CN114686785A - High-thermal stability aluminum-based metal glass and preparation method thereof - Google Patents

Abstract

The invention discloses an aluminum-based metallic glass with high thermal stability, the atomic percentage composition formula is Al_aY_bFe_cX_dWherein X is a high melting point metal element; the atomic percentage of each component is as follows: 81 < a < 90, 6 < b < 8, 4 < c < 6, 0 < d < 5, a + b + c + d equal to 100. The aluminum-based metal glass has high glass forming capability and high thermal stability. The invention also provides a preparation method of the high-thermal stability aluminum-based metal glass, which comprises the following steps: preparing materials according to the atomic percentage composition of the high-heat-stability aluminum-based metallic glass, heating and smelting by electric arc to obtain a first master alloy, smelting the first master alloy by induction heating to obtain a master alloy ingot, melting the master alloy ingot, and then spraying the melted master alloy ingot onto the surface of a rotating copper roller to obtain the banded high-heat-stability aluminum-based metallic glass. The preparation method is simple, efficient and suitable for industrial production.

Description

High-thermal stability aluminum-based metal glass and preparation method thereof

Technical Field

The invention belongs to the technical field of new materials, and particularly relates to high-thermal stability aluminum-based metal glass and a preparation method thereof.

Background

The metallic glass is also called amorphous alloy, and is obtained by a liquid melt through a rapid cooling process, and the atomic structure of the metallic glass shows the characteristics of a short-range ordered and long-range disordered liquid-like structure. They have both solid and liquid characteristics and thus exhibit excellent mechanical properties, oxidation corrosion resistance and soft magnetic properties.

The aluminum-based metal glass material not only has extremely high specific strength, but also has good toughness, superplasticity and corrosion resistance, and is a novel metal structure material with wide application prospect. Can be widely applied to the fields of aviation, aerospace, navigation, national defense, automobiles, military, microelectronics and the like, and has already received wide attention from basic scientific research and industry at home and abroad. In recent decades, researchers have developed a variety of aluminum-based metallic glass systems, however, these aluminum-based systems have low glass forming ability and thermal stability, which severely affect their engineering applications. Therefore, it is of great importance to prepare aluminum-based metallic glasses with high glass forming ability and high thermal stability.

For metallic glasses, systems with better glass forming ability and thermal stability are generally near the eutectic point of the alloy components, such as zirconium-based, lanthanum-based, iron-based, titanium-based, and the like systems. However, in aluminum-based metallic glass systems, the alloying constituents with better glass forming ability and thermal stability are not at the eutectic point, but in the pseudo-eutectic compositional region of the rapid solidification. Particularly close to the eutectic point but offset from the eutectic point. Therefore, the conventional basis for determining the glass forming ability and thermal stability based on the eutectic point composition of the phase diagram is not applicable to aluminum-based metallic glasses. For aluminum-based metallic glass, the glass forming ability and thermal stability are mainly influenced by the nano crystallization process caused by rapid aluminum atom diffusion, and effective inhibition of rapid aluminum atom diffusion is the key for improving the forming ability and thermal stability of the aluminum-based metallic glass.

Chinese patent No. CN104388843A discloses an A1-MR-TM-TE aluminum-based amorphous alloy and a preparation method thereof, wherein MR is a single rare earth element or mixed rare earth, such as La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Y, and the like; TM is a transition metal element such as Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Zr, Nb, Mo, Hf, Ta or W; TE is a trace element such As B, Si, Ga, Ge, As, Se, Sb or Te. The amorphous alloy comprises the following components: a185.0-92.0 at.%, MR 4.0-9.0 at.%, TM 3.0-12.0 at.%, TE 0-1.0 at.%. The amorphous alloy is prepared by preparing materials according to nominal components and then preparing master alloy through vacuum induction melting; and rapidly spinning under the protection of Ar gas to prepare the amorphous strip material, wherein the linear velocity of a copper roller is 35-45m/s during spinning, the injection pressure of a melt is 0.1-0.3MPa, and the vacuum degree is 2-10 Pa. However, the glass forming ability and thermal stability of the aluminum-based systems are low, which seriously affects their engineering applications. Therefore, it is of great importance to prepare aluminum-based metallic glasses with high glass forming ability and high thermal stability.

