CN114686785B - A kind of high heat stable aluminum-based metallic glass and its preparation method - Google Patents

Abstract

The invention discloses a high-thermal-stable aluminum-based metallic glass, the atomic percentage composition formula is Al _a Y _b Fe _c X _d , wherein X is a high-melting point metal element; the atomic percentage of each component is: 81≦a<90, 6≦b≦8, 4≦c≦6, 0<d≦5, a+b+c+d=100. The aluminum-based metallic glass has high glass-forming ability and high thermal stability. The present invention also provides a method for preparing a high-heat-stable aluminum-based metallic glass, which includes: mixing ingredients according to the atomic percentage composition formula of the high-thermal-stable aluminum-based metallic glass, obtaining the first master alloy by arc heating and melting, and melting by induction heating A master alloy ingot is obtained from the first master alloy, and the master alloy ingot is melted and sprayed onto the surface of a rotating copper roller to obtain a strip-shaped high-heat-stable aluminum-based metallic glass. The preparation method is simple, efficient and suitable for industrial production.

Description

A kind of high thermal stability aluminum-based metallic glass and preparation method thereof

Technical Field

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

Background Art

Metallic glass, also known as amorphous alloy, is obtained by rapid cooling of liquid melt, and its atomic structure shows short-range order and long-range disorder. They have both solid and liquid properties, and therefore show excellent mechanical properties, oxidation corrosion resistance and soft magnetic properties.

Aluminum-based metallic glass materials not only have extremely high specific strength, but also have good toughness, superplasticity and corrosion resistance. They are a new type of metal structural material with broad application prospects. They can be widely used in aviation, aerospace, navigation, national defense, automobiles, military and microelectronics, and have received extensive 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, but the glass-forming ability and thermal stability of these aluminum-based systems are very low, which seriously affects their application in engineering. Therefore, it is of great significance to prepare aluminum-based metallic glass with high glass-forming ability and high thermal stability.

For metallic glass, 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 other systems. However, in the aluminum-based metallic glass system, the alloy components with better glass forming ability and thermal stability are not at the eutectic point, but in the rapidly solidified pseudo-eutectic component area. Specifically, it is close to the eutectic point but also deviates from the eutectic point. Therefore, the traditional basis for judging the glass forming ability and thermal stability based on the eutectic point composition of the phase diagram is not applicable to aluminum-based metallic glass. For aluminum-based metallic glass, the glass forming ability and thermal stability are mainly affected by the nanocrystallization process caused by the rapid diffusion of aluminum atoms. Effectively inhibiting the rapid diffusion of aluminum atoms is the key to improving the glass forming ability and thermal stability of aluminum-based metallic glass.

The Chinese patent with patent number 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 a mixed rare earth, such as La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Y, etc.; 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, etc.; TE is a trace element, such as B, Si, Ga, Ge, As, Se, Sb or Te, etc. The amorphous alloy composition is: A1 85.0-92.0at.%, MR 4.0-9.0at.%, TM 3.0-12.0at.%, TE 0-1.0at.%. The method for preparing the amorphous alloy is to prepare a master alloy by vacuum induction melting after batching according to the nominal composition; and to prepare an amorphous ribbon material by rapid belt spinning under Ar gas protection, wherein the copper roller linear speed is 35-45 m/s, the melt injection pressure is 0.1-0.3 MPa, and the vacuum degree is 2-10 Pa. However, the glass forming ability and thermal stability of the aluminum-based system are very low, which seriously affects their application in engineering. Therefore, it is of great significance to prepare aluminum-based metallic glass with high glass forming ability and high thermal stability.

Summary of the invention

The present invention provides a highly thermally stable aluminum-based metallic glass with high glass-forming ability and high thermal stability.

A high thermally stable aluminum-based metallic glass has an atomic percentage composition formula of Al _a Y _b Fe _c X _d , wherein X is a high melting point metal element; the atomic percentage of each component is: 81≦a<90, 6≦b≦8, 4≦c≦6, 0<d≦5, a+b+c+d=100.

