloys are listed in Table 1.

Comparative example 5

Proportion according to Zr51.9Al10Cu30Ni7Er1.1. Metal zirconium adopts metal Zr with a purity greater than 99%, and Al, Cu, Ni, and Er adopts elemental metal with a purity greater than 99%.

After the proportioning is completed, put it into a vacuum melting furnace, and fill it with 99.99% argon for atmosphere protection, and carry out alloy smelting. The smelting temperature is 1000°C, and the smelting time is 5Min. The smelting temperature in the smelting process is obtained by infrared temperature measurement. The melting point is tested by STA409C synchronous thermal analyzer, the temperature rise rate is 20°/Min, and the protective gas is argon.

After the smelting is completed, the melt is cast into a metal mold to obtain a metal casting with a diameter ranging from 0.5mm to 15mm, and the casting is cut to obtain a metal cross section for critical dimension testing. The critical dimension is measured by the D/Max2500PCXRD diffractometer of Rigaku Co., Ltd. The diffraction angle is 2theta between 20°~60°, the scanning speed is 4°/min, the scanning voltage is 40Kv, and the current is 200mA.

The preparation conditions and test results of amorphous alloys are listed in Table 1.

Table 1: Preparation conditions and test data of amorphous alloys

It can be seen from Table 1 that for Examples 1-4 using the preparation process of the present invention, low-purity industrial-grade raw materials can be used to prepare amorphous alloys with large critical sizes. In addition, Ni, Fe, Co, Mn, Cr, Ti, Hf, Ta, Nb and other elements can be added according to the requirements of the alloy properties, and have a small impact on the critical dimension. In addition, the amorphous alloy with a large critical size obtained from the above embodiment has high specific strength and is easy to be cast and formed, and is especially suitable for manufacturing structural parts of 3C products, and has potential industrial application prospects.

In addition, it can be seen from Comparative Example 1 that in the absence of metal Er, although high-purity raw materials can be used to prepare an amorphous alloy with a large critical size close to the present invention, the manufacturing cost of the alloy is greatly increased , its application prospects will be greatly limited.

From Comparative Examples 2 and 3, it can be seen that in the absence of metal Er, it is difficult to prepare amorphous alloys with large critical dimensions using low-purity raw materials, and amorphous alloys with critical dimensions less than 1 mm are difficult to apply to industrial production.

As can be seen from Comparative Examples 4 and 5, even if the alloy composition of the present invention is adopted, if the smelting temperature is lower than the smelting temperature of the present invention or the smelting time is lower than the smelting time of the present invention, the criticality of the amorphous alloy will be greatly reduced. The size affects its industrial application.

In the description of this specification, descriptions referring to the terms "one embodiment", "some embodiments", "example", "specific examples", or "some examples" mean that specific features described in connection with the embodiment or example , structure, material or characteristic is included in at least one embodiment or example of the present invention. In this specification, schematic representations of the above terms do not necessarily refer to the same embodiment or example. Furthermore, the specific features, structures, materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.

Although the embodiments of the present invention have been shown and described above, it can be understood that the above embodiments are exemplary and cannot be construed as limitations to the present invention. Variations, modifications, substitutions, and modifications to the above-described embodiments are possible within the scope of the present invention.

Claims (7)

1. a preparation method of zirconium-based amorphous alloy, is characterized in that, the composition of described zirconium-based amorphous alloy meets following chemical formula (1): ZraCubAlcMdEre(I) Where M represents one or several elements in Ni, Fe, Co, Mn, Cr, Ti, Hf, Nb, a, b, c, d, e are atomic percentages, 40≤a≤70, 15≤b≤ 35, 5≤c≤15, 5≤d≤15, 0<e≤2.5, and a+b+c+d+e=100, the preparation method of the zirconium-based amorphous alloy comprises the following steps: a) weighing metals containing Zr, Al, Cu, M and Er according to the composition of the above chemical formula (I) respectively and mixing to obtain a mixed material, Wherein, the raw material of Er is an elemental metal with a purity greater than 98%; b) placing the mixed material in a smelting furnace for smelting under vacuum or an inert atmosphere to obtain a melt, Wherein, the smelting temperature is 100°C higher than the melting point of the zirconium-based amorphous alloy, and the smelting time is 15 to 30 minutes; c) casting the melt to obtain the zirconium-based amorphous alloy. 2. the preparation method of zirconium-based amorphous alloy as claimed in claim 1 is characterized in that, the raw material of Zr is the alloy that the total mass percent of Zr and Hf is greater than 99%, and the raw material of Cu, Al, M is element quality Elemental metals with a percentage greater than 99%. 3. the preparation method of zirconium-based amorphous alloy as claimed in claim 1 or 2 is characterized in that, the raw material of Er is AlEr master alloy. 4. The preparation method of zirconium-based amorphous alloy according to claim 1, characterized in that, in the step b), the smelting atmosphere adopts a vacuum atmosphere with a vacuum degree of less than 10 Pa. 5. The preparation method of zirconium-based amorphous alloy according to claim 1, characterized in that, in the step b), the smelting atmosphere adopts an inert gas protective atmosphere. 6. A zirconium-based amorphous alloy, characterized in that it is prepared according to the preparation method of the zirconium-based amorphous alloy according to claims 1-5. 7. The zirconium-based amorphous alloy according to claim 6, wherein the critical dimension of the zirconium-based amorphous alloy is greater than 3 mm.