Disclosure of Invention

The invention provides a high-thermal stability aluminum-based metal glass with higher glass forming capability and higher thermal stability.

A high-heat-stability Al-base metallic glass contains Al as atomic percentage_aY_bFe_cX_dWherein X is a high melting point metal element; the atomic percentage of each component is as follows: 81 < a < 90, 6 < b < 8, 4 < c < 6, 0 < d < 5, a + b + c + d equal to 100.

The high-melting-point metal elements Ta, Re or W in the Al-based amorphous alloy play a role in pinning Al atoms, inhibit the diffusion of the Al atoms, and improve the activation energy of the Al-based amorphous alloy from an amorphous state to a crystalline state, so that the Al-based amorphous alloy with higher glass forming capability and higher thermal stability is obtained.

The addition of the Y element enables Al atoms to be combined with Y to form uniformly dispersed atom clusters, and then the pinning effect of the high-melting-point metal is combined, so that the segregation of the Al atoms is avoided, the Al-based amorphous crystal is avoided, and the glass has high glass forming capability and high thermal stability.

The X element is a high-melting-point metal element Ta, Re or W. The high-melting-point metal element X has extremely high melting point, has very strong corresponding metal valence bond, is difficult to generate atomic diffusion at high temperature, plays a very strong pinning effect and avoids the crystallization of the Al-based amorphous alloy. On the other hand, the enthalpy of mixing between the high-melting-point metal element X and the Al atom is negative, which indicates that the valence bond between the high-melting-point metal element X and the Al atom is stronger, and segregation and crystallization of the Al atom are avoided, so that the glass forming capability and the thermal stability of the Al-based amorphous alloy are greatly improved.

The atomic percentage content of the X element is more than 0 and less than or equal to 5. The optimal addition atomic percentage content of the X element is between 1 and 3. The element X is less than 1, which results in a decrease in the improvement of the thermal stability of the Al-based amorphous alloy. The element X higher than 3 may reduce the glass forming ability of the Al-based amorphous alloy.

The supercooled liquid phase region of the high-heat-stability aluminum-based metal glass is 120-130 ℃, and the crystallization activation energy is 360-380 kJ/mol.

The elastic modulus of the high-heat-stability aluminum-based metal glass is 58-62GPa, and the hardness is 4.3-4.6 GPa.

The invention also provides a preparation method of the high-thermal stability aluminum-based metal glass, which comprises the following steps:

preparing materials according to the atomic percentage composition of the high-heat-stability aluminum-based metallic glass, heating and smelting by electric arc to obtain a first master alloy, smelting the first master alloy by induction heating to obtain a master alloy ingot, melting the master alloy ingot, and then spraying the melted master alloy ingot onto the surface of a rotating copper roller to obtain the banded high-heat-stability aluminum-based metallic glass.

Melting Al-based alloy through electric arc heating, high-melting metal element Ta, Re or W are wrapped up by melting Al, thereby it leads to melting inhomogeneous to form the space with Al melting in-process with avoiding high-melting metal element to form the oxide film, then through induction heating melting high-melting metal element, and will be by in the Al base member by the high-melting metal element evenly distributed of Al parcel through the induction magnetic field vortex, pinning effect through high-melting metal has avoided the quick diffusion of aluminium atom, aluminum-based metallic glass forming ability and thermal stability have been promoted.

The arc heating smelting to obtain a first master alloy, comprising:

(1) putting the raw materials obtained by proportioning into a vacuum arc melting furnace, and adjusting the vacuum degree in the vacuum arc melting furnace to be less than 1 multiplied by 10^-2Pa, filling inert gas to the pressure of (1-5) x 10^-1Pa, regulating the vacuum degree in the vacuum arc melting furnace againLess than 1 x 10^-2Pa；

(2) Repeating the step (1) for 3-4 times, and filling inert gas again until the gas pressure is (1-5) x 10^-1Pa, heating temperature of 2000-3000 ℃, smelting time of 5-10 minutes, repeatedly smelting for 5-6 times, cooling along with the furnace, and taking out to obtain the first master alloy.

The inert gas is introduced for a plurality of times, so that the oxygen content in the furnace is less, the oxide film with metal elements is prevented from being formed in the smelting process, and the raw materials are evenly smelted by a plurality of times of smelting.