The high melting point metal elements Ta, Re or W in the Al-based amorphous alloy of the present invention play a pinning role on Al atoms, inhibit the diffusion of Al atoms, and increase the activation energy of the Al-based amorphous alloy from an amorphous state to a crystalline state, thereby obtaining an Al-based amorphous alloy with higher glass forming ability and higher thermal stability.

The addition of Y element makes Al atoms combine with Y to form evenly dispersed atomic clusters. Combined with the pinning effect of high melting point metal, the segregation of Al atoms is avoided and the formation of crystals from Al-based amorphous is avoided, thus having higher glass forming ability and higher thermal stability.

The X element is a high melting point metal element Ta, Re or W. The high melting point metal element X has an extremely high melting point, and its corresponding metal valence bond is very strong. It is difficult for atomic diffusion to occur under high temperature conditions, and it plays a strong pinning role to avoid crystallization of Al-based amorphous alloys. On the other hand, the mixing enthalpy between the high melting point metal element X and the Al atom is negative, indicating that the valence bond between the high melting point metal element X and the Al atom is relatively strong, which avoids the segregation and crystallization of the Al atom, thereby greatly improving the glass forming ability and thermal stability of the Al-based amorphous alloy.

The atomic percentage content of the X element is 0＜d≦5. The optimal atomic percentage content of the X element is 1≦d≦3. If the X element is less than 1, the degree of improvement of the thermal stability of the Al-based amorphous alloy will be reduced. If the X element is more than 3, the glass forming ability of the Al-based amorphous alloy will be reduced.

The supercooled liquid phase region of the high thermal stability aluminum-based metallic glass is 120-130° C., and the crystallization activation energy is 360-380 kJ/mol.

The high thermal stability aluminum-based metallic glass has an elastic modulus of 58-62 GPa and a hardness of 4.3-4.6 GPa.

The present invention also provides a method for preparing a high thermally stable aluminum-based metallic glass, comprising:

The ingredients are prepared according to the atomic percentage composition formula of the high thermally stable aluminum-based metallic glass, and a first mother alloy is obtained by arc heating melting. The first mother alloy is melted by induction heating to obtain a mother alloy ingot, and the mother alloy ingot is melted and sprayed onto the surface of a rotating copper roller to obtain a strip of high thermally stable aluminum-based metallic glass.

The Al-based alloy is melted by arc heating, and the high-melting-point metal elements Ta, Re or W are wrapped by the molten Al to prevent the high-melting-point metal elements from forming an oxide film and forming gaps with the Al during the melting process, resulting in uneven melting. The high-melting-point metal elements are then melted by induction heating, and the high-melting-point metal elements wrapped by Al are evenly distributed into the Al matrix by the induced magnetic field eddy current. The pinning effect of the high-melting-point metal avoids the rapid diffusion of aluminum atoms, thereby improving the glass forming ability and thermal stability of the aluminum-based metallic glass.

The arc heating and melting to obtain the first master alloy comprises:

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

(2) Repeat step (1) 3-4 times, fill in inert gas again until the pressure is (1-5)×10 ^-1 Pa, heat to 2000-3000°C, smelt for 5-10 minutes, repeat smelting 5-6 times, cool in the furnace and take out to obtain the first mother alloy.

By introducing inert gas multiple times, there is less oxygen in the furnace, which avoids the formation of oxide film with metal elements during the smelting process. Multiple smelting makes the raw materials melt evenly.

The method of obtaining a master alloy ingot by melting the first master alloy by induction heating comprises:

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

(2) Repeat step (1) 3-4 times, and fill in inert gas again until the pressure is (1-5)×10 ^-1 Pa. The power used is 30-60 kW, the melting temperature is 1500-2500° C., and the melting time is 5-10 minutes.

The rotation speed of the copper roller is 1000-4000 rpm.

The strip-shaped high thermally stable aluminum-based metallic glass has a width of 5-10 mm and a thickness of 10-30 μm.

Compared with the prior art, the present invention has the following beneficial effects:

(1) The present invention utilizes the pinning effect of high melting point metal elements to inhibit the diffusion of Al molecules and increase the activation energy of the Al crystalline alloy from the amorphous state to the crystalline state, thereby obtaining an Al-based amorphous alloy with higher glass forming ability and higher thermal stability.

(2) In the preparation method provided by the present invention, the Al-based alloy is first melted by electric arc heating, and the high-melting-point metal elements Ta, Re or W are wrapped by the molten Al. Then, the high-melting-point metal elements are melted by induction heating, and the high-melting-point metal elements wrapped by Al are evenly distributed into the Al matrix by induction magnetic field eddy currents, thereby achieving the purpose of evenly distributing the high-melting-point metal elements in the Al-based alloy system. The preparation method is simple, efficient, and suitable for industrial production.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG1 is an XRD spectrum of the Al ₈₅ Y ₈ Fe ₆ Ta ₁ metallic glass ribbon prepared in Example 1 of the present invention.

FIG. 2 is a conventional DSC spectrum of the Al ₈₅ Y ₈ Fe ₆ Ta ₁ metallic glass ribbon prepared in Example 1 of the present invention.

FIG3 is a flash heating DSC spectrum of the Al ₈₅ Y ₈ Fe ₆ Ta ₁ metallic glass ribbon prepared in Example 1 of the present invention.

FIG. 4 is an XRD spectrum of the Al ₈₅ Y ₈ Fe ₆ Re ₁ metallic glass ribbon prepared in Example 2 of the present invention.

FIG5 is a conventional DSC spectrum of the Al ₈₅ Y ₈ Fe ₆ Re ₁ metallic glass ribbon prepared in Example 2 of the present invention.

FIG6 is a flash heating DSC spectrum of the Al ₈₅ Y ₈ Fe ₆ Re ₁ metallic glass ribbon prepared in Example 2 of the present invention.

FIG. 7 is an XRD spectrum of the Al ₈₅ Y ₈ Fe ₆ W ₁ metallic glass ribbon prepared in Example 3 of the present invention.

FIG8 is a conventional DSC spectrum of the Al ₈₅ Y ₈ Fe ₆ W ₁ metallic glass ribbon prepared in Example 3 of the present invention.

FIG9 is a flash heating DSC spectrum of the Al ₈₅ Y ₈ Fe ₆ W ₁ metallic glass ribbon prepared in Example 3 of the present invention.

FIG. 10 is an XRD spectrum of the Al _87.5 Y ₇ Fe ₅ Ta _0.5 metallic glass ribbon prepared in Example 4 of the present invention.

FIG. 11 is a conventional DSC spectrum of the Al _87.5 Y ₇ Fe ₅ Ta _0.5 metallic glass ribbon prepared in Example 4 of the present invention.

FIG. 12 is a flash heating DSC spectrum of the Al _87.5 Y ₇ Fe ₅ Ta _0.5 metallic glass ribbon prepared in Example 4 of the present invention.

FIG. 13 is an XRD spectrum of the Al ₈₇ Y ₆ Fe ₄ W ₃ metallic glass ribbon prepared in Example 5 of the present invention.

FIG. 14 is a conventional DSC spectrum of the Al ₈₇ Y ₆ Fe ₄ W ₃ metallic glass ribbon prepared in Example 5 of the present invention.

FIG. 15 is a flash heating DSC spectrum of the Al ₈₇ Y ₆ Fe ₄ W ₃ metallic glass ribbon prepared in Example 5 of the present invention.

16 is a comparison diagram of the supercooled liquid regions of Al ₈₅ Y ₈ Fe ₆ Ta ₁ , Al ₈₅ Y ₈ Fe ₆ Re ₁ , Al ₈₅ Y ₈ Fe ₆ W ₁ , Al _87.5 Y ₇ Fe ₅ Ta _0.5 , and Al ₈₇ Y ₆ Fe ₄ W ₃ prepared in Examples 1, 2, 3, 4, and 5 of the present invention.

17 is a calculation diagram of the crystallization activation energy of Al ₈₅ Y ₈ Fe ₆ Ta ₁ , Al ₈₅ Y ₈ Fe ₆ Re ₁ , Al ₈₅ Y ₈ Fe ₆ W ₁ , Al _87.5 Y ₇ Fe ₅ Ta _0.5 , and Al ₈₇ Y ₆ Fe ₄ W ₃ prepared in Examples 1, 2, 3, 4, and 5 of the present invention.