The smelting of the first master alloy by induction heating to obtain a master alloy ingot comprises:

(1) putting the first master alloy into a vacuum arc melting furnace, and adjusting the vacuum degree in the vacuum arc melting furnace to be less than 1 multiplied by 10^-2Pa, filling inert gas to the pressure of (1-5) x 10^-1Pa, regulating the vacuum degree in the vacuum arc melting furnace to be less than 1 multiplied by 10^-2Pa；

(2) Repeating the step (1) for 3-4 times, and filling inert gas again until the gas pressure is (1-5) x 10^-1Pa, the power of the used power supply is 30-60kW, the smelting temperature is 1500-.

The rotation rate of the copper roller is 1000-.

The width of the banded high-heat-stability aluminum-based metal glass is 5-10 mm, and the thickness of the banded high-heat-stability aluminum-based metal glass is 10-30 microns.

Compared with the prior art, the invention has the beneficial effects that:

(1) the invention utilizes the pinning effect of the high-melting-point metal element to inhibit the diffusion of Al molecules and improve the activation energy of the Al crystal alloy from an amorphous state to a crystalline state, thereby obtaining the Al-based amorphous alloy with higher glass forming capability and higher thermal stability.

(2) The preparation method provided by the invention has the advantages that the Al-based alloy is melted by electric arc heating, the high-melting-point metal elements Ta, Re or W are wrapped by the melted Al, then the high-melting-point metal elements are melted by induction heating, and the high-melting-point metal elements wrapped by the Al are uniformly distributed in the Al matrix by induction magnetic field eddy current, so that the purpose of uniformly distributing the high-melting-point metal elements in the Al-based alloy system is achieved.

Drawings

FIG. 1 shows Al prepared in example 1 of the present invention₈₅Y₈Fe₆Ta₁XRD pattern of metallic glass ribbon.

FIG. 2 shows Al prepared in example 1 of the present invention₈₅Y₈Fe₆Ta₁Conventional DSC spectra of thin metallic glass ribbons.

FIG. 3 shows Al prepared in example 1 of the present invention₈₅Y₈Fe₆Ta₁Flash temperature rise DSC spectrum of the metal glass thin strip.

FIG. 4 shows Al prepared in example 2 of the present invention₈₅Y₈Fe₆Re₁XRD pattern of the metallic glass ribbon.

FIG. 5 shows Al prepared in example 2 of the present invention₈₅Y₈Fe₆Re₁Conventional DSC spectra of thin metallic glass ribbons.

FIG. 6 shows Al prepared in example 2 of the present invention₈₅Y₈Fe₆Re₁Flash temperature rise DSC spectra of the metal glass thin strip.

FIG. 7 shows Al prepared in example 3 of the present invention₈₅Y₈Fe₆W₁XRD pattern of metallic glass ribbon.

FIG. 8 shows Al prepared in example 3 of the present invention₈₅Y₈Fe₆W₁Conventional DSC spectra of thin metallic glass ribbons.

FIG. 9 shows Al prepared in example 3 of the present invention₈₅Y₈Fe₆W₁Flash temperature rise DSC spectrum of the metal glass thin strip.

FIG. 10 shows Al prepared in example 4 of the present invention_87.5Y₇Fe₅Ta_0.5XRD pattern of the metallic glass ribbon.

FIG. 11 shows Al prepared in example 4 of the present invention_87.5Y₇Fe₅Ta_0.5Conventional DSC spectra of thin metallic glass ribbons.

FIG. 12 shows Al prepared in example 4 of the present invention_87.5Y₇Fe₅Ta_0.5Flash temperature rise DSC spectrum of the metal glass thin strip.

FIG. 13 shows Al prepared in example 5 of the present invention₈₇Y₆Fe₄W₃XRD pattern of the metallic glass ribbon.

FIG. 14 shows Al prepared in example 5 of the present invention₈₇Y₆Fe₄W₃Conventional DSC spectra of thin metallic glass ribbons.

FIG. 15 shows Al prepared in example 5 of the present invention₈₇Y₆Fe₄W₃Flash temperature rise DSC spectrum of the metal glass thin strip.

FIG. 16 shows Al prepared in examples 1, 2, 3, 4 and 5 of the present invention₈₅Y₈Fe₆Ta₁、Al₈₅Y₈Fe₆Re₁、Al₈₅Y₈Fe₆W₁、Al_87.5Y₇Fe₅Ta_0.5、Al₈₇Y₆Fe₄W₃A comparison of supercooled liquid regions.