18 is a comparison chart of the crystallization activation energies of Al ₈₅ Y ₈ Fe ₆ Ta ₁ , Al ₈₅ Y ₈ Fe ₆ Re ₁ , Al ₈₅ Y ₈ Fe ₆ W ₁ , Al _87.5 Y ₇ Fe ₅ Ta _0.5 , and Al ₈₇ Y ₆ Fe ₄ W ₃ prepared in Examples 1, 2, 3, 4, and 5 of the present invention.

19 is a comparative curve of the relationship between the nanoindentation load and the indentation depth of Al ₈₅ Y ₈ Fe ₆ Ta ₁ , Al ₈₅ Y ₈ Fe ₆ Re ₁ , Al ₈₅ Y ₈ Fe ₆ W ₁ , Al _87.5 Y ₇ Fe ₅ Ta _0.5 , and Al ₈₇ Y ₆ Fe ₄ W ₃ prepared in Examples 1, 2, 3, 4, and 5 of the present invention.

FIG20 is a hardness comparison chart of Al ₈₅ Y ₈ Fe ₆ Ta ₁ , Al ₈₅ Y ₈ Fe ₆ Re ₁ , Al ₈₅ Y ₈ Fe ₆ W ₁ , Al _87.5 Y ₇ Fe ₅ Ta _0.5 , and Al ₈₇ Y ₆ Fe ₄ W ₃ prepared in Examples 1, 2, 3, 4, and 5 of the present invention.

21 is a comparison chart of the elastic moduli of Al ₈₅ Y ₈ Fe ₆ Ta ₁ , Al ₈₅ Y ₈ Fe ₆ Re ₁ , Al ₈₅ Y ₈ Fe ₆ W ₁ , Al _87.5 Y ₇ Fe ₅ Ta _0.5 , and Al ₈₇ Y ₆ Fe ₄ W ₃ prepared in Examples 1, 2, 3, 4, and 5 of the present invention.

DETAILED DESCRIPTION

The technical solution provided by the present invention is further explained below with reference to specific embodiments in conjunction with the accompanying drawings. Unless otherwise specified, the raw materials used in the present invention are all commercially available.

Example 1: Preparation of Al ₈₅ Y ₈ Fe ₆ Ta ₁ metallic glass ribbon sample with a rotation rate of 2000 rpm by copper single roller rotation quenching method

The preparation method is as follows:

(1) According to the atomic ratio of the components, weigh the raw materials of each element, the total weight is about 30g, the raw materials are Al, Y, Fe, Ta with a purity of 99.9%, wash them in an ultrasonic cleaner with alcohol and set aside.

(2) Stack the cleaned raw materials in the order of placing the ones with lower melting points on the lower layer and the ones with higher melting points on the upper layer, and put them into the copper crucible of the vacuum arc furnace in a regular manner. Turn on the vacuum pump to evacuate the furnace until the pressure is lower than 1× ^10-2 Pa, open the valve, fill with argon to 0.5Pa, and then close the valve to continue evacuating to 1× ^10-2 Pa. Repeat this step 3-4 times to ensure that the residual oxygen in the furnace is reduced as much as possible. Finally, flush with argon to 0.5Pa, use the arc for preliminary smelting, the heating temperature is 2000-3000℃, the smelting time is 5-10 minutes, and the smelting is repeated 5-6 times to obtain the master alloy ingot.

(3) The master alloy ingot obtained in step (2) is placed in a quartz crucible and placed in an induction melting furnace. Evacuate to 1×10 ^-2 Pa, fill with argon to 0.5 Pa, then close the valve and continue to evacuate to less than 1×10 ^-2 Pa. Repeat this step 3-4 times to ensure that the residual oxygen in the furnace is reduced as much as possible. Finally, argon is injected to 0.5 Pa, and smelting is carried out by induction current heating. The power used is 30-60kW, the smelting temperature is 1500-2500℃, and it is maintained for 5-10 minutes to finally obtain a master alloy ingot with uniform composition.

(4) The master alloy ingot obtained in step (3) is placed in a quartz crucible and placed in an induction melting furnace. Evacuate to 1×10 ^{- 2} Pa, fill with argon to 0.5 Pa, then close the valve and continue to evacuate to 1×10 ^-2 Pa. Repeat this step 3-4 times to ensure that the residual oxygen in the furnace is reduced as much as possible. Finally, fill with argon to 0.5 Pa, use induction current to heat and melt, and maintain for 5-10 minutes to finally obtain a master alloy ingot with uniform composition.

(5) Crush the master alloy ingot obtained in step (4) and then clean it. Take the broken pieces and put them into a quartz tube with a small hole on the top. Connect the opening of the quartz tube to the nozzle of the spray casting equipment and seal it. Evacuate to 1×10 ^-3 Pa and pass argon gas. Turn on the induction power supply, melt the alloy pieces, and use a copper single-roll rotary quenching device to make the molten alloy into a strip sample with a width of 2 mm and a thickness of 0.3 mm.

Thermodynamic and mechanical analysis methods are as follows:

(6) The phase structure of the Al ₈₅ Y ₈ Fe ₆ Ta ₁ metallic glass ribbon obtained in step (5) is analyzed by an X-ray diffraction apparatus. See the X-ray diffraction pattern shown in FIG1 .

(7) The thermodynamic parameters of the Al ₈₅ Y ₈ Fe ₆ Ta ₁ metallic glass ribbon obtained in step (5) were measured using a conventional differential scanning calorimeter (DSC). The heating rate was 0.33 K/s, as shown in FIG2 .

(8) The thermodynamic parameters of the Al ₈₅ Y ₈ Fe ₆ Ta ₁ metallic glass ribbon obtained in step (5) were measured using a flash scanning calorimeter (Flash DSC) as a function of the heating rate. The heating rate range was 10-200 K/s, as shown in FIG3 .

(9) The mechanical properties of the Al ₈₅ Y ₈ Fe ₆ Ta ₁ metallic glass ribbon obtained in step (5) were tested using a nanoindenter, including the change in load with the indenter's penetration depth, elastic modulus, and hardness, as shown in FIGS. 19 , 20 , and 21 .

(10) The microstructure, glass forming ability, thermal stability and mechanical properties of the Al ₈₅ Y ₈ Fe ₆ Ta ₁ metallic glass ribbon obtained in step (5) were analyzed using an X-ray diffractometer, a differential scanning calorimeter (DSC), a flash scanning calorimeter (Flash DSC) and a nanoindenter.

As can be seen from Figure 1, the prepared Al ₈₅ Y ₈ Fe ₆ Ta ₁ alloy strip shows a clear diffuse peak, indicating that the alloy composition is amorphous. As can be seen from Figure 2, the prepared Al ₈₅ Y ₈ Fe ₆ Ta ₁ alloy strip shows a glass transition temperature T _g and an initial crystallization temperature T _x . The parameters for determining the glass forming ability and thermal stability of metallic glass are the supercooled liquid phase region ΔT (T _x -T _g ) and the crystallization activation energy _Ex . As shown in Figure 2, the supercooled liquid phase region ΔT is 122K, as shown in Figure 16. According to Figure 3, the heat flow curve shown in Figure 17 changes with the heating rate, and the crystallization activation energy _Ex can be calculated to be 364.5kJ/mol, as shown in Figure 18.

According to the relationship curve between load and indenter penetration depth shown in FIG19 , specific hardness and elastic modulus values can be obtained, as shown in FIGS. 20 and 21 .

The thermodynamic parameters and mechanical parameters of this Example 1 are shown in Table 1.

Example 2: Preparation of Al ₈₅ Y ₈ Fe ₆ Re ₁ metallic glass ribbon sample with a rotation rate of 2000 rpm by copper single roller rotation quenching method

The preparation method, thermodynamic and mechanical analysis methods are the same as those in Example 1.

(1) The phase structure of the Al ₈₅ Y ₈ Fe ₆ Re ₁ metallic glass ribbon was analyzed by an X-ray diffraction pattern as shown in FIG4 .

(2) The thermodynamic parameters of the Al ₈₅ Y ₈ Fe ₆ Re ₁ metallic glass ribbon were measured by conventional differential scanning calorimetry (DSC) at a heating rate of 0.33 K/s, as shown in FIG5 .