FIG. 17 shows Al prepared in examples 1, 2, 3, 4 and 5 of the present invention₈₅Y₈Fe₆Ta₁、Al₈₅Y₈Fe₆Re₁、Al₈₅Y₈Fe₆W₁、Al_87.5Y₇Fe₅Ta_0.5、Al₈₇Y₆Fe₄W₃Calculated graph of crystallization activation energy.

FIG. 18 shows Al prepared in examples 1, 2, 3, 4 and 5 of the present invention₈₅Y₈Fe₆Ta₁、Al₈₅Y₈Fe₆Re₁、Al₈₅Y₈Fe₆W₁、Al_87.5Y₇Fe₅Ta_0.5、Al₈₇Y₆Fe₄W₃Comparative graph of crystallization activation energy.

FIG. 19 shows Al prepared in examples 1, 2, 3, 4 and 5 of the present invention₈₅Y₈Fe₆Ta₁、Al₈₅Y₈Fe₆Re₁、Al₈₅Y₈Fe₆W₁、Al_87.5Y₇Fe₅Ta_0.5、Al₈₇Y₆Fe₄W₃The curve of the nano indentation load and the indenter indentation depth is compared with a graph.

FIG. 20 shows Al prepared in examples 1, 2, 3, 4 and 5 of the present invention₈₅Y₈Fe₆Ta₁、Al₈₅Y₈Fe₆Re₁、Al₈₅Y₈Fe₆W₁、Al_87.5Y₇Fe₅Ta_0.5、Al₈₇Y₆Fe₄W₃Hardness comparison graph of (2).

FIG. 21 shows Al prepared in examples 1, 2, 3, 4 and 5 of the present invention₈₅Y₈Fe₆Ta₁、Al₈₅Y₈Fe₆Re₁、Al₈₅Y₈Fe₆W₁、Al_87.5Y₇Fe₅Ta_0.5、Al₈₇Y₆Fe₄W₃Comparative figure of elastic modulus.

Detailed Description

The technical scheme provided by the invention is further explained by specific embodiments in the following with reference to the attached drawings. The starting materials used in the present invention are commercially available unless otherwise specified.

Example 1 preparation of Al with a rotation Rate of 2000rmp by a copper Single-roll Rotary quench method₈₅Y₈Fe₆Ta₁Metallic glass ribbon sample

The preparation method comprises the following steps:

(1) weighing each element raw material according to the component atomic ratio, wherein the total weight is about 30g, and the raw materials are Al, Y, Fe and Ta with the purity of 99.9%, and putting the raw materials into an ultrasonic cleaning machine by using alcohol for cleaning for later use.

(2) The cleaned raw materials are placed on the lower layer according to the low melting point and the upper layer according to the high melting point, and are regularly placed into a copper crucible of a vacuum arc furnace. Vacuumizing by a vacuum pump until the pressure in the furnace is lower than 1 x 10^-2Pa, opening the valve and filling argonThe gas is pumped to 0.5Pa, then the valve is closed, and the vacuum pumping is continued to 1 multiplied by 10^-2Pa. This operation is repeated 3-4 times to ensure that the residual oxygen in the furnace is reduced as much as possible. And finally, injecting argon to 0.5Pa, performing primary smelting by using an electric arc, heating at the temperature of 2000-3000 ℃, smelting for 5-10 minutes, and repeatedly smelting for 5-6 times to obtain a master alloy ingot.

(3) And (3) putting the master alloy ingot obtained in the step (2) into a quartz crucible, and putting the quartz crucible into an induction smelting furnace. Vacuum-pumping to 1 × 10^-2Pa, filling argon to 0.5Pa, then closing the valve and continuing to vacuumize below 1 × 10^-2Pa. This operation is repeated 3-4 times to ensure that the residual oxygen in the furnace is reduced as much as possible. And finally, injecting argon to 0.5Pa, heating and smelting by using induction current, wherein the power of a used power supply is 30-60kW, the smelting temperature is 1500-.