(3) The thermodynamic parameters of the Al ₈₅ Y ₈ Fe ₆ Re ₁ metallic glass ribbon measured by flash scanning calorimetry (Flash DSC) vary with the heating rate in the range of 10-200 K/s, as shown in FIG6 .

(4) The mechanical properties of the Al ₈₅ Y ₈ Fe ₆ Re ₁ metallic glass ribbon tested by a nanoindenter include the change in load with the indenter penetration depth, elastic modulus and hardness, as shown in Figures 19, 20 and 21.

(5) The microstructure, glass forming ability, thermal stability and mechanical properties of Al ₈₅ Y ₈ Fe ₆ Re ₁ metallic glass ribbons were analyzed by X-ray diffractometer, differential scanning calorimeter (DSC), flash scanning calorimeter (FlashDSC) and nanoindenter.

As can be seen from Figure 4, the prepared Al ₈₅ Y ₈ Fe ₆ Re ₁ alloy strip shows a clear diffuse peak, indicating that the alloy composition is amorphous. As can be seen from Figure 5, the prepared Al ₈₅ Y ₈ Fe ₆ Ta ₁ alloy strip shows a glass transition temperature T _g and an initial crystallization temperature T _x . The parameters for determining the glass forming ability and thermal stability of metallic glass are the supercooled liquid phase region ΔT (T _x -T _g ) and the crystallization activation energy _Ex . As shown in Figure 5, the supercooled liquid phase region ΔT is 124K, as shown in Figure 16. According to the change of the heat flow curve with the heating rate shown in Figure 3 and Figure 17, the crystallization activation energy _Ex can be calculated to be 372kJ/mol, as shown in Figure 18.

According to the relationship curve between load and indenter penetration depth shown in FIG19 , specific hardness and elastic modulus values can be obtained, as shown in FIGS. 20 and 21 .

The thermodynamic parameters and mechanical parameters of this Example 2 are shown in Table 1.

Example 3: Preparation of Al ₈₅ Y ₈ Fe ₆ W ₁ metallic glass ribbon sample with a rotation rate of 2000 rpm by copper single roller rotation quenching method

The preparation method, thermodynamic and mechanical analysis methods are the same as those in Example 1.

(1) The phase structure of the Al ₈₅ Y ₈ Fe ₆ W ₁ metallic glass ribbon was analyzed by an X-ray diffraction pattern as shown in FIG7 .

(2) The thermodynamic parameters of the Al ₈₅ Y ₈ Fe ₆ W ₁ metallic glass ribbon were measured by conventional differential scanning calorimetry (DSC) at a heating rate of 0.33 K/s, as shown in FIG8 .

(3) The thermodynamic parameters of the Al ₈₅ Y ₈ Fe ₆ W ₁ metallic glass ribbon measured by flash scanning calorimetry (Flash DSC) vary with the heating rate. The heating rate range is 10-200 K/s, as shown in FIG9 .

(4) The mechanical properties of the Al ₈₅ Y ₈ Fe ₆ W ₁ metallic glass ribbon tested by a nanoindenter include the change in load with the indenter penetration depth, elastic modulus and hardness, as shown in Figures 19, 20 and 21.

(5) The microstructure, glass forming ability, thermal stability and mechanical properties of Al ₈₅ Y ₈ Fe ₆ W ₁ metallic glass ribbons were analyzed by X-ray diffractometer, differential scanning calorimeter (DSC), flash scanning calorimeter (FlashDSC) and nanoindenter.

As can be seen from Figure 7, the prepared Al ₈₅ Y ₈ Fe ₆ W ₁ alloy strip shows a clear diffuse peak, indicating that the alloy composition is amorphous. As can be seen from Figure 8, the prepared Al ₈₅ Y ₈ Fe ₆ W ₁ alloy strip shows a glass transition temperature T _g and an initial crystallization temperature T _x . The parameters for determining the glass forming ability and thermal stability of metallic glass are the supercooled liquid phase region ΔT (T _x -T _g ) and the crystallization activation energy _Ex . As shown in Figure 8, the supercooled liquid phase region ΔT is 127K, as shown in Figure 16. According to the change of the heat flow curve with the heating rate shown in Figure 9 and Figure 17, the crystallization activation energy _Ex can be calculated to be 377kJ/mol, as shown in Figure 18.