(4) And (4) putting the master alloy ingot obtained in the step (3) into a quartz crucible and putting the quartz crucible into an induction smelting furnace. Vacuum-pumping to 1 × 10^{- 2}Pa, filling argon to 0.5Pa, then closing the valve and continuing to vacuumize to 1 × 10^-2Pa. This operation is repeated 3-4 times to ensure that the residual oxygen in the furnace is reduced as much as possible. And finally, injecting argon to 0.5Pa, heating and smelting by using induction current, and keeping for 5-10 minutes to finally obtain a master alloy ingot with uniform components.

(5) And (4) crushing the master alloy ingot obtained in the step (4), and then cleaning. The fragments are put into a quartz tube with a small hole at the top end, and the opening of the quartz tube is connected into a nozzle of spray casting equipment and sealed. Vacuum-pumping to 1 × 10^-3Pa, introducing argon. And (3) turning on an induction power supply, melting the alloy fragments, and preparing the molten alloy into a strip-shaped sample with the width of 2mm and the thickness of 0.3mm by using a copper single-roller rotary quenching device.

The thermodynamic and mechanical analysis methods are as follows:

(6) analyzing the Al obtained in the step (5) by an X-ray apparatus₈₅Y₈Fe₆Ta₁The phase structure of the metallic glass ribbon is shown in the X-ray diffraction diagram of FIG. 1.

(7) Measurement of Al obtained in step (5) with a conventional Differential Scanning Calorimeter (DSC)₈₅Y₈Fe₆Ta₁The thermodynamic parameter and the temperature rise rate of the metallic glass ribbon are 0.33K/s, and are shown in figure 2.

(8) Measuring the Al obtained in the step (5) by using a Flash scanning calorimeter (Flash DSC)₈₅Y₈Fe₆Ta₁The thermodynamic parameters of the metallic glass ribbon change with the temperature rise rate, and the temperature rise rate ranges from 10K/s to 200K/s, and is shown in figure 3.

(9) Detecting the Al obtained in the step (5) by using a nano indenter (Nanoindener)₈₅Y₈Fe₆Ta₁The mechanical properties of the metallic glass ribbon, including load variation with indenter penetration depth, modulus of elasticity, and hardness, are shown in figures 19, 20, and 21.

(10) Analyzing the Al obtained in the step (5) by adopting an X-ray diffractometer, a Differential Scanning Calorimeter (DSC), a Flash scanning calorimeter (Flash DSC) and a Nanoindenter (Nanoinder)₈₅Y₈Fe₆Ta₁Microstructure, glass forming ability, thermal stability and mechanical properties of the metallic glass ribbon.

As can be seen from FIG. 1, Al is produced₈₅Y₈Fe₆Ta₁The alloy strip shows obvious diffuse peaks, which indicates that the alloy component is amorphous. As can be seen from FIG. 2, Al is produced₈₅Y₈Fe₆Ta₁The alloy strip shows a glass transition temperature T_gInitial crystallization temperature T_x. The parameter for judging the forming ability and the thermal stability of the metallic glass is a supercooling liquid phase region delta T (T)_x-T_g) And crystallization activation energy E_x. According to FIG. 2, the supercooled liquid region Δ T is 122K, as shown in FIG. 16. According to FIG. 3, the crystallization activation energy E can be calculated from the change of the heat flow curve shown in FIG. 17 with the temperature increase rate_xIt was 364.5kJ/mol, as shown in FIG. 18.

Specific values of hardness and modulus of elasticity can be obtained from the load versus indenter penetration curve shown in fig. 19, as shown in fig. 20 and 21.

The thermodynamic and mechanical parameters of this example 1 are shown in table 1.

Example 2Preparing Al with the rotation rate of 2000rmp by adopting a copper single-roller rotary quenching method₈₅Y₈Fe₆Re₁Metallic glass ribbon sample

The preparation method, thermodynamic and mechanical analysis methods were the same as in example 1.

(1) Al obtained by analysis with X-ray apparatus₈₅Y₈Fe₆Re₁The phase structure of the metallic glass ribbon is shown in the X-ray diffraction diagram of fig. 4.

(2) Al obtained by measurement with a conventional Differential Scanning Calorimeter (DSC)₈₅Y₈Fe₆Re₁The thermodynamic parameters of the metallic glass ribbon and the temperature rise rate are 0.33K/s, and are shown in figure 5.