According to the relationship curve between load and indenter penetration depth shown in FIG19 , specific hardness and elastic modulus values can be obtained, as shown in FIGS. 20 and 21 .

The thermodynamic parameters and mechanical parameters of this Example 3 are shown in Table 1.

Example 4: Preparation of Al _87.5 Y ₇ Fe ₅ Ta _0.5 metallic glass ribbon sample with a rotation rate of 2000 rpm by copper single roller rotation quenching method

The preparation method, thermodynamic and mechanical analysis methods are the same as those in Example 1.

(6) The phase structure of the Al _87.5 Y ₇ Fe ₅ Ta _0.5 metallic glass ribbon was analyzed by X-ray diffraction analysis, as shown in FIG10 .

(7) The thermodynamic parameters of the Al _87.5 Y ₇ Fe ₅ Ta _0.5 metallic glass ribbon were measured by conventional differential scanning calorimetry (DSC) at a heating rate of 0.33 K/s, as shown in FIG11 .

(8) The thermodynamic parameters of the Al _87.5 Y ₇ Fe ₅ Ta _0.5 metallic glass ribbon measured by flash scanning calorimetry (Flash DSC) vary with the heating rate in the range of 10-200 K/s, as shown in FIG12 .

(9) The mechanical properties of the Al _87.5 Y ₇ Fe ₅ Ta _0.5 metallic glass ribbon tested by a nanoindenter include the change in load with the indenter penetration depth, elastic modulus and hardness, as shown in Figures 19, 20 and 21.

(10) The microstructure, glass forming ability, thermal stability and mechanical properties of Al _87.5 Y ₇ Fe ₅ Ta _0.5 metallic glass ribbons were analyzed by X-ray diffractometer, differential scanning calorimeter (DSC), flash scanning calorimeter (Flash DSC) and nanoindenter.

As can be seen from Figure 10, the prepared Al _87.5 Y ₇ Fe ₅ Ta _0.5 alloy strip shows an obvious diffuse peak, indicating that the alloy composition is amorphous. As can be seen from Figure 11, the prepared Al _87.5 Y ₇ Fe ₅ Ta _0.5 alloy strip shows a glass transition temperature T _g and an initial crystallization temperature T _x . The parameters for determining the glass forming ability and thermal stability of metallic glass are the supercooled liquid phase region ΔT (T _x -T _g ) and the crystallization activation energy _Ex . As shown in Figure 11, the supercooled liquid phase region ΔT is 116K, as shown in Figure 16. According to the change of the heat flow curve with the heating rate shown in Figure 12, it can be calculated that the crystallization activation energy _Ex is 360kJ/mol, as shown in Figure 18.

According to the relationship curve between load and indenter penetration depth shown in FIG19 , specific hardness and elastic modulus values can be obtained, as shown in FIGS. 20 and 21 .

The thermodynamic parameters and mechanical parameters of this Example 4 are shown in Table 1.

Example 5: Preparation of Al ₈₇ Y ₆ Fe ₄ W ₃ metallic glass ribbon sample with a rotation rate of 2000 rpm by copper single roller rotation quenching method

The preparation method, thermodynamic and mechanical analysis methods are the same as those in Example 1.

(11) The phase structure of the Al ₈₇ Y ₆ Fe ₄ W ₃ metallic glass ribbon was analyzed by X-ray diffraction analysis, as shown in FIG13 .

(12) The thermodynamic parameters of the Al ₈₇ Y ₆ Fe ₄ W ₃ metallic glass ribbon were measured by conventional differential scanning calorimetry (DSC) with a heating rate of 0.33 K/s, as shown in FIG14 .

(13) The thermodynamic parameters of Al ₈₇ Y ₆ Fe ₄ W ₃ metallic glass ribbons measured by flash scanning calorimetry (Flash DSC) vary with heating rate in the range of 10–200 K/s, as shown in FIG15 .