(3) Al determined by Flash scanning calorimeter (Flash DSC)₈₅Y₈Fe₆Re₁The thermodynamic parameters of the metallic glass ribbon change with the temperature rise rate, and the temperature rise rate ranges from 10K/s to 200K/s, as shown in FIG. 6.

(4) The obtained Al was detected by Nanoindenter (Nanoindener)₈₅Y₈Fe₆Re₁The mechanical properties of the metallic glass ribbon, including load variation with indenter penetration depth, modulus of elasticity, and hardness, are shown in figures 19, 20, and 21.

(5) Al obtained by X-ray diffractometer, Differential Scanning Calorimeter (DSC), flash scanning calorimeter (FlashDSC) and nano-indenter (Nanoindender) analysis₈₅Y₈Fe₆Re₁Microstructure, glass forming ability, thermal stability and mechanical properties of the metallic glass ribbon.

As can be seen from FIG. 4, Al is produced₈₅Y₈Fe₆Re₁The alloy strip shows obvious diffuse peaks, which indicates that the alloy component is amorphous. As can be seen from FIG. 5, Al is produced₈₅Y₈Fe₆Ta₁The alloy strip shows a glass transition temperature T_gInitial crystallization temperature T_x. The parameter for determining the forming ability and the thermal stability of the metallic glass is a supercooled liquid phase region delta T (T)_x-T_g) And crystallization activation energy E_x. According to fig. 5As shown, the supercooled liquid region Δ T was 124K, as shown in FIG. 16. According to the change of the heat flow curve shown in FIG. 17 with the temperature rise rate in FIG. 3, the crystallization activation energy E can be calculated_xAt 372kJ/mol, as shown in FIG. 18.

Specific values of hardness and modulus of elasticity can be obtained from the load versus indenter penetration curve shown in fig. 19, as shown in fig. 20 and 21.

The thermodynamic and mechanical parameters of this example 2 are shown in table 1.

Example 3 preparation of Al with a rotation Rate of 2000rmp by means of a copper Single-roll Rotary quench method₈₅Y₈Fe₆W₁Metallic glass strip sample

The preparation method, thermodynamic and mechanical analysis methods were the same as in example 1.

(1) Al obtained by analysis with X-ray apparatus₈₅Y₈Fe₆W₁The phase structure of the metallic glass ribbon is shown in the X-ray diffraction pattern of fig. 7.

(2) Al obtained by measurement with a conventional Differential Scanning Calorimeter (DSC)₈₅Y₈Fe₆W₁The thermodynamic parameters of the metallic glass ribbon and the temperature rise rate are 0.33K/s, and are shown in figure 8.

(3) Al determined by Flash scanning calorimeter (Flash DSC)₈₅Y₈Fe₆W₁The thermodynamic parameters of the metallic glass ribbon change with the temperature rise rate, and the temperature rise rate ranges from 10K/s to 200K/s, and is shown in figure 9.

(4) The obtained Al was detected by a Nanoindenter (Nanoindenter)₈₅Y₈Fe₆W₁The mechanical properties of the metallic glass ribbon, including load variation with indenter penetration depth, modulus of elasticity, and hardness, are shown in figures 19, 20, and 21.

(5) Al obtained by X-ray diffractometer, Differential Scanning Calorimeter (DSC), flash scanning calorimeter (FlashDSC) and nano-indenter (Nanoindender) analysis₈₅Y₈Fe₆W₁Microstructure, glass forming ability, thermal stability and mechanical properties of the metallic glass ribbon.

From FIG. 7To see that Al produced₈₅Y₈Fe₆W₁The alloy strip shows obvious diffuse peaks, which indicates that the alloy component is amorphous. As can be seen from FIG. 8, Al produced₈₅Y₈Fe₆W₁The alloy strip shows a glass transition temperature T_gInitial crystallization temperature T_x. The parameter for judging the forming ability and the thermal stability of the metallic glass is a supercooling liquid phase region delta T (T)_x-T_g) And crystallization activation energy E_x. According to FIG. 8, the supercooled liquid region Δ T is 127K, as shown in FIG. 16. According to FIG. 9, the crystallization activation energy E can be calculated from the change of the heat flow curve shown in FIG. 17 with the temperature increase rate_x377kJ/mol, as shown in FIG. 18.

Specific values of hardness and modulus of elasticity can be obtained from the load versus indenter penetration curve shown in fig. 19, as shown in fig. 20 and 21.

The thermodynamic and mechanical parameters of this example 3 are shown in table 1.

Example 4 preparation of Al with a rotation Rate of 2000rmp by means of a copper Single-roll Rotary quench method_87.5Y₇Fe₅Ta_0.5Metallic glass strip sample

The preparation method, thermodynamic and mechanical analysis methods were the same as in example 1.

(6) Al obtained by analysis with X-ray apparatus_87.5Y₇Fe₅Ta_0.5The phase structure of the metallic glass ribbon is shown in the X-ray diffraction diagram of fig. 10.

(7) Al obtained by measurement with a conventional Differential Scanning Calorimeter (DSC)_87.5Y₇Fe₅Ta_0.5The thermodynamic parameter and the temperature rise rate of the metallic glass ribbon are 0.33K/s, and are shown in figure 11.

(8) Al determined by Flash scanning calorimeter (Flash DSC)_87.5Y₇Fe₅Ta_0.5The thermodynamic parameters of the metallic glass ribbon change with the temperature rise rate, and the temperature rise rate ranges from 10K/s to 200K/s, as shown in figure 12.

(9) The obtained Al was detected by a Nanoindenter (Nanoindenter)_87.5Y₇Fe₅Ta_0.5The mechanical properties of the metallic glass ribbon, including load variation with indenter penetration depth, modulus of elasticity, and hardness, are shown in figures 19, 20, and 21.

(10) Al obtained by X-ray diffractometer, Differential Scanning Calorimeter (DSC), Flash scanning calorimeter (Flash DSC) and nano indenter (Nanoindender) analysis_87.5Y₇Fe₅Ta_0.5Microstructure, glass forming ability, thermal stability and mechanical properties of the metallic glass ribbon.

As can be seen from FIG. 10, Al is produced_87.5Y₇Fe₅Ta_0.5The alloy strip shows obvious diffuse peaks, which indicates that the alloy component is amorphous. As can be seen from FIG. 11, Al produced_87.5Y₇Fe₅Ta_0.5The alloy strip shows a glass transition temperature T_gInitial crystallization temperature T_x. The parameter for determining the forming ability and the thermal stability of the metallic glass is a supercooled liquid phase region delta T (T)_x-T_g) And crystallization activation energy E_x. According to FIG. 11, the supercooled liquid region Δ T is 116K, as shown in FIG. 16. The crystallization activation energy E can be calculated from the change of the heat flow curve with the temperature rise rate shown in FIG. 12_xIt was 360kJ/mol as shown in FIG. 18.

Specific values of hardness and modulus of elasticity can be obtained from the load versus indenter penetration curve shown in fig. 19, as shown in fig. 20 and 21.

The thermodynamic and mechanical parameters of this example 4 are shown in table 1.

Example 5 preparation of Al with a rotation Rate of 2000rmp by means of a copper Single-roll Rotary quench method₈₇Y₆Fe₄W₃Metallic glass ribbon sample

The preparation method, thermodynamic and mechanical analysis methods were the same as in example 1.

(11) Al obtained by analysis with X-ray apparatus₈₇Y₆Fe₄W₃The phase structure of the metallic glass ribbon is shown in the X-ray diffraction pattern of fig. 13.

(12) Measured by conventional Differential Scanning Calorimetry (DSC)Al obtained₈₇Y₆Fe₄W₃The thermodynamic parameter and the temperature rise rate of the metallic glass ribbon are 0.33K/s, and are shown in figure 14.

(13) Al determined by Flash scanning calorimeter (Flash DSC)₈₇Y₆Fe₄W₃The thermodynamic parameters of the metallic glass ribbon change with the temperature rise rate, and the temperature rise rate ranges from 10K/s to 200K/s, as shown in figure 15.

(14) The obtained Al was detected by Nanoindenter (Nanoindener)₈₇Y₆Fe₄W₃The mechanical properties of the metallic glass ribbon, including load variation with indenter penetration depth, modulus of elasticity, and hardness, are shown in figures 19, 20, and 21.

(15) Al obtained by X-ray diffractometer, Differential Scanning Calorimeter (DSC), Flash scanning calorimeter (Flash DSC) and nano indenter (Nanoindender) analysis₈₇Y₆Fe₄W₃Microstructure, glass forming ability, thermal stability and mechanical properties of the metallic glass ribbon.