(14) The mechanical properties of Al ₈₇ Y ₆ Fe ₄ W ₃ metallic glass ribbons tested by nanoindenter include the change of load with the penetration depth of the indenter, elastic modulus and hardness, as shown in Figures 19, 20 and 21.

(15) The microstructure, glass forming ability, thermal stability and mechanical properties of Al ₈₇ Y ₆ Fe ₄ W ₃ metallic glass ribbons were analyzed by X-ray diffractometer, differential scanning calorimeter (DSC), flash scanning calorimeter (Flash DSC) and nanoindenter.

As can be seen from Figure 13, the prepared Al ₈₇ Y ₆ Fe ₄ W ₃ alloy strip shows an obvious diffuse peak, indicating that the alloy composition is amorphous. As can be seen from Figure 14, the prepared Al ₈₇ Y ₆ Fe ₄ W ₃ alloy strip shows a glass transition temperature T _g and an initial crystallization temperature T _x . The parameters for determining the glass forming ability and thermal stability of metallic glass are the supercooled liquid phase region ΔT (T _x -T _g ) and the crystallization activation energy _Ex . As shown in Figure 14, the supercooled liquid phase region ΔT is 129K, as shown in Figure 16. According to the change of the heat flow curve with the heating rate shown in Figure 15, it can be calculated that the crystallization activation energy _Ex is 379kJ/mol, as shown in Figure 18.

According to the relationship curve between load and indenter penetration depth shown in FIG19 , specific hardness and elastic modulus values can be obtained, as shown in FIGS. 20 and 21 .

The thermodynamic parameters and mechanical parameters of Example 5 are shown in Table 1.

Table 1

Claims (3)

1. A high-heat-stability aluminum-based metallic glass is characterized in that the atomic percentage formula is Al _a Y _b Fe _c X _d Wherein X is a high-melting-point metal element; the atomic percentages of the components are as follows: 81.ltoreq.a < 90,6.ltoreq.b.ltoreq.8, 4.ltoreq.c.ltoreq.6, 0 < d.ltoreq.5, a+b+c+d=100;

the preparation method of the high-heat-stability aluminum-based metal glass is characterized by comprising the following steps of:

batching according to the atomic percentage of the high-heat-stability aluminum-based metal glass, obtaining a first master alloy through electric arc heating smelting, obtaining a master alloy ingot through induction heating smelting of the first master alloy, melting the master alloy ingot, and then spraying the molten master alloy ingot onto the surface of a rotating copper roller to obtain the strip-shaped high-heat-stability aluminum-based metal glass;

the arc heating and smelting to obtain a first master alloy comprises the following steps:

(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 ^-2 Pa, filling inert gas to the gas pressure of (1-5) x 10 ^-1 Pa, re-adjusting the vacuum degree in the vacuum arc melting furnace to be less than 1 multiplied by 10 ^-2 Pa；

(2) Repeating the step (1) for 3-4 times, and charging inert gas again until the gas pressure is (1-5) multiplied by 10 ^-1 Pa, heating at 2000-3000 ℃, smelting for 5-10 minutes, repeatedly smelting for 5-6 times, cooling along with a furnace, and taking out to obtain a first master alloy;

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

(1) Placing a 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 ^-2 Pa, filling inert gas to the gas pressure of (1-5) x 10 ^-1 Pa, re-adjusting the vacuum degree in the vacuum arc melting furnace to be less than 1 multiplied by 10 ^-2 Pa；

(2) Repeating the step (1) for 3-4 times, and charging inert gas again until the gas pressure is (1-5) multiplied by 10 ^-1 Pa, the power of the used power supply is 30-60kW, the smelting temperature is 1500-2500 ℃, and the smelting time is 5-10 minutes;

x is Ta, re or W;

the high-heat-stability aluminum-based metallic glass has the elastic modulus of 58-62GPa and the hardness of 4.3-4.6GPa.

2. The high thermal stability aluminum-based metallic glass according to claim 1, wherein the supercooled liquid region of the high thermal stability aluminum-based metallic glass is 120 to 130 ℃, and the crystallization activation energy is 360 to 380kJ/mol.

3. The method for producing a high thermal stability aluminum-based metallic glass according to claim 1, wherein the rotation rate of the copper roller is 1000 to 4000rmp.

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