As can be seen from FIG. 13, Al produced₈₇Y₆Fe₄W₃The alloy strip shows obvious diffuse peaks, which indicates that the alloy component is amorphous. As can be seen from FIG. 14, Al produced₈₇Y₆Fe₄W₃The alloy strip shows a glass transition temperature T_gInitial crystallization temperature T_x. The parameter for judging the forming ability and the thermal stability of the metallic glass is a supercooling liquid phase region delta T (T)_x-T_g) And crystallization activation energy E_x. According to FIG. 14, the supercooled liquid region Δ T was 129K, as shown in FIG. 16. The crystallization activation energy E can be calculated from the change of the heat flow curve with the temperature rise rate shown in FIG. 15_x379kJ/mol, as shown in FIG. 18.

Specific values of hardness and modulus of elasticity can be obtained from the load versus indenter penetration curve shown in fig. 19, as shown in fig. 20 and 21.

The thermodynamic and mechanical parameters of this example 5 are shown in table 1.

TABLE 1

Claims (9)

1. A high-heat-stability aluminum-based metallic glass is characterized in that the atomic percentage composition formula is Al_aY_bFe_cX_dWherein X is a high melting point metal element; the atomic percentage of each component is as follows: 81 < a < 90, 6 < b < 8, 4 < c < 6, 0 < d < 5, a + b + c + d equal to 100.

2. A highly thermally stable aluminium-based metallic glass according to claim 1, characterised in that X is Ta, Re or W.

3. A highly thermally stable aluminium based metallic glass according to claim 1, characterised in that the atomic percentage content of X is 0 < d ≦ 5.

4. The high-heat-stability aluminum-based metallic glass as defined in claim 1, wherein the supercooled liquid region of the high-heat-stability aluminum-based metallic glass is 120-130 ℃, and the crystallization activation energy is 360-380 kJ/mol.

5. A highly thermally stable aluminum based metallic glass according to claim 1, characterized in that it has a modulus of elasticity of 58-62GPa and a hardness of 4.3-4.6 GPa.

6. A method for producing a highly thermally stable aluminum-based metallic glass according to any one of claims 1 to 5, comprising:

preparing materials according to the atomic percentage composition of the high-heat-stability aluminum-based metallic glass, heating and smelting by electric arc to obtain a first master alloy, smelting the first master alloy by induction heating to obtain a master alloy ingot, melting the master alloy ingot, and then spraying the melted master alloy ingot onto the surface of a rotating copper roller to obtain the banded high-heat-stability aluminum-based metallic glass.

7. A method according to claim 6, wherein said arc melting produces a first master alloy comprising:

(1) putting the raw materials obtained by proportioning into a vacuum arc melting furnace, and adjusting the vacuum degree in the vacuum arc melting furnace to be less than 1 multiplied by 10^-2Pa, filling inert gas to the pressure of (1-5) x 10^-1Pa, regulating the vacuum degree in the vacuum arc melting furnace to be less than 1 multiplied by 10 again^-2Pa；

(2) Repeating the step (1) for 3-4 times, and filling inert gas again until the gas pressure is (1-5) x 10^-1Pa, heating temperature of 2000-3000 ℃, smelting time of 5-10 minutes, repeatedly smelting for 5-6 times, cooling along with the furnace, and taking out to obtain the first master alloy.

8. The method for producing a highly thermally stable aluminum-based metallic glass according to claim 6, wherein said melting said first master alloy by induction heating to obtain a master alloy ingot comprises:

(1) putting the first master alloy into a vacuum arc melting furnace, and adjusting the vacuum degree in the vacuum arc melting furnace to be less than 1 multiplied by 10^-2Pa, filling inert gas to the pressure of (1-5) x 10^-1Pa, regulating the vacuum degree in the vacuum arc melting furnace to be less than 1 multiplied by 10 again^-2Pa；

(2) Repeating the step (1) for 3-4 times, and filling inert gas again until the gas pressure is (1-5) x 10^-1Pa, the power of the used power supply is 30-60kW, the smelting temperature is 1500-.

9. The method as claimed in claim 6, wherein the rotation rate of the copper roller is 1000-4000 rmp.